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Acta Cryst. (2009). E65, m36    [ doi:10.1107/S1600536808040786 ]

[4-Chloro-N'-(3-methoxy-2-oxidobenzylidene)benzohydrazidato]dimethyltin(IV)

J. Cui, Y. Qiao and H. Yin

Abstract top

In the title molecule, [Sn(CH3)2(C15H11ClN2O3)], the two benzene rings form a dihedral angle of 6.37 (2)°. The Sn atom is coordinated by one N [Sn-N = 2.187 (3) Å], two O [Sn-O = 2.123 (3) and 2.174 (3) Å] and two C [Sn-C = 2.096 (4) and 2.101 (4) Å] atoms in a distorted trigonal-bipyramidal geometry. The crystal packing exhibits weak intermolecular C-H...O hydrogen bonds, which link the molecules into centrosymmetric dimers with an Sn...Sn separation of 4.330 (6) Å, and [pi]-[pi] interactions [centroid-centroid distance of 3.690 (5) Å between the benzene rings of neighbouring molecules].

Comment top

The molecular structure of the title compound, (I), is shown in Fig. 1. The Sn atom has distorted trigonal-bipyramidal coordination geometry, with atoms O1 and O2 in axial positions [O1—Sn1—O2 = 153.92 (11)°] and the atoms C16, C17 and N2 in equatorial positions. The sum of the equatorial angles C16—Sn1—C17, C16—Sn1—N2 and C17—Sn—N2 is 359.4 (1) °, indicating approximate coplanarity for these atoms. The Sn1—N2 bond length is 2.187 (3) Å close to the sum of the non-polar covalent radii 2.15 Å, indicating a strong Sn—N interaction. The Sn-O coordinating bond lengths are close to those in the reported compound [Sn(C6H5)2(C14H10N2O3)].C2H6O (Hong et al., 2006). The crystal packing exhibits weak intermolecular C—H···O hydrogen bonds (Table 2), which link the molecules into centrosymmetric dimers with Sn···Sn separation of 4.330 (6) Å, and π–π interactions proved by short distance of 3.690 (5) between the centroids of benzene rings from the neighbouring molecules (Table 1).

Related literature top

For a related crystal structure, see Hong et al. (2006).

Experimental top

The reaction was carried out under nitrogen atmosphere. o-vanillin 4-chlorobenzhydrazone(1 mmol) and sodium ethoxide (1.2 mmol) were added to the solution of benzene(30 ml) in a Schlenk flask and stirred for 0.5 h. Dimethyltin dichloride (1 mmol) was then added to the reactor and the reaction mixture was stirred for 4 h at 313 K.The resulting clear solution was evaporated under vacuum. The product was crystallized from a mixture of dichloromethane/methanol (1:1). Analysis calculated (75%) for C17H17ClN2O3Sn (Mr = 451.47): C, 45.22; H, 3.80; N, 6.20, found: C, 45.09; H, 3.76; N, 6.35.

Refinement top

All H atoms attached to C atoms were fixed geometrically and treated as riding with, with aromatic C—H distances of 0.93 Å, methyl C—H distances of 0.96 Å. The Uiso(H) values were set at 1.5Uiso(C) for the methyl H atoms, and at 1.2Uiso(C) for the other H atoms.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme. H atoms have been omitted for clarity.
[4-Chloro-N'-(3-methoxy-2- oxidobenzylidene)benzohydrazidato]dimethyltin(IV) top
Crystal data top
[Sn(CH3)2(C15H11ClN2O3)]F(000) = 1792
Mr = 451.47Dx = 1.687 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 30.015 (3) ÅCell parameters from 4052 reflections
b = 9.5039 (10) Åθ = 2.3–28.1°
c = 13.5615 (18) ŵ = 1.60 mm−1
β = 113.189 (2)°T = 298 K
V = 3556.0 (7) Å3Block, orange
Z = 80.50 × 0.20 × 0.08 mm
Data collection top
Siemens SMART CCD area-detector
diffractometer		3113 independent reflections
Radiation source: fine-focus sealed tube2392 reflections with I > 2σ(I)
graphiteRint = 0.061
φ and ω scansθmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −35→35
Tmin = 0.501, Tmax = 0.882k = −10→11
8568 measured reflectionsl = −8→16
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.0351P)2 + 0.1164P]
where P = (Fo2 + 2Fc2)/3
3113 reflections(Δ/σ)max = 0.001
220 parametersΔρmax = 0.66 e Å−3
0 restraintsΔρmin = −0.56 e Å−3
Crystal data top
[Sn(CH3)2(C15H11ClN2O3)]V = 3556.0 (7) Å3
Mr = 451.47Z = 8
Monoclinic, C2/cMo Kα radiation
a = 30.015 (3) ŵ = 1.60 mm−1
b = 9.5039 (10) ÅT = 298 K
c = 13.5615 (18) Å0.50 × 0.20 × 0.08 mm
β = 113.189 (2)°
Data collection top
Siemens SMART CCD area-detector
diffractometer		3113 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2392 reflections with I > 2σ(I)
Tmin = 0.501, Tmax = 0.882Rint = 0.061
8568 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.080Δρmax = 0.66 e Å−3
S = 1.00Δρmin = −0.56 e Å−3
3113 reflectionsAbsolute structure: ?
220 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Sn10.032667 (8)0.79772 (3)0.059696 (18)0.03884 (12)
Cl10.23989 (4)0.12286 (15)0.38025 (11)0.0824 (4)
N10.03655 (10)0.5011 (3)0.1544 (2)0.0386 (7)
N20.00348 (9)0.6097 (3)0.1058 (2)0.0343 (7)
O10.08954 (9)0.6394 (3)0.1128 (2)0.0516 (7)
O2−0.04042 (8)0.8667 (3)0.0035 (2)0.0481 (7)
O3−0.11949 (8)1.0208 (3)−0.0695 (2)0.0593 (8)
C10.07925 (12)0.5289 (4)0.1536 (3)0.0375 (9)
C20.11826 (12)0.4249 (4)0.2063 (3)0.0373 (9)
C30.11002 (14)0.3030 (4)0.2523 (3)0.0452 (10)
H30.07880.28370.24720.054*
C40.14663 (14)0.2095 (4)0.3054 (3)0.0484 (10)
H40.14050.12820.33610.058*
C50.19244 (14)0.2392 (5)0.3119 (3)0.0515 (11)
C60.20167 (14)0.3569 (5)0.2656 (4)0.0706 (14)
H60.23280.37470.26960.085*
C70.16426 (14)0.4496 (5)0.2123 (4)0.0603 (12)
H70.17040.52970.18030.072*
C8−0.03937 (12)0.5902 (4)0.1040 (3)0.0394 (9)
H8−0.04450.50600.13300.047*
C9−0.07999 (13)0.6841 (4)0.0622 (3)0.0392 (9)
C10−0.07884 (13)0.8150 (4)0.0152 (3)0.0396 (9)
C11−0.12244 (12)0.8960 (4)−0.0225 (3)0.0446 (10)
C12−0.16337 (14)0.8486 (5)−0.0114 (3)0.0570 (12)
H12−0.19110.9040−0.03510.068*
C13−0.16372 (15)0.7186 (5)0.0348 (4)0.0655 (14)
H13−0.19170.68720.04170.079*
C14−0.12297 (13)0.6366 (5)0.0703 (3)0.0529 (11)
H14−0.12360.54880.10010.063*
C15−0.16273 (14)1.1007 (5)−0.1172 (4)0.0785 (16)
H15A−0.18741.0434−0.16830.118*
H15B−0.15661.1810−0.15290.118*
H15C−0.17331.1315−0.06260.118*
C160.03486 (14)0.8041 (4)−0.0928 (3)0.0450 (10)
H16A0.03100.8996−0.11800.068*
H16B0.00910.7475−0.14160.068*
H16C0.06540.7683−0.08870.068*
C170.05918 (14)0.9110 (4)0.2044 (3)0.0508 (11)
H17A0.08960.87170.25150.076*
H17B0.03630.90530.23780.076*
H17C0.06371.00770.19010.076*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.03741 (16)0.0408 (2)0.04022 (17)0.00259 (12)0.01728 (12)0.00166 (12)
Cl10.0532 (6)0.0705 (9)0.1054 (10)0.0202 (6)0.0120 (7)0.0138 (8)
N10.0381 (16)0.0376 (19)0.0420 (17)0.0032 (14)0.0179 (13)0.0047 (15)
N20.0349 (15)0.0350 (18)0.0347 (15)−0.0004 (14)0.0156 (13)−0.0008 (14)
O10.0453 (15)0.0475 (18)0.0701 (18)0.0051 (13)0.0315 (14)0.0148 (16)
O20.0381 (13)0.0485 (18)0.0603 (16)0.0043 (12)0.0222 (13)0.0120 (14)
O30.0347 (14)0.0504 (19)0.086 (2)0.0068 (13)0.0167 (14)0.0133 (17)
C10.041 (2)0.040 (2)0.0346 (19)0.0022 (17)0.0176 (16)−0.0034 (17)
C20.0383 (19)0.036 (2)0.040 (2)−0.0003 (16)0.0178 (16)−0.0031 (17)
C30.042 (2)0.045 (3)0.048 (2)−0.0001 (19)0.0167 (18)−0.002 (2)
C40.048 (2)0.041 (3)0.054 (2)0.0014 (19)0.0167 (19)0.008 (2)
C50.043 (2)0.048 (3)0.055 (2)0.008 (2)0.0104 (19)−0.002 (2)
C60.033 (2)0.073 (3)0.101 (4)0.002 (2)0.022 (2)0.019 (3)
C70.047 (2)0.055 (3)0.082 (3)0.001 (2)0.029 (2)0.018 (3)
C80.045 (2)0.041 (2)0.0353 (19)−0.0024 (18)0.0191 (16)−0.0051 (17)
C90.0394 (19)0.048 (3)0.0317 (18)0.0020 (18)0.0152 (16)−0.0009 (17)
C100.0358 (19)0.047 (3)0.0346 (19)−0.0015 (17)0.0128 (16)−0.0051 (18)
C110.039 (2)0.045 (3)0.047 (2)0.0023 (19)0.0141 (17)−0.001 (2)
C120.038 (2)0.063 (3)0.071 (3)0.006 (2)0.022 (2)0.011 (3)
C130.039 (2)0.087 (4)0.076 (3)0.002 (2)0.029 (2)0.019 (3)
C140.042 (2)0.064 (3)0.056 (2)−0.001 (2)0.0234 (19)0.011 (2)
C150.041 (2)0.067 (3)0.113 (4)0.011 (2)0.014 (3)0.023 (3)
C160.053 (2)0.042 (2)0.045 (2)0.0016 (19)0.0245 (18)0.0022 (19)
C170.056 (2)0.047 (3)0.044 (2)−0.005 (2)0.0149 (19)−0.002 (2)
Geometric parameters (Å, °) top
Sn1—C162.096 (4)C6—H60.9300
Sn1—C172.101 (4)C7—H70.9300
Sn1—O22.123 (2)C8—C91.436 (5)
Sn1—O12.174 (3)C8—H80.9300
Sn1—N22.187 (3)C9—C101.404 (5)
Cl1—C51.752 (4)C9—C141.412 (5)
N1—C11.313 (4)C10—C111.428 (5)
N1—N21.403 (4)C11—C121.371 (5)
N2—C81.290 (4)C12—C131.387 (6)
O1—C11.281 (4)C12—H120.9300
O2—C101.319 (4)C13—C141.368 (6)
O3—C111.365 (5)C13—H130.9300
O3—C151.421 (5)C14—H140.9300
C1—C21.483 (5)C15—H15A0.9600
C2—C71.371 (5)C15—H15B0.9600
C2—C31.383 (5)C15—H15C0.9600
C3—C41.376 (5)C16—H16A0.9600
C3—H30.9300C16—H16B0.9600
C4—C51.372 (6)C16—H16C0.9600
C4—H40.9300C17—H17A0.9600
C5—C61.364 (6)C17—H17B0.9600
C6—C71.386 (6)C17—H17C0.9600
Sn1···Sn1i4.3302 (6)Cg1···Cg2ii3.690 (5)
C16—Sn1—C17139.41 (15)C14—C13—H13119.9
C16—Sn1—O293.81 (13)C12—C13—H13119.9
C17—Sn1—O297.74 (13)C13—C14—C9120.5 (4)
C16—Sn1—O191.21 (13)C13—C14—H14119.7
C17—Sn1—O194.93 (13)C9—C14—H14119.7
O2—Sn1—O1153.92 (11)O3—C15—H15A109.5
C16—Sn1—N2118.54 (12)O3—C15—H15B109.5
C17—Sn1—N2101.45 (14)H15A—C15—H15B109.5
O2—Sn1—N283.18 (10)O3—C15—H15C109.5
O1—Sn1—N271.99 (10)H15A—C15—H15C109.5
C16—Sn1—Sn1i77.92 (10)H15B—C15—H15C109.5
C17—Sn1—Sn1i81.00 (11)Sn1—C16—H16A109.5
O2—Sn1—Sn1i48.68 (7)Sn1—C16—H16B109.5
O1—Sn1—Sn1i156.79 (7)H16A—C16—H16B109.5
N2—Sn1—Sn1i131.22 (7)Sn1—C16—H16C109.5
C1—N1—N2111.2 (3)H16A—C16—H16C109.5
C8—N2—N1114.8 (3)H16B—C16—H16C109.5
C8—N2—Sn1128.4 (3)Sn1—C17—H17A109.5
N1—N2—Sn1116.5 (2)Sn1—C17—H17B109.5
C1—O1—Sn1114.8 (2)H17A—C17—H17B109.5
C10—O2—Sn1132.1 (2)Sn1—C17—H17C109.5
C11—O3—C15117.4 (3)H17A—C17—H17C109.5
O1—C1—N1124.8 (3)H17B—C17—H17C109.5
O1—C1—C2118.4 (3)C3—CG1—C5119.9 (3)
N1—C1—C2116.7 (3)C3—CG1—C7119.8 (2)
C7—C2—C3118.1 (4)C5—CG1—C7120.3 (2)
C7—C2—C1120.0 (4)C3—CG1—C6179.4 (3)
C3—C2—C1121.9 (3)C5—CG1—C659.6 (3)
C2—C3—C4121.9 (4)C7—CG1—C660.6 (2)
C2—C3—H3119.0C3—CG1—C460.1 (2)
C4—C3—H3119.0C5—CG1—C459.8 (2)
C5—C4—C3118.3 (4)C7—CG1—C4179.6 (3)
C5—C4—H4120.8C6—CG1—C4119.4 (3)
C3—C4—H4120.8C3—CG1—C260.4 (2)
C6—C5—C4121.3 (4)C5—CG1—C2179.2 (2)
C6—C5—Cl1119.4 (3)C7—CG1—C259.5 (2)
C4—C5—Cl1119.3 (4)C6—CG1—C2120.1 (3)
C5—C6—C7119.5 (4)C4—CG1—C2120.5 (2)
C5—C6—H6120.3C3—CG1—CG2ii91.56 (16)
C7—C6—H6120.3C5—CG1—CG2ii102.81 (18)
C2—C7—C6120.8 (4)C7—CG1—CG2ii75.46 (19)
C2—C7—H7119.6C6—CG1—CG2ii88.2 (2)
C6—C7—H7119.6C4—CG1—CG2ii104.11 (17)
N2—C8—C9127.1 (4)C2—CG1—CG2ii77.95 (14)
N2—C8—H8116.4C11—CG2—C1259.4 (2)
C9—C8—H8116.4C11—CG2—C14178.1 (2)
C10—C9—C14120.4 (3)C12—CG2—C14118.9 (2)
C10—C9—C8124.2 (4)C11—CG2—C13119.3 (2)
C14—C9—C8115.5 (4)C12—CG2—C1359.9 (2)
O2—C10—C9124.3 (3)C14—CG2—C1359.0 (2)
O2—C10—C11118.5 (4)C11—CG2—C9120.8 (2)
C9—C10—C11117.2 (3)C12—CG2—C9179.5 (2)
O3—C11—C12124.2 (3)C14—CG2—C961.0 (2)
O3—C11—C10114.6 (3)C13—CG2—C9120.0 (2)
C12—C11—C10121.2 (4)C11—CG2—C1061.1 (2)
C11—C12—C13120.6 (4)C12—CG2—C10120.4 (2)
C11—C12—H12119.7C14—CG2—C10120.6 (2)
C13—C12—H12119.7C13—CG2—C10179.6 (3)
C14—C13—C12120.1 (4)C9—CG2—C1059.7 (2)
Symmetry codes: (i) −x, −y+2, −z; (ii) −x, −y+1, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C15—H15B···O1i0.962.533.290 (6)136
Symmetry codes: (i) −x, −y+2, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C15—H15B···O1i0.962.533.290 (6)136
Symmetry codes: (i) −x, −y+2, −z.
Acknowledgements top

We acknowledge the financial support of the Shandong Provincial Science Foundation and the State Key Laboratory of Crystalline Materials, Shandong University.

references
References top

Hong, M., Yin, H.-D. & Wang, D.-Q. (2006). Acta Cryst. E62, m1504–m1505.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.