Supporting Information Effect of Ligand Substituent on The ... · S3 Materials: All the chemicals and solvents were obtained from commercial sources and were used as supplied, unless

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Supporting Information

Effect of Ligand Substituent on The Reactivity of Ni(II)

Complexes Towards Oxygen**

Samir Ghorai and Chandan Mukherjee*

*Corresponding address:

Dr. Chandan Mukherjee, Department of Chemistry, Indian Institute of Technology, Guwahati, 781039, Assam, India

Email: [email protected]

Phone No. +91-361-258-2327

Fax: +91-361-258-2349

Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2013

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Contents Page

Material and Physical Methods S3 Experimental Section: Synthesis and Characterization of H3SamiMixed(H), 1, 2 and 2a

(including IR and mass spectra) S3-S8

X-band EPR spectra for 1, 2, and 2a S8 ORTEP representation of molecular structure of H3SamiMixed, 1, 2 and 2a S9-S10 Intermolecular Ni••••H interaction present in 1 and 2a S11 Time dependent change in X-Band EPR signal intensity during oxygen gas purging to the CH2Cl2 solution of 2

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Time−dependent absorption changes upon addition of mCPBA (1 equiv.) to 2. Inset showing change in X−band EPR signal

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Mass spectrum showing the formation of Ni-oxygen species S12 Comparative structural study between 1 and 2 S13 Selected bond distances (Å) and bond angles (°) for 2 S14-S15 Crystallographic data and structure refinement for 2 S16


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Materials:

All the chemicals and solvents were obtained from commercial sources and were used as

supplied, unless noted otherwise. 3,5−di−tert−butylcatechol, 2−aminobenzonitrile,

3,5−di−tert−butyl salicyaldehyde and LiAlH4 were purchased from Sigma−Aldrich. Solvents

were obtained from Merck (India). THF was dried before used. Kinetics was performed in

HPLC grade CH2Cl2.

Physical Method:

X−ray crystallographic data were collected using a Bruker SMART APEX−II CCD

diffractometer, equipped with a fine focus 1.75 kW sealed tube Mo−Kα radiation ( l =

0.71073 Å) at 296(2) K, with increasing w (width of 0.3° per frame) at a scan speed of 3

s/frame. Structures were solved by direct methods using SHELXS−97 and refined with

fullmatrix least squares on F2 using SHELXL−97. Single crystal of C28H31N2NiO2 was

measured on a Super Nova, Single source at offset, Eos diffractometer. Using Olex21,

structure was solved with the Superflip2 structure solution program using Charge Flipping

and refined with the olex2.refine3 refinement package using Gauss−Newton minimisation.

All then non−hydrogen atoms were refined anisotropically.

IR spectra were recorded on Perkin Elmer Instrument at normal temperature making KBr

pellet grinding the sample with KBr (IR Grade). UV−vis/NIR spectra were recorded on

Perkin Elmer, Lamda 750, UV/VIS/NIR spectrometer preparing a known concentration of the

samples in HPLC Grade CH2Cl2 at room temperature using cuvette of 1 cm width. EPR

spectra were measured on X−Band Microwave Unit, JES−FA200 ESR spectrometer. Mass

spectral data were obtained from QTOF MS Spectrometer.

Experimental Section: Synthesis of H2SamiCN has already been reported.4

Synthesis of [C21H30N2O], A: To H2SamiCN (1.290 g, 4 mmol) in dry THF (5 mL), LiAlH4

(0.76 g, 20 mmol) was added and the reaction mixture was allowed to stir at room

temperature (30 °C) for 16 h under argon. After that, the reaction was quenched with ice cold

water. The resulting solution was filtered through a Celite pad and the pad was rinsed with

ethyl acetate (50 mL). The filtrate was extracted with ethyl acetate (100 mL), washed thrice

with brine. The combined organic part was dried over anhydrous Na2SO4. Solvent was

removed under reduced pressure and super dried under high vacuum to have amorphous


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solid. Addition of hexane (10 mL) to the solid and followed by slow evaporation provided A

as white solid. Yield: 0.913 g (70%). FTIR (KBr pellet, cm−1): 3395, 3357, 3293, 3195, 3042,

2957, 2906, 2867, 2616, 1605, 1586, 1502, 1481, 1459, 1423, 1390, 1362, 1310, 1224, 1200,

1158, 1116, 1047, 1020, 977, 750, 653. 1H NMR (399.85 MHz, CDCl3): δ 1.27 (s, 9H), 1.43

(s, 9H), 4.03 (s, 2H), 6.54 (d, J = 8.4 Hz, 1H), 6.75 (t, J = 7.2 Hz, 1H), 7.02 (d, J = 2.4 Hz,

1H), 7.08 (d, J = 7.2 Hz, 2H), 7.17 (d, J = 2.4 Hz, 1H), 7.25 (s, 1H) ppm. 13C NMR (100.55

MHz, CDCl3): δ 29.86 (3C), 31.85 (3C), 35.26, 44.21, 114.72, 119.19, 121.21, 121.43,

124.59, 128.61, 129.4, 130.19, 136.00, 142.19, 146.55, 148.95 ppm. ESI−MS (+ve) m/z for

(C21H30N2O + H): calcd. 327.24; Found. 327.12. Anal. Calcd for

C21H30N2O•0.35C6H12•0.5H2O: C, 76.02; H, 9.72; N, 7.68. Found: C, 75.75; H, 9.97; N,

7.70.

Synthesis of [C28H34N2O2], H3SamiMixed(H)

. To an ethanolic (5 mL) solution of A (0.815 g,

2.5 mmol), salicyaldehyde (0.305 g, 2.5 mmol) in EtOH (5 mL) was added dropwise. The

reaction mixture was then stirred at room temperature for 5 h. A yellow precipitation

occurred during the course. The precipitate was filtered washed with EtOH (15 mL) dried

under air. Yield: 0.753 g (70%). FTIR (KBr pellet, cm−1): 3463, 3365, 2999, 2962, 2906,

2865, 1631, 1607, 1586, 1509, 1485, 1462, 1427, 1387, 1361, 1320, 1294, 1267, 1240, 1214,

1193, 1151, 1123, 1036, 1012, 987, 976, 924, 883, 827, 781, 757, 746, 651, 604, 461. 1HNMR (CDCl3, 399.85 MHz): δ 1.25 (s, 9H), 1.44 (s, 9H), 4.87 (s, 2H), 5.38 (s, 1H), 6.27

(s, 1H), 6.54 (d, J = 8 Hz, 1H), 6.88 (m, 2H), 6.96 (s, 1H), 6.98 (d, J = 2.4 Hz, 1H), 7.16 (td,

J = 7.2 Hz, 1H), 7.28−7.21 (m, 3H), 7.32 (td, J = 7.6 Hz, 1H), 8.48 (s, 1H), 13.02 (s, 1H)

ppm. 13C NMR (CDCl3, 100.55 MHz): δ 29.8, 31.8, 34.6, 35.2, 60.6, 115.3, 117.3, 118.95,

119, 120.2, 121.6, 122, 124.4, 127.9, 129.4, 129.9, 131.8, 132.9, 135.7, 142.7, 145, 149.1,

161.1, 166.4 ppm. ESI−MS (+ve) m/z for [C28H34N2O2 + H]: calcd. 431.27; Found. 431.17.

Anal. Calcd for H3SamiMixed: C, 78.09; H, 7.96; N, 6.51. Found: C, 78.21; H, 8.10; N, 6.44.

UV−Vis/NIR (CH2Cl2) λmax, nm (ε, M−1cm−1): 280(11200), 340(1050)sh.

Synthesis of [C28H31N2NiO2], 1. To a methanolic (10 mL) solution of H3SamiMixed(H) (0.215

g, 0.5 mmol), NiCl2•6H2O (0.125 g, 0.52 mmol), and Et3N (0.1 mL) were added,

sequentially. The resulting reaction mixture was allowed to reflux for 1 h. After cooling, it

was further stirred for 5 h at room temperature (30 °C). This caused precipitation of a green

solid. It was filtered and washed with MeOH (15 mL). Recrystallization from a 1:1

CH2Cl2:EtOH solvent mixture provided needle shaped microcrystalline compound which was


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suitable for single crystal X−ray diffraction study. Yield: 0.125 g, 51%. FTIR (KBr pellet,

cm−1): 3434, 2960, 2944, 2903, 2868, 1612, 1536, 1475, 1452, 1432, 1399, 1385, 1353, 1325,

1257, 1212, 1175, 1148, 1115, 1026, 911, 865, 857, 770, 758, 739, 646, 494. ESI−MS (+ve)

m/z for C28H31N2NiO2: calcd. 485.17; Found. 485.10. Anal. Calcd for C28H31N2O2•0.6H2O:

C, 67.74; H, 6.54; N, 5.64. Found: C, 67.59; H, 6.14; N, 5.30. UV−Vis/NIR (CH2Cl2) λmax,

nm (ε, M−1cm−1): 1100(1300), 790(4100), 630(1950), 500(1950), 385(12900), 365(11100)sh,

300(10700).

Synthesis of 2, [C36H47N2NiO2]. A (0.326 g, 1 mmol) and 3,5-di-tert-butylsalicylaldehyde

(0.234 g, 1 mmol) were added in CH3CN (20 ml) and the solution was allowed to reflux for 3

h. NiCl2•6H2O (0.240 g, 1.01 mmol) and Et3N (0.3 ml) were added to the solution at room

temperature, and the resulting solution was then allowed to reflux for 2 h. After that, 1 h

room temperature stirring provided complex 1 as blue green solid. Filtered and washed with

CH3CN. Solid was then dissolved in CH2Cl2 (20 mL) and filtered to discard undissolved

particles. Solvent was removed. The resulting solid was dried under vacuum and kept under

argon. Single crystal suitable for X-ray diffraction study was obtained by recrystallization of

solid in 2:1 Et2O:CH3CN solvent mixture. Yield: 0.240 g, 40%. FTIR (KBr pellet, cm-1):

2957, 2946, 2901, 2862, 1611, 1534, 1476, 1451, 1438, 1326, 1257, 1237, 1201, 1176, 753.

TOF MS ESI(+) m/z: M+ calcd for C36H47N2NiO2, 597.30; found, 597.19. UV−Vis/NIR

(CH2Cl2) λmax, nm (ε, M−1cm−1): 1180(1800), 835(5500), 625(2550), 520(2150), 385(15450),

365(12000)sh.

Synthesis of 2a, [C36H45N2NiO3]. Complex 1 (0.100 g, 0.167 mmol) was dissolved in a 5:1:1

CH2Cl2:CH3CN:EtOH solvent mixture and allowed for slow solvent evaporation for three

days. During the time brown colour crystalline compound, suitable for X-ray diffraction

single crystal study, was obtained. Yield: 0.097 g, 95%. FTIR (KBr disc, cm-1): 2959, 2948,

2904, 2866, 1661, 1620, 1560, 1530, 1474, 1431, 1350, 1334, 1292, 1198, 1183, 1112, 1056,

1020, 1003, 915, 753. TOF MS ESI(+) m/z: M+ calcd for C36H45N2NiO3, 611.28; found,

611.18. Anal. Calcd for C36H45N2NiO3: C, 70.60; H, 7.41; N, 4.57. Found: C, 70.42; H, 7.36;

N, 4.48. UV−Vis/NIR (CH2Cl2) λmax, nm (ε, M−1cm−1): 1200(1900), 810(4300), 645(3150),

485(10800), 450(10200)sh, 385(21500), 300(32550).


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Figure 1. Infrared spectrum of H3SamiMixed(H).

Figure 2. Infrared spectrum of 1.

Figure 3. Infrared spectra of 2 (top) and 2a (bottom).


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Figure 4. Experimental and simulated mass spectra for H3SamiMixed(H) [C28H34N2O2+H] have been shown.

Figure 5. Experimental and simulated mass spectra for H3SamiMixed(tBu) [C36H50N2O2+H] have been shown.

Figure 6. Experimental and simulated mass spectra for 1[C28H31N2NiO2] have been shown.


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Figure 7. Experimental and simulated mass spectra for 2[C36H47N2NiO2] have been shown.

Figure 8. Experimental and simulated mass spectra for 2a[C36H45N2NiO3] have been shown.

Figure 9. X−band EPR spectra of 1, 2 & 2a (X-band microwave frequency (MHz), 9452.247[1], 9442.441 [2], 9451.240 [2a]; modulation frequency (kHz), 100 [1, 2 & 2a]; modulation amplitude (G), 1.0 [1], 2.0 [2], 1.0 [2a]; and microwave power, 0.998000 mW) [1, 2 & 2a].


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Figure 10. Molecular structure of H3SamiMixed(H) (top) and 1 (bottom); thermal ellipsoids are drawn at the 50% probability level.


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Figure 11. Molecular structure of 2 (top) and 2a (bottom); thermal ellipsoids are drawn at the 50% probability level.


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Figure 12. Showing a molecular chain formation via Ni•••H bonding in the crystal structure of 1 (left, Ni•••H = 2.79 Å), and 2a (right, Ni•••H = 2.45 Å).

Figure 13. Showing change in X-Band EPR signal intensity during oxygen gas purging to the CH2Cl2 solution of 2.


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Figure 14. Time−dependent absorption changes upon addition of mCPBA (1 equiv.) to 2. Inset showing change in X−band EPR signal.

Figure 15. Experimental and simulated mass spectra for m/z = 613.27; [C36H47N2NiO2+O], and m/z = 631.26; [{C36H47N2NiO2+OOH}+H] have been shown. Labelling experiment using 18O2 showed m/z = 613.34 for [C36H45N2Ni16O2

18O], and m/z = 615.29 for [C36H47N2NiO2+

18O], indicating the formation of 2a with 18O and Ni-monooxygen [(2+O)]+ species, respectively, and confirming the incorporation of molecular oxygen in to 2 for the formation of 2a.


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Table 1. Comparative structural studies between complex 1 and complex 2.

Comparing factors* Complex 1 Complex 2 Angle between P and Q planes 43.9 46.3 Angle between Q and R planes 54.2 58.2 Angle between P and R planes 26.6 23.6 Angle between N1−−−−C7−−−−C12−−−−C13 and C13−−−−N2−−−−C14−−−−C15−−−−C16−−−−C17−−−−C18−−−−C19−−−−C20−−−−O2 planes

49.6 54.9

Angle between N1−−−−C7−−−−C12−−−−C13 and N2−−−−C14−−−−C15−−−−C16−−−−C17−−−−C18−−−−C19−−−−C20−−−−O2 planes

49.5 54.7

Distance of Ni1 atom from plane P -0.072 -0.304 Distance of Ni1 atom from plane Q 1.310 1.079 Distance of Ni1 atom from plane R 0.044 0.339 Distance of N1 atom from Ni1-C7-C12-N2 plane -0.475 -0.352 Distance of benzyl C13 atom from Ni1-C7-C12-N2 plane 0.609 0.662 Distance of Ni1 atom from O1-C1-C2-C3-C3-C4-C5-C6-N1 plane -0.154 -0.251 Distance of Ni1 atom from N2-C14-C15-C16-C17-C18-C19-C20-O2 plane (salen plane)

-0.012 0.300

* Here –ve sign indicates the position towards benzyl C13 atom. The angles are in deg(°) and distances are in Å.


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Table 2. Bond distances (Å) and bond angles (Å) for H3SamiMixed(H), 1, 2, and 2a are given.

H3SamiMixed

1 2 2a

Ni1—O2 Ni1—O1 Ni1—N2 Ni1—N1 O1—C2 O2—C20 N1—C1 N1—C7 N2—C14 N2—C13 C1—C6 C1—C2 C7—C12 C7—C8 C12—C11 C12—C13 C3—C4 C3—C2 C15—C16 C15—C14 C6—C5 C5—C4 C9—C10 C9—C8 C10—C11 C17—C18 C17—C16 C19—C18 C20—C19 C20—C15

1.375(5) 1.355(3) 1.434(5) 1.403(5) 1.275(4) 1.470(4) 1.390(5) 1.390(4) 1.404(4) 1.392(4) 1.380(5) 1.513(4) 1.389(5) 1.400(5) 1.402(4) 1.447(4) 1.380(5) 1.396(4) 1.369(4) 1.379(5) 1.387(4) 1.375(5) 1.375(5) 1.366(4) 1.384(4) 1.397(5)

1.840(8) 1.856(6) 1.860(5) 1.870(8) 1.293(8) 1.296(7) 1.364(6) 1.404(7) 1.287(8) 1.485(9) 1.410(8) 1.446(7) 1.390(8) 1.407(8) 1.384(9) 1.500(8) 1.371(10) 1.412(9) 1.407(9) 1.434(10) 1.364(8) 1.418(8) 1.372(10) 1.377(9) 1.374(9) 1.373(9) 1.372(10) 1.357(9) 1.417(10) 1.424(8)

1.818(1) 1.860(2) 1.849(2) 1.860(2) 1.310(3) 1.318(3) 1.371(4) 1.397(3) 1.302(3) 1.485(3) 1.415(3) 1.426(3) 1.403(4) 1.402(3) 1.381(4) 1.502(3) 1.369(4) 1.430(4) 1.414(4) 1.437(3) 1.372(4) 1.415(3) 1.379(6) 1.370(4) 1.384(4) 1.411(4) 1.364(3) 1.386(4) 1.425(3) 1.408(3)

1.834(3) 1.869(3) 1.864(4) 1.862(4) 1.305(5) 1.284(5) 1.380(5) 1.391(6) 1.336(6) 1.430(7) 1.415(6) 1.428(6) 1.414(6) 1.390(7) 1.394(8) 1.456(7) 1.374(7) 1.423(6) 1.422(7) 1.392(7) 1.356(6) 1.430(6) 1.391(8) 1.366(8) 1.357(8) 1.418(7) 1.350(8) 1.383(6) 1.446(6) 1.423(6)

O2—Ni1—N2 95.83(17) 94.74(8) 95.83(17) O2—Ni1—O1 87.17(16) 86.55(7) 166.18(17) N2—Ni1—O1 165.84(18) 169.34(9) 165.84(18) O2—Ni1—N1 166.18(17) 168.04(7) 166.18(17) N2—Ni1—N1 94.66(18) 94.96(8) 94.66(18) O1—Ni1—N1 84.84(17) 85.20(8) 84.84(17) C2—O1—Ni1 114.49(34) 112.87(16) 121.77(29) C20—O2—Ni1 127.29(36) 127.39(13) 125.27(31) C1—N1—Ni1 112.34(30) 112.83(14) 110.94(26) C7—N1—Ni1 121.63(28) 123.44(14) 125.83(30) C1—N1—C7 121.48(13) 124.19(38) 122.91(19) 123.19(37) C14—N2—Ni1 125.15(38) 125.30(18) 129.69(27) C13—N2—Ni1 118.31(33) 116.72(14) 112.62(39) C14—N2—C13 118.46(18) 115.74(45) 117.32(17) 112.63(24) N1—C1—C6 120.98(15) 127.22(40) 127.04(21) 127.23(35) N1—C1—C2 118.64(15) 112.75(40) 111.93(20) 112.34(37)


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O1—C2—C1 118.73(18) 114.58(47) 116.16(19) 115.53(36) O1—C2—C3 120.35(15) 126.08(52) 123.90(21) 124.55(37) C1—C2—C3 120.92(16) 119.30(48) 119.93(21) 119.91(39) C4—C3—C2 116.33(16) 117.12(54) 115.77(22) 115.92(41) C3—C4—C5 124.41(20) 124.86(55) 125.69(22) 124.99(40) C6—C5—C4 117.07(16) 118.03(52) 118.35(23) 118.09(41) C5—C6—C1 120.92(16) 120.53(44) 119.31(22) 120.11(36) N1—C7—C12 119.55(14) 117.60(42) 117.93(21) 119.71(40) N1—C7—C8 121.61(15) 122.1(4) 122.88(20) 121.85(44) C12—C7—C8 118.81(15) 120.1(5) 119.08(24) 118.43(40) C9—C8—C7 120.61(16) 118.72(51) 120.03(23) 122.20(47) C8—C9—C10 120.97(19) 121.15(59) 121.14(30) 119.16(51) C9—C10—C11 118.82(19) 120.15(64) 119.10(32) 119.78(52) C12—C11—C10 121.64(17) 120.46(55) 121.19(22) 122.31(53) C11—C12—C7 119.14(15) 119.39(49) 119.33(24) 117.96(44) C11—C12—C13 119.46(15) 120.47(52) 121.41(19) 116.26(46) C7—C12—C13 121.35(15) 120.13(48) 119.26(22) 125.74(42) N2—C13—C12 110.39(16) 110.92(45) 111.16(17) 119.43(46) O3—C13—N2 120.66(46) O3—C13—C12 119.91(47) N2—C14—C15 122.62(20) 125.78(54) 125.19(19) 128.60(42) C20—C15—C16 118.15(18) 119.55(52) 120.18(21) 120.96(39) C20—C15—C14 121.51(18) 121.25(52) 121.26(20) 121.09(42) C16—C15—C14 120.33(21) 119.18(54) 118.55(19) 117.95(42) C17—C16—C15 120.81(23) 121.17(56) 121.75(20) 122.00(48) C16—C17—C18 119.72(22) 118.56(58) 116.93(22) 116.58(45) C19—C18—C17 120.86(21) 123.09(62) 124.44(24) 125.59(42) C18—C19—C20 120.11(23) 120.19(55) 117.35(19) 117.10(38) O2—C20—C15 121.37(17) 124.02(51) 121.92(21) 122.52(38) O2—C20—C19 118.29(20) 118.57(52) 118.96(18) 119.74(37) C15—C20—C19 120.34(19) 117.40(52) 119.1(2) 117.74(39)


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Table 3. Crystallographic data and structure refinement for H3SamiMixed(H), 1, 2, and 2a.

H3SamiMixed(H) 1 2 2a

Empirical formula C28H34N2O2 C28H31N2NiO2 C36H47N2NiO2 C36H45N2NiO3 Formula weight 430.57 486.26 598.47 612.45 Crystal habit, colour block / yellow Needle / green Block / green needle, brown Crystal size, mm3 0.52 Χ 0.38 Χ 0.26 0.32 X 0.06 X 0.04 0.54 X 0.44 X 0.38 0.44 Χ 0.28 Χ 0.20 Temperature, T 296(2) K 296(2) K 296(2) K 296(2) K Wavelength, λ 0.71073 Å 0.71073 Å 0.71073 Å 0.71073 Å Crystal system triclinic monoclinic monoclinic orthorhombic Space group P -1 P 21/a C1 2/c1 P 21 21 21 Unit cell dimensions a = 9.5342(8) Å

b = 12.0945(10) Å c = 12.3345(11) Å α = 62.280(4)°, γ = 83.074(5)°, β = 81.490(5)°

a = 19.4933(18) Å b = 6.1948(6) Å c = 20.415(2) Å α = 90.00°, γ = 90.00°, β = 96.986(9)°

a = 28.2555(10) Å b = 13.6775(4) Å c = 19.3826(6) Å α = 90.00°, γ = 90.00°, β = 114.585(2)°

a = 6.4633(3) Å b = 18.9923(9) Å c = 27.1870(13) Å α = β = γ = 90°

Volume, V 1243.03(18) Å3 2447.0(4) Å3 6811.6(4) Å3 3337.3(3) Å3 Z 2 4 8 4 Calculated density, Mg·m−3

1.150 1.320 1.167 1.219 Mg·m−3

Absorption coefficient, µ 0.072 mm−1 0.820 mm−1 0.601 mm−1 0.617 mm−1 F(000) 464 1028 2568 1308 θ range for data collection

1.87 to 25.00° 3.08 to 26.00° 1.59 to 25.00 1.31 to 24.99°

Limiting indices –10 ≤ h ≤ 11, –14 ≤ k ≤ 13, –14 ≤ l ≤ 14

–24 ≤ h ≤ 23, –7 ≤ k ≤ 6, –25 ≤ l ≤ 24

–24 ≤ h ≤ 33, –16 ≤ k ≤ 16, –23 ≤ l ≤ 20

–7 ≤ h ≤ 7, –22 ≤ k ≤ 22, –32 ≤ l ≤ 32

Reflection collected / unique

13117 / 3931 [R(int) = 0.0610]

10057 / 4806 [R(int) = 0.0638]

29563 / 5871 [R(int) = 0.0344]

25383 / 5666 [R(int) = 0.0840]

Completeness to θ 89.9 % (θ = 25.00°) 99.8 % (θ = 26.00°) 97.8 % (θ = 25.00°) 97.0 %, (θ = 24.99°)

Max. and min. transmission

0.981 / 0.968 0.968 / 0.943 0.796 / 0.735 0.884 / 0.813

Refinement method 'SHELXL−97 (Sheldrick, 1997)'

'SHELXL−97 (Sheldrick, 1997)'



Data / restraints / parameters

3931 / 0 / 297 4806 / 0 / 304 5871 / 0 / 382 5666 / 0 / 391

Goodness−of−fit on F2 1.020 1.086 1.052 1.061 Final R indices [I>2sigma(I)]

R1 = 0.0499, wR2 = 0.1496

R1 = 0.0703, wR2 = 0.1306

R1 = 0.0350, wR2 = 0.1041

R1 = 0.0481, wR2 = 0.0913

R indices (all data) R1 = 0.0618, wR2 = 0.1599

R1 = 0.1117, wR2 = 0.1560

R1 = 0.0521, wR2 = 0.1195

R1 = 0.0940, wR2 = 0.1180

Largest diff. peak and hole

0.325 and −0.372 e·Å−3

0.932 and −0.818 e·Å−3

0.319 and −0.236 e·Å−3

0.312, −0.330 e·Å−3

References.

1. Dolomanov, O. V.; Bourhis, L. J.; Gildea, R. J.; Howard, J. A. K. Puschmann, H. J. Appl. Cryst., 2009, 42, 339-341.

2. Palatinus, L.; Chapuis, G. J. Appl. Cryst., 2007, 40, 786-790. 3. olex2.refine (L.J. Bourhis, O.V. Dolomanov, R.J. Gildea, J.A.K. Howard, H. Puschmann, in

preparation, 2011). 4. Ghorai, S.; Mukherjee. C. Chem. Commun., 2012, 10180-10182.


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Supporting Information Effect of Ligand Substituent on The ... · S3 Materials: All the chemicals and solvents were obtained from commercial sources and were used as supplied, unless