metal-organic compounds
Dimethylbis(pyrazine-2-carboxylato-κ2N1,O)tin(IV)
aDepartment of Chemistry, General Campus, Shahid Beheshti University, Tehran 1983963113, Iran, and bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: m-pouramini@cc.sbu.ac.ir
In the title compound, [Sn(CH3)2(C5H3N2O2)2], the SnIV atom is twice N,O-chelated by two pyrazine-2-carboxylate ligands. The distorted six-coordination is completed by two tin-bound methyl C atoms. The C2N2O2 donor set defines a skewed trapezoidal–bipyramidal geometry. Intermolecular π–π interactions between the pyrazine rings [centroid–centroid distance = 3.8112 (13) Å] are observed.
Related literature
For background to organotin compounds, see: Dakternieks et al. (2003); Tiekink (1991); Yin et al. (2005).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (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: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
10.1107/S160053681204295X/hy2594sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S160053681204295X/hy2594Isup2.hkl
Dimethyltin dichloride (0.22 g, 1 mmol) was treated with sodium methoxide (0.1 g, 2 mmol) in methanol (10 ml) to produce dimethyltin dimethoxide and sodium chloride. The sodium chloride precipitate was removed by filtration and then pyrazine-2-carboxylic acid (0.248 g, 2 mmol) in methanol (20 ml) was added to the filtrate. The solution was refluxed for 3 h. Evaporation of the solvent yielded a white solid, which was purified by recrystallization from methanol (yield: 70%. m.p.: 118–120°C).
H atoms were placed in calculated positions and refined as riding atoms, with C–H = 0.93 (CH) and 0.96 (CH3) Å and with Uiso(H) = 1.2(1.5 for methyl)Ueq(C). Omitted reflections owing to bad disagreement were (-9 10 6), (-6 13 3), (8 0 4), (2 0 8) and (-1 8 6).
Data collection: APEX2 (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: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. |
[Sn(CH3)2(C5H3N2O2)2] | F(000) = 776 |
Mr = 394.95 | Dx = 1.863 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5890 reflections |
a = 9.2887 (6) Å | θ = 2.3–28.3° |
b = 12.3253 (7) Å | µ = 1.84 mm−1 |
c = 12.6596 (7) Å | T = 295 K |
β = 103.738 (1)° | Prism, colorless |
V = 1407.88 (14) Å3 | 0.40 × 0.40 × 0.20 mm |
Z = 4 |
Bruker APEXII CCD diffractometer | 3193 independent reflections |
Radiation source: fine-focus sealed tube | 2892 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ϕ and ω scans | θmax = 27.5°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→11 |
Tmin = 0.527, Tmax = 0.710 | k = −16→13 |
8657 measured reflections | l = −15→16 |
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)] = 0.020 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.051 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0201P)2 + 0.7349P] where P = (Fo2 + 2Fc2)/3 |
3193 reflections | (Δ/σ)max = 0.001 |
192 parameters | Δρmax = 0.35 e Å−3 |
0 restraints | Δρmin = −0.47 e Å−3 |
[Sn(CH3)2(C5H3N2O2)2] | V = 1407.88 (14) Å3 |
Mr = 394.95 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.2887 (6) Å | µ = 1.84 mm−1 |
b = 12.3253 (7) Å | T = 295 K |
c = 12.6596 (7) Å | 0.40 × 0.40 × 0.20 mm |
β = 103.738 (1)° |
Bruker APEXII CCD diffractometer | 3193 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2892 reflections with I > 2σ(I) |
Tmin = 0.527, Tmax = 0.710 | Rint = 0.022 |
8657 measured reflections |
R[F2 > 2σ(F2)] = 0.020 | 0 restraints |
wR(F2) = 0.051 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.35 e Å−3 |
3193 reflections | Δρmin = −0.47 e Å−3 |
192 parameters |
x | y | z | Uiso*/Ueq | ||
Sn1 | 0.826212 (14) | 0.699389 (11) | 0.602141 (11) | 0.02943 (6) | |
O1 | 0.87907 (17) | 0.71196 (14) | 0.44616 (13) | 0.0415 (4) | |
O2 | 0.99121 (19) | 0.78275 (16) | 0.32619 (13) | 0.0493 (4) | |
O3 | 0.62830 (16) | 0.65997 (14) | 0.48535 (12) | 0.0374 (3) | |
O4 | 0.39196 (17) | 0.61066 (15) | 0.43503 (13) | 0.0469 (4) | |
N1 | 1.09601 (19) | 0.77904 (14) | 0.61292 (14) | 0.0320 (4) | |
N2 | 1.3488 (2) | 0.87890 (18) | 0.57415 (17) | 0.0478 (5) | |
N3 | 0.62453 (19) | 0.65022 (15) | 0.69497 (14) | 0.0340 (4) | |
N4 | 0.3759 (2) | 0.57674 (16) | 0.76062 (16) | 0.0421 (4) | |
C1 | 0.7815 (3) | 0.86219 (19) | 0.6305 (2) | 0.0466 (6) | |
H1A | 0.8346 | 0.9084 | 0.5918 | 0.070* | |
H1B | 0.8123 | 0.8772 | 0.7070 | 0.070* | |
H1C | 0.6770 | 0.8755 | 0.6057 | 0.070* | |
C2 | 0.9233 (3) | 0.54697 (19) | 0.6433 (2) | 0.0444 (5) | |
H2A | 1.0075 | 0.5391 | 0.6123 | 0.067* | |
H2B | 0.8523 | 0.4912 | 0.6155 | 0.067* | |
H2C | 0.9546 | 0.5408 | 0.7210 | 0.067* | |
C3 | 0.9857 (2) | 0.76167 (19) | 0.41998 (17) | 0.0346 (4) | |
C4 | 1.1116 (2) | 0.79754 (16) | 0.51203 (17) | 0.0302 (4) | |
C5 | 1.2359 (3) | 0.8484 (2) | 0.49323 (19) | 0.0405 (5) | |
H5 | 1.2409 | 0.8618 | 0.4219 | 0.049* | |
C6 | 1.3319 (3) | 0.86057 (19) | 0.67419 (19) | 0.0417 (5) | |
H6 | 1.4074 | 0.8812 | 0.7331 | 0.050* | |
C7 | 1.2068 (3) | 0.81211 (17) | 0.69396 (18) | 0.0361 (5) | |
H7 | 1.1996 | 0.8023 | 0.7654 | 0.043* | |
C12 | 0.6207 (3) | 0.6469 (2) | 0.79961 (18) | 0.0445 (6) | |
H12 | 0.7030 | 0.6696 | 0.8523 | 0.053* | |
C13 | 0.4970 (3) | 0.6103 (2) | 0.83094 (19) | 0.0449 (6) | |
H13 | 0.4986 | 0.6092 | 0.9047 | 0.054* | |
C14 | 0.3798 (2) | 0.58104 (18) | 0.65644 (18) | 0.0367 (5) | |
H14 | 0.2974 | 0.5577 | 0.6042 | 0.044* | |
C15 | 0.5024 (2) | 0.61905 (16) | 0.62266 (16) | 0.0295 (4) | |
C16 | 0.5045 (2) | 0.62962 (16) | 0.50495 (17) | 0.0321 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn1 | 0.02845 (8) | 0.03258 (9) | 0.02919 (9) | 0.00030 (5) | 0.01068 (6) | 0.00025 (5) |
O1 | 0.0333 (8) | 0.0637 (11) | 0.0291 (8) | −0.0101 (7) | 0.0106 (6) | −0.0007 (7) |
O2 | 0.0415 (9) | 0.0830 (13) | 0.0266 (8) | −0.0074 (8) | 0.0144 (7) | 0.0015 (8) |
O3 | 0.0337 (8) | 0.0518 (9) | 0.0280 (7) | −0.0071 (7) | 0.0097 (6) | 0.0015 (7) |
O4 | 0.0346 (8) | 0.0667 (11) | 0.0359 (8) | −0.0095 (8) | 0.0012 (7) | −0.0012 (8) |
N1 | 0.0310 (9) | 0.0379 (9) | 0.0296 (9) | 0.0011 (7) | 0.0123 (7) | 0.0020 (7) |
N2 | 0.0421 (11) | 0.0589 (13) | 0.0449 (11) | −0.0164 (9) | 0.0151 (9) | −0.0052 (10) |
N3 | 0.0278 (8) | 0.0442 (10) | 0.0309 (9) | −0.0032 (7) | 0.0088 (7) | −0.0047 (8) |
N4 | 0.0380 (10) | 0.0471 (11) | 0.0464 (11) | −0.0019 (8) | 0.0203 (9) | 0.0023 (9) |
C1 | 0.0429 (13) | 0.0383 (12) | 0.0571 (15) | 0.0043 (10) | 0.0089 (11) | −0.0073 (11) |
C2 | 0.0437 (13) | 0.0380 (12) | 0.0511 (14) | 0.0060 (10) | 0.0104 (11) | 0.0047 (10) |
C3 | 0.0303 (10) | 0.0456 (12) | 0.0303 (10) | 0.0039 (9) | 0.0119 (8) | −0.0010 (9) |
C4 | 0.0287 (10) | 0.0363 (10) | 0.0289 (10) | 0.0026 (8) | 0.0134 (8) | −0.0002 (8) |
C5 | 0.0397 (12) | 0.0510 (13) | 0.0353 (11) | −0.0075 (10) | 0.0175 (9) | 0.0000 (10) |
C6 | 0.0394 (12) | 0.0449 (13) | 0.0404 (12) | −0.0090 (10) | 0.0082 (10) | −0.0043 (10) |
C7 | 0.0402 (12) | 0.0396 (11) | 0.0296 (11) | 0.0002 (9) | 0.0106 (9) | −0.0006 (8) |
C12 | 0.0348 (11) | 0.0687 (16) | 0.0308 (11) | −0.0037 (11) | 0.0093 (9) | −0.0065 (11) |
C13 | 0.0424 (12) | 0.0627 (15) | 0.0338 (11) | 0.0054 (11) | 0.0171 (10) | 0.0010 (11) |
C14 | 0.0301 (10) | 0.0415 (12) | 0.0399 (12) | −0.0040 (9) | 0.0109 (9) | −0.0025 (9) |
C15 | 0.0276 (9) | 0.0286 (10) | 0.0333 (10) | 0.0016 (7) | 0.0091 (8) | −0.0016 (8) |
C16 | 0.0305 (10) | 0.0330 (10) | 0.0328 (10) | −0.0004 (8) | 0.0079 (8) | −0.0006 (8) |
Sn1—C1 | 2.097 (2) | C1—H1A | 0.9600 |
Sn1—C2 | 2.095 (2) | C1—H1B | 0.9600 |
Sn1—O1 | 2.1506 (16) | C1—H1C | 0.9600 |
Sn1—O3 | 2.1238 (15) | C2—H2A | 0.9600 |
Sn1—N1 | 2.6646 (18) | C2—H2B | 0.9600 |
Sn1—N3 | 2.5107 (18) | C2—H2C | 0.9600 |
O1—C3 | 1.274 (3) | C3—C4 | 1.508 (3) |
O2—C3 | 1.228 (3) | C4—C5 | 1.383 (3) |
O3—C16 | 1.288 (3) | C5—H5 | 0.9300 |
O4—C16 | 1.221 (2) | C6—C7 | 1.382 (3) |
N1—C7 | 1.332 (3) | C6—H6 | 0.9300 |
N1—C4 | 1.339 (3) | C7—H7 | 0.9300 |
N2—C6 | 1.332 (3) | C12—C13 | 1.378 (3) |
N2—C5 | 1.334 (3) | C12—H12 | 0.9300 |
N3—C12 | 1.334 (3) | C13—H13 | 0.9300 |
N3—C15 | 1.334 (3) | C14—C15 | 1.389 (3) |
N4—C13 | 1.324 (3) | C14—H14 | 0.9300 |
N4—C14 | 1.329 (3) | C15—C16 | 1.501 (3) |
C2—Sn1—C1 | 154.98 (10) | Sn1—C2—H2C | 109.5 |
C2—Sn1—O3 | 102.62 (8) | H2A—C2—H2C | 109.5 |
C1—Sn1—O3 | 99.44 (8) | H2B—C2—H2C | 109.5 |
C2—Sn1—O1 | 96.58 (8) | O2—C3—O1 | 124.5 (2) |
C1—Sn1—O1 | 100.72 (9) | O2—C3—C4 | 118.9 (2) |
O3—Sn1—O1 | 74.09 (6) | O1—C3—C4 | 116.63 (18) |
C2—Sn1—N3 | 89.54 (8) | N1—C4—C5 | 121.7 (2) |
C1—Sn1—N3 | 87.17 (9) | N1—C4—C3 | 116.59 (18) |
O3—Sn1—N3 | 69.63 (6) | C5—C4—C3 | 121.71 (19) |
O1—Sn1—N3 | 143.67 (6) | N2—C5—C4 | 122.1 (2) |
C2—Sn1—N1 | 88.49 (8) | N2—C5—H5 | 118.9 |
C1—Sn1—N1 | 82.01 (8) | C4—C5—H5 | 118.9 |
O3—Sn1—N1 | 140.17 (5) | N2—C6—C7 | 122.7 (2) |
O1—Sn1—N1 | 66.64 (6) | N2—C6—H6 | 118.7 |
N3—Sn1—N1 | 149.56 (5) | C7—C6—H6 | 118.7 |
C3—O1—Sn1 | 129.40 (14) | N1—C7—C6 | 121.4 (2) |
C16—O3—Sn1 | 126.66 (13) | N1—C7—H7 | 119.3 |
C7—N1—C4 | 116.35 (18) | C6—C7—H7 | 119.3 |
C7—N1—Sn1 | 134.17 (14) | N3—C12—C13 | 121.1 (2) |
C4—N1—Sn1 | 109.12 (13) | N3—C12—H12 | 119.5 |
C6—N2—C5 | 115.7 (2) | C13—C12—H12 | 119.5 |
C12—N3—C15 | 116.99 (19) | N4—C13—C12 | 122.8 (2) |
C12—N3—Sn1 | 132.12 (15) | N4—C13—H13 | 118.6 |
C15—N3—Sn1 | 110.85 (13) | C12—C13—H13 | 118.6 |
C13—N4—C14 | 115.86 (19) | N4—C14—C15 | 122.4 (2) |
Sn1—C1—H1A | 109.5 | N4—C14—H14 | 118.8 |
Sn1—C1—H1B | 109.5 | C15—C14—H14 | 118.8 |
H1A—C1—H1B | 109.5 | N3—C15—C14 | 120.76 (19) |
Sn1—C1—H1C | 109.5 | N3—C15—C16 | 116.52 (18) |
H1A—C1—H1C | 109.5 | C14—C15—C16 | 122.70 (18) |
H1B—C1—H1C | 109.5 | O4—C16—O3 | 124.5 (2) |
Sn1—C2—H2A | 109.5 | O4—C16—C15 | 119.47 (19) |
Sn1—C2—H2B | 109.5 | O3—C16—C15 | 116.07 (17) |
H2A—C2—H2B | 109.5 | ||
C2—Sn1—O1—C3 | −98.1 (2) | C7—N1—C4—C5 | −0.1 (3) |
C1—Sn1—O1—C3 | 63.8 (2) | Sn1—N1—C4—C5 | 173.91 (17) |
O3—Sn1—O1—C3 | 160.6 (2) | C7—N1—C4—C3 | −179.20 (18) |
N3—Sn1—O1—C3 | 163.69 (17) | Sn1—N1—C4—C3 | −5.2 (2) |
N1—Sn1—O1—C3 | −12.59 (18) | O2—C3—C4—N1 | 175.7 (2) |
C2—Sn1—O3—C16 | 83.58 (19) | O1—C3—C4—N1 | −3.5 (3) |
C1—Sn1—O3—C16 | −84.53 (19) | O2—C3—C4—C5 | −3.4 (3) |
O1—Sn1—O3—C16 | 176.92 (19) | O1—C3—C4—C5 | 177.4 (2) |
N3—Sn1—O3—C16 | −1.15 (17) | C6—N2—C5—C4 | −2.2 (4) |
N1—Sn1—O3—C16 | −173.35 (15) | N1—C4—C5—N2 | 2.0 (4) |
C2—Sn1—N1—C7 | −81.4 (2) | C3—C4—C5—N2 | −178.9 (2) |
C1—Sn1—N1—C7 | 75.4 (2) | C5—N2—C6—C7 | 0.7 (4) |
O3—Sn1—N1—C7 | 170.55 (17) | C4—N1—C7—C6 | −1.4 (3) |
O1—Sn1—N1—C7 | −179.2 (2) | Sn1—N1—C7—C6 | −173.53 (16) |
N3—Sn1—N1—C7 | 5.1 (3) | N2—C6—C7—N1 | 1.2 (4) |
C2—Sn1—N1—C4 | 106.05 (15) | C15—N3—C12—C13 | 1.5 (4) |
C1—Sn1—N1—C4 | −97.16 (15) | Sn1—N3—C12—C13 | −175.99 (18) |
O3—Sn1—N1—C4 | −1.98 (18) | C14—N4—C13—C12 | −0.5 (4) |
O1—Sn1—N1—C4 | 8.22 (13) | N3—C12—C13—N4 | 0.0 (4) |
N3—Sn1—N1—C4 | −167.44 (13) | C13—N4—C14—C15 | −0.5 (3) |
C2—Sn1—N3—C12 | 77.7 (2) | C12—N3—C15—C14 | −2.4 (3) |
C1—Sn1—N3—C12 | −77.5 (2) | Sn1—N3—C15—C14 | 175.58 (16) |
O3—Sn1—N3—C12 | −178.7 (2) | C12—N3—C15—C16 | 176.3 (2) |
O1—Sn1—N3—C12 | 178.2 (2) | Sn1—N3—C15—C16 | −5.6 (2) |
N1—Sn1—N3—C12 | −8.5 (3) | N4—C14—C15—N3 | 2.0 (3) |
C2—Sn1—N3—C15 | −99.93 (15) | N4—C14—C15—C16 | −176.7 (2) |
C1—Sn1—N3—C15 | 104.88 (15) | Sn1—O3—C16—O4 | 177.83 (17) |
O3—Sn1—N3—C15 | 3.72 (13) | Sn1—O3—C16—C15 | −1.4 (3) |
O1—Sn1—N3—C15 | 0.6 (2) | N3—C15—C16—O4 | −174.2 (2) |
N1—Sn1—N3—C15 | 173.84 (12) | C14—C15—C16—O4 | 4.6 (3) |
Sn1—O1—C3—O2 | −164.70 (18) | N3—C15—C16—O3 | 5.1 (3) |
Sn1—O1—C3—C4 | 14.5 (3) | C14—C15—C16—O3 | −176.11 (19) |
Experimental details
Crystal data | |
Chemical formula | [Sn(CH3)2(C5H3N2O2)2] |
Mr | 394.95 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 295 |
a, b, c (Å) | 9.2887 (6), 12.3253 (7), 12.6596 (7) |
β (°) | 103.738 (1) |
V (Å3) | 1407.88 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.84 |
Crystal size (mm) | 0.40 × 0.40 × 0.20 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.527, 0.710 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8657, 3193, 2892 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.020, 0.051, 1.06 |
No. of reflections | 3193 |
No. of parameters | 192 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.35, −0.47 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).
Sn1—C1 | 2.097 (2) | Sn1—O3 | 2.1238 (15) |
Sn1—C2 | 2.095 (2) | Sn1—N1 | 2.6646 (18) |
Sn1—O1 | 2.1506 (16) | Sn1—N3 | 2.5107 (18) |
Acknowledgements
We thank Shahid Beheshti University for supporting this study.
References
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The reaction of appropriate amount of dimethyltin dichloride and pyrazine-2-carboxylic acid in dry methanol provided the title compound in good yield. The six-coordinated geometry around the SnIV atom is better described as skew-trapezoidal bipyramidal (Fig. 1, Table 1). Intermolecular π–π interactions between the pyrazine rings [centroid–centroid distance = 3.8112 (13) Å] stabilize the structure.