(4,6-Dimethyl-2-sulfanylidenepyrimidin-1-ium) trichlorido(thio­urea-κS)zinc(II)

The title compound, (C₆H₉N₂S)[ZnCl₃{SC(NH₂)₂}], exists as a zincate where the zinc(II) centre is coordinated by three chloride ligands and a thio­urea ligand to form the anion. The organic cation adopts the protonated 4,6-dimethyl-2-sulfanyl­idenepyrimidin-1-ium (L) form of 4,6-dimethyl­pyrimidine-2(1H)-thione. Two short N—H...Cl hydrogen bonds involving the pyrimidine H atoms and the [ZnCl₃L]⁻ anion form a crystallographically centrosymmetric dimeric unit consisting of two anions and two cations. The packing structure is completed by longer-range hydrogen bonds donated by the thio­urea NH₂ groups to chloride ligand hydrogen-bond acceptors.

Computing details

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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).

(4,6-Dimethyl-2-sulfanylidenepyrimidin-1-ium) trichlorido(thiourea-κS)zinc(II)

Crystal data

(C6H9N2S)[ZnCl3(CH4N2S)]	F(000) = 1568
Mr = 389.05	Dx = 1.720 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9718 reflections
a = 15.3648 (4) Å	θ = 3.1–36.3°
b = 7.3374 (2) Å	µ = 2.43 mm^−1
c = 26.7111 (6) Å	T = 123 K
β = 93.919 (1)°	Block, colourless
V = 3004.31 (13) Å^3	0.17 × 0.15 × 0.14 mm
Z = 8

Data collection

Bruker APEXII CCD area-detector diffractometer	3285 independent reflections
Radiation source: fine-focus sealed tube	3166 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
φ and ω scans	θmax = 27.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −19→19
Tmin = 0.683, Tmax = 0.727	k = −9→9
40204 measured reflections	l = −34→34

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.015	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.040	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0175P)^2 + 3.2453P] where P = (Fo^2 + 2Fc^2)/3
3285 reflections	(Δ/σ)max = 0.001
174 parameters	Δρmax = 0.31 e Å^−3
2 restraints	Δρmin = −0.19 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.158445 (9)	0.36606 (2)	0.143070 (5)	0.01699 (5)
C1	1.01043 (8)	0.83474 (17)	0.13185 (5)	0.0191 (2)
C2	1.06449 (8)	0.83285 (17)	0.04895 (5)	0.0178 (2)
C3	0.92225 (8)	0.71085 (18)	0.06348 (5)	0.0203 (2)
C4	0.93385 (8)	0.75250 (18)	0.11398 (5)	0.0213 (3)
H4	0.8897	0.7249	0.1360	0.026*
C5	1.02883 (9)	0.8889 (2)	0.18534 (5)	0.0255 (3)
H5A	1.0834	0.8320	0.1986	0.038*
H5B	0.9809	0.8485	0.2050	0.038*
H5C	1.0344	1.0217	0.1876	0.038*
C6	0.84299 (9)	0.6208 (2)	0.03986 (6)	0.0292 (3)
H6A	0.8289	0.6733	0.0066	0.044*
H6B	0.7939	0.6398	0.0609	0.044*
H6C	0.8539	0.4899	0.0366	0.044*
C7	0.31245 (9)	0.66412 (17)	0.16888 (5)	0.0213 (3)
Cl1	0.04641 (2)	0.33090 (5)	0.083500 (11)	0.02363 (7)
Cl2	0.09307 (2)	0.43667 (4)	0.214950 (11)	0.02243 (7)
Cl3	0.228033 (19)	0.09711 (4)	0.159042 (11)	0.01977 (7)
N1	1.07231 (7)	0.86972 (15)	0.09959 (4)	0.0181 (2)
H1	1.1205 (7)	0.921 (2)	0.1108 (6)	0.022*
N2	0.98620 (7)	0.75282 (15)	0.03367 (4)	0.0187 (2)
H2	0.9787 (10)	0.732 (2)	0.0020 (3)	0.022*
N3	0.38639 (8)	0.75308 (17)	0.16300 (6)	0.0283 (3)
H3A	0.4115 (12)	0.806 (3)	0.1873 (7)	0.034*
H3B	0.4036 (11)	0.764 (3)	0.1328 (7)	0.034*
N4	0.28743 (9)	0.64036 (18)	0.21465 (5)	0.0281 (3)
H4B	0.3136 (12)	0.692 (3)	0.2380 (7)	0.034*
H4A	0.2399 (13)	0.593 (3)	0.2192 (7)	0.034*
S1	1.14037 (2)	0.87802 (5)	0.010083 (12)	0.02336 (7)
S2	0.25353 (2)	0.58583 (4)	0.115888 (12)	0.02081 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.01646 (8)	0.01852 (8)	0.01574 (8)	0.00082 (5)	−0.00078 (5)	−0.00103 (5)
C1	0.0209 (6)	0.0174 (6)	0.0191 (6)	0.0040 (5)	0.0015 (5)	0.0007 (5)
C2	0.0180 (6)	0.0160 (6)	0.0191 (6)	0.0018 (5)	−0.0008 (5)	0.0015 (5)
C3	0.0155 (6)	0.0194 (6)	0.0258 (6)	0.0018 (5)	−0.0002 (5)	0.0007 (5)
C4	0.0170 (6)	0.0232 (6)	0.0240 (6)	0.0009 (5)	0.0039 (5)	0.0001 (5)
C5	0.0272 (7)	0.0292 (7)	0.0202 (6)	−0.0001 (6)	0.0012 (5)	−0.0029 (5)
C6	0.0195 (7)	0.0380 (8)	0.0298 (7)	−0.0063 (6)	−0.0013 (5)	−0.0035 (6)
C7	0.0197 (6)	0.0154 (6)	0.0284 (7)	0.0033 (5)	−0.0012 (5)	0.0008 (5)
Cl1	0.02204 (15)	0.02911 (16)	0.01874 (14)	0.00231 (12)	−0.00582 (11)	−0.00248 (12)
Cl2	0.02158 (15)	0.02705 (16)	0.01908 (14)	0.00397 (12)	0.00450 (11)	0.00046 (12)
Cl3	0.01821 (14)	0.01841 (14)	0.02238 (14)	0.00181 (11)	−0.00090 (11)	−0.00059 (11)
N1	0.0154 (5)	0.0196 (5)	0.0187 (5)	−0.0012 (4)	−0.0015 (4)	−0.0009 (4)
N2	0.0181 (5)	0.0213 (5)	0.0163 (5)	−0.0001 (4)	−0.0019 (4)	−0.0001 (4)
N3	0.0209 (6)	0.0257 (6)	0.0380 (7)	−0.0023 (5)	−0.0002 (5)	−0.0002 (5)
N4	0.0293 (7)	0.0323 (7)	0.0221 (6)	−0.0085 (5)	−0.0030 (5)	−0.0044 (5)
S1	0.02034 (16)	0.02867 (17)	0.02140 (15)	−0.00419 (13)	0.00389 (12)	0.00046 (13)
S2	0.02219 (15)	0.02254 (15)	0.01770 (14)	−0.00115 (12)	0.00141 (12)	0.00199 (12)

Geometric parameters (Å, º)

Zn1—Cl3	2.2710 (3)	C5—H5B	0.9800
Zn1—Cl1	2.2775 (3)	C5—H5C	0.9800
Zn1—Cl2	2.2863 (3)	C6—H6A	0.9800
Zn1—S2	2.3252 (4)	C6—H6B	0.9800
C1—N1	1.3507 (17)	C6—H6C	0.9800
C1—C4	1.3782 (18)	C7—N4	1.3179 (19)
C1—C5	1.4912 (18)	C7—N3	1.3289 (18)
C2—N2	1.3753 (16)	C7—S2	1.7257 (14)
C2—N1	1.3767 (16)	N1—H1	0.866 (9)
C2—S1	1.6469 (13)	N2—H2	0.860 (9)
C3—N2	1.3422 (17)	N3—H3A	0.828 (19)
C3—C4	1.3826 (18)	N3—H3B	0.869 (19)
C3—C6	1.4876 (18)	N4—H4B	0.81 (2)
C4—H4	0.9500	N4—H4A	0.82 (2)
C5—H5A	0.9800
Cl3—Zn1—Cl1	110.883 (13)	H5B—C5—H5C	109.5
Cl3—Zn1—Cl2	105.508 (12)	C3—C6—H6A	109.5
Cl1—Zn1—Cl2	104.946 (13)	C3—C6—H6B	109.5
Cl3—Zn1—S2	111.316 (13)	H6A—C6—H6B	109.5
Cl1—Zn1—S2	108.749 (13)	C3—C6—H6C	109.5
Cl2—Zn1—S2	115.248 (13)	H6A—C6—H6C	109.5
N1—C1—C4	118.92 (12)	H6B—C6—H6C	109.5
N1—C1—C5	117.71 (12)	N4—C7—N3	118.73 (13)
C4—C1—C5	123.36 (12)	N4—C7—S2	123.16 (11)
N2—C2—N1	113.03 (11)	N3—C7—S2	118.12 (11)
N2—C2—S1	122.78 (10)	C1—N1—C2	124.86 (11)
N1—C2—S1	124.19 (10)	C1—N1—H1	119.0 (10)
N2—C3—C4	118.51 (12)	C2—N1—H1	116.1 (10)
N2—C3—C6	117.49 (12)	C3—N2—C2	125.65 (11)
C4—C3—C6	124.00 (12)	C3—N2—H2	119.3 (10)
C1—C4—C3	119.00 (12)	C2—N2—H2	115.0 (10)
C1—C4—H4	120.5	C7—N3—H3A	119.6 (13)
C3—C4—H4	120.5	C7—N3—H3B	118.1 (12)
C1—C5—H5A	109.5	H3A—N3—H3B	122.0 (17)
C1—C5—H5B	109.5	C7—N4—H4B	119.3 (13)
H5A—C5—H5B	109.5	C7—N4—H4A	120.6 (13)
C1—C5—H5C	109.5	H4B—N4—H4A	118.6 (18)
H5A—C5—H5C	109.5	C7—S2—Zn1	106.28 (5)
N1—C1—C4—C3	−0.94 (19)	C6—C3—N2—C2	−178.69 (12)
C5—C1—C4—C3	178.69 (12)	N1—C2—N2—C3	−0.51 (18)
N2—C3—C4—C1	−0.20 (19)	S1—C2—N2—C3	179.26 (10)
C6—C3—C4—C1	179.44 (13)	N4—C7—S2—Zn1	−18.07 (13)
C4—C1—N1—C2	1.48 (19)	N3—C7—S2—Zn1	162.16 (10)
C5—C1—N1—C2	−178.17 (12)	Cl3—Zn1—S2—C7	−78.35 (5)
N2—C2—N1—C1	−0.76 (17)	Cl1—Zn1—S2—C7	159.20 (5)
S1—C2—N1—C1	179.48 (10)	Cl2—Zn1—S2—C7	41.74 (5)
C4—C3—N2—C2	0.97 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl3^i	0.87 (1)	2.40 (1)	3.2420 (11)	164 (1)
N2—H2···Cl1^ii	0.86 (1)	2.34 (1)	3.1952 (11)	178 (2)
N3—H3A···Cl2^iii	0.828 (19)	2.787 (19)	3.5216 (16)	148.7 (16)
N3—H3B···Cl1^iv	0.869 (19)	2.680 (18)	3.4050 (14)	141.6 (15)
N4—H4B···Cl2^iii	0.81 (2)	2.57 (2)	3.3410 (14)	158.6 (18)
N4—H4A···Cl2	0.82 (2)	2.53 (2)	3.3399 (14)	168.8 (18)

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