Organometallics, 1998, 17(5), 832-838, DOI:10.1021/om970909z

Terms & ConditionsElectronic Supporting Information files are available without a subscription to ACS Web Editions. The American ChemicalSociety holds a copyright ownership interest in any copyrightable Supporting Information. Files available from the ACSwebsite may be downloaded for personal use only. Users are not otherwise permitted to reproduce, republish,redistribute, or sell any Supporting Information from the ACS website, either in whole or in part, in either machine-readable form or any other form without permission from the American Chemical Society. For permission to reproduce,republish and redistribute this material, requesters must process their own requests via the RightsLink permissionsystem. Information about how to use the RightsLink permission system can be found athttp://pubs.acs.org/page/copyright/permissions.html

Copyright © 1998 American Chemical Society

C22

C12C31

C32 SiC1o

C13

C21

Lil

C43 C4T

C42

C33

Sni

01T

C52

C1T

C2T

C3T

C53C41

Table 1. Crystal data and structure refinement for 5

IdentIfication code

Empirical formula

Formula weight

Temperature

Wavelength

Crystal system

Space group

Unit cell dimensions

Volume, Z

Density (calculated)

Absorption coefficient

F(000)

Crystal size

0 range for data collection

Limiting indices

Reflections collected

Independent reflections

Absorption correction

Max. and min. transmission

Refinement method

Data / restraints / parameters

Goodness-of-fit on F2

Final R indices [I>2a(I))]

R indices (all data)

Extinction coefficient

Largest diff. peak and hole

nsu

C 24H 51LiN3 0 3SSi 2Sn

643.55

193(2) K

71.073 pm

Triclinic

a = 1141.3(2) pm

b = 1186.1(2) pm

c = 1221.5(2) pm

31.6053(5) nm , 2

1.331 Mg/m3

0.963 mm-1

674

alpha = 93.815(7)o

beta = 95.791(8)0

gamma = 101.563(8)0

0.50 x 0.40 x 0.40 mm

2.26 to 25.030

-15 as 15, -16 sk a 15, 0 a 1 S16

14213

5629 (Rint = 0.077)

Semi empirical

0.7861 and 0.7348

Full-matrix least-squares on F2

5629 / 105 / 324

1.090

R1 = 0.0466, wR2 = 0.1254

RI = 0.0475, wR2 = 0.1264

0.017(2)

2371 and -1252 e.nm-3

Table 2. Atomic coordinates ( x 10 4) and equivalent isotropic2 -1

displacement parameters (pm x 10 ) for 5. U(eq) is defined as

one third of the trace of the orthogonalized Ui) tensor.

x y z U(eq)

Sn(1) 6674(1) 6609(1) 902(1) 19(1)Li(1) 7175(6) 7440(5) 3448(5) 25(1)

S(1) 6304(1) 8822(1) 2010(1) 19(1)N(1) 6938(3) 9080(3) 3246(3) 24(1)C(10) 7096(3) 10258(3) 3843(3) 26(1)C(11) 8403(4) 10944(4) 3837(4) 41(1)

C(12) 6222(4) 10995(3) 3375(4) 37(1)C (13) 6893(5) 10052(4) 5036(4) 46(1)N(2) 5622(3) 7409(3) 2002(3) 22(1)C(20) 4355(3) 7144(3) 2274(3) 25(1)C(21) 4357(4) 6940(5) 3513(4) 42(1)

C(22) 3680(4) 8127(4) 2055(5) 45(1)

C(23) 3674(4) 6041(4) 1576(5) 43(1)N(3) 7291(3) 8493(2) 1151(3) 20(1)C(30) 7431(3) 9217(3) 195(3) 25(1)C(31) 6257(4) 9019(4) -611(4) 37(1)C(32) 7832(4) 10523(3) 590(4) 37(1)C(33) 8425(4) 8846(4) -413(4) 36(1)N(4) 7942(3) 6293(2) 2357(2) 19(1)Si(1) 7600(1) 4817(1) 2594(1) 23(1)C(41) 8271(5) 3864(4) 1653(4) 42(1)C(42) 8054(4) 4534(4) 4054(4) 40(1)C(43) 5920(4) 4209(4) 2361(4) 38(1)Si(2) 9466(1) 6908(1) 2291(1) 23(1)C(51) 9874(3) 8512(3) 2728(4) 31(1)C(52) 9910(4) 6649(4) 861(4) 36(1)C(53) 10533(4) 6288(4) 3238(4) 39(1)O(1T) 7391(2) 7114(3) 5014(2) 33(1)C(1T) 6558(4) 6786(5) 5805(4) 46(1)C2Ta 7207(9) 7221(14) 6938(8) 46(2)C3Ta 8482(10) 7085(14) 6751(8) 43(2)C(4T) 8601(4) 7495(4) 5590(4) 40(1)C2T'b 7390(8) 6634(10) 6839(7) 46(2)C3T'b 8486(9) 7622(11) 6792(7) 47(2)

Table 3. Bond lengths [pm] and angles (] for 5.

Sn(1) -N (2)Sn(1) -N(4)Li(l)-O(lT)Li(1)-N(4)Li(1)-S(1)S(1) -N (3)N(1)-C (10)C(10)-C(12)N(2) -C(20)C(20)-C(22)N(3) -C(30)C(30) -C(31)N (4) -Si(2)Si(l)-C(42)Si(l)-C(43)Si(2)-C(52)0(1T)-C(lT)

C(1T) -C2TaC2Ta-C3TaC(4T)-C3T'b

218.2 (3)227.6(3)197.7(7)220.6(7)272.9(6)169.8(3)150.1(5)154.4(6)149.3(4)154.4(6)149.8(4)154.9(6)175.8(3)187.8(4)189.4(4)189.0(4)144.1(5)150.9(10)153.4(12)148.7(9)

Sn(1) -N (3)Sn(1)-Li(1)Li (1) -N (1)Li (1) -N (2)

S (1) -N (1)S (1) -N(2)

C(10)-C(13)C(10)-C(11)C(20)-C(23)C(20)-C(21)C(30)-C(33)C(30)-C(32)N(4) -Si (1)Si(1)-C(41)Si(2)-C(53)Si(2)-C(51)O(1T)-C(4T)C(lT)-C2T'bC3Ta-C (4T)C2T'b-C3T'b

C(1T)-O(1T)-Li(1)

O(lT)-C(iT)-C2TaC(1T) -C2Ta-C3TaO(1T)-C(4T)-C3T'bC3T'b-C2T'b-C (IT)219.4(3)

316.0(7)204.4(7)236.6(7)158.9(3)169.9(3)152.7(6)155.0(5)153.3(6)154.8(6)153.6(6)155.3(5)176.5(3)188.0(5)188.5(4)189.2(4)145.5(5)154.5(9)154.0(10)154.1(11)

133.0(3) C(4T)-0(1T)-Li(1)107.4(5)

99.6 (8)107.3(5)101.5 (7)

0(1T)-C(lT)-C2T'bC2Ta-C3Ta-C(4T)O(1T)-C(4T) -C3TaC(4T) -C3T'b-C2T'b

Symmetry transformations used to generate equivalent atoms:

N(2)-Sn{1)-N(3)

N(3) -Sn(1) -N(4)

N(3)-Sn(1)-Li(1)

O(1T)-Li(1)-N(1)

N(1)-Li(1)-N(4)

N(1)-Li(1)-N(2)

0(1T)-Li(1)-S(l)

N(4) -Li (1) -S(1)0(1T)-Li(1)-Sn(1)N(4)-Li(l)-Sn(l1)

S(1)-Li()-Sn(1)

N(2)-S(1)-Li(1)

C(10)-N(1)-Li(1)

N1()-C(10)-C(13)C(13)-C(10)-C(12)C(13) -C(10) -C (11)C(20)-N(2) -S(1)S(1) -N (2) -Sn(1)S(1)-N{2)-Li(1)

N(2)-C(20)-C(23)C(23)-C(20)-C(22)C(23) -C(20) -C(21)C(30)-N(3)-S(1)S(1)-N(3)-Sn(l)

N(3)-C(30)-C(31)

N() -C (30) -C (32)C(31)-C{30)-C(32)Si(2)-N(4)-Li(1)

Si(2)-N(4)-Sn(1)

Li{1)-N(4)-Sn(1)

N(4) -Si (1)-C (41)N(4) -Si (1) -C (43)

C(41)-Si(1)-C(43)N(4)-Si(2)-C(52)N(4) -Si(2) -C(51)C(52)-Si(2)-C(51)

67.76(11)93.46(11)69.43(14)

113.4(3)128.9(3)69.8(2)

144.9(3)102.5(3)151.2(3)46.07(14)60.70(13)

100.9(2)48.1(2)59.3(2)

142.9(3)105.7(3)109.5(4)108.2(4)117.6(2)100.41(14)82.6(2)

108.8(3)108.8(3)109.1(4)114.9(2)

99.98(13)112.0(3)111.5(3)109.3(3)109.3 (2)114.03(14)89.7(2)

114.0(2)111.5(2)105.1(2)111.6(2)113.3(2)108.9(2)

N(2)-Sn (1)-N (4)N(2) -Sn(1) -Li(1)N(4)-Sn(2)-Li(1)0(1T)-Li(1)-N(4)0(2T)-Li(1)-N(2)

N(4)-Li(1)-N(2)N(1)-Li(1)-S(1)

N(2) -Li(1) -S(1)N(1)-Li(3)-Sn(1)N(2)-Li(1)-Sn(1)N(1)-S(1)-N(3)l

N(3)-S(1)-N(2)

N(3)-S(1)-Li{(1)C(10)-N(1)-S(1)

S(1)-N{-Li()

N(4)-C(10)-C(12)N(1)-C(10)-C(11)

C(12)-C(10)-C(11)

C(20)-N(2)-Sn(1)C(20)-N(2)-Li(l)

Sn(1)-N(2)-Li(1)N(2)-C{20)-C(22)

N(2)-C(20)-C(21)

C(22)-C(20)-C(21)

C(30)-N(3)-Sn(1)

N(3)-C(30)-C(33)

C(33)-C(30)-C(31)

C(33)-C(30)-C(32)

Si(2)-N(4)-Si(1)

Si(1)-N{4)-Li(1)

Si (1) -N (4) -Sn (1)N(4)-Si(1)-C(42)

C(42)-Si{1)-C(41)

C(42)-Si(1)-C(43)

N(4)-Si(2)-C(53)

C (53) -Si (2) -C (52)

C(53)-Si(2)-C(51)

C(1T)-O(1T)-C{4T)

116.3(3)102.9(4)102.5 (8)103.6(5)

99.5 (7)

91.49(11)48.44(14)44.28(13)

112.5(3)140.2(3)88.5(3)35.35(14)38.13(12)94.8(2)43.65(13)

110.3(2)91.8(2)87.5(2)

120.4(3)96.5(2)

114.7(3)110.2(3)108.4(3)135.6(2)117.5(3)

87.9(2)113.1(3)109.3(3)107.8(4)121.5(2)106.3 (3)109.1(3)108.6(3)116.6(2)115.0(2)109.31(14)113.6(2)107.7(2)104.2(2)113.4(2)105.2(2)103.8(2)109.4(3)

2 -1Table 4. Anisotropic displacement parameters [pm x 10 1 for 5.

The anisotropic displacement factor exponent takes the form:

2 * 2 * *-21r [ (ha*) Ull + ... + 2hkabU

Ull U22 U33 U23 U13 U12

Sn (1)Li (1)S(1)N(1)

C (10)C (11)C(12)C (13)N(2)

C (20)C (21)C (22)C (23)N(3)

C (30)C(31)C(32)C(33)N (4)

Si (1)C (41)C (42)C (43)Si (2)C(51)C (52)

C(53)0 (1T)C (1T)C2TaC3Ta

C (4T)C2T'bC3T'b

20(1)25(3)16(1)25(2)22(2)28(2)35(2)62(3)17(1)11(2)27(2)22(2)26(2)22(2)31(2)47(3)51(3)43 (2)18 (1)24(1)

54(3)51(3)29(2)16(1)

19(2)32(2)20(2)28(1)34(2)41(4)42(3)28(2)43(4)41(3)

13(1)

17(3)12(1)15(2)

16(2)24(2)19(2)36(3)14(1)20(2)50(3)31(2)30(2)16(1)

14(2)29(2)16(2)33(2)14(1)13(1)20(2)23(2)26(2)21(1)

25(2)33(2)40(2)40(2)62(3)56(5)51(5)48(3)57(5)53(5)

21(1)

32(4)27(1)30(2)34(2)61(3)53(3)39(3)31(2)41(2)46(3)81(4)65(3)24(2)26(2)34(2)40(3)31(2)23(2)31(1)52(3)42(3)56(3)31(1)

44(2)43(3)57(3)30(2)34(2)33(3)32(3)40(2)32(3)35(3)

-1(1)

3(2)0(1)

-4(1)-10(2)-12(2)-11(2)-13(2)-1(1)

1(2)10(2)

9(2)-6(2)6(1)

8(1)5(2)7(2)8(2)4(1)

5(1)-1(2)15(2)15(2)5(1)

1(2)7(2)

16(2)7(1)5(2)

-5(4)-2(4)1(2)6(3)

-5(4)

-1(1)

1(3)1(1)2(1)3(2)2(2)3(2)

11(2)5(1)

-1(2)6(2)8(2)3(2)6(1)4(2)

-5(2)9(2)

12(2)1(1)1(1)

8(2)-2(2)

3(2)4(1)

-1(2)16(2)

3(2)4(1)6(2)7(3)

-4(3)3(2)4(3)

-1(3)

0(1)

2(2)-1(1)-1(1)

-3(1)-7(2)5(2)9(2)

-2(1)

-4(1)-4(2)2(2)

-5(2)3(1)-1(1)7(2)

-5(2)2(2)

-1(1)0(1)9(2)1(2)

-5(2)2(1)

-6(2)5(2)7(2)-1(1)

-10(2)-5(4)5(4)

-4(2)-7(4)-8(4)

Table 5. Hydrogen coordinates ( x 10 4) and isotropic

displacement parameters (pm2 x 10- ) for 5.

x y z U(eq)

H(11A)H (11B)

H (11C)H (12A)H(12B)

H(12C)*(13A)

H (13B)

H (13C)

H(21A)

H (21B)

H (21C)

H (22A)

H (22B)H (22C)

H (23A)H (23B)

H (23C)H (31A)

H (31B)

H (31C)

H(32A)H (32B)

H (32C)H (33A)

H(3 3B)

H(33C)H (41A)H (41B)

H (41C)H (42A)

H (42B)

H (42C)

H (43A)

H (43B)

H (43C)

H (51A)

H (51B)

H(s1C)

H(52A)H (52B)

H (52C)

H (53A)H (53B)

H (53C)H1T3b

H1T4b

H1T1a

H1T2a

H2T1a

H2T2a

H3T1aH3T2a

85078559896963685390635574836078698947764771352628463684408040843655284956046044638072047963858286068151

91529150803579768925

78447630

5757

562455109731

93761072610694

93039962

113651037910410

59816104

6287

5843

6883

7175

8561

9093

116941106410507

11737

1058511130

96289599

10796764863116734789282888824540761705842920282099520

107711096810652

93488044891140593984305448103702494134054241466686478913880771476829583866245448646960557396593571326738803662707574

4263307541713822339526105349505554713963367236872217127925301723

7911768-214-916

-1214978-51

1091-1007

-729107

1810883

1778423841294558254515852833349922552656

804310726

31263074400755405958575056617514713567707310

H4T1aH4T2aH4T3bH4T4bH2T3bH2T4bH3T3bH3T4b

88629185899390967009761683209212

83467136824369206729587083847500

56275220534454337523678970257246

4949494955555656

C13

C21

01

02

Table 1. Crystal data and structure refinement for 4

Identification code

Empirical formula

Formula weight

Temperature

Wavelength

Crystal system

Space group

Unit cell dimensions

Volume, Z

Density (calculated)

Absorption coefficient

F(000)

Crystal size

0 range for data collection

Limiting indices

Reflections collected

Independent reflections

Absorption correction

Max. and min. transmission

Refinement method

Data / restraints / parameters

Goodness-of-fit on F2

Final R indices [I>2a(I)]

R indices (all data)

Largest diff. peak and hole

brava

C H Ba 2LiN 02 S 2Si

1077.07

153(2) K

71.073 pm

Triclinic

pl

a = 1178.3(3) pm alpha = 94.290(10)o

b = 1281.0(3) pm beta = 104.35 (2)0

c = 1974.6(5) pm gamma = 93.84(2)o

32.8681(12) nm , 2

1.247 Mg/m3

1.512 mm-1

1112

0.40 x 0.30 x 0.20 mm

3.20 to 22.500

-12 sh 512, -13 sk z13, -14 s 1 5 21

7661

7475 (R, = 0.0566)IntSemi empirical using Psi-scans

0.7851 and 0.7391

2Full-matrix least-squares on F

7475 / 1188 / 660

1.070

RI = 0.0459, wR2 = 0.1347

RI = 0.0555, wR2 = 0.1450

1788 and -933 e.nm-3

Table 2. Atomic coordinates ( x 10 4) and equivalent isotropic2 -l

displacement parameters (pm x 10 ) for 4. U(eq) is defined as

one third of the trace of the orthogonalized UI) tensor.

x y z U(eq)

Ba(1)Ba (2)

S(1)N(1)

C(10)C(11)C(12)C(13)N(2)

C(20)C (21)C(22)C (23)N(3)C(30)

C(31)C(32)C (33)S(2)

N(4)

C(40)

C41aC42a

C43a

C41'bC42'b

C43'bN(5)

C(50)C51aC52aC53aC51'bC52'bC53 'bN(6)

C(60)C61aC62aC63aC61'bC62'bC63'bLi (1)N(7)

Si (1)C(71)

C(72)C(73)Si (2)C(81)C(82)

348(1)2330(1)-255(2)

-13(5)-478(7)-382(9)248(9)

-1756(8)-69(5)

-1176(7)-2193(7)-851(8)

-1587(8)939(6)776(9)937(13)

1759(11)-430(10)3281(2)3213(5)4184(7)4541(14)5288(11)3778(12)4110(4)5420(2)3780(3)2359(5)2772(7)3009(11)1725(11)3866(11)2340(3)2230(3)4095(14)2587(5)3117(6)2261(16)3310(2)4311(13)2710(2)2610(2)4458(11)1732(11)3607(6)2844(2)1337(9)3465(11)2614(13)4979(3)4990(14)5915(12)

5651(1)8467(1)8241(1)7221(5)7221(6)6111(7)7982(8)7486(10)7724(5)7638(6)6978(7)7109(7)8722(7)9032(4)

10181(6)10690(7)10653(7)10414(8)6228(1)7429(5)7835(6)8957(8)7239(12)7976(15)9001(13)7540(3)7280(3)5434(5)4580(6)5035(10)3788(10)4117(13)4310(3)3622(19)4430(3)6385(5)5876(6)6034(18)4712 (10)6498(17)6390(2)4716(11)5880(2)7838(10)9801(5)

10165(2)9454(9)9831(10)

11606(9)10240(3)11155(10)10955 (12)

2588(1)2408(1)2986(1)3456(3)4081(4)4300(5)4700(5)3942(6)2223(3)1650(4)1816(5)1015(4)1471(5)3341(3)3406(5)2755(6)4034(6)3520(7)3257(1)3598(3)4224(4)4060(8)4331(11)4899(6)4360(2)4250(3)4813(14)3494(3)3913(4)4711(5)3836(8)3813(9)4536(12)3335(13)4020(2)2431(3)1896(4)1191(8)1929(11)1952(11)1218(10)1763 (13)2103(13)3846(6)1820(3)1060(1)801(5)291(5)

1070(8)2254(2)3041(6)1763(7)

39(1)41(1)45(1)42(1)58(2)76(2)86(3)96(3)43(1)53(2)67(2)66(2)69(2)50(2)68(2)

102 (3)96(3)98(3)40(1)47(1)59(2)75(4)62(3)76(4)77(6)64(6)67(6)48(1)66(2)67(3)82(4)72(4)76(5)79(6)62(6)44(1)57(2)65(4)79(4)79(4)66(5)69(5)79(5)51(3)56(2)59(1)87(3)97(4)

124(5)81(1)

131(6)133 (6)

C(83)0(1)ClTaC2TaC3TaC4TaC1'TbC2'TbC3'ThC4'Tb0(2)C5TaC6TaC7TaC8TaCS'TbC6'ThC7'TbCB 'Tb

5871(11)-1561(6)-2774(12)-3149(17)-2228(18)-1468(15)-2742(15)-3489(17)-2710(2)-1530(2)-411(6)-250(2)

-1000(2)-1060(3)

-870(3)210(16)

-694(19)-1813(18)-1520(18)

9089(13)4264(6)4517(15)3980(15)3258(15)3252(12)4270(3)3900(3)3620(3)3600(3)4032(5)2999(11)2274(13)2827(13)3966(12)3116(14)2263(13)2772(13)3910(13)

2539(8)2817(4)2724(11)3285(13)3548(10)3061(13)2427(14)2873(18)3532(14)3404(14)1472(3)1723(9)1140(10)486(8)726(7)

1372(16)1020(16)755(14)951(13)

136(6)91(2)92(3)93(3)96(3)98(3)96(3)96(3)94(3)93(3)90(2)96(3)

102(4)105(4)101(4)101(4)103(4)100(4)96(4)

Table 3. Bond lengths [pm] and angles [0] for 4.

Ba(1) -N(5)Ba(1) -0(2)Ba(1)-N(2)Ba(1) -S(2)

Ba(1)-Li(1)3a(2) -N(6)

1a(2) -N(4)Sa(2)-N(2)3a (2)-S (1)S(1) -N(3)

S(1) -N(2)

N(1) -C(10)C(10)-C(11)C(10)-C(12)C(20)-C(22)C(20) -C(23)N (3) -Li(1)C(30)-C(31)S(2) -N(S)

S(2)-N(6)

N(4) -Li(1)C(40)-C42'bC(40) -C42aC(40)-C43'bC(50)-C51'bC(50) -C52aC(50) -C51aN(6) -C(60)C(60) -C62aC(60) -C61aC (60) -C63aN(7) -Si(2)Si(1)-C(72)Si(2)-C(81)Si(2)-C(83)0(1) -C4Ta

0(1) -C4'TbC2Ta-C3TaC1'Tb-C2'TbC3'Tb-C4'Tb0(2)-C8'Tb0(2)-C5TaC6Ta-C7Ta

CS'Tb-C6'TbC7'Tb-C8'Tb

N(5) -Ba(1) -N(l)

N(1) -Ba(1) -0(2)

N(l)-Ba(1)-N(6)

N(5) -Ba(1) -N(2)

0(2) -Ba(1) -N(2)N(5)-Ba(1)-0(1)

0(2) -Ba(1) -0(1)

U(2)-Ba(1)-O(1)

R(l)-Ba(1)-S(2)

N (6) -Ba (1) -S (2)

0(1) -Ba(1) -S(2)

R(1)-Ba(1)-S(1)IT(6) -Ba (1) -S (1)

263.8(6)283.7(6)284.5(6)338.8(2)360.7(13)270.7(6)279.5(6)284.6(6)350.9(2)164.6(7)167.2(6)147.0(9)152.0(9)154.0(10)152.4(11)153.7(11)204(2)153.3(13)161.5(6)166.6(6)202(2)152.5(14)153.0(11)155.9(14)149.7(13)151.3(11)158.8(11)148.6(9)152.6 (12)154.1(12)154.5(12)166.8(7)187.6(10)187.3(13)190.6(14)141.9(13)147.9(14)149.4(14)147(2)147(2)143.9 (13)145.5(13)151(2)147.5(14)147.5(14)

89.0(2)153.2(2)100.0(2)116.5 (2)115.6(2)111.4(2)

69.2 (2)119.8(2)

88.66(13)29.38(12)

139.1(2)26.95(13)90.51(12)

Ba(1) -N(1)Ba(1) -N(6)

Ba(1) -0(1)Ba(1) -S(1)

Ba(1)-Ba(2)

Ba(2) -N(7)Ba(2) -N(3)

Ba(2)-Li(1)

Ba(2) -S(2)S (1) -N(1)

S (1) -Li (1)N(1) -Li(1)C(10)-C(13)N(2) -C(20)C(20)-C(21)N(3) -C(30)C(30)-C(32)C(30)-C(33)S (2) -N(4)

N(4) -C(40)C(40)-C41'bC (40) -C43aC(40) -C41aN(5) -C(50)C(50) -C53aC(50)-C53'bC(50)-C52'bC(60)-C61'bC(60) -C63'bC(60)-C62'bN(7) -Si(1)Si(1)-C(71)Si(1)-C(73)Si(2)-C(82)0(1) -C1'Tb0(1) -CITaC1Ta-C2TaC3Ta-C4TaC2'Tb-C3'Tb0(2)-C8Ta0(2)-C5'TbC5Ta-C6TaC7Ta-C8TaC6'Tb-C7'Tb

N(5) -Ba(l) -0(2)

N(5)-Ba(1)-N(6)

0(2)-Ba(l)-N(6)

N(1) -Ba(l) -N(2)N(6)-Ba(1)-N(2)

N(l)-Ba(1)-0(1)

N(6) -Ba(1) -0(1)

N(5)-Ba(1)-S(2)

0(2)-Ba(1)-S(2)

N(2) -Ba(1) -S(2)

N(S)-Ba(1)-S(1)

0(2) -Ba(1) -S(1)N(2)-Ba(l)-S(1)

266.9(6)283.8(6)291.7(6)351.2(2)425.00(12)271.1(6)283.9(6)323.4(12)353.6(2)165.7(6)263.6(13)208.6(14)152.8(9)149.2(9)153.6(11)149.8(9)152.5(14)153.7(14)164.8(6)149.3(9)150.8(14)152.6(10)155.0(11)145.7(10)150.5(11)155.0(14)159.6(14)152.5(13)153.0(12)154.3(12)166.4(7)187.3(10)188.3(11)187.7(11)141(2)145.7(12)148.9(13)146.8(14)148(2)143.1(13)145.1(14)148.0(14)148.5(14)ISO(2)

115.8 (2)55.7(2)

102.4(2)55.0 (2)79.1(2)93.2(2)

161.0 (2)27.68(13)

117.9(2)94.28(12)

104.46(14)138.17(14)28.07(12)

0(1)-Ba(l)-S(l)N(5)-Ba(l)-Li(1)0(2)-Ba(l)-Li(l)

N(2)-Ba(l)-Li(l)

S(2)-Ba(1)-Li(1)N(S)-Ba(l)-Ba(2)

0(2)-Ba(11-Ba(2)

N(2) -Ba(l)-Ba(2)

S(2)-Ba(1)-Ba(2)

Li(1)-Ba(l)-Ba(2)

N(6) -Ba(2)-N(4)N(6) -Ba(2) -N(3)N(4) -Ba(2) -N(3)N(7) -Ba(2)-N(2)N(3)-Ba(2)-N(2)N(7)-Ba(2)-Li(l)

N(3) -Ba(2) -Li (1)

N(6)-Ba(2)-S(1)N(4)-Ba(2)-S(1)

N(2) -Ba(2) -S(1)N(6) -Ba(2) -S(2)

N(4)-Ba(2)-S(2)N(2)-Ba(2)-S(2)

S(1) -Ba(2)-S(2)

N(7) -Ba(2) -Ba(l)N(3) -Ba(2)-Ba()

Li(1)-Ba(2)-Ba(l)

S(2)-Ba(2)-Ba(l)

N(3) -S(1) -N(2)

N(3) -S (1) -Li (1)

N(2)-S(1)-Li(l)N(l)-S(1)-Ba(2)Li(1) -S(1) -Ba(2)

N(1)-S(1)-Ba(l)

Li(l)-S(1)-Ba(l)

C (10) -N(1) -S (1)S(1)-N(1)-Li(l)S(1)-N(l)-Ba(l)N(1) -C(10) -C(11)C(1l)-C(10)-C(13)C(11)-C(10)-C(12)C(20)-N(2)-S(1)S(1) -N(2) -Ba(1)S(1) -N(2) -Ba (2)

N(2) -C(20) -C(22)C(22)-C(20)-C(21)C (22)-C (20) -C (23)C(30)-N(3)-S(1)S(1)-N(3)-Li(1)

S(1) -N(3) -Ba(2)

N(3)-C(30)-C(32)

C (32)-C(30)-C(31)C(32) -C(30) -C(33)N(5) -S(2) -N(4)N(4) -S(2) -N(6)N(4)-S(2)-Ba(l)

N(5) -S (2)-Ba (2)

N(6) -S (2)-Ba (2)

C (40) -N(4) -S (2)S(2)-N(4)-Li(1)

S(2) -N(4)-Ba(2)

N(4) -C(40) -C41'bC41'b-C(40)-C42'b

107.1(2)61.0(3)

169.4(3)61.5(2)54.0(2)79.47(13)

122.7(2)41.70(12)53.73(3)47.8(2)53.8(2)

108.2(2)75.4 (2)

138.2(2)55.4(2)

145.9(3)38.6(3)92.78(13)82.44(13)28.10(12)27.01(13)27.08(12)91.17(12)90.02(5)

157.20(14)74.24 (12)55.7(2)50.58(3)

105.5(3)50.7(4)

100.2(3)100.5(2)61.6(3)46.9(2)70.2(3)

116.9(5)88.8(4)

106.2(3)105.0(6)109.8(8)107.7(7)112.2(5)

98.7(3)98.6(3)

104.5(6)109.9(7)108.6(7)116.1(6)90.7(4)99.5(3)

105.2(7)108.2 (9)110.4(8)109.0(3)

97.5(3)96.8(2)

120.6(2)47.5(2)

116.4(5)120.3(5)102.4(3)108(2)113(2)

S (2) -Ba(1) -S(1)

N(1)-Ba(1)-Li(1)N(6) -Ba(1) -Li(1)

0(1)-Ba(1)-Li(1)S(1) -Ba(1) -Li(1)

N(1) -Ba(1) -Ba(2)

N(6) -Ba(1) -Ba(2)0(1) -Ba(1) -Ba(2)

S(1)-Ba (1)-Ba (2)

N(6)-Ba(2)-N(7)N(7) -Ba(2) -N(4)N(7) -Ba(2) -N(3)N(6) -Ba(2) -N(2)

N(4) -Ba(2) -N(2)N(6) -Ba(2) -Li(1)N(4)-Ba(2)-Li(1)N(2)-Ba(2)-Li(1)

N(7)-Ba(2)-S(1)N(3) -Ba(2) -S (1)

Li (1) -Ba (2) -S(1)N(7) -Ba(2) -S(2)N(3) -Ba(2) -S (2)

Li(1) -Ba(2) -S(2)

N(6)-Ba(2)-Ba(1)N(4)-Ba(2)-Ba(1)N(2)-Ba(2)-Ba(1)

S(1)-Ba(2)-Ba(1)

N(3)-S(1)-N(1)

N(1)-S(1)-N(2)

N(1)-S(1)-Li(1)

N(3)-S(1)-Ba(2)N(2)-S(1)-Ba(2)

N(3)-S(1)-Ba(1)N(2)-S(1)-Ba(l)

Ba(2) -S(1)-Ba(1)

C(10) -N(1) -Li (1)C(10)-N(1)-Ba(1)

Li(1)-N(1)-Ba(1)N(1)-C(10)-C(13)N(1)-C(10)-C(12)

C(13)-C(10)-C(12)C(20) -N(2)-Ba(1)C(20)-N(2)-Ba(2)

Ba(1)-N(2)-Ba(2)

N(2)-C(20)-C(21)N(2) -C (20) -C (23)C(21)-C(20)-C(23)C(30)-N(3)-Li(1)

C(30)-N(3)-Ba(2)

Li(1)-N(3)-Ba(2)

N(3)-C(30)-C(31)N(3) -C (30) -C (33)C(31)-C(30)-C(33)N(S)-S(2)-N(6)

N(5)-S(2) -Ba(l)

N(6)-S(2) -Ba(1)

N(4)-S(2)-Ba(2)

Ba(l)-S(2)-Ba(2)

C(40)-N(4)-Li(1)

C(40)-N(4)-Ba(2)Li(1)-N(4)-Ba(2)N(4)-C(40)-C42'bN(4)-C(40)-C43a

92.45(5)34.9(2)67.3(2)

121.3(2)43.4(2)69.33(12)38.84(11)

159.7(2)52.72(4)

123.8(2)125.6(2)126.6(2)81.3(2)96.1(2)74.6(3)38.2(3)66.8(3)

142.0(2)27.55(13)45.8(2)

126.9(2)94.11(13)55.9(2)41.11(13)64.15(13)41.68(12)52.77(3)

101.5(3)100.0(3)52.3(3)52.9(2)53.3(2)

113.1(2)53.2(2)74.51(4)

104.1(5)131.5(4)97.9(4)

113.4(7)113.2(6)107.6(8)107.0(4)137.0(4)

96.6(2)113.2(6)112.1(7)108.5(7)144.7(6)113.9(5)81.3(4)

110.8(7)113.4(8)108.7(9)102.8(3)49.3(2)56.7(2)50.5(2)75.69(4)

104.8(5)127.1(4)

82.8(4)118(2)113.2(8)

N(4) -C(40) -C42aN(4)-C(40)-C41aC42a-C(40)-C41aC41'b-C(40)-C43'bC(50)-N(5)-8(2)

S(2)-N(5)-Ba(1)

N(S)-C(50)-C53aC53a-C(50)-C52aC51'b-C(50)-C53'bC53a-C(50) -C51aN(5)-C(50)-C52'bC53'b-C(50)-C52'bC(60) -N(6) -Ba(2)C(60) -N(6) -Ba (1)

Ba(2)-N(6)-Ba(1)

N(6)-C(60)-C62aC61'b-C(60)-C63'bC62a-C(60)-C61aC61'b-C(60)-C62'bN(6)-C(60)-C63aC61a-C(60)-C63aN(4)-Li(1)-N(1)

N(4) -Li(1) -S(1)

N(1)-Li(1)-S(1)

N(3)-Li(1)-Ba(2)

S(1)-Li(1)-Ba(2)

N(3)-Li(1)-Ba(1)

S (1) -Li (1) -Ba (1)Si(1) -N(7) -Si(2)

Sl(2)-N(7)-Ba(2)

N(7)-Si(1)-C(72)

N(7)-Si(1)-C(73)

C(72)-Si(1)-C(73)

N(7) -Si(2) -C(82)N(7)-Si(2)-C(83)

C(82)-Si(2)-C(83)

C1'Tb-O(1)-C4'TbC4Ta-0(1)-Ba(1)

C4'Tb-0(1)-Ba(1)

CITa-C2Ta-C3Ta

0(1)-C4Ta-C3Ta

C1'Tb-C2'Tb-C3'TbC3'Tb-C4'Tb-0(1)C8Ta-0(2) -CSTa

C8'Tb-0(2)-Ba(1)

C5Ta-0(2) -Ba(1)

C5Ta-C6Ta-C7Ta0(2) -C8Ta-C7TaC5'Tb-C6'Tb-C7'Tb0(2)-C8'Tb-C7'Tb

115.1(9)103.6(7)106.7(9)108(2)120.5(5)103.0(3)117.3(9)114.7(10)112(2)108.2 (9)

98.1(12)99.3(14)

117.7(4)122.0(4)100.1(2)117.5(10)110.6(12)109.5(11)108.2(12)107.6(9)109.2(10)130.9(7)127.9(6)38.9(3)60.2(3)72.6(3)99.4(4)66.4(3)

126.9(4)

119.7(3)114.9(5)114.6(6)106.6(6)117.8(5)110.1(5)102.0(7)108.7(12)126.4(8)127.6(10)106.1(10)102.6(11)107.7(12)104.8(13)111.8(10)126.7(9)111.3 (7)105.7(12)105.8(10)106.6(12)106.9(11)

C43a-C(40) -C42aC43a-C(40)-C41aN(4)-C(40)-C43'bC42'b-C(40)-C43'bC(50)-N(S)-Ba(1)

N(S)-C(50)-C51'bN(S)-C(50)-C52aN(S)-C(50)-C53'bN(S)-C(50)-CSlaC52a-C (50) -C51aCS1'b-C(50)-C52'bC(60)-N(6)-S(2)S(2) -N(6) -Ba(2)

S(2)-N(6) -Ba(1)

N(6)-C(60)-C61'bN(6)-C(60)-C63'bN(6)-C(60)-C61aN(6)-C(60)-C62'bC63'b-C(60)-C62'bC62a-C(60)-C63aN(4)-Li(1)-N(3)N(3)-Li(1)-N(1)

N(3)-Li(1)-S(1)

N(4)-Li(1)-Ba(2)

N(1)-Li(1)-Ba(2)N(4)-Li(1)-Ba(1)

N(1)-Li(1)-Ba(1)

Ba(2)-Li(1)-Ba(1)

Si(1)-N(7)-Ba(2)N(7)-Si(1)-C(71)C(71)-Si(1)-C(72)C(71)-Si(1)-C(73)N(7)-Si(2)-C(81)C(81)-Si(2)-C(82)C(81)-Si(2)-C(83)C4Ta-O(1)-CITaC1'Tb-0(1)-Ba(1)ClTa-O(1)-Ba(1)0(1)-ClTa-C2TaC4Ta-C3Ta-C2Ta0(1)-C1'Tb-C2'TbC4'Tb-C3'Tb-C2'TbC8'Tb-0(2)-C5'TbC8Ta-0(2)-Ba(1)CS'Tb-0(2)-Ba(1)0(2) -C5Ta-C6TaC8Ta-C7Ta-C6Ta0(2) -C5'Tb-C6'ThC8'Tb-C7'Tb-C6'Tb

used to generate equivalent atoms:

111.3 (10)105.9(8)100.8(14)107(2)132.2(5)123.6(14)107.1(7)115(2)106.3(7)101.8 (8)103.8(14)114.1(4)105.4 (3)93.9 (2)

108.0(12)115.9(11)104.0(10)106.7(10)107.1(11)108.8(10)116.3 (6)76.6(5)38.6(3)59.0(3)100.1(4)83.8(4)47.1(3)76.6(3)

113.2(3)110.3(4)103.8(5)105.8(6)111.0(6)105.7(6)109.8(7)108.2(10)122.9(11)125.3(7)102.9(10)106.2(11)107.2(13)105.9(13)107.7(11)136.8(7)125.3(9)103.6(11)105.5(12)106.4 (12)106.1(12)

Symmetry transformations

Table 4. Anisotropic displacement parameters [pm2 x 10- 1] for 4.

The anisotropic displacement factor exponent takes the form:

-2r2 [ (ha )2 1 + ... + 2hka b*U1 2 1

Ull U22 U33 U23 013 U12

Ba(1) 40(1)

Ba(2

) 47(1)

S(1) 50(1)N(1) 45(3)C(10) 60(4)C(11) 101(7)

C(12) 110(6)C(13) 69(5)N(2) 44(3)C(20) 48(4)C(21) 48(4)C(22) 64(5)C(23) 62(5)N(3) 66(4)

C(30) 102(5)C(31) 184(10)

C(32) 135(7)C(33) 121(6)S(2) 38(1)N(4) 47(3)

C(40) 56(4)C41a 81(9)C42a 39(5)C43a 80(7)C41'b 82(13)

C42'b 47(5)C43'b 70(11)

N(5) 45(3)

C(50) 66(4)C51a 71(7)

C52a 101(6)C53a 90(6)C51'b 79(10)

C52'b 89(12)

C53'b 76(6)N(6) 54(3)C(60) 63(4)

C61a 82(9)C62a 91(12)C63a 65(6)C61'b 78(12)C62'b 84(11)C63'b 62(5)Li(1) 52(8)

N(7) 62(4)

Si(1) 71(2)C(71) 69(6)C(72) 112(9)

C(73) 158(13)

Si(2) 73(2)

C(81) 183(15)C(82) 103(10)

35(1)35(1)43(1)45(3)73(4)79(4)96(6)

155(9)45(3)61(4)80(5)80(5)76(4)33(3)32(3)39(5)41(5)54(6)41(1)42(3)65(4)60(5)71(8)88(10)67(6)69(14)84(12)48(3)58(4)71(7)53(6)52(9)66(11)48(5)45(14)44(3)61(4)80(11)67(5)

100 (10)81(11)55(5)

101(13)61(8)52(4)55(1)

123(9)117(9)

79(8)94(2)

110(10)174(14)

40(1)39(1)46(1)40(3)48(4)61(5)54(5)87(7)41(3)44(4)66(5)43(4)65(5)53(4)69(4)91(5)96(6)

122(8)41(1)45(3)46(3)66(8)61(8)49(4)60(13)61(13)39(6)52(3)70(4)62(4)92(8)69(9)84(8)94(10)62(14)37(2)51(3)41(4)77(10)81(10)50(6)68(11)79(10)37(7)56(4)57(1)66(6)70(7)

168(13)69(2)74(8)

117(10)

2(1)

7(1)

5(1)

4(3)10(3)23(4)

-11(4)45(6)

5(2)11(3)15(4)1(4)

25(4)-1(2)-3 (3)13(4)

-17(4)-11(5)

8(1)1(2)

-4(3)-12(5)

2(7)-16(6)-18(7)

3(13)-11(10)19(2)28(3)34(4)30(5)19(6)44(7)25 (8)17(11)7(2)0(3)9(7)

-9(6)5(10)9(8)

-7(6)0(11)4(6)

12(3)18(1)31(6)7(6)

58 (9)17(2)-5(7)20(10)

6(1)9(1)

14(1)18(3)24(4)41(5)37(4)43(5)

8(2)0(3)0(4)

-1(3)-1(4)17(3)22(4)42(6)3(6)

34(6)7(1)

-2(2)-3(3)-4(6)-9(4)4(5)

-15(12)-7(6)4(8)8(3)3(4)

12(5)18(6)3(6)

12(8)8(11)5(7)

14(2)21(3)27(6)16(9)36(6)35(8)18(11)28(6)8(6)

17(3)24(1)4(5)

37(6)79(11)11(1)11(8)36(8)

C(83) 72(8)0(1) 77(3)

CITa 77(5)C2Ta 74(6)C3Ta 82(6)C4Ta 82(6)C1'Tb 82(5)C2'Tb 77(5)C3'Tb 79(6)C4'Th 80(6)0(2) 104(5)CSTa 115(7)C6Ta 121(7)C7Ta 128(8)CSTa 120(8)CS'Tb 114(7)C6'Tb 122(7)C7'Th 115(7)C8'Tb 110(7)

1(1)1(1)

16(1)9(3)

13(4)9(5)

-6(6)37(5)

9(2)8(3)0(4)1(4)

20(4)12(3)17(4)23 (6)

8(5)44(5)7(1)7(2)

-1(3)-12(5)-13(5)-1(7)1(8)

-11(9)2(12)6(2)5(3)

10(5)-7(5)29(6)2(10)

-2(10)25(7)15(3)20(3)14(8)37 (6)17(7)20(10)24(7)24(7)-4(6)-6(3)11(1)6(6)

17 (7)49(8)

-35(2)-72(10)-66(10)

177(15)

88(4)94(6)

97(7)92(6)89(6)98(7)98(7)95(7)89(7)69(3)70(5)73(4)79(5)78(5)75(5)72(4)74(5)73(5)

152(13)112 (5)

106 (7)110(7)115(7)124(7)111(7)114(8)113(7)114(7)76(4)83(6)89(6)84(6)80(5)92(7)91(7)87(7)80(7)

50(11)10(4)

16(5)

18(6)19(5)11(6)17(6)17(7)18(6)14(5)

-20(3)-15(4)-19(4)-21(4)-15(5)-23(5)-19(5)-21(6)-19(6)

0(8)38(4)29(5)

32(5)29(5)32(5)31(5)32(6)34(5)34(6)-6(3)-5(6)-7(6)-9(6)

-11(6)-9(6)

-10(6)-10(6)-11(6)

18(9)-13 (3)-12(5)-12(5)-11 (5)

-9(5)-14(6)-14(6)-14(6)-11(6)

4(3)3 (6)2(5)2(6)4(6)

10(4)6(5)1(5)5(5)

Table 5. Hydrogen coordinates ( x 10 4) and isotropic2 1l

displacement parameters (pm x 10 ) for 4.

x y z U(eq)

H(11A)H(11B)

H (11C)

H (12A)

H (12B)

H(12C)H(13A)

H (13B)

H(13C)

H (2 1A)H (21B)

H(21C)

H (22A)H(22B)

H (22C)

H (23A)

H(23B)H (23C)H(31A)

H (31B)

H (31C)H (32A)

H(32B)

H(32C)

H(33A)

H(33B)

H(33C)

H41Aa

H41BaH4lCa

H42Aa

H42BaH42CaH43AaH43Ba

H43CaH41Db

H4lEbH4lFbH42DbH42EbH42FbH43DbH43EbH43FbHS1AaH51BaHSlCaH52AaH52BaH52CaH53AaH53Ba

428-916-595

2381061

-92-2049-2237-1802-1983-2903-2340

-228-1544

-571-1771

-2291-961

767399

1750168325221704-563

-1048-44838554832516055205122592730754406359232994370462354275960568438082976430723023665320610541923152045003708

592756176074870277937936737670298222625669777281755170136423908286329141

114281031710652114061055510303100611015611174

93678913930071526547763783658368728591379366925767757832783165227439754253335584446741533280341946803759

435539404748456448285103435635383841186914322254

897614

112518811077134127912334272141193935445139213098361539853636445638894483469148165269504643433995482042014694385947334807527147894823501539104185336338763339

114114114128128128145145145100100100989898

104104104154154154144144144147147147112112112939393

114114114115115115959595

101101101101101101124124124108108

H53CaHS1DbHSlEb

H51IFbH52DbH52EbH52FbH53DbH53EbH53FbH61AaH61BaH61CaH62AaH62BaH62CaH63Aa

H63BaH63CaH61DbH61EbH61FbH62DbH62EbH62FbH63DbH63EbH63FbH (71A)

H (7i)H (71C)

H (72A)

H(72B)

H(72C)

H(73A)

H (73B)H (73C)H (81A)H(8 15)

H(81C)

H(82A)H(82B)

H(82C)

H (83A)H(83B)

H(83C)H1TlaH1T2aH2T1a

H2T2aH3T1aH3T2aH4T1a

H4T2aHI' lbH1'2bH2'lbH2'2bH3'1lbH3'2bH4'1lbH4'2bH5Tla

4103150227812459245113662524433542294559214815032587385536332552420146294863184829713043286828821746470448154715

9091402

911288236594178336722992058578644484740

552660246682667159025498

-3264-2820-3925-3208-1767-2593

-647-1756-2891-2910-4024-3970-2696-2975-1362

-913-512

361244104762357237433565296845923697489767835638578246134467430972476248639263726018712843654364468355406605549496478694964999259099

10296120141181811735112581085411834115641048211195

93558634868542415286357845003513254131532692379049833287446941402917287939012945

415944494952461428993244350535924102441811671152

8042377154118911932156023971088

84212872192138316292538217617281153

773343

-145287329

11141469

63233523294288915751375208227992123284122532788309536704030355533052670199023012630297939293644327338262159

H5T2aH6T1aH6T2aH7T1aH7T2aH8T1aH8T2aH5'lbH5'2bH6' lbH6'2bH7' lbH7'2bH8'lbH8'2b

585-1790

-641-450

-1843-302

-1619665760

-801-461

-2102-2431-1456-2138

284821311600261326594322430029193262175018902625250342734213

181312141104

254151505604

183010771355

625239975535

1144

116122122126126121121122122124124120120115115

C72'

C73'

C73A

C72A

Table 1. Crystal data and structure refinement for 3

Identification code

Empirical formula

Formula weight

Temperature

pride

C18 H39 Ca.50 LiN301.50

380.56

193(2) K

4Table 2. Atomic coordinates ( x 10 ) and equivalent isotropic

2 -1displacement parameters (pm x 10 ) for 3. U(eq) is defined as

one third of the trace of the orthogonalized U tensor.

x y z U(eq)

Wavelength

Crystal system

Space group

Unit cell dimensions

Volume, Z

Density (calculated)

Absorption coefficient

F (000)

Crystal size

9 range for data collection

Limiting indices

Reflections collected

Independent reflections

Max. and min. transmission

Refinement method

Data / restraints / parameters

2Goodness-of-fit on F

Final R indices (I>2a(I)]

R indices (all data)

Largest diff. peak and hole

71.073 pm

Orthorhombic

Pccn

a = 1517.00(2) pm alpha = 900

b = 1577.24(2) pm beta = 90

c = 1923.09 (3) pm gamma = 900

34.60133(11) nm , 8

1.099 Mg/m3

0.264 mm

1672

0.50 x 0.50 x 0.40 mm

2.14 to 23.250

0 sbs 17, 0 Sk a 18, 0 s I s 22

43546

3308 (Rint = 0.0642)

0.9190 and 0.9361

2Full-matrix least-squares on F

3308 / 799 / 394

1.095

Rl = 0.0847, wR2 = 0.2137

R1 = 0.0967, wR2 = 0.2233

445 and -546 e.nm-3

CalaLilbLi2bS (1)N(1)C (10)ClaC12aC13aCll'bC12'bC13 'bN2aC20aC21aC22aC23aN2 IhC20'bC21'bC22'bC23'bN (3)C (30)C (31)C(32)C (33)o1aC7 laC72aC73aC74aOl'bC71'bC72'bC73'bC74'b0(2)C (91)C(92)C (93)C (94)

8518 (3)8710 (3)7801(9)7574(1)8533 (2)9166 (4)9057 (10)

10100 (7)8965 (18)9454(11)9994 (7)8870 (19)7245 (6)7386 (7)6772 (9)7189 (13)8328 (9)7306(6)7332 (6)7188 (8)6616 (8)8213 (9)6916 (2)6214 (3)5439 (4)5918(5)6524 (5)9838 (10)9867 (9)

10693 (9)11294 (9)10694 (9)

9843 (10)10241(8)11138 (9)11183 (10)10429 (9)

7770 (2)7390 (3)7210 (3)7420 (3)7910 (3)

2595(4)2630(4)2367 (10)978(1)

1417 (2)935(4)-37 (7)

1178(11)1055 (15)101(9)

1537 (9)837 (16)

1128 (6)470 (6)656 (10)-430(7)466 (12)

1624 (5)1140 (6)1800 (7)

459 (8)728(11)

1474 (2)965 (3)835 (6)

1445(5)92(4)

2601(13)2384(11)2624(12)2673 (13)2914 (12)2667 (12)1926(8)2138 (9)3077 (9)3383 (9)7382 (15)8163 (16)8060 (2)7213 (17)6840 (2)

377 (3)480 (3)

1673 (7)900(1)

1015 (2)1453 (3)1304 (10)1284(11)2228 (6)1149(11)1455 (9)2204(7)

145(4)-383 (5)-990(6)-128(7)-643(11)177(4)

-487(4)-1055 (5)

-519 (7)-633 (10)1435 (2)1760 (3)1270(4)2399(4)2006(4)-252(11)-992 (9)

-1252 (8)-647 (9)

-72 (8)-215(11)-500(9)-653 (11)-694(11)-321(10)

-1359 (9)-1617 (13)-2342 (12)-2530 (12)-1959 (13)

39(1)43(5)46(3)48(1)53(1)79(1)

100(4)104(4)79(4)

108 (5)89(4)84(5)56(2)70(2)

100(4)132 (5)102(4)46(2)58(2)79(3)86(3)79(3)54(1)67(1)

115 (3)124(3)115(3)95(2)

117 (3)130 (3)130(3)117 (3)

92(2)103(3)126(3)126(3)110 (3)242 (7)240(7)237 (7)235 (7)236 (7)

0Table 3. Bond lengths [pmJ and angles [ I for 3.

Cala-N(1)Cala-N2a#1Cala-S(1)#1Cala-S(1)

h.ilb-N2'b#1T.ilb-N(1)TAlb-Li2bfLilb-Li2b#11.i2b-N(3)#1

Li2b-N(1)1.i2b-Lilb#l

S (1) -N(1)S(1)-N2'b5(1) -Lilb#1C(10)-Cl2aC(10)-C13'bC(10)-C1laN2a-C20aC20a-C23aC20a-C22aN2'b-Lilb#lC20'b-C21'bN(3) -C(30)N(3) -Lilb#1C(30)-C(32)C(30)-C(33)Ola-C71aC72a-C73a01'b-C71'bC71'b-C72'bC73'b-C74'b0(2)-C(91)C(92)-C(93)

N(1) -Cala-OlaOla-Cala-N2a#1Ola-Cala-N(3) #1N(1) -Cala-S (1)#1N2a#1-Cala-S (1)#1N(1)-Cala-N2aN2a#1-Cala-N2aS (1) #1-Cala-N2aOla-Cala-S (1)N(3) #l-Cala-S (1)N2a-Cala-S (1)Ola-Cala-Cala#lN(3)#1-Cala-Cala#1N2a-Cala-Cala#1N2'b#l-Lilb-0l'b01'b-Lilb-N (1)01'b-Lilb-N(3) #1N2'b#1-Lilb-Li2bN(1) -Lilb-Li2bN2'b#1-Lilb-S(1)#1N (1) -Lilb-S (1) #1Li2b-Lilb-S (1) #101'b-Lilb-Li2b#lN(3) #1-Lilb-Li2b#1S (1) #l-Lilb-Li2b#1

222.7 (8)236.5(11)296.9(7)309.3(6)203(5)219 (6)271(6)325(5)193 (2)225(2)325 (5)162.8(4)177.0(8)304 (6)150.2(11)152.1(11)156.8(11)146.7(11)151.3 (12)153.2(12)203 (5)152.6(11)147.3(6)

250 (6)151.2(7)153.0(7)146 (2)148.0(14)143 (2)143.2(12)143.3(13)145(2)142(2)

106.2 (6)108.5 (7)128.4(5)116.8(2)

31.3 (2)56.9(2)

108.0(3)105.8 (2)124.6 (6)95.4(2)29.3 (2)

148.5(5)78.6(2)

45.2 (2)114 (3)114 (3)138 (2)87(2)53.4(12)33.9(10)

115(2)63.9(12)

173 (2)

38.0(8)50.1(9)

Cala-OlaCala-N (3) #1Cala-N2aCala-Cala#lLilb-O1'bLilb-N(3)#lLilb-S (1) #1

Li2b-Li2b#1Li2b-N(3)Li2b-S (1)S (1) -N2aS(1) -N(3)S(1) -Cala#lN(1) -C(10)C(10) -C11'bC(10) -C13aC(10)-C12'bN2a-Cala#1C20a-C2laN2'b-C20'bC20'b-C23'bC20'b-C22'bN(3) -Li2b#1N(3) -Cala#1C(30)-C(31)Ola-C74aC71a-C72aC73a-C74a01'b-C74'bC72'b-C73'b0(2) -C(94)C(91)-C (92)C(93)-C(94)

N(1) -Cala-N2a#1N(1) -Cala-N(3)#1N2a#1-Cala-N(3) #1Ola-Cala-S(1)#1N(3) #1-Cala-S (1) #101a-Cala-N2aN(3)#1-Cala-N2aN(1) -Cala-S (1)N2a#1-Cala-S (1)S(1) #1-Cala-S (1)N(1) -Cala-Cala#1N2a#1-Cala-Cala#1S (1) #1-Cala-Cala#1S(1) -Cala-Cala#1N2'b#1-Lilb-N(1)N2'b#1-Lilb-N(3) #1

N(1) -Lilb-N(3) #101'b-Lilb-Li2bN(3)#1-Lilb-Li2b01'b-Lilb-S (1) #1N(3) #1-Lilb-S (1) #1N2'b#1-Lilb-Li2b#1N(1) -Lilb-Li2b#1Li2b-Lilb-Li2b#1Li2b#1-Li2b-N(3) #1

234 (2)259.3(7)304.8(11)310.3(9)217 (5)250 (6)304 (6)101(3)200 (2)267(2)155.2(8)163.3(4)296.9(7)148.5(6)150.5(11)153.4(11)157.4(11)236.5(11)152.2(11)148.9(10)151.2(11)152.9(11)193 (2)259.3(7)152.1(7)143.1(14)140.2(13)148.2(13)145.2 (14)148.5(14)145 (2)143 (2)145 (2)

145.0 (3)92.4(2)62.7 (3)

130.5(6)33.29(11)

118.0(5)112.6 (3)30.44 (12)

122.5(3)104.9 (2)

86.0 (2)66.2(3)61.2 (2)57.3 (2)

123 (2)66(2)96(2)

158 (2)43.3(9)

131(3)32.4(7)70.3 (14)65.2(13)16.5 (6)79(2)

LI;MFl±-L I Z0-M J

Li2b#l-Li2b-N(1)N(3)-Li2b-N(1)N(3)#1-Li2b-S (1)N(1) -Li2b-S (1)N(3)#1-Li2b-LilbN(1) -Li2b-LilbLi2b#1-Li2b-Lilb#1N(3) -Li2b-Lilb#1S(1)-Li2b-Lilb#lN2a-S (1) -N(1)N(1) -S(1) -N(3)N(3) -S(1) -N2'bN(3) -S (1) -Li2bN2a-S (1) -Cala#lN(3) -S(1) -Cala#1N(3) -S(1) -Lilb#1Li2b-S(1)-Lilb#1N(1) -S (1) -CalaCala#1-S (1) -CalaC(10) -N(1) -LilbC (10) -N(1) -CalaC(10)-N(1)-Li2bLilb-N(1)-Li2bN(1)-C(10)-C11'bC11'b-C(10) -C13'bC12a-C(10) -Cl3aC12a-C(10)-ClaN(1) -C(10) -C12'bC13'b-C(10)-C12'bC20a-N2a-Cala#1C20a-N2a-CalaCala#1-N2a-CalaN2a-C20a-C21aN2a-C20a-C22aC21a-C20a-C22aC20'b-N2'b-Lilb#1.N2'b-C20'b-C23'bC23'b-C20'b-C21'bC23'b-C20'b-C22'bC (30) -N(3) -S (1)S (1) -N(3) -Li2b#1

S(1) -N(3) -Li2bC(30) -N(3) -Lilb#1

Li2b#1-N(3) -Lilb#1

C(30)-N(3)-Cala#1N(3) -C(30)-C(32)C(32) -C(30) -C (31)C(32)-C(30)-C(33)C74a-01a-C7laC71a-Ola-CalaC71a-C72a-C73a

Ola-C74a-C73aC71'b-01'b-Lilb01'b-C71'b-C72'bC74'b-C73'b-C72'bC(94)-0(2) -C(91)C(93)-C(92)-C(91)C(93) -C(94) -0(2)

136.5(12)74.6(5)

132.2 (6)37.4 (2)62.5(14)51.4(13)50.0(11)50.3 (10)61.0(11)

110.6(4)104.8 (2)

94.5 (3)48.3(3)52.3 (3)60.6(2)55.2 (9)68.9(11)43.9(2)61.54 (13)

129.2 (10)138.2 (3)109.9(4)75(2)

114.6(9)111.4 (12)111.5 (12)108.1(9)102.0(7)107.1(11)143.5(7)123.0(6)

68.6(3)107.8(8)113.9(9)107.7 (10)124(2)113.8(9)106.6(10)108.6(10)116.6 (3)117.9(4)94.1(4)

110.0(10)74.2(14)

117.3(3)106.7 (5)110.0(6)106.8(5)106.7(11)121.8(11)106.4 (12)106.8(11)123 (2)106.9(10)105.8(10)107 (2)108(2)107 (2)

Symmetry transformations used to generate equivalent atoms:

#1 -x+3/2,-y+1/2,z

N(3)#1-Li2b-N(1)Li2b#1-Li2b-S(1)N(3) -Li2b-S (1)

Li2b#1-Li2b-LilbN(3) -Li2b-LilbS (1) -Li2b-LilbN(3) #l-Li2b-Lilb#1N(1) -Li2b-Lilb#1Lilb-Li2b-Lilb#1N2a-S (1) -N(3)N(1) -S (1) -N2'bN(1) -S(1) -Li2b

N2'b-S (1) -Li2b

N(1) -S(1) -Cala#l

N(1) -S(1) -Lilb#1N2'b-S (1) -Lilb#1

N2a-S(1)-CalaN(3) -S(1) -CalaC(10) -N(1) -S(1)S (1) -N(1) -LilbS (1) -N(1) -Cala

S (1)-N (1) -Li2b

N(1)-C(10)-Cl2aN(1)-C(10)-C13'bN(1) -C(10) -C13a

N(1) -C(10) -ClaC13a-C(10)-CllaC11'b-C(10) -C12'b

C20a-N2a-S(1)S(1) -N2a-Cala#1S(1) -N2a-CalaN2a-C20a-C23aC23a-C20a-C21aC23a-C20a-C22aC20'b-N2'b-S (1)

S(1)-N2'b-Lilb#1N2'b-C20'b-C21'bN2'b-C20'b-C22'bC21'b-C20'b-C22'bC(30) -N(3) -Li2b#1C(30)-N(3) -Li2bLi2b#1-N(3) -Li2b

S(1) -N(3) -Lilb#1Li2b-N(3) -Lilb#1S(1)-N(3)-Cala#1N(3) -C(30) -C(31)N(3) -C(30) -C(33)C(31)-C(30)-C(33)C74a-Ola-CalaC72a-C71a-01aC72a-C73a-C74aC71'b-Ol'b-C74 'b

C74'b-01'b-LilbC71'b-C72'b-C73'bC73'b-C74'b-01'bC(92) -C(91) -0(2)C(92)-C(93)-C(94)

112.7(6)103(2)37.6 (3)

113.6(13)105.0(11)

73.9(12)89.4(11)87.3(10)76.4(14)

108.6(4)93.9 (3)57.2 (3)89.7(4)

102.9 (2)107.7 (10)39.7 (8)73.7(4)95.3 (2)

115.9 (3)114.8 (10)105.7 (2)85.4(4)

110.9(8)113.5(12)111.0(11)109.2 (8)106.0(10)107.3 (8)119.5(7)

96.4(4)77.0(4)

111.7 (10)109.0(11)106.6(11)111.8 (6)106(2)105.1(7)112.2(7)110.4(9)125.1(5)140.5 (5)

29.6 (8)92.4(11)91.7 (13)86.1(2)

111.7 (4)113.5(4)107.9(6)130.8(11)108.2(11)102.8 (10)108.9 (10)126(2)106.7(10)107.3 (10)108 (2)107.4(14)

Table 4. Anisotropic displacement parameters [pm2 x 10 ] for 3.

The anisotropic displacement factor exponent takes the form:

2 * 2 * *-27 [ (ha*) U + ... + 2hka bU ]

11 12

U11 U22 U33 U23 U13 U12

CalaLilbLi2b

S(1)

N(1)C(10)

C11a

C12a

C13a

C11'bC12'b

C13'b

N2aC20a

C2 la

C22a

C23a

N2'b

C20'bC21'b

C22'b

C23 'bN(3)C(30)C(31)

C(32)C(33)OlaC7 la

C72a

C73a

C74aO1'b

C71 'bC72'b

C73'b

C74'b

0(2)C(91)C(92)C(93)C(94)

31(2)32(11)48(9)56(1)

45(2)

69(3)

106(11)55(4)76(9)83(10)35(4)81(9)66(4)87(5)

104M(7)

224(14)92(5)

58(4)69(4)

108(8)100(6)88(5)

57(2)

65(3)

74(4)124(6)111(6)60(3)

88(4)91(5)76(4)71(4)58(3)81(5)86(5)

83(5)

72(5)

294(18)295(18)288(18)285(18)285(18)

50(1)

55(9)55(10)41(1)

63(2)103(3)98(4)

159(11)101(10)125(7)150(9)110(12)

59(4)67(4)

122(8)67(5)

119(11)44(4)62(4)

88(6)90(6)

87(9)47(2)

77(4)168(7)154(7)

96(5)98(5)

125(6)144(7)139(7)130(6)96(4)

99(5)121(6)124(6)104(5)165(12)156(12)155(12)156(13)159(12)

36(2)

41(10)35(6)47(1)

52(2)

65(3)

97(9)100(10)

61(4)115(9)82(9)

63(4)

43(3)56(4)75(6)

103(9)95(9)36(3)

44(3)40(4)

67(6)

63(6)

58(2)

58(3)

103(5)

95(5)138(6)127(4)139(5)156(5)176(6)150(5)121(4)128(6)172(6)171(6)154(6)267(14)269(15)269(15)264(14)264(15)

-2(1)

0(8)

9(6)0(1)7(2)

10(3)

6(6)14(9)

19(5)

-3(7)6(8)

17(6)

-8(4)-20(4)-41(6)-26(5)

-33(9)-4(3)

-16(3)-10(4)-36(5)-23(6)-1(2)14(3)

29(5)-12(5)52(5)-3(4)

-18(5)-12(6)-2(7)

-2(5)

-6(4)

-6(5)-8(6)

-1(6)

-5(5)17(13)17(13)22(13)20(13)19(13)

-1(1)

-2(8)-11(5)

4(1)-5(2)

-13(2)-5(9)2(5)

-14(5)-3(8)

-3(5)-17(5)-2(3)

-4(4)-27(6)

6(9)9(6)

-5(3)0(4)

-15(5)-15(6)

0(5)16(2)12(3)-2(4)

53(5)

37(5)32(3)

37(4)52(4)

47(4)30(4)

31(3)39(5)52(5)

55(4)40(5)

-63(16)-55(16)-58(17)-60(16)-60(16)

-1(2)2(10)

-6(8)-3(1)

10(2)

34(3)74(6)60(6)

14(9)

71(6)41(5)18(8)

6(4)9(5)

12(7)

-20(8)41(7)

2(4)

5(3)22(5)

-20(5)31(5)-3(2)

-13(3)-52(5)-28(5)-19(4)

1(4)

-3(5)-1(5)-2(6)

-7(5)-2(3)

7(4)8(5)

-7(5)

-7(4)28(13)21(13)21(13)22(13)25(13)

Table 5. Hydrogen coordinates ( x 1042 -1

displacement parameters (pm x 10 )for 3.

and isotropic

x y z U(eq)

H11AaH1lBaHlCaH12AaH12BaH12CaH13AaH13BaH13CaH11DbHl1EbH11Fb

H12DbH12EbH12FbH13DbH13EbH13FbH21Aa

H21BaH21CaH22Aa

H22BaH22Ca

H23AaH23Ba

H23CaH21DbK21EbH21Fb

K22Db

H22EbH22FbH23DbH23EbH23FbH(31A)

H(31B)

H(31C)

H(32A)

H (32B)

H(32C)H (33A)

H (33B)

H (33C)H7 lAaH71BaH72AaH72BaH73Aa

H73BaH74AaH74Ba

952191048479

101471026610494

9406837789849627896699579825

1021910455

93438344873161996693702777426897680287298467839865847281760666986657603586848219830850165650514964155442570370206711603997789394

106541090911755115781089510679

-352-140-2261797

934963751830

1660182

-305-119209515981293

575476

1395843140

1103-712-750-403356

101922

201915382268

57156726

1149509260442598

1380150711312007160

-245-19717672687318122003108211926593538

1548803

14701261

8341647250523312343

662117314131636

9801751247622222398-812

-1268-1281

-1-499280

-254-849-995

-1027-1512

-993-135-963-480-578

-1110-3061483

8301183272026292263232716042244

-1054-1244-1487-1591

-719-556371-17

H71CbH7l1DbH72CbH72DbH73CbH73DbH74Cb

H74DbH(91A)

H (9 1B)H(92A)

H(92B)

H(93A)H(93B)

H(94A)

H(94B)

99301021611320115341173411163101281061268417810658675787783687485407688

1750145418821926328832673832362382928638818184627205688868106263

-928-161

-1101-282-479

-1184-591

132-1363-1544-2438-2617-2959-2617-2074-1862

124124152152151151132132288288285285282282283283

151151151157157157119119119162162162133133133127127127150150150197197197153153153118118118129129129119119119172172172186186186173173173141141156156

157157140140