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SUPPLEMENTARY DATA
Fluorescent biogenic Schiff base compounds of dimethyltin
Navjot Singha,b, Neha Srivastava, Raghubir Singhb*, Varinder Kaura*, Erica Brendlerc, Jörg
Waglerd, Edwin Kroked
aDepartment of Chemistry, Panjab University, Sector-14, Chandigarh-160014,
bDepartment of Chemistry, DAV college, Sector 10, Chandigarh-160011
cInstitut für Analytische Chemie, Technische Universität Bergakademie, Freiberg – 09596
Freiberg, Germany
dInstitut für Anorganische Chemie, Technische Universität Bergakademie, Freiberg – 09596
Freiberg, Germany
1. Synthesis
1.1. Synthetic procedure for 4. A suspension of Me2SnO (0.20 g, 1.21 mmol), 2-hydroxy-4-
methoxybenzophenone (0.28 g, 1.21 mmol), and alanine (0.11 g, 1.21 mmol), in methanol
(60 mL) was heated to reflux in a Dean-stark apparatus for 8 h. Solution was concentrated to
one-fifth of its original volume under vacuum and the remaining solvent was removed
completely and the product was extracted with chloroform. The chloroform was evaporated
to obtain yellow solid, which was washed with ether to remove soluble impurities.
6-Aza-11-methoxy-2,2,5-trimethyl-1,3-dioxa-7-phenyl-2-stannabenzocyclononen-4(5H)-
one (4).
Yield (crude product) 40 %. (0.21 g, 0.47 mmol). M.p.: decomposed, 217-220 °C. IR (cm-1):
461 s (υ Sn←N), 548 s (υ Sn–O), 706 s (υs Sn–C), 1411 m (υs C=O), 1597 s (C=N), 1670 s
(υas C=O). 1H NMR (400 MHz, CDCl3): δ (ppm) 0.69 (s, 3 H, SnCH3, 2J(1H-117Sn) = 74 Hz,
2J(1H-119Sn) = 77 Hz), 1.01 (s, 3 H, SnCH3 2J(1H-117Sn) = 77 Hz, 2J(1H-119Sn) = 80 Hz), 1.33
(d, 3 H, CCH313, 3J(1H-1H) = 7 Hz), 3.80 (s, 3 H, OCH3), 4.19 (q, 1 H, NCH, 3J(1H-1H) = 7
Hz, 4J(1H-117Sn) = 36 Hz, 4J(1H-119Sn) = 50 Hz), 6.15 (dd, 1 H4, 4J(1H-1H) = 3 Hz, 3J(1H-1H)
= 9 Hz), 6.53 (d, 1 H2, 4J(1H-1H) = 3 Hz), 6.62 (d, 1 H5, 3J(1H-1H) = 9 Hz), 7.12-7.14 (m, 1
H8), 7.29-7.31 (m, 1 H12), 7.51-7.59 (m, 3 H9,10,11), 8.32 (s, 1 H, NH). 13C NMR (100 MHz,
CDCl3): δ (ppm) -1.7 (3 H, SnCH3, 1J(13C-117Sn) = 613 Hz, 1J(13C-119Sn) = 642 Hz), 1.3 (3 H,
SnCH3, 1J(13C-117Sn) = 652 Hz, 1J(13C-119Sn) = 689 Hz), 21.3 (C13), 55.5 (OCH3), 59.4
(NCH), 104.5 (C2), 107.7 (C4), 113.9 (C6), 126.0 (C12), 127.2 (C8), 129.1 (C9), 129.2 (C11),
129.9 (C10), 134.3 (C5), 136.4 (C7), 166.7 (C1), 170.5 (C3), 175.3 (C=N), 179.8 (C=O). 119Sn
Electronic Supplementary Material (ESI) for New Journal of Chemistry.This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2017
2
NMR (149 MHz, CDCl3): δ (ppm) -163. MS (% relative abundance of m/z assignment): 300
(100) [L + H]+, 322 (3.7) [L + Na]+, 338 (12.7) [L + K]+, 446 (2.4) [M]+, 448 (3.7) [M +
2H]+, 470 (4.0) [M + Na + H]+. C19H21NO4Sn (446.08): calcd. C 51.16, H 4.75, N 3.14;
found C 51.15, H 4.74, N 3.13.
1.2. Synthetic procedure for 2-aminoethanol derivative. A solution of the Schiff base
ligand (derived from condensation reaction of 2-aminoethanol and
2-hydroxy-4-methoxybenzophenone in methanol; unpublished)
(1.00 g, 3.69 mmol) and dimethyltin(IV) oxide (0.91 g, 3.69 mmol)
was refluxed in 50 ml of toluene-methanol (4:6). for 8 h using a
Dean-Stark trap. After cooling to room temperature the solvents
were evaporated under vacuum to obtain a yellow product. It was
washed with hexane, dried and stored under inert atmosphere.
N[CH2CH2O][C(Ph)(OMe-C6H3)O]SnMe2:
Yield 75% (1.17 g, 2.79 mmol). M.p. 124-126°C. IR (cm-1): 409 (Sn‒N), 559 (Sn‒O), 1589
(C=N). 1H NMR (400 MHz, CDCl3): δ (ppm) 0.66 (s, 6H17,18, 2J(1H-117Sn) = 72.3 Hz, 2J(1H-
119Sn) = 75.3 Hz), 3.24 (t, 2H15, 3J(1H-1H) = 5.5 Hz), 3.75 (s, 3H7), 3.92 (t, 2H16, 3J(1H-1H) =
5.5 Hz), 6.05 (dd, 1H4, 4J(1H-1H) = 2.5 Hz, 3J(1H-1H) = 9.2 Hz), 6.26 (d, 1H5, 4J(1H-1H) = 2.5
Hz), 6.54 (d, 1H2, 3J(1H-1H) = 9.2 Hz), 7.22-7.26 (m, 2H10,14), 7.46-7.55 (m, 3H11-13). 13C
NMR (75 MHz, CDCl3): δ (ppm) 0.68 (C17,18), 21.5 (C15), 55.4 (C16), 60.7 (C7), 104.4 (C2),
106.4 (C4), 114.5 (C6), 126.3 (C9), 128.3 (C11), 129.1 (C13), 129.3 (C12), 135.9 (C10), 136.0
(C14), 136.4 (C5), 165.5 (C1), 170.4 (C3), 180.1 (C8). 119Sn NMR (149 MHz, CDCl3): δ (ppm)
-160. MS (% relative abundance of m/z assignment): 272 (100) [L]+, 294 (29.7) [L + Na]+,
544 (6.4) [M + C7H6O2 + H]+, 565 (10.7) [M – C13H14O – OCH3 – C6H5]+, 836 [2M], 852
(3.2) [2M + NH3 - H]+. C18H21NO3Sn (418.08): calcd. C, 51.71; H, 5.06; N, 3.35; found C,
51.54; H, 4.99; N, 3.67.
3
2. Detailed spectra for 1-4
Compound 1
10 9 8 7 6 5 4 3 2 1 0 ppm
0.7447
0.7487
0.8436
0.9387
0.9426
1.6718
1.6834
2.0285
3.4540
3.4639
3.7990
3.8400
3.8679
3.8959
6.1197
6.1262
6.1428
6.1493
6.2780
6.2844
6.6102
6.6333
7.1627
7.1662
7.1769
7.1814
7.1860
7.2866
7.5266
7.5291
7.5360
7.5399
7.5452
7.5570
7.5643
7.5756
7.5795
7.5866
6.12
1.49
0.81
4.24
3.06
2.06
1.01
1.00
1.01
2.00
3.04
Current Data Parameters
NAME Feb15-2016
EXPNO 220
PROCNO 1
F2 - Acquisition Parameters
Date_ 20160215
Time 23.29
INSTRUM spect
PROBHD 5 mm PABBO BB-
PULPROG zg30
TD 65536
SOLVENT CDCl3
NS 8
DS 2
SWH 12019.230 Hz
FIDRES 0.183399 Hz
AQ 2.7263477 sec
RG 161
DW 41.600 usec
DE 6.00 usec
TE 294.8 K
D1 1.00000000 sec
TD0 1
======== CHANNEL f1 ========
NUC1 1H
P1 10.90 usec
PL1 -3.00 dB
SFO1 400.1324710 MHz
F2 - Processing parameters
SI 32768
SF 400.1299991 MHz
WDW EM
SSB 0
LB 0.30 Hz
GB 0
PC 1.00
GLY+ME2BRUKER
AVANCE II 400 NMR
Spectrometer
SAIFPanjab University
Chandigarh
Fig. S1a 1H NMR spectra of compound 1.
-10200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
0.61
50.68
54.47
55.52
76.77
77.09
77.41
104.28
107.77
113.28
125.65
129.63
129.80
135.84
136.60
166.95
170.91
171.21
181.06
Current Data Parameters
NAME Feb15-2016
EXPNO 221
PROCNO 1
F2 - Acquisition Parameters
Date_ 20160215
Time 23.59
INSTRUM spect
PROBHD 5 mm PABBO BB-
PULPROG zgpg30
TD 65536
SOLVENT CDCl3
NS 512
DS 4
SWH 29761.904 Hz
FIDRES 0.454131 Hz
AQ 1.1010548 sec
RG 645
DW 16.800 usec
DE 6.00 usec
TE 295.2 K
D1 2.00000000 sec
d11 0.03000000 sec
DELTA 1.89999998 sec
TD0 1
======== CHANNEL f1 ========
NUC1 13C
P1 9.60 usec
PL1 -2.00 dB
SFO1 100.6228298 MHz
======== CHANNEL f2 ========
CPDPRG2 waltz16
NUC2 1H
PCPD2 80.00 usec
PL2 -3.00 dB
PL12 14.31 dB
PL13 18.00 dB
SFO2 400.1316005 MHz
F2 - Processing parameters
SI 32768
SF 100.6127691 MHz
WDW EM
SSB 0
LB 1.00 Hz
GB 0
PC 1.40
GLY+ME2 BRUKER
AVANCE II 400 NMR
Spectrometer
SAIF
Panjab University
Chandigarh
GLY+ME2 BRUKER
AVANCE II 400 NMR
Spectrometer
SAIF
Panjab University
Chandigarh
4
Fig. S1b 13C NMR spectra of compound 1.
-450-400-350-300-250-200-150-100-500 ppm
-160.29
Current Data Parameters
NAME Feb15-2016
EXPNO 222
PROCNO 1
F2 - Acquisition Parameters
Date_ 20160216
Time 0.20
INSTRUM spect
PROBHD 5 mm PABBO BB-
PULPROG zgig30
TD 65536
SOLVENT CDCl3
NS 1000
DS 4
SWH 375000.000 Hz
FIDRES 5.722046 Hz
AQ 0.0874313 sec
RG 2050
DW 1.333 usec
DE 6.00 usec
TE 294.8 K
D1 1.00000000 sec
d11 0.03000000 sec
TD0 1
======== CHANNEL f1 ========
NUC1 119Sn
P1 10.00 usec
PL1 -2.00 dB
SFO1 149.1214792 MHz
======== CHANNEL f2 ========
CPDPRG2 waltz16
NUC2 1H
PCPD2 80.00 usec
PL2 -3.00 dB
PL12 14.31 dB
SFO2 400.1316005 MHz
F2 - Processing parameters
SI 32768
SF 149.2110060 MHz
WDW EM
SSB 0
LB 5.00 Hz
GB 0
PC 1.40
GLY+ME2 BRUKER
AVANCE II 400 NMR
Spectrometer
SAIF
Panjab University
Chandigarh
GLY+ME2 BRUKER
AVANCE II 400 NMR
Spectrometer
SAIF
Panjab University
Chandigarh
Fig. S1c 119Sn NMR spectra of compound 1.
5
Fig. S1d Mass spectrum of compound 1.
Compound 2’
10 9 8 7 6 5 4 3 2 1 0 ppm
-0.0707
0.0000
0.3842
0.3873
0.4264
0.4448
0.4632
0.4748
0.5624
0.5655
0.8201
0.8239
0.9212
0.9350
0.9650
0.9836
0.9997
1.0180
1.0362
1.3443
1.3617
1.3791
1.3961
1.4137
1.4892
1.5060
1.5220
1.5382
1.6076
3.4131
3.4202
3.7331
3.8003
4.1131
4.1264
6.0744
6.0808
6.0974
6.1039
6.2517
6.2580
6.4428
6.4658
7.0268
7.0314
7.0362
7.0416
7.0451
7.1915
7.1979
7.2066
7.2120
7.4227
7.4268
7.4323
7.4376
7.4433
7.4489
7.4560
7.4599
7.4654
7.4689
7.4776
7.4820
7.4849
7.4940
5.71
5.68
1.82
1.05
1.07
1.66
1.71
3.08
1.00
1.00
1.00
1.03
1.00
1.51
3.17
Current Data Parameters
NAME Feb15-2016
EXPNO 170
PROCNO 1
F2 - Acquisition Parameters
Date_ 20160215
Time 18.48
INSTRUM spect
PROBHD 5 mm PABBO BB-
PULPROG zg30
TD 65536
SOLVENT CDCl3
NS 8
DS 2
SWH 12019.230 Hz
FIDRES 0.183399 Hz
AQ 2.7263477 sec
RG 322
DW 41.600 usec
DE 6.00 usec
TE 295.0 K
D1 1.00000000 sec
TD0 1
======== CHANNEL f1 ========
NUC1 1H
P1 10.90 usec
PL1 -3.00 dB
SFO1 400.1324710 MHz
F2 - Processing parameters
SI 32768
SF 400.1300346 MHz
WDW EM
SSB 0
LB 0.30 Hz
GB 0
PC 1.00
ISOLEU+ME2BRUKER
AVANCE II 400 NMR
Spectrometer
SAIFPanjab University
Chandigarh
Fig. S2a 1H NMR spectra of compound 2'.
-10200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
-2.74
2.35
11.22
15.44
26.54
41.44
50.91
55.55
67.03
76.76
77.07
77.39
104.59
107.78
114.35
126.78
128.66
129.03
129.04
130.06
134.72
136.50
166.54
171.24
172.72
179.87
Current Data Parameters
NAME Feb15-2016
EXPNO 171
PROCNO 1
F2 - Acquisition Parameters
Date_ 20160215
Time 19.18
INSTRUM spect
PROBHD 5 mm PABBO BB-
PULPROG zgpg30
TD 65536
SOLVENT CDCl3
NS 512
DS 4
SWH 29761.904 Hz
FIDRES 0.454131 Hz
AQ 1.1010548 sec
RG 575
DW 16.800 usec
DE 6.00 usec
TE 295.5 K
D1 2.00000000 sec
d11 0.03000000 sec
DELTA 1.89999998 sec
TD0 1
======== CHANNEL f1 ========
NUC1 13C
P1 9.60 usec
PL1 -2.00 dB
SFO1 100.6228298 MHz
======== CHANNEL f2 ========
CPDPRG2 waltz16
NUC2 1H
PCPD2 80.00 usec
PL2 -3.00 dB
PL12 14.31 dB
PL13 18.00 dB
SFO2 400.1316005 MHz
F2 - Processing parameters
SI 32768
SF 100.6127655 MHz
WDW EM
SSB 0
LB 1.00 Hz
GB 0
PC 1.40
ISOLEU+ME2 BRUKER
AVANCE II 400 NMR
Spectrometer
SAIF
Panjab University
Chandigarh
ISOLEU+ME2 BRUKER
AVANCE II 400 NMR
Spectrometer
SAIF
Panjab University
Chandigarh
6
Fig. S2b 13C NMR spectra of compound 2'.
-450-400-350-300-250-200-150-100-500 ppm
-159.60
Current Data Parameters
NAME Feb15-2016
EXPNO 172
PROCNO 1
F2 - Acquisition Parameters
Date_ 20160215
Time 19.39
INSTRUM spect
PROBHD 5 mm PABBO BB-
PULPROG zgig30
TD 65536
SOLVENT CDCl3
NS 1000
DS 4
SWH 375000.000 Hz
FIDRES 5.722046 Hz
AQ 0.0874313 sec
RG 2050
DW 1.333 usec
DE 6.00 usec
TE 295.1 K
D1 1.00000000 sec
d11 0.03000000 sec
TD0 1
======== CHANNEL f1 ========
NUC1 119Sn
P1 10.00 usec
PL1 -2.00 dB
SFO1 149.1214792 MHz
======== CHANNEL f2 ========
CPDPRG2 waltz16
NUC2 1H
PCPD2 80.00 usec
PL2 -3.00 dB
PL12 14.31 dB
SFO2 400.1316005 MHz
F2 - Processing parameters
SI 32768
SF 149.2110060 MHz
WDW EM
SSB 0
LB 5.00 Hz
GB 0
PC 1.40
ISOLEU+ME2 BRUKER
AVANCE II 400 NMR
Spectrometer
SAIF
Panjab University
Chandigarh
ISOLEU+ME2 BRUKER
AVANCE II 400 NMR
Spectrometer
SAIF
Panjab University
Chandigarh
Fig. S2c 119Sn NMR spectra of compound 2'.
WATERS, Q-TOF MICROMASS (LC-MS) SAIF/CIL,PANJAB UNIVERSITY,CHANDIGARH
m/z100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000
%
0
100
NAVJOT ME2SnA2- 6 (0.220) Cm (4:11) TOF MS ES+ 2.26e4490.23
22649
488.2418703
486.2610671
342.483381
491.246711
492.263288
512.212682
998.622401
996.611902
995.63768
1000.641725
7
Fig. S2d Mass spectrum of compound 2'.
Compound 3’
10 9 8 7 6 5 4 3 2 1 0 ppm
0.0000
0.5438
0.6367
0.7279
0.9123
1.0119
1.1118
1.6914
1.8427
1.8573
1.8625
1.8675
1.8771
1.8875
1.8908
1.9018
1.9165
1.9360
1.9498
1.9679
1.9934
2.0041
2.3096
2.3252
2.3337
2.3423
2.3492
2.3577
2.3663
2.3819
2.4541
2.4675
2.4793
2.4869
2.4925
2.5002
2.5118
2.5253
3.4851
3.8044
4.2590
4.2727
4.2788
4.2925
6.1405
6.1468
6.1636
6.1699
6.3053
6.3114
6.5137
6.5368
7.1123
7.1171
7.1258
7.1295
7.2701
7.2802
7.2868
7.2912
7.5204
7.5327
7.5416
7.5504
7.5664
7.5825
3.22
3.43
1.11
1.21
4.14
1.09
1.05
3.00
3.27
1.05
1.04
1.06
1.09
1.07
1.63
3.28
Current Data Parameters
NAME Feb15-2016
EXPNO 210
PROCNO 1
F2 - Acquisition Parameters
Date_ 20160215
Time 22.33
INSTRUM spect
PROBHD 5 mm PABBO BB-
PULPROG zg30
TD 65536
SOLVENT CDCl3
NS 8
DS 2
SWH 12019.230 Hz
FIDRES 0.183399 Hz
AQ 2.7263477 sec
RG 322
DW 41.600 usec
DE 6.00 usec
TE 294.9 K
D1 1.00000000 sec
TD0 1
======== CHANNEL f1 ========
NUC1 1H
P1 10.90 usec
PL1 -3.00 dB
SFO1 400.1324710 MHz
F2 - Processing parameters
SI 32768
SF 400.1300058 MHz
WDW EM
SSB 0
LB 0.30 Hz
GB 0
PC 1.00
METHEONINE+ME2BRUKER
AVANCE II 400 NMR
Spectrometer
SAIFPanjab University
Chandigarh
Fig. S3a 1H NMR spectra of compound 3'.
-10200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
-1.96
1.89
15.59
30.12
35.59
50.93
55.60
62.90
76.78
77.10
77.42
104.56
107.95
114.10
126.52
127.90
129.27
129.40
130.19
134.53
136.60
166.84
171.17
173.42
180.06
Current Data Parameters
NAME Feb15-2016
EXPNO 211
PROCNO 1
F2 - Acquisition Parameters
Date_ 20160215
Time 23.03
INSTRUM spect
PROBHD 5 mm PABBO BB-
PULPROG zgpg30
TD 65536
SOLVENT CDCl3
NS 512
DS 4
SWH 29761.904 Hz
FIDRES 0.454131 Hz
AQ 1.1010548 sec
RG 645
DW 16.800 usec
DE 6.00 usec
TE 295.3 K
D1 2.00000000 sec
d11 0.03000000 sec
DELTA 1.89999998 sec
TD0 1
======== CHANNEL f1 ========
NUC1 13C
P1 9.60 usec
PL1 -2.00 dB
SFO1 100.6228298 MHz
======== CHANNEL f2 ========
CPDPRG2 waltz16
NUC2 1H
PCPD2 80.00 usec
PL2 -3.00 dB
PL12 14.31 dB
PL13 18.00 dB
SFO2 400.1316005 MHz
F2 - Processing parameters
SI 32768
SF 100.6127633 MHz
WDW EM
SSB 0
LB 1.00 Hz
GB 0
PC 1.40
METHEONINE+ME2 BRUKER
AVANCE II 400 NMR
Spectrometer
SAIF
Panjab University
Chandigarh
METHEONINE+ME2 BRUKER
AVANCE II 400 NMR
Spectrometer
SAIF
Panjab University
Chandigarh
8
Fig. S3b 13C NMR spectra of compound 3'.
-450-400-350-300-250-200-150-100-500 ppm
-160.91
Current Data Parameters
NAME Feb15-2016
EXPNO 212
PROCNO 1
F2 - Acquisition Parameters
Date_ 20160215
Time 23.24
INSTRUM spect
PROBHD 5 mm PABBO BB-
PULPROG zgig30
TD 65536
SOLVENT CDCl3
NS 1000
DS 4
SWH 375000.000 Hz
FIDRES 5.722046 Hz
AQ 0.0874313 sec
RG 2050
DW 1.333 usec
DE 6.00 usec
TE 294.8 K
D1 1.00000000 sec
d11 0.03000000 sec
TD0 1
======== CHANNEL f1 ========
NUC1 119Sn
P1 10.00 usec
PL1 -2.00 dB
SFO1 149.1214792 MHz
======== CHANNEL f2 ========
CPDPRG2 waltz16
NUC2 1H
PCPD2 80.00 usec
PL2 -3.00 dB
PL12 14.31 dB
SFO2 400.1316005 MHz
F2 - Processing parameters
SI 32768
SF 149.2110060 MHz
WDW EM
SSB 0
LB 5.00 Hz
GB 0
PC 1.40
METHEONINE+ME2 BRUKER
AVANCE II 400 NMR
Spectrometer
SAIF
Panjab University
Chandigarh
METHEONINE+ME2 BRUKER
AVANCE II 400 NMR
Spectrometer
SAIF
Panjab University
Chandigarh
Fig. S3c 119Sn NMR spectra of compound 3'. WATERS, Q-TOF MICROMASS (LC-MS) SAIF/CIL,PANJAB UNIVERSITY,CHANDIGARH
m/z100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000
%
0
100
NAVJOT METHIONE Me2Sn- 6 (0.220) Cm (3:11) TOF MS ES+ 1.70e4508.18
16962
506.1912901
504.206342
360.422849
361.43530
509.194169
510.202786
530.162352 1034.50
1542
Fig. S3d Mass spectrum of compound 3'.
9
Compound 4
10 9 8 7 6 5 4 3 2 1 0 ppm
0.0000
0.5912
0.5946
0.6873
0.7800
0.7834
0.9114
0.9152
1.0118
1.1083
1.1120
1.3270
1.3446
2.3267
2.4344
3.4450
3.8004
3.8717
4.1679
4.1855
4.2032
4.2210
6.1354
6.1418
6.1584
6.1648
6.3052
6.3115
6.5174
6.5405
7.1177
7.1223
7.1250
7.1315
7.1350
7.2903
7.2942
7.3020
7.3078
7.5046
7.5115
7.5187
7.5232
7.5277
7.5312
7.5383
7.5447
7.5491
7.5532
7.5595
7.5646
7.5687
7.5778
7.5858
3.10
3.06
3.10
3.01
1.26
9.25
3.04
1.00
1.00
1.01
1.05
1.01
1.15
3.20
Current Data Parameters
NAME Feb15-2016
EXPNO 200
PROCNO 1
F2 - Acquisition Parameters
Date_ 20160215
Time 21.38
INSTRUM spect
PROBHD 5 mm PABBO BB-
PULPROG zg30
TD 65536
SOLVENT CDCl3
NS 8
DS 2
SWH 12019.230 Hz
FIDRES 0.183399 Hz
AQ 2.7263477 sec
RG 101
DW 41.600 usec
DE 6.00 usec
TE 294.9 K
D1 1.00000000 sec
TD0 1
======== CHANNEL f1 ========
NUC1 1H
P1 10.90 usec
PL1 -3.00 dB
SFO1 400.1324710 MHz
F2 - Processing parameters
SI 32768
SF 400.1299904 MHz
WDW EM
SSB 0
LB 0.30 Hz
GB 0
PC 1.00
ALAN+ME2BRUKER
AVANCE II 400 NMR
Spectrometer
SAIFPanjab University
Chandigarh
Fig. S4a 1H NMR spectra of compound 4.
-10200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
-1.67
1.31
21.27
50.46
55.48
59.44
76.78
77.10
77.42
104.46
107.70
113.95
126.04
127.27
129.11
129.24
129.94
134.26
136.44
166.67
170.55
175.29
179.80
Current Data Parameters
NAME Feb15-2016
EXPNO 201
PROCNO 1
F2 - Acquisition Parameters
Date_ 20160215
Time 22.07
INSTRUM spect
PROBHD 5 mm PABBO BB-
PULPROG zgpg30
TD 65536
SOLVENT CDCl3
NS 512
DS 4
SWH 29761.904 Hz
FIDRES 0.454131 Hz
AQ 1.1010548 sec
RG 575
DW 16.800 usec
DE 6.00 usec
TE 295.3 K
D1 2.00000000 sec
d11 0.03000000 sec
DELTA 1.89999998 sec
TD0 1
======== CHANNEL f1 ========
NUC1 13C
P1 9.60 usec
PL1 -2.00 dB
SFO1 100.6228298 MHz
======== CHANNEL f2 ========
CPDPRG2 waltz16
NUC2 1H
PCPD2 80.00 usec
PL2 -3.00 dB
PL12 14.31 dB
PL13 18.00 dB
SFO2 400.1316005 MHz
F2 - Processing parameters
SI 32768
SF 100.6127705 MHz
WDW EM
SSB 0
LB 1.00 Hz
GB 0
PC 1.40
ALAN+ME2 BRUKER
AVANCE II 400 NMR
Spectrometer
SAIF
Panjab University
Chandigarh
ALAN+ME2 BRUKER
AVANCE II 400 NMR
Spectrometer
SAIF
Panjab University
Chandigarh
10
Fig. S4b 13C NMR spectra of compound 4.
-450-400-350-300-250-200-150-100-500 ppm
-163.51
Current Data Parameters
NAME Feb15-2016
EXPNO 202
PROCNO 1
F2 - Acquisition Parameters
Date_ 20160215
Time 22.28
INSTRUM spect
PROBHD 5 mm PABBO BB-
PULPROG zgig30
TD 65536
SOLVENT CDCl3
NS 1000
DS 4
SWH 375000.000 Hz
FIDRES 5.722046 Hz
AQ 0.0874313 sec
RG 2050
DW 1.333 usec
DE 6.00 usec
TE 294.9 K
D1 1.00000000 sec
d11 0.03000000 sec
TD0 1
======== CHANNEL f1 ========
NUC1 119Sn
P1 10.00 usec
PL1 -2.00 dB
SFO1 149.1214792 MHz
======== CHANNEL f2 ========
CPDPRG2 waltz16
NUC2 1H
PCPD2 80.00 usec
PL2 -3.00 dB
PL12 14.31 dB
SFO2 400.1316005 MHz
F2 - Processing parameters
SI 32768
SF 149.2110060 MHz
WDW EM
SSB 0
LB 5.00 Hz
GB 0
PC 1.40
ALAN+ME2 BRUKER
AVANCE II 400 NMR
Spectrometer
SAIF
Panjab University
Chandigarh
ALAN+ME2 BRUKER
AVANCE II 400 NMR
Spectrometer
SAIF
Panjab University
Chandigarh
Fig. S4c 119Sn NMR spectra of compound 4. WATERS, Q-TOF MICROMASS (ESI-MS) SAIF/CIL,PANJAB UNIVERSITY,CHANDIGARH
m/z50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
%
0
100
NEHA Alan Me2 7 (0.172) Cm (4:13-17:43) TOF MS ES+ 6.05e3300.2002
6053
301.22211018
338.1703768
379.2070310
470.1765241
Fig. S4d Mass spectrum of compound 4.
11
2-Aminoethanol derivative
Fig. S5a 1H NMR spectra of 2-aminoethanol analogue.
Fig. S5b 13C NMR spectra of 2-aminoethanol analogue.
12
Fig. S5c 119Sn NMR spectra of 2-aminoethanol analogue.
WATERS, Q-TOF MICROMASS (LC-MS) SAIF/CIL,PANJAB UNIVERSITY,CHANDIGARH
m/z100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500
%
0
100
NEHA Me2SNJL 15 (0.158) Cm (10:22) TOF MS ES+ 1.79e4272.1
17872
272.85832
294.15311
565.31915
544.11141
852.4576
Fig. S5d Mass spectra of 2-aminoethanol analogue.
13
2. Structural Aspects
Only one signal is observed for solution-state 119Sn NMR spectra (for pentacoordinate Sn
atoms).
Fig. S6 Solution-state δ (CDCl3 solution, ppm) values for 119Sn NMR spectra of compound 2ʹ
and 3ʹ.
Table S1 Data of the 119Sn chemical shift anisotropy (CSA) tensors for compounds 2ʹ and 3ʹ.
The order of the principal values 11,22,33 as well as span and skew are reported according
to the Herzfeld-Berger notation. (*For compound 3ʹ the asymmetric signal at ca. -153 pm was
analyzed by deconvolution into two individual contributions.)
compound 2ʹ 3ʹ
iso -152.8 -245.9 -152.5* -152.9* -244.9
11 286.9 235.8 272.5 280.2 245.9
22 -50.3 -71.4 -111.6 -49.8 -59.7
33 -695.0 -902.2 -615.5 -689.1 -920.9
981.8 1137.9 887.9 969.4 1166.8
0.31 0.46 0.13 0.32 0.48
3. Description of crystal structure
Table S2: Selected bond lengths (Å) and bond angles (°) for 1.MeOH.
X-ray Crystal Data
Bond angles Sn(1)-O(1) 2.0974(12) O(1)-Sn(1)-C(17) 98.03(6) O(1)-Sn(1)-O(5) 74.66(5)
Sn(1)-C(17) 2.0992(18) O(1)-Sn(1)-C(18) 99.79(6) C(17)-Sn(1)-O(5) 80.44(6)
Sn(1)-C(18) 2.1039(18) C(17)-Sn(1)-C(18) 152.32(8) C(18)-Sn(1)-O(5) 84.06(6)
Sn(1)-N(1) 2.2383(14) O(1)-Sn(1)-N(1) 78.80(5) N(1)-Sn(1)-O(5) 153.39(5)
Sn(1)-O(3) 2.3750(12) C(17)-Sn(1)-N(1) 101.63(7) O(3)-Sn(1)-O(5) 136.47(4)
Sn(1)-O(5) 2.5533(13) C(18)-Sn(1)-N(1) 102.49(7) C(16)-O(3)-Sn(1) 116.60(11)
O(3)-C(16) 1.273(2) O(1)-Sn(1)-O(3) 148.86(4) C(19)-O(5)-Sn(1) 122.72(13)
14
O(4)-C(16) 1.239(2) C(17)-Sn(1)-O(3) 88.83(6) C(1)-O(1)-Sn(1) 122.76(10)
O(5)-H(5O) 0.79(3) C(18)-Sn(1)-O(3) 86.78(6) C(19)-O(5)-H(5O) 105.9(18)
N(1)-C(7) 1.303(2) N(1)-Sn(1)-O(3) 70.07(5) Sn(1)-O(5)-H(5O) 106.3(18)
Fig. S7 Intermolecular hydrogen bonding pattern of 1-MeOH.
C-H······π interactions are encountered between benzophenone ring systems of
neighbouring molecules with a distance of 2.79 Å, which produces a 1-D architecture along
crystallographic b-axis shown in Fig. S8. In this architecture, the phenyl ring is oriented at an
angle of 71.86° due to the edge to face C-H······π interactions and are placed parallel to the
phenyl rings in the neighbouring molecules at a distance of 3.76 Å and 4.20 Å.
Fig. S8 C-H···π interactions in 1-MeOH leading to 1-D chains.
15
Table S3: Selected bond lengths (Å) and bond angles (°) for 2ʹ and 3ʹ.
2ʹ 3ʹ
Parameter X-ray Crystal Data Parameter X-ray Crystal Data
Sn(1)-O(2) /Sn(4)-O(3) 2.005(4)/2.009(4) Sn(1)-O(1) 2.020(4)
Sn(1)-C(2) /Sn(4)-C(8) 2.108(7)/2.112(6) Sn(1)-C(2) 2.112(8)
Sn(1)-C(1) /Sn(4)-C(7) 2.111(6)/2.112(6) Sn(1)-C(1) 2.129(9)
Sn(1)-O(11) /Sn(4)-O(7) 2.169(4)/2.170(4) Sn(1)-O(3) 2.220(4)
Sn(1)-O(1) /Sn(4)-O(4) 2.194(4)/2.195(4) Sn(1)-O(2) 2.214(4)
Sn(2)-O(2) /Sn(3)-O(3) 2.054(4)/2.050(4) Sn(2)-O(1) 2.030(4)
Sn(2)-C(3) /Sn(3)-C(5) 2.106(7)/2.111(7) Sn(2)-C(3) 2.141(9)
Sn(2)-C(4) /Sn(3)-C(6) 2.112(7)/2.116(6) Sn(2)-C(4) 2.095(8)
Sn(2)-O(3) /Sn(3)-O(2) 2.144(4)/2.136(4) Sn(2)-O(1) 2.123(4)
Sn(2)-O(1) /Sn(3)-O(4) 2.164(4)/2.163(4) Sn(2)-O(2) 2.176(4)
O(11)-C(46) /O(7)-C(26) 1.296(6)/1.287(7) O(3)-C(21) 1.291(8)
O(12)-C(46) /O(8)-C(26) 1.224(7)/1.224(7) O(4)-C(21) 1.224(9)
O(2)-Sn(1)-C(2)/O(3)-Sn(4)-C(8) 114.8(3)/115.6(3) O(1)-Sn(1)-C(2) 103.5(3)
O(2)-Sn(1)-C(1)/O(3)-Sn(4)-C(7) 116.6(3)/116.4(3) O(1)-Sn(1)-C(1) 105.8(3)
C(2)-Sn(1)-C(1)/C(8)-Sn(4)-C(7) 127.4(3)/126.8(3) C(2)-Sn(1)-C(1) 150.6(3)
O(2)-Sn(1)-O(11)/O(3)-Sn(4)-O(7) 81.51(15)/81.54(15) O(1)-Sn(1)-O(3) 79.84(18)
C(2)-Sn(1)-O(11)/C(8)-Sn(4)-O(7) 99.6(3)/99.3(3) C(2)-Sn(1)-O(3) 92.2(3)
C(1)-Sn(1)-O(11)/C(7)-Sn(4)-O(7) 97.7(3)/98.2(3) C(1)-Sn(1)-O(3) 95.5(4)
O(2)-Sn(1)-O(1)/O(3)-Sn(4)-O(4) 72.35(16)/72.59(15) O(1)-Sn(1)-O(2) 72.68(16)
C(2)-Sn(1)-O(1)/C(8)-Sn(4)-O(4) 92.8(3)/92.9(3) C(2)-Sn(1)-O(2) 92.2(3)
C(1)-Sn(1)-O(1)/C(7)-Sn(4)-O(4) 92.7(3)/92.4(3) C(1)-Sn(1)-O(2) 93.8(3)
O(11)-Sn(1)-O(1)/O(7)-Sn(4)-O(4) 153.82(15)/154.11(16) O(2)-Sn(1)-O(3) 152.45(18)
O(2)-Sn(2)-C(3)/O(3)-Sn(3)-C(5) 109.3(2)/108.8(2) O(1)-Sn(2)-C(3) 116.2(4)
O(2)-Sn(2)-C(4)/O(3)-Sn(3)-C(6) 110.7(2)/112.9(2) O(1)-Sn(2)-C(4) 111.4(3)
C(3)-Sn(2)-C(4)/C(5)-Sn(3)-C(6) 140.0(3)/138.3(3) C(4)-Sn(2)-C(3) 132.4(4)
O(2)-Sn(2)-O(3)/O(3)-Sn(3)-O(2) 74.11(14)/74.36(14) O(1)-Sn(2)-O(1)#1 73.80(18)
C(3)-Sn(2)-O(3)/C(5)-Sn(3)-O(2) 95.1(2)/95.3(2) O(1)#1-Sn(2)-C(3) 95.8(3)
C(4)-Sn(2)-O(3)/C(6)-Sn(3)-O(2) 94.6(2)/95.1(2) C(4)-Sn(2)-O(1)#1 97.7(3)
O(2)-Sn(2)-O(1)/O(3)-Sn(3)-O(4) 72.09(14)/72.50(15) O(1)-Sn(2)-O(2) 73.32(17)
C(3)-Sn(2)-O(1)/C(5)-Sn(3)-O(4) 96.3(3)/96.8(3) C(3)-Sn(2)-O(2) 97.4(3)
C(4)-Sn(2)-O(1)/C(6)-Sn(3)-O(4) 96.7(3)/96.2(2) C(4)-Sn(2)-O(2) 95.3(4)
O(3)-Sn(2)-O(1)/O(2)-Sn(3)-O(4) 146.20(14)/146.82(15) O(1)#1-Sn(2)-O(2) 147.09(16)
16
Table S4 Intra- and intermolecular interactions; interatomic distance (Å) and bond angles (°)
in compound 2ʹ.
Bond interactions (D–H···A) D–H H···A D···A D–H···A
Intr
a-
mole
cula
r N1–H1N···O5 0.877(79) 1.755(79) 2.558(6) 151.19(798)
N2–H2N···O9 0.841(81) 1.779(79) 2.535(6) 148.70(817)
C49–H49B···O12 0.988(6) 2.498(5) 3.166(8) 124.60(37)
Inte
r-
mole
cula
r C20–H20···O5 0.951(8) 2.428(4) 3.363(9) 167.92(44)
C21–H21···O10 0.951(8) 2.393(5) 3.242(9) 148.53(50)
C42–H42···O9 0.949(7) 2.375(4) 3.314(8) 147.26(42)
Apparently, the 2-D structure of compound 2ʹ shows a series of intra- and inter-
molecular hydrogen bonds via weak to strong interactions (Fig. S9). The hydrogen bond
lengths d(D-H), d(H···A), d(D···A), and angle (DHA) are given in Table S4. Ortho-
substituted O5 and O9 are involved in bifurcated intra- (N1–H1N···O5 and N2–H2N···O9)
and inter-molecular (C20–H20···O5 and C42–H42···O9) interactions. Furthermore, O10 is
involved in intermolecular (C21–H21···O10) interactions, whereas O6 is not involved in any
interactions leading to the generation of the non-centrosymmetric ladder type crystal
structure.
Fig. S9 The crystal packing of 2ʹ showing the intra- and intermolecular hydrogen bonding
network. For clarity, H atoms that are not involved in hydrogen bonding have been omitted.
17
Fig. S10 View along the plane of the Sn4O4 core in the ladder-like compound 3ʹ.
Strong intermolecular interactions led to a 1-D architecture by virtue of intermolecular
bonds (Sn1-O4* and Sn1*-O4). The extension of a one-dimensional network constructed a
chain like structure equipped with a uniform distribution of 8-membered (2Sn, 4O, 2C) cage
and tricyclic ladders.
Fig. S11 The packing arrangement of molecules of 3ʹ viewed down the b axis. The dashed
lines show H5O····N1 and H5O*····N1* hydrogen bonds and moderate coordinative
interaction between Sn1-O4* and Sn1*-O4. Only H atoms involved in hydrogen bonds are
shown.
4. Comparison of geometry for 1, 2ʹ and 3ʹ
The 1MeOH has an extra coordination provided by the trans disposed nitrogen atom at
sixth position of the coordination sphere of Sn. The average Sn-C distance is 2.101 Å in 1-
MeOH and is thus shorter as compared to the corresponding distances in pentacoordinate 2ʹ
(2.111 Å) and 3ʹ (2.119 Å). The average Sn-O bond length is 2.342 Å in 1-MeOH and hence
18
is longer than those found in related pentacoordinate 2ʹ (2.121 Å) and 3ʹ (2.131 Å). The C-
Sn-C angles reflect the change from a pentacoordinate (126.8(3), 138.3(3), 140.0(3) and
127.4(3) for 2ʹ) and (150.6(3) and 132.4(4) for 3ʹ) to a hexacoordinated tin atom (152.32(8)
for 1-MeOH).
5. Fluorescence studies
Fig. S12 Fluorescence emission spectra of methanolic solutions of 1 (0.19 mM, 2 (0.07
mM), 3 (0.07 mM) and 2-hydroxy-4-methoxybenzophenone (0.2 mM)
Fig. S13 Fluorescence emission of 3 (0. 14 mM) with the incremental addition of Cu2+ ions
and 3 (0. 07 mM) with the incremental addition of Fe3+ ions
19
Fig. S14 Fluorescence emission spectra of 3 (0.07 mM) with incremental addition of Cr3+,
Pb2+, Cd2+ and 3 (0.14 mM) with incremental addition of Co2+, Ni2+ ions.
Quantum Yield
Quantum yield was calculated according to the following equation.
F is the integral photon flux, A is the absorption factor, η is the refractive index of the solvent
and QY is the quantum yield. The index X denotes the sample, and the index ST denotes the
standard. Anthracene in ethanol was used as the reference (QY = 0.27).
Fluorescence Lifetime
Fluorescence life-time was calculated by using the following equation.
Fluorescence life-time (τ) = (
Where B1, B2, T1 and T2 were parameters calculated from fitted fluorescence decay data for
each individual system. The values of B1, B2, T1 and T2 are given below.
20
Compound Parameters (B1, B2, T1 and T2)
1 B1 = 2.166259 10-2, B2 = 6.644229 10-4
T1 = 25.28073, T2 = 133.1196
2 B1 = 2.890307, B2 = 2.204127 10-2
T1 = 0.6716222, T2 = 22.95243
3 B1 = 1.177165 10-2, B2 = 2.341968 10-4
T1 = 26.4969, T2 = 230.6804
3 in the presence of Cu2+ B1 = 8.904384 10-2, B2 = 3.730271 10-3
T1 = 24.96141, T2 = 114.3369
3 in the presence of Fe3+ B1 = 0.8589792, B2 = 1.518083 10-2
T1 = 1.482797, T2 = 24.36
A B
Fig. S15 Fluorescence decay graphs of 1-3 and 3 in the presence of Fe3+ (A) and 3 in the
presence of Cu2+ (B)
21
Fig. S16 Fluorescence emission spectra of 3 and its 2-aminoethanol analogue (100 µM) at
excitation wavelength of 365 nm
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