Acta Cryst. (2010). E66, m466 [ doi:10.1107/S160053681001113X ]
![[kappa]](/logos/entities/kappa_rmgif.gif)
O]chlorido(2,2'-diamino-4,4'-bi-1,3-thiazole-2N3,N3')zinc(II) monohydrateIn the title compound, [Zn(C4H5O2)Cl(C6H6N4S2)]·H2O, the ZnII cation is coordinated by a bidentate diaminobithiazole (DABT) ligand, a but-2-enoate anion and a Cl- anion in a distorted tetrahedral geometry. Within the DABT ligand, the two thiazole rings are twisted to each other at a dihedral angle of 4.38 (10)°. An intramolecular N-H
O interaction occurs. The centroid-centroid distance of 3.6650 (17) Å and partially overlapped arrangement between nearly parallel thiazole rings of adjacent complexes indicate the existence of ![[pi]](/logos/entities/pi_rmgif.gif)
- stacking in the crystal structure. Extensive O-HCl, O-HO, N-HCl and N-HO hydrogen bonding helps to stabilize the crystal structure.
A water-ethanol solution (20 ml, 1:1) of DABT (0.10 g, 0.5 mmol) and ZnCl2 (0.07 g, 0.5 mmol) was refluxed for 10 min, then an aqueous solution (20 ml) of (E)-but-2-enoatic acid (0.09 g, 1 mmol) and NaOH (0.04 g, 1 mmol) was mixed with the above solution. The mixture was refluxed for 6 h and then filtered. The single crystals of the title compound were obtained from the filtrate after a week.
H atoms of water molecule were located in a difference Fourier map and were refined as riding in as-found relative positions with Uiso(H) = 1.2Ueq(O). Other H atoms were placed in calculated positions with C—H = 0.96 Å (methyl), 0.93 Å (aromatic) and N—H = 0.86 Å, and refined in the riding model with Uiso(H) = 1.5Ueq(C) for methyl and 1.2Ueq(C,N) for the others.
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./ng2750fig1thm.gif)
| Fig. 1. The molecular structure of the title compound with 40% probability displacement ellipsoids. Dashed lines indicate the hydrogen bonding. |
![[Figure 2]](./ng2750fig2thm.gif)
| Fig. 2. The partially overlapped arrangement between thiazole rings showing π-π stacking [symmetry code: (i) 1-x, -y, 1-z]. |
| [Zn(C4H5O2)Cl(C6H6N4S2)]·H2O | F(000) = 816 |
| Mr = 402.18 | Dx = 1.725 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 3446 reflections |
| a = 7.2782 (13) Å | θ = 2.0–24.6° |
| b = 16.2846 (16) Å | µ = 2.04 mm−1 |
| c = 13.237 (2) Å | T = 294 K |
| β = 99.252 (16)° | Block, yellow |
| V = 1548.5 (4) Å3 | 0.36 × 0.30 × 0.24 mm |
| Z = 4 |
| Rigaku R-AXIS RAPID IP diffractometer | 2735 independent reflections |
| Radiation source: fine-focus sealed tube | 2293 reflections with I > 2σ(I) |
| graphite | Rint = 0.026 |
| ω scans | θmax = 25.0°, θmin = 2.0° |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −8→8 |
| Tmin = 0.75, Tmax = 0.88 | k = −12→19 |
| 7862 measured reflections | l = −15→15 |
| 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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.080 | H-atom parameters constrained |
| S = 1.05 | w = 1/[σ2(Fo2) + (0.0353P)2 + 1.093P] where P = (Fo2 + 2Fc2)/3 |
| 2735 reflections | (Δ/σ)max = 0.002 |
| 191 parameters | Δρmax = 0.71 e Å−3 |
| 0 restraints | Δρmin = −0.45 e Å−3 |
| [Zn(C4H5O2)Cl(C6H6N4S2)]·H2O | V = 1548.5 (4) Å3 |
| Mr = 402.18 | Z = 4 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 7.2782 (13) Å | µ = 2.04 mm−1 |
| b = 16.2846 (16) Å | T = 294 K |
| c = 13.237 (2) Å | 0.36 × 0.30 × 0.24 mm |
| β = 99.252 (16)° |
| Rigaku R-AXIS RAPID IP diffractometer | 2735 independent reflections |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 2293 reflections with I > 2σ(I) |
| Tmin = 0.75, Tmax = 0.88 | Rint = 0.026 |
| 7862 measured reflections | θmax = 25.0° |
| R[F2 > 2σ(F2)] = 0.032 | H-atom parameters constrained |
| wR(F2) = 0.080 | Δρmax = 0.71 e Å−3 |
| S = 1.05 | Δρmin = −0.45 e Å−3 |
| 2735 reflections | Absolute structure: ? |
| 191 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 | ||
| Zn | 0.77894 (5) | 0.12724 (2) | 0.64617 (2) | 0.03260 (13) | |
| Cl1 | 1.01129 (13) | 0.21725 (6) | 0.67179 (7) | 0.0541 (3) | |
| S1 | 0.93933 (12) | −0.14538 (5) | 0.65212 (7) | 0.0433 (2) | |
| S2 | 0.56191 (12) | 0.09881 (5) | 0.30033 (6) | 0.0418 (2) | |
| N1 | 0.8456 (3) | 0.00649 (15) | 0.64140 (17) | 0.0314 (6) | |
| N2 | 0.9835 (4) | −0.03495 (18) | 0.8057 (2) | 0.0483 (7) | |
| H2A | 0.9737 | 0.0134 | 0.8305 | 0.058* | |
| H2B | 1.0326 | −0.0740 | 0.8447 | 0.058* | |
| N3 | 0.6716 (3) | 0.10813 (15) | 0.49432 (17) | 0.0299 (5) | |
| N4 | 0.5365 (4) | 0.22969 (16) | 0.4215 (2) | 0.0444 (7) | |
| H4A | 0.5508 | 0.2545 | 0.4796 | 0.053* | |
| H4B | 0.4859 | 0.2549 | 0.3670 | 0.053* | |
| O1 | 0.5737 (3) | 0.15367 (14) | 0.72007 (17) | 0.0471 (6) | |
| O2 | 0.7729 (4) | 0.11162 (17) | 0.8535 (2) | 0.0630 (7) | |
| O1W | 0.4071 (4) | 0.29467 (17) | 0.6138 (2) | 0.0726 (8) | |
| H1A | 0.2909 | 0.2835 | 0.6079 | 0.087* | |
| H1B | 0.4522 | 0.2592 | 0.6587 | 0.087* | |
| C1 | 0.9224 (4) | −0.04933 (19) | 0.7066 (2) | 0.0351 (7) | |
| C2 | 0.8373 (4) | −0.10659 (19) | 0.5354 (2) | 0.0396 (8) | |
| H2 | 0.8137 | −0.1368 | 0.4751 | 0.047* | |
| C3 | 0.7965 (4) | −0.02684 (18) | 0.5437 (2) | 0.0316 (7) | |
| C4 | 0.7091 (4) | 0.02855 (18) | 0.4637 (2) | 0.0309 (7) | |
| C5 | 0.6607 (4) | 0.0136 (2) | 0.3637 (2) | 0.0386 (7) | |
| H5 | 0.6782 | −0.0363 | 0.3325 | 0.046* | |
| C6 | 0.5924 (4) | 0.15275 (19) | 0.4159 (2) | 0.0333 (7) | |
| C7 | 0.6148 (5) | 0.1325 (2) | 0.8138 (3) | 0.0448 (8) | |
| C8 | 0.4511 (6) | 0.1316 (2) | 0.8698 (3) | 0.0541 (9) | |
| H8 | 0.3377 | 0.1509 | 0.8357 | 0.065* | |
| C9 | 0.4583 (6) | 0.1061 (2) | 0.9613 (3) | 0.0623 (11) | |
| H9 | 0.5745 | 0.0909 | 0.9963 | 0.075* | |
| C10 | 0.2972 (7) | 0.0984 (3) | 1.0172 (3) | 0.0724 (13) | |
| H10A | 0.3061 | 0.1397 | 1.0696 | 0.109* | |
| H10B | 0.2981 | 0.0450 | 1.0479 | 0.109* | |
| H10C | 0.1834 | 0.1057 | 0.9702 | 0.109* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Zn | 0.0384 (2) | 0.0298 (2) | 0.0298 (2) | −0.00060 (15) | 0.00584 (14) | −0.00417 (15) |
| Cl1 | 0.0597 (6) | 0.0545 (6) | 0.0507 (5) | −0.0236 (4) | 0.0161 (4) | −0.0186 (4) |
| S1 | 0.0460 (5) | 0.0295 (4) | 0.0551 (5) | 0.0035 (4) | 0.0103 (4) | 0.0042 (4) |
| S2 | 0.0460 (5) | 0.0489 (5) | 0.0286 (4) | −0.0057 (4) | 0.0004 (3) | −0.0015 (4) |
| N1 | 0.0353 (14) | 0.0292 (13) | 0.0305 (13) | −0.0011 (11) | 0.0076 (10) | 0.0008 (11) |
| N2 | 0.0629 (19) | 0.0439 (17) | 0.0357 (15) | 0.0110 (14) | 0.0010 (13) | 0.0064 (13) |
| N3 | 0.0316 (13) | 0.0310 (13) | 0.0279 (12) | −0.0041 (11) | 0.0069 (10) | −0.0008 (10) |
| N4 | 0.0572 (18) | 0.0363 (16) | 0.0371 (15) | 0.0029 (13) | 0.0001 (13) | 0.0059 (12) |
| O1 | 0.0528 (15) | 0.0469 (14) | 0.0449 (14) | 0.0028 (11) | 0.0173 (11) | −0.0083 (11) |
| O2 | 0.0653 (19) | 0.0609 (17) | 0.0627 (17) | 0.0061 (14) | 0.0103 (14) | −0.0015 (14) |
| O1W | 0.0642 (18) | 0.072 (2) | 0.084 (2) | −0.0139 (15) | 0.0188 (15) | −0.0228 (16) |
| C1 | 0.0323 (17) | 0.0348 (17) | 0.0397 (18) | −0.0008 (14) | 0.0100 (13) | 0.0035 (14) |
| C2 | 0.046 (2) | 0.0319 (18) | 0.0428 (18) | −0.0028 (14) | 0.0115 (15) | −0.0064 (14) |
| C3 | 0.0298 (16) | 0.0315 (17) | 0.0353 (16) | −0.0052 (13) | 0.0110 (12) | −0.0043 (13) |
| C4 | 0.0310 (16) | 0.0304 (16) | 0.0329 (16) | −0.0055 (13) | 0.0098 (12) | −0.0025 (13) |
| C5 | 0.0449 (19) | 0.0372 (18) | 0.0343 (17) | −0.0060 (15) | 0.0081 (14) | −0.0069 (14) |
| C6 | 0.0337 (17) | 0.0347 (17) | 0.0309 (16) | −0.0053 (13) | 0.0038 (13) | 0.0006 (13) |
| C7 | 0.056 (2) | 0.0315 (18) | 0.050 (2) | −0.0028 (16) | 0.0166 (17) | −0.0093 (16) |
| C8 | 0.062 (2) | 0.051 (2) | 0.051 (2) | 0.0083 (18) | 0.0151 (18) | −0.0034 (18) |
| C9 | 0.079 (3) | 0.050 (2) | 0.062 (3) | 0.014 (2) | 0.022 (2) | 0.002 (2) |
| C10 | 0.097 (3) | 0.063 (3) | 0.069 (3) | 0.017 (2) | 0.048 (3) | 0.011 (2) |
| Zn—O1 | 1.961 (2) | O1—C7 | 1.275 (4) |
| Zn—N1 | 2.029 (2) | O2—C7 | 1.234 (4) |
| Zn—N3 | 2.060 (2) | O1W—H1A | 0.8564 |
| Zn—Cl1 | 2.2223 (9) | O1W—H1B | 0.8550 |
| S1—C2 | 1.723 (3) | C2—C3 | 1.340 (4) |
| S1—C1 | 1.735 (3) | C2—H2 | 0.9300 |
| S2—C5 | 1.718 (3) | C3—C4 | 1.457 (4) |
| S2—C6 | 1.747 (3) | C4—C5 | 1.336 (4) |
| N1—C1 | 1.315 (4) | C5—H5 | 0.9300 |
| N1—C3 | 1.395 (4) | C7—C8 | 1.502 (5) |
| N2—C1 | 1.336 (4) | C8—C9 | 1.273 (5) |
| N2—H2A | 0.8600 | C8—H8 | 0.9300 |
| N2—H2B | 0.8600 | C9—C10 | 1.490 (5) |
| N3—C6 | 1.321 (4) | C9—H9 | 0.9300 |
| N3—C4 | 1.398 (4) | C10—H10A | 0.9600 |
| N4—C6 | 1.323 (4) | C10—H10B | 0.9600 |
| N4—H4A | 0.8600 | C10—H10C | 0.9600 |
| N4—H4B | 0.8600 | ||
| O1—Zn—N1 | 115.69 (10) | C2—C3—N1 | 115.2 (3) |
| O1—Zn—N3 | 108.68 (10) | C2—C3—C4 | 128.1 (3) |
| N1—Zn—N3 | 83.01 (9) | N1—C3—C4 | 116.7 (2) |
| O1—Zn—Cl1 | 113.65 (7) | C5—C4—N3 | 115.0 (3) |
| N1—Zn—Cl1 | 117.66 (7) | C5—C4—C3 | 128.5 (3) |
| N3—Zn—Cl1 | 114.11 (7) | N3—C4—C3 | 116.5 (2) |
| C2—S1—C1 | 89.60 (15) | C4—C5—S2 | 111.1 (2) |
| C5—S2—C6 | 89.66 (15) | C4—C5—H5 | 124.5 |
| C1—N1—C3 | 111.0 (2) | S2—C5—H5 | 124.5 |
| C1—N1—Zn | 136.7 (2) | N3—C6—N4 | 125.2 (3) |
| C3—N1—Zn | 112.28 (18) | N3—C6—S2 | 112.9 (2) |
| C1—N2—H2A | 120.0 | N4—C6—S2 | 121.9 (2) |
| C1—N2—H2B | 120.0 | O2—C7—O1 | 123.1 (3) |
| H2A—N2—H2B | 120.0 | O2—C7—C8 | 123.1 (3) |
| C6—N3—C4 | 111.3 (2) | O1—C7—C8 | 113.7 (3) |
| C6—N3—Zn | 137.1 (2) | C9—C8—C7 | 124.0 (4) |
| C4—N3—Zn | 111.23 (18) | C9—C8—H8 | 118.0 |
| C6—N4—H4A | 120.0 | C7—C8—H8 | 118.0 |
| C6—N4—H4B | 120.0 | C8—C9—C10 | 125.8 (4) |
| H4A—N4—H4B | 120.0 | C8—C9—H9 | 117.1 |
| C7—O1—Zn | 110.3 (2) | C10—C9—H9 | 117.1 |
| H1A—O1W—H1B | 100.6 | C9—C10—H10A | 109.5 |
| N1—C1—N2 | 124.2 (3) | C9—C10—H10B | 109.5 |
| N1—C1—S1 | 113.6 (2) | H10A—C10—H10B | 109.5 |
| N2—C1—S1 | 122.1 (2) | C9—C10—H10C | 109.5 |
| C3—C2—S1 | 110.6 (2) | H10A—C10—H10C | 109.5 |
| C3—C2—H2 | 124.7 | H10B—C10—H10C | 109.5 |
| S1—C2—H2 | 124.7 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1W—H1A···Cl1i | 0.86 | 2.56 | 3.345 (3) | 152 |
| O1W—H1B···O1 | 0.86 | 2.04 | 2.859 (4) | 160 |
| N2—H2A···O2 | 0.86 | 2.22 | 2.959 (4) | 144 |
| N2—H2B···O1Wii | 0.86 | 2.23 | 3.032 (4) | 154 |
| N4—H4A···O1W | 0.86 | 2.30 | 3.043 (4) | 145 |
| N4—H4B···Cl1iii | 0.86 | 2.66 | 3.393 (3) | 144 |
| Symmetry codes: (i) x−1, y, z; (ii) −x+3/2, y−1/2, −z+3/2; (iii) x−1/2, −y+1/2, z−1/2. |
| Zn—O1 | 1.961 (2) | Zn—N3 | 2.060 (2) |
| Zn—N1 | 2.029 (2) | Zn—Cl1 | 2.2223 (9) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1W—H1A···Cl1i | 0.86 | 2.56 | 3.345 (3) | 152 |
| O1W—H1B···O1 | 0.86 | 2.04 | 2.859 (4) | 160 |
| N2—H2A···O2 | 0.86 | 2.22 | 2.959 (4) | 144 |
| N2—H2B···O1Wii | 0.86 | 2.23 | 3.032 (4) | 154 |
| N4—H4A···O1W | 0.86 | 2.30 | 3.043 (4) | 145 |
| N4—H4B···Cl1iii | 0.86 | 2.66 | 3.393 (3) | 144 |
| Symmetry codes: (i) x−1, y, z; (ii) −x+3/2, y−1/2, −z+3/2; (iii) x−1/2, −y+1/2, z−1/2. |
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Some metal complexes with 2,2'-diamino-4,4'-bi-1,3-thiazole (DABT) have shown the potential application in the biological field (Waring, 1981; Fisher et al., 1985). As a part of serial structural investigation of metal complexes with DABT, the title ZnII complex was prepared in the laboratory and its X-ray structure is presented here.
The molecular structure of the title compound is shown in Fig. 1. The ZnII cation is coordinated by a diaminobithiazole (DABT) ligand, a but-2-enoate anion and a Cl- anion in a distorted tetrahedral geometry (Table 1). Within the DABT ligand the two thiazole rings are twisted to each other at a dihedral angle of 4.38 (10)°, which agrees with 9.51 (17)° found in a PbII complex of DABT (Du et al., 2010) and 9.5 (2)° found in a CdII complex of DABT (Zhang et al., 2006). The partially overlapped arrangement of centroids distance of 3.6650 (17) Å between nearly parallel thiazole rings of the adjacent complexes indicate the existence of π-π stacking in the crystal structure (Fig. 2). The extensive hydrogen bonding help to stabilize the crystal structure (Table 2).