Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101017577/ln1123sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101017577/ln1123Isup2.hkl |
CCDC reference: 180136
Solutions of zinc acetate (0.257 g, 1.17 mmol) and tetrahydropyrimidine-2-thione (0.271 g, 2.34 mmol) in acetonitrile were mixed in a 1:2 molar ratio in a 50 ml flask and the mixture was stirred for about 30 minutes. The solution was then filtered into another flask and left to evaporate slowly. After a few days, some single crystals were collected, washed with hexane and dried (m.p. 400 K).
After checking their presence in the difference map, the positions of all H atoms of the Zn complex were geometrically idealized and allowed to ride on their parent atoms with C—H distances in the range 0.96–0.97 Å, N—H distances of 0.88 Å and fixed displacement parameters defined by Uiso(H) = 1.2Ueq(parent atom) or 1.5Ueq(Cmethyl). The H atoms of the water molecule were refined isotropically. Owing to large fraction of weak data at higher angles, the 2θ maximum was limited to 50°. The highest peak and the deepest hole are 0.97 and 1.03 Å from O3 and Zn1, respectively. Atom C11 in one of the trimethylenethiourea rings is disordered and was refined with an occupancy ratio of 0.75:0.25.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995), PLATON (Spek, 1990).
C12H22N4O4S2Zn·H2O | Dx = 1.453 Mg m−3 |
Mr = 433.84 | Melting point: 400K K |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 8.7517 (1) Å | Cell parameters from 8192 reflections |
b = 17.3654 (2) Å | θ = 2.0–29.4° |
c = 13.0543 (2) Å | µ = 1.48 mm−1 |
β = 90.837 (1)° | T = 293 K |
V = 1983.74 (4) Å3 | Slab, colourless |
Z = 4 | 0.16 × 0.12 × 0.10 mm |
F(000) = 904 |
Siemens SMART CCD area-detector diffractometer | 3495 independent reflections |
Radiation source: fine-focus sealed tube | 2645 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.097 |
Detector resolution: 8.33 pixels mm-1 | θmax = 25.0°, θmin = 2.0° |
ω scans | h = −9→10 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −20→19 |
Tmin = 0.798, Tmax = 0.867 | l = −15→10 |
11176 measured reflections |
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)] = 0.054 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.138 | w = 1/[σ2(Fo2) + (0.0693P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.98 | (Δ/σ)max < 0.001 |
3495 reflections | Δρmax = 0.54 e Å−3 |
238 parameters | Δρmin = −1.37 e Å−3 |
2 restraints | Extinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0165 (16) |
C12H22N4O4S2Zn·H2O | V = 1983.74 (4) Å3 |
Mr = 433.84 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.7517 (1) Å | µ = 1.48 mm−1 |
b = 17.3654 (2) Å | T = 293 K |
c = 13.0543 (2) Å | 0.16 × 0.12 × 0.10 mm |
β = 90.837 (1)° |
Siemens SMART CCD area-detector diffractometer | 3495 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 2645 reflections with I > 2σ(I) |
Tmin = 0.798, Tmax = 0.867 | Rint = 0.097 |
11176 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | 2 restraints |
wR(F2) = 0.138 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.98 | Δρmax = 0.54 e Å−3 |
3495 reflections | Δρmin = −1.37 e Å−3 |
238 parameters |
Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 30 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was -35°. Crystal decay was monitored by repeating thirty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible. |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Zn1 | 0.57847 (4) | 0.250169 (19) | 0.53877 (3) | 0.0358 (2) | |
S1 | 0.76157 (11) | 0.31906 (6) | 0.44927 (7) | 0.0499 (3) | |
S2 | 0.34630 (11) | 0.24216 (5) | 0.44875 (8) | 0.0451 (3) | |
O1 | 0.6330 (3) | 0.14138 (14) | 0.56550 (18) | 0.0507 (7) | |
O2 | 0.6449 (4) | 0.10394 (15) | 0.4038 (2) | 0.0618 (8) | |
O3 | 0.5858 (3) | 0.27839 (14) | 0.68607 (17) | 0.0464 (6) | |
O4 | 0.4660 (3) | 0.38806 (15) | 0.65645 (18) | 0.0536 (7) | |
N1 | 0.6499 (4) | 0.23990 (17) | 0.2885 (3) | 0.0505 (9) | |
H1A | 0.6629 | 0.2006 | 0.3277 | 0.061* | |
N2 | 0.6875 (4) | 0.36776 (18) | 0.2620 (2) | 0.0531 (8) | |
H2A | 0.7165 | 0.4118 | 0.2855 | 0.064* | |
N3 | 0.1875 (3) | 0.34003 (17) | 0.3369 (2) | 0.0432 (7) | |
H3A | 0.1687 | 0.2998 | 0.3005 | 0.052* | |
N4 | 0.3255 (4) | 0.39478 (16) | 0.4667 (2) | 0.0487 (8) | |
H4A | 0.3880 | 0.3885 | 0.5175 | 0.058* | |
C1 | 0.6593 (5) | 0.0923 (2) | 0.4966 (3) | 0.0492 (9) | |
C2 | 0.7095 (7) | 0.0134 (2) | 0.5336 (4) | 0.0832 (16) | |
H2B | 0.8057 | 0.0177 | 0.5694 | 0.125* | |
H2C | 0.7204 | −0.0203 | 0.4759 | 0.125* | |
H2D | 0.6343 | −0.0071 | 0.5789 | 0.125* | |
C3 | 0.5250 (4) | 0.34119 (19) | 0.7156 (3) | 0.0389 (8) | |
C4 | 0.5290 (5) | 0.3577 (3) | 0.8281 (3) | 0.0589 (11) | |
H4B | 0.4762 | 0.3176 | 0.8638 | 0.088* | |
H4C | 0.4801 | 0.4061 | 0.8408 | 0.088* | |
H4D | 0.6332 | 0.3599 | 0.8519 | 0.088* | |
C5 | 0.6940 (4) | 0.30764 (19) | 0.3243 (3) | 0.0419 (8) | |
C6 | 0.5805 (7) | 0.2266 (3) | 0.1874 (3) | 0.0710 (14) | |
H6A | 0.4992 | 0.1889 | 0.1925 | 0.085* | |
H6B | 0.6566 | 0.2067 | 0.1411 | 0.085* | |
C7 | 0.5176 (6) | 0.3007 (3) | 0.1467 (3) | 0.0680 (13) | |
H7A | 0.4268 | 0.3147 | 0.1842 | 0.082* | |
H7B | 0.4888 | 0.2945 | 0.0751 | 0.082* | |
C8 | 0.6346 (6) | 0.3636 (3) | 0.1570 (3) | 0.0702 (13) | |
H8A | 0.7199 | 0.3531 | 0.1126 | 0.084* | |
H8B | 0.5898 | 0.4125 | 0.1367 | 0.084* | |
C9 | 0.2838 (4) | 0.33344 (19) | 0.4158 (2) | 0.0370 (8) | |
C10 | 0.1116 (5) | 0.4125 (2) | 0.3085 (3) | 0.0573 (10) | |
H10A | 0.0151 | 0.4168 | 0.3437 | 0.069* | 0.75 |
H10B | 0.0910 | 0.4135 | 0.2353 | 0.069* | 0.75 |
H10C | 0.0046 | 0.4031 | 0.2925 | 0.069* | 0.25 |
H10D | 0.1591 | 0.4344 | 0.2485 | 0.069* | 0.25 |
C11A | 0.2140 (8) | 0.4780 (3) | 0.3380 (5) | 0.0673 (17) | 0.75 |
H11A | 0.2990 | 0.4797 | 0.2912 | 0.081* | 0.75 |
H11B | 0.1576 | 0.5258 | 0.3305 | 0.081* | 0.75 |
C11B | 0.1257 (18) | 0.4666 (9) | 0.3961 (13) | 0.049 (4) | 0.25 |
H11C | 0.0956 | 0.5174 | 0.3725 | 0.059* | 0.25 |
H11D | 0.0534 | 0.4510 | 0.4478 | 0.059* | 0.25 |
C12 | 0.2750 (6) | 0.4727 (2) | 0.4445 (3) | 0.0680 (13) | |
H12A | 0.3601 | 0.5080 | 0.4531 | 0.082* | 0.75 |
H12B | 0.1962 | 0.4875 | 0.4922 | 0.082* | 0.75 |
H12C | 0.2691 | 0.5025 | 0.5072 | 0.082* | 0.25 |
H12D | 0.3459 | 0.4980 | 0.3990 | 0.082* | 0.25 |
O1W | 0.2152 (4) | 0.47623 (19) | 0.7228 (3) | 0.0646 (8) | |
H1W1 | 0.182 (7) | 0.457 (4) | 0.779 (4) | 0.14 (3)* | |
H2W1 | 0.277 (6) | 0.446 (3) | 0.707 (5) | 0.12 (2)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0469 (3) | 0.0312 (3) | 0.0292 (3) | 0.00422 (16) | −0.0008 (2) | −0.00182 (14) |
S1 | 0.0564 (6) | 0.0465 (6) | 0.0466 (6) | −0.0130 (4) | −0.0005 (4) | 0.0017 (4) |
S2 | 0.0473 (6) | 0.0366 (5) | 0.0511 (7) | −0.0026 (4) | −0.0114 (4) | −0.0032 (4) |
O1 | 0.0792 (19) | 0.0347 (13) | 0.0382 (15) | 0.0122 (12) | −0.0008 (12) | −0.0029 (11) |
O2 | 0.108 (2) | 0.0390 (15) | 0.0391 (17) | −0.0013 (15) | 0.0103 (14) | −0.0018 (11) |
O3 | 0.0658 (17) | 0.0402 (14) | 0.0332 (14) | 0.0130 (13) | −0.0029 (11) | −0.0062 (11) |
O4 | 0.0799 (18) | 0.0445 (15) | 0.0358 (14) | 0.0166 (13) | −0.0117 (12) | −0.0011 (11) |
N1 | 0.080 (3) | 0.0390 (18) | 0.0323 (19) | −0.0068 (15) | 0.0064 (16) | 0.0036 (12) |
N2 | 0.073 (2) | 0.0404 (18) | 0.046 (2) | −0.0016 (16) | 0.0104 (16) | 0.0070 (14) |
N3 | 0.0529 (18) | 0.0409 (17) | 0.0357 (17) | −0.0010 (14) | −0.0077 (13) | −0.0043 (13) |
N4 | 0.069 (2) | 0.0394 (17) | 0.0375 (17) | 0.0030 (15) | −0.0204 (14) | −0.0047 (13) |
C1 | 0.065 (2) | 0.0324 (19) | 0.050 (3) | 0.0035 (17) | 0.0095 (18) | 0.0001 (17) |
C2 | 0.139 (5) | 0.046 (3) | 0.065 (3) | 0.033 (3) | 0.002 (3) | 0.004 (2) |
C3 | 0.049 (2) | 0.0343 (18) | 0.0338 (19) | −0.0006 (16) | −0.0030 (15) | −0.0059 (15) |
C4 | 0.078 (3) | 0.066 (3) | 0.032 (2) | 0.024 (2) | −0.0161 (18) | −0.0139 (18) |
C5 | 0.047 (2) | 0.0363 (19) | 0.043 (2) | −0.0018 (16) | 0.0124 (16) | 0.0032 (16) |
C6 | 0.114 (4) | 0.057 (3) | 0.042 (3) | −0.022 (3) | 0.011 (2) | −0.004 (2) |
C7 | 0.075 (3) | 0.093 (4) | 0.035 (2) | 0.000 (3) | −0.007 (2) | 0.002 (2) |
C8 | 0.111 (4) | 0.051 (2) | 0.049 (3) | 0.011 (3) | 0.017 (2) | 0.012 (2) |
C9 | 0.0406 (18) | 0.0412 (19) | 0.0294 (18) | −0.0015 (15) | 0.0044 (14) | 0.0004 (14) |
C10 | 0.067 (3) | 0.054 (3) | 0.051 (2) | 0.007 (2) | −0.0092 (19) | 0.0046 (19) |
C11A | 0.092 (5) | 0.048 (3) | 0.062 (4) | −0.005 (3) | −0.032 (4) | 0.014 (3) |
C11B | 0.048 (9) | 0.047 (9) | 0.052 (10) | 0.008 (7) | −0.001 (7) | 0.005 (7) |
C12 | 0.103 (4) | 0.040 (2) | 0.060 (3) | 0.004 (2) | −0.027 (2) | −0.0026 (19) |
O1W | 0.089 (2) | 0.0424 (16) | 0.063 (2) | 0.0147 (16) | 0.0091 (17) | 0.0125 (15) |
Zn1—O1 | 1.978 (2) | C4—H4C | 0.9600 |
Zn1—O3 | 1.984 (2) | C4—H4D | 0.9600 |
Zn1—S1 | 2.328 (1) | C6—C7 | 1.494 (7) |
Zn1—S2 | 2.337 (1) | C6—H6A | 0.9700 |
S1—C5 | 1.739 (4) | C6—H6B | 0.9700 |
S2—C9 | 1.729 (3) | C7—C8 | 1.502 (6) |
O1—C1 | 1.263 (4) | C7—H7A | 0.9700 |
O2—C1 | 1.233 (4) | C7—H7B | 0.9700 |
O3—C3 | 1.276 (4) | C8—H8A | 0.9700 |
O4—C3 | 1.230 (4) | C8—H8B | 0.9700 |
N1—C5 | 1.322 (4) | C10—C11B | 1.484 (16) |
N1—C6 | 1.463 (6) | C10—C11A | 1.496 (7) |
N1—H1A | 0.8600 | C10—H10A | 0.9700 |
N2—C5 | 1.324 (4) | C10—H10B | 0.9700 |
N2—C8 | 1.442 (6) | C10—H10C | 0.9700 |
N2—H2A | 0.8600 | C10—H10D | 0.9700 |
N3—C9 | 1.326 (4) | C11A—C12 | 1.485 (7) |
N3—C10 | 1.468 (5) | C11A—H11A | 0.9700 |
N3—H3A | 0.8600 | C11A—H11B | 0.9700 |
N4—C9 | 1.305 (4) | C11B—C12 | 1.447 (16) |
N4—C12 | 1.452 (5) | C11B—H11C | 0.9700 |
N4—H4A | 0.8600 | C11B—H11D | 0.9700 |
C1—C2 | 1.516 (5) | C12—H12A | 0.9700 |
C2—H2B | 0.9600 | C12—H12B | 0.9700 |
C2—H2C | 0.9600 | C12—H12C | 0.9700 |
C2—H2D | 0.9600 | C12—H12D | 0.9700 |
C3—C4 | 1.497 (5) | O1W—H1W1 | 0.86 (4) |
C4—H4B | 0.9600 | O1W—H2W1 | 0.79 (4) |
O1—Zn1—O3 | 93.48 (10) | C8—C7—H7A | 109.6 |
O1—Zn1—S1 | 114.42 (8) | C6—C7—H7B | 109.6 |
O3—Zn1—S1 | 110.28 (8) | C8—C7—H7B | 109.6 |
O1—Zn1—S2 | 103.74 (8) | H7A—C7—H7B | 108.1 |
O3—Zn1—S2 | 121.17 (8) | N2—C8—C7 | 109.3 (3) |
S1—Zn1—S2 | 112.22 (4) | N2—C8—H8A | 109.8 |
C5—S1—Zn1 | 100.68 (12) | C7—C8—H8A | 109.8 |
C9—S2—Zn1 | 109.89 (12) | N2—C8—H8B | 109.8 |
C1—O1—Zn1 | 124.4 (2) | C7—C8—H8B | 109.8 |
C3—O3—Zn1 | 119.7 (2) | H8A—C8—H8B | 108.3 |
C5—N1—C6 | 125.1 (3) | N4—C9—N3 | 119.7 (3) |
C5—N1—H1A | 117.5 | N4—C9—S2 | 122.4 (3) |
C6—N1—H1A | 117.5 | N3—C9—S2 | 117.9 (3) |
C5—N2—C8 | 123.7 (3) | N3—C10—C11B | 108.4 (6) |
C5—N2—H2A | 118.2 | N3—C10—C11A | 108.7 (4) |
C8—N2—H2A | 118.2 | N3—C10—H10A | 110.0 |
C9—N3—C10 | 123.4 (3) | C11A—C10—H10A | 110.0 |
C9—N3—H3A | 118.3 | N3—C10—H10B | 110.0 |
C10—N3—H3A | 118.3 | C11A—C10—H10B | 110.0 |
C9—N4—C12 | 125.2 (3) | H10A—C10—H10B | 108.3 |
C9—N4—H4A | 117.4 | N3—C10—H10C | 110.0 |
C12—N4—H4A | 117.4 | C11B—C10—H10C | 110.0 |
O2—C1—O1 | 124.9 (3) | N3—C10—H10D | 110.0 |
O2—C1—C2 | 119.1 (4) | C11B—C10—H10D | 110.0 |
O1—C1—C2 | 116.0 (4) | H10C—C10—H10D | 108.4 |
C1—C2—H2B | 109.5 | C12—C11A—C10 | 113.6 (5) |
C1—C2—H2C | 109.5 | C12—C11A—H11A | 108.9 |
H2B—C2—H2C | 109.5 | C10—C11A—H11A | 108.9 |
C1—C2—H2D | 109.5 | C12—C11A—H11B | 108.9 |
H2B—C2—H2D | 109.5 | C10—C11A—H11B | 108.9 |
H2C—C2—H2D | 109.5 | H11A—C11A—H11B | 107.7 |
O4—C3—O3 | 123.3 (3) | C12—C11B—C10 | 116.6 (11) |
O4—C3—C4 | 119.6 (3) | C12—C11B—H11C | 108.1 |
O3—C3—C4 | 117.1 (3) | C10—C11B—H11C | 108.1 |
C3—C4—H4B | 109.5 | C12—C11B—H11D | 108.1 |
C3—C4—H4C | 109.5 | C10—C11B—H11D | 108.1 |
H4B—C4—H4C | 109.5 | H11C—C11B—H11D | 107.3 |
C3—C4—H4D | 109.5 | C11B—C12—N4 | 106.8 (7) |
H4B—C4—H4D | 109.5 | N4—C12—C11A | 110.4 (4) |
H4C—C4—H4D | 109.5 | N4—C12—H12A | 109.6 |
N1—C5—N2 | 118.4 (4) | C11A—C12—H12A | 109.6 |
N1—C5—S1 | 121.8 (3) | N4—C12—H12B | 109.6 |
N2—C5—S1 | 119.8 (3) | C11A—C12—H12B | 109.6 |
N1—C6—C7 | 109.3 (4) | H12A—C12—H12B | 108.1 |
N1—C6—H6A | 109.8 | C11B—C12—H12C | 110.4 |
C7—C6—H6A | 109.8 | N4—C12—H12C | 110.4 |
N1—C6—H6B | 109.8 | C11B—C12—H12D | 110.4 |
C7—C6—H6B | 109.8 | N4—C12—H12D | 110.4 |
H6A—C6—H6B | 108.3 | H12C—C12—H12D | 108.6 |
C6—C7—C8 | 110.3 (4) | H1W1—O1W—H2W1 | 102 (6) |
C6—C7—H7A | 109.6 | ||
O1—Zn1—S1—C5 | 93.70 (15) | Zn1—S1—C5—N1 | −46.2 (3) |
O3—Zn1—S1—C5 | −162.48 (14) | Zn1—S1—C5—N2 | 134.5 (3) |
S2—Zn1—S1—C5 | −24.15 (13) | C5—N1—C6—C7 | −19.8 (6) |
O1—Zn1—S2—C9 | −178.43 (13) | N1—C6—C7—C8 | 48.7 (5) |
O3—Zn1—S2—C9 | 78.81 (15) | C5—N2—C8—C7 | 30.2 (6) |
S1—Zn1—S2—C9 | −54.40 (13) | C6—C7—C8—N2 | −53.9 (5) |
O3—Zn1—O1—C1 | −173.9 (3) | C12—N4—C9—N3 | 0.0 (6) |
S1—Zn1—O1—C1 | −59.8 (3) | C12—N4—C9—S2 | −178.7 (3) |
S2—Zn1—O1—C1 | 62.8 (3) | C10—N3—C9—N4 | −6.3 (5) |
O1—Zn1—O3—C3 | −164.1 (3) | C10—N3—C9—S2 | 172.4 (3) |
S1—Zn1—O3—C3 | 78.2 (3) | Zn1—S2—C9—N4 | −24.5 (3) |
S2—Zn1—O3—C3 | −55.8 (3) | Zn1—S2—C9—N3 | 156.8 (2) |
Zn1—O1—C1—O2 | −5.1 (6) | C9—N3—C10—C11B | −15.7 (9) |
Zn1—O1—C1—C2 | 176.0 (3) | C9—N3—C10—C11A | 30.5 (6) |
Zn1—O3—C3—O4 | −3.1 (5) | N3—C10—C11A—C12 | −48.8 (7) |
Zn1—O3—C3—C4 | 177.7 (3) | N3—C10—C11B—C12 | 45.8 (14) |
C6—N1—C5—N2 | −5.9 (6) | C10—C11B—C12—N4 | −50.6 (14) |
C6—N1—C5—S1 | 174.8 (4) | C9—N4—C12—C11B | 27.5 (9) |
C8—N2—C5—N1 | 0.1 (6) | C9—N4—C12—C11A | −19.4 (7) |
C8—N2—C5—S1 | 179.4 (3) | C10—C11A—C12—N4 | 44.0 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2 | 0.86 | 1.96 | 2.801 (4) | 166 |
N4—H4A···O4 | 0.86 | 1.93 | 2.752 (4) | 160 |
O1W—H2W1···O4 | 0.78 (5) | 2.05 (5) | 2.823 (4) | 167 (5) |
N2—H2A···O1Wi | 0.86 | 2.04 | 2.846 (5) | 156 |
N3—H3A···O3ii | 0.86 | 2.14 | 2.974 (4) | 164 |
O1W—H1W1···O2iii | 0.86 (6) | 1.97 (6) | 2.818 (5) | 167 (6) |
C4—H4D···S2iv | 0.96 | 2.86 | 3.615 (5) | 137 |
C10—H10B···O1ii | 0.97 | 2.45 | 3.315 (5) | 149 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1/2, −y+1/2, z−1/2; (iii) x−1/2, −y+1/2, z+1/2; (iv) x+1/2, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C12H22N4O4S2Zn·H2O |
Mr | 433.84 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 8.7517 (1), 17.3654 (2), 13.0543 (2) |
β (°) | 90.837 (1) |
V (Å3) | 1983.74 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.48 |
Crystal size (mm) | 0.16 × 0.12 × 0.10 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.798, 0.867 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11176, 3495, 2645 |
Rint | 0.097 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.138, 0.98 |
No. of reflections | 3495 |
No. of parameters | 238 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.54, −1.37 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL, PARST (Nardelli, 1995), PLATON (Spek, 1990).
Zn1—O1 | 1.978 (2) | S2—C9 | 1.729 (3) |
Zn1—O3 | 1.984 (2) | N1—C5 | 1.322 (4) |
Zn1—S1 | 2.328 (1) | N2—C5 | 1.324 (4) |
Zn1—S2 | 2.337 (1) | N3—C9 | 1.326 (4) |
S1—C5 | 1.739 (4) | N4—C9 | 1.305 (4) |
O1—Zn1—O3 | 93.48 (10) | O1—Zn1—S2 | 103.74 (8) |
O1—Zn1—S1 | 114.42 (8) | O3—Zn1—S2 | 121.17 (8) |
O3—Zn1—S1 | 110.28 (8) | S1—Zn1—S2 | 112.22 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2 | 0.86 | 1.96 | 2.801 (4) | 166 |
N4—H4A···O4 | 0.86 | 1.93 | 2.752 (4) | 160 |
O1W—H2W1···O4 | 0.78 (5) | 2.05 (5) | 2.823 (4) | 167 (5) |
N2—H2A···O1Wi | 0.86 | 2.04 | 2.846 (5) | 156 |
N3—H3A···O3ii | 0.86 | 2.14 | 2.974 (4) | 164 |
O1W—H1W1···O2iii | 0.86 (6) | 1.97 (6) | 2.818 (5) | 167 (6) |
C4—H4D···S2iv | 0.96 | 2.86 | 3.615 (5) | 137 |
C10—H10B···O1ii | 0.97 | 2.45 | 3.315 (5) | 149 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1/2, −y+1/2, z−1/2; (iii) x−1/2, −y+1/2, z+1/2; (iv) x+1/2, −y+1/2, z+1/2. |
Zn1···C3 | 2.842 (4) | Zn1···C9 | 3.346 (3) |
Zn1···C1 | 2.886 (4) | Zn1···N4 | 3.469 (3) |
Zn1···O4 | 3.018 (3) | S1···N2 | 2.658 (3) |
Zn1···O2 | 3.150 (3) | S1···N1 | 2.681 (4) |
Zn1···C5 | 3.153 (4) | S2···N3 | 2.625 (3) |
Zn1···N1 | 3.340 (4) | S2···N4 | 2.667 (3) |
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Complexes of metal acetate with thioamides such as bis(acetato)bis(ethylenethiourea)cobalt(II) (Holt, et al., 1970) and bis(acetato)bis(thiourea)zinc(II) (Cavalca, et al., 1967) show weak metal–oxygen interactions in addition to the normal metal–oxygen bond with the acetato group. Our interest in the structures of zinc(II) halides complexed with S-donor ligands led us to the X-ray crystallographic investigation of the title complex, (I). It is also interesting to see the effects of the presence of the weak zinc–oxygen interactions and the water molecules on the structure.
Scheme I
The average lengths of the thioamide N—C [1.319 (4) Å] and S—C [1.734 (4) Å] bonds in the trimethylenethiourea ligands are comparable to the values reported in the free ligand [N—C = 1.334 (6), S—C = 1.722 (7) Å; Dias & Truter, 1964). The reduction of π-electron density in the exocyclic S—C bond for the S atom coordinated to a metal atom results in the lengthening of the S—C bond. This reduction contributes to increased π-electron density in the thioamide N—C bonds, and the corresponding shortening of these N—C bonds. The average Zn—S and Zn—O bond lengths, 2.333 (1) and 1.981 (3) Å, respectively, are comparable with the average values reported in the complexes of [Zn(C2Cl3O2)2(CH4N2S)2]·H2O [Zn—S = 2.304 (2), Zn—O = 2.006 (5) Å; Potočňák et al., 1994], Zn[SC(NHCH2)2]2S2O3 [Zn—S = 2.320 (8), Zn—O = 2.022 (18) Å; Baggio et al., 1974] and [Zn(C6H5COO)2{CS(NH2)2}2] [Zn—S = 2.367 (1), Zn—O = 1.964 (2) Å; Černák et al., 1995].
The Zn atom is coordinated by a S atom from each of two trimetylenethiourea ligands and one O atom from each of two acetate groups. This ZnO2S2 coordination forms a distorted tetrahedron with the angles around the Zn atom ranging from 93.48 (10) to 121.17 (8)°. This type of coordination is also observed in the structures reported by Černák et al. (1995) and Potočňák et al. (1994).
In the crystal, all the N atoms of the thioamide ligands and the water molecules act as hydrogen donors to form N—H···O and O—H···O intramolecular and intermolecular hydrogen bonds. There are also C—H···S and C—H···O intermolecular interactions observed in the crystal (Table 2). Within the asymmetric unit, the water molecule forms an intermolecular O1W-H2W1···O4 hydrogen bond with the Zn complex. The molecules are stacked into columns along the a axis. These columns are interconnected by the N3—H3A···O3(-1/2 + x, 1/2 - y, -1/2 + z) hydrogen bond and the C4—H4D···S2(1/2 + x, 1/2 - y, 1/2 + z) and C10—H10B···O1(-1/2 + x, 1/2 - y, -1/2 + z) interactions into layers which lie perpendicular to the b axis. The layers are then linked by the water molecules through N2—H2A···O1W(1 - x, 1 - y, -z) and O1W-H1W1···O2(-1/2 + x, 1/2 - y, 1/2 + z) interactions. These hydrogen bonds and interactions form a three-dimensional framework throughout the structure.
The Zn1 atom is also involved in weaker interactions with the other two O atoms, O2 and O4, from the carboxylate ligands (Table 3). The Zn1—O1—C1 and Zn1—O3—C3 bond angles are 124.4 (2) and 119.7 (2)°, respectively. The orientation of the planes of the two acetates are determined by the Zn1—O1, Zn1—O2, Zn1—O3 and Zn1—O4 interactions (Cavalca et al., 1967). The two acetate groups are nearly co-planar, the dihedral angle between them being 11.1 (3)°. The Zn1 atom lies 0.116 (1) and 0.075 (1) Å from the acetate planes defined by O1, O2, C1 and C2, and O3, O4, C3 and C4, respectively. As a result, the orientations of the acetate planes are such that Zn1 lies virtually on them. This observation is also reported by Cavalca et al. (1967) [Zn···O = 2.996 (5) and 2.891 (9) Å, Zn—O—C = 119.4 (6) and 118.2 (7)°, Zn–Planeacetates = 0.095 and 0.036 Å]. Other short contacts observed in the structure are listed in Table 3.