[5-Chloro-2-hy­droxy-N′-(2-oxidobenzyl­idene)benzohydrazidato]dimethyl­tin(IV)

In the title compound, [Sn(CH₃)₂(C₁₄H₉ClN₂O₃)], the Sn^IV ion is coordinated by one N and two O atoms from the tridentate 5-chloro-2-hy­droxy-N′-(2-oxidobenzyl­idene)benzohydrazidate (L) ligand and two methyl groups in a distorted trigonal–bipyramidal geometry. In the ligand, the hy­droxy group is involved in an intra­molecular O—H...N hydrogen bond and the two aromatic rings form a dihedral angle of 5.5 (1)°. In the crystal, weak inter­molecular C—H...O hydrogen bonds and π–π inter­actions between the aromatic rings [centroid–centroid distance = 3.816 (3) Å] link the mol­ecules into centrosymmetric dimers.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.029
• wR factor = 0.071
• Data-to-parameter ratio = 14.0

checkCIF/PLATON results

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PLAT125_ALERT_4_C No '_symmetry_space_group_name_Hall' Given .....          ?
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          2
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.595          9

Alert level G
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PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still          60 Perc.

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
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   2 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
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S1. Comment

Organotin(IV) compounds of hydrazone Schiff bases were reported by Hong et al. (2010). In continuation of our study of hydrazone Schiff base organotin(IV) compounds (Li et al., 2009), we have synthesized the title compound, (I).

In (I) (Fig. 1), the tin center is five-coordinated in a distorted trigonal bipyramidal geometry, being surrounded by two C atoms from the alkyl and one N atom, two O atoms from the Schiff base ligand. So the ligand coordinated to the tin atom as a tridentate ligand. In the tridentate ligand, two aromatic rings form a dihedral angle of 5.5 (1)°. The O atoms coordinate the Sn center with different bond lengths - for carbonyl O2 atom Sn—O2 = 2.183 (2) Å, and for hydroxy O3 atom Sn—O3 = 2.078 (3) Å. Similar structural parameters were observed in the related compound (Yearwood et al., 2002). In (I), the angles o C15–Sn–C16, C15–Sn–O3 and C16–Sn–O3 are 129.30 (15)°, 100.22 (14)° and 95.08 (14)°, respectively, indicating the distorted trigonal bipyramidal coordination geometry.

In the crystal structure, weak intermolecular C—H···O hydrogen bonds (Table 1) and π—π interactions between the aromatic rings [centroid-to-centroid distance of 3.816 (3) Å] link the molecules into centrosymmetric dimers (Fig.2 ).

Related literature

For related structures, see: Yearwood et al. (2002); Hong et al. (2010); Li et al. (2009).

S2. Experimental

The reaction was carried out under nitrogen atmosphere. The Schiff base ligand (0.2 mmol) was added to 30 ml e thanol with sodium ethoxide (0.4 mmol). The mixture was stirred for 0.5 h and then dichlorodimethyltin (0.2 mmol) was added.And the mixture was stirred for 12 h under reflux. After cooling to room temperature, the mixture was filtered and evaporated to dryness. The resulting solid, was then recrystallized from dichloromethane-petroleum ether (1:1, v/v). Anal. Calcd (%) for C₁₆H₁₅Cl_N2_O3_Sn (Mr = 437.44): C, 43.93; H, 3.46; N, 6.40; O, 10.97. Found (%): C, 43.90; H, 3.42; N, 6.35; O, 10.9.

S3. Refinement

The H atoms were positioned geometrically (C–H 0.93-0.96 Å; O–H 0.82 Å), and refined as riding, with U_iso(H) = 1.2-1.5 U_eq of the parent atom.

Computing details

Data collection: SMART (Bruker, 2007); cell refinement: 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); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I) showing the atomic numbering and 50% probability displacement ellipsoids.
	Fig. 2. Centrosymmetric dimer in the crystal structure of (I) [symmetry code: (a) - x + 1,-y + 1,-z + 1]. Dashed lines denote intermolecular C—H···O hydrogen bonds and π—π interactions.

[5-Chloro-2-hydroxy-N'-(2- oxidobenzylidene)benzohydrazidato]dimethyltin(IV)

Crystal data

[Sn(CH3)2(C14H9ClN2O3)]	F(000) = 864
Mr = 437.44	Dx = 1.712 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.5096 (5) Å	Cell parameters from 4020 reflections
b = 20.965 (2) Å	θ = 3.3–27.2°
c = 10.8344 (11) Å	µ = 1.68 mm^−1
β = 95.634 (1)°	T = 298 K
V = 1697.5 (3) Å^3	Block, yellow
Z = 4	0.48 × 0.41 × 0.23 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2975 independent reflections
Radiation source: fine-focus sealed tube	2357 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
ϕ and ω scans	θmax = 25.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −8→8
Tmin = 0.500, Tmax = 0.699	k = −24→23
8414 measured reflections	l = −12→12

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.029	H-atom parameters constrained
wR(F^2) = 0.071	w = 1/[σ^2(Fo^2) + (0.026P)^2 + 0.2305P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
2975 reflections	Δρmax = 0.44 e Å^−3
212 parameters	Δρmin = −0.67 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0182 (6)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Sn1	0.36782 (3)	0.466514 (11)	0.80395 (2)	0.03921 (13)
Cl1	−0.1037 (2)	0.21038 (5)	0.43753 (11)	0.0807 (4)
N1	0.2415 (4)	0.48410 (14)	0.5277 (3)	0.0413 (7)
N2	0.3277 (4)	0.51754 (13)	0.6279 (3)	0.0365 (7)
O1	0.1173 (5)	0.46606 (13)	0.3001 (2)	0.0606 (8)
H1	0.1802	0.4835	0.3564	0.091*
O2	0.2336 (4)	0.40168 (12)	0.6672 (2)	0.0498 (7)
O3	0.4514 (4)	0.55533 (12)	0.8723 (2)	0.0534 (7)
C1	0.1973 (5)	0.42608 (17)	0.5585 (3)	0.0369 (8)
C2	0.1016 (5)	0.38655 (16)	0.4607 (3)	0.0372 (8)
C3	0.0701 (5)	0.40754 (18)	0.3373 (3)	0.0413 (9)
C4	−0.0106 (5)	0.36639 (19)	0.2477 (3)	0.0501 (10)
H4	−0.0283	0.3799	0.1656	0.060*
C5	−0.0637 (6)	0.30721 (19)	0.2777 (3)	0.0492 (10)
H5	−0.1184	0.2805	0.2168	0.059*
C6	−0.0362 (5)	0.28668 (17)	0.3994 (3)	0.0455 (9)
C7	0.0456 (5)	0.32594 (17)	0.4898 (3)	0.0407 (9)
H7	0.0635	0.3116	0.5713	0.049*
C8	0.3792 (5)	0.57425 (17)	0.6034 (3)	0.0409 (9)
H8	0.3597	0.5870	0.5210	0.049*
C9	0.4634 (5)	0.62022 (16)	0.6886 (3)	0.0405 (9)
C10	0.5084 (5)	0.67917 (18)	0.6401 (4)	0.0532 (10)
H10	0.4906	0.6858	0.5549	0.064*
C11	0.5786 (6)	0.72764 (19)	0.7158 (4)	0.0607 (12)
H11	0.6094	0.7666	0.6826	0.073*
C12	0.6020 (6)	0.7170 (2)	0.8418 (4)	0.0611 (12)
H12	0.6478	0.7497	0.8936	0.073*
C13	0.5603 (6)	0.66031 (19)	0.8930 (4)	0.0554 (11)
H13	0.5786	0.6551	0.9785	0.066*
C14	0.4897 (5)	0.60941 (18)	0.8185 (3)	0.0444 (9)
C15	0.6154 (5)	0.41890 (19)	0.8108 (4)	0.0536 (10)
H15A	0.6874	0.4378	0.7521	0.080*
H15B	0.5956	0.3747	0.7907	0.080*
H15C	0.6761	0.4224	0.8927	0.080*
C16	0.1613 (6)	0.45669 (19)	0.9204 (4)	0.0528 (11)
H16A	0.2094	0.4617	1.0052	0.079*
H16B	0.1083	0.4152	0.9091	0.079*
H16C	0.0719	0.4887	0.8999	0.079*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sn1	0.0436 (2)	0.03337 (18)	0.04025 (17)	−0.00176 (11)	0.00207 (11)	0.00346 (11)
Cl1	0.1181 (11)	0.0464 (7)	0.0724 (8)	−0.0281 (7)	−0.0178 (7)	0.0042 (6)
N1	0.049 (2)	0.0347 (17)	0.0402 (16)	−0.0027 (14)	0.0022 (14)	0.0004 (14)
N2	0.0372 (18)	0.0300 (16)	0.0424 (16)	0.0005 (13)	0.0037 (13)	0.0041 (13)
O1	0.087 (2)	0.0491 (18)	0.0438 (16)	−0.0106 (15)	−0.0039 (15)	0.0111 (13)
O2	0.0696 (19)	0.0399 (15)	0.0378 (14)	−0.0116 (14)	−0.0056 (13)	0.0044 (12)
O3	0.078 (2)	0.0340 (14)	0.0468 (15)	−0.0133 (14)	0.0014 (14)	0.0037 (13)
C1	0.035 (2)	0.037 (2)	0.040 (2)	0.0052 (16)	0.0058 (16)	0.0016 (16)
C2	0.036 (2)	0.038 (2)	0.0373 (19)	0.0063 (16)	0.0004 (15)	−0.0022 (16)
C3	0.045 (2)	0.036 (2)	0.043 (2)	0.0046 (17)	0.0081 (17)	0.0042 (17)
C4	0.057 (3)	0.054 (3)	0.038 (2)	0.000 (2)	−0.0014 (18)	−0.0012 (19)
C5	0.053 (3)	0.050 (2)	0.044 (2)	0.001 (2)	−0.0006 (18)	−0.0085 (19)
C6	0.050 (3)	0.038 (2)	0.047 (2)	−0.0004 (18)	0.0005 (18)	−0.0006 (17)
C7	0.043 (2)	0.042 (2)	0.0366 (19)	0.0005 (17)	−0.0003 (16)	0.0010 (17)
C8	0.042 (2)	0.036 (2)	0.047 (2)	0.0040 (17)	0.0100 (17)	0.0106 (17)
C9	0.039 (2)	0.030 (2)	0.054 (2)	0.0014 (16)	0.0118 (18)	0.0011 (17)
C10	0.056 (3)	0.038 (2)	0.066 (3)	0.0014 (19)	0.010 (2)	0.008 (2)
C11	0.063 (3)	0.033 (2)	0.089 (3)	−0.007 (2)	0.020 (3)	0.001 (2)
C12	0.058 (3)	0.044 (3)	0.082 (3)	−0.011 (2)	0.009 (2)	−0.011 (2)
C13	0.064 (3)	0.041 (2)	0.061 (3)	−0.007 (2)	0.004 (2)	−0.008 (2)
C14	0.040 (2)	0.038 (2)	0.056 (2)	0.0007 (18)	0.0088 (18)	−0.0022 (19)
C15	0.050 (3)	0.047 (2)	0.064 (3)	0.009 (2)	0.007 (2)	0.010 (2)
C16	0.052 (3)	0.062 (3)	0.045 (2)	0.001 (2)	0.0056 (19)	0.0049 (19)

Geometric parameters (Å, º)

Sn1—O3	2.078 (3)	C6—C7	1.378 (5)
Sn1—C16	2.103 (4)	C7—H7	0.9300
Sn1—C15	2.105 (4)	C8—C9	1.437 (5)
Sn1—N2	2.182 (3)	C8—H8	0.9300
Sn1—O2	2.183 (2)	C9—C10	1.398 (5)
Cl1—C6	1.740 (4)	C9—C14	1.420 (5)
N1—C1	1.312 (4)	C10—C11	1.377 (6)
N1—N2	1.397 (4)	C10—H10	0.9300
N2—C8	1.286 (4)	C11—C12	1.377 (6)
O1—C3	1.349 (4)	C11—H11	0.9300
O1—H1	0.8200	C12—C13	1.362 (6)
O2—C1	1.288 (4)	C12—H12	0.9300
O3—C14	1.319 (4)	C13—C14	1.409 (5)
C1—C2	1.476 (5)	C13—H13	0.9300
C2—C7	1.385 (5)	C15—H15A	0.9600
C2—C3	1.405 (5)	C15—H15B	0.9600
C3—C4	1.393 (5)	C15—H15C	0.9600
C4—C5	1.353 (5)	C16—H16A	0.9600
C4—H4	0.9300	C16—H16B	0.9600
C5—C6	1.383 (5)	C16—H16C	0.9600
C5—H5	0.9300	CG1—CG2^i	3.8154 (2)
O3—Sn1—C16	95.08 (14)	C6—C7—H7	119.7
O3—Sn1—C15	100.23 (14)	C2—C7—H7	119.7
C16—Sn1—C15	129.29 (15)	N2—C8—C9	127.6 (3)
O3—Sn1—N2	83.30 (10)	N2—C8—H8	116.2
C16—Sn1—N2	121.70 (13)	C9—C8—H8	116.2
C15—Sn1—N2	108.00 (13)	C10—C9—C14	119.9 (3)
O3—Sn1—O2	154.56 (10)	C10—C9—C8	117.3 (3)
C16—Sn1—O2	91.59 (13)	C14—C9—C8	122.6 (3)
C15—Sn1—O2	94.35 (13)	C11—C10—C9	121.4 (4)
N2—Sn1—O2	72.36 (10)	C11—C10—H10	119.3
C1—N1—N2	112.1 (3)	C9—C10—H10	119.3
C8—N2—N1	115.4 (3)	C12—C11—C10	118.4 (4)
C8—N2—Sn1	128.0 (2)	C12—C11—H11	120.8
N1—N2—Sn1	116.6 (2)	C10—C11—H11	120.8
C3—O1—H1	109.5	C13—C12—C11	122.2 (4)
C1—O2—Sn1	114.5 (2)	C13—C12—H12	118.9
C14—O3—Sn1	133.1 (2)	C11—C12—H12	118.9
O2—C1—N1	124.4 (3)	C12—C13—C14	121.1 (4)
O2—C1—C2	118.6 (3)	C12—C13—H13	119.4
N1—C1—C2	117.1 (3)	C14—C13—H13	119.4
C7—C2—C3	118.6 (3)	O3—C14—C13	118.9 (3)
C7—C2—C1	119.3 (3)	O3—C14—C9	124.0 (3)
C3—C2—C1	122.1 (3)	C13—C14—C9	117.0 (4)
O1—C3—C4	117.7 (3)	Sn1—C15—H15A	109.5
O1—C3—C2	123.0 (3)	Sn1—C15—H15B	109.5
C4—C3—C2	119.4 (4)	H15A—C15—H15B	109.5
C5—C4—C3	121.3 (4)	Sn1—C15—H15C	109.5
C5—C4—H4	119.4	H15A—C15—H15C	109.5
C3—C4—H4	119.4	H15B—C15—H15C	109.5
C4—C5—C6	119.6 (4)	Sn1—C16—H16A	109.5
C4—C5—H5	120.2	Sn1—C16—H16B	109.5
C6—C5—H5	120.2	H16A—C16—H16B	109.5
C7—C6—C5	120.4 (4)	Sn1—C16—H16C	109.5
C7—C6—Cl1	120.0 (3)	H16A—C16—H16C	109.5
C5—C6—Cl1	119.5 (3)	H16B—C16—H16C	109.5
C6—C7—C2	120.7 (3)
C1—N1—N2—C8	178.1 (3)	C7—C2—C3—C4	−2.1 (5)
C1—N1—N2—Sn1	0.5 (4)	C1—C2—C3—C4	175.8 (3)
O3—Sn1—N2—C8	10.7 (3)	O1—C3—C4—C5	−179.2 (4)
C16—Sn1—N2—C8	102.5 (3)	C2—C3—C4—C5	1.8 (6)
C15—Sn1—N2—C8	−87.9 (3)	C3—C4—C5—C6	−0.6 (6)
O2—Sn1—N2—C8	−176.8 (3)	C4—C5—C6—C7	−0.4 (6)
O3—Sn1—N2—N1	−172.0 (2)	C4—C5—C6—Cl1	−179.7 (3)
C16—Sn1—N2—N1	−80.1 (3)	C5—C6—C7—C2	0.1 (6)
C15—Sn1—N2—N1	89.4 (3)	Cl1—C6—C7—C2	179.4 (3)
O2—Sn1—N2—N1	0.5 (2)	C3—C2—C7—C6	1.2 (5)
O3—Sn1—O2—C1	16.0 (4)	C1—C2—C7—C6	−176.8 (3)
C16—Sn1—O2—C1	121.4 (3)	N1—N2—C8—C9	177.0 (3)
C15—Sn1—O2—C1	−109.0 (3)	Sn1—N2—C8—C9	−5.6 (5)
N2—Sn1—O2—C1	−1.5 (2)	N2—C8—C9—C10	179.8 (4)
C16—Sn1—O3—C14	−132.8 (4)	N2—C8—C9—C14	−4.8 (6)
C15—Sn1—O3—C14	95.7 (4)	C14—C9—C10—C11	0.1 (6)
N2—Sn1—O3—C14	−11.5 (4)	C8—C9—C10—C11	175.6 (4)
O2—Sn1—O3—C14	−28.3 (5)	C9—C10—C11—C12	−0.7 (6)
Sn1—O2—C1—N1	2.6 (4)	C10—C11—C12—C13	0.9 (7)
Sn1—O2—C1—C2	−178.2 (2)	C11—C12—C13—C14	−0.3 (7)
N2—N1—C1—O2	−2.1 (5)	Sn1—O3—C14—C13	−174.0 (3)
N2—N1—C1—C2	178.7 (3)	Sn1—O3—C14—C9	6.4 (6)
O2—C1—C2—C7	3.3 (5)	C12—C13—C14—O3	180.0 (4)
N1—C1—C2—C7	−177.4 (3)	C12—C13—C14—C9	−0.4 (6)
O2—C1—C2—C3	−174.6 (3)	C10—C9—C14—O3	−179.9 (4)
N1—C1—C2—C3	4.8 (5)	C8—C9—C14—O3	4.8 (6)
C7—C2—C3—O1	179.0 (3)	C10—C9—C14—C13	0.5 (5)
C1—C2—C3—O1	−3.1 (5)	C8—C9—C14—C13	−174.8 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15A···O1^i	0.96	2.59	3.430 (5)	147
O1—H1···N1	0.82	1.87	2.577 (4)	144

Symmetry code: (i) −x+1, −y+1, −z+1.