Dichloro[1,1′-(5,9-dithia-2,12-diazoniatrideca-1,12-diene-1,13-diyl)dinaphthalen-2-olato-κ²O,O′]dimethyltin(IV) acetonitrile solvate

Reaction of the potentially hexadentate ligand 1,9-bis(2-hydroxy-1-naphthalene­methyl­imino)-3,7-di­thia­nonane with di­methyl­tin chloride gave the title 1:1 adduct, in which the long ligand wraps around the SnCl₂Me₂ unit and in which the stereochemistry is fully trans. This compound crystallizes from aceto­nitrile as the 1:1 solvate [Sn(CH₃)₂(C₂₉H₃₀N₂­O₂S₂)Cl₂]·­C₂H₃N. During the reaction, the hydroxyl protons move to the N atoms. Most of the chemically equivalent bond lengths agree to within experimental uncertainty, but the Sn—Cl bond that is inside the ligand pocket is substantially longer than the Sn—Cl bond that points away from the long ligand [2.668 (1) versus 2.528 (1) Å]. The O—Sn—O angle is 166.0 (1)°. Comparison of the Sn—O, C—O and aryl C—C bond lengths with those of related compounds shows that the most important resonance forms for the Schiff base aryl­oxide ligand are double zwitterions, but that the uncharged resonance forms having carbonyl groups also contribute significantly.

S1. Comment

The structure of the title complex, (I), was determined as part of a continuing study (see Bajue et al., 1998) of organotin adducts of potentially hexadentate Schiff base ligands. In most of the known structures of this type, there are two (or more) metal centers per ligand (e.g. Bajue et al., 1998; Degaonkar et al., 1994; Wang et al., 1994), but in (I) there is only one. The number of donor atoms bonded to the Sn varies from two to six in the comparison structures, but in (I) the ligand is bidentate. In this structure, the two ends of the long ligand wrap around the trans-SnCl₂Me₂ fragment so that the most basic ligand donors, the O atoms, coordinate in a trans arrangement. \sch

The refined structure of (I) shows that the hydroxyl H atoms of the dinaphthol ligand migrate during the coordination reaction to the N atoms; a double zwitterion is formed if there is no rearrangement of the double bonds. The distances (Table 1) suggest, however, that the naphthoxy resonance forms (see Scheme below) without local charges, and in which O1—C1, O2—C20, C10—C11 and C29—C19 are all double bonds, may also be important. Resonance forms in which one side of the ligand is zwitterionic and the other uncharged must also be considered. The transfer of the H atoms from the O to the N atoms upon coordination can be attributed to an increase in the acidity of the naphthols upon coordination to the Lewis acidic Sn^IV center. The coordinated O atoms are weaker bases than are the uncoordinated N atoms.

In the Cambridge Structural Database (CSD, Version?; Allen, 2002), there are five structures, with R factors of 0.05 or less, of six-coordinate Sn complexes that have two halo ligands, two C ligands and one or two Schiff base aryloxide ligands: DAHVEN (Kamwaya & Khoo, 1985), KUDKID (Teoh et al., 1991), LAZXEP (Hazell et al., 1994), NOZMEU (Yeap & Ishizawa, 1998) and SODBUI (Fun et al., 1991). In all five structures, the C1—C10 bond (numbering as in Fig. 1) is at least 0.048 Å longer than the C2—C3 bond; the maximum difference is 0.076 Å. These differences suggest that the uncharged resonance form having a carbonyl group is important. The two bond-length differences in this study [both 0.075 (6) Å] are among the largest found.

The structures in the literature have all been formulated as zwitterions; the precedent for this description seems to be Bullock et al. (1979). Further justification for the conclusion that the resonance forms with charge separation are more important than the uncharged forms comes from the comparison of the Sn—O and C—O bond lengths in the six Schiff base aryloxide complexes [the five literature structures plus (I)] with the corresponding Sn—O and C—O bonds in the three true Sn-ketone structures found in the CSD using search criteria analogous to those listed above. The Sn-ketone structures are BENFOP10 (Ng et al., 1982), MASYUA (Howie & Wardell, 2000) and SUZWOZ (Howie & Wardell, 2001). The average Sn—O distance in the true ketone complexes [2.444 (7) Å from four contributing values] is 0.206 (7) Å longer than in the Schiff base aryloxide complexes [2.238 (2) Å from seven contributing values]. The average C—O distance in the ketone complexes [1.227 (1) Å] is 0.077 (2) Å shorter than in the Schiff base aryloxide complexes [1.304 (2) Å].

We conclude that there is charge separation in the most important resonance forms of the Schiff base aryloxide ligand in six-coordinate Sn complexes. The non-zwitterionic resonance forms, however, are also important.

Formulating a name for the compound proved difficult. The oxidation state of the Sn atom is IV, but if the ligand is a double zwitterion then the formal charge on the Sn is −2.

The O—Sn—O bond in (I) is nonlinear (Table 1 and Fig. 1), because the SnCl₂Me₂ fragment cannot fit further down into the ligand pocket. The determining contacts appear to be between Cl2 and the (calculated) H atoms on C12 (2.99 Å) and C17 (3.11 Å). The exact rotation of the SnCl₂Me₂ unit around the O1···O2 vector and the overall distortions of the molecule from potential mirror symmetry are almost certainly determined by both intra- and intermolecular contacts. There might be room in the ligand pocket for the SnCl₂Me₂ unit to make 180° jumps, but there is no evidence of the Cl/Me disorder that would result from 90° jumps.

The difference in lengths of the Sn—Cl bonds [0.140 (1) Å] is noteworthy, because all other pairs of chemically equivalent bonds are essentially equal in length. The longer Sn—Cl bond, which is inside the ligand pocket, may be the result of steric crowding. The distances of Cl2 to H10 and H20 (H atoms attached to N1 and N2) are 2.75 and 2.77 Å, while the sum of the van der Waals radii for Cl and H (Bondi, 1964) is 2.95 Å. These Cl2···H distances would be even shorter if the Sn—Cl2 bond were as short as the Sn—Cl1 bond.

The packing diagram for (I) (Fig. 2) is surprisingly simple. The widths of the naphthyl units and of the S(CH₂)₃S units are similar, so that 2:1 stacks are formed. There is no evidence, however, of strong π–π stacking interactions; distances between corresponding C atoms in overlapping naphthyl fragments vary from 3.65 to 4.16 Å. The SnCl₂Me₂ units are substantially thinner than the repeat unit of the 2:1 stack, so acetonitrile molecules are included in the unit cell. The shortest S···S contact [3.646 (1) Å] is between two S1 atoms related by an inversion center; the shortest contacts involving S2 are to the disordered solvent molecule.

S2. Experimental

1,9-Diamino-3,7-dithianonane, H₂N(CH₂)₂S(CH₂)₃S(CH₂)₂NH₂ (ete), was prepared using the published procedure of Dwyer et al. (1952). 1,9-Bis(2-hydroxy-1-naphthalenemethylimino)-3,7-dithianonane (H2L), was prepared as follows. Under vigorous stirring, 2-hydroxy-1-napthaldehyde (10 g) in ethanol (30 ml) was added slowly to ete (5 g) in ethanol (20 ml). Stripping off the ethanol from the mixture left a pale-yellow oil, which changed to a green-yellow solid after several days at 276 K. The product was recrystallized several times from ethanol (yield 7.5 g, 57%; m.p. 423–424 K). Analysis, found: C 69.22, H 6.11, N 5.62%; calculated: C 69.29, H 6.02, N 5.57%. The title compound was prepared by adding H2L (0.344 g, 0.0068 mol) to dimethyldichlorotin(IV) (0.365 g, 0.0017 mol) in ethanol (50 ml). After refluxing for 2 h, the yellow solid that separated from the solution was cooled and filtered. The product was recrystallized from acetonitrile to give a pale-yellow material, (I) (m.p. 481–483 K). Analysis, found: C 52.05, H 5.19, N 5.45%; calculated: C 51.92, H 5.15, N 5.50%.

S3. Refinement

The acetonitrile solvent molecule is disordered. The two methyl C atoms lie so close together that they are indistinguishable; the displacement parameters for each of the other sets of atoms [C33A/C33B and N3A/N3B; occupancy factor 0.80 (1) for C33A] were restrained to be equal. The H atoms for the minor orientation were not included because their positions could not be determined. The rotations of the idealized methyl H atoms around C30—Sn, C31—Sn and C32—C33A were varied. All other H atoms on C atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.97 Å. Is this added text OK? The H atoms attached to atoms N1 and N2 were initially refined isotropically and without restraints, but the resulting N—H distances [0.78 (4) and 0.67 (2) Å] deviated enough from the standard value that restraints [DFIX 0.86 0.01; SHELXL97 (Sheldrick, 1997)] were imposed on the two distances. The U values for H10 and H20 [0.080 (12) and 0.041 (7) Ų in the restrained refinement] were sufficiently reasonable that the attachment of the H atoms to N1 and N2 (rather than to O1 and O2) was certain. Omitting atoms H10 and H20 from the least-squares refinement, the two highest peaks in the difference Fourier map (0.54 and 0.39 e Å⁻³) were located ca 1 Å from the N atoms and ca 2 Å from the O atoms.

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1990).

Figures

	Fig. 1. A perspective drawing of the molecule of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for the sake of clarity.
	Fig. 2. A drawing showing the crystal packing in (I), as viewed down the a axis; the c axis points from left to right and b points downwards. Both c and b point slightly out of the plane of the paper. Molecules have been removed from the leftmost layer so that the overlap of naphthyl units can be seen more clearly.

Dichloro[2,2'-(5,9-dithia-2,12-diazoniatrideca-1,12-diene-1,13- diyl)dinaphthalenolato-κ²O,O']dimethyltin(IV) acetonitrile solvate

Crystal data

[Sn(CH3)2Cl2(C29H30N2O2S2)]·C2H3N	F(000) = 780
Mr = 763.38	Dx = 1.448 Mg m^−3
Triclinic, P1	Melting point = 481–483 K
a = 12.334 (2) Å	Mo Kα radiation, λ = 0.71070 Å
b = 12.765 (2) Å	Cell parameters from 19845 reflections
c = 12.832 (2) Å	θ = 2.9–25.0°
α = 84.32 (2)°	µ = 1.04 mm^−1
β = 66.41 (2)°	T = 293 K
γ = 71.10 (2)°	Rod, yellow
V = 1750.6 (6) Å^3	0.5 × 0.3 × 0.2 mm
Z = 2

Data collection

Nonius KappaCCD area-detector diffractometer	6059 independent reflections
Radiation source: fine-focus sealed tube	5462 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
Detector resolution: 18 pixels mm^-1	θmax = 25.0°, θmin = 2.9°
ϕ and ω scans with 1.0° steps	h = −14→14
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997)	k = −14→15
Tmin = 0.75, Tmax = 0.81	l = −15→15
19845 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + 0.66P] where P = (Fo^2 + 2Fc^2)/3
6059 reflections	(Δ/σ)max = 0.003
406 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.53 e Å^−3

Special details

Experimental. The crystal-to-detector distance was 25 mm. Each frame was measured for 240 s. The number of scan sets measured was 3; the total number of frames measured was 263.

Refinement. The N-atom end of the acetonitrile solvent molecule is disordered over two sites (occupancy 0.804 (9) for the major orientation.) Atoms N3A and N3B and atoms C33A and C33B were required to have the same anisotropic displacement parameters. The H atoms for the methyl group of the minor orientation were omitted.

The H atoms attached to N1 and N2 were first refined isotropically and without restraints, but the resulting N—H distances (0.78 (4) and 0.67 (2) Å) deviated enough from the standard value that restraints (DFIX 0.86 0.01) were imposed on the two distances. Rotations of the CH₃ groups around the bonds Sn—C30, Sn—C31, and C33A—C32 were varied. All other H atoms were placed in idealized positions and constrained to ride on the attached atom.

The major features in the final difference Fourier map are near the Sn atom.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Sn	0.294379 (15)	0.234569 (13)	0.309742 (14)	0.03861 (8)
Cl1	0.23802 (8)	0.21348 (7)	0.14574 (7)	0.0636 (2)
Cl2	0.34657 (7)	0.25051 (6)	0.48914 (6)	0.05563 (18)
S1	0.07621 (8)	0.52430 (6)	0.84959 (6)	0.0601 (2)
S2	0.16512 (8)	0.06745 (6)	0.85720 (6)	0.0595 (2)
O1	0.2064 (2)	0.41709 (15)	0.33493 (16)	0.0536 (5)
O2	0.38426 (19)	0.05605 (15)	0.32520 (16)	0.0531 (5)
N1	0.1961 (2)	0.52287 (19)	0.50354 (19)	0.0474 (5)
H10	0.204 (3)	0.4628 (18)	0.473 (3)	0.080 (12)*
N2	0.3625 (2)	−0.02522 (18)	0.52340 (18)	0.0432 (5)
H20	0.361 (2)	0.0297 (15)	0.4812 (19)	0.041 (7)*
C1	0.2077 (2)	0.5063 (2)	0.2758 (2)	0.0456 (6)
C2	0.2257 (3)	0.5059 (3)	0.1592 (3)	0.0568 (7)
H2	0.2377	0.4406	0.1237	0.068*
C3	0.2257 (3)	0.5991 (3)	0.0995 (3)	0.0617 (8)
H3	0.2400	0.5956	0.0229	0.074*
C4	0.2049 (3)	0.7021 (3)	0.1487 (3)	0.0556 (7)
C5	0.2063 (3)	0.7976 (3)	0.0835 (3)	0.0758 (10)
H5	0.2227	0.7928	0.0065	0.091*
C6	0.1843 (4)	0.8961 (3)	0.1311 (4)	0.0846 (12)
H6	0.1871	0.9581	0.0868	0.101*
C7	0.1575 (3)	0.9041 (3)	0.2463 (4)	0.0734 (10)
H7	0.1398	0.9725	0.2793	0.088*
C8	0.1568 (3)	0.8127 (2)	0.3124 (3)	0.0595 (8)
H8	0.1389	0.8200	0.3895	0.071*
C9	0.1829 (2)	0.7081 (2)	0.2649 (2)	0.0466 (6)
C10	0.1890 (2)	0.6073 (2)	0.3286 (2)	0.0417 (6)
C11	0.1862 (2)	0.6078 (2)	0.4393 (2)	0.0436 (6)
H11	0.1764	0.6753	0.4693	0.052*
C12	0.2001 (3)	0.5249 (2)	0.6156 (2)	0.0505 (7)
H12A	0.2176	0.5913	0.6252	0.061*
H12B	0.2667	0.4613	0.6211	0.061*
C13	0.0776 (3)	0.5227 (3)	0.7092 (2)	0.0540 (7)
H13A	0.0603	0.4567	0.6983	0.065*
H13B	0.0116	0.5864	0.7030	0.065*
C14	0.1789 (3)	0.3880 (2)	0.8546 (2)	0.0487 (6)
H14A	0.2584	0.3778	0.7912	0.058*
H14B	0.1932	0.3834	0.9241	0.058*
C15	0.1301 (3)	0.2944 (2)	0.8499 (3)	0.0534 (7)
H15A	0.1195	0.2959	0.7788	0.064*
H15B	0.0494	0.3049	0.9117	0.064*
C16	0.2190 (3)	0.1827 (2)	0.8592 (2)	0.0483 (6)
H16A	0.2311	0.1827	0.9294	0.058*
H16B	0.2992	0.1725	0.7966	0.058*
C17	0.1996 (3)	0.0552 (2)	0.7076 (2)	0.0469 (6)
H17A	0.1449	0.0204	0.6977	0.056*
H17B	0.1842	0.1285	0.6766	0.056*
C18	0.3335 (3)	−0.0129 (2)	0.6437 (2)	0.0501 (7)
H18A	0.3880	0.0226	0.6529	0.060*
H18B	0.3490	−0.0856	0.6759	0.060*
C19	0.3931 (2)	−0.1184 (2)	0.4709 (2)	0.0408 (6)
H19	0.3959	−0.1810	0.5147	0.049*
C20	0.4159 (2)	−0.0429 (2)	0.2827 (2)	0.0405 (6)
C21	0.4467 (3)	−0.0608 (2)	0.1654 (2)	0.0507 (7)
H21	0.4437	−0.0009	0.1178	0.061*
C22	0.4799 (3)	−0.1637 (2)	0.1226 (2)	0.0543 (7)
H22	0.5000	−0.1733	0.0454	0.065*
C23	0.4855 (2)	−0.2583 (2)	0.1907 (2)	0.0473 (6)
C24	0.5182 (3)	−0.3649 (3)	0.1431 (3)	0.0613 (8)
H24	0.5353	−0.3730	0.0663	0.074*
C25	0.5251 (3)	−0.4555 (3)	0.2078 (3)	0.0688 (9)
H25	0.5468	−0.5252	0.1754	0.083*
C26	0.4995 (3)	−0.4444 (2)	0.3231 (3)	0.0652 (9)
H26	0.5042	−0.5068	0.3672	0.078*
C27	0.4675 (3)	−0.3418 (2)	0.3721 (3)	0.0527 (7)
H27	0.4521	−0.3358	0.4488	0.063*
C28	0.4579 (2)	−0.2454 (2)	0.3073 (2)	0.0421 (6)
C29	0.4226 (2)	−0.1350 (2)	0.3544 (2)	0.0384 (5)
C30	0.4683 (3)	0.2524 (3)	0.2013 (3)	0.0571 (7)
H30A	0.4567	0.3082	0.1475	0.086*
H30B	0.5223	0.1831	0.1614	0.086*
H30C	0.5050	0.2738	0.2457	0.086*
C31	0.1234 (3)	0.2187 (3)	0.4290 (3)	0.0592 (8)
H31A	0.1391	0.1541	0.4726	0.089*
H31B	0.0743	0.2116	0.3896	0.089*
H31C	0.0791	0.2832	0.4791	0.089*
C32	0.0501 (4)	0.8214 (4)	0.8547 (4)	0.0904 (12)
H32A	0.0338	0.8951	0.8804	0.136*	0.804 (9)
H32B	0.1052	0.7696	0.8851	0.136*	0.804 (9)
H32C	−0.0268	0.8045	0.8801	0.136*	0.804 (9)
C33A	0.1076 (5)	0.8137 (4)	0.7314 (5)	0.0786 (17)	0.804 (9)
N3A	0.1507 (6)	0.8078 (4)	0.6353 (5)	0.119 (2)	0.804 (9)
C33B	0.175 (2)	0.7750 (17)	0.772 (2)	0.0786 (17)	0.196 (9)
N3B	0.263 (2)	0.7464 (18)	0.6983 (18)	0.119 (2)	0.196 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sn	0.03960 (11)	0.03938 (11)	0.03585 (11)	−0.00729 (7)	−0.01700 (8)	−0.00174 (7)
Cl1	0.0709 (5)	0.0777 (5)	0.0511 (4)	−0.0161 (4)	−0.0362 (4)	−0.0072 (4)
Cl2	0.0716 (5)	0.0486 (4)	0.0541 (4)	−0.0070 (3)	−0.0399 (4)	−0.0040 (3)
S1	0.0755 (5)	0.0490 (4)	0.0388 (4)	−0.0023 (4)	−0.0173 (3)	−0.0047 (3)
S2	0.0809 (5)	0.0560 (4)	0.0349 (4)	−0.0278 (4)	−0.0102 (3)	−0.0008 (3)
O1	0.0733 (13)	0.0376 (10)	0.0465 (11)	−0.0053 (9)	−0.0289 (10)	−0.0002 (8)
O2	0.0713 (13)	0.0368 (10)	0.0494 (11)	−0.0045 (9)	−0.0302 (10)	−0.0041 (8)
N1	0.0563 (14)	0.0428 (13)	0.0382 (12)	−0.0099 (10)	−0.0169 (10)	−0.0021 (10)
N2	0.0488 (12)	0.0412 (12)	0.0342 (11)	−0.0049 (10)	−0.0169 (10)	−0.0035 (10)
C1	0.0414 (14)	0.0468 (15)	0.0439 (15)	−0.0032 (11)	−0.0205 (11)	0.0023 (12)
C2	0.0584 (17)	0.0624 (18)	0.0471 (16)	−0.0090 (14)	−0.0251 (14)	−0.0023 (14)
C3	0.0658 (19)	0.078 (2)	0.0448 (16)	−0.0206 (16)	−0.0291 (15)	0.0135 (15)
C4	0.0451 (15)	0.0637 (19)	0.0599 (18)	−0.0150 (13)	−0.0274 (14)	0.0180 (15)
C5	0.076 (2)	0.088 (3)	0.076 (2)	−0.033 (2)	−0.044 (2)	0.037 (2)
C6	0.091 (3)	0.073 (3)	0.106 (3)	−0.034 (2)	−0.058 (2)	0.046 (2)
C7	0.066 (2)	0.0479 (18)	0.107 (3)	−0.0186 (15)	−0.038 (2)	0.0198 (18)
C8	0.0486 (16)	0.0488 (17)	0.075 (2)	−0.0123 (13)	−0.0215 (15)	0.0089 (15)
C9	0.0317 (12)	0.0477 (15)	0.0571 (17)	−0.0088 (11)	−0.0185 (12)	0.0091 (12)
C10	0.0343 (12)	0.0399 (13)	0.0429 (14)	−0.0038 (10)	−0.0131 (11)	0.0003 (11)
C11	0.0356 (13)	0.0399 (14)	0.0453 (15)	−0.0039 (10)	−0.0106 (11)	−0.0046 (11)
C12	0.0549 (16)	0.0535 (16)	0.0403 (15)	−0.0112 (13)	−0.0189 (13)	−0.0039 (12)
C13	0.0540 (16)	0.0552 (17)	0.0413 (15)	−0.0035 (13)	−0.0179 (13)	0.0027 (12)
C14	0.0549 (16)	0.0501 (15)	0.0419 (15)	−0.0118 (12)	−0.0231 (12)	0.0008 (12)
C15	0.0524 (16)	0.0535 (17)	0.0543 (17)	−0.0111 (13)	−0.0241 (14)	−0.0018 (13)
C16	0.0559 (16)	0.0499 (15)	0.0401 (14)	−0.0124 (12)	−0.0223 (12)	−0.0023 (12)
C17	0.0533 (16)	0.0487 (15)	0.0398 (14)	−0.0164 (12)	−0.0176 (12)	−0.0045 (11)
C18	0.0542 (16)	0.0569 (16)	0.0357 (14)	−0.0055 (13)	−0.0218 (12)	−0.0051 (12)
C19	0.0354 (13)	0.0415 (14)	0.0419 (14)	−0.0068 (10)	−0.0151 (11)	−0.0003 (11)
C20	0.0377 (13)	0.0411 (14)	0.0393 (13)	−0.0044 (10)	−0.0161 (10)	−0.0069 (10)
C21	0.0552 (16)	0.0512 (16)	0.0420 (15)	−0.0098 (13)	−0.0196 (13)	−0.0023 (12)
C22	0.0537 (16)	0.0631 (19)	0.0397 (15)	−0.0097 (13)	−0.0154 (13)	−0.0126 (13)
C23	0.0379 (13)	0.0469 (15)	0.0522 (16)	−0.0070 (11)	−0.0136 (12)	−0.0165 (12)
C24	0.0533 (17)	0.0604 (19)	0.064 (2)	−0.0122 (14)	−0.0148 (15)	−0.0268 (16)
C25	0.0581 (19)	0.0493 (18)	0.090 (3)	−0.0149 (14)	−0.0150 (17)	−0.0255 (18)
C26	0.0540 (17)	0.0407 (16)	0.094 (3)	−0.0123 (13)	−0.0238 (17)	−0.0005 (16)
C27	0.0507 (16)	0.0429 (15)	0.0598 (18)	−0.0116 (12)	−0.0181 (13)	−0.0037 (13)
C28	0.0303 (12)	0.0415 (14)	0.0508 (15)	−0.0072 (10)	−0.0132 (11)	−0.0080 (11)
C29	0.0334 (12)	0.0382 (13)	0.0412 (14)	−0.0066 (10)	−0.0141 (10)	−0.0064 (10)
C30	0.0524 (16)	0.0651 (19)	0.0520 (17)	−0.0209 (14)	−0.0175 (13)	0.0067 (14)
C31	0.0468 (16)	0.072 (2)	0.0515 (17)	−0.0171 (14)	−0.0137 (13)	0.0035 (14)
C32	0.099 (3)	0.087 (3)	0.082 (3)	−0.039 (2)	−0.023 (2)	−0.006 (2)
C33A	0.082 (4)	0.068 (3)	0.079 (4)	−0.041 (3)	−0.006 (2)	−0.018 (2)
N3A	0.145 (5)	0.107 (4)	0.092 (4)	−0.080 (4)	0.005 (3)	−0.030 (3)
C33B	0.082 (4)	0.068 (3)	0.079 (4)	−0.041 (3)	−0.006 (2)	−0.018 (2)
N3B	0.145 (5)	0.107 (4)	0.092 (4)	−0.080 (4)	0.005 (3)	−0.030 (3)

Geometric parameters (Å, º)

Sn—Cl1	2.5276 (7)	C27—C28	1.414 (4)
Sn—Cl2	2.6681 (7)	C28—C29	1.450 (3)
Sn—O1	2.223 (2)	C32—C33A	1.450 (7)
Sn—O2	2.216 (2)	C33A—N3A	1.130 (7)
Sn—C30	2.110 (3)	C32—C33B	1.44 (2)
Sn—C31	2.113 (3)	C33B—N3B	1.10 (3)
S1—C13	1.797 (3)	C2—H2	0.93
S1—C14	1.803 (3)	C3—H3	0.93
S2—C16	1.806 (3)	C5—H5	0.93
S2—C17	1.804 (3)	C6—H6	0.93
O1—C1	1.306 (3)	C7—H7	0.93
O2—C20	1.300 (3)	C8—H8	0.93
N1—C11	1.299 (3)	C11—H11	0.93
N1—C12	1.462 (4)	C12—H12A	0.97
N1—H10	0.86 (3)	C12—H12B	0.97
N2—C18	1.452 (3)	C13—H13A	0.97
N2—C19	1.294 (3)	C13—H13B	0.97
N2—H20	0.84 (3)	C14—H14A	0.97
C1—C2	1.422 (4)	C14—H14B	0.97
C1—C10	1.425 (4)	C15—H15A	0.97
C2—C3	1.350 (4)	C15—H15B	0.97
C3—C4	1.416 (5)	C16—H16A	0.97
C4—C5	1.410 (5)	C16—H16B	0.97
C4—C9	1.411 (4)	C17—H17A	0.97
C5—C6	1.350 (6)	C17—H17B	0.97
C6—C7	1.386 (6)	C18—H18A	0.97
C7—C8	1.374 (4)	C18—H18B	0.97
C8—C9	1.409 (4)	C19—H19	0.93
C9—C10	1.452 (4)	C21—H21	0.93
C10—C11	1.408 (4)	C22—H22	0.93
C12—C13	1.514 (4)	C24—H24	0.93
C14—C15	1.516 (4)	C25—H25	0.93
C15—C16	1.520 (4)	C26—H26	0.93
C17—C18	1.511 (4)	C27—H27	0.93
C19—C29	1.410 (4)	C30—H30A	0.96
C20—C21	1.421 (4)	C30—H30B	0.96
C20—C29	1.421 (4)	C30—H30C	0.96
C21—C22	1.346 (4)	C31—H31A	0.96
C22—C23	1.418 (4)	C31—H31B	0.96
C23—C24	1.414 (4)	C31—H31C	0.96
C23—C28	1.410 (4)	C32—H32A	0.96
C24—C25	1.356 (5)	C32—H32B	0.96
C25—C26	1.395 (5)	C32—H32C	0.96
C26—C27	1.377 (4)
Cl1—Sn—Cl2	177.06 (3)	C2—C3—H3	118.6
Cl1—Sn—O1	96.68 (5)	C4—C3—H3	118.6
Cl1—Sn—O2	96.95 (5)	C4—C5—H5	119.5
Cl2—Sn—O1	84.62 (5)	C6—C5—H5	119.5
Cl2—Sn—O2	81.62 (5)	C5—C6—H6	120.1
Cl1—Sn—C30	93.13 (9)	C7—C6—H6	120.1
Cl1—Sn—C31	91.27 (9)	C6—C7—H7	119.5
Cl2—Sn—C30	89.46 (9)	C8—C7—H7	119.5
Cl2—Sn—C31	86.15 (9)	C7—C8—H8	119.6
O1—Sn—O2	166.03 (7)	C9—C8—H8	119.6
O1—Sn—C30	91.72 (11)	N1—C11—H11	116.9
O1—Sn—C31	87.57 (11)	C10—C11—H11	116.9
O2—Sn—C30	90.56 (10)	N1—C12—H12A	109.5
O2—Sn—C31	89.10 (11)	N1—C12—H12B	109.5
C30—Sn—C31	175.59 (12)	C13—C12—H12A	109.5
C13—S1—C14	102.10 (13)	C13—C12—H12B	109.5
C16—S2—C17	100.87 (13)	S1—C13—H13A	108.9
Sn—O1—C1	139.17 (17)	S1—C13—H13B	108.9
Sn—O2—C20	144.59 (17)	C12—C13—H13A	108.9
C11—N1—C12	124.7 (2)	C12—C13—H13B	108.9
C11—N1—H10	114 (3)	S1—C14—H14A	108.7
C12—N1—H10	122 (3)	S1—C14—H14B	108.7
C18—N2—C19	124.7 (2)	C15—C14—H14A	108.7
C18—N2—H20	121 (2)	C15—C14—H14B	108.7
C19—N2—H20	114 (2)	C14—C15—H15A	109.4
O1—C1—C2	121.5 (3)	C14—C15—H15B	109.4
O1—C1—C10	119.8 (2)	C16—C15—H15A	109.4
C2—C1—C10	118.7 (3)	C16—C15—H15B	109.4
C1—C2—C3	120.7 (3)	S2—C16—H16A	108.9
C2—C3—C4	122.8 (3)	S2—C16—H16B	108.9
C3—C4—C5	121.2 (3)	C15—C16—H16A	108.9
C3—C4—C9	118.9 (3)	C15—C16—H16B	108.9
C5—C4—C9	119.8 (3)	S2—C17—H17A	109.4
C4—C5—C6	121.0 (4)	S2—C17—H17B	109.4
C5—C6—C7	119.7 (3)	C18—C17—H17A	109.4
C6—C7—C8	121.1 (4)	C18—C17—H17B	109.4
C7—C8—C9	120.7 (3)	N2—C18—H18A	109.3
C4—C9—C8	117.5 (3)	N2—C18—H18B	109.3
C4—C9—C10	118.8 (3)	C17—C18—H18A	109.3
C8—C9—C10	123.7 (3)	C17—C18—H18B	109.3
C1—C10—C9	119.9 (2)	N2—C19—H19	116.5
C1—C10—C11	120.1 (2)	C29—C19—H19	116.5
C9—C10—C11	119.8 (2)	C20—C21—H21	119.8
N1—C11—C10	126.1 (3)	C22—C21—H21	119.8
N1—C12—C13	110.9 (2)	C21—C22—H22	118.7
S1—C13—C12	113.4 (2)	C23—C22—H22	118.7
S1—C14—C15	114.2 (2)	C23—C24—H24	119.6
C14—C15—C16	111.1 (2)	C25—C24—H24	119.6
S2—C16—C15	113.5 (2)	C24—C25—H25	120.0
S2—C17—C18	111.0 (2)	C26—C25—H25	120.0
N2—C18—C17	111.8 (2)	C25—C26—H26	119.7
N2—C19—C29	126.9 (2)	C27—C26—H26	119.7
O2—C20—C21	121.1 (2)	C26—C27—H27	119.6
O2—C20—C29	119.4 (2)	C28—C27—H27	119.6
C21—C20—C29	119.4 (2)	Sn—C30—H30A	109.5
C20—C21—C22	120.4 (3)	Sn—C30—H30B	109.5
C21—C22—C23	122.5 (3)	Sn—C30—H30C	109.5
C22—C23—C24	120.8 (3)	Sn—C31—H31A	109.5
C22—C23—C28	119.4 (2)	Sn—C31—H31B	109.5
C24—C23—C28	119.8 (3)	Sn—C31—H31C	109.5
C23—C24—C25	120.8 (3)	H12A—C12—H12B	108.0
C24—C25—C26	120.1 (3)	H13A—C13—H13B	107.7
C25—C26—C27	120.5 (3)	H14A—C14—H14B	107.6
C26—C27—C28	120.8 (3)	H15A—C15—H15B	108.0
C23—C28—C27	117.9 (2)	H16A—C16—H16B	107.7
C23—C28—C29	118.7 (2)	H17A—C17—H17B	108.0
C27—C28—C29	123.4 (3)	H18A—C18—H18B	107.9
C19—C29—C20	120.0 (2)	H30A—C30—H30B	109.5
C19—C29—C28	120.5 (2)	H30A—C30—H30C	109.5
C20—C29—C28	119.6 (2)	H30B—C30—H30C	109.5
N3A—C33A—C32	179.0 (6)	H31A—C31—H31B	109.5
N3B—C33B—C32	170 (2)	H31A—C31—H31C	109.5
C1—C2—H2	119.6	H31B—C31—H31C	109.5
C3—C2—H2	119.6
C30—Sn—O1—C1	40.5 (3)	N1—C12—C13—S1	179.7 (2)
C31—Sn—O1—C1	−143.9 (3)	C14—S1—C13—C12	−70.6 (2)
Cl1—Sn—O1—C1	−52.9 (3)	C13—S1—C14—C15	−65.7 (2)
Cl2—Sn—O1—C1	129.8 (3)	S1—C14—C15—C16	−177.7 (2)
C30—Sn—O2—C20	−91.5 (3)	C14—C15—C16—S2	178.8 (2)
C31—Sn—O2—C20	92.9 (3)	C17—S2—C16—C15	77.1 (2)
Cl1—Sn—O2—C20	1.8 (3)	C16—S2—C17—C18	84.0 (2)
Cl2—Sn—O2—C20	179.2 (3)	C19—N2—C18—C17	−115.3 (3)
Sn—O1—C1—C2	32.7 (4)	S2—C17—C18—N2	179.0 (2)
Sn—O1—C1—C10	−148.3 (2)	C18—N2—C19—C29	−179.7 (2)
O1—C1—C2—C3	179.4 (3)	Sn—O2—C20—C29	−151.2 (2)
C10—C1—C2—C3	0.3 (4)	Sn—O2—C20—C21	30.1 (4)
C1—C2—C3—C4	−1.7 (5)	O2—C20—C21—C22	179.6 (3)
C2—C3—C4—C5	179.6 (3)	C29—C20—C21—C22	1.0 (4)
C2—C3—C4—C9	−0.1 (5)	C20—C21—C22—C23	0.4 (4)
C9—C4—C5—C6	−1.5 (5)	C21—C22—C23—C28	−1.4 (4)
C3—C4—C5—C6	178.8 (3)	C21—C22—C23—C24	178.6 (3)
C4—C5—C6—C7	−1.2 (6)	C28—C23—C24—C25	−0.8 (4)
C5—C6—C7—C8	2.1 (6)	C22—C23—C24—C25	179.2 (3)
C6—C7—C8—C9	−0.2 (5)	C23—C24—C25—C26	0.0 (5)
C7—C8—C9—C4	−2.4 (4)	C24—C25—C26—C27	−0.1 (5)
C7—C8—C9—C10	177.3 (3)	C25—C26—C27—C28	1.0 (5)
C5—C4—C9—C8	3.2 (4)	C24—C23—C28—C27	1.6 (4)
C3—C4—C9—C8	−177.1 (3)	C22—C23—C28—C27	−178.4 (2)
C5—C4—C9—C10	−176.5 (3)	C24—C23—C28—C29	−179.0 (2)
C3—C4—C9—C10	3.2 (4)	C22—C23—C28—C29	1.0 (4)
O1—C1—C10—C11	8.8 (4)	C26—C27—C28—C23	−1.7 (4)
C2—C1—C10—C11	−172.2 (2)	C26—C27—C28—C29	178.9 (3)
O1—C1—C10—C9	−176.3 (2)	N2—C19—C29—C20	−2.4 (4)
C2—C1—C10—C9	2.8 (4)	N2—C19—C29—C28	178.6 (2)
C8—C9—C10—C11	−9.2 (4)	O2—C20—C29—C19	1.0 (4)
C4—C9—C10—C11	170.4 (2)	C21—C20—C29—C19	179.6 (2)
C8—C9—C10—C1	175.8 (2)	O2—C20—C29—C28	180.0 (2)
C4—C9—C10—C1	−4.5 (4)	C21—C20—C29—C28	−1.4 (4)
C12—N1—C11—C10	176.3 (2)	C23—C28—C29—C19	179.3 (2)
C1—C10—C11—N1	−2.0 (4)	C27—C28—C29—C19	−1.3 (4)
C9—C10—C11—N1	−176.9 (2)	C23—C28—C29—C20	0.3 (3)
C11—N1—C12—C13	105.1 (3)	C27—C28—C29—C20	179.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H10···O1	0.86 (3)	1.90 (4)	2.601 (3)	138 (3)
N2—H20···O2	0.84 (3)	1.92 (3)	2.594 (3)	137 (3)