catena-Poly[[trimethyl­tin(IV)]-μ-4-methyl-4H-1,2,4-triazole-3-thiol­ato-κ2S:N1]

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

doi:10.1107/S1600536806033654

metal-organic compounds

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Volume 62| Part 9| September 2006| Pages m2328-m2329

https://doi.org/10.1107/S1600536806033654

catena-Poly[[trimethyltin(IV)]-μ-4-methyl-4H-1,2,4-triazole-3-thiolato-κ²S:N¹]

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

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

(Received 8 August 2006; accepted 22 August 2006; online 25 August 2006)

The crystal structure of the title compound, [Sn(CH₃)₃(C₃H₄N₃S)]_n, consists of a linear chain in which adjacent trimethyltin groups are bridged by the 4-methyl-4H-1,2,4-triazole-3-thiolate anion through its N and S atoms.

Comment

The synthesis and structural chemistry of organotin compounds is still a fertile area of research because of their extensive biological applications. However, there is relatively little information available on organotin compounds as anticancer agents in vivo. Diorganotins represent the largest group of tin compounds to have been extensively examined for cytotoxicity in vitro; they have been found to be less toxic than platinum complexes (Narayan, 1983 ). We report here the structure of the title compound, (I), in a continuation of our work on the synthesis and structural characterization of organotin complexes of sulfur donor ligands (Shahzadi, Ali, Bhatti et al., 2006 , Shahzadi, Ali & Fettouhi, 2006 ).

In the crystal structure of (I) (Fig. 1), the Sn atom is bonded to three methyl groups in equatorial positions. The axial positions are occupied by N and S atoms of a 4-methyl-4H-1,2,4-triazole-3-thiolate anion, with an almost linear S—Sn—N angle; the Sn atom has a distorted trigonal–bipyramidal coordination geometry. The Sn—S bond length is 2.7116 (7) Å, which is shorter than the Sn—S bond distance reported earlier (Shahzadi, Ali, Bhatti et al., 2006, Shahzadi, Ali & Fettouhi, 2006).

Figure 1
The structure of (I), with displacement ellipsoids drawn at the 50% probability level. [Symmetry code: (i) −x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , z + $[{1\over 2}]$ .]

Experimental

3-Mercapto-4-methyl-4H-1,2,4-triazole (0.15 g, 1 mmol) and triethylamine (0.1 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 stirred for 25 min at room temperature and then trimethyltin chloride (0.2 g, 1 mmol) was added. The reaction mixture was refluxed for 4–5 h. After cooling at room temperature, triethylammonium chloride 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 crystals suitable for X-ray analysis (yield 80%; m.p. 433 K).

Crystal data

[Sn(CH₃)₃(C₃H₄N₃S)]
M_r = 277.94
Orthorhombic, P n a 2₁
a = 13.7254 (11) Å
b = 11.0183 (9) Å
c = 6.6998 (5) Å
V = 1013.21 (14) Å³
Z = 4
D_x = 1.822 Mg m⁻³
Mo Kα radiation
μ = 2.68 mm⁻¹
T = 100 (2) K
Plate, colourless
0.40 × 0.30 × 0.05 mm

Data collection

Bruker APEX CCD diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.414, T_max = 0.878
7581 measured reflections
2051 independent reflections
2032 reflections with I > 2σ(I)
R_int = 0.025
θ_max = 26.3°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.017
wR(F²) = 0.042
S = 1.07
2051 reflections
104 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0189P)² + 0.5609P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.003
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.25 e Å⁻³
Absolute structure: Flack (1983 ), 928 Friedel pairs
Flack parameter: 0.06 (2)

H atoms were included in calculated positions using the riding method, with C—H = 0.95–0.98 Å and U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C).

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536806033654/ng2066sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806033654/ng2066Isup2.hkl

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.

catena-Poly[trimethyltin(IV)-µ-4-methyl-4H-1,2,4-triazole-3-thiolato- κ²S:N¹] top

Crystal data top

[Sn(CH₃)₃(C₃H₄N₃S)]	D_x = 1.822 Mg m⁻³
M_r = 277.94	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna2₁	Cell parameters from 6370 reflections
a = 13.7254 (11) Å	θ = 2.4–26.4°
b = 11.0183 (9) Å	µ = 2.68 mm⁻¹
c = 6.6998 (5) Å	T = 100 K
V = 1013.21 (14) Å³	Plate, colourless
Z = 4	0.40 × 0.30 × 0.05 mm
F(000) = 544

Data collection top

Bruker APEX CCD diffractometer	2051 independent reflections
Radiation source: fine-focus sealed tube	2032 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
φ and ω scans	θ_max = 26.3°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −17→17
T_min = 0.414, T_max = 0.878	k = −13→13
7581 measured reflections	l = −8→8

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.017	H-atom parameters constrained
wR(F²) = 0.042	w = 1/[σ²(F_o²) + (0.0189P)² + 0.5609P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.003
2051 reflections	Δρ_max = 0.65 e Å⁻³
104 parameters	Δρ_min = −0.25 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 928 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.06 (2)

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	0.307904 (10)	0.849930 (13)	0.50000 (4)	0.01597 (6)
S1	0.45004 (5)	0.68083 (6)	0.45904 (9)	0.01853 (14)
N1	0.43802 (16)	0.6160 (2)	0.0649 (3)	0.0171 (4)
N3	0.31104 (16)	0.4998 (2)	0.0555 (4)	0.0202 (5)
N4	0.32403 (17)	0.5347 (2)	0.2536 (4)	0.0182 (5)
C1	0.40084 (19)	0.6056 (2)	0.2553 (4)	0.0155 (5)
C2	0.3798 (2)	0.5489 (2)	−0.0520 (4)	0.0197 (6)
H2	0.3875	0.5388	−0.1919	0.024*
C3	0.52432 (17)	0.6837 (2)	0.0019 (6)	0.0242 (5)
H3A	0.5830	0.6379	0.0373	0.036*
H3B	0.5255	0.7627	0.0692	0.036*
H3C	0.5223	0.6959	−0.1429	0.036*
C4	0.4086 (2)	0.9616 (3)	0.6575 (5)	0.0250 (6)
H4A	0.3730	1.0240	0.7318	0.037*
H4B	0.4529	1.0005	0.5623	0.037*
H4C	0.4462	0.9116	0.7507	0.037*
C5	0.2120 (2)	0.7243 (3)	0.6375 (5)	0.0219 (6)
H5A	0.1450	0.7407	0.5943	0.033*
H5B	0.2163	0.7326	0.7829	0.033*
H5C	0.2302	0.6416	0.5989	0.033*
C6	0.2961 (2)	0.8696 (3)	0.1844 (5)	0.0261 (7)
H6A	0.2774	0.7916	0.1251	0.039*
H6B	0.3589	0.8955	0.1298	0.039*
H6C	0.2464	0.9306	0.1534	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.01775 (9)	0.01547 (9)	0.01468 (9)	0.00015 (5)	−0.00075 (9)	−0.00140 (9)
S1	0.0168 (3)	0.0211 (3)	0.0177 (4)	0.0030 (2)	−0.0027 (2)	−0.0036 (2)
N1	0.0174 (11)	0.0145 (9)	0.0194 (11)	−0.0007 (9)	0.0019 (8)	0.0001 (8)
N3	0.0257 (13)	0.0171 (11)	0.0179 (14)	0.0021 (8)	0.0004 (8)	−0.0016 (9)
N4	0.0212 (11)	0.0174 (11)	0.0159 (12)	−0.0007 (9)	−0.0002 (9)	−0.0004 (9)
C1	0.0172 (12)	0.0133 (12)	0.0160 (12)	0.0032 (10)	−0.0016 (10)	−0.0012 (9)
C2	0.0223 (13)	0.0161 (12)	0.0205 (16)	0.0006 (10)	−0.0005 (9)	−0.0005 (10)
C3	0.0216 (11)	0.0267 (12)	0.0242 (13)	−0.0071 (9)	0.0043 (15)	−0.0060 (19)
C4	0.0235 (14)	0.0236 (14)	0.0278 (16)	−0.0035 (12)	−0.0016 (12)	−0.0064 (12)
C5	0.0195 (14)	0.0204 (15)	0.0258 (16)	−0.0002 (11)	0.0010 (11)	0.0015 (12)
C6	0.0320 (17)	0.0289 (17)	0.0173 (16)	0.0078 (12)	−0.0013 (12)	−0.0020 (12)

Geometric parameters (Å, º) top

Sn1—C5	2.121 (3)	C2—H2	0.9500
Sn1—C4	2.130 (3)	C3—H3A	0.9800
Sn1—C6	2.131 (3)	C3—H3B	0.9800
Sn1—N3ⁱ	2.351 (2)	C3—H3C	0.9800
Sn1—S1	2.7116 (7)	C4—H4A	0.9800
S1—C1	1.734 (3)	C4—H4B	0.9800
N1—C2	1.341 (3)	C4—H4C	0.9800
N1—C1	1.378 (3)	C5—H5A	0.9800
N1—C3	1.462 (3)	C5—H5B	0.9800
N3—C2	1.306 (3)	C5—H5C	0.9800
N3—N4	1.393 (3)	C6—H6A	0.9800
N3—Sn1ⁱⁱ	2.351 (2)	C6—H6B	0.9800
N4—C1	1.312 (4)	C6—H6C	0.9800

C5—Sn1—C4	124.37 (12)	N1—C3—H3A	109.5
C5—Sn1—C6	116.73 (13)	N1—C3—H3B	109.5
C4—Sn1—C6	118.82 (12)	H3A—C3—H3B	109.5
C5—Sn1—N3ⁱ	87.61 (10)	N1—C3—H3C	109.5
C4—Sn1—N3ⁱ	88.09 (10)	H3A—C3—H3C	109.5
C6—Sn1—N3ⁱ	91.88 (11)	H3B—C3—H3C	109.5
C5—Sn1—S1	92.42 (8)	Sn1—C4—H4A	109.5
C4—Sn1—S1	88.86 (8)	Sn1—C4—H4B	109.5
C6—Sn1—S1	91.38 (9)	H4A—C4—H4B	109.5
N3ⁱ—Sn1—S1	176.33 (6)	Sn1—C4—H4C	109.5
C1—S1—Sn1	97.35 (9)	H4A—C4—H4C	109.5
C2—N1—C1	105.9 (2)	H4B—C4—H4C	109.5
C2—N1—C3	126.5 (2)	Sn1—C5—H5A	109.5
C1—N1—C3	127.5 (2)	Sn1—C5—H5B	109.5
C2—N3—N4	108.6 (2)	H5A—C5—H5B	109.5
C2—N3—Sn1ⁱⁱ	134.93 (19)	Sn1—C5—H5C	109.5
N4—N3—Sn1ⁱⁱ	115.70 (17)	H5A—C5—H5C	109.5
C1—N4—N3	106.0 (2)	H5B—C5—H5C	109.5
N4—C1—N1	109.8 (2)	Sn1—C6—H6A	109.5
N4—C1—S1	127.2 (2)	Sn1—C6—H6B	109.5
N1—C1—S1	123.0 (2)	H6A—C6—H6B	109.5
N3—C2—N1	109.7 (2)	Sn1—C6—H6C	109.5
N3—C2—H2	125.2	H6A—C6—H6C	109.5
N1—C2—H2	125.2	H6B—C6—H6C	109.5

C5—Sn1—S1—C1	77.35 (13)	C3—N1—C1—N4	−178.4 (2)
C4—Sn1—S1—C1	−158.29 (12)	C2—N1—C1—S1	−178.03 (19)
C6—Sn1—S1—C1	−39.48 (13)	C3—N1—C1—S1	3.1 (4)
N3ⁱ—Sn1—S1—C1	167.8 (9)	Sn1—S1—C1—N4	−71.9 (2)
C2—N3—N4—C1	0.7 (3)	Sn1—S1—C1—N1	106.3 (2)
Sn1ⁱⁱ—N3—N4—C1	171.96 (17)	N4—N3—C2—N1	−0.4 (3)
N3—N4—C1—N1	−0.7 (3)	Sn1ⁱⁱ—N3—C2—N1	−169.27 (18)
N3—N4—C1—S1	177.73 (19)	C1—N1—C2—N3	0.0 (3)
C2—N1—C1—N4	0.5 (3)	C3—N1—C2—N3	178.8 (2)

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

Acknowledgements

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

References

Bruker (2001). SMART (Version 5.625), SADABS (Version 2.03a) and SHELXTL (Version 6.12). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2002). SAINT. Version 6.36a. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Narayan, V. L. (1983). Organotin Compounds as Antitumour Agents. In Structure–Activity Relationship of Antitumour Agents, edited by D. N. Reinhoudt, T. A. Connors, H. M. Pinedo & K. W. Van De Poll, pp. 77-106. The Hague: Martinus Nijhoff. Google Scholar
Shahzadi, S., Ali, S., Bhatti, M. H., Fettouhi, M. & Athar, M. (2006). J. Organomet. Chem. 691, 1797–1802. Web of Science CSD CrossRef CAS Google Scholar
Shahzadi, S., Ali, S. & Fettouhi, M. (2006). Acta Cryst. E62, m1178–m1180. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 62| Part 9| September 2006| Pages m2328-m2329

https://doi.org/10.1107/S1600536806033654

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