Tetra­kis(μ₂-4-amino­benzoato)di-μ₃-oxido-tetra­kis[dibutyl­tin(IV)]

The mol­ecule of the title compound, [Sn₄(C₄H₉)₈(C₇H₆NO₂)₄O₂], lies about an inversion centre and is a tetra­nuclear bis­(tetra­butyl­dicarboxyl­ato­distannoxane) complex containing a planar Sn₄O₂ core in which two μ₃-oxide O atoms connect an Sn₂O₂ ring to two exocyclic Sn atoms. Each Sn atom has a highly distorted octa­hedral coordination. In the mol­ecule, the carboxyl­ate groups of two amino­benzoate ligands bridge the central and exocyclic Sn atoms, while two further amino­benzoate ligands have highly asymmetric bidentate chelation to the exocyclic Sn atoms plus long O...Sn inter­actions with the central Sn atoms. Each Sn atom is also coordinated by two pendant n-butyl ligands, which extend roughly perpendicular to the plane of the Sn₄O₁₀ core. Only one of the four unique hydrogen-bond donor sites is involved in a classic N—H...O hydrogen bond, and the resulting supra­molecular hydrogen-bonded structure is an extended two-dimensional network which lies parallel to the (100) plane and consists of a checkerboard pattern of four-connected mol­ecular cores acting as nodes. The amine groups not involved in the hydrogen-bonding inter­actions have significant N—H...π inter­actions with neighbouring amino­benzene rings.

S1. Comment

Bis(dicarboxylatotetraorganodistannoxanes), {[R₂Sn(O₂CR')]₂O}₂, are of interest because of their useful applications in biology and catalysis (Blair et al., 1997; Petrosyan et al., 1996); Ribot et al., 1998; Tiekink et al., 1995). We have previously reported the crystal structures of related bis(dicarboxylatotetraorganodistannoxanes) prepared from various carboxylates, viz. β-{[(E)-1-(2-hydroxy-3-methylphenyl)ethylidene]amino}propionate, β-{[(2Z)-(3-hydroxy-1-methyl-2-butenylidene)]amino}propionate (Basu Baul, Masharing et al., 2006), and 5-[(E)-2-(aryl)-1-diazenyl]-2-hydroxybenzoates, where aryl is 2-methoxy, 3-methyl (Basu Baul et al., 2007) and 4-unsubstituted, 4-methyl, 4-chloro and 4-bromo (Basu Baul, Rynjah et al., 2006). During an extension of these studies into the coordination chemistry of substituted carboxylates with organotin species, 4-aminobenzoic acid was reacted with dibutyltin(IV) oxide to form the title tetranuclear compound, {[Bu₂Sn(O₂CC₆H₄-p-NH₂)]₂O}₂, (I) (Bu = n-butyl), and its crystal structure is reported here.

The molecular structure of (I) is shown in Fig. 1. The molecule lies about an inversion centre and is a tetranuclear bis(dicarboxylatotetrabutyldistannoxane) complex containing a planar Sn₄O₂ core, in which two µ₃-oxo O atoms connect an Sn₂O₂ ring (endocyclic Sn atoms) to two exocyclic Sn atoms to give an R₈Sn₄O₂ central unit. The central Sn2···Sn2(-x + 1,-y,-z + 1) contact is 3.3140 (2) Å, while the two unique exo-Sn···endo-Sn distances are 3.6334 (2) and 3.7660 (2) Å. Two symmetry-related aminobenzoate ligands each bridge one endocyclic to one exocyclic Sn centre via the two carboxylate O atoms, with the Sn—O distances being quite similar (Table 1). Two additional aminobenzoate ligands each have highly asymmetric bidentate chelation via the two carboxylate O atoms to an exocyclic Sn atom, with the longer Sn1···O5 interactions being quite long [2.9053 (18) Å]. Additionally, the other carboxylate O atom in each of these ligands coordinates via a second long Sn2···O4(1 - x, -y, 1 - z) bond [2.7841 (17) Å] to an endocyclic Sn atom. Each Sn atom is also coordinated by two pendant Bu ligands, which subtend angles of about 140° at their parent Sn atoms. If the longer Sn···O distances are considered as part of the primary coordination environment, each Sn atom has a highly distorted octahedral coordination, with some of the distortion arising from bite angle constraints. Alternatively, ignoring Sn···O distances greater than 2.3 Å yields distorted trigonal–bipyramidal geometry about each Sn atom, with, in each case, the Bu ligands occupying equatorial positions.

The Sn₄O₁₀ core of the molecule forms an essentially planar system, although the six-membered ring formed by Sn1, Sn2, the µ₃-oxo atom O7 and the bridging carboxylate group is somewhat twisted towards a screw boat form, forcing atoms O1 and O2 out of the plane of the remainder of the core atoms by 0.323 (2) and -0.505 (2) Å, respectively. The aminobenzene rings are slightly tilted out of the plane of the Sn₄O₁₀ core, with dihedral angles between the benzene ring planes and core plane in the range 12.8 (3)–24.6 (2)° (the presented range includes both disordered conformations in one aminobenzoate ligand). Nonetheless, the Sn₄O₁₀ core and associated carboxylate ligands can be considered as a fairly planar entity with the pendant Bu ligands extending roughly perpendicular to this plane (Fig. 2).

The aminobenzene moiety of the aminobenzoate ligand containing atoms O1 and O2 is disordered over two conformations. The major conformation is present in approximately 59% of the molecules.

The structures of many dimeric dicarboxylatotetraorganodistannoxanes are known and have been reviewed (Tiekink, 1991, 1994). Five predominant patterns of carboxylate ligand coordination about the Sn₄O₂ core seem to recur, but by far the most common motif is the centrosymmetric variant displayed by compound (I). The Cambridge Structural Database (Version 5.30, update 4 of September 2009; Allen, 2002) contains entries for 135 structures displaying the same basic coordination motif as (I). In structures of this type, the Sn coordination geometry, as well as the distribution of Sn—O distances, is usually much the same.

Although two symmetry-independent amine groups offering four potential hydrogen-bond donor sites are present in the molecule of (I), only one of these is involved in a classic N—H···O hydrogen bond (Table 2). This intermolecular interaction is with a carboxylate O atom in the same carboxylate ligand in a neighbouring tetranuclear molecule related by a c-glide operation and serves to link the molecules into extended zigzag chains which run parallel to the [001] direction (Fig. 3) and which can be described by a graph-set motif of C(8) (see Bernstein et al., 1995 for a description of graph-set motifs). The path of this motif involves only the atoms of a single unique carboxylate ligand. As the molecule lies about an inversion centre, each molecule accepts and donates two of these hydrogen bonds, so that both sides of the molecule are involved in two antiparallel adjacent chains. A consequence of this is that the same hydrogen-bonding interactions also yield further zigzag chains which run via the core of each molecule parallel to [010] and which can be described by a graph-set motif of C(14). Effectively, the core of each molecule cross-links two adjacent [001] chains, and neighbouring molecules in each such chain cross-link different chains, resulting in a checkerboard pattern of four-connected molecular cores acting as nodes between the chains (Fig. 3). The overall supramolecular hydrogen-bonded structure arising out of these interactions is thus an extended two-dimensional network which lies parallel to the (100) plane. The hydrogen-bonded ring motif within each of the checkerboard squares is R⁴₄(22).

There are no significant π–π interactions in the structure, but one unique strong N—H···π interaction is present between the amine group not involved in the hydrogen-bonding interactions described above and the aminobenzene ring defined by atoms C9–C14 (centroid Cg1) in a neighbouring molecule [N1B···Cg1ⁱ = 3.706 (10) Å, H13···Cg1ⁱ = 2.84 Å, H13···ring plane = 2.67 Å, N1B—H13···Cg1ⁱ = 168°; symmetry code: (i) -x + 1, y - 1/2, -z + 3/2]. The interaction appears to involve only the minor conformation of the disordered aminobenzene ring; although the major conformation of the aminobenzene ring has an H atom at a similar distance from the plane of the Cg1ⁱ ring, it is significantly offset from the centre of the ring.

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S2. Experimental

A suspension of Bu₂SnO (1.036 g, 3.64 mmol) and p-aminobenzoic acid (0.5 g, 3.64 mmol) in anhydrous toluene (50 ml) were refluxed for 3 h in a flask equipped with a Dean–Stark water separator and a water-cooled condenser. After the reaction, a clear solution was obtained and this was filtered while hot. The solvent was evaporated in vacuo, and the white residue was washed thoroughly with hexane and dried in vacuo. The residue was dissolved in chloroform and the solution was filtered to remove any undissolved particles. The filtrate was left to crystallize at room temperature. The crude product was obtained after evaporation and this was then recrystallized from a chloroform–hexane solution (1:1, v/v) to yield colourless prismatic crystals of (I) in 65% yield (m.p. 379–381 K). Analysis, calculated for C₆₀H₉₆N₄O₁₀Sn₄: C 47.78, H 6.42, N 3.71%; found: C 47.80, H 6.23, N 3.66%. Spectroscopic analysis: IR (Medium?, cm^-1): 1621 ν(OCO)_asym, 643 ν(Sn—O—Sn); ¹H NMR (CDCl₃, δ, p.p.m.): 7.91 (br d, 2H, H2), 6.68 (d, 2H, H3), 4.0 (br s, 2H, NH₂); Sn–ⁿBu skeleton: 0.80 (br m, 6H, H4*), 1.35 (br m, 4H, H3*), 1.70 (br m, 8H, H1* and H2*); ¹³C NMR (CDCl₃, δ, p.p.m.), ligand skeleton: 113.7 (C3), 123.2 (C1), 131.9 (C2), 150.0 (C4), 172.8 (CO₂); Sn–ⁿBu skeleton: 28.1, 27.7, 27.4, 26.8 and 26.1 (C1*, C2* and C3*), 13.6 (C4*). For the ¹H and ¹³C NMR assignments, the atoms marked with an asterisk (*) refer to the n-butyl ligand numbered outwards from the Sn atom; the other C atoms belong to the aminobenzene ring, starting from the ring C atom closest to the carboxylate group.

S3. Refinement

The entire aminobenzene moiety of one of the two symmetry-independent carboxylate ligands is disordered over two conformations. Two sets of overlapping positions were defined for the atoms of this group and the site-occupation factors of each conformation were refined while restraining their sum to unity. The site-occupation factor of the major conformation refined to 0.585 (5). Similarity restraints with tolerance s.u.s of 0.005 were applied to the chemically equivalent bond lengths and angles involving all disordered atoms, while neighbouring atoms within and between each conformation were restrained to have similar atomic displacement parameters within a tolerance s.u. of 0.01. Each conformation of the disordered aminobenzene group was further restrained to be planar, also with a tolerance s.u. of 0.01. The H atoms of the ordered amine group were placed in the positions indicated by a difference electron-density map and their positions were allowed to refine, together with individual isotropic displacement parameters. The methyl H atoms were constrained to an ideal geometry (C—H = 0.98 Å), with U_iso(H) = 1.5U_eq(C), but were allowed to rotate freely about the adjacent C—C bonds. All other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.95 (aromatic) or 0.99 Å (methylene) and N—H distances of 0.88 Å, and with U_iso(H) = 1.2U_eq(C). Seven low-angle reflections were omitted from the final cycles of refinement because their observed intensities were much lower than the calculated values, as a result of being partially obscured by the beam stop.

Computing details

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997) and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. A view of the molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Only one conformation of the disordered aminobenzene ring is shown. H atoms bonded to C atoms have been omitted for clarity. [Symmetry code: (i) -x + 1, -y, -z + 1.]
	Fig. 2. The disposition of the pendant n-butyl ligands perpendicular to the plane of the Sn4O10 core and the carboxylate ligands in the molecule of (I). H atoms bonded to C atoms have been omitted for clarity and only one of the arrangements of the disordered aminobenzene ring is shown.
	Fig. 3. The supramolecular hydrogen-bonded layer in the structure of (I). H atoms bonded to C atoms have been omitted for clarity and only one of the arrangements of the disordered aminobenzene ring is shown.

Tetrakis(µ₂-4-aminobenzoato)di-µ₃-oxido-tetrakis[dibutyltin(IV)]

Crystal data

[Sn4(C4H9)8(C7H6NO2)4O2]	F(000) = 1528
Mr = 1507.84	Dx = 1.538 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 123213 reflections
a = 12.3017 (1) Å	θ = 2.0–30.0°
b = 17.1436 (1) Å	µ = 1.57 mm^−1
c = 15.8633 (1) Å	T = 160 K
β = 103.3015 (5)°	Prism, colourless
V = 3255.75 (4) Å^3	0.22 × 0.20 × 0.17 mm
Z = 2

Data collection

Nonius KappaCCD area-detector diffractometer	9527 independent reflections
Radiation source: Nonius FR590 sealed tube generator	7900 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	Rint = 0.060
Detector resolution: 9 pixels mm^-1	θmax = 30.0°, θmin = 2.6°
ϕ and ω scans with κ offsets	h = −17→17
Absorption correction: multi-scan (Blessing, 1995)	k = −24→24
Tmin = 0.646, Tmax = 0.764	l = −21→22
94040 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)] = 0.032	Hydrogen site location: geom & difmap
wR(F^2) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ^2(Fo^2) + (0.0337P)^2 + 2.756P] where P = (Fo^2 + 2Fc^2)/3
9520 reflections	(Δ/σ)max = 0.002
428 parameters	Δρmax = 1.46 e Å^−3
231 restraints	Δρmin = −0.89 e Å^−3

Special details

Experimental. Solvent used: hexane/chloroform. Cooling Device: Oxford Cryosystems Cryostream 700. Crystal mount: glued on a glass fibre. Mosaicity (deg.): 0.534 (1). Frames collected: 769. Seconds exposure per frame: 10. Degrees rotation per frame: 1.0. Crystal-Detector distance (mm): 30.0.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Sn1	0.648666 (13)	0.085429 (10)	0.676151 (10)	0.02239 (5)
Sn2	0.422589 (13)	−0.048024 (9)	0.555501 (10)	0.02104 (5)
O1	0.52865 (16)	0.05288 (11)	0.75993 (12)	0.0327 (4)
O2	0.45047 (17)	−0.05692 (11)	0.69951 (11)	0.0316 (4)
O4	0.73583 (14)	0.11888 (10)	0.57594 (11)	0.0252 (3)
O5	0.84955 (15)	0.17750 (12)	0.68629 (11)	0.0313 (4)
O7	0.55488 (13)	0.02801 (10)	0.57320 (10)	0.0227 (3)
N2	0.9752 (2)	0.36113 (18)	0.37072 (19)	0.0407 (6)
H21	0.953 (3)	0.355 (2)	0.319 (2)	0.043 (10)*
H22	1.028 (3)	0.387 (2)	0.391 (3)	0.055 (12)*
C1	0.4656 (2)	−0.00522 (14)	0.75823 (15)	0.0249 (5)
N1A	0.1883 (5)	−0.0181 (3)	1.0003 (4)	0.0677 (17)	0.585 (5)
H11	0.1393	−0.0560	0.9976	0.081*	0.585 (5)
H12	0.1920	0.0195	1.0386	0.081*	0.585 (5)
C2A	0.3927 (3)	−0.00862 (14)	0.82186 (18)	0.0259 (16)	0.585 (5)
C3A	0.4023 (5)	0.0465 (3)	0.8871 (4)	0.0370 (14)	0.585 (5)
H3A	0.4563	0.0868	0.8918	0.044*	0.585 (5)
C4A	0.3346 (6)	0.0437 (3)	0.9452 (4)	0.0468 (13)	0.585 (5)
H4A	0.3387	0.0841	0.9868	0.056*	0.585 (5)
C5A	0.2607 (6)	−0.0177 (3)	0.9433 (4)	0.0465 (12)	0.585 (5)
C6A	0.2567 (5)	−0.0762 (3)	0.8825 (4)	0.0376 (13)	0.585 (5)
H6A	0.2088	−0.1197	0.8822	0.045*	0.585 (5)
C7A	0.3210 (7)	−0.0720 (4)	0.8224 (4)	0.0307 (17)	0.585 (5)
H7A	0.3168	−0.1124	0.7808	0.037*	0.585 (5)
N1B	0.2800 (9)	−0.0611 (5)	1.0471 (5)	0.077 (2)	0.415 (5)
H13	0.2365	−0.1017	1.0478	0.092*	0.415 (5)
H14	0.2972	−0.0301	1.0925	0.092*	0.415 (5)
C2B	0.4147 (7)	−0.0184 (4)	0.8327 (4)	0.0150 (12)	0.415 (5)
C3B	0.4378 (7)	0.0311 (4)	0.9033 (4)	0.0305 (17)	0.415 (5)
H3B	0.4867	0.0741	0.9039	0.037*	0.415 (5)
C4B	0.3906 (8)	0.0185 (4)	0.9728 (4)	0.0407 (15)	0.415 (5)
H4B	0.4052	0.0536	1.0204	0.049*	0.415 (5)
C5B	0.3217 (9)	−0.0455 (5)	0.9735 (4)	0.0514 (17)	0.415 (5)
C6B	0.2952 (8)	−0.0936 (5)	0.9016 (4)	0.0436 (19)	0.415 (5)
H6B	0.2453	−0.1361	0.9006	0.052*	0.415 (5)
C7B	0.3409 (11)	−0.0803 (6)	0.8315 (6)	0.031 (2)	0.415 (5)
H7B	0.3221	−0.1134	0.7822	0.037*	0.415 (5)
C8	0.8153 (2)	0.16828 (14)	0.60714 (15)	0.0244 (5)
C9	0.86057 (19)	0.21556 (14)	0.54406 (15)	0.0241 (5)
C10	0.8127 (2)	0.21338 (15)	0.45511 (16)	0.0277 (5)
H10	0.7522	0.1788	0.4338	0.033*
C11	0.8514 (2)	0.26040 (16)	0.39763 (16)	0.0289 (5)
H111	0.8175	0.2577	0.3375	0.035*
C12	0.9401 (2)	0.31188 (16)	0.42726 (17)	0.0292 (5)
C13	0.9901 (2)	0.31320 (16)	0.51650 (17)	0.0311 (5)
H131	1.0517	0.3467	0.5379	0.037*
C14	0.9501 (2)	0.26610 (16)	0.57318 (17)	0.0285 (5)
H141	0.9844	0.2682	0.6333	0.034*
C15	0.5890 (2)	0.20095 (15)	0.68781 (18)	0.0298 (5)
H151	0.6112	0.2171	0.7493	0.036*
H152	0.6255	0.2369	0.6540	0.036*
C16	0.4625 (2)	0.20941 (16)	0.65671 (17)	0.0295 (5)
H161	0.4387	0.1870	0.5978	0.035*
H162	0.4258	0.1793	0.6956	0.035*
C17	0.4241 (2)	0.29408 (16)	0.65461 (19)	0.0344 (6)
H171	0.4595	0.3240	0.6147	0.041*
H172	0.4494	0.3169	0.7132	0.041*
C18	0.2976 (2)	0.30201 (19)	0.6254 (2)	0.0434 (7)
H181	0.2722	0.2798	0.5673	0.065*
H182	0.2770	0.3573	0.6242	0.065*
H183	0.2622	0.2740	0.6659	0.065*
C19	0.7654 (2)	0.00620 (16)	0.74997 (16)	0.0281 (5)
H191	0.8040	0.0326	0.8041	0.034*
H192	0.7237	−0.0385	0.7665	0.034*
C20	0.8534 (2)	−0.02547 (18)	0.70553 (18)	0.0344 (6)
H201	0.8988	0.0185	0.6921	0.041*
H202	0.8156	−0.0501	0.6500	0.041*
C21	0.9305 (2)	−0.08505 (19)	0.7603 (2)	0.0401 (7)
H211	0.8847	−0.1265	0.7784	0.048*
H212	0.9737	−0.0592	0.8133	0.048*
C22	1.0115 (3)	−0.1222 (2)	0.7120 (3)	0.0538 (9)
H221	0.9694	−0.1449	0.6575	0.081*
H222	1.0546	−0.1631	0.7480	0.081*
H223	1.0626	−0.0822	0.6995	0.081*
C23	0.2847 (2)	0.02652 (15)	0.55535 (17)	0.0272 (5)
H231	0.3115	0.0699	0.5960	0.033*
H232	0.2609	0.0495	0.4968	0.033*
C24	0.1822 (2)	−0.00831 (16)	0.57903 (18)	0.0299 (5)
H241	0.2060	−0.0393	0.6328	0.036*
H242	0.1449	−0.0441	0.5323	0.036*
C25	0.0984 (2)	0.05394 (17)	0.59271 (19)	0.0342 (6)
H251	0.0874	0.0919	0.5444	0.041*
H252	0.0256	0.0286	0.5910	0.041*
C26	0.1355 (3)	0.0973 (2)	0.6776 (2)	0.0452 (8)
H261	0.1470	0.0601	0.7258	0.068*
H262	0.0780	0.1351	0.6836	0.068*
H263	0.2056	0.1248	0.6785	0.068*
C27	0.4785 (2)	−0.16563 (14)	0.56821 (16)	0.0267 (5)
H271	0.4429	−0.1927	0.6100	0.032*
H272	0.4541	−0.1921	0.5115	0.032*
C28	0.6053 (2)	−0.17281 (16)	0.59888 (17)	0.0309 (5)
H281	0.6413	−0.1476	0.5562	0.037*
H282	0.6304	−0.1452	0.6548	0.037*
C29	0.6414 (3)	−0.25800 (19)	0.6099 (2)	0.0424 (7)
H291	0.6088	−0.2819	0.6553	0.051*
H292	0.6109	−0.2861	0.5550	0.051*
C30	0.7676 (3)	−0.2686 (3)	0.6344 (3)	0.0645 (11)
H301	0.8008	−0.2438	0.5906	0.097*
H302	0.7855	−0.3244	0.6375	0.097*
H303	0.7979	−0.2445	0.6909	0.097*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sn1	0.02155 (8)	0.02725 (9)	0.01930 (8)	−0.00124 (6)	0.00660 (6)	−0.00217 (6)
Sn2	0.01998 (8)	0.02389 (9)	0.02078 (8)	0.00064 (6)	0.00783 (6)	−0.00007 (6)
O1	0.0337 (10)	0.0369 (10)	0.0325 (10)	−0.0055 (8)	0.0177 (8)	−0.0044 (8)
O2	0.0441 (11)	0.0311 (10)	0.0222 (8)	0.0009 (8)	0.0126 (8)	0.0006 (7)
O4	0.0244 (8)	0.0303 (9)	0.0222 (8)	−0.0037 (7)	0.0079 (6)	−0.0008 (7)
O5	0.0335 (10)	0.0408 (11)	0.0202 (8)	−0.0053 (8)	0.0077 (7)	−0.0018 (7)
O7	0.0204 (8)	0.0289 (8)	0.0194 (7)	−0.0026 (6)	0.0058 (6)	−0.0024 (6)
N2	0.0348 (14)	0.0539 (17)	0.0332 (14)	−0.0059 (12)	0.0074 (11)	0.0151 (12)
C1	0.0250 (11)	0.0285 (12)	0.0222 (11)	0.0052 (9)	0.0077 (9)	0.0013 (9)
N1A	0.092 (4)	0.072 (3)	0.060 (3)	−0.034 (3)	0.059 (3)	−0.018 (3)
C2A	0.030 (3)	0.026 (2)	0.021 (2)	0.009 (2)	0.007 (2)	0.0078 (18)
C3A	0.051 (3)	0.032 (3)	0.035 (3)	−0.008 (2)	0.026 (2)	−0.002 (2)
C4A	0.066 (3)	0.042 (3)	0.044 (3)	−0.014 (2)	0.035 (2)	−0.009 (2)
C5A	0.061 (3)	0.047 (3)	0.041 (2)	−0.013 (2)	0.032 (2)	−0.003 (2)
C6A	0.041 (3)	0.039 (3)	0.036 (2)	−0.013 (2)	0.014 (2)	0.002 (2)
C7A	0.033 (3)	0.034 (3)	0.025 (2)	−0.003 (2)	0.008 (2)	0.004 (2)
N1B	0.102 (5)	0.094 (5)	0.049 (4)	−0.049 (4)	0.048 (4)	−0.015 (4)
C2B	0.015 (2)	0.015 (2)	0.014 (2)	0.008 (2)	0.001 (2)	0.007 (2)
C3B	0.038 (3)	0.028 (3)	0.028 (3)	−0.001 (3)	0.013 (3)	−0.001 (2)
C4B	0.057 (4)	0.043 (3)	0.028 (3)	−0.019 (3)	0.022 (3)	−0.011 (3)
C5B	0.067 (4)	0.061 (4)	0.035 (3)	−0.022 (3)	0.029 (3)	−0.004 (3)
C6B	0.052 (4)	0.050 (4)	0.033 (3)	−0.018 (3)	0.020 (3)	0.002 (3)
C7B	0.036 (4)	0.032 (3)	0.024 (3)	−0.004 (3)	0.005 (3)	−0.001 (3)
C8	0.0233 (11)	0.0280 (12)	0.0236 (11)	0.0017 (9)	0.0086 (9)	−0.0010 (9)
C9	0.0228 (11)	0.0261 (12)	0.0253 (11)	0.0011 (9)	0.0095 (9)	−0.0013 (9)
C10	0.0281 (12)	0.0319 (13)	0.0237 (11)	−0.0015 (10)	0.0075 (9)	−0.0020 (10)
C11	0.0291 (12)	0.0375 (14)	0.0209 (11)	0.0031 (10)	0.0072 (9)	0.0012 (10)
C12	0.0256 (12)	0.0343 (13)	0.0303 (12)	0.0057 (10)	0.0116 (10)	0.0067 (11)
C13	0.0224 (12)	0.0373 (14)	0.0330 (13)	−0.0037 (10)	0.0053 (10)	0.0018 (11)
C14	0.0253 (12)	0.0343 (13)	0.0256 (12)	0.0000 (10)	0.0054 (9)	−0.0005 (10)
C15	0.0265 (12)	0.0294 (13)	0.0344 (13)	−0.0029 (10)	0.0089 (10)	−0.0082 (10)
C16	0.0259 (12)	0.0325 (13)	0.0312 (13)	0.0002 (10)	0.0086 (10)	−0.0078 (11)
C17	0.0335 (14)	0.0335 (14)	0.0365 (14)	0.0035 (11)	0.0086 (11)	−0.0053 (11)
C18	0.0369 (15)	0.0430 (17)	0.0515 (18)	0.0099 (13)	0.0124 (14)	−0.0047 (14)
C19	0.0245 (12)	0.0361 (14)	0.0234 (11)	−0.0015 (10)	0.0053 (9)	0.0051 (10)
C20	0.0305 (13)	0.0424 (15)	0.0328 (13)	0.0062 (11)	0.0129 (11)	0.0094 (12)
C21	0.0332 (15)	0.0482 (18)	0.0415 (16)	0.0111 (12)	0.0140 (12)	0.0175 (13)
C22	0.0444 (18)	0.058 (2)	0.068 (2)	0.0209 (16)	0.0309 (17)	0.0248 (18)
C23	0.0236 (12)	0.0301 (12)	0.0306 (12)	0.0036 (10)	0.0120 (10)	0.0008 (10)
C24	0.0229 (11)	0.0349 (14)	0.0334 (13)	0.0003 (10)	0.0093 (10)	−0.0017 (11)
C25	0.0257 (13)	0.0419 (15)	0.0374 (14)	0.0077 (11)	0.0125 (11)	0.0025 (12)
C26	0.0381 (16)	0.0475 (18)	0.0531 (19)	0.0073 (13)	0.0170 (14)	−0.0096 (15)
C27	0.0282 (12)	0.0253 (12)	0.0273 (12)	0.0040 (9)	0.0081 (10)	0.0005 (9)
C28	0.0284 (13)	0.0361 (14)	0.0282 (12)	0.0057 (11)	0.0063 (10)	0.0013 (11)
C29	0.0468 (17)	0.0449 (17)	0.0368 (15)	0.0207 (14)	0.0122 (13)	0.0063 (13)
C30	0.051 (2)	0.085 (3)	0.054 (2)	0.036 (2)	0.0048 (17)	0.001 (2)

Geometric parameters (Å, º)

Sn1—O1	2.2717 (18)	C11—H111	0.9500
Sn1—O4	2.1886 (16)	C12—C13	1.408 (4)
Sn1—O5	2.9053 (18)	C13—C14	1.380 (4)
Sn1—O7	2.0249 (16)	C13—H131	0.9500
Sn1—C19	2.123 (2)	C14—H141	0.9500
Sn1—C15	2.135 (3)	C15—C16	1.527 (3)
Sn2—O2	2.2359 (17)	C15—H151	0.9900
Sn2—O4^i	2.7841 (17)	C15—H152	0.9900
Sn2—O7	2.0534 (16)	C16—C17	1.525 (4)
Sn2—O7^i	2.1501 (16)	C16—H161	0.9900
Sn2—C23	2.123 (2)	C16—H162	0.9900
Sn2—C27	2.125 (2)	C17—C18	1.525 (4)
O1—C1	1.259 (3)	C17—H171	0.9900
O2—C1	1.268 (3)	C17—H172	0.9900
O4—C8	1.302 (3)	C18—H181	0.9800
O5—C8	1.239 (3)	C18—H182	0.9800
N2—C12	1.372 (4)	C18—H183	0.9800
N2—H21	0.82 (4)	C19—C20	1.521 (4)
N2—H22	0.79 (4)	C19—H191	0.9900
C1—C2B	1.475 (4)	C19—H192	0.9900
C1—C2A	1.497 (4)	C20—C21	1.522 (4)
N1A—C5A	1.408 (5)	C20—H201	0.9900
N1A—H11	0.8800	C20—H202	0.9900
N1A—H12	0.8800	C21—C22	1.529 (4)
C2A—C3A	1.387 (5)	C21—H211	0.9900
C2A—C7A	1.400 (4)	C21—H212	0.9900
C3A—C4A	1.377 (5)	C22—H221	0.9800
C3A—H3A	0.9500	C22—H222	0.9800
C4A—C5A	1.387 (6)	C22—H223	0.9800
C4A—H4A	0.9500	C23—C24	1.519 (3)
C5A—C6A	1.385 (6)	C23—H231	0.9900
C6A—C7A	1.374 (5)	C23—H232	0.9900
C6A—H6A	0.9500	C24—C25	1.534 (4)
C7A—H7A	0.9500	C24—H241	0.9900
N1B—C5B	1.406 (6)	C24—H242	0.9900
N1B—H13	0.8800	C25—C26	1.515 (4)
N1B—H14	0.8800	C25—H251	0.9900
C2B—C3B	1.382 (5)	C25—H252	0.9900
C2B—C7B	1.394 (5)	C26—H261	0.9800
C3B—C4B	1.377 (6)	C26—H262	0.9800
C3B—H3B	0.9500	C26—H263	0.9800
C4B—C5B	1.387 (6)	C27—C28	1.529 (3)
C4B—H4B	0.9500	C27—H271	0.9900
C5B—C6B	1.385 (6)	C27—H272	0.9900
C6B—C7B	1.375 (5)	C28—C29	1.525 (4)
C6B—H6B	0.9500	C28—H281	0.9900
C7B—H7B	0.9500	C28—H282	0.9900
C8—C9	1.492 (3)	C29—C30	1.523 (5)
C9—C14	1.394 (3)	C29—H291	0.9900
C9—C10	1.399 (3)	C29—H292	0.9900
C10—C11	1.381 (4)	C30—H301	0.9800
C10—H10	0.9500	C30—H302	0.9800
C11—C12	1.398 (4)	C30—H303	0.9800
O7—Sn1—C19	108.76 (9)	C11—C12—C13	118.3 (2)
O7—Sn1—C15	112.17 (9)	C14—C13—C12	120.5 (2)
C19—Sn1—C15	138.45 (10)	C14—C13—H131	119.8
O7—Sn1—O4	79.92 (6)	C12—C13—H131	119.8
C19—Sn1—O4	100.72 (8)	C13—C14—C9	121.4 (2)
C15—Sn1—O4	93.19 (9)	C13—C14—H141	119.3
O7—Sn1—O1	91.49 (7)	C9—C14—H141	119.3
C19—Sn1—O1	88.19 (8)	C16—C15—Sn1	113.91 (17)
C15—Sn1—O1	83.94 (9)	C16—C15—H151	108.8
O4—Sn1—O1	169.20 (7)	Sn1—C15—H151	108.8
O7—Sn1—O5	128.92 (6)	C16—C15—H152	108.8
C19—Sn1—O5	81.85 (8)	Sn1—C15—H152	108.8
C15—Sn1—O5	78.25 (8)	H151—C15—H152	107.7
O4—Sn1—O5	49.10 (5)	C17—C16—C15	112.6 (2)
O1—Sn1—O5	139.47 (6)	C17—C16—H161	109.1
O7—Sn2—C23	103.05 (9)	C15—C16—H161	109.1
O7—Sn2—C27	111.14 (8)	C17—C16—H162	109.1
C23—Sn2—C27	144.31 (10)	C15—C16—H162	109.1
O7—Sn2—O7^i	75.95 (7)	H161—C16—H162	107.8
C23—Sn2—O7^i	100.39 (8)	C16—C17—C18	112.4 (2)
C27—Sn2—O7^i	97.58 (8)	C16—C17—H171	109.1
O7—Sn2—O2	88.46 (7)	C18—C17—H171	109.1
C23—Sn2—O2	88.68 (8)	C16—C17—H172	109.1
C27—Sn2—O2	82.42 (8)	C18—C17—H172	109.1
O7^i—Sn2—O2	163.35 (7)	H171—C17—H172	107.9
O7—Sn2—O4^i	140.86 (6)	C17—C18—H181	109.5
C23—Sn2—O4^i	80.82 (8)	C17—C18—H182	109.5
C27—Sn2—O4^i	79.19 (8)	H181—C18—H182	109.5
O7^i—Sn2—O4^i	65.13 (5)	C17—C18—H183	109.5
O2—Sn2—O4^i	130.68 (6)	H181—C18—H183	109.5
C1—O1—Sn1	131.46 (16)	H182—C18—H183	109.5
C1—O2—Sn2	131.68 (16)	C20—C19—Sn1	115.85 (17)
C8—O4—Sn1	110.17 (14)	C20—C19—H191	108.3
C8—O4—Sn2^i	154.62 (15)	Sn1—C19—H191	108.3
Sn1—O4—Sn2^i	93.11 (6)	C20—C19—H192	108.3
C8—O5—Sn1	77.77 (14)	Sn1—C19—H192	108.3
Sn1—O7—Sn2	134.87 (8)	H191—C19—H192	107.4
Sn1—O7—Sn2^i	120.95 (8)	C19—C20—C21	113.0 (2)
Sn2—O7—Sn2^i	104.05 (7)	C19—C20—H201	109.0
C12—N2—H21	120 (3)	C21—C20—H201	109.0
C12—N2—H22	116 (3)	C19—C20—H202	109.0
H21—N2—H22	122 (4)	C21—C20—H202	109.0
O1—C1—O2	123.6 (2)	H201—C20—H202	107.8
O1—C1—C2B	118.5 (3)	C20—C21—C22	112.7 (2)
O2—C1—C2B	117.6 (3)	C20—C21—H211	109.1
O1—C1—C2A	118.55 (16)	C22—C21—H211	109.1
O2—C1—C2A	117.31 (16)	C20—C21—H212	109.1
C5A—N1A—H11	120.0	C22—C21—H212	109.1
C5A—N1A—H12	120.0	H211—C21—H212	107.8
H11—N1A—H12	120.0	C21—C22—H221	109.5
C3A—C2A—C7A	118.0 (3)	C21—C22—H222	109.5
C3A—C2A—C1	121.1 (2)	H221—C22—H222	109.5
C7A—C2A—C1	120.6 (2)	C21—C22—H223	109.5
C4A—C3A—C2A	121.0 (4)	H221—C22—H223	109.5
C4A—C3A—H3A	119.5	H222—C22—H223	109.5
C2A—C3A—H3A	119.5	C24—C23—Sn2	118.15 (18)
C3A—C4A—C5A	120.4 (4)	C24—C23—H231	107.8
C3A—C4A—H4A	119.8	Sn2—C23—H231	107.8
C5A—C4A—H4A	119.8	C24—C23—H232	107.8
C6A—C5A—C4A	118.9 (4)	Sn2—C23—H232	107.8
C6A—C5A—N1A	121.2 (4)	H231—C23—H232	107.1
C4A—C5A—N1A	119.9 (4)	C23—C24—C25	112.7 (2)
C7A—C6A—C5A	120.8 (4)	C23—C24—H241	109.1
C7A—C6A—H6A	119.6	C25—C24—H241	109.1
C5A—C6A—H6A	119.6	C23—C24—H242	109.1
C6A—C7A—C2A	120.6 (4)	C25—C24—H242	109.1
C6A—C7A—H7A	119.7	H241—C24—H242	107.8
C2A—C7A—H7A	119.7	C26—C25—C24	113.1 (2)
C5B—N1B—H13	120.0	C26—C25—H251	109.0
C5B—N1B—H14	120.0	C24—C25—H251	109.0
H13—N1B—H14	120.0	C26—C25—H252	109.0
C3B—C2B—C7B	119.4 (3)	C24—C25—H252	109.0
C3B—C2B—C1	120.5 (4)	H251—C25—H252	107.8
C7B—C2B—C1	120.1 (4)	C25—C26—H261	109.5
C4B—C3B—C2B	120.4 (4)	C25—C26—H262	109.5
C4B—C3B—H3B	119.8	H261—C26—H262	109.5
C2B—C3B—H3B	119.8	C25—C26—H263	109.5
C3B—C4B—C5B	120.1 (4)	H261—C26—H263	109.5
C3B—C4B—H4B	120.0	H262—C26—H263	109.5
C5B—C4B—H4B	120.0	C28—C27—Sn2	113.00 (17)
C6B—C5B—C4B	119.6 (4)	C28—C27—H271	109.0
C6B—C5B—N1B	120.6 (5)	Sn2—C27—H271	109.0
C4B—C5B—N1B	119.8 (5)	C28—C27—H272	109.0
C7B—C6B—C5B	120.3 (4)	Sn2—C27—H272	109.0
C7B—C6B—H6B	119.9	H271—C27—H272	107.8
C5B—C6B—H6B	119.9	C29—C28—C27	111.2 (2)
C6B—C7B—C2B	120.1 (4)	C29—C28—H281	109.4
C6B—C7B—H7B	120.0	C27—C28—H281	109.4
C2B—C7B—H7B	120.0	C29—C28—H282	109.4
O5—C8—O4	121.2 (2)	C27—C28—H282	109.4
O5—C8—C9	121.2 (2)	H281—C28—H282	108.0
O4—C8—C9	117.5 (2)	C30—C29—C28	113.4 (3)
C14—C9—C10	117.9 (2)	C30—C29—H291	108.9
C14—C9—C8	120.3 (2)	C28—C29—H291	108.9
C10—C9—C8	121.8 (2)	C30—C29—H292	108.9
C11—C10—C9	121.4 (2)	C28—C29—H292	108.9
C11—C10—H10	119.3	H291—C29—H292	107.7
C9—C10—H10	119.3	C29—C30—H301	109.5
C10—C11—C12	120.5 (2)	C29—C30—H302	109.5
C10—C11—H111	119.7	H301—C30—H302	109.5
C12—C11—H111	119.7	C29—C30—H303	109.5
N2—C12—C11	120.5 (3)	H301—C30—H303	109.5
N2—C12—C13	121.2 (3)	H302—C30—H303	109.5
O7—Sn1—O1—C1	29.3 (2)	C1—C2A—C7A—C6A	178.0 (6)
C19—Sn1—O1—C1	−79.4 (2)	O1—C1—C2B—C3B	−1.3 (10)
C15—Sn1—O1—C1	141.5 (2)	O2—C1—C2B—C3B	172.9 (6)
O4—Sn1—O1—C1	66.4 (4)	O1—C1—C2B—C7B	177.4 (8)
O5—Sn1—O1—C1	−154.58 (19)	O2—C1—C2B—C7B	−8.4 (10)
O7—Sn2—O2—C1	47.6 (2)	C7B—C2B—C3B—C4B	1.5 (14)
C23—Sn2—O2—C1	−55.5 (2)	C1—C2B—C3B—C4B	−179.7 (8)
C27—Sn2—O2—C1	159.1 (2)	C2B—C3B—C4B—C5B	1.8 (15)
O7^i—Sn2—O2—C1	68.0 (3)	C3B—C4B—C5B—C6B	−4.1 (16)
O4^i—Sn2—O2—C1	−132.2 (2)	C3B—C4B—C5B—N1B	175.6 (10)
O7—Sn1—O4—C8	175.86 (16)	C4B—C5B—C6B—C7B	3.0 (17)
C19—Sn1—O4—C8	−76.76 (17)	N1B—C5B—C6B—C7B	−176.7 (12)
C15—Sn1—O4—C8	63.90 (17)	C5B—C6B—C7B—C2B	0.4 (19)
O1—Sn1—O4—C8	138.1 (3)	C3B—C2B—C7B—C6B	−2.6 (17)
O5—Sn1—O4—C8	−7.55 (14)	C1—C2B—C7B—C6B	178.7 (10)
O7—Sn1—O4—Sn2^i	6.17 (6)	Sn1—O5—C8—O4	−11.4 (2)
C19—Sn1—O4—Sn2^i	113.56 (8)	Sn1—O5—C8—C9	166.2 (2)
C15—Sn1—O4—Sn2^i	−105.78 (8)	Sn1—O4—C8—O5	15.8 (3)
O1—Sn1—O4—Sn2^i	−31.6 (4)	Sn2^i—O4—C8—O5	171.2 (2)
O5—Sn1—O4—Sn2^i	−177.24 (9)	Sn1—O4—C8—C9	−161.89 (16)
O7—Sn1—O5—C8	11.94 (18)	Sn2^i—O4—C8—C9	−6.5 (5)
C19—Sn1—O5—C8	119.51 (16)	O5—C8—C9—C14	6.1 (4)
C15—Sn1—O5—C8	−97.17 (16)	O4—C8—C9—C14	−176.2 (2)
O4—Sn1—O5—C8	7.62 (14)	O5—C8—C9—C10	−171.3 (2)
O1—Sn1—O5—C8	−163.01 (15)	O4—C8—C9—C10	6.4 (3)
C19—Sn1—O7—Sn2	77.67 (14)	C14—C9—C10—C11	−0.9 (4)
C15—Sn1—O7—Sn2	−94.98 (14)	C8—C9—C10—C11	176.6 (2)
O4—Sn1—O7—Sn2	175.67 (13)	C9—C10—C11—C12	−0.1 (4)
O1—Sn1—O7—Sn2	−10.92 (13)	C10—C11—C12—N2	−177.0 (3)
O5—Sn1—O7—Sn2	172.36 (9)	C10—C11—C12—C13	1.4 (4)
C19—Sn1—O7—Sn2^i	−107.33 (11)	N2—C12—C13—C14	176.7 (3)
C15—Sn1—O7—Sn2^i	80.01 (12)	C11—C12—C13—C14	−1.6 (4)
O4—Sn1—O7—Sn2^i	−9.33 (9)	C12—C13—C14—C9	0.7 (4)
O1—Sn1—O7—Sn2^i	164.07 (9)	C10—C9—C14—C13	0.6 (4)
O5—Sn1—O7—Sn2^i	−12.65 (13)	C8—C9—C14—C13	−176.9 (2)
C23—Sn2—O7—Sn1	77.94 (14)	O7—Sn1—C15—C16	32.2 (2)
C27—Sn2—O7—Sn1	−91.61 (14)	C19—Sn1—C15—C16	−137.29 (18)
O7^i—Sn2—O7—Sn1	175.58 (17)	O4—Sn1—C15—C16	112.60 (19)
O2—Sn2—O7—Sn1	−10.34 (12)	O1—Sn1—C15—C16	−56.95 (19)
O4^i—Sn2—O7—Sn1	169.39 (8)	O5—Sn1—C15—C16	159.6 (2)
C23—Sn2—O7—Sn2^i	−97.63 (9)	Sn1—C15—C16—C17	−172.42 (18)
C27—Sn2—O7—Sn2^i	92.82 (9)	C15—C16—C17—C18	−178.7 (2)
O7^i—Sn2—O7—Sn2^i	0.0	O7—Sn1—C19—C20	65.5 (2)
O2—Sn2—O7—Sn2^i	174.08 (8)	C15—Sn1—C19—C20	−124.8 (2)
O4^i—Sn2—O7—Sn2^i	−6.18 (13)	O4—Sn1—C19—C20	−17.4 (2)
Sn1—O1—C1—O2	−6.6 (4)	O1—Sn1—C19—C20	156.5 (2)
Sn1—O1—C1—C2B	167.3 (4)	O5—Sn1—C19—C20	−62.9 (2)
Sn1—O1—C1—C2A	−178.22 (13)	Sn1—C19—C20—C21	−177.0 (2)
Sn2—O2—C1—O1	−43.4 (4)	C19—C20—C21—C22	174.7 (3)
Sn2—O2—C1—C2B	142.7 (4)	O7—Sn2—C23—C24	−156.29 (19)
Sn2—O2—C1—C2A	128.32 (17)	C27—Sn2—C23—C24	6.9 (3)
O1—C1—C2A—C3A	−6.6 (4)	O7^i—Sn2—C23—C24	125.88 (19)
O2—C1—C2A—C3A	−178.8 (4)	O2—Sn2—C23—C24	−68.2 (2)
O1—C1—C2A—C7A	179.9 (5)	O4^i—Sn2—C23—C24	63.45 (19)
O2—C1—C2A—C7A	7.7 (5)	Sn2—C23—C24—C25	169.43 (18)
C7A—C2A—C3A—C4A	−6.8 (9)	C23—C24—C25—C26	−74.9 (3)
C1—C2A—C3A—C4A	179.5 (5)	O7—Sn2—C27—C28	7.0 (2)
C2A—C3A—C4A—C5A	4.6 (11)	C23—Sn2—C27—C28	−155.32 (17)
C3A—C4A—C5A—C6A	0.4 (11)	O7^i—Sn2—C27—C28	84.86 (18)
C3A—C4A—C5A—N1A	−177.0 (7)	O2—Sn2—C27—C28	−78.34 (18)
C4A—C5A—C6A—C7A	−2.8 (11)	O4^i—Sn2—C27—C28	147.64 (18)
N1A—C5A—C6A—C7A	174.5 (8)	Sn2—C27—C28—C29	178.17 (18)
C5A—C6A—C7A—C2A	0.5 (12)	C27—C28—C29—C30	176.0 (3)
C3A—C2A—C7A—C6A	4.3 (11)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O5^ii	0.82 (4)	2.26 (4)	3.051 (4)	164 (3)

Symmetry code: (ii) x, −y+1/2, z−1/2.