(3-Amino-4-chloro­benzoato)trimethyl­tin(IV)

Aziz-ur-Rehman; Ali, S.; Helliwell, M.; Shahzadi, S.

doi:10.1107/S1600536806025517

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 62| Part 8| August 2006| Pages m1778-m1779

https://doi.org/10.1107/S1600536806025517

(3-Amino-4-chlorobenzoato)trimethyltin(IV)

Aziz-ur-Rehman,^a Saqib Ali,^a ^* Madeleine Helliwell ^b and Saira Shahzadi ^a

^aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, and ^bSchool of Chemistry, University of Manchester, Manchester, M13 9PL, England
^*Correspondence e-mail: drsa54@yahoo.com

(Received 23 June 2006; accepted 3 July 2006; online 12 July 2006)

In the title compound, [Sn(CH₃)₃(C₇H₅ClNO₂)], the Sn atom is bonded to three methyl groups and one O atom in a distorted tetrahedral geometry, with Sn—C bond lengths of 2.118 (2)–2.119 (2) Å and an Sn—O bond length of 2.0804 (12) Å.

Comment

In view of our interest in the synthesis, characterization, biological applications and crystal structures of organotin carboxylates (Danish et al., 1995 ; Parvez et al., 2002 ; Sadiq-ur-Rehman et al., 2006 ), we have synthesized a new organotin(IV) carboxylate of 4-chloro-3-aminobenzoic acid, the title compound, (I).

In compound (I) (Fig. 1), atom Sn1 is bonded to three methyl groups with essentially identical Sn—C distances, comparable with the values reported for the related structure (C₁₆H₁₃O₃)Sn(CH₃)₃ (Tahir et al., 1997 ). The coordination geometry around Sn1 is distorted tetrahedral (Table 1).

The crystal structure of (I) contains centrosymmetric dimers formed via intermolecular N—H⋯O hydrogen bonds (Fig. 2, Table 2).

Figure 1
The molecular structure of (I)

, with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radii.

Figure 2
Centrosymmetric dimers formed through intermolecular hydrogen bonding (dashed lines). H atoms not involved in hydrogen bonding have been omitted for clarity.

Experimental

The sodium salt of 4-chloro-3-aminobenzoic acid (0.194 g, 1 mmol) and trimethyltin chloride (0.199 g, 1 mmol) were suspended in dry toluene (150 ml) in a two-necked round-bottomed flask equipped with a water condenser. The mixture was refluxed for 8–10 h, the NaCl formed was filtered off, and the solvent was removed on a rotary evaporator under reduced pressure. The solid product was recrystallized from chloroform to obtain colourless crystals of (I) (yield 70%; m.p. 403–406 K).

Crystal data

[Sn(CH₃)₃(C₇H₅ClNO₂)]
M_r = 334.36
Monoclinic, P 2₁ /c
a = 11.9077 (7) Å
b = 9.1237 (5) Å
c = 12.6554 (7) Å
β = 113.086 (1)°
V = 1264.80 (12) Å³
Z = 4
D_x = 1.756 Mg m⁻³
Mo Kα radiation
μ = 2.21 mm⁻¹
T = 100 (2) K
Block, colourless
0.40 × 0.30 × 0.30 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.435, T_max = 0.515
9722 measured reflections
2586 independent reflections
2528 reflections with I > 2σ(I)
R_int = 0.017
θ_max = 26.4°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.015
wR(F²) = 0.038
S = 1.11
2586 reflections
147 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0146P)² + 0.9615P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.005
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Sn1—O1	2.0804 (12)
Sn1—C8	2.118 (2)
Sn1—C9	2.119 (2)
Sn1—C10	2.119 (2)

O1—Sn1—C8	102.26 (7)
O1—Sn1—C10	96.02 (6)
C8—Sn1—C10	115.55 (9)
O1—Sn1—C9	106.60 (6)
C8—Sn1—C9	118.66 (9)
C10—Sn1—C9	113.69 (8)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H2N⋯O2ⁱ	0.83 (2)	2.14 (2)	2.947 (2)	166 (2)
Symmetry code: (i) -x+2, -y+2, -z+1.

H atoms bound to C atoms were included in calculated positions and allowed to ride during subsequent refinement, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C) for Csp², and C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C) for the methyl groups. The methyl groups were allowed to rotate about their local threefold axes. H atoms bound to N1 were located in a difference Fourier map and refined isotropically, with final N—H distances of 0.80 (2) and 0.83 (2) Å.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2002 ); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536806025517/bi2027sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806025517/bi2027Isup2.hkl

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

(3-Amino-4-chlorobenzoato)trimethyltin(IV) top

Crystal data top

[Sn(CH₃)₃(C₇H₅ClNO₂)]	F(000) = 656
M_r = 334.36	D_x = 1.756 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 403–406 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 11.9077 (7) Å	Cell parameters from 8154 reflections
b = 9.1237 (5) Å	θ = 2.8–26.4°
c = 12.6554 (7) Å	µ = 2.21 mm⁻¹
β = 113.086 (1)°	T = 100 K
V = 1264.80 (12) Å³	Block, colourless
Z = 4	0.40 × 0.30 × 0.30 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2586 independent reflections
Radiation source: fine-focus sealed tube	2528 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ω scans	θ_max = 26.4°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −14→14
T_min = 0.435, T_max = 0.515	k = −11→11
9722 measured reflections	l = −15→15

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)] = 0.015	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.038	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ²(F_o²) + (0.0146P)² + 0.9615P] where P = (F_o² + 2F_c²)/3
2586 reflections	(Δ/σ)_max = 0.005
147 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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 (Å²) top

	x	y	z	U_iso*/U_eq
Sn1	0.758545 (10)	0.680159 (12)	0.129024 (9)	0.01696 (5)
Cl1	0.63628 (4)	1.43820 (4)	0.49036 (3)	0.02033 (9)
O1	0.70022 (11)	0.85101 (13)	0.20397 (10)	0.0173 (2)
O2	0.89305 (11)	0.87859 (15)	0.32613 (11)	0.0269 (3)
N1	0.87650 (15)	1.28807 (19)	0.59015 (14)	0.0252 (3)
C1	0.78575 (15)	0.91776 (18)	0.28834 (14)	0.0164 (3)
C2	0.74554 (14)	1.04716 (18)	0.33707 (14)	0.0150 (3)
C3	0.82684 (14)	1.10631 (18)	0.43995 (14)	0.0156 (3)
H3	0.9053	1.0633	0.4770	0.019*
C4	0.79528 (15)	1.22799 (19)	0.48994 (14)	0.0163 (3)
C5	0.67799 (15)	1.28591 (18)	0.43147 (14)	0.0155 (3)
C6	0.59600 (15)	1.22758 (19)	0.32933 (14)	0.0169 (3)
H6	0.5173	1.2698	0.2924	0.020*
C7	0.62928 (15)	1.10714 (18)	0.28108 (14)	0.0161 (3)
H7	0.5738	1.0662	0.2111	0.019*
C8	0.7946 (2)	0.5117 (2)	0.25317 (19)	0.0388 (5)
H8A	0.8668	0.5374	0.3216	0.058*
H8B	0.8095	0.4194	0.2211	0.058*
H8C	0.7242	0.5001	0.2742	0.058*
C9	0.90513 (18)	0.7631 (2)	0.09166 (17)	0.0291 (4)
H9A	0.9051	0.8704	0.0949	0.044*
H9B	0.8956	0.7315	0.0146	0.044*
H9C	0.9825	0.7257	0.1482	0.044*
C10	0.59313 (17)	0.6591 (2)	−0.01744 (17)	0.0269 (4)
H10A	0.5240	0.6761	0.0046	0.040*
H10B	0.5875	0.5601	−0.0492	0.040*
H10C	0.5914	0.7312	−0.0754	0.040*
H1N	0.855 (2)	1.355 (3)	0.6190 (18)	0.021 (5)*
H2N	0.943 (2)	1.248 (3)	0.6245 (18)	0.025 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.01860 (7)	0.01495 (7)	0.01740 (7)	0.00233 (4)	0.00713 (5)	−0.00167 (4)
Cl1	0.01977 (19)	0.01832 (19)	0.0220 (2)	0.00442 (15)	0.00727 (16)	−0.00461 (15)
O1	0.0180 (6)	0.0170 (6)	0.0170 (6)	−0.0001 (5)	0.0069 (5)	−0.0036 (5)
O2	0.0193 (6)	0.0336 (7)	0.0231 (7)	0.0098 (5)	0.0031 (5)	−0.0086 (6)
N1	0.0176 (8)	0.0267 (8)	0.0245 (8)	0.0061 (7)	0.0007 (7)	−0.0108 (7)
C1	0.0188 (8)	0.0173 (8)	0.0138 (7)	0.0020 (6)	0.0071 (6)	0.0016 (6)
C2	0.0168 (8)	0.0147 (8)	0.0153 (7)	0.0000 (6)	0.0084 (6)	0.0010 (6)
C3	0.0122 (7)	0.0169 (8)	0.0176 (8)	0.0012 (6)	0.0058 (6)	0.0000 (6)
C4	0.0161 (8)	0.0168 (8)	0.0165 (8)	−0.0003 (6)	0.0070 (6)	0.0004 (6)
C5	0.0183 (8)	0.0132 (7)	0.0175 (8)	0.0013 (6)	0.0098 (7)	−0.0005 (6)
C6	0.0145 (7)	0.0184 (8)	0.0174 (8)	0.0031 (6)	0.0058 (6)	0.0026 (6)
C7	0.0155 (8)	0.0181 (8)	0.0137 (7)	−0.0009 (6)	0.0048 (6)	−0.0003 (6)
C8	0.0566 (14)	0.0229 (10)	0.0363 (12)	0.0075 (10)	0.0177 (11)	0.0083 (9)
C9	0.0251 (9)	0.0346 (11)	0.0324 (10)	−0.0037 (8)	0.0163 (8)	−0.0112 (8)
C10	0.0232 (9)	0.0283 (10)	0.0253 (9)	0.0000 (7)	0.0054 (8)	−0.0097 (8)

Geometric parameters (Å, º) top

Sn1—O1	2.0804 (12)	C4—C5	1.402 (2)
Sn1—C8	2.118 (2)	C5—C6	1.385 (2)
Sn1—C9	2.119 (2)	C6—C7	1.388 (2)
Sn1—C10	2.119 (2)	C6—H6	0.950
Cl1—C5	1.7387 (16)	C7—H7	0.950
O1—C1	1.302 (2)	C8—H8A	0.980
O2—C1	1.229 (2)	C8—H8B	0.980
N1—C4	1.372 (2)	C8—H8C	0.980
N1—H1N	0.80 (2)	C9—H9A	0.980
N1—H2N	0.83 (2)	C9—H9B	0.980
C1—C2	1.495 (2)	C9—H9C	0.980
C2—C3	1.391 (2)	C10—H10A	0.980
C2—C7	1.396 (2)	C10—H10B	0.980
C3—C4	1.400 (2)	C10—H10C	0.980
C3—H3	0.950

O1—Sn1—C8	102.26 (7)	C5—C6—C7	119.77 (15)
O1—Sn1—C10	96.02 (6)	C5—C6—H6	120.1
C8—Sn1—C10	115.55 (9)	C7—C6—H6	120.1
O1—Sn1—C9	106.60 (6)	C6—C7—C2	118.97 (15)
C8—Sn1—C9	118.66 (9)	C6—C7—H7	120.5
C10—Sn1—C9	113.69 (8)	C2—C7—H7	120.5
C1—O1—Sn1	115.51 (10)	Sn1—C8—H8A	109.5
C4—N1—H1N	119.1 (16)	Sn1—C8—H8B	109.5
C4—N1—H2N	119.6 (16)	H8A—C8—H8B	109.5
H1N—N1—H2N	121 (2)	Sn1—C8—H8C	109.5
O2—C1—O1	122.87 (15)	H8A—C8—H8C	109.5
O2—C1—C2	121.43 (15)	H8B—C8—H8C	109.5
O1—C1—C2	115.70 (14)	Sn1—C9—H9A	109.5
C3—C2—C7	120.71 (15)	Sn1—C9—H9B	109.5
C3—C2—C1	118.33 (14)	H9A—C9—H9B	109.5
C7—C2—C1	120.96 (15)	Sn1—C9—H9C	109.5
C2—C3—C4	121.26 (15)	H9A—C9—H9C	109.5
C2—C3—H3	119.4	H9B—C9—H9C	109.5
C4—C3—H3	119.4	Sn1—C10—H10A	109.5
N1—C4—C3	121.18 (15)	Sn1—C10—H10B	109.5
N1—C4—C5	122.16 (16)	H10A—C10—H10B	109.5
C3—C4—C5	116.65 (15)	Sn1—C10—H10C	109.5
C6—C5—C4	122.64 (15)	H10A—C10—H10C	109.5
C6—C5—Cl1	119.47 (13)	H10B—C10—H10C	109.5
C4—C5—Cl1	117.89 (13)

C8—Sn1—O1—C1	75.15 (13)	C2—C3—C4—N1	−178.61 (16)
C10—Sn1—O1—C1	−167.03 (12)	C2—C3—C4—C5	0.4 (2)
C9—Sn1—O1—C1	−50.09 (13)	N1—C4—C5—C6	178.94 (17)
Sn1—O1—C1—O2	−3.8 (2)	C3—C4—C5—C6	0.0 (2)
Sn1—O1—C1—C2	175.90 (10)	N1—C4—C5—Cl1	−0.4 (2)
O2—C1—C2—C3	−12.0 (2)	C3—C4—C5—Cl1	−179.37 (12)
O1—C1—C2—C3	168.30 (14)	C4—C5—C6—C7	−0.2 (3)
O2—C1—C2—C7	168.20 (16)	Cl1—C5—C6—C7	179.18 (13)
O1—C1—C2—C7	−11.5 (2)	C5—C6—C7—C2	0.0 (2)
C7—C2—C3—C4	−0.5 (2)	C3—C2—C7—C6	0.4 (2)
C1—C2—C3—C4	179.62 (15)	C1—C2—C7—C6	−179.81 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H2N···O2ⁱ	0.83 (2)	2.14 (2)	2.947 (2)	166 (2)

Symmetry code: (i) −x+2, −y+2, −z+1.

Acknowledgements

AR is grateful to the HEC (Higher Education Commision, Islamabad, Pakistan) for financial support under the PhD Fellowship Scheme Batch-II (PIN Code 042-111621-PS2-179).

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