metal-organic compounds
Di-μ-methanolato-κ4O:O-bis[trichlorido(dimethylformamide-κO)tin(IV)]
aCollege of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China
*Correspondence e-mail: handongyin@163.com
The title compound, [Sn2(CH3O)2Cl6(C3H7NO)2], contains two hexacoordinated SnIV 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 SnIV 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).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 2007); cell SAINT (Bruker, 2007); data reduction: SAINT; 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.
Supporting information
10.1107/S1600536810053997/hy2391sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536810053997/hy2391Isup2.hkl
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%.
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 Uiso(H) = 1.2(1.5 for methyl)Ueq(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.
Data collection: SMART (Bruker, 2007); cell
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).[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) Å3 | 0.22 × 0.17 × 0.16 mm |
Z = 2 |
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 on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 1.14 | w = 1/[σ2(Fo2) + (0.065P)2] where P = (Fo2 + 2Fc2)/3 |
1903 reflections | (Δ/σ)max = 0.012 |
103 parameters | Δρmax = 1.54 e Å−3 |
13 restraints | Δρmin = −2.07 e Å−3 |
[Sn2(CH3O)2Cl6(C3H7NO)2] | V = 1085.9 (10) Å3 |
Mr = 658.34 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.589 (8) Å | µ = 3.05 mm−1 |
b = 11.4444 (13) Å | T = 298 K |
c = 11.8453 (10) Å | 0.22 × 0.17 × 0.16 mm |
β = 111.155 (1)° |
Bruker APEX CCD diffractometer | 1903 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1554 reflections with I > 2σ(I) |
Tmin = 0.553, Tmax = 0.641 | Rint = 0.063 |
5512 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 13 restraints |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 1.14 | Δρmax = 1.54 e Å−3 |
1903 reflections | Δρmin = −2.07 e Å−3 |
103 parameters |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
Sn1—O1 | 2.106 (5) | O2—C2 | 1.259 (7) |
Sn1—O1i | 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—Sn1i | 2.101 (5) | C4—H4C | 0.9600 |
O1i—Sn1—O2 | 87.65 (18) | O1—C1—H1A | 109.5 |
O1i—Sn1—O1 | 73.1 (2) | O1—C1—H1B | 109.5 |
O2—Sn1—O1 | 84.69 (19) | H1A—C1—H1B | 109.5 |
O1i—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 |
O1i—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 |
O1i—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—Sn1i | 124.2 (4) | N1—C4—H4C | 109.5 |
C1—O1—Sn1 | 123.0 (4) | H4A—C4—H4C | 109.5 |
Sn1i—O1—Sn1 | 106.9 (2) | H4B—C4—H4C | 109.5 |
C2—O2—Sn1 | 124.0 (4) | ||
O1i—Sn1—O1—C1 | 154.0 (6) | Cl2—Sn1—O1—Sn1i | −25.5 (7) |
O2—Sn1—O1—C1 | 64.8 (5) | O1i—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) |
O1i—Sn1—O1—Sn1i | 0.0 | Sn1—O2—C2—N1 | −171.9 (5) |
O2—Sn1—O1—Sn1i | −89.1 (2) | C4—N1—C2—O2 | 1.6 (10) |
Cl3—Sn1—O1—Sn1i | −174.30 (17) | C3—N1—C2—O2 | 178.8 (7) |
Cl1—Sn1—O1—Sn1i | 91.72 (19) |
Symmetry code: (i) −x+2, −y, −z+1. |
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···Cl3ii | 0.96 | 2.95 | 3.895 (11) | 170 |
C4—H4B···Cl1iii | 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. |
Experimental details
Crystal data | |
Chemical formula | [Sn2(CH3O)2Cl6(C3H7NO)2] |
Mr | 658.34 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 8.589 (8), 11.4444 (13), 11.8453 (10) |
β (°) | 111.155 (1) |
V (Å3) | 1085.9 (10) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 3.05 |
Crystal size (mm) | 0.22 × 0.17 × 0.16 |
Data collection | |
Diffractometer | Bruker APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.553, 0.641 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5512, 1903, 1554 |
Rint | 0.063 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.117, 1.14 |
No. of reflections | 1903 |
No. of parameters | 103 |
No. of restraints | 13 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.54, −2.07 |
Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and X-SEED (Barbour, 2001), SHELXTL (Sheldrick, 2008).
Sn1—O1 | 2.106 (5) | Sn1—Cl1 | 2.372 (2) |
Sn1—O1i | 2.101 (5) | Sn1—Cl2 | 2.3743 (18) |
Sn1—O2 | 2.108 (4) | Sn1—Cl3 | 2.368 (2) |
Symmetry code: (i) −x+2, −y, −z+1. |
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···Cl3ii | 0.96 | 2.95 | 3.895 (11) | 170 |
C4—H4B···Cl1iii | 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. |
Acknowledgements
We acknowledge the National Natural Science Foundation of China (grant No. 20771053), the National Basic Research Program (grant No. 2010CB234601) and the Natural Science Foundation of Shandong Province (Y2008B48) for financial support. This work was also supported by the Shandong Tai-Shan Scholar Research Fund.
References
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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The title compound (Fig.1) consists of six Cl anions, two methoxo anions, two SnIV 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 SnIV 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.