Di-μ-methanolato-κ⁴O:O-bis[tri­chlorido(dimethyl­formamide-κO)tin(IV)]

The title compound, [Sn₂(CH₃O)₂Cl₆(C₃H₇NO)₂], contains two hexa­coordinated Sn^IV atoms symmetrically bridged by two deprotonated methanol ligands, with an inversion center in the middle of the planar Sn₂O₂ ring. The other sites of the distorted octa­hedral coordination geometry of the Sn^IV atom are occupied by three Cl atoms and one O atom from a dimethyl­formamide mol­ecule. The complex mol­ecules are connected by weak C—H...Cl hydrogen bonds into a two-dimensional supra­molecular network parallel to (10).

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](N-C) = 0.011 Å
• R factor = 0.044
• wR factor = 0.117
• Data-to-parameter ratio = 18.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Sn1    --  O1      ..       8.67 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Sn1    --  O1_a    ..       5.34 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Sn1
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.595          8
PLAT971_ALERT_2_C Large Calcd. Non-Metal Positive Residual Density       1.58 eA-3
PLAT971_ALERT_2_C Large Calcd. Non-Metal Positive Residual Density       1.54 eA-3
PLAT972_ALERT_2_C Large Calcd. Non-Metal Negative Residual Density      -1.82 eA-3
PLAT480_ALERT_4_C Long H...A H-Bond Reported H3A    ..  CL3     ..       2.95 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H4B    ..  CL1     ..       2.90 Ang.

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         13
PLAT128_ALERT_4_G Alternate Setting of Space-group P21/c   .......      P21/n
PLAT794_ALERT_5_G Note: Tentative Bond Valency for Sn1     .......       4.07

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   9 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 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
   3 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

The title compound (Fig.1) consists of six Cl anions, two methoxo anions, two Sn^IV ions and two dimethylformamide molecules. The molecule has an inversion center in the middle of the Sn₂O₂ ring. This ring is planar and can be described as rhombic, with the endocyclic angles at the O atoms larger than those at the Sn atoms [Sn1ⁱ—O1—Sn1 = 106.9 (2), O1ⁱ—Sn1—O1 = 73.1 (2)°. Symmetry code: (i) -x+2, -y, -z+1]. The Sn1—O1 distance [2.106 (5) Å] is very close to the Sn1—O1ⁱ distance [2.101 (5) Å] (Table 1). Each Sn^IV atom is hexacoordinated with two methoxo anions, three Cl anions and one dimethylformamide molecule in a distorted octahedral geometry.

As is indicated from Fig. 2 and Table 2, the intramolecular interactions, C1—H1C···Cl3, strengthen the dimeric unit and the intermolecular ones, C3—H3A···Cl3ⁱⁱ and C4—H4B···Cl1ⁱⁱⁱ [symmetry codes: (ii) x+1/2, -y+1/2, z+1/2; (iii) -x+3/2, y+1/2, -z+1/2], give rise to a two-dimensional polymer-like supramolecular network.

Related literature

For related tin(IV) compounds, see: Mao & You (1990); Reuter & Schröder (1992).

S2. Experimental

Stannic chloride hydrate (0.4 mmol, 0.14 g) was dissolved in methanol (20 ml) and dimethylformamide (5 ml) was added with stirring at room temperature. The mixture was allowed to react for 6 h and was then filtered. Colorless crystals suitable for X-ray analysis were obtained by slow evaporation of methanol over a period of two weeks (yield: 60%). Analysis, calculated for C₈H₂₀Cl₆N₂O₄Sn₂: C 14.59, H 3.06, N 4.25%; found: C 14.58, H 3.04, N 4.27%.

S3. Refinement

H atoms were placed in calculated positions and treated as riding on their parent atoms, with C—H = 0.93 (CH) and 0.96 (CH₃) Å and with U_iso(H) = 1.2(1.5 for methyl)U_eq(C). The highest residual electron density was found at 0.72 Å from H1A atom and the deepest hole at 1.01 Å from Sn1 atom.

Computing details

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and X-SEED (Barbour, 2001); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of the title compound, with 50% probability displacement ellipsoids. [Symmetry code: (i) -x+2, -y, -z+1.]
	Fig. 2. A view of the two-dimensional polymer-like supramolecular network in the title compound.

Di-µ-methanolato-κ⁴O:O-bis[trichlorido(dimethylformamide- κO)tin(IV)]

Crystal data

[Sn2(CH3O)2Cl6(C3H7NO)2]	F(000) = 632
Mr = 658.34	Dx = 2.013 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2694 reflections
a = 8.589 (8) Å	θ = 2.6–27.0°
b = 11.4444 (13) Å	µ = 3.05 mm^−1
c = 11.8453 (10) Å	T = 298 K
β = 111.155 (1)°	Block, colourless
V = 1085.9 (10) Å^3	0.22 × 0.17 × 0.16 mm
Z = 2

Data collection

Bruker APEX CCD diffractometer	1903 independent reflections
Radiation source: fine-focus sealed tube	1554 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.063
ϕ and ω scans	θmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→10
Tmin = 0.553, Tmax = 0.641	k = −13→12
5512 measured reflections	l = −14→14

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.117	H-atom parameters constrained
S = 1.14	w = 1/[σ^2(Fo^2) + (0.065P)^2] where P = (Fo^2 + 2Fc^2)/3
1903 reflections	(Δ/σ)max = 0.012
103 parameters	Δρmax = 1.54 e Å^−3
13 restraints	Δρmin = −2.07 e Å^−3

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

	x	y	z	Uiso*/Ueq
Sn1	0.99552 (5)	0.07346 (3)	0.37511 (4)	0.0383 (2)
Cl1	1.1769 (3)	−0.06088 (15)	0.3320 (2)	0.0619 (5)
Cl2	1.1500 (2)	0.24014 (15)	0.35788 (19)	0.0586 (5)
Cl3	0.7989 (3)	0.07190 (15)	0.17440 (19)	0.0629 (5)
N1	0.7652 (7)	0.3252 (5)	0.5241 (5)	0.0498 (14)
O1	0.8762 (6)	−0.0591 (4)	0.4372 (5)	0.0511 (10)
O2	0.8269 (5)	0.1862 (4)	0.4134 (4)	0.0461 (10)
C1	0.7018 (10)	−0.0904 (6)	0.3757 (7)	0.0556 (11)
H1A	0.6323	−0.0359	0.3974	0.083*
H1B	0.6828	−0.1677	0.3993	0.083*
H1C	0.6750	−0.0881	0.2897	0.083*
C2	0.8701 (8)	0.2657 (5)	0.4921 (6)	0.0438 (15)
H2	0.9832	0.2824	0.5290	0.053*
C3	0.8233 (14)	0.4147 (7)	0.6175 (10)	0.078 (3)
H3A	0.9420	0.4236	0.6411	0.117*
H3B	0.7968	0.3919	0.6864	0.117*
H3C	0.7696	0.4876	0.5864	0.117*
C4	0.5869 (9)	0.3028 (7)	0.4732 (9)	0.072 (2)
H4A	0.5679	0.2218	0.4517	0.109*
H4B	0.5372	0.3501	0.4023	0.109*
H4C	0.5377	0.3217	0.5319	0.109*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sn1	0.0438 (3)	0.0350 (3)	0.0425 (3)	0.00087 (17)	0.0231 (2)	0.00141 (16)
Cl1	0.0809 (14)	0.0551 (10)	0.0707 (13)	0.0188 (9)	0.0527 (11)	0.0088 (8)
Cl2	0.0610 (11)	0.0488 (9)	0.0764 (13)	−0.0084 (8)	0.0371 (10)	0.0094 (8)
Cl3	0.0709 (13)	0.0691 (12)	0.0452 (10)	0.0061 (9)	0.0165 (9)	0.0006 (8)
N1	0.056 (4)	0.044 (3)	0.059 (4)	0.008 (3)	0.032 (3)	0.000 (3)
O1	0.0531 (15)	0.0515 (15)	0.0514 (15)	−0.0033 (12)	0.0221 (12)	0.0004 (12)
O2	0.043 (2)	0.044 (2)	0.056 (3)	−0.001 (2)	0.023 (2)	−0.008 (2)
C1	0.0560 (14)	0.0550 (13)	0.0553 (14)	−0.0025 (9)	0.0195 (9)	0.0009 (9)
C2	0.048 (4)	0.044 (3)	0.044 (3)	0.003 (3)	0.022 (3)	−0.004 (3)
C3	0.097 (7)	0.065 (5)	0.083 (7)	0.001 (4)	0.046 (6)	−0.030 (4)
C4	0.051 (5)	0.071 (5)	0.099 (7)	0.016 (4)	0.031 (4)	0.000 (5)

Geometric parameters (Å, º)

Sn1—O1	2.106 (5)	O2—C2	1.259 (7)
Sn1—O1^i	2.101 (5)	C1—H1A	0.9600
Sn1—O2	2.108 (4)	C1—H1B	0.9600
Sn1—Cl1	2.372 (2)	C1—H1C	0.9600
Sn1—Cl2	2.3743 (18)	C2—H2	0.9300
Sn1—Cl3	2.368 (2)	C3—H3A	0.9600
N1—C2	1.291 (8)	C3—H3B	0.9600
N1—C4	1.452 (9)	C3—H3C	0.9600
N1—C3	1.457 (10)	C4—H4A	0.9600
O1—C1	1.455 (9)	C4—H4B	0.9600
O1—Sn1^i	2.101 (5)	C4—H4C	0.9600
O1^i—Sn1—O2	87.65 (18)	O1—C1—H1A	109.5
O1^i—Sn1—O1	73.1 (2)	O1—C1—H1B	109.5
O2—Sn1—O1	84.69 (19)	H1A—C1—H1B	109.5
O1^i—Sn1—Cl3	166.73 (15)	O1—C1—H1C	109.5
O2—Sn1—Cl3	85.64 (14)	H1A—C1—H1C	109.5
O1—Sn1—Cl3	94.86 (16)	H1B—C1—H1C	109.5
O1^i—Sn1—Cl1	92.45 (15)	O2—C2—N1	123.2 (6)
O2—Sn1—Cl1	177.31 (12)	O2—C2—H2	118.4
O1—Sn1—Cl1	92.76 (15)	N1—C2—H2	118.4
Cl3—Sn1—Cl1	93.72 (9)	N1—C3—H3A	109.5
O1^i—Sn1—Cl2	93.32 (14)	N1—C3—H3B	109.5
O2—Sn1—Cl2	88.59 (13)	H3A—C3—H3B	109.5
O1—Sn1—Cl2	165.05 (15)	N1—C3—H3C	109.5
Cl3—Sn1—Cl2	97.94 (8)	H3A—C3—H3C	109.5
Cl1—Sn1—Cl2	94.09 (8)	H3B—C3—H3C	109.5
C2—N1—C4	121.9 (6)	N1—C4—H4A	109.5
C2—N1—C3	120.6 (7)	N1—C4—H4B	109.5
C4—N1—C3	117.4 (6)	H4A—C4—H4B	109.5
C1—O1—Sn1^i	124.2 (4)	N1—C4—H4C	109.5
C1—O1—Sn1	123.0 (4)	H4A—C4—H4C	109.5
Sn1^i—O1—Sn1	106.9 (2)	H4B—C4—H4C	109.5
C2—O2—Sn1	124.0 (4)
O1^i—Sn1—O1—C1	154.0 (6)	Cl2—Sn1—O1—Sn1^i	−25.5 (7)
O2—Sn1—O1—C1	64.8 (5)	O1^i—Sn1—O2—C2	42.9 (5)
Cl3—Sn1—O1—C1	−20.3 (5)	O1—Sn1—O2—C2	116.2 (5)
Cl1—Sn1—O1—C1	−114.3 (5)	Cl3—Sn1—O2—C2	−148.5 (5)
Cl2—Sn1—O1—C1	128.5 (6)	Cl2—Sn1—O2—C2	−50.4 (5)
O1^i—Sn1—O1—Sn1^i	0.0	Sn1—O2—C2—N1	−171.9 (5)
O2—Sn1—O1—Sn1^i	−89.1 (2)	C4—N1—C2—O2	1.6 (10)
Cl3—Sn1—O1—Sn1^i	−174.30 (17)	C3—N1—C2—O2	178.8 (7)
Cl1—Sn1—O1—Sn1^i	91.72 (19)

Symmetry code: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1C···Cl3	0.96	2.72	3.356 (8)	124
C3—H3A···Cl3^ii	0.96	2.95	3.895 (11)	170
C4—H4B···Cl1^iii	0.96	2.90	3.837 (9)	164

Symmetry codes: (ii) x+1/2, −y+1/2, z+1/2; (iii) −x+3/2, y+1/2, −z+1/2.