Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105025989/jz1743sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105025989/jz1743Isup2.hkl |
CCDC reference: 187212
The title compound was prepared according to the method of Dokorou (2005). The crystals used for data collection were grown from an ethanol solution by slow evaporation.
All C-bound H atoms were placed in calculated positions and were refined as riding on their adjacent C atom, with C—H distances in the range 0.93–0.97 Å and with Uiso(H) = 1.2Ueq(Cnon-methyl) or 1.5Ueq(Cmethyl)]. The methyl groups were allowed to rotate about their local threefold axis (AFIX 137). The N-bound H atom was found in the difference Fourier synthesis and was refined as riding on its parent N atom at an N—H distance of 0.92 Å, with the isotropic displacement parameter free to refine. [Please check added distances]
Data collection: CrysAlis CCD (UNIL IC and Kuma, 2000); cell refinement: CrysAlis RED (UNIL IC and Kuma, 2000); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL/PC (Sheldrick, 1990b) and ORTEP-3 for Windows (version 1.062; Farrugia 1997); software used to prepare material for publication: SHELXL97.
[Sn4(CH3)8(C13H8Cl2NO2)2(C2H5O)2O2] | F(000) = 1248 |
Mr = 1279.36 | Dx = 1.785 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 14.0875 (6) Å | Cell parameters from 6140 reflections |
b = 9.7613 (4) Å | θ = 2–20° |
c = 17.5858 (8) Å | µ = 2.35 mm−1 |
β = 100.106 (3)° | T = 291 K |
V = 2380.74 (18) Å3 | Needle, orange |
Z = 2 | 0.53 × 0.07 × 0.07 mm |
Kuma KM4 CCD area-detector diffractometer | 4230 independent reflections |
Radiation source: fine-focus sealed tube | 3656 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
ω scans | θmax = 25.1°, θmin = 3.4° |
Absorption correction: numerical (X-RED; Stoe & Cie, 1999) | h = −16→16 |
Tmin = 0.518, Tmax = 0.894 | k = 10→11 |
27541 measured reflections | l = −20→20 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: structure-invariant direct methods |
R[F2 > 2σ(F2)] = 0.027 | Hydrogen site location: diffmap |
wR(F2) = 0.063 | H-atom parameters constrained |
S = 1.15 | w = 1/[σ2(Fo2) + (0.0294P)2 + 0.8584P] where P = (Fo2 + 2Fc2)/3 |
4230 reflections | (Δ/σ)max = 0.001 |
259 parameters | Δρmax = 1.10 e Å−3 |
0 restraints | Δρmin = −0.50 e Å−3 |
[Sn4(CH3)8(C13H8Cl2NO2)2(C2H5O)2O2] | V = 2380.74 (18) Å3 |
Mr = 1279.36 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 14.0875 (6) Å | µ = 2.35 mm−1 |
b = 9.7613 (4) Å | T = 291 K |
c = 17.5858 (8) Å | 0.53 × 0.07 × 0.07 mm |
β = 100.106 (3)° |
Kuma KM4 CCD area-detector diffractometer | 4230 independent reflections |
Absorption correction: numerical (X-RED; Stoe & Cie, 1999) | 3656 reflections with I > 2σ(I) |
Tmin = 0.518, Tmax = 0.894 | Rint = 0.036 |
27541 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
wR(F2) = 0.063 | H-atom parameters constrained |
S = 1.15 | Δρmax = 1.10 e Å−3 |
4230 reflections | Δρmin = −0.50 e Å−3 |
259 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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. |
x | y | z | Uiso*/Ueq | ||
Sn1 | 0.471301 (17) | 0.03647 (2) | 0.085414 (14) | 0.03253 (8) | |
O3 | 0.55398 (17) | −0.0917 (2) | 0.03312 (13) | 0.0367 (6) | |
O4 | 0.53620 (19) | −0.1049 (3) | 0.17197 (14) | 0.0426 (6) | |
Sn2 | 0.608001 (18) | −0.24902 (2) | 0.102016 (14) | 0.03517 (8) | |
C1 | 0.7400 (3) | −0.4772 (4) | −0.0642 (2) | 0.0396 (9) | |
C2 | 0.7974 (3) | −0.5958 (4) | −0.0615 (2) | 0.0441 (9) | |
C3 | 0.8211 (3) | −0.6448 (5) | −0.1307 (3) | 0.0591 (12) | |
H3 | 0.8576 | −0.7243 | −0.1300 | 0.071* | |
C4 | 0.7918 (4) | −0.5788 (5) | −0.1986 (3) | 0.0650 (13) | |
H4 | 0.8081 | −0.6140 | −0.2438 | 0.078* | |
C5 | 0.7385 (4) | −0.4606 (5) | −0.2016 (3) | 0.0635 (13) | |
H5 | 0.7197 | −0.4148 | −0.2482 | 0.076* | |
C6 | 0.7130 (3) | −0.4107 (5) | −0.1347 (2) | 0.0532 (11) | |
H6 | 0.6768 | −0.3307 | −0.1368 | 0.064* | |
N1 | 0.8241 (3) | −0.6661 (4) | 0.0071 (2) | 0.0551 (9) | |
H1N | 0.7852 | −0.6562 | 0.0435 | 0.061 (13)* | |
C8 | 0.9060 (3) | −0.7469 (4) | 0.0284 (2) | 0.0445 (10) | |
C9 | 0.9049 (3) | −0.8484 (4) | 0.0842 (2) | 0.0403 (9) | |
C10 | 0.9864 (3) | −0.9260 (4) | 0.1103 (2) | 0.0493 (10) | |
C11 | 1.0694 (3) | −0.9083 (5) | 0.0809 (3) | 0.0634 (13) | |
H11 | 1.1231 | −0.9631 | 0.0974 | 0.076* | |
C12 | 1.0716 (3) | −0.8076 (5) | 0.0265 (3) | 0.0658 (13) | |
H12 | 1.1279 | −0.7933 | 0.0068 | 0.079* | |
C13 | 0.9917 (3) | −0.7275 (5) | 0.0004 (3) | 0.0584 (12) | |
H13 | 0.9951 | −0.6598 | −0.0362 | 0.070* | |
Cl1 | 0.80140 (8) | −0.87167 (13) | 0.12217 (7) | 0.0619 (3) | |
Cl2 | 0.98415 (9) | −1.05157 (14) | 0.17976 (8) | 0.0743 (4) | |
C7 | 0.7039 (3) | −0.4257 (4) | 0.0053 (2) | 0.0427 (9) | |
O1 | 0.66257 (19) | −0.3075 (3) | −0.00124 (15) | 0.0471 (7) | |
O2 | 0.7110 (2) | −0.4937 (3) | 0.06478 (17) | 0.0583 (8) | |
C14 | 0.3271 (3) | −0.0202 (5) | 0.0867 (3) | 0.0549 (11) | |
H14A | 0.3130 | −0.1045 | 0.0589 | 0.082* | |
H14B | 0.2847 | 0.0504 | 0.0628 | 0.082* | |
H14C | 0.3181 | −0.0324 | 0.1392 | 0.082* | |
C15 | 0.5441 (3) | 0.2151 (4) | 0.1320 (3) | 0.0582 (12) | |
H15A | 0.5985 | 0.1898 | 0.1703 | 0.087* | |
H15B | 0.5010 | 0.2709 | 0.1553 | 0.087* | |
H15C | 0.5658 | 0.2657 | 0.0915 | 0.087* | |
C16 | 0.5010 (3) | −0.3983 (5) | 0.1015 (3) | 0.0644 (13) | |
H16A | 0.4388 | −0.3581 | 0.0840 | 0.097* | |
H16B | 0.5039 | −0.4335 | 0.1528 | 0.097* | |
H16C | 0.5112 | −0.4715 | 0.0674 | 0.097* | |
C17 | 0.7414 (3) | −0.2255 (5) | 0.1761 (3) | 0.0644 (13) | |
H17A | 0.7922 | −0.2235 | 0.1462 | 0.097* | |
H17B | 0.7515 | −0.3010 | 0.2116 | 0.097* | |
H17C | 0.7415 | −0.1413 | 0.2043 | 0.097* | |
C18 | 0.5096 (4) | −0.1322 (5) | 0.2448 (2) | 0.0657 (13) | |
H18A | 0.5361 | −0.2202 | 0.2635 | 0.079* | |
H18B | 0.4400 | −0.1384 | 0.2383 | 0.079* | |
C19 | 0.5436 (5) | −0.0270 (6) | 0.3027 (3) | 0.095 (2) | |
H19A | 0.6126 | −0.0211 | 0.3099 | 0.143* | |
H19B | 0.5245 | −0.0509 | 0.3508 | 0.143* | |
H19C | 0.5160 | 0.0598 | 0.2853 | 0.143* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn1 | 0.03505 (14) | 0.02918 (14) | 0.03465 (14) | 0.00643 (10) | 0.00966 (10) | 0.00158 (10) |
O3 | 0.0429 (14) | 0.0338 (13) | 0.0355 (13) | 0.0155 (11) | 0.0126 (11) | 0.0084 (11) |
O4 | 0.0581 (17) | 0.0379 (14) | 0.0340 (14) | 0.0146 (13) | 0.0142 (12) | 0.0090 (11) |
Sn2 | 0.03702 (15) | 0.02837 (14) | 0.04002 (15) | 0.00708 (10) | 0.00652 (11) | 0.00750 (11) |
C1 | 0.036 (2) | 0.038 (2) | 0.047 (2) | 0.0020 (17) | 0.0116 (17) | 0.0004 (18) |
C2 | 0.050 (2) | 0.036 (2) | 0.049 (2) | 0.0044 (18) | 0.0135 (19) | 0.0023 (18) |
C3 | 0.075 (3) | 0.051 (3) | 0.056 (3) | 0.014 (2) | 0.023 (2) | −0.005 (2) |
C4 | 0.082 (3) | 0.071 (3) | 0.046 (3) | 0.010 (3) | 0.023 (2) | −0.003 (2) |
C5 | 0.078 (3) | 0.073 (3) | 0.041 (2) | 0.015 (3) | 0.016 (2) | 0.013 (2) |
C6 | 0.052 (3) | 0.055 (3) | 0.054 (3) | 0.011 (2) | 0.012 (2) | 0.010 (2) |
N1 | 0.069 (2) | 0.052 (2) | 0.050 (2) | 0.0281 (19) | 0.0238 (18) | 0.0087 (18) |
C8 | 0.047 (2) | 0.040 (2) | 0.047 (2) | 0.0107 (18) | 0.0113 (19) | −0.0054 (18) |
C9 | 0.039 (2) | 0.041 (2) | 0.040 (2) | 0.0067 (17) | 0.0059 (16) | −0.0084 (17) |
C10 | 0.049 (2) | 0.046 (2) | 0.050 (2) | 0.0079 (19) | 0.0000 (19) | −0.0020 (19) |
C11 | 0.042 (3) | 0.071 (3) | 0.075 (3) | 0.011 (2) | 0.004 (2) | 0.000 (3) |
C12 | 0.042 (3) | 0.076 (3) | 0.083 (4) | 0.002 (2) | 0.020 (2) | −0.011 (3) |
C13 | 0.065 (3) | 0.049 (3) | 0.065 (3) | 0.001 (2) | 0.020 (2) | 0.000 (2) |
Cl1 | 0.0511 (6) | 0.0751 (8) | 0.0623 (7) | 0.0134 (6) | 0.0182 (5) | 0.0153 (6) |
Cl2 | 0.0695 (8) | 0.0776 (9) | 0.0724 (8) | 0.0205 (7) | 0.0028 (6) | 0.0250 (7) |
C7 | 0.037 (2) | 0.042 (2) | 0.050 (2) | 0.0080 (17) | 0.0104 (18) | 0.0017 (19) |
O1 | 0.0566 (17) | 0.0371 (15) | 0.0507 (16) | 0.0180 (13) | 0.0180 (13) | 0.0050 (13) |
O2 | 0.078 (2) | 0.0546 (18) | 0.0481 (17) | 0.0291 (16) | 0.0268 (15) | 0.0146 (15) |
C14 | 0.040 (2) | 0.072 (3) | 0.054 (3) | −0.002 (2) | 0.013 (2) | 0.006 (2) |
C15 | 0.058 (3) | 0.043 (2) | 0.070 (3) | 0.000 (2) | 0.002 (2) | −0.004 (2) |
C16 | 0.064 (3) | 0.055 (3) | 0.076 (3) | −0.012 (2) | 0.017 (2) | −0.004 (3) |
C17 | 0.048 (3) | 0.072 (3) | 0.068 (3) | 0.008 (2) | −0.005 (2) | 0.003 (3) |
C18 | 0.093 (4) | 0.062 (3) | 0.045 (3) | 0.016 (3) | 0.020 (2) | 0.015 (2) |
C19 | 0.142 (6) | 0.094 (4) | 0.050 (3) | 0.014 (4) | 0.018 (3) | −0.011 (3) |
Sn1—O3 | 2.036 (2) | C9—Cl1 | 1.722 (4) |
Sn1—C14 | 2.109 (4) | C10—C11 | 1.370 (6) |
Sn1—C15 | 2.114 (4) | C10—Cl2 | 1.734 (4) |
Sn1—O3i | 2.122 (2) | C11—C12 | 1.376 (7) |
Sn1—O4 | 2.137 (2) | C11—H11 | 0.9300 |
O3—Sn1i | 2.122 (2) | C12—C13 | 1.381 (6) |
Sn2—O3 | 2.020 (2) | C12—H12 | 0.9300 |
O4—C18 | 1.421 (5) | C13—H13 | 0.9300 |
Sn2—O4 | 2.226 (2) | C7—O2 | 1.229 (5) |
Sn2—C16 | 2.096 (4) | C7—O1 | 1.289 (4) |
Sn2—C17 | 2.103 (4) | C14—H14A | 0.9600 |
Sn2—O1 | 2.169 (3) | C14—H14B | 0.9600 |
C1—C6 | 1.393 (5) | C14—H14C | 0.9600 |
C1—C2 | 1.409 (5) | C15—H15A | 0.9600 |
C1—C7 | 1.490 (5) | C15—H15B | 0.9600 |
C2—N1 | 1.380 (5) | C15—H15C | 0.9600 |
C2—C3 | 1.401 (6) | C16—H16A | 0.9600 |
C3—C4 | 1.357 (6) | C16—H16B | 0.9600 |
C3—H3 | 0.9300 | C16—H16C | 0.9600 |
C4—C5 | 1.373 (6) | C17—H17A | 0.9600 |
C4—H4 | 0.9300 | C17—H17B | 0.9600 |
C5—C6 | 1.377 (6) | C17—H17C | 0.9600 |
C5—H5 | 0.9300 | C18—C19 | 1.466 (7) |
C6—H6 | 0.9300 | C18—H18A | 0.9700 |
N1—C8 | 1.394 (5) | C18—H18B | 0.9700 |
N1—H1N | 0.9187 | C19—H19A | 0.9600 |
C8—C13 | 1.393 (6) | C19—H19B | 0.9600 |
C8—C9 | 1.396 (5) | C19—H19C | 0.9600 |
C9—C10 | 1.385 (5) | ||
O3—Sn1—C14 | 118.17 (15) | C11—C10—C9 | 121.2 (4) |
O3—Sn1—C15 | 113.89 (15) | C11—C10—Cl2 | 118.5 (3) |
C14—Sn1—C15 | 127.94 (18) | C9—C10—Cl2 | 120.3 (3) |
O3—Sn1—O3i | 73.92 (10) | C10—C11—C12 | 118.6 (4) |
C14—Sn1—O3i | 94.68 (13) | C10—C11—H11 | 120.7 |
C15—Sn1—O3i | 99.06 (15) | C12—C11—H11 | 120.7 |
O3—Sn1—O4 | 73.61 (9) | C11—C12—C13 | 121.2 (4) |
C14—Sn1—O4 | 96.61 (14) | C11—C12—H12 | 119.4 |
C15—Sn1—O4 | 97.98 (14) | C13—C12—H12 | 119.4 |
O3i—Sn1—O4 | 147.22 (9) | C12—C13—C8 | 120.8 (4) |
Sn2—O3—Sn1 | 112.42 (11) | C12—C13—H13 | 119.6 |
Sn2—O3—Sn1i | 139.72 (12) | C8—C13—H13 | 119.6 |
Sn1—O3—Sn1i | 106.08 (10) | O2—C7—O1 | 121.9 (4) |
C18—O4—Sn1 | 128.0 (2) | O2—C7—C1 | 121.8 (3) |
C18—O4—Sn2 | 126.6 (2) | O1—C7—C1 | 116.3 (3) |
Sn1—O4—Sn2 | 101.16 (10) | C7—O1—Sn2 | 112.5 (2) |
O3—Sn2—C16 | 109.31 (16) | Sn1—C14—H14A | 109.5 |
O3—Sn2—C17 | 119.36 (15) | Sn1—C14—H14B | 109.5 |
C16—Sn2—C17 | 129.99 (19) | H14A—C14—H14B | 109.5 |
O3—Sn2—O1 | 81.33 (9) | Sn1—C14—H14C | 109.5 |
C16—Sn2—O1 | 100.01 (15) | H14A—C14—H14C | 109.5 |
C17—Sn2—O1 | 97.92 (16) | H14B—C14—H14C | 109.5 |
O3—Sn2—O4 | 72.00 (9) | Sn1—C15—H15A | 109.5 |
C16—Sn2—O4 | 92.61 (15) | Sn1—C15—H15B | 109.5 |
C17—Sn2—O4 | 91.84 (15) | H15A—C15—H15B | 109.5 |
O1—Sn2—O4 | 153.04 (9) | Sn1—C15—H15C | 109.5 |
C6—C1—C2 | 118.6 (4) | H15A—C15—H15C | 109.5 |
C6—C1—C7 | 119.6 (4) | H15B—C15—H15C | 109.5 |
C2—C1—C7 | 121.8 (3) | Sn2—C16—H16A | 109.5 |
N1—C2—C3 | 121.3 (4) | Sn2—C16—H16B | 109.5 |
N1—C2—C1 | 120.3 (4) | H16A—C16—H16B | 109.5 |
C3—C2—C1 | 118.3 (4) | Sn2—C16—H16C | 109.5 |
C4—C3—C2 | 121.4 (4) | H16A—C16—H16C | 109.5 |
C4—C3—H3 | 119.3 | H16B—C16—H16C | 109.5 |
C2—C3—H3 | 119.3 | Sn2—C17—H17A | 109.5 |
C3—C4—C5 | 120.8 (4) | Sn2—C17—H17B | 109.5 |
C3—C4—H4 | 119.6 | H17A—C17—H17B | 109.5 |
C5—C4—H4 | 119.6 | Sn2—C17—H17C | 109.5 |
C4—C5—C6 | 119.2 (4) | H17A—C17—H17C | 109.5 |
C4—C5—H5 | 120.4 | H17B—C17—H17C | 109.5 |
C6—C5—H5 | 120.4 | O4—C18—C19 | 112.9 (4) |
C5—C6—C1 | 121.7 (4) | O4—C18—H18A | 109.0 |
C5—C6—H6 | 119.2 | C19—C18—H18A | 109.0 |
C1—C6—H6 | 119.2 | O4—C18—H18B | 109.0 |
C2—N1—C8 | 127.0 (4) | C19—C18—H18B | 109.0 |
C2—N1—H1N | 116.8 | H18A—C18—H18B | 107.8 |
C8—N1—H1N | 116.1 | C18—C19—H19A | 109.5 |
C13—C8—N1 | 123.7 (4) | C18—C19—H19B | 109.5 |
C13—C8—C9 | 117.5 (4) | H19A—C19—H19B | 109.5 |
N1—C8—C9 | 118.7 (4) | C18—C19—H19C | 109.5 |
C10—C9—C8 | 120.7 (4) | H19A—C19—H19C | 109.5 |
C10—C9—Cl1 | 120.5 (3) | H19B—C19—H19C | 109.5 |
C8—C9—Cl1 | 118.7 (3) | ||
C1—C7—O1—Sn2 | 177.5 (3) |
Symmetry code: (i) −x+1, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···Cl1 | 0.92 | 2.51 | 2.908 (4) | 107 |
N1—H1N···O2 | 0.92 | 1.97 | 2.639 (4) | 128 |
Experimental details
Crystal data | |
Chemical formula | [Sn4(CH3)8(C13H8Cl2NO2)2(C2H5O)2O2] |
Mr | 1279.36 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 291 |
a, b, c (Å) | 14.0875 (6), 9.7613 (4), 17.5858 (8) |
β (°) | 100.106 (3) |
V (Å3) | 2380.74 (18) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.35 |
Crystal size (mm) | 0.53 × 0.07 × 0.07 |
Data collection | |
Diffractometer | Kuma KM4 CCD area-detector diffractometer |
Absorption correction | Numerical (X-RED; Stoe & Cie, 1999) |
Tmin, Tmax | 0.518, 0.894 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 27541, 4230, 3656 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.063, 1.15 |
No. of reflections | 4230 |
No. of parameters | 259 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.10, −0.50 |
Computer programs: CrysAlis CCD (UNIL IC and Kuma, 2000), CrysAlis RED (UNIL IC and Kuma, 2000), CrysAlis RED, SHELXS97 (Sheldrick, 1990a), SHELXL97 (Sheldrick, 1997), XP in SHELXTL/PC (Sheldrick, 1990b) and ORTEP-3 for Windows (version 1.062; Farrugia 1997), SHELXL97.
Sn1—O3 | 2.036 (2) | Sn2—O3 | 2.020 (2) |
Sn1—C14 | 2.109 (4) | Sn2—O4 | 2.226 (2) |
Sn1—C15 | 2.114 (4) | Sn2—C16 | 2.096 (4) |
Sn1—O3i | 2.122 (2) | Sn2—C17 | 2.103 (4) |
Sn1—O4 | 2.137 (2) | Sn2—O1 | 2.169 (3) |
O3—Sn1—C14 | 118.17 (15) | O3—Sn2—C16 | 109.31 (16) |
O3—Sn1—C15 | 113.89 (15) | O3—Sn2—C17 | 119.36 (15) |
C14—Sn1—C15 | 127.94 (18) | C16—Sn2—C17 | 129.99 (19) |
O3—Sn1—O3i | 73.92 (10) | O3—Sn2—O1 | 81.33 (9) |
C14—Sn1—O3i | 94.68 (13) | C16—Sn2—O1 | 100.01 (15) |
C15—Sn1—O3i | 99.06 (15) | C17—Sn2—O1 | 97.92 (16) |
O3—Sn1—O4 | 73.61 (9) | O3—Sn2—O4 | 72.00 (9) |
C14—Sn1—O4 | 96.61 (14) | C16—Sn2—O4 | 92.61 (15) |
C15—Sn1—O4 | 97.98 (14) | C17—Sn2—O4 | 91.84 (15) |
O3i—Sn1—O4 | 147.22 (9) | O1—Sn2—O4 | 153.04 (9) |
Symmetry code: (i) −x+1, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···Cl1 | 0.92 | 2.51 | 2.908 (4) | 107 |
N1—H1N···O2 | 0.92 | 1.97 | 2.639 (4) | 128 |
2-[(2,3-Dichlorophenyl)amino]benzoic acid is a member of the class of non-steroidal anti-inflammatory drugs (NSAIDs). All NSAIDs are derivatives of N-phenylanthranilic acid and many of them are frequently used in medicine (Dokorou et al., 2001;), e.g. as analgesics, anti-inflammatories and antipyretics, because they have fewer side effects of sedation, respiratory depression or addiction than other pharmaceuticals with similar properties, such as steroids (Berner et al., 1970; Vedres et al., 1973; Bauman et al., 2005). NSAIDs inhibit cyclooxygenase (COX) activity and in consequence depress the synthesis of prostaglandins (Insel, 1996; Lands & Hanel, 1983; Reynolds et al., 1993). They have also been used in combination with cytotoxic drugs (Thicher et al., 1994, Gomez-Gaviro et al., 2002). At non-toxic levels, they significantly increase the cytotoxicity of the anthracyclines doxorubicin, daunorubicin, epirubicin, teniposide, VP-16 and vincristine (Duffy et al., 1998). 2-[(2,3-Dichlorophenyl)amino]benzoic acid can be considered as an analogue of tolfenamic and flufenamic acids and other clinically used fenamates (Kovala-Demertzi et al., 2001).
Organotin(IV) carboxylates are an important class of compounds that have very varied applications, from catalysis to biocides (antifouling agents) and as wood preservatives (Davies, 2004; Smith, 1998). However, applications of tin compounds are often limited because of their high toxicity, e.g. antifouling paints (WS Atkins International Ltd., 1998). Tin–organic compounds have also shown antitumour activity (Gielen, 1989). Thus, combining in one compound the pharmacologically important 2-[(2,3-dichlorophenyl)amino]benzoate ligand and potentially biologically active organotin moieties could lead to compounds with interesting properties and applications. We have therefore synthesized the title compound, (I), and present its crystal structure here.
A perspective view of the title compound (I) is shown in Fig. 1. A l l interatomic distances between non-metal atoms can be considered normal. The structure is composed of a centrosymmetric dimer, with three four-membered Sn—O—Sn—O rings in a linearly fused arrangement.
In the Cambridge Structural Database (CSD, Version 5.25; Allen, 2002), 108 compounds can be found containing the (Sn2O2)3 ring system. In 81 of them there are additional geometrical constraints imposed by chelating or bridging substituents; thus, a comparison of geometries was performed for only 27 compounds (CSD refcodes ASUJED, BEKDAX, CATGOT, CATGUZ, EKAMUY, EKANAF, HUTYIE, HUTYIE, LIRNUV, MASYOU, MOQXOF, NIVXEV, NUZMIE, OLONIM, QASMIG, QAYNOT, QAYNUZ, QIZREW, QOHPUY, QOHQAF, RACFOQ, ROGJIG, TIPSNB, UBIFOA, VOFDAV, XAKSAD, YELRAI, ZABPIB). Except for CATGUZ, in all these compounds the central ring (Sn2O2) is ideally planar; in CATGUZ the atoms deviate by only 0.04 Å from the mass-weighted least-squares plane of the ring. The peripheral rings are close to planarity in all compounds; the maximum deviation is 0.085 Å for compound TIPSNB. The interplanar angle between the central ring and the peripheral rings varies from 0.58° (QAYNOT) to 5.61° (MOQXOF).
In (I), the mass-weighted least-squares plane of the Sn1/O3/Sn2/O4 ring is slightly distorted from planarity [the largest deviation is 0.0665 (10) Å for atom O3] and subtends an angle of 7.62 (17)° with the central Sn1/O3/Sn1i/O3i ring, which is planar by symmetry [symmetry code: (i) 1 − x, −y, −z]. The overall arrangement of the central unit is closely similar to those previously reported for bis(3-(4-methylcoumarinyl-7-oxy)(µ2-methoxy)- 1,1,3,3-tetramethyl-distannoxane) (Zhang et al., 2003; CSD refcode OLONIM), bis[[(µ3-oxo)(µ2-(1,4-oxazin-4-yl)carbonylthioacetato]- [(1,4-oxazin-4-yl)carbonylthioacetato]-tetra-n-butyl-ditin] [Please check nesting of brackets] ethanol solvate (Ng et al., 2000; CSD refcode QASMIG), and bis[bis(di-n-butyl)(µ3-oxo)(µ2-2-methoxyphenoxo-O,O)- (2-methoxyphenoxy-O)-di-tin] (Vatsa et al., 1991; CSD refcode: VOFDAV).
The coordination polyhedron of Sn2 can be described as trigonal–bipyramidal [atoms O1 and O4 axial, and atoms O3, C16 and C17 equatorial; sum of the squares of the deviations from ideal angles Σσ(Φ) = 1514°2 (Favas & Kepert, 1980)] distorted toward a tetragonal pyramid [atom O3 apical, and atoms O1, O4, C16 and C17 basal; Σσ(Φ) = 5326°2]. The coordination polyhedron around atom Sn1 is more distorted towards square-pyramidal but can be described in the same general way [trigonal–bipyramidal with atoms O4 and O3i axial, and atoms O3, C14 and C15 equatorial, Σσ(Φ) = 1917°2, or square-pyramidal with atom O3 apical, and atoms O3i, O4, C14 and C15 basal, Σσ(Φ) = 4860°2]. The major deformations originate from constraints imposed by the rigid four-membered Sn2O2 rings.
The benzene rings of the 2-[(2,3-dichlorophenyl)amino]benzoate ligand subtend an angle of 50.49 (17)°. The carboxylic acid group makes an angle of 12.3 (5)° with its parent aromatic ring. The C1—C7—O1—Sn2 torsion angle is 177.5 (2)°. The conformation of the ligand is stabilized by intramolecular N—H···Cl and N—H···O hydrogen bonds involving the same H atom (Table 2, Fig. 1). The packing further involves π–π stacking interactions (Hunter & Sanders, 1990) between pairs of adjacent Cl-bearing aromatic rings [symmetry code: 2 − x, −y − 1, −z; ring centroid distance 3.929 (6) Å, perpendicular distance between symmetry-parallel rings 3.504 (6) Å, angle between the vector linking ring centroids and the normal to one plane 26.9 (3)°, offset 1.777 (6) Å]. Via these interactions, a π-bonded chain is created parallel to [120].