Chloridodiphen­yl{[1-(1,3-thia­zol-2-yl-κN)ethyl­idene]-4-phenyl­thio­semicarbazidato-κ2N1,S}tin(IV) methanol monosolvate

Arumugam, S.R.; Dasary, S.S.R.; Venkatraman, R.; Yu, H.; Fronczek, F.R.

doi:10.1107/S1600536811037627

Chloridodiphenyl{[1-(1,3-thiazol-2-yl-κN)ethylidene]-4-phenylthiosemicarbazidato-κ²N¹,S}tin(IV) methanol monosolvate

S. R. Arumugam, S. S. R. Dasary, R. Venkatraman, H. Yu and F. R. Fronczek

The title compound, [Sn(C₆H₅)₂(C₁₂H₁₁N₄S₂)Cl]·CH₄O, is formed during the reaction between 2-acetylthiazole 4-phenylthiosemicarbazone (Hacthptsc) and diphenyltin(IV) dichloride in methanol. In the crystal structure, the Sn atom exhibits an octahedral geometry with the [N₂S] anionic tridentate thiosemicarbazone ligand having chloride trans to the central N and the two phenyl groups trans to each other. The Sn—Cl distance is 2.5929 (6), Sn—S is 2.4896 (6) and Sn—N to the central N is 2.3220 (16) Å. The MeOH molecules link the Sn complexes into one-dimensional chains via N—H

O and O—H

Cl hydrogen bonds.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536811037627/zk2029sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536811037627/zk2029Isup2.hkl Contains datablock I

CCDC reference: 850381

checkCIF report

Key indicators

Single-crystal X-ray study
T = 297 K
Mean (C-C) = 0.004 Å
R factor = 0.032
wR factor = 0.070
Data-to-parameter ratio = 26.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C7
PLAT331_ALERT_2_C Small Average Phenyl   C-C Dist. C7     -C12           1.37 Ang.
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          4
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600        787
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          2

Alert level G
REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values
           From the CIF: _diffrn_reflns_theta_max           32.00
           From the CIF: _reflns_number_total               8479
           From the CIF: _diffrn_reflns_limit_ max hkl   12.   25.   23.
           From the CIF: _diffrn_reflns_limit_ min hkl  -12.  -28.  -23.
           TEST1: Expected hkl limits for theta max
           Calculated maximum hkl   12.   30.   23.
           Calculated minimum hkl  -12.  -30.  -23.
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT128_ALERT_4_G Alternate Setting of Space-group P21/c   .......      P21/n
PLAT951_ALERT_5_G Reported and Calculated Kmax Values Differ by ..          2

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   5 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   4 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

Comment top

Metal complexes of heterocyclic thiosemicarbazones have been the subject of intensive research for the past three decades. Among the non-transitional metals, organotin(IV) based compounds received prominence due to their structural features and potent biological activity (Teoh et al., 1999; Gielen et al., 2005; Chaudhary et al., 2009; Bamgboye & Bamgboye, 1988; Barberi et al., 1993; Casas et al., 1994; Casas, et al., 1996; Casas et al., 1997; De Sousa et al., 2001; Li et al., 2011). Continuing with this type of study (Venkatraman et al., 2009; Venkatraman et al., 2007; Swesi et al., 2006a,b,c; Venkatraman et al., 2004), we describe here the structure of a diphenyltin chloro derivative of thiazole-2-carbaldehyde N(4)-phenyl-3-thiosemicarbazone.

The tin atom is coordinated by the tridentate ligand through the thiazole ring nitrogen, the azomethine nitrogen and thiolate sulfur atom. The octahedral complex also contains one chloro ligand trans to the central N atom of the tridentate ligand and two diphenyl groups trans to each other, as shown in Fig. 1. The tridentate ligand is reasonably planar, its 18 nonhydrogen atoms having a mean deviation of 0.082 Å from coplanarity, and a maximum of 0.176 (3) Å for methyl group C5. The bite angles of the 5-membered chelate rings are N1—Sn1—S1, 76.39 (4)° and N1—Sn1—N3, 67.57 (6)°. The two phenyl groups form a trans angle C13—Sn1—C19 154.86 (8)°, and the chloro ligand forms a trans angle N1—Sn1—Cl1 165.94 (4)°. The Sn—Cl bond is in the range of normal covalent radii (2.37–2.60 Å, Casas et al., 1997; Davies, 1998). The Sn—C (phenyl) distances are similar to those in other tin complexes reported by us earlier(Venkatraman et al., 2004; 2007; 2009; Swesi et al., 2006a,b,c). The bond length Sn—C increases with an increase in coordination number, being longer in the title compound than in four-coordinate Ph₂SnCl₂ [2.122 (2) Å] and is higher than expected (Dey et al., 2003). The C—S bond distance of 1.755 (2) Å is slightly shorter than a C—S single bond (1.81 Å) but longer than a C—S double bond (1.62 Å) (Macias et al., 1989; Huheey et al., 1993). The relatively shorter bond length of Sn—N1 (imine) (2.3322 Å) compared with Sn—N3 (thiazole) is attributed stronger base nature of thiazole nitrogen (Sreekanth & Kurup, 2004; Mendes et al., 2008; Li et al., 2011).

Two types of intermolecular hydrogen bonds are present, each involving both the Sn complex and the methanol solvent molecule. The amino N4—H group donates to methanol O1, and the methanol O1—H donates to the chloro ligand at 1/2 + x, 1/2 - y, 1/2 + z. The combination of the two hydrogen bonds forms chains of alternating Sn complexes and methanol molecules in the [1 0 1] direction, having graph set C²₂(8) (Etter, 1990), as shown in Fig. 2.

Related literature top

For the biological activity and structural characteristics of tin compounds of thiosemicarbazones, see: Teoh et al. (1999); Gielen et al. (2005); Chaudhary et al. (2009); Bamgboye & Bamgboye (1988); Barberi et al. (1993); Casas et al. (1994, 1996, 1997); De Sousa et al. (2001); Li et al. (2011); Macias et al. (1989); Huheey et al. (1993). For related structures, see: Venkatraman et al. (2004, 2007, 2009); Swesi et al. (2006a,b,c); Sreekanth Sreekanth & Kurup (2004); Mendes et al. (2008); Li et al. (2011). For reference bond lengths [ok as edited?], see: Allen et al. (1979); Davies (1998); Dey et al. (2003). For graph-set analysis, see: Etter (1990).

Experimental top

Equimolar amounts of diphenyltin dichloride and 2-acetylthiazole 4-phenylthiosemicarbazone in dry methanol were refluxed for a period of 2 h and then allowed to cool to room temperature in presence of air. Yellow crystals of the tin complex (1) appeared in about a week.

Structure description top

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 40% probability level, and the solvent is not shown.
	Fig. 2. The unit cell, showing hydrogen-bonded chains.

Chloridodiphenyl{[1-(1,3-thiazol-2-yl-κN)ethylidene]-4- phenylthiosemicarbazidato-κ²N¹,S}tin(IV) methanol monosolvate top

Crystal data top

[Sn(C₆H₅)₂(C₁₂H₁₁N₄S₂)Cl]·CH₄O	F(000) = 1240
M_r = 615.75	D_x = 1.526 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7958 reflections
a = 8.5971 (10) Å	θ = 2.5–32.0°
b = 20.182 (3) Å	µ = 1.23 mm⁻¹
c = 15.794 (2) Å	T = 297 K
β = 102.050 (7)°	Fragment, yellow
V = 2680.0 (6) Å³	0.30 × 0.20 × 0.17 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	8479 independent reflections
Radiation source: fine-focus sealed tube	6194 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ω and φ scans	θ_max = 32.0°, θ_min = 2.6°
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	h = −12→12
T_min = 0.709, T_max = 0.818	k = −28→25
31922 measured reflections	l = −23→23

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.070	w = 1/[σ²(F_o²) + (0.0236P)² + 0.9273P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.002
8479 reflections	Δρ_max = 0.35 e Å⁻³
316 parameters	Δρ_min = −0.58 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00176 (19)

Crystal data top

[Sn(C₆H₅)₂(C₁₂H₁₁N₄S₂)Cl]·CH₄O	V = 2680.0 (6) Å³
M_r = 615.75	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.5971 (10) Å	µ = 1.23 mm⁻¹
b = 20.182 (3) Å	T = 297 K
c = 15.794 (2) Å	0.30 × 0.20 × 0.17 mm
β = 102.050 (7)°

Data collection top

Nonius KappaCCD diffractometer	8479 independent reflections
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	6194 reflections with I > 2σ(I)
T_min = 0.709, T_max = 0.818	R_int = 0.027
31922 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.070	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.35 e Å⁻³
8479 reflections	Δρ_min = −0.58 e Å⁻³
316 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Sn1	0.400041 (15)	0.263309 (7)	0.526902 (8)	0.03515 (5)
Cl1	0.66803 (7)	0.21480 (4)	0.50486 (4)	0.06294 (17)
S1	0.35758 (7)	0.31789 (3)	0.38254 (3)	0.04796 (14)
S2	0.09795 (9)	0.29250 (4)	0.75637 (4)	0.06512 (19)
N1	0.17015 (18)	0.32507 (8)	0.52098 (10)	0.0356 (4)
N2	0.10480 (19)	0.36198 (9)	0.44956 (11)	0.0403 (4)
N3	0.2829 (2)	0.24841 (9)	0.66321 (12)	0.0419 (4)
N4	0.1258 (2)	0.39796 (10)	0.31437 (12)	0.0426 (4)
H4N	0.175 (3)	0.3937 (12)	0.2732 (15)	0.051*
C1	0.1632 (2)	0.28859 (11)	0.66081 (13)	0.0396 (4)
C2	0.2388 (3)	0.23643 (14)	0.80026 (17)	0.0615 (7)
H2	0.2540	0.2202	0.8565	0.074*
C3	0.3249 (3)	0.21897 (13)	0.74245 (15)	0.0540 (6)
H3	0.4080	0.1887	0.7554	0.065*
C4	0.0950 (2)	0.32769 (11)	0.58439 (13)	0.0402 (5)
C5	−0.0537 (3)	0.36652 (15)	0.58116 (17)	0.0617 (7)
H5A	−0.0412	0.4101	0.5590	0.092*
H5B	−0.0746	0.3700	0.6384	0.092*
H5C	−0.1410	0.3445	0.5440	0.092*
C6	0.1826 (2)	0.36139 (10)	0.38687 (13)	0.0367 (4)
C7	−0.0056 (2)	0.44193 (11)	0.29689 (14)	0.0430 (5)
C8	−0.0943 (4)	0.46150 (16)	0.35598 (19)	0.0756 (9)
H8	−0.0706	0.4451	0.4122	0.091*
C9	−0.2185 (4)	0.50555 (18)	0.3312 (2)	0.0845 (10)
H9	−0.2779	0.5181	0.3715	0.101*
C10	−0.2564 (3)	0.53100 (16)	0.2506 (2)	0.0739 (8)
H10	−0.3395	0.5611	0.2354	0.089*
C11	−0.1695 (3)	0.51142 (17)	0.1920 (2)	0.0796 (9)
H11	−0.1941	0.5281	0.1360	0.096*
C12	−0.0455 (3)	0.46717 (15)	0.21483 (17)	0.0631 (7)
H12	0.0118	0.4543	0.1738	0.076*
C13	0.2818 (3)	0.17040 (12)	0.49558 (13)	0.0445 (5)
C14	0.1166 (3)	0.16993 (15)	0.47549 (18)	0.0676 (8)
H14	0.0612	0.2091	0.4787	0.081*
C15	0.0335 (4)	0.11204 (19)	0.4508 (2)	0.0847 (10)
H15	−0.0771	0.1127	0.4377	0.102*
C16	0.1118 (5)	0.05441 (17)	0.4454 (2)	0.0839 (10)
H16	0.0553	0.0156	0.4288	0.101*
C17	0.2748 (5)	0.05366 (15)	0.4646 (2)	0.0842 (10)
H17	0.3289	0.0142	0.4609	0.101*
C18	0.3598 (4)	0.11156 (13)	0.48954 (17)	0.0652 (7)
H18	0.4704	0.1105	0.5023	0.078*
C19	0.5337 (2)	0.33492 (11)	0.61156 (13)	0.0408 (5)
C20	0.6194 (3)	0.31871 (15)	0.69410 (15)	0.0557 (6)
H20	0.6246	0.2749	0.7127	0.067*
C21	0.6963 (3)	0.36751 (19)	0.74819 (17)	0.0714 (9)
H21	0.7518	0.3564	0.8034	0.086*
C22	0.6916 (3)	0.43192 (19)	0.7215 (2)	0.0784 (10)
H22	0.7428	0.4645	0.7588	0.094*
C23	0.6124 (3)	0.44858 (15)	0.6407 (2)	0.0732 (8)
H23	0.6114	0.4924	0.6223	0.088*
C24	0.5321 (3)	0.39994 (13)	0.58489 (17)	0.0544 (6)
H24	0.4776	0.4116	0.5297	0.065*
O1	0.2782 (3)	0.38699 (13)	0.16545 (14)	0.0795 (7)
H1S	0.252 (5)	0.357 (2)	0.137 (3)	0.119*
C25	0.4439 (4)	0.38909 (18)	0.1816 (2)	0.0845 (10)
H25A	0.4819	0.4219	0.2250	0.127*
H25B	0.4780	0.4003	0.1292	0.127*
H25C	0.4860	0.3465	0.2016	0.127*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.03442 (8)	0.03828 (8)	0.03287 (8)	0.00389 (6)	0.00732 (5)	−0.00039 (6)
Cl1	0.0524 (3)	0.0723 (4)	0.0704 (4)	0.0224 (3)	0.0273 (3)	0.0048 (3)
S1	0.0483 (3)	0.0618 (4)	0.0370 (3)	0.0164 (3)	0.0163 (2)	0.0096 (2)
S2	0.0809 (4)	0.0739 (5)	0.0516 (4)	0.0144 (4)	0.0391 (3)	0.0095 (3)
N1	0.0337 (8)	0.0375 (9)	0.0366 (9)	0.0025 (7)	0.0096 (7)	0.0025 (7)
N2	0.0351 (8)	0.0463 (11)	0.0394 (9)	0.0050 (7)	0.0072 (7)	0.0068 (8)
N3	0.0436 (9)	0.0452 (11)	0.0387 (10)	0.0031 (8)	0.0129 (8)	0.0029 (7)
N4	0.0435 (10)	0.0478 (11)	0.0363 (10)	0.0051 (8)	0.0078 (8)	0.0054 (8)
C1	0.0424 (10)	0.0421 (11)	0.0380 (11)	−0.0025 (9)	0.0171 (9)	−0.0008 (9)
C2	0.0757 (17)	0.0685 (18)	0.0436 (13)	0.0027 (14)	0.0202 (12)	0.0133 (12)
C3	0.0571 (14)	0.0582 (16)	0.0458 (13)	0.0055 (12)	0.0089 (11)	0.0108 (11)
C4	0.0361 (10)	0.0438 (12)	0.0431 (11)	−0.0001 (9)	0.0137 (9)	0.0022 (9)
C5	0.0471 (13)	0.0786 (19)	0.0665 (17)	0.0212 (13)	0.0285 (12)	0.0139 (14)
C6	0.0356 (10)	0.0370 (11)	0.0359 (10)	−0.0009 (8)	0.0038 (8)	0.0009 (8)
C7	0.0411 (11)	0.0379 (12)	0.0463 (12)	−0.0010 (9)	0.0004 (9)	0.0034 (10)
C8	0.086 (2)	0.079 (2)	0.0632 (18)	0.0403 (17)	0.0187 (15)	0.0179 (15)
C9	0.084 (2)	0.088 (2)	0.083 (2)	0.0415 (18)	0.0211 (17)	0.0145 (19)
C10	0.0612 (16)	0.0656 (19)	0.085 (2)	0.0173 (14)	−0.0066 (15)	0.0078 (16)
C11	0.0730 (19)	0.090 (2)	0.0663 (19)	0.0237 (17)	−0.0076 (15)	0.0245 (17)
C12	0.0585 (14)	0.0755 (19)	0.0516 (15)	0.0139 (13)	0.0030 (12)	0.0135 (13)
C13	0.0581 (13)	0.0454 (13)	0.0306 (10)	−0.0060 (10)	0.0104 (9)	−0.0026 (9)
C14	0.0623 (16)	0.0642 (18)	0.080 (2)	−0.0180 (13)	0.0245 (14)	−0.0305 (15)
C15	0.083 (2)	0.093 (3)	0.084 (2)	−0.041 (2)	0.0294 (17)	−0.0394 (19)
C16	0.129 (3)	0.066 (2)	0.0580 (18)	−0.045 (2)	0.0219 (19)	−0.0142 (15)
C17	0.143 (3)	0.0404 (16)	0.0615 (19)	−0.0015 (18)	0.0033 (19)	−0.0003 (13)
C18	0.0880 (19)	0.0441 (15)	0.0547 (15)	0.0070 (14)	−0.0050 (13)	0.0002 (12)
C19	0.0299 (9)	0.0526 (14)	0.0417 (11)	−0.0009 (9)	0.0115 (8)	−0.0092 (10)
C20	0.0470 (12)	0.0766 (18)	0.0439 (13)	−0.0096 (12)	0.0106 (10)	−0.0023 (12)
C21	0.0528 (15)	0.119 (3)	0.0429 (14)	−0.0235 (16)	0.0124 (11)	−0.0221 (16)
C22	0.0642 (17)	0.098 (3)	0.077 (2)	−0.0290 (17)	0.0238 (16)	−0.0406 (19)
C23	0.0661 (17)	0.0568 (18)	0.098 (2)	−0.0130 (14)	0.0212 (16)	−0.0207 (16)
C24	0.0479 (12)	0.0528 (15)	0.0614 (15)	0.0000 (11)	0.0089 (11)	−0.0047 (12)
O1	0.0758 (14)	0.1003 (19)	0.0638 (14)	0.0098 (13)	0.0178 (11)	−0.0101 (11)
C25	0.084 (2)	0.095 (3)	0.080 (2)	−0.0011 (19)	0.0276 (17)	0.0158 (18)

Geometric parameters (Å, º) top

Sn1—C19	2.134 (2)	C10—H10	0.9300
Sn1—C13	2.141 (2)	C11—C12	1.379 (4)
Sn1—N1	2.3220 (16)	C11—H11	0.9300
Sn1—S1	2.4896 (6)	C12—H12	0.9300
Sn1—N3	2.5779 (18)	C13—C18	1.377 (3)
Sn1—Cl1	2.5929 (6)	C13—C14	1.389 (3)
S1—C6	1.755 (2)	C14—C15	1.383 (4)
S2—C2	1.696 (3)	C14—H14	0.9300
S2—C1	1.718 (2)	C15—C16	1.355 (5)
N1—C4	1.301 (2)	C15—H15	0.9300
N1—N2	1.371 (2)	C16—C17	1.371 (5)
N2—C6	1.306 (2)	C16—H16	0.9300
N3—C1	1.304 (3)	C17—C18	1.391 (4)
N3—C3	1.364 (3)	C17—H17	0.9300
N4—C6	1.364 (3)	C18—H18	0.9300
N4—C7	1.418 (3)	C19—C24	1.377 (3)
N4—H4N	0.85 (2)	C19—C20	1.396 (3)
C1—C4	1.459 (3)	C20—C21	1.379 (4)
C2—C3	1.337 (3)	C20—H20	0.9300
C2—H2	0.9300	C21—C22	1.364 (5)
C3—H3	0.9300	C21—H21	0.9300
C4—C5	1.491 (3)	C22—C23	1.358 (4)
C5—H5A	0.9600	C22—H22	0.9300
C5—H5B	0.9600	C23—C24	1.401 (4)
C5—H5C	0.9600	C23—H23	0.9300
C7—C12	1.368 (3)	C24—H24	0.9300
C7—C8	1.380 (3)	O1—C25	1.395 (4)
C8—C9	1.382 (4)	O1—H1S	0.76 (4)
C8—H8	0.9300	C25—H25A	0.9600
C9—C10	1.348 (4)	C25—H25B	0.9600
C9—H9	0.9300	C25—H25C	0.9600
C10—C11	1.363 (4)

C19—Sn1—C13	154.86 (8)	C10—C9—H9	118.9
C19—Sn1—N1	90.24 (7)	C8—C9—H9	118.9
C13—Sn1—N1	95.85 (8)	C9—C10—C11	118.1 (3)
C19—Sn1—S1	103.35 (6)	C9—C10—H10	120.9
C13—Sn1—S1	101.78 (6)	C11—C10—H10	120.9
N1—Sn1—S1	76.39 (4)	C10—C11—C12	120.9 (3)
C19—Sn1—N3	78.98 (7)	C10—C11—H11	119.5
C13—Sn1—N3	80.88 (7)	C12—C11—H11	119.5
N1—Sn1—N3	67.57 (6)	C7—C12—C11	121.0 (3)
S1—Sn1—N3	143.93 (4)	C7—C12—H12	119.5
C19—Sn1—Cl1	87.85 (5)	C11—C12—H12	119.5
C13—Sn1—Cl1	91.74 (6)	C18—C13—C14	117.9 (2)
N1—Sn1—Cl1	165.94 (4)	C18—C13—Sn1	123.85 (18)
S1—Sn1—Cl1	90.49 (2)	C14—C13—Sn1	118.16 (19)
N3—Sn1—Cl1	125.54 (4)	C15—C14—C13	120.9 (3)
C6—S1—Sn1	98.55 (7)	C15—C14—H14	119.5
C2—S2—C1	89.55 (12)	C13—C14—H14	119.5
C4—N1—N2	115.29 (16)	C16—C15—C14	120.6 (3)
C4—N1—Sn1	123.10 (14)	C16—C15—H15	119.7
N2—N1—Sn1	121.61 (11)	C14—C15—H15	119.7
C6—N2—N1	115.61 (16)	C15—C16—C17	119.6 (3)
C1—N3—C3	110.72 (19)	C15—C16—H16	120.2
C1—N3—Sn1	110.27 (13)	C17—C16—H16	120.2
C3—N3—Sn1	137.91 (15)	C16—C17—C18	120.4 (3)
C6—N4—C7	129.29 (18)	C16—C17—H17	119.8
C6—N4—H4N	115.9 (16)	C18—C17—H17	119.8
C7—N4—H4N	114.8 (16)	C13—C18—C17	120.6 (3)
N3—C1—C4	122.62 (17)	C13—C18—H18	119.7
N3—C1—S2	113.78 (16)	C17—C18—H18	119.7
C4—C1—S2	123.59 (16)	C24—C19—C20	118.6 (2)
C3—C2—S2	110.3 (2)	C24—C19—Sn1	118.94 (17)
C3—C2—H2	124.9	C20—C19—Sn1	122.45 (19)
S2—C2—H2	124.9	C21—C20—C19	120.2 (3)
C2—C3—N3	115.7 (2)	C21—C20—H20	119.9
C2—C3—H3	122.2	C19—C20—H20	119.9
N3—C3—H3	122.2	C22—C21—C20	120.7 (3)
N1—C4—C1	115.86 (18)	C22—C21—H21	119.7
N1—C4—C5	123.70 (19)	C20—C21—H21	119.7
C1—C4—C5	120.43 (18)	C23—C22—C21	120.2 (3)
C4—C5—H5A	109.5	C23—C22—H22	119.9
C4—C5—H5B	109.5	C21—C22—H22	119.9
H5A—C5—H5B	109.5	C22—C23—C24	120.2 (3)
C4—C5—H5C	109.5	C22—C23—H23	119.9
H5A—C5—H5C	109.5	C24—C23—H23	119.9
H5B—C5—H5C	109.5	C19—C24—C23	120.2 (3)
N2—C6—N4	118.77 (18)	C19—C24—H24	119.9
N2—C6—S1	127.81 (16)	C23—C24—H24	119.9
N4—C6—S1	113.42 (15)	C25—O1—H1S	107 (3)
C12—C7—C8	118.0 (2)	O1—C25—H25A	109.5
C12—C7—N4	116.7 (2)	O1—C25—H25B	109.5
C8—C7—N4	125.3 (2)	H25A—C25—H25B	109.5
C7—C8—C9	119.7 (3)	O1—C25—H25C	109.5
C7—C8—H8	120.1	H25A—C25—H25C	109.5
C9—C8—H8	120.1	H25B—C25—H25C	109.5
C10—C9—C8	122.2 (3)

C19—Sn1—S1—C6	−87.39 (9)	Sn1—S1—C6—N2	−0.3 (2)
C13—Sn1—S1—C6	92.81 (9)	Sn1—S1—C6—N4	179.95 (14)
N1—Sn1—S1—C6	−0.44 (8)	C6—N4—C7—C12	−173.6 (2)
N3—Sn1—S1—C6	2.17 (11)	C6—N4—C7—C8	7.1 (4)
Cl1—Sn1—S1—C6	−175.30 (7)	C12—C7—C8—C9	−0.3 (5)
C19—Sn1—N1—C4	−74.56 (18)	N4—C7—C8—C9	179.0 (3)
C13—Sn1—N1—C4	81.01 (17)	C7—C8—C9—C10	−0.5 (6)
S1—Sn1—N1—C4	−178.25 (17)	C8—C9—C10—C11	0.9 (6)
N3—Sn1—N1—C4	3.41 (16)	C9—C10—C11—C12	−0.4 (5)
Cl1—Sn1—N1—C4	−156.65 (15)	C8—C7—C12—C11	0.7 (4)
C19—Sn1—N1—N2	104.97 (15)	N4—C7—C12—C11	−178.6 (3)
C13—Sn1—N1—N2	−99.46 (15)	C10—C11—C12—C7	−0.4 (5)
S1—Sn1—N1—N2	1.28 (14)	C19—Sn1—C13—C18	−76.4 (3)
N3—Sn1—N1—N2	−177.06 (16)	N1—Sn1—C13—C18	−179.58 (19)
Cl1—Sn1—N1—N2	22.9 (3)	S1—Sn1—C13—C18	103.14 (19)
C4—N1—N2—C6	177.74 (19)	N3—Sn1—C13—C18	−113.5 (2)
Sn1—N1—N2—C6	−1.8 (2)	Cl1—Sn1—C13—C18	12.27 (19)
C19—Sn1—N3—C1	88.85 (16)	C19—Sn1—C13—C14	107.3 (2)
C13—Sn1—N3—C1	−106.27 (16)	N1—Sn1—C13—C14	4.12 (19)
N1—Sn1—N3—C1	−6.02 (14)	S1—Sn1—C13—C14	−73.16 (18)
S1—Sn1—N3—C1	−8.76 (19)	N3—Sn1—C13—C14	70.24 (18)
Cl1—Sn1—N3—C1	168.14 (13)	Cl1—Sn1—C13—C14	−164.03 (18)
C19—Sn1—N3—C3	−77.5 (2)	C18—C13—C14—C15	0.4 (4)
C13—Sn1—N3—C3	87.4 (2)	Sn1—C13—C14—C15	176.9 (2)
N1—Sn1—N3—C3	−172.3 (2)	C13—C14—C15—C16	−0.2 (5)
S1—Sn1—N3—C3	−175.08 (19)	C14—C15—C16—C17	−0.1 (5)
Cl1—Sn1—N3—C3	1.8 (2)	C15—C16—C17—C18	0.1 (5)
C3—N3—C1—C4	178.9 (2)	C14—C13—C18—C17	−0.4 (4)
Sn1—N3—C1—C4	8.7 (3)	Sn1—C13—C18—C17	−176.7 (2)
C3—N3—C1—S2	0.5 (2)	C16—C17—C18—C13	0.2 (5)
Sn1—N3—C1—S2	−169.73 (10)	C13—Sn1—C19—C24	−161.17 (19)
C2—S2—C1—N3	−0.6 (2)	N1—Sn1—C19—C24	−56.77 (17)
C2—S2—C1—C4	−179.0 (2)	S1—Sn1—C19—C24	19.30 (17)
C1—S2—C2—C3	0.5 (2)	N3—Sn1—C19—C24	−123.84 (17)
S2—C2—C3—N3	−0.3 (3)	Cl1—Sn1—C19—C24	109.30 (16)
C1—N3—C3—C2	−0.1 (3)	C13—Sn1—C19—C20	17.0 (3)
Sn1—N3—C3—C2	166.14 (19)	N1—Sn1—C19—C20	121.42 (17)
N2—N1—C4—C1	179.97 (17)	S1—Sn1—C19—C20	−162.51 (16)
Sn1—N1—C4—C1	−0.5 (3)	N3—Sn1—C19—C20	54.35 (16)
N2—N1—C4—C5	1.2 (3)	Cl1—Sn1—C19—C20	−72.51 (16)
Sn1—N1—C4—C5	−179.29 (18)	C24—C19—C20—C21	2.0 (3)
N3—C1—C4—N1	−6.4 (3)	Sn1—C19—C20—C21	−176.23 (17)
S2—C1—C4—N1	171.93 (17)	C19—C20—C21—C22	−0.9 (4)
N3—C1—C4—C5	172.5 (2)	C20—C21—C22—C23	−0.8 (4)
S2—C1—C4—C5	−9.2 (3)	C21—C22—C23—C24	1.4 (4)
N1—N2—C6—N4	−178.91 (18)	C20—C19—C24—C23	−1.4 (3)
N1—N2—C6—S1	1.4 (3)	Sn1—C19—C24—C23	176.88 (18)
C7—N4—C6—N2	4.4 (3)	C22—C23—C24—C19	−0.3 (4)
C7—N4—C6—S1	−175.87 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4N···O1	0.85 (2)	2.08 (2)	2.930 (3)	175 (2)
O1—H1S···Cl1ⁱ	0.76 (4)	2.52 (4)	3.248 (2)	162 (4)

Symmetry code: (i) x−1/2, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	[Sn(C₆H₅)₂(C₁₂H₁₁N₄S₂)Cl]·CH₄O
M_r	615.75
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	297
a, b, c (Å)	8.5971 (10), 20.182 (3), 15.794 (2)
β (°)	102.050 (7)
V (Å³)	2680.0 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.23
Crystal size (mm)	0.30 × 0.20 × 0.17

Data collection
Diffractometer	Nonius KappaCCD
Absorption correction	Multi-scan (SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.709, 0.818
No. of measured, independent and observed [I > 2σ(I)] reflections	31922, 8479, 6194
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.746

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.070, 1.01
No. of reflections	8479
No. of parameters	316
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.58

Computer programs: COLLECT (Nonius, 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).