Aqua­trimeth­yl[2-(4-methyl­pyrimidin-2-ylsulfan­yl)acetato-κO]tin(IV)

Gao, Z.; Zhang, J.; Hao, X.; Wang, D.; Zhang, T.

doi:10.1107/S1600536813012622

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 6| June 2013| Page m313

doi:10.1107/S1600536813012622

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Aquatrimethyl[2-(4-methylpyrimidin-2-ylsulfanyl)acetato-κO]tin(IV)

Zhiqing Gao,^a Junhong Zhang,^b ^* Xuyi Hao,^c Daqi Wang ^b and Tingting Zhang ^b

^aDongcheng College of Liaocheng University, Shandong 252059, People's Republic of China, ^bCollege of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059, People's Republic of China, and ^cTancheng Middle School, Linyin 276000, People's Republic of China
^*Correspondence e-mail: zhangjunhong@lcu.edu.cn

(Received 28 April 2013; accepted 8 May 2013; online 15 May 2013)

In the title compound, [Sn(CH₃)₃(C₇H₇N₂O₂S)(H₂O)], the Sn^IV atom has a distorted trigonal–bipyramidal coordination geometry, with one carboxylate O atom of the 2-(4-methylpyrimidine-2-sulfanyl)acetate ligand and the O atom of a water molecule in axial positions, and three methyl groups in equatorial positions. In the crystal, molecules are linked via O—H⋯O and O—H⋯N hydrogen bonds, forming double-stranded chains propagating along [010].

Related literature

For related structures, see: Zhang et al. (2007 ); Zhu et al. (2011 ).

Experimental

Crystal data

[Sn(CH₃)₃(C₇H₇N₂O₂S)(H₂O)]
M_r = 365.01
Monoclinic, P 2₁ /c
a = 7.7658 (4) Å
b = 11.0901 (4) Å
c = 18.8261 (8) Å
β = 113.575 (4)°
V = 1486.05 (11) Å³
Z = 4
Cu Kα radiation
μ = 15.00 mm⁻¹
T = 293 K
0.05 × 0.04 × 0.04 mm

Data collection

Xcalibur (Eos, Gemini) diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.521, T_max = 0.585
8393 measured reflections
2666 independent reflections
2151 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.132
S = 1.05
2664 reflections
159 parameters
H-atom parameters constrained
Δρ_max = 1.52 e Å⁻³
Δρ_min = −0.78 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3D⋯O1ⁱ	0.85	2.03	2.798 (6)	149
O3—H3F⋯N1ⁱⁱ	0.85	2.14	2.884 (7)	146
Symmetry codes: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) x, y+1, z.

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); 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/S1600536813012622/su2595sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813012622/su2595Isup2.hkl

checkCIF report

Comment top

The title compound is a trimethyltin ester of 4-methylpyrimidine-2-thioglycolic acid, Fig. 1. The geometry of tin atom, Sn1, is a slightly distorted trigonal bipyramid, surrounded axially by atom O2 of the ligand and atom O3 of a water molecule. The axial angle O2—Sn1—O3 is 176.66 (16) Å close to a linear arrangement. Three carbon atoms of the methyl groups are located in the equatorially plane and the sum of the trigonal C—Sn—C angles is 358.1°, which illustrates that the three methyl C atoms and the tin atom are nearly coplanar. The Sn—O distances of 2.144 (4) Å and 2.488 (5) Å, are a little longer than the covalent bond length of tin and oxygen (Zhang et al., 2007) but similar to the same distances reported for other triorganotin polymeric structures (Zhu et al., 2011).

In the crystal, molecules are linked via O-H···O and O-H···N hydrogen bonds forming double-stranded chains propagating along [010]; see Table 1 and Fig. 2.

Related literature top

For related structures, see: Zhang et al. (2007); Zhu et al. (2011).

Experimental top

The reaction was carried out under an atmosphere of nitrogen. 4-methylpyrimidine-2-thioglycolic acid (1 mmol) and sodium ethanol (1 mmol) were added to a stirred solution of ethanol (30 ml) in a Schlenk flask and stirred for 30 min. Trimethyltin chloride (1 mmol) was then added to the reactor and the reaction mixture was stirred for 12 h at 353 K. The resulting clear solution was evaporated under vacuum. The product was crystallized from dichloromethane to yield colourless block-like crystals of the title compound [Yield 80%; M.p. 430 K]. Anal. Calcd (%) for C₁₀H₁₈N₂O₃SSn (Mr = 365.01): C, 32.90; H, 4.97; N, 7.67; Found (%): C, 32.87; H, 4.94; N, 7.71.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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 complex, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A partial view along the a axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines; see Table 1 for details.

Aquatrimethyl[2-(4-methylpyrimidin-2-ylsulfanyl)acetato-κO]tin(IV) top

Crystal data top

[Sn(CH₃)₃(C₇H₇N₂O₂S)(H₂O)]	F(000) = 728
M_r = 365.01	D_x = 1.631 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 2652 reflections
a = 7.7658 (4) Å	θ = 4.0–70.5°
b = 11.0901 (4) Å	µ = 15.00 mm⁻¹
c = 18.8261 (8) Å	T = 293 K
β = 113.575 (4)°	Block, colourless
V = 1486.05 (11) Å³	0.05 × 0.04 × 0.04 mm
Z = 4

Data collection top

Xcalibur (Eos, Gemini) [CHECK! BRUKER SOFTWARE?] diffractometer	2666 independent reflections
Radiation source: Enhance (Cu) X-ray Source	2151 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
Detector resolution: 16.2563 pixels mm^-1	θ_max = 67.3°, θ_min = 4.7°
phi and ω scans	h = −6→9
Absorption correction: multi-scan (SADABS; Bruker, 2007)	k = −13→13
T_min = 0.521, T_max = 0.585	l = −22→21
8393 measured reflections

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)] = 0.047	H-atom parameters constrained
wR(F²) = 0.132	w = 1/[σ²(F_o²) + (0.0753P)²] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
2664 reflections	Δρ_max = 1.52 e Å⁻³
159 parameters	Δρ_min = −0.78 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00176 (18)

Crystal data top

[Sn(CH₃)₃(C₇H₇N₂O₂S)(H₂O)]	V = 1486.05 (11) Å³
M_r = 365.01	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 7.7658 (4) Å	µ = 15.00 mm⁻¹
b = 11.0901 (4) Å	T = 293 K
c = 18.8261 (8) Å	0.05 × 0.04 × 0.04 mm
β = 113.575 (4)°

Data collection top

Xcalibur (Eos, Gemini) [CHECK! BRUKER SOFTWARE?] diffractometer	2666 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	2151 reflections with I > 2σ(I)
T_min = 0.521, T_max = 0.585	R_int = 0.059
8393 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.132	H-atom parameters constrained
S = 1.05	Δρ_max = 1.52 e Å⁻³
2664 reflections	Δρ_min = −0.78 e Å⁻³
159 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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 > 2sigma(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	0.88830 (6)	1.02871 (3)	0.61937 (2)	0.0477 (2)
S1	0.8813 (3)	0.51496 (13)	0.57463 (11)	0.0572 (6)
O1	1.0216 (7)	0.7546 (4)	0.6551 (2)	0.0631 (14)
O2	0.8531 (6)	0.8672 (4)	0.5524 (2)	0.0559 (14)
O3	0.9257 (8)	1.2230 (4)	0.6901 (3)	0.082 (2)
N1	0.6645 (8)	0.4207 (4)	0.6350 (3)	0.0534 (18)
N2	0.5982 (8)	0.6263 (5)	0.5937 (3)	0.0566 (17)
C1	0.7227 (12)	1.1295 (7)	0.5191 (4)	0.075 (3)
C2	1.1824 (10)	1.0401 (6)	0.6541 (5)	0.071 (3)
C3	0.7556 (13)	0.9649 (7)	0.6896 (5)	0.074 (3)
C4	0.9201 (9)	0.7672 (5)	0.5856 (4)	0.049 (2)
C5	0.8680 (10)	0.6603 (5)	0.5312 (3)	0.054 (2)
C6	0.6941 (9)	0.5235 (5)	0.6040 (4)	0.0457 (19)
C8	0.4562 (10)	0.6241 (8)	0.6160 (4)	0.068 (3)
C9	0.4131 (11)	0.5250 (8)	0.6490 (5)	0.071 (3)
C10	0.5225 (10)	0.4220 (6)	0.6579 (4)	0.060 (2)
C12	0.4868 (13)	0.3083 (7)	0.6930 (5)	0.091 (4)
H1A	0.61760	1.08170	0.48660	0.1130*
H1B	0.79770	1.15070	0.49100	0.1130*
H1C	0.67800	1.20150	0.53440	0.1130*
H2A	1.23750	1.07840	0.70390	0.1070*
H2B	1.20970	1.08670	0.61690	0.1070*
H2C	1.23360	0.96050	0.65730	0.1070*
H3A	0.72540	0.88110	0.67880	0.1110*
H3B	0.64240	1.00990	0.67900	0.1110*
H3C	0.83830	0.97440	0.74320	0.1110*
H3D	0.96840	1.20950	0.73860	0.1230*
H3F	0.81920	1.25720	0.67570	0.1230*
H5A	0.94970	0.66000	0.50340	0.0650*
H5B	0.74050	0.67200	0.49320	0.0650*
H8	0.38290	0.69300	0.60890	0.0820*
H9	0.31430	0.52630	0.66500	0.0850*
H12A	0.47470	0.24180	0.65860	0.1360*
H12B	0.37290	0.31660	0.70110	0.1360*
H12C	0.58980	0.29360	0.74170	0.1360*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.0622 (3)	0.0338 (3)	0.0444 (3)	−0.0027 (2)	0.0186 (2)	0.0027 (2)
S1	0.0757 (11)	0.0341 (7)	0.0735 (11)	−0.0025 (7)	0.0420 (9)	−0.0056 (7)
O1	0.082 (3)	0.050 (2)	0.047 (2)	−0.007 (2)	0.015 (2)	−0.0018 (19)
O2	0.074 (3)	0.038 (2)	0.051 (2)	−0.004 (2)	0.020 (2)	−0.0014 (18)
O3	0.121 (5)	0.046 (3)	0.067 (3)	0.009 (3)	0.024 (3)	−0.009 (2)
N1	0.072 (4)	0.035 (2)	0.054 (3)	−0.010 (2)	0.026 (3)	−0.004 (2)
N2	0.059 (3)	0.048 (3)	0.064 (3)	0.005 (2)	0.026 (3)	0.010 (2)
C1	0.103 (6)	0.057 (4)	0.053 (4)	0.006 (4)	0.018 (4)	0.005 (3)
C2	0.052 (4)	0.056 (4)	0.091 (6)	−0.013 (3)	0.013 (4)	−0.010 (4)
C3	0.098 (6)	0.065 (5)	0.079 (5)	0.005 (4)	0.057 (5)	0.010 (4)
C4	0.063 (4)	0.041 (3)	0.051 (4)	−0.018 (3)	0.030 (3)	−0.011 (3)
C5	0.081 (5)	0.036 (3)	0.053 (3)	−0.012 (3)	0.035 (3)	−0.004 (3)
C6	0.054 (4)	0.034 (3)	0.047 (3)	−0.009 (2)	0.018 (3)	−0.006 (2)
C8	0.054 (4)	0.076 (5)	0.071 (5)	0.014 (4)	0.022 (4)	0.018 (4)
C9	0.053 (4)	0.093 (6)	0.065 (5)	0.001 (4)	0.023 (4)	0.002 (4)
C10	0.069 (4)	0.058 (4)	0.049 (3)	−0.022 (3)	0.021 (3)	−0.003 (3)
C12	0.131 (8)	0.067 (5)	0.088 (6)	−0.033 (5)	0.059 (6)	0.004 (4)

Geometric parameters (Å, º) top

Sn1—O2	2.144 (4)	C10—C12	1.500 (11)
Sn1—O3	2.488 (5)	C1—H1A	0.9600
Sn1—C1	2.127 (7)	C1—H1B	0.9600
Sn1—C2	2.113 (9)	C1—H1C	0.9600
Sn1—C3	2.098 (10)	C2—H2A	0.9600
S1—C5	1.792 (6)	C2—H2B	0.9600
S1—C6	1.752 (8)	C2—H2C	0.9600
O1—C4	1.236 (8)	C3—H3A	0.9600
O2—C4	1.277 (7)	C3—H3B	0.9600
O3—H3D	0.8500	C3—H3C	0.9600
O3—H3F	0.8500	C5—H5A	0.9700
N1—C6	1.342 (8)	C5—H5B	0.9700
N1—C10	1.335 (10)	C8—H8	0.9300
N2—C8	1.328 (10)	C9—H9	0.9300
N2—C6	1.333 (8)	C12—H12A	0.9600
C4—C5	1.512 (8)	C12—H12B	0.9600
C8—C9	1.368 (12)	C12—H12C	0.9600
C9—C10	1.393 (12)

O2—Sn1—O3	176.66 (16)	Sn1—C1—H1C	109.00
O2—Sn1—C1	91.6 (2)	H1A—C1—H1B	109.00
O2—Sn1—C2	95.7 (2)	H1A—C1—H1C	109.00
O2—Sn1—C3	96.3 (2)	H1B—C1—H1C	109.00
O3—Sn1—C1	85.4 (2)	Sn1—C2—H2A	109.00
O3—Sn1—C2	84.4 (2)	Sn1—C2—H2B	109.00
O3—Sn1—C3	86.4 (3)	Sn1—C2—H2C	109.00
C1—Sn1—C2	116.0 (3)	H2A—C2—H2B	109.00
C1—Sn1—C3	117.5 (4)	H2A—C2—H2C	110.00
C2—Sn1—C3	124.6 (3)	H2B—C2—H2C	110.00
C5—S1—C6	101.1 (3)	Sn1—C3—H3A	109.00
Sn1—O2—C4	120.4 (4)	Sn1—C3—H3B	109.00
Sn1—O3—H3F	109.00	Sn1—C3—H3C	110.00
H3D—O3—H3F	109.00	H3A—C3—H3B	109.00
Sn1—O3—H3D	110.00	H3A—C3—H3C	109.00
C6—N1—C10	116.0 (6)	H3B—C3—H3C	109.00
C6—N2—C8	115.1 (6)	S1—C5—H5A	108.00
O1—C4—C5	120.9 (5)	S1—C5—H5B	108.00
O1—C4—O2	125.4 (6)	C4—C5—H5A	108.00
O2—C4—C5	113.8 (5)	C4—C5—H5B	108.00
S1—C5—C4	116.4 (4)	H5A—C5—H5B	107.00
S1—C6—N1	113.5 (5)	N2—C8—H8	119.00
S1—C6—N2	119.1 (5)	C9—C8—H8	119.00
N1—C6—N2	127.4 (7)	C8—C9—H9	121.00
N2—C8—C9	122.9 (8)	C10—C9—H9	121.00
C8—C9—C10	117.7 (8)	C10—C12—H12A	109.00
N1—C10—C9	120.9 (7)	C10—C12—H12B	109.00
N1—C10—C12	117.1 (7)	C10—C12—H12C	109.00
C9—C10—C12	122.1 (8)	H12A—C12—H12B	109.00
Sn1—C1—H1A	109.00	H12A—C12—H12C	109.00
Sn1—C1—H1B	109.00	H12B—C12—H12C	109.00

C1—Sn1—O2—C4	−176.2 (6)	C6—N1—C10—C9	0.4 (10)
C2—Sn1—O2—C4	67.5 (6)	C6—N1—C10—C12	−179.8 (6)
C3—Sn1—O2—C4	−58.3 (6)	C8—N2—C6—S1	178.6 (5)
C6—S1—C5—C4	69.3 (6)	C8—N2—C6—N1	−1.1 (10)
C5—S1—C6—N1	176.1 (5)	C6—N2—C8—C9	1.6 (10)
C5—S1—C6—N2	−3.6 (6)	O1—C4—C5—S1	22.7 (10)
Sn1—O2—C4—O1	−6.7 (10)	O2—C4—C5—S1	−158.6 (5)
Sn1—O2—C4—C5	174.7 (5)	N2—C8—C9—C10	−1.2 (12)
C10—N1—C6—S1	−179.6 (5)	C8—C9—C10—N1	0.1 (11)
C10—N1—C6—N2	0.1 (10)	C8—C9—C10—C12	−179.7 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3D···O1ⁱ	0.85	2.03	2.798 (6)	149
O3—H3F···N1ⁱⁱ	0.85	2.14	2.884 (7)	146

Symmetry codes: (i) −x+2, y+1/2, −z+3/2; (ii) x, y+1, z.

Experimental details

Crystal data
Chemical formula	[Sn(CH₃)₃(C₇H₇N₂O₂S)(H₂O)]
M_r	365.01
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.7658 (4), 11.0901 (4), 18.8261 (8)
β (°)	113.575 (4)
V (Å³)	1486.05 (11)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	15.00
Crystal size (mm)	0.05 × 0.04 × 0.04

Data collection
Diffractometer	Xcalibur (Eos, Gemini) [CHECK! BRUKER SOFTWARE?] diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.521, 0.585
No. of measured, independent and observed [I > 2σ(I)] reflections	8393, 2666, 2151
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.598

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.132, 1.05
No. of reflections	2664
No. of parameters	159
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.52, −0.78

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), 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
O3—H3D···O1ⁱ	0.85	2.03	2.798 (6)	149
O3—H3F···N1ⁱⁱ	0.85	2.14	2.884 (7)	146

Symmetry codes: (i) −x+2, y+1/2, −z+3/2; (ii) x, y+1, z.

Acknowledgements

The authors thank the Liaocheng University Foundation (xo9013), the Liaocheng University State Key Laboratory of Crystal Materials (SF2012068), the Project of Shandong Provincial Education Department (J12LD13) and Liaocheng University Funds (31805) for Young Scientists for financial support.

References

Bruker (2007). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, J.-H., Ma, C.-L. & Zhang, R.-F. (2007). Acta Cryst. E63, m2161. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zhu, Q. & Zhang, R. (2011). Acta Cryst. E67, m1834. Web of Science CSD CrossRef IUCr Journals Google Scholar