{4-Hy­droxy-N′-[(2E,3Z)-4-oxido-4-phenyl­but-3-en-2-yl­idene]benzo­hydrazidato}dimethyl­tin(IV)

The Sn^IV atom in the title compound, [Sn(CH₃)₂(C₁₇H₁₄N₂O₃)], is five-coordinated within a C₂N₂O donor set provided by the N,N,O-tridentate ligand and two methyl groups. The resultant coordination geometry is inter­mediate between trigonal-bipyramidal and square-pyramidal. In the crystal, supra­molecular zigzag chains propagating along the c- axis direction are mediated by O—H...O hydrogen bonds, and weak C—H...π inter­actions consolidate the packing.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.032
• wR factor = 0.081
• Data-to-parameter ratio = 13.6

checkCIF/PLATON results

No syntax errors found



Alert level C
THETM01_ALERT_3_C  The value of sine(theta_max)/wavelength is less than 0.590
            Calculated sin(theta_max)/wavelength =    0.5878
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.588         27

Alert level G
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still          79 Perc.

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   1 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The title compound, (I), was examined in connection with on-going structural studies (Affan et al., 2010) of organotin derivatives of biological interest (Affan et al., 2009), and compliments the structure of the diphenyltin analogue (Affan et al., 2011).

The Sn atom in (I), Fig. 1, is five-coordinated by the tridentate ligand and two methyl groups, Table 1. The resulting C₂NO₂ donor set defines a coordination geometry intermediate between square pyramidal and trigonal bipyramidal geometry. This is quantified by the value of τ = 0.51 which compare to the τ values of 0.0 and 1.0 for ideal square pyramidal and trigonal bipyramidal geometries, respectively (Addison et al., 1984). For comparison, the values of τ for the two independent molecules in the structure of the diphenyltin analogue are 0.55 and 0.47 (Affan et al., 2011).

While the five-membered SnCN₂O chelate ring is almost planar with a r.m.s. deviation = 0.063 Å [max. deviations of 0.039 (1) and -0.052 (2) Å for the Sn and O1 atoms, respectively], there is considerable distortion in the SnC₃NO six-membered chelate [r.m.s. deviation = 0.226 Å] with the Sn and O3 atoms lying -0.209 (1) and 0.245 (3) Å out of the least-squares plane. Each of the benzene rings is twisted out of the plane from the adjacent chelate ring as seen in the O1—C1—C2—C3 and O3—C11—C12—C13 torsion angles of 13.7 (5) and -150.4 (4)°, respectively. The dihedral angle between the two benzene rings is 68.14 (18) °, indicating a twist in the tridentate ligand.

The crystal packing is dominated by O—H···O hydrogen bonding, Table 2, which leads to a zigzag supramolecular chain along the c axis, Fig. 2. These are consolidated in the crystal structure by C—H···π interactions, Table 2.

Related literature

For background to the biological interest of related compounds, see: Affan et al. (2010). For related structures, see: Affan et al. (2009, 2011). For additional structural analysis, see: Addison et al. (1984).

S2. Experimental

Benzoylacetone 4-hydroxybenzhydrazone (0.59 g, 2 mmol) was dissolved in distilled methanol (20 ml) under a nitrogen atmosphere. Potassium hydroxide (0.23 g, 4 mmol) dissolved in methanol (10 ml) was added drop wise to the solution. The colour of the solution changed from yellow to orange. The resulting mixture was refluxed for 1 h and then treated with dimethyltin dichloride (0.439 g, 2 mmol) in distilled methanol (10 ml). The resulting mixture was heated under reflux conditions for 4 h and allowed to cool to room temperature. Potassium chloride (KCl) was removed via filtration. The filtrate was evaporated to dryness using a rotary evaporator to yield yellow microcrystals. The microcrystals were filtered off and washed with ethanol and dried in vacuo over P₂O₅ overnight. Yellow blocks of (I) were obtained by slow evaporation of its acetone solution at room temperature. Yield: 0.94 g, 75%. M.pt.: 504–506 K. IR (ν_max, cm^-1, KBr): 3569 (OH), 1591 (C═N—N═C), 949 (N—N), 562 (Sn—C), 525 (Sn—O), 447 (Sn—N).

S3. Refinement

Carbon-bound H-atoms were placed in calculated positions (O—H = 0.84 Å; C—H = 0.95 to 0.98 Å) and were included in the refinement in the riding model approximation with U_iso(H) set to 1.2-U_eq(C) and 1.5-U_eq(O, methyl-C).

Computing details

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures

	Fig. 1. The molecular structure of (I) showing displacement ellipsoids at the 50% probability level.
	Fig. 2. A view of the supramolecular chain aligned along [001] in (I). The O—H···O hydrogen bonds are shown as orange dashed lines.
	Fig. 3. A view in projection down the c axis of the crystal packing in (I). The O—H···O hydrogen bonds and C—H···π interactions are shown as orange and purple dashed lines, respectively.

{4-Hydroxy-N-[(2E,3Z)-4-oxido-4-phenylbut-3-en-2- ylidene]benzohydrazidato}dimethyltin(IV)

Crystal data

[Sn(CH3)2(C17H14N2O3)]	F(000) = 888
Mr = 443.06	Dx = 1.590 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 3495 reflections
a = 8.0784 (2) Å	θ = 4.0–74.2°
b = 20.5410 (5) Å	µ = 11.15 mm^−1
c = 11.1678 (3) Å	T = 150 K
β = 93.025 (2)°	Block, yellow
V = 1850.58 (8) Å^3	0.22 × 0.16 × 0.10 mm
Z = 4

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector	3124 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	2690 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.038
ω scans	θmax = 65.0°, θmin = 4.5°
Absorption correction: analytical (CrysAlis PRO; Agilent, 2011)	h = −6→9
Tmin = 0.696, Tmax = 0.822	k = −24→24
5718 measured reflections	l = −13→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.081	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0384P)^2] where P = (Fo^2 + 2Fc^2)/3
3124 reflections	(Δ/σ)max < 0.001
230 parameters	Δρmax = 0.76 e Å^−3
0 restraints	Δρmin = −0.72 e Å^−3

Special details

Experimental. Agilent Technologies (2011) CrysAlis PRO Software system, version 1.171.34.49, Agilent Technologies UK Ltd, Oxford, UK

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.

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

	x	y	z	Uiso*/Ueq
Sn	0.18670 (3)	0.011355 (13)	0.22279 (2)	0.02375 (11)
O1	0.0690 (3)	0.09638 (13)	0.2930 (2)	0.0267 (6)
O2	−0.0780 (3)	0.34947 (13)	0.5942 (2)	0.0309 (6)
H2o	−0.0354	0.3553	0.6636	0.046*
O3	0.3618 (3)	−0.06412 (14)	0.2237 (2)	0.0333 (7)
N1	0.1880 (4)	0.06513 (16)	0.4764 (3)	0.0242 (7)
N2	0.2394 (4)	0.01068 (16)	0.4134 (3)	0.0232 (7)
C1	0.1054 (4)	0.10630 (19)	0.4079 (3)	0.0230 (8)
C2	0.0519 (4)	0.16830 (19)	0.4610 (3)	0.0208 (8)
C3	−0.0628 (5)	0.2084 (2)	0.3999 (3)	0.0263 (9)
H3	−0.1131	0.1942	0.3256	0.032*
C4	−0.1051 (5)	0.2685 (2)	0.4452 (3)	0.0275 (9)
H4	−0.1835	0.2952	0.4020	0.033*
C5	−0.0331 (5)	0.28957 (19)	0.5535 (3)	0.0240 (8)
C6	0.0800 (4)	0.2492 (2)	0.6178 (3)	0.0250 (8)
H6	0.1282	0.2631	0.6929	0.030*
C7	0.1213 (4)	0.18929 (19)	0.5719 (3)	0.0245 (8)
H7	0.1975	0.1621	0.6159	0.029*
C8	0.2979 (5)	−0.0386 (2)	0.4775 (3)	0.0247 (8)
C9	0.3027 (5)	−0.0339 (2)	0.6122 (3)	0.0311 (9)
H9A	0.3736	0.0027	0.6385	0.047*
H9B	0.3474	−0.0744	0.6472	0.047*
H9C	0.1903	−0.0269	0.6385	0.047*
C10	0.3544 (5)	−0.0971 (2)	0.4265 (3)	0.0268 (9)
H10	0.3750	−0.1326	0.4797	0.032*
C11	0.3827 (5)	−0.1079 (2)	0.3075 (3)	0.0255 (9)
C12	0.4463 (4)	−0.1711 (2)	0.2669 (3)	0.0243 (8)
C13	0.4076 (5)	−0.2292 (2)	0.3228 (4)	0.0286 (9)
H13	0.3440	−0.2285	0.3919	0.034*
C14	0.4607 (5)	−0.2880 (2)	0.2787 (4)	0.0340 (10)
H14	0.4317	−0.3274	0.3169	0.041*
C15	0.5565 (5)	−0.2900 (2)	0.1787 (4)	0.0365 (10)
H15	0.5938	−0.3304	0.1489	0.044*
C16	0.5966 (5)	−0.2323 (2)	0.1232 (4)	0.0351 (10)
H16	0.6629	−0.2332	0.0554	0.042*
C17	0.5410 (5)	−0.1731 (2)	0.1658 (4)	0.0295 (9)
H17	0.5674	−0.1339	0.1260	0.035*
C18	0.3273 (6)	0.0647 (2)	0.1034 (4)	0.0379 (11)
H18A	0.4406	0.0701	0.1380	0.057*
H18B	0.2767	0.1076	0.0896	0.057*
H18C	0.3302	0.0413	0.0271	0.057*
C19	−0.0261 (6)	−0.0439 (2)	0.1720 (4)	0.0451 (12)
H19A	−0.0003	−0.0739	0.1074	0.068*
H19B	−0.1158	−0.0146	0.1439	0.068*
H19C	−0.0611	−0.0688	0.2411	0.068*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sn	0.02822 (16)	0.02438 (17)	0.01860 (15)	0.00018 (11)	0.00060 (10)	−0.00033 (10)
O1	0.0341 (15)	0.0238 (15)	0.0217 (14)	0.0056 (12)	−0.0027 (10)	−0.0038 (11)
O2	0.0410 (17)	0.0274 (16)	0.0237 (15)	0.0055 (13)	−0.0045 (12)	−0.0050 (12)
O3	0.0419 (17)	0.0311 (16)	0.0277 (15)	0.0123 (14)	0.0084 (12)	0.0059 (13)
N1	0.0271 (17)	0.0232 (18)	0.0222 (16)	0.0013 (14)	0.0008 (13)	−0.0027 (14)
N2	0.0250 (16)	0.0260 (18)	0.0192 (16)	0.0003 (14)	0.0042 (13)	0.0003 (14)
C1	0.0199 (18)	0.029 (2)	0.0200 (19)	−0.0050 (16)	0.0023 (14)	0.0008 (17)
C2	0.0194 (18)	0.024 (2)	0.0195 (18)	−0.0024 (16)	0.0012 (14)	0.0012 (15)
C3	0.025 (2)	0.033 (2)	0.0200 (19)	−0.0033 (18)	−0.0027 (15)	−0.0012 (17)
C4	0.029 (2)	0.029 (2)	0.0241 (19)	0.0065 (18)	−0.0018 (15)	−0.0001 (17)
C5	0.026 (2)	0.025 (2)	0.0218 (19)	−0.0037 (17)	0.0009 (14)	−0.0006 (16)
C6	0.025 (2)	0.029 (2)	0.0204 (18)	−0.0059 (17)	−0.0005 (15)	−0.0040 (17)
C7	0.0220 (19)	0.028 (2)	0.0238 (19)	−0.0009 (17)	−0.0001 (14)	0.0034 (17)
C8	0.0236 (19)	0.029 (2)	0.0211 (19)	−0.0008 (18)	0.0019 (14)	0.0010 (17)
C9	0.044 (2)	0.029 (2)	0.020 (2)	0.002 (2)	0.0029 (17)	−0.0001 (18)
C10	0.030 (2)	0.027 (2)	0.0237 (19)	0.0031 (18)	0.0024 (15)	0.0033 (17)
C11	0.0230 (19)	0.027 (2)	0.026 (2)	−0.0023 (17)	0.0008 (15)	−0.0008 (17)
C12	0.0177 (18)	0.028 (2)	0.027 (2)	0.0000 (16)	−0.0033 (14)	−0.0035 (17)
C13	0.023 (2)	0.032 (2)	0.031 (2)	−0.0025 (18)	0.0005 (16)	−0.0011 (18)
C14	0.027 (2)	0.027 (2)	0.047 (3)	−0.0004 (19)	−0.0059 (18)	−0.001 (2)
C15	0.031 (2)	0.036 (3)	0.041 (3)	0.009 (2)	−0.0062 (18)	−0.011 (2)
C16	0.028 (2)	0.046 (3)	0.031 (2)	0.008 (2)	0.0005 (17)	−0.004 (2)
C17	0.026 (2)	0.034 (2)	0.028 (2)	0.0020 (19)	0.0032 (15)	0.0007 (19)
C18	0.043 (3)	0.040 (3)	0.031 (2)	−0.008 (2)	0.0029 (18)	0.003 (2)
C19	0.045 (3)	0.042 (3)	0.048 (3)	−0.011 (2)	0.006 (2)	−0.020 (2)

Geometric parameters (Å, º)

Sn—O1	2.156 (3)	C8—C9	1.506 (5)
Sn—O3	2.099 (3)	C9—H9A	0.9800
Sn—N2	2.148 (3)	C9—H9B	0.9800
Sn—C18	2.105 (4)	C9—H9C	0.9800
Sn—C19	2.112 (4)	C10—C11	1.377 (5)
O1—C1	1.317 (4)	C10—H10	0.9500
O2—C5	1.367 (5)	C11—C12	1.476 (5)
O2—H2O	0.8400	C12—C13	1.390 (6)
O3—C11	1.303 (5)	C12—C17	1.398 (5)
N1—C1	1.300 (5)	C13—C14	1.380 (6)
N1—N2	1.396 (4)	C13—H13	0.9500
N2—C8	1.313 (5)	C14—C15	1.393 (6)
C1—C2	1.479 (5)	C14—H14	0.9500
C2—C3	1.391 (5)	C15—C16	1.384 (6)
C2—C7	1.400 (5)	C15—H15	0.9500
C3—C4	1.384 (6)	C16—C17	1.388 (6)
C3—H3	0.9500	C16—H16	0.9500
C4—C5	1.383 (5)	C17—H17	0.9500
C4—H4	0.9500	C18—H18A	0.9800
C5—C6	1.404 (5)	C18—H18B	0.9800
C6—C7	1.381 (5)	C18—H18C	0.9800
C6—H6	0.9500	C19—H19A	0.9800
C7—H7	0.9500	C19—H19B	0.9800
C8—C10	1.417 (5)	C19—H19C	0.9800
O3—Sn—C18	90.09 (15)	C8—C9—H9B	109.5
O3—Sn—C19	98.26 (16)	H9A—C9—H9B	109.5
O1—Sn—O3	155.08 (10)	C8—C9—H9C	109.5
C18—Sn—C19	124.65 (18)	H9A—C9—H9C	109.5
O3—Sn—N2	83.82 (11)	H9B—C9—H9C	109.5
C18—Sn—N2	123.05 (15)	C11—C10—C8	126.7 (4)
C19—Sn—N2	112.24 (16)	C11—C10—H10	116.7
C18—Sn—O1	94.10 (15)	C8—C10—H10	116.7
C19—Sn—O1	99.46 (15)	O3—C11—C10	124.1 (4)
N2—Sn—O1	73.31 (11)	O3—C11—C12	114.8 (3)
C1—O1—Sn	113.6 (2)	C10—C11—C12	121.0 (4)
C5—O2—H2O	109.5	C13—C12—C17	118.8 (4)
C11—O3—Sn	125.1 (2)	C13—C12—C11	121.8 (3)
C1—N1—N2	112.4 (3)	C17—C12—C11	119.3 (4)
C8—N2—N1	116.8 (3)	C14—C13—C12	120.7 (4)
C8—N2—Sn	126.3 (3)	C14—C13—H13	119.7
N1—N2—Sn	116.5 (2)	C12—C13—H13	119.7
N1—C1—O1	123.6 (4)	C13—C14—C15	120.5 (4)
N1—C1—C2	118.4 (3)	C13—C14—H14	119.7
O1—C1—C2	118.0 (3)	C15—C14—H14	119.7
C3—C2—C7	118.5 (4)	C16—C15—C14	119.1 (4)
C3—C2—C1	121.0 (3)	C16—C15—H15	120.4
C7—C2—C1	120.5 (3)	C14—C15—H15	120.4
C4—C3—C2	121.3 (4)	C15—C16—C17	120.6 (4)
C4—C3—H3	119.3	C15—C16—H16	119.7
C2—C3—H3	119.3	C17—C16—H16	119.7
C5—C4—C3	119.9 (4)	C16—C17—C12	120.3 (4)
C5—C4—H4	120.1	C16—C17—H17	119.9
C3—C4—H4	120.1	C12—C17—H17	119.9
O2—C5—C4	117.8 (3)	Sn—C18—H18A	109.5
O2—C5—C6	122.6 (3)	Sn—C18—H18B	109.5
C4—C5—C6	119.6 (4)	H18A—C18—H18B	109.5
C7—C6—C5	120.0 (3)	Sn—C18—H18C	109.5
C7—C6—H6	120.0	H18A—C18—H18C	109.5
C5—C6—H6	120.0	H18B—C18—H18C	109.5
C6—C7—C2	120.7 (4)	Sn—C19—H19A	109.5
C6—C7—H7	119.7	Sn—C19—H19B	109.5
C2—C7—H7	119.7	H19A—C19—H19B	109.5
N2—C8—C10	123.3 (3)	Sn—C19—H19C	109.5
N2—C8—C9	119.0 (4)	H19A—C19—H19C	109.5
C10—C8—C9	117.7 (4)	H19B—C19—H19C	109.5
C8—C9—H9A	109.5
O3—Sn—O1—C1	−17.4 (4)	C3—C4—C5—O2	179.6 (3)
C18—Sn—O1—C1	−116.5 (3)	C3—C4—C5—C6	−1.3 (6)
C19—Sn—O1—C1	117.4 (3)	O2—C5—C6—C7	−179.7 (3)
N2—Sn—O1—C1	6.8 (2)	C4—C5—C6—C7	1.2 (6)
C18—Sn—O3—C11	158.3 (3)	C5—C6—C7—C2	0.3 (6)
C19—Sn—O3—C11	−76.6 (3)	C3—C2—C7—C6	−1.7 (5)
N2—Sn—O3—C11	35.0 (3)	C1—C2—C7—C6	175.6 (3)
O1—Sn—O3—C11	58.3 (4)	N1—N2—C8—C10	179.9 (3)
C1—N1—N2—C8	−168.5 (3)	Sn—N2—C8—C10	8.0 (5)
C1—N1—N2—Sn	4.2 (4)	N1—N2—C8—C9	1.2 (5)
O3—Sn—N2—C8	−24.1 (3)	Sn—N2—C8—C9	−170.7 (3)
C18—Sn—N2—C8	−110.2 (3)	N2—C8—C10—C11	11.3 (6)
C19—Sn—N2—C8	72.3 (3)	C9—C8—C10—C11	−170.0 (4)
O1—Sn—N2—C8	165.9 (3)	Sn—O3—C11—C10	−30.7 (5)
O3—Sn—N2—N1	164.0 (3)	Sn—O3—C11—C12	151.4 (3)
C18—Sn—N2—N1	78.0 (3)	C8—C10—C11—O3	0.6 (6)
C19—Sn—N2—N1	−99.5 (3)	C8—C10—C11—C12	178.3 (4)
O1—Sn—N2—N1	−5.9 (2)	O3—C11—C12—C13	−150.4 (4)
N2—N1—C1—O1	2.4 (5)	C10—C11—C12—C13	31.7 (5)
N2—N1—C1—C2	−176.3 (3)	O3—C11—C12—C17	26.3 (5)
Sn—O1—C1—N1	−7.7 (5)	C10—C11—C12—C17	−151.6 (4)
Sn—O1—C1—C2	171.1 (2)	C17—C12—C13—C14	−0.5 (6)
N1—C1—C2—C3	−167.5 (3)	C11—C12—C13—C14	176.2 (4)
O1—C1—C2—C3	13.7 (5)	C12—C13—C14—C15	1.1 (6)
N1—C1—C2—C7	15.3 (5)	C13—C14—C15—C16	−0.6 (6)
O1—C1—C2—C7	−163.5 (3)	C14—C15—C16—C17	−0.6 (6)
C7—C2—C3—C4	1.7 (6)	C15—C16—C17—C12	1.3 (6)
C1—C2—C3—C4	−175.6 (3)	C13—C12—C17—C16	−0.7 (6)
C2—C3—C4—C5	−0.2 (6)	C11—C12—C17—C16	−177.5 (4)

Hydrogen-bond geometry (Å, º)

Cg1, Cg2 and Cg3 are the centroids of the C12–C17, Sn,O1,C1,N1,N2 and C2–C7 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2o···O1^i	0.84	1.91	2.702 (3)	156
C4—H4···Cg1^ii	0.95	2.91	3.624 (4)	133
C9—H9c···Cg2^iii	0.98	2.88	3.777 (4)	152
C16—H16···Cg3^iv	0.95	2.89	3.668 (4)	140

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x, y+1/2, −z+1/2; (iii) −x, −y, −z+1; (iv) −x+1, y−1/2, −z+1/2.