supplementary materials


lh5669 scheme

Acta Cryst. (2013). E69, m688    [ doi:10.1107/S1600536813031826 ]

{4-Chloro-N'-[(2-oxidonaphthalen-1-yl-[kappa]O)methyl­idene]benzohydrazidato-[kappa]2N',O}di­methyl­tin(IV)

J. Cui, Y. Qiao and F. Wang

Abstract top

In the title complex, [Sn(CH3)2(C18H11ClN2O2)], the SnIV ion is coordinated by two O atoms and an N atom from a 4-chloro-N'-[(2-oxidonaphthalen-1-yl)methyl­idene]benzohydrazidate ligand and two C atoms from two methyl ligands in a distorted trigonal-bipyramidal geometry [Sn-O = 2.092 (3) and 2.144 (3) Å; Sn-N = 2.160 (4) Å]. The dihedral angle between the naphthalene ring system and the benzene ring is 8.6 (2)°. In the crystal, adjacent mol­ecules are linked by weak C-H...O hydrogen bonds, forming a chain along the b-axis direction.

Comment top

The chemistry of organotin(IV) derivatives is a subject of study with growing interest due to their significant antimicrobial properties as well as antitumor activities (Hong et al., 2013). As a part of our ongoing investigations in this field we have synthesized the title compound and present its crystal structure here. The molecular structure of the title compound, (I), is shown in Fig. 1. The Sn atom has distorted trigonal-bipyramidal geometry, with atoms O1 and O2 in axial positions [O1—Sn1—O2 = 153.39 (13) °] and the atoms C19, C20 and N2 in equatorial positions. The sum of the equatorial angles is 359.9 °, indicating approximate coplanarity for these atoms. The Sn1—N2 bond length is 2.160 (4) Å close to the sum of the non-polar covalent radii 2.15 Å, indicating a strong Sn—N interaction. The O atoms coordinate to the Sn atom with one shorter [2.092 (3) Å] and one longer [2.144 (3) Å] bond. The dihedral angle between the naphthalene ring system (C9-C18) and the benzene ring (C1-C6) is 8.6 (2)°.

Related literature top

For the biological activity and related structures of organotin compounds, see: Hong et al. (2013).

Experimental top

2-hydroxy-1-naphthaldehyde 4-chlorobenzoylhydrazone (1 mmol) and sodium ethoxide (1 mmol) were added to the solution of dry methanol(30 ml) and stirred for 10 mins. Dimeyltin dichloride (1 mmol) was then added to the reactor and the reaction mixture was stirred for 4 h. The resulting clear solution was evaporated under vacuum. The product was crystallized from a mixture of dichloromethane/ethanol(1:1) to yield orange blocks of the title compound (yield 73%).

Refinement top

The H atoms were positioned geometrically, with methyl C—H distances of 0.96 Å and aromatic and aldehydic C—H distances of 0.93 Å, and refined as riding on their parent atoms, with Uiso(H) = 1.2 Ueq(C) or 1.5 Ueq(C) for the methyl groups.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (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 the title compound, showing 50% probability displacement ellipsoids. H atoms have been omitted for clarity.
{4-Chloro-N'-[(2-oxidonaphthalen-1-yl-κO)methylidene]benzohydrazidato-κ2N',O}dimethyltin(IV) top
Crystal data top
[Sn(CH3)2(C18H11ClN2O2)]F(000) = 936
Mr = 471.50Dx = 1.655 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2600 reflections
a = 8.7927 (8) Åθ = 2.6–28.5°
b = 17.4170 (15) ŵ = 1.51 mm1
c = 12.5014 (12) ÅT = 293 K
β = 98.690 (9)°Block, orange
V = 1892.5 (3) Å30.24 × 0.23 × 0.13 mm
Z = 4
Data collection top
Siemens SMART CCD area-detector
diffractometer
3343 independent reflections
Radiation source: fine-focus sealed tube2584 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.047
φ and ω scansθmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 810
Tmin = 0.714, Tmax = 0.828k = 2019
11127 measured reflectionsl = 1414
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)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0488P)2 + 0.4409P]
where P = (Fo2 + 2Fc2)/3
3343 reflections(Δ/σ)max = 0.001
237 parametersΔρmax = 0.83 e Å3
0 restraintsΔρmin = 0.61 e Å3
Crystal data top
[Sn(CH3)2(C18H11ClN2O2)]V = 1892.5 (3) Å3
Mr = 471.50Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.7927 (8) ŵ = 1.51 mm1
b = 17.4170 (15) ÅT = 293 K
c = 12.5014 (12) Å0.24 × 0.23 × 0.13 mm
β = 98.690 (9)°
Data collection top
Siemens SMART CCD area-detector
diffractometer
3343 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2584 reflections with I > 2σ(I)
Tmin = 0.714, Tmax = 0.828Rint = 0.047
11127 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.107Δρmax = 0.83 e Å3
S = 1.06Δρmin = 0.61 e Å3
3343 reflectionsAbsolute structure: ?
237 parametersAbsolute structure parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Sn10.14514 (4)0.026153 (19)0.73069 (3)0.04369 (15)
O10.1839 (4)0.1313 (2)0.8117 (3)0.0542 (9)
O20.0073 (4)0.0641 (2)0.6906 (3)0.0597 (10)
N10.0353 (5)0.1015 (2)0.9316 (3)0.0511 (10)
N20.0421 (5)0.0380 (2)0.8630 (3)0.0447 (10)
C10.1055 (5)0.2148 (3)0.9621 (4)0.0408 (11)
C20.0132 (5)0.2290 (3)1.0615 (4)0.0457 (12)
H20.06450.19451.08740.055*
C30.0355 (6)0.2931 (3)1.1216 (4)0.0532 (13)
H30.02610.30191.18780.064*
C40.1512 (6)0.3443 (3)1.0820 (4)0.0528 (13)
C50.2422 (6)0.3321 (3)0.9852 (4)0.0534 (13)
H50.31920.36710.95990.064*
C60.2204 (6)0.2679 (3)0.9248 (4)0.0503 (12)
H60.28260.25990.85870.060*
C70.0849 (5)0.1448 (3)0.8972 (4)0.0446 (11)
C80.1604 (5)0.0072 (3)0.8915 (4)0.0420 (11)
H80.22570.00620.95430.050*
C90.2008 (5)0.0748 (3)0.8370 (4)0.0411 (11)
C100.1179 (6)0.0978 (3)0.7378 (4)0.0466 (12)
C110.1701 (6)0.1620 (3)0.6826 (4)0.0530 (13)
H110.11400.17760.61700.064*
C120.2989 (6)0.2008 (3)0.7233 (4)0.0555 (13)
H120.33040.24200.68470.067*
C130.3880 (5)0.1797 (3)0.8248 (4)0.0454 (12)
C140.5222 (6)0.2202 (3)0.8669 (4)0.0543 (13)
H140.55540.26020.82680.065*
C150.6041 (6)0.2024 (3)0.9642 (4)0.0551 (13)
H150.69320.22940.99040.066*
C160.5533 (6)0.1430 (3)1.0250 (4)0.0539 (13)
H160.60720.13151.09300.065*
C170.4242 (5)0.1012 (3)0.9852 (4)0.0478 (12)
H170.39320.06141.02670.057*
C180.3378 (5)0.1170 (3)0.8833 (4)0.0413 (11)
C190.1543 (7)0.0779 (4)0.5774 (4)0.0695 (16)
H19A0.05240.09200.56620.104*
H19B0.21780.12290.57390.104*
H19C0.19700.04230.52230.104*
C200.3234 (7)0.0415 (4)0.7770 (5)0.0732 (18)
H20A0.36260.07550.71890.110*
H20B0.40470.00880.79320.110*
H20C0.28410.07110.83990.110*
Cl10.1839 (2)0.42381 (10)1.16029 (14)0.0880 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.0436 (2)0.0429 (2)0.0436 (2)0.00084 (15)0.00346 (16)0.00068 (16)
O10.0518 (19)0.054 (2)0.054 (2)0.0098 (17)0.0001 (17)0.0102 (18)
O20.057 (2)0.067 (2)0.050 (2)0.017 (2)0.0076 (17)0.0145 (19)
N10.048 (2)0.047 (3)0.059 (3)0.004 (2)0.006 (2)0.007 (2)
N20.048 (2)0.039 (2)0.046 (2)0.0002 (18)0.0058 (19)0.0097 (19)
C10.042 (2)0.034 (3)0.048 (3)0.004 (2)0.010 (2)0.000 (2)
C20.040 (3)0.044 (3)0.053 (3)0.005 (2)0.006 (2)0.002 (2)
C30.051 (3)0.056 (3)0.050 (3)0.006 (3)0.001 (2)0.006 (3)
C40.060 (3)0.044 (3)0.055 (3)0.007 (3)0.010 (3)0.005 (3)
C50.057 (3)0.049 (3)0.051 (3)0.018 (3)0.000 (3)0.001 (3)
C60.052 (3)0.050 (3)0.046 (3)0.005 (2)0.000 (2)0.001 (3)
C70.045 (3)0.040 (3)0.048 (3)0.004 (2)0.008 (2)0.000 (2)
C80.040 (3)0.044 (3)0.040 (3)0.001 (2)0.001 (2)0.003 (2)
C90.040 (2)0.041 (3)0.043 (3)0.002 (2)0.009 (2)0.001 (2)
C100.050 (3)0.046 (3)0.045 (3)0.000 (2)0.011 (2)0.004 (2)
C110.064 (3)0.052 (3)0.041 (3)0.009 (3)0.002 (2)0.005 (3)
C120.066 (3)0.050 (3)0.052 (3)0.008 (3)0.015 (3)0.006 (3)
C130.049 (3)0.043 (3)0.047 (3)0.002 (2)0.015 (2)0.005 (2)
C140.058 (3)0.045 (3)0.062 (3)0.007 (3)0.013 (3)0.004 (3)
C150.048 (3)0.052 (3)0.066 (3)0.007 (2)0.007 (3)0.014 (3)
C160.044 (3)0.060 (3)0.055 (3)0.003 (3)0.002 (2)0.009 (3)
C170.050 (3)0.046 (3)0.048 (3)0.003 (2)0.009 (2)0.005 (2)
C180.044 (3)0.037 (3)0.044 (3)0.003 (2)0.008 (2)0.002 (2)
C190.091 (4)0.066 (4)0.051 (3)0.007 (3)0.008 (3)0.008 (3)
C200.067 (4)0.073 (4)0.082 (5)0.025 (3)0.018 (4)0.008 (3)
Cl10.1110 (13)0.0687 (10)0.0780 (10)0.0321 (9)0.0065 (9)0.0259 (9)
Geometric parameters (Å, º) top
Sn1—O22.092 (3)C9—C101.399 (7)
Sn1—C192.108 (5)C9—C181.455 (6)
Sn1—C202.111 (5)C10—C111.426 (7)
Sn1—O12.144 (3)C11—C121.351 (7)
Sn1—N22.160 (4)C11—H110.9300
O1—C71.294 (5)C12—C131.435 (7)
O2—C101.306 (6)C12—H120.9300
N1—C71.317 (6)C13—C141.406 (7)
N1—N21.407 (5)C13—C181.422 (6)
N2—C81.310 (6)C14—C151.353 (7)
C1—C61.397 (7)C14—H140.9300
C1—C21.400 (7)C15—C161.397 (7)
C1—C71.489 (6)C15—H150.9300
C2—C31.377 (7)C16—C171.377 (7)
C2—H20.9300C16—H160.9300
C3—C41.387 (7)C17—C181.408 (6)
C3—H30.9300C17—H170.9300
C4—C51.362 (7)C19—H19A0.9600
C4—Cl11.745 (5)C19—H19B0.9600
C5—C61.379 (7)C19—H19C0.9600
C5—H50.9300C20—H20A0.9600
C6—H60.9300C20—H20B0.9600
C8—C91.431 (6)C20—H20C0.9600
C8—H80.9300
O2—Sn1—C1992.74 (19)C10—C9—C18119.8 (4)
O2—Sn1—C2097.3 (2)C8—C9—C18118.5 (4)
C19—Sn1—C20124.0 (3)O2—C10—C9124.2 (4)
O2—Sn1—O1153.39 (13)O2—C10—C11116.4 (4)
C19—Sn1—O194.45 (19)C9—C10—C11119.4 (5)
C20—Sn1—O199.8 (2)C12—C11—C10121.5 (5)
O2—Sn1—N281.53 (13)C12—C11—H11119.2
C19—Sn1—N2125.1 (2)C10—C11—H11119.2
C20—Sn1—N2110.8 (2)C11—C12—C13121.4 (5)
O1—Sn1—N273.39 (13)C11—C12—H12119.3
C7—O1—Sn1114.3 (3)C13—C12—H12119.3
C10—O2—Sn1135.1 (3)C14—C13—C18120.1 (5)
C7—N1—N2111.0 (4)C14—C13—C12121.2 (5)
C8—N2—N1114.3 (4)C18—C13—C12118.8 (4)
C8—N2—Sn1129.3 (3)C15—C14—C13121.6 (5)
N1—N2—Sn1116.3 (3)C15—C14—H14119.2
C6—C1—C2118.2 (4)C13—C14—H14119.2
C6—C1—C7120.1 (4)C14—C15—C16119.3 (5)
C2—C1—C7121.7 (4)C14—C15—H15120.4
C3—C2—C1121.1 (4)C16—C15—H15120.4
C3—C2—H2119.4C17—C16—C15120.6 (5)
C1—C2—H2119.4C17—C16—H16119.7
C2—C3—C4118.9 (5)C15—C16—H16119.7
C2—C3—H3120.5C16—C17—C18121.7 (5)
C4—C3—H3120.5C16—C17—H17119.1
C5—C4—C3121.2 (5)C18—C17—H17119.1
C5—C4—Cl1119.8 (4)C17—C18—C13116.7 (4)
C3—C4—Cl1118.9 (4)C17—C18—C9124.2 (4)
C4—C5—C6120.1 (5)C13—C18—C9119.1 (4)
C4—C5—H5120.0Sn1—C19—H19A109.5
C6—C5—H5120.0Sn1—C19—H19B109.5
C5—C6—C1120.5 (5)H19A—C19—H19B109.5
C5—C6—H6119.7Sn1—C19—H19C109.5
C1—C6—H6119.7H19A—C19—H19C109.5
O1—C7—N1124.8 (5)H19B—C19—H19C109.5
O1—C7—C1118.5 (4)Sn1—C20—H20A109.5
N1—C7—C1116.7 (4)Sn1—C20—H20B109.5
N2—C8—C9127.5 (4)H20A—C20—H20B109.5
N2—C8—H8116.3Sn1—C20—H20C109.5
C9—C8—H8116.3H20A—C20—H20C109.5
C10—C9—C8121.6 (4)H20B—C20—H20C109.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5···O2i0.932.543.388 (6)152
Symmetry code: (i) x1/2, y+1/2, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5···O2i0.932.543.388 (6)152
Symmetry code: (i) x1/2, y+1/2, z+3/2.
Acknowledgements top

We acknowledge the Students Science and Technology Innovation Fund of Liaocheng University (SF2013096).

references
References top

Hong, M., Yin, H., Zhang, X., Li, C., Yue, C. & Cheng, S. (2013). J. Organomet. Chem., 724, 23–31.

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.