catena-Poly[[trimethyl­tin(IV)]-μ-1,2,3-benzotriazol-1-ido-κ2N1:N3]

Li, Y.; Liu, J.; Li, D.

doi:10.1107/S1600536811055176

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page m169

doi:10.1107/S1600536811055176

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catena-Poly[[trimethyltin(IV)]-μ-1,2,3-benzotriazol-1-ido-κ²N¹:N³]

Yuanyuan Li,^a ^* Jianmin Liu ^a and Dacheng Li ^a

^aSchool of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China
^*Correspondence e-mail: lidacheng@lcu.edu.cn

(Received 20 December 2011; accepted 22 December 2011; online 18 January 2012)

In the title coordination polymer, [Sn(CH₃)₃(C₆H₄N₃)]_n, the Sn^IV atom is five-coordinated in a distorted trigonal–bipyramidal geometry with the methyl groups in equatorial positions and two N atoms of two symmetry-related benzotriazolide anions in axial positions. The anion bridges adjacent metal atoms, forming zigzag polymeric chains parallel to [011] and [0 $[\overline{1}]$ 1].

Related literature

For the biological activity of organotin complexes with nitrogen donor ligands, see: Pettinari et al. (1996 ). For related structures, see: Blaschette et al. (1992 ); Wirth et al. (1998 ); Berceanc et al. (2002 ).

Experimental

Crystal data

[Sn(CH₃)₃(C₆H₄N₃)]
M_r = 281.93
Orthorhombic, P n a 2₁
a = 14.8168 (14) Å
b = 10.6687 (9) Å
c = 7.3518 (7) Å
V = 1162.14 (18) Å³
Z = 4
Mo Kα radiation
μ = 2.16 mm⁻¹
T = 298 K
0.48 × 0.41 × 0.35 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008 ) T_min = 0.424, T_max = 0.518
5549 measured reflections
1920 independent reflections
1253 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.137
S = 1.00
1920 reflections
122 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.49 e Å⁻³
Absolute structure: Flack (1983 ), 801 Fiedel pairs
Flack parameter: −0.11 (13)

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/S1600536811055176/rz2693sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811055176/rz2693Isup2.hkl

checkCIF report

Comment top

Several efforts have been made to prepare and study organotin compounds with nitrogen donor ligands not only because of their antitumor activity but also for the important role these compounds play in many biological processes (Pettinari et al., 1996). Since then, only a few such complexes have been reported (Blaschette et al., 1992; Wirth et al., 1998; Berceanc et al., 2002). As a contribution to this field, we report herein the crystal structure of the polymeric title compound.

In the title compound (Fig. 1), the Sn atom displays a distorted trigonal bipyramidal coordination geometry with the equatorial positions occupied by the carbon atoms of the three methyl groups and the apices by the N atoms of two symmetry-related benzotriazolato anion. The Sn—N bond distances are not remarkably different [Sn1—N1ⁱ = 2.356 (8); Sn1—N3 = 2.329 (8) Å; symmetry code: (i) 1/2-x, -1/2+y, 1/2-z], with an average value in agreement with those observed in related compounds. In the crystal structure, the benzotriazolato anions link adjacent Sn(Me)₃ units into zig-zag polymeric chains running parallel to the [011] and [011] direction. Packing is stabilized only by van der Waals forces.

Related literature top

For the biological activity of organotin complexes with nitrogen donor ligands, see: Pettinari et al. (1996). For related structures, see: Blaschette et al. (1992); Wirth et al. (1998); Berceanc et al. (2002).

Experimental top

The title compound was prepared by mixing trimethyltin (0.2 g, 1 mmol) and 1,2,3-benzotriazole (0.12 g, 1 mmol) in methanol (10 mL). The mixture was stirred for 7h, then the undissolved substance was filtered off. The title compound crystallized as red crystals after three weeks on slow evaporation of the solvent. Yield: 56%. Anal. Calc (%) for C₁₈H₂₆N₆Sn₂ (563.83): C, 38.31; H, 5.51. Found (%): C, 37.02; H, 5.36.

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 title compound with 30% probability displacement ellipsoids. Symmetry code: (A) 1/2-x, 1/2+y, -1/2+z.

catena-Poly[[trimethyltin(IV)]-µ-1,2,3-benzotriazol-1-ido- κ²N¹:N³] top

Crystal data top

[Sn(CH₃)₃(C₆H₄N₃)]	F(000) = 552
M_r = 281.93	D_x = 1.611 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 2591 reflections
a = 14.8168 (14) Å	θ = 2.3–28.1°
b = 10.6687 (9) Å	µ = 2.16 mm⁻¹
c = 7.3518 (7) Å	T = 298 K
V = 1162.14 (18) Å³	Block, red
Z = 4	0.48 × 0.41 × 0.35 mm

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	1920 independent reflections
Radiation source: fine-focus sealed tube	1253 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
phi and ω scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	h = −15→17
T_min = 0.424, T_max = 0.518	k = −12→12
5549 measured reflections	l = −7→8

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.030	w = 1/[σ²(F_o²) + (0.0835P)² + 1.6416P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.137	(Δ/σ)_max = 0.002
S = 1.00	Δρ_max = 0.49 e Å⁻³
1920 reflections	Δρ_min = −0.49 e Å⁻³
122 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.025 (2)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 801 Fiedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.11 (13)

Crystal data top

[Sn(CH₃)₃(C₆H₄N₃)]	V = 1162.14 (18) Å³
M_r = 281.93	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 14.8168 (14) Å	µ = 2.16 mm⁻¹
b = 10.6687 (9) Å	T = 298 K
c = 7.3518 (7) Å	0.48 × 0.41 × 0.35 mm

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	1920 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	1253 reflections with I > 2σ(I)
T_min = 0.424, T_max = 0.518	R_int = 0.031
5549 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	H-atom parameters constrained
wR(F²) = 0.137	Δρ_max = 0.49 e Å⁻³
S = 1.00	Δρ_min = −0.49 e Å⁻³
1920 reflections	Absolute structure: Flack (1983), 801 Fiedel pairs
122 parameters	Absolute structure parameter: −0.11 (13)
1 restraint

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

	x	y	z	U_iso*/U_eq
N1	0.1848 (6)	0.4850 (7)	0.0322 (11)	0.065 (2)
Sn1	0.25035 (3)	0.15544 (4)	0.3757 (6)	0.0479 (3)
C4	−0.0362 (7)	0.3651 (9)	−0.123 (2)	0.081 (3)
H4	−0.0862	0.3824	−0.1949	0.097*
C5	0.0335 (6)	0.4485 (8)	−0.120 (2)	0.075 (3)
H5	0.0331	0.5201	−0.1917	0.090*
N3	0.1867 (5)	0.3116 (7)	0.1954 (13)	0.067 (2)
C6	0.1055 (7)	0.4217 (8)	−0.0033 (13)	0.061 (2)
C7	0.3625 (7)	0.2679 (9)	0.4423 (16)	0.079 (3)
H7A	0.4164	0.2180	0.4382	0.118*
H7B	0.3549	0.3014	0.5625	0.118*
H7C	0.3673	0.3354	0.3565	0.118*
C1	0.1073 (7)	0.3123 (8)	0.0980 (14)	0.060 (2)
C9	0.1374 (7)	0.1572 (11)	0.555 (2)	0.102 (5)
H9A	0.1208	0.2423	0.5812	0.152*
H9B	0.1530	0.1152	0.6662	0.152*
H9C	0.0875	0.1149	0.4987	0.152*
N2	0.2332 (6)	0.4168 (8)	0.1502 (15)	0.067 (2)
C8	0.2505 (6)	0.0421 (12)	0.139 (2)	0.076 (4)
H8A	0.3055	0.0554	0.0726	0.115*
H8B	0.2000	0.0640	0.0637	0.115*
H8C	0.2462	−0.0445	0.1732	0.115*
C2	0.0372 (9)	0.2279 (11)	0.0931 (19)	0.085 (4)
H2	0.0384	0.1557	0.1639	0.102*
C3	−0.0351 (10)	0.2533 (11)	−0.020 (2)	0.088 (4)
H3	−0.0828	0.1969	−0.0286	0.106*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.074 (5)	0.059 (5)	0.062 (6)	0.000 (4)	0.001 (4)	0.014 (4)
Sn1	0.0570 (4)	0.0380 (4)	0.0489 (4)	0.0003 (2)	0.0018 (3)	0.0109 (3)
C4	0.083 (7)	0.084 (7)	0.075 (7)	0.001 (6)	−0.009 (9)	0.004 (8)
C5	0.082 (6)	0.068 (6)	0.075 (7)	0.001 (5)	0.004 (9)	0.020 (7)
N3	0.073 (5)	0.058 (5)	0.069 (6)	0.001 (4)	0.001 (5)	0.013 (4)
C6	0.073 (6)	0.057 (5)	0.054 (6)	0.005 (5)	0.003 (5)	0.001 (5)
C7	0.097 (7)	0.054 (6)	0.086 (8)	0.002 (5)	−0.018 (6)	0.012 (5)
C1	0.067 (6)	0.053 (5)	0.060 (7)	−0.005 (5)	−0.002 (5)	0.004 (5)
C9	0.083 (8)	0.103 (10)	0.119 (12)	0.018 (6)	0.022 (9)	0.042 (8)
N2	0.087 (6)	0.040 (4)	0.073 (7)	−0.001 (4)	−0.009 (5)	0.015 (4)
C8	0.096 (9)	0.053 (6)	0.080 (9)	−0.003 (4)	−0.020 (6)	−0.018 (5)
C2	0.087 (7)	0.073 (7)	0.094 (10)	−0.005 (6)	−0.002 (8)	0.018 (7)
C3	0.078 (7)	0.075 (8)	0.112 (11)	−0.010 (6)	−0.009 (8)	0.008 (7)

Geometric parameters (Å, º) top

N1—N2	1.340 (11)	C6—C1	1.385 (12)
N1—C6	1.380 (12)	C7—H7A	0.9600
N1—Sn1ⁱ	2.356 (8)	C7—H7B	0.9600
Sn1—C7	2.107 (10)	C7—H7C	0.9600
Sn1—C8	2.120 (13)	C1—C2	1.375 (13)
Sn1—C9	2.131 (13)	C9—H9A	0.9600
Sn1—N3	2.329 (8)	C9—H9B	0.9600
Sn1—N1ⁱⁱ	2.356 (8)	C9—H9C	0.9600
C4—C5	1.364 (12)	C8—H8A	0.9600
C4—C3	1.411 (16)	C8—H8B	0.9600
C4—H4	0.9300	C8—H8C	0.9600
C5—C6	1.397 (15)	C2—C3	1.384 (19)
C5—H5	0.9300	C2—H2	0.9300
N3—N2	1.359 (11)	C3—H3	0.9300
N3—C1	1.376 (12)

N2—N1—C6	108.2 (7)	H7A—C7—H7B	109.5
N2—N1—Sn1ⁱ	121.1 (6)	Sn1—C7—H7C	109.5
C6—N1—Sn1ⁱ	129.2 (6)	H7A—C7—H7C	109.5
C7—Sn1—C8	121.0 (5)	H7B—C7—H7C	109.5
C7—Sn1—C9	118.1 (6)	N3—C1—C2	131.0 (9)
C8—Sn1—C9	120.9 (5)	N3—C1—C6	107.5 (8)
C7—Sn1—N3	92.5 (3)	C2—C1—C6	121.5 (10)
C8—Sn1—N3	86.6 (5)	Sn1—C9—H9A	109.5
C9—Sn1—N3	91.6 (4)	Sn1—C9—H9B	109.5
C7—Sn1—N1ⁱⁱ	90.3 (4)	H9A—C9—H9B	109.5
C8—Sn1—N1ⁱⁱ	87.7 (5)	Sn1—C9—H9C	109.5
C9—Sn1—N1ⁱⁱ	91.4 (4)	H9A—C9—H9C	109.5
N3—Sn1—N1ⁱⁱ	174.3 (4)	H9B—C9—H9C	109.5
C5—C4—C3	122.3 (11)	N1—N2—N3	109.6 (8)
C5—C4—H4	118.9	Sn1—C8—H8A	109.5
C3—C4—H4	118.9	Sn1—C8—H8B	109.5
C4—C5—C6	117.1 (10)	H8A—C8—H8B	109.5
C4—C5—H5	121.5	Sn1—C8—H8C	109.5
C6—C5—H5	121.5	H8A—C8—H8C	109.5
N2—N3—C1	107.6 (8)	H8B—C8—H8C	109.5
N2—N3—Sn1	121.6 (6)	C3—C2—C1	118.2 (11)
C1—N3—Sn1	130.2 (6)	C3—C2—H2	120.9
N1—C6—C1	107.1 (9)	C1—C2—H2	120.9
N1—C6—C5	131.8 (9)	C2—C3—C4	119.7 (12)
C1—C6—C5	121.1 (9)	C2—C3—H3	120.1
Sn1—C7—H7A	109.5	C4—C3—H3	120.1
Sn1—C7—H7B	109.5

C3—C4—C5—C6	−2.8 (17)	N2—N3—C1—C6	−1.6 (12)
C7—Sn1—N3—N2	10.1 (9)	Sn1—N3—C1—C6	−173.1 (7)
C8—Sn1—N3—N2	−110.8 (9)	N1—C6—C1—N3	0.9 (11)
C9—Sn1—N3—N2	128.3 (9)	C5—C6—C1—N3	178.9 (10)
C7—Sn1—N3—C1	−179.4 (10)	N1—C6—C1—C2	179.8 (11)
C8—Sn1—N3—C1	59.7 (9)	C5—C6—C1—C2	−2.2 (16)
C9—Sn1—N3—C1	−61.2 (10)	C6—N1—N2—N3	−1.2 (12)
N2—N1—C6—C1	0.1 (11)	Sn1ⁱ—N1—N2—N3	−168.6 (7)
Sn1ⁱ—N1—C6—C1	166.2 (7)	C1—N3—N2—N1	1.7 (12)
N2—N1—C6—C5	−177.5 (11)	Sn1—N3—N2—N1	174.1 (6)
Sn1ⁱ—N1—C6—C5	−11.5 (16)	N3—C1—C2—C3	−179.8 (13)
C4—C5—C6—N1	−179.9 (10)	C6—C1—C2—C3	1.6 (19)
C4—C5—C6—C1	2.7 (15)	C1—C2—C3—C4	−2 (2)
N2—N3—C1—C2	179.6 (12)	C5—C4—C3—C2	2 (2)
Sn1—N3—C1—C2	8.2 (19)

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

Experimental details

Crystal data
Chemical formula	[Sn(CH₃)₃(C₆H₄N₃)]
M_r	281.93
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	298
a, b, c (Å)	14.8168 (14), 10.6687 (9), 7.3518 (7)
V (Å³)	1162.14 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.16
Crystal size (mm)	0.48 × 0.41 × 0.35

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2008)
T_min, T_max	0.424, 0.518
No. of measured, independent and observed [I > 2σ(I)] reflections	5549, 1920, 1253
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.137, 1.00
No. of reflections	1920
No. of parameters	122
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.49
Absolute structure	Flack (1983), 801 Fiedel pairs
Absolute structure parameter	−0.11 (13)

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

Acknowledgements

This work was supported by the National Natural Science Foundation of P. R. China (project No. 20971063 and 21101086) and the Natural Science Foundation of Shandong Province (Y2007B01).

References

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