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The title compound, (C
6H
9N
2S)[ZnCl
3{SC(NH
2)
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(1
H)-thione. Two short N—H
Cl hydrogen bonds involving the pyrimidine H atoms and the [ZnCl
3L]
− 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 NH
2 groups to chloride ligand hydrogen-bond acceptors.
Supporting information
CCDC reference: 934608
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)
top
Crystal data top
(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) Å3 | 0.17 × 0.15 × 0.14 mm |
Z = 8 | |
Data collection top
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 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) = 0.040 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0175P)2 + 3.2453P] where P = (Fo2 + 2Fc2)/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 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 | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl3i | 0.87 (1) | 2.40 (1) | 3.2420 (11) | 164 (1) |
N2—H2···Cl1ii | 0.86 (1) | 2.34 (1) | 3.1952 (11) | 178 (2) |
N3—H3A···Cl2iii | 0.828 (19) | 2.787 (19) | 3.5216 (16) | 148.7 (16) |
N3—H3B···Cl1iv | 0.869 (19) | 2.680 (18) | 3.4050 (14) | 141.6 (15) |
N4—H4B···Cl2iii | 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. |
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