Bis(acetohydroxamato-κ2O,O′)diphenyl­tin(IV)

Yue, C.; Wu, Q.; Yin, H.

doi:10.1107/S160053681102558X

metal-organic compounds

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Volume 67| Part 8| August 2011| Page m1034

doi:10.1107/S160053681102558X

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Bis(acetohydroxamato-κ²O,O′)diphenyltin(IV)

Caihong Yue,^a Qingkun Wu ^a and Handong Yin ^a ^*

^aCollege of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China
^*Correspondence e-mail: handongyin@163.com

(Received 10 June 2011; accepted 29 June 2011; online 6 July 2011)

The complex molecule of the title compound, [Sn(C₆H₅)₂(C₂H₄NO₂)₂], has crystallographically imposed twofold symmetry. The Sn atom is coordinated by four O atoms from two acetohydroxamate ligands and by two C atoms from phenyl groups in a distorted octahedral geometry. In the crystal, molecules are connected by N—H⋯O hydrogen-bonding interactions, forming a chain structure along the c axis

Related literature

For the biological activity of diorganotin(IV) complexes with hydroxamates, see: Shang et al. (2007 ). For a related structure, see: Harrison et al. (1976 ). For van der Waals radii, see: Bondi (1964 ).

Experimental

Crystal data

[Sn(C₆H₅)₂(C₂H₄NO₂)₂]
M_r = 421.01
Monoclinic, C 2/c
a = 18.7713 (17) Å
b = 10.2683 (8) Å
c = 9.8326 (6) Å
β = 112.842 (1)°
V = 1746.6 (2) Å³
Z = 4
Mo Kα radiation
μ = 1.48 mm⁻¹
T = 298 K
0.38 × 0.33 × 0.19 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.603, T_max = 0.766
4295 measured reflections
1542 independent reflections
1367 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.077
S = 1.00
1542 reflections
106 parameters
H-atom parameters constrained
Δρ_max = 0.72 e Å⁻³
Δρ_min = −0.94 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	2.03	2.847 (4)	159
Symmetry code: (i) $[x, -y+1, z-{\script{1\over 2}}]$ .

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681102558X/rz2612sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681102558X/rz2612Isup2.hkl

checkCIF report

Comment top

Among many multidentate organic ligands, hydroxamic acids are of particular importance, because of their remarkable structural diversity and biological applications (Shang et al. , 2007). As a continuation of our interest in this area, we have synthesized the title compound and report its crystal structure herein.

The molecular structure of the compound is depicted in Fig. 1. The complex molecule has crystallographically imposed two-fold symmetry. The tin atom is six-coordinated in a distorted octahedral geometry. The Sn–O bond distances (Sn1–O2 = 2.103 (2) Å; Sn1–O = 2.275 (3) Å) are close to the sum of the covalent radii (2.13 Å; Bondi, 1964), and the Sn–C distance (Sn1–C3 = 2.147 (4) Å) are in the range observed in a related compound (2.14–2.18 Å; Harrison et al., 1976). In the crystal packing, the molecules are linked by N—H···O hydrogen bonds (Table 1) into a one-dimensional chains parallel to the c axis (Fig. 2).

Related literature top

For the biological activity of diorganotin(IV) complexes with hydroxamates, see: Shang et al. (2007). For a related structure, see: Harrison et al. (1976). For van der Waals radii, see: Bondi (1964).

Experimental top

The reaction was carried out under nitrogen atmosphere. Acetohydroxamic acid (0.4 mmol) and KOH (0.4 mmol) in methanol (30 ml) were added to a Schlenk flask and stirred for 30 min. Diphenyltin dichloride (0.2 mmol) was then added to the reactor. The reaction mixture was stirred for 8 h at room temperature and then filtrated. The filtrate was evaporated in vacuo to dryness. The obtained solid was recrystallized from a dichloromethane-petroleum ether (3:1 v/v) solution (yield 86%; m. p. 431 K). Anal. Calcd (%) for C₁₆H₁₈N₂O₄Sn (Mr = 421.01): C, 45.64; H, 4.31; N, 6.65; O, 15.20. Found (%): C, 45.60; H, 4.25; N, 6.62; O,15.16.

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

	Fig. 1. The molecular structure of the compound, showing 50% probability displacement ellipsoids. H atoms are omitted for clarity. Symmetry code: (A) = -x, y, -z + 1/2.
	Fig. 2. View of the one-dimensional linear chain structure in the title compound.

Bis(acetohydroxamato-κ²O,O')diphenyltin(IV) top

Crystal data top

[Sn(C₆H₅)₂(C₂H₄NO₂)₂]	F(000) = 840
M_r = 421.01	D_x = 1.601 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2602 reflections
a = 18.7713 (17) Å	θ = 2.3–26.2°
b = 10.2683 (8) Å	µ = 1.48 mm⁻¹
c = 9.8326 (6) Å	T = 298 K
β = 112.842 (1)°	Block, colourless
V = 1746.6 (2) Å³	0.38 × 0.33 × 0.19 mm
Z = 4

Data collection top

Siemens SMART CCD area-detector diffractometer	1542 independent reflections
Radiation source: fine-focus sealed tube	1367 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
phi and ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −22→14
T_min = 0.603, T_max = 0.766	k = −12→11
4295 measured reflections	l = −11→11

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.077	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0322P)² + 6.1631P] where P = (F_o² + 2F_c²)/3
1542 reflections	(Δ/σ)_max < 0.001
106 parameters	Δρ_max = 0.72 e Å⁻³
0 restraints	Δρ_min = −0.94 e Å⁻³

Crystal data top

[Sn(C₆H₅)₂(C₂H₄NO₂)₂]	V = 1746.6 (2) Å³
M_r = 421.01	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 18.7713 (17) Å	µ = 1.48 mm⁻¹
b = 10.2683 (8) Å	T = 298 K
c = 9.8326 (6) Å	0.38 × 0.33 × 0.19 mm
β = 112.842 (1)°

Data collection top

Siemens SMART CCD area-detector diffractometer	1542 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1367 reflections with I > 2σ(I)
T_min = 0.603, T_max = 0.766	R_int = 0.048
4295 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.077	H-atom parameters constrained
S = 1.00	Δρ_max = 0.72 e Å⁻³
1542 reflections	Δρ_min = −0.94 e Å⁻³
106 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Sn1	0.0000	0.27983 (4)	0.2500	0.03426 (15)
O1	−0.07784 (14)	0.4550 (3)	0.2287 (3)	0.0377 (6)
O2	−0.04374 (15)	0.3345 (3)	0.0264 (3)	0.0399 (6)
N1	−0.07653 (16)	0.4552 (3)	0.0036 (3)	0.0371 (7)
H1	−0.0874	0.4929	−0.0802	0.045*
C1	−0.0919 (2)	0.5148 (4)	0.1067 (4)	0.0356 (8)
C2	−0.1242 (3)	0.6484 (5)	0.0813 (5)	0.0599 (12)
H2A	−0.1762	0.6467	0.0766	0.090*
H2B	−0.1241	0.6812	−0.0101	0.090*
H2C	−0.0932	0.7039	0.1608	0.090*
C3	0.0918 (2)	0.1575 (4)	0.2454 (4)	0.0393 (9)
C4	0.0752 (3)	0.0355 (5)	0.1751 (5)	0.0591 (12)
H4	0.0244	0.0061	0.1339	0.071*
C5	0.1343 (4)	−0.0411 (6)	0.1669 (7)	0.0833 (19)
H5	0.1228	−0.1216	0.1200	0.100*
C6	0.2094 (3)	0.0010 (7)	0.2273 (7)	0.0827 (18)
H6	0.2485	−0.0494	0.2182	0.099*
C7	0.2269 (3)	0.1177 (6)	0.3013 (6)	0.0710 (15)
H7	0.2781	0.1450	0.3452	0.085*
C8	0.1685 (2)	0.1946 (5)	0.3103 (5)	0.0506 (11)
H8	0.1811	0.2731	0.3612	0.061*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.0343 (2)	0.0369 (2)	0.0340 (2)	0.000	0.01590 (15)	0.000
O1	0.0429 (14)	0.0422 (16)	0.0321 (13)	0.0038 (12)	0.0190 (11)	0.0018 (11)
O2	0.0462 (15)	0.0414 (16)	0.0324 (13)	−0.0006 (13)	0.0158 (11)	−0.0028 (12)
N1	0.0322 (16)	0.049 (2)	0.0299 (16)	−0.0002 (14)	0.0117 (13)	0.0062 (14)
C1	0.0300 (18)	0.043 (2)	0.0332 (19)	−0.0028 (16)	0.0122 (15)	0.0030 (16)
C2	0.073 (3)	0.055 (3)	0.061 (3)	0.019 (3)	0.036 (2)	0.015 (2)
C3	0.040 (2)	0.043 (2)	0.0341 (19)	0.0034 (18)	0.0137 (16)	−0.0027 (17)
C4	0.057 (3)	0.051 (3)	0.061 (3)	0.003 (2)	0.014 (2)	−0.017 (2)
C5	0.089 (4)	0.069 (4)	0.087 (4)	0.020 (3)	0.029 (3)	−0.031 (3)
C6	0.068 (4)	0.091 (5)	0.091 (4)	0.033 (3)	0.034 (3)	−0.012 (4)
C7	0.043 (3)	0.080 (4)	0.087 (4)	0.014 (3)	0.022 (2)	0.002 (3)
C8	0.042 (2)	0.046 (3)	0.063 (3)	0.0045 (19)	0.019 (2)	−0.003 (2)

Geometric parameters (Å, º) top

Sn1—O2ⁱ	2.103 (2)	C2—H2C	0.9600
Sn1—O2	2.103 (2)	C3—C8	1.383 (6)
Sn1—C3ⁱ	2.147 (4)	C3—C4	1.406 (6)
Sn1—C3	2.147 (4)	C4—C5	1.388 (7)
Sn1—O1ⁱ	2.275 (3)	C4—H4	0.9300
Sn1—O1	2.275 (3)	C5—C6	1.371 (9)
O1—C1	1.281 (4)	C5—H5	0.9300
O2—N1	1.363 (4)	C6—C7	1.374 (8)
N1—C1	1.308 (5)	C6—H6	0.9300
N1—H1	0.8600	C7—C8	1.381 (7)
C1—C2	1.482 (6)	C7—H7	0.9300
C2—H2A	0.9600	C8—H8	0.9300
C2—H2B	0.9600

O2ⁱ—Sn1—O2	149.02 (16)	C1—C2—H2B	109.5
O2ⁱ—Sn1—C3ⁱ	97.18 (12)	H2A—C2—H2B	109.5
O2—Sn1—C3ⁱ	100.81 (12)	C1—C2—H2C	109.5
O2ⁱ—Sn1—C3	100.81 (12)	H2A—C2—H2C	109.5
O2—Sn1—C3	97.18 (12)	H2B—C2—H2C	109.5
C3ⁱ—Sn1—C3	108.4 (2)	C8—C3—C4	117.7 (4)
O2ⁱ—Sn1—O1ⁱ	73.53 (10)	C8—C3—Sn1	122.0 (3)
O2—Sn1—O1ⁱ	82.02 (10)	C4—C3—Sn1	120.3 (3)
C3ⁱ—Sn1—O1ⁱ	162.29 (13)	C5—C4—C3	120.2 (5)
C3—Sn1—O1ⁱ	88.41 (13)	C5—C4—H4	119.9
O2ⁱ—Sn1—O1	82.02 (10)	C3—C4—H4	119.9
O2—Sn1—O1	73.53 (10)	C6—C5—C4	120.5 (5)
C3ⁱ—Sn1—O1	88.41 (13)	C6—C5—H5	119.7
C3—Sn1—O1	162.29 (13)	C4—C5—H5	119.7
O1ⁱ—Sn1—O1	75.54 (13)	C5—C6—C7	119.9 (5)
C1—O1—Sn1	110.9 (2)	C5—C6—H6	120.1
N1—O2—Sn1	112.5 (2)	C7—C6—H6	120.1
C1—N1—O2	121.3 (3)	C6—C7—C8	120.0 (5)
C1—N1—H1	119.4	C6—C7—H7	120.0
O2—N1—H1	119.4	C8—C7—H7	120.0
O1—C1—N1	118.3 (4)	C7—C8—C3	121.5 (5)
O1—C1—C2	121.6 (4)	C7—C8—H8	119.2
N1—C1—C2	120.1 (3)	C3—C8—H8	119.2
C1—C2—H2A	109.5

O2ⁱ—Sn1—O1—C1	144.7 (2)	C3ⁱ—Sn1—C3—C8	−148.3 (4)
O2—Sn1—O1—C1	−16.0 (2)	O1ⁱ—Sn1—C3—C8	26.0 (4)
C3ⁱ—Sn1—O1—C1	−117.8 (3)	O1—Sn1—C3—C8	50.8 (6)
C3—Sn1—O1—C1	44.1 (5)	O2ⁱ—Sn1—C3—C4	133.1 (4)
O1ⁱ—Sn1—O1—C1	69.8 (2)	O2—Sn1—C3—C4	−72.2 (4)
O2ⁱ—Sn1—O2—N1	−24.99 (19)	C3ⁱ—Sn1—C3—C4	31.7 (3)
C3ⁱ—Sn1—O2—N1	99.4 (2)	O1ⁱ—Sn1—C3—C4	−154.0 (4)
C3—Sn1—O2—N1	−150.2 (2)	O1—Sn1—C3—C4	−129.2 (4)
O1ⁱ—Sn1—O2—N1	−62.9 (2)	C8—C3—C4—C5	−2.7 (7)
O1—Sn1—O2—N1	14.3 (2)	Sn1—C3—C4—C5	177.3 (4)
Sn1—O2—N1—C1	−12.8 (4)	C3—C4—C5—C6	0.1 (9)
Sn1—O1—C1—N1	15.1 (4)	C4—C5—C6—C7	2.3 (10)
Sn1—O1—C1—C2	−164.6 (3)	C5—C6—C7—C8	−2.2 (10)
O2—N1—C1—O1	−2.5 (5)	C6—C7—C8—C3	−0.4 (9)
O2—N1—C1—C2	177.2 (3)	C4—C3—C8—C7	2.8 (7)
O2ⁱ—Sn1—C3—C8	−46.9 (4)	Sn1—C3—C8—C7	−177.2 (4)
O2—Sn1—C3—C8	107.8 (4)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱⁱ	0.86	2.03	2.847 (4)	159

Symmetry code: (ii) x, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	[Sn(C₆H₅)₂(C₂H₄NO₂)₂]
M_r	421.01
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	18.7713 (17), 10.2683 (8), 9.8326 (6)
β (°)	112.842 (1)
V (Å³)	1746.6 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.48
Crystal size (mm)	0.38 × 0.33 × 0.19

Data collection
Diffractometer	Siemens SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.603, 0.766
No. of measured, independent and observed [I > 2σ(I)] reflections	4295, 1542, 1367
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.077, 1.00
No. of reflections	1542
No. of parameters	106
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.72, −0.94

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.03	2.847 (4)	159

Symmetry code: (i) x, −y+1, z−1/2.

Acknowledgements

We acknowledge the National Natural Science Foundation of China (20771053), the National Basic Research Program (No. 2010CB234601) and the Natural Science Foundation of Shandong Province (Y2008B48) for financial support.

References

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