Tetra­chloridodi-μ₃-oxido-tetra­kis­(μ₂-propan-2-olato-κ²O:O)ditin(II)ditin(IV)

The centrosymmetric tetranuclear title molecule, [Sn₄(C₃H₇O)₄Cl₄O₂], contains two types of Sn atoms, Sn^II and Sn^IV. The Sn^II atom has a trigonal–pyramidal coordination environment and is bonded to two O atoms from two iso­propano­late groups and one μ₃-oxide atom. The Sn^IV atom has an octa­hedral coordination environment, formed by two chloride atoms, two μ₃-oxide atoms and two O atoms from iso­propano­late groups.

Related literature

For the synthesis and structures of related tin and titanium complexes, see: Boyle et al. (2002); Eslava et al. (2010); Fric & Schubert (2008); Harrison et al. (1978); Mijatovic et al. (2001); Mokal et al. (1994); Vatsa et al. (1991); Verdenelli et al. (2000).

Experimental

Crystal data

• [Sn₄(C₃H₇O)₄Cl₄O₂]

• M_r = 884.98

• Monoclinic, P 2₁ /c

• a = 6.4423 (3) Å

• b = 17.8302 (7) Å

• c = 11.6843 (5) Å

• β = 105.474 (2)°

• V = 1293.5 (1) ų

• Z = 2

• Mo Kα radiation

• μ = 4.25 mm⁻¹

• T = 296 K

• 0.36 × 0.17 × 0.12 mm

Data collection

• Nonius KappaCCD diffractometer

• Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997) T_min = 0.310, T_max = 0.629

• 14221 measured reflections

• 3853 independent reflections

• 2930 reflections with I > 2σ(I)

• R_int = 0.041

Refinement

• R[F² > 2σ(F²)] = 0.038

• wR(F²) = 0.061

• S = 1.10

• 3853 reflections

• 118 parameters

• H-atom parameters constrained

• Δρ_max = 0.93 e Å⁻³

• Δρ_min = −0.80 e Å⁻³

Table 1
Selected bond lengths (Å)

Sn1—O1	2.099 (3)
Sn1—O2	2.084 (3)
Sn1—O3	2.109 (2)
Sn1—O3^i	2.081 (3)
Sn1—Cl1	2.3808 (12)
Sn1—Cl2	2.3604 (11)
Sn2—O1^i	2.165 (3)
Sn2—O2	2.168 (3)
Sn2—O3	2.105 (2)
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97.

Supporting information

S1. Comment

Compound with the same symmetry and similar coordination environment as in the title compound was studied in the work of Boyle et al. (2002). However it has tin atoms with equal oxidation state, in opposite with our compound, which has different oxidation states and coordination environments of metal atoms. The same situation persists with other compounds of tin and titanium with similar coordination geometry and identical oxidation states of the metal atoms (Eslava et al., 2010; Fric & Schubert, 2008; Harrison et al., 1978; Mijatovic et al., 2001; Mokal et al., 1994; Vatsa et al., 1991; Verdenelli et al., 2000). The title compound has two types of tin atoms. The Sn^II atom is three-coordinated and has a trigonal-pyramidal environment. The Sn^IV atom is hexa-coordinated and has an octahedral environment. Literature search did not provide any information about similar compounds, which have simultaneously two tin atoms with different oxidation states. In the title compound this is possible due to two chloride atoms for each Sn^IV atom.

Related literature

For the synthesis and structures of related tin and titanium complexes, see: Boyle et al. (2002); Eslava et al. (2010); Fric & Schubert (2008); Harrison et al. (1978); Mijatovic et al. (2001); Mokal et al. (1994); Vatsa et al. (1991); Verdenelli et al. (2000).

S2. Experimental

To a solution of (diisopropoxydichlorido)tin (1.54 g, 5 mmol) in 5 ml of toluene was added N,N,N-tris(trimethylsilyl)aminoiminophosphorane (0.695 g, 2.5 mmol) in 3 ml of toluene and stirred for 4 h. The resulting solution was concentrated to 4 ml and cooled to -25°C. After two days, resulting crystals were filtered from the solution and dried in vacuum (yield: 0.454 g, 41%). Analysis, calculated for C₁₂H₂₈Cl₄O₆Sn₄: C 16.26, H 3.16, Cl 16.03, O 10.83, Sn 53.72%; found: C 16.01, H 3.56, Cl 16.25, O 10.94, Sn 53.24%.

S3. Refinement

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.98 (CH₂) and 0.96 (CH₃) Å and with U_iso(H) = 1.2(1.5 for methyl)U_eq(C).

Computing details

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted. [Symmetry code: (i) 1-x, 1-y, 1-z.]

Tetrachloridodi-µ₃-oxido-tetrakis(µ₂-propan-2-olato-κ²O:O)ditin(II)ditin(IV)

Crystal data

[Sn4(C3H7O)4Cl4O2]	F(000) = 832
Mr = 884.98	Dx = 2.272 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3853 reflections
a = 6.4423 (3) Å	θ = 2.1–31.1°
b = 17.8302 (7) Å	µ = 4.25 mm^−1
c = 11.6843 (5) Å	T = 296 K
β = 105.474 (2)°	Block, colorless
V = 1293.5 (1) Å^3	0.36 × 0.17 × 0.12 mm
Z = 2

Data collection

Nonius KappaCCD diffractometer	3853 independent reflections
Radiation source: fine-focus sealed tube	2930 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
φ and ω scans with κ offset	θmax = 31.1°, θmin = 2.1°
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	h = −9→9
Tmin = 0.310, Tmax = 0.629	k = −25→21
14221 measured reflections	l = −16→15

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.061	H-atom parameters constrained
S = 1.10	w = 1/[σ^2(Fo^2) + (0.P)^2 + 2.1387P] where P = (Fo^2 + 2Fc^2)/3
3853 reflections	(Δ/σ)max = 0.001
118 parameters	Δρmax = 0.93 e Å^−3
0 restraints	Δρmin = −0.80 e Å^−3

Special details

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 > 2sigma(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
Sn1	0.47306 (5)	0.589199 (15)	0.51770 (2)	0.02814 (8)
Sn2	0.07243 (5)	0.494763 (16)	0.33749 (3)	0.03368 (8)
Cl1	0.1984 (2)	0.65257 (7)	0.58158 (12)	0.0527 (3)
Cl2	0.6589 (2)	0.69913 (7)	0.49108 (12)	0.0538 (3)
O1	0.6730 (5)	0.57626 (15)	0.6906 (2)	0.0358 (7)
O2	0.2858 (5)	0.58942 (15)	0.3422 (2)	0.0347 (7)
O3	0.2987 (4)	0.48801 (13)	0.5045 (2)	0.0271 (6)
C1	0.6845 (8)	0.6280 (3)	0.7884 (4)	0.0430 (11)
H1	0.6029	0.6732	0.7566	0.052*
C2	0.9156 (9)	0.6503 (3)	0.8431 (5)	0.0674 (17)
H2A	0.9729	0.6733	0.7838	0.101*
H2B	0.9987	0.6065	0.8737	0.101*
H2C	0.9223	0.6852	0.9066	0.101*
C3	0.5808 (11)	0.5926 (4)	0.8751 (5)	0.083 (2)
H3A	0.4334	0.5810	0.8360	0.124*
H3B	0.5860	0.6268	0.9393	0.124*
H3C	0.6562	0.5474	0.9056	0.124*
C4	0.2592 (8)	0.6511 (2)	0.2583 (4)	0.0423 (11)
H4	0.3093	0.6973	0.3024	0.051*
C5	0.3896 (12)	0.6379 (4)	0.1741 (6)	0.100 (3)
H5A	0.5384	0.6332	0.2170	0.150*
H5B	0.3728	0.6794	0.1199	0.150*
H5C	0.3425	0.5926	0.1304	0.150*
C6	0.0244 (10)	0.6592 (3)	0.1970 (6)	0.086 (2)
H6A	−0.0541	0.6678	0.2549	0.130*
H6B	−0.0269	0.6142	0.1536	0.130*
H6C	0.0039	0.7009	0.1431	0.130*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sn1	0.02865 (15)	0.02228 (14)	0.03221 (15)	0.00089 (12)	0.00591 (11)	−0.00050 (12)
Sn2	0.03055 (16)	0.03210 (16)	0.03533 (16)	−0.00024 (13)	0.00347 (12)	0.00033 (13)
Cl1	0.0432 (7)	0.0410 (7)	0.0770 (9)	0.0083 (5)	0.0215 (6)	−0.0119 (6)
Cl2	0.0424 (7)	0.0356 (6)	0.0738 (9)	−0.0129 (5)	−0.0009 (6)	0.0116 (6)
O1	0.0380 (17)	0.0359 (17)	0.0309 (15)	0.0064 (13)	0.0044 (13)	−0.0096 (13)
O2	0.0364 (17)	0.0268 (15)	0.0370 (15)	−0.0058 (13)	0.0032 (13)	0.0050 (13)
O3	0.0297 (15)	0.0200 (14)	0.0302 (14)	0.0016 (11)	0.0058 (11)	−0.0004 (11)
C1	0.053 (3)	0.040 (3)	0.033 (2)	0.007 (2)	0.005 (2)	−0.014 (2)
C2	0.062 (4)	0.076 (4)	0.060 (3)	−0.013 (3)	0.011 (3)	−0.035 (3)
C3	0.103 (5)	0.098 (5)	0.058 (3)	−0.031 (4)	0.042 (4)	−0.035 (3)
C4	0.049 (3)	0.031 (2)	0.042 (3)	−0.003 (2)	0.003 (2)	0.014 (2)
C5	0.137 (7)	0.088 (5)	0.102 (5)	0.023 (5)	0.078 (5)	0.041 (4)
C6	0.079 (5)	0.064 (4)	0.093 (5)	0.004 (3)	−0.017 (4)	0.042 (4)

Geometric parameters (Å, º)

Sn1—O1	2.099 (3)	C2—H2A	0.9600
Sn1—O2	2.084 (3)	C2—H2B	0.9600
Sn1—O3	2.109 (2)	C2—H2C	0.9600
Sn1—O3^i	2.081 (3)	C3—H3A	0.9600
Sn1—Cl1	2.3808 (12)	C3—H3B	0.9600
Sn1—Cl2	2.3604 (11)	C3—H3C	0.9600
Sn1—Sn1^i	3.2382 (5)	C4—C5	1.473 (7)
Sn2—O1^i	2.165 (3)	C4—C6	1.498 (7)
Sn2—O2	2.168 (3)	C4—H4	0.9800
Sn2—O3	2.105 (2)	C5—H5A	0.9600
O1—C1	1.456 (5)	C5—H5B	0.9600
O2—C4	1.453 (5)	C5—H5C	0.9600
C1—C3	1.494 (7)	C6—H6A	0.9600
C1—C2	1.508 (7)	C6—H6B	0.9600
C1—H1	0.9800	C6—H6C	0.9600
O3^i—Sn1—O2	96.97 (10)	C3—C1—C2	113.2 (4)
O3^i—Sn1—O1	76.99 (10)	O1—C1—H1	108.3
O2—Sn1—O1	173.28 (10)	C3—C1—H1	108.3
O3^i—Sn1—O3	78.77 (11)	C2—C1—H1	108.3
O2—Sn1—O3	76.86 (10)	C1—C2—H2A	109.5
O1—Sn1—O3	98.87 (10)	C1—C2—H2B	109.5
O3^i—Sn1—Cl2	97.63 (8)	H2A—C2—H2B	109.5
O2—Sn1—Cl2	92.84 (8)	C1—C2—H2C	109.5
O1—Sn1—Cl2	90.89 (9)	H2A—C2—H2C	109.5
O3—Sn1—Cl2	168.46 (7)	H2B—C2—H2C	109.5
O3^i—Sn1—Cl1	164.20 (8)	C1—C3—H3A	109.5
O2—Sn1—Cl1	91.38 (9)	C1—C3—H3B	109.5
O1—Sn1—Cl1	93.83 (8)	H3A—C3—H3B	109.5
O3—Sn1—Cl1	90.17 (8)	C1—C3—H3C	109.5
Cl2—Sn1—Cl1	95.32 (5)	H3A—C3—H3C	109.5
O3^i—Sn1—Sn1^i	39.70 (7)	H3B—C3—H3C	109.5
O2—Sn1—Sn1^i	85.98 (7)	O2—C4—C5	110.1 (4)
O1—Sn1—Sn1^i	87.47 (7)	O2—C4—C6	108.6 (4)
O3—Sn1—Sn1^i	39.06 (7)	C5—C4—C6	112.3 (5)
Cl2—Sn1—Sn1^i	136.34 (4)	O2—C4—H4	108.6
Cl1—Sn1—Sn1^i	128.33 (3)	C5—C4—H4	108.6
O3—Sn2—O1^i	75.04 (10)	C6—C4—H4	108.6
O3—Sn2—O2	75.14 (10)	C4—C5—H5A	109.5
O1^i—Sn2—O2	87.61 (11)	C4—C5—H5B	109.5
C1—O1—Sn1	125.2 (2)	H5A—C5—H5B	109.5
C1—O1—Sn2^i	127.4 (3)	C4—C5—H5C	109.5
Sn1—O1—Sn2^i	102.33 (11)	H5A—C5—H5C	109.5
C4—O2—Sn1	126.8 (2)	H5B—C5—H5C	109.5
C4—O2—Sn2	127.8 (2)	C4—C6—H6A	109.5
Sn1—O2—Sn2	102.71 (11)	C4—C6—H6B	109.5
Sn1^i—O3—Sn2	105.05 (11)	H6A—C6—H6B	109.5
Sn1^i—O3—Sn1	101.23 (11)	C4—C6—H6C	109.5
Sn2—O3—Sn1	104.02 (10)	H6A—C6—H6C	109.5
O1—C1—C3	109.0 (4)	H6B—C6—H6C	109.5
O1—C1—C2	109.7 (4)
O3^i—Sn1—O1—C1	162.0 (3)	O1^i—Sn2—O3—Sn1^i	−5.91 (11)
O3—Sn1—O1—C1	−121.8 (3)	O2—Sn2—O3—Sn1^i	−97.42 (13)
Cl2—Sn1—O1—C1	64.4 (3)	O1^i—Sn2—O3—Sn1	100.06 (12)
Cl1—Sn1—O1—C1	−31.0 (3)	O2—Sn2—O3—Sn1	8.55 (10)
Sn1^i—Sn1—O1—C1	−159.3 (3)	O3^i—Sn1—O3—Sn1^i	0.0
O3^i—Sn1—O1—Sn2^i	5.81 (11)	O2—Sn1—O3—Sn1^i	99.98 (12)
O3—Sn1—O1—Sn2^i	82.02 (12)	O1—Sn1—O3—Sn1^i	−74.73 (11)
Cl2—Sn1—O1—Sn2^i	−91.81 (10)	Cl2—Sn1—O3—Sn1^i	72.8 (4)
Cl1—Sn1—O1—Sn2^i	172.79 (10)	Cl1—Sn1—O3—Sn1^i	−168.64 (9)
Sn1^i—Sn1—O1—Sn2^i	44.54 (9)	O3^i—Sn1—O3—Sn2	−108.82 (14)
O3^i—Sn1—O2—C4	−112.5 (3)	O2—Sn1—O3—Sn2	−8.83 (11)
O3—Sn1—O2—C4	170.8 (3)	O1—Sn1—O3—Sn2	176.45 (11)
Cl2—Sn1—O2—C4	−14.4 (3)	Cl2—Sn1—O3—Sn2	−36.0 (4)
Cl1—Sn1—O2—C4	81.0 (3)	Cl1—Sn1—O3—Sn2	82.55 (10)
Sn1^i—Sn1—O2—C4	−150.7 (3)	Sn1^i—Sn1—O3—Sn2	−108.82 (14)
O3^i—Sn1—O2—Sn2	85.22 (12)	Sn1—O1—C1—C3	108.1 (4)
O3—Sn1—O2—Sn2	8.53 (10)	Sn2^i—O1—C1—C3	−101.7 (4)
Cl2—Sn1—O2—Sn2	−176.73 (10)	Sn1—O1—C1—C2	−127.4 (4)
Cl1—Sn1—O2—Sn2	−81.33 (10)	Sn2^i—O1—C1—C2	22.8 (5)
Sn1^i—Sn1—O2—Sn2	47.00 (9)	Sn1—O2—C4—C5	102.9 (5)
O3—Sn2—O2—C4	−170.6 (3)	Sn2—O2—C4—C5	−99.2 (5)
O1^i—Sn2—O2—C4	114.2 (3)	Sn1—O2—C4—C6	−133.8 (4)
O3—Sn2—O2—Sn1	−8.61 (10)	Sn2—O2—C4—C6	24.1 (5)
O1^i—Sn2—O2—Sn1	−83.76 (12)

Symmetry code: (i) −x+1, −y+1, −z+1.