Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807031741/xu2284sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807031741/xu2284Isup2.hkl |
CCDC reference: 657527
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.006 Å
- R factor = 0.038
- wR factor = 0.086
- Data-to-parameter ratio = 12.5
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O21 PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.27 PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.50 PLAT322_ALERT_2_C Check Hybridisation of S11 in Main Residue . ? PLAT322_ALERT_2_C Check Hybridisation of S12 in Main Residue . ? PLAT322_ALERT_2_C Check Hybridisation of S21 in Main Residue . ? PLAT322_ALERT_2_C Check Hybridisation of S22 in Main Residue . ? PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 4
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1 (2) 2.03 PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn2 (2) 2.01
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 7 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 2 ALERT type 5 Informative message, check
For general background, see: Sun et al. (1997); Liu & Xu (2004); Luo et al. (2004). For related structures, see: Wu et al. (2003).
An ethanol solution (20 ml) containing DABT (0.20 g, 1 mmol) and ZnCl2 (0.14 g, 1 mmol) was mixed with an aqueous solution (10 ml) of malonic acid (0.21 g, 2 mmol) and NaOH (0.16 g, 4 mmol). The mixture was refluxed for 6 h. After cooling to room temperature the solution was filtered. Single crystals of the title compound were obtained from the filtrate after 2 d.
H atoms on carbon atoms were placed in calculated positions, with C—H distances = 0.93 Å (aromatic) or C—H = 0.97 (methylene), and were included in the final cycles of refinement in riding mode with Uiso(H) = 1.2Ueq(C). H atoms on amino groups and coordinated water molecules were located in a difference Fourier map and included in the structure factor calculations with fixed positional and isotropic displacement parameters Uiso(H) = 0.05 Å2. H atoms of lattice water were located in a difference Fourier map and included in the final cycles of refinement in riding mode with Uiso(H) = 1.5Ueq(O).
Transition metal complexes of 2,2'-diamino-4,4'-bi-1,3-thiazole (DABT) have shown potential application in the field of soft magnetic material (Sun et al., 1997). As part of serial structural investigation of metal complexes with DABT (Liu & Xu, 2004; Luo et al., 2004), the title ZnII complex was recently prepared and its X-ray structure is presented here.
Asymmetric unit of the crystal of the title compound contains two independent ZnII complexes (Fig. 1). Each ZnII ion has a distorted square pyramid coordination geometry (Table 1) formed by one of DABT ligand, one of malonate dianion and one water molecules. The O atom of coordinated water lies on the apical position of square pyramid. The The Zn1 and Zn2 atoms are out of the base plane of pyramidal by 0.437 (2) Å and 0.413 (2) Å, respectively.
Within the complex, each DABT moiety is approximately coplanar with a dihedral angles of 3.23 (19)° for Zn1 complex and 2.54 (18)° for Zn1 and Zn2 complex respectively. The average distances of 1.334 (4) Å of C—N(amino) within Zn1 complex and 1.329 (4) Å of C—N(amino) within Zn2 complex imply the existence of electron delocalization between thiazole rings and amino groups. This feature of electron delocalization of DABT agrees with reported CuII complex of DABT (Wu et al., 2003).
The malonate dianion chelates to the ZnII atom with a nearly planar configuration with the maximum atomic deviation of 0.025 (2) Å (C17) to the mean plane defined by O11 O13 C17 C18 C19 and 0.071 (3) Å (C29) to the mean plane defined by O21 O23 C27 C28 C29. The extensive hydrogen bonding between lattice water and complex molecules helps to stabilize the crystal structure (Fig. 1. and Table 2).
For general background, see: Sun et al. (1997); Liu & Xu (2004); Luo et al. (2004). For related structures, see: Wu et al. (2003).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; 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, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
[Zn(C3H2O4)(C6H6N4S2)(H2O)]·H2O | Z = 4 |
Mr = 401.72 | F(000) = 816 |
Triclinic, P1 | Dx = 1.850 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.4695 (11) Å | Cell parameters from 4880 reflections |
b = 12.5509 (15) Å | θ = 2.4–25.0° |
c = 14.8615 (19) Å | µ = 2.03 mm−1 |
α = 68.895 (1)° | T = 295 K |
β = 88.074 (2)° | Prism, yellow |
γ = 78.337 (2)° | 0.25 × 0.22 × 0.15 mm |
V = 1442.1 (3) Å3 |
Rigaku R-AXIS RAPID diffractometer | 4992 independent reflections |
Radiation source: fine-focus sealed tube | 3768 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
Detector resolution: 10.0 pixels mm-1 | θmax = 25.0°, θmin = 2.4° |
ω scans | h = −4→10 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −13→14 |
Tmin = 0.628, Tmax = 0.735 | l = −17→17 |
7536 measured reflections |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.086 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0347P)2] where P = (Fo2 + 2Fc2)/3 |
4992 reflections | (Δ/σ)max < 0.001 |
398 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.40 e Å−3 |
[Zn(C3H2O4)(C6H6N4S2)(H2O)]·H2O | γ = 78.337 (2)° |
Mr = 401.72 | V = 1442.1 (3) Å3 |
Triclinic, P1 | Z = 4 |
a = 8.4695 (11) Å | Mo Kα radiation |
b = 12.5509 (15) Å | µ = 2.03 mm−1 |
c = 14.8615 (19) Å | T = 295 K |
α = 68.895 (1)° | 0.25 × 0.22 × 0.15 mm |
β = 88.074 (2)° |
Rigaku R-AXIS RAPID diffractometer | 4992 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 3768 reflections with I > 2σ(I) |
Tmin = 0.628, Tmax = 0.735 | Rint = 0.024 |
7536 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.086 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.41 e Å−3 |
4992 reflections | Δρmin = −0.40 e Å−3 |
398 parameters |
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 | ||
Zn1 | 0.88504 (5) | 0.31911 (3) | 0.43082 (3) | 0.02935 (14) | |
Zn2 | 0.56845 (6) | 0.21371 (3) | 0.00971 (3) | 0.03282 (14) | |
O1 | 0.7108 (3) | 0.3062 (2) | 0.34771 (16) | 0.0329 (6) | |
H1A | 0.6546 | 0.3730 | 0.3207 | 0.050* | |
H1B | 0.6473 | 0.2649 | 0.3787 | 0.050* | |
O2 | 0.7538 (3) | 0.2748 (2) | 0.04109 (18) | 0.0449 (7) | |
H2A | 0.7802 | 0.2460 | 0.0973 | 0.050* | |
H2B | 0.7539 | 0.3481 | 0.0215 | 0.050* | |
O11 | 1.0722 (3) | 0.2090 (2) | 0.40389 (18) | 0.0435 (7) | |
O12 | 1.2746 (3) | 0.0620 (2) | 0.42855 (19) | 0.0468 (8) | |
O13 | 0.8758 (3) | 0.1976 (2) | 0.56278 (18) | 0.0444 (7) | |
O14 | 0.9634 (4) | 0.0497 (2) | 0.69622 (18) | 0.0543 (8) | |
O21 | 0.3790 (4) | 0.3220 (2) | 0.03881 (18) | 0.0488 (8) | |
O22 | 0.2502 (4) | 0.4952 (2) | 0.03062 (18) | 0.0487 (8) | |
O23 | 0.5257 (3) | 0.3127 (2) | −0.13198 (17) | 0.0375 (7) | |
O24 | 0.4464 (3) | 0.4715 (2) | −0.25955 (17) | 0.0427 (7) | |
O1W | 0.5480 (3) | 0.1515 (2) | 0.4527 (2) | 0.0537 (8) | |
H1WA | 0.4756 | 0.1321 | 0.4266 | 0.080* | |
H1WB | 0.6035 | 0.0889 | 0.4913 | 0.080* | |
O2W | 0.8814 (4) | 0.1887 (2) | 0.22125 (19) | 0.0658 (10) | |
H2WA | 0.8984 | 0.1175 | 0.2440 | 0.099* | |
H2WB | 0.8361 | 0.2155 | 0.2600 | 0.099* | |
N11 | 0.9577 (4) | 0.4616 (2) | 0.3251 (2) | 0.0305 (7) | |
N12 | 1.0922 (4) | 0.3928 (3) | 0.2089 (2) | 0.0526 (10) | |
H12A | 1.1403 | 0.4132 | 0.1546 | 0.050* | |
H12B | 1.0719 | 0.3237 | 0.2330 | 0.050* | |
N13 | 0.7881 (3) | 0.4519 (2) | 0.4811 (2) | 0.0269 (7) | |
N14 | 0.6448 (4) | 0.3689 (3) | 0.6174 (2) | 0.0370 (8) | |
H14A | 0.6717 | 0.3002 | 0.6188 | 0.050* | |
H14B | 0.5762 | 0.3871 | 0.6580 | 0.050* | |
N21 | 0.6930 (3) | 0.0708 (2) | −0.02042 (19) | 0.0270 (7) | |
N22 | 0.7906 (4) | 0.1492 (3) | −0.1752 (2) | 0.0374 (8) | |
H22A | 0.7284 | 0.2120 | −0.1813 | 0.050* | |
H22B | 0.8373 | 0.1333 | −0.2221 | 0.050* | |
N23 | 0.5398 (4) | 0.0760 (2) | 0.1367 (2) | 0.0332 (8) | |
N24 | 0.3770 (4) | 0.1607 (3) | 0.2345 (2) | 0.0560 (11) | |
H24A | 0.3584 | 0.2254 | 0.1907 | 0.050* | |
H24B | 0.3253 | 0.1501 | 0.2879 | 0.050* | |
S11 | 1.08320 (13) | 0.61328 (9) | 0.19332 (7) | 0.0411 (3) | |
S12 | 0.65560 (13) | 0.59502 (8) | 0.56222 (7) | 0.0373 (3) | |
S21 | 0.87839 (14) | −0.08109 (9) | −0.07459 (8) | 0.0464 (3) | |
S22 | 0.48746 (14) | −0.07143 (9) | 0.30120 (7) | 0.0417 (3) | |
C11 | 0.9206 (4) | 0.5639 (3) | 0.3433 (3) | 0.0291 (9) | |
C12 | 0.9765 (5) | 0.6532 (3) | 0.2810 (3) | 0.0383 (10) | |
H12 | 0.9602 | 0.7271 | 0.2844 | 0.046* | |
C13 | 1.0418 (5) | 0.4746 (3) | 0.2469 (3) | 0.0336 (9) | |
C14 | 0.8246 (4) | 0.5596 (3) | 0.4274 (3) | 0.0285 (8) | |
C15 | 0.7636 (5) | 0.6456 (3) | 0.4602 (3) | 0.0354 (9) | |
H15 | 0.7777 | 0.7221 | 0.4318 | 0.043* | |
C16 | 0.6984 (4) | 0.4580 (3) | 0.5546 (2) | 0.0276 (8) | |
C17 | 1.1553 (4) | 0.1141 (3) | 0.4571 (2) | 0.0276 (8) | |
C18 | 1.1183 (4) | 0.0575 (3) | 0.5623 (2) | 0.0307 (9) | |
H18A | 1.1101 | −0.0217 | 0.5714 | 0.037* | |
H18B | 1.2133 | 0.0514 | 0.5999 | 0.037* | |
C19 | 0.9751 (5) | 0.1053 (3) | 0.6098 (3) | 0.0309 (9) | |
C21 | 0.7058 (4) | −0.0363 (3) | 0.0549 (3) | 0.0297 (9) | |
C22 | 0.7968 (5) | −0.1257 (3) | 0.0372 (3) | 0.0448 (11) | |
H22 | 0.8140 | −0.2027 | 0.0799 | 0.054* | |
C23 | 0.7787 (4) | 0.0603 (3) | −0.0939 (3) | 0.0282 (8) | |
C24 | 0.6192 (4) | −0.0337 (3) | 0.1401 (3) | 0.0291 (9) | |
C25 | 0.6045 (5) | −0.1218 (3) | 0.2222 (3) | 0.0388 (10) | |
H25 | 0.6514 | −0.1997 | 0.2347 | 0.047* | |
C26 | 0.4637 (5) | 0.0694 (3) | 0.2172 (3) | 0.0332 (9) | |
C27 | 0.3292 (5) | 0.4292 (3) | −0.0072 (3) | 0.0339 (9) | |
C28 | 0.3635 (5) | 0.4842 (3) | −0.1126 (3) | 0.0464 (12) | |
H28A | 0.2600 | 0.5246 | −0.1460 | 0.056* | |
H28B | 0.4233 | 0.5439 | −0.1168 | 0.056* | |
C29 | 0.4506 (4) | 0.4174 (3) | −0.1717 (2) | 0.0277 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0343 (3) | 0.0237 (2) | 0.0243 (2) | −0.0011 (2) | 0.00842 (19) | −0.00496 (19) |
Zn2 | 0.0455 (3) | 0.0231 (2) | 0.0225 (2) | 0.0025 (2) | 0.0076 (2) | −0.00518 (19) |
O1 | 0.0318 (15) | 0.0292 (14) | 0.0308 (14) | −0.0005 (12) | 0.0044 (12) | −0.0062 (12) |
O2 | 0.070 (2) | 0.0277 (15) | 0.0331 (16) | −0.0085 (14) | −0.0064 (14) | −0.0061 (12) |
O11 | 0.0491 (18) | 0.0325 (15) | 0.0308 (15) | 0.0100 (14) | 0.0134 (13) | −0.0007 (12) |
O12 | 0.0482 (18) | 0.0398 (16) | 0.0350 (16) | 0.0096 (14) | 0.0164 (14) | −0.0041 (13) |
O13 | 0.0508 (18) | 0.0331 (15) | 0.0300 (15) | 0.0095 (14) | 0.0192 (13) | 0.0001 (12) |
O14 | 0.069 (2) | 0.0470 (17) | 0.0237 (15) | 0.0155 (16) | 0.0163 (14) | −0.0006 (13) |
O21 | 0.070 (2) | 0.0270 (15) | 0.0307 (15) | 0.0098 (14) | 0.0227 (14) | 0.0000 (12) |
O22 | 0.078 (2) | 0.0261 (14) | 0.0360 (16) | −0.0020 (15) | 0.0293 (15) | −0.0110 (13) |
O23 | 0.0520 (18) | 0.0281 (14) | 0.0237 (14) | 0.0078 (13) | 0.0059 (12) | −0.0080 (12) |
O24 | 0.0509 (18) | 0.0408 (16) | 0.0191 (14) | 0.0118 (14) | 0.0089 (13) | −0.0023 (12) |
O1W | 0.0516 (19) | 0.0375 (16) | 0.056 (2) | −0.0105 (15) | −0.0030 (16) | 0.0026 (14) |
O2W | 0.098 (3) | 0.0513 (19) | 0.0321 (17) | 0.0173 (18) | 0.0027 (17) | −0.0139 (15) |
N11 | 0.0317 (18) | 0.0269 (17) | 0.0268 (17) | −0.0026 (14) | 0.0137 (14) | −0.0056 (14) |
N12 | 0.076 (3) | 0.0297 (19) | 0.050 (2) | −0.0131 (19) | 0.039 (2) | −0.0127 (17) |
N13 | 0.0268 (17) | 0.0264 (16) | 0.0251 (16) | −0.0019 (14) | 0.0049 (14) | −0.0086 (13) |
N14 | 0.043 (2) | 0.0363 (19) | 0.0308 (18) | −0.0071 (16) | 0.0177 (16) | −0.0125 (15) |
N21 | 0.0307 (18) | 0.0220 (16) | 0.0226 (16) | 0.0000 (14) | 0.0065 (14) | −0.0049 (13) |
N22 | 0.046 (2) | 0.0349 (18) | 0.0275 (18) | −0.0055 (16) | 0.0147 (16) | −0.0097 (15) |
N23 | 0.042 (2) | 0.0300 (17) | 0.0212 (16) | −0.0002 (15) | 0.0091 (15) | −0.0061 (14) |
N24 | 0.080 (3) | 0.044 (2) | 0.0281 (19) | 0.009 (2) | 0.0252 (19) | −0.0081 (16) |
S11 | 0.0486 (7) | 0.0357 (6) | 0.0340 (6) | −0.0127 (5) | 0.0187 (5) | −0.0058 (5) |
S12 | 0.0432 (6) | 0.0350 (6) | 0.0352 (6) | −0.0034 (5) | 0.0111 (5) | −0.0178 (5) |
S21 | 0.0559 (7) | 0.0343 (6) | 0.0405 (6) | 0.0091 (5) | 0.0123 (5) | −0.0141 (5) |
S22 | 0.0538 (7) | 0.0376 (6) | 0.0256 (5) | −0.0099 (5) | 0.0104 (5) | −0.0020 (4) |
C11 | 0.025 (2) | 0.029 (2) | 0.029 (2) | −0.0022 (17) | 0.0013 (17) | −0.0071 (17) |
C12 | 0.044 (3) | 0.034 (2) | 0.037 (2) | −0.011 (2) | 0.010 (2) | −0.0127 (19) |
C13 | 0.034 (2) | 0.027 (2) | 0.029 (2) | −0.0031 (18) | 0.0053 (18) | 0.0002 (17) |
C14 | 0.026 (2) | 0.029 (2) | 0.027 (2) | −0.0060 (17) | 0.0013 (17) | −0.0073 (17) |
C15 | 0.043 (2) | 0.031 (2) | 0.032 (2) | −0.0102 (19) | 0.0073 (19) | −0.0104 (18) |
C16 | 0.024 (2) | 0.031 (2) | 0.024 (2) | −0.0004 (17) | 0.0037 (16) | −0.0093 (17) |
C17 | 0.031 (2) | 0.027 (2) | 0.027 (2) | −0.0074 (18) | 0.0052 (17) | −0.0114 (17) |
C18 | 0.032 (2) | 0.030 (2) | 0.025 (2) | −0.0012 (17) | 0.0060 (17) | −0.0066 (17) |
C19 | 0.038 (2) | 0.025 (2) | 0.025 (2) | −0.0013 (18) | 0.0074 (18) | −0.0071 (17) |
C21 | 0.034 (2) | 0.025 (2) | 0.029 (2) | −0.0055 (17) | 0.0037 (17) | −0.0089 (17) |
C22 | 0.058 (3) | 0.028 (2) | 0.036 (2) | 0.004 (2) | 0.009 (2) | −0.0044 (19) |
C23 | 0.028 (2) | 0.028 (2) | 0.028 (2) | −0.0013 (17) | 0.0041 (17) | −0.0119 (17) |
C24 | 0.031 (2) | 0.0252 (19) | 0.027 (2) | −0.0037 (17) | 0.0017 (17) | −0.0065 (17) |
C25 | 0.049 (3) | 0.026 (2) | 0.031 (2) | −0.0023 (19) | 0.0037 (19) | −0.0007 (17) |
C26 | 0.039 (2) | 0.033 (2) | 0.0206 (19) | −0.0034 (18) | 0.0033 (17) | −0.0029 (17) |
C27 | 0.039 (2) | 0.027 (2) | 0.031 (2) | −0.0031 (18) | 0.0064 (18) | −0.0067 (18) |
C28 | 0.065 (3) | 0.038 (2) | 0.023 (2) | 0.009 (2) | 0.010 (2) | −0.0076 (18) |
C29 | 0.030 (2) | 0.025 (2) | 0.023 (2) | −0.0004 (17) | 0.0032 (17) | −0.0066 (16) |
Zn1—O1 | 2.023 (2) | N21—C23 | 1.323 (4) |
Zn1—O11 | 2.013 (2) | N21—C21 | 1.392 (4) |
Zn1—O13 | 2.016 (2) | N22—C23 | 1.334 (4) |
Zn1—N11 | 2.098 (3) | N22—H22A | 0.8308 |
Zn1—N13 | 2.077 (3) | N22—H22B | 0.8556 |
Zn2—O2 | 2.016 (3) | N23—C26 | 1.324 (4) |
Zn2—O21 | 2.026 (3) | N23—C24 | 1.388 (4) |
Zn2—O23 | 2.023 (2) | N24—C26 | 1.333 (4) |
Zn2—N21 | 2.076 (3) | N24—H24A | 0.8259 |
Zn2—N23 | 2.097 (3) | N24—H24B | 0.8748 |
O1—H1A | 0.8365 | S11—C12 | 1.725 (4) |
O1—H1B | 0.8334 | S11—C13 | 1.737 (4) |
O2—H2A | 0.8010 | S12—C15 | 1.728 (4) |
O2—H2B | 0.8594 | S12—C16 | 1.729 (4) |
O11—C17 | 1.248 (4) | S21—C22 | 1.721 (4) |
O12—C17 | 1.238 (4) | S21—C23 | 1.729 (3) |
O13—C19 | 1.265 (4) | S22—C25 | 1.722 (4) |
O14—C19 | 1.232 (4) | S22—C26 | 1.735 (4) |
O21—C27 | 1.258 (4) | C11—C12 | 1.332 (5) |
O22—C27 | 1.239 (4) | C11—C14 | 1.459 (5) |
O23—C29 | 1.268 (4) | C12—H12 | 0.9300 |
O24—C29 | 1.234 (4) | C14—C15 | 1.343 (5) |
O1W—H1WA | 0.8536 | C15—H15 | 0.9300 |
O1W—H1WB | 0.8432 | C17—C18 | 1.517 (5) |
O2W—H2WA | 0.8169 | C18—C19 | 1.511 (5) |
O2W—H2WB | 0.8148 | C18—H18A | 0.9700 |
N11—C13 | 1.319 (4) | C18—H18B | 0.9700 |
N11—C11 | 1.379 (4) | C21—C22 | 1.331 (5) |
N12—C13 | 1.334 (4) | C21—C24 | 1.449 (5) |
N12—H12A | 0.8687 | C22—H22 | 0.9300 |
N12—H12B | 0.8623 | C24—C25 | 1.342 (5) |
N13—C16 | 1.326 (4) | C25—H25 | 0.9300 |
N13—C14 | 1.391 (4) | C27—C28 | 1.513 (5) |
N14—C16 | 1.324 (4) | C28—C29 | 1.501 (5) |
N14—H14A | 0.8392 | C28—H28A | 0.9700 |
N14—H14B | 0.8809 | C28—H28B | 0.9700 |
O11—Zn1—O13 | 88.83 (10) | C12—C11—N11 | 115.4 (3) |
O11—Zn1—O1 | 99.45 (11) | C12—C11—C14 | 129.0 (3) |
O13—Zn1—O1 | 106.13 (11) | N11—C11—C14 | 115.6 (3) |
O11—Zn1—N13 | 152.32 (12) | C11—C12—S11 | 111.0 (3) |
O13—Zn1—N13 | 91.05 (11) | C11—C12—H12 | 124.5 |
O1—Zn1—N13 | 107.14 (10) | S11—C12—H12 | 124.5 |
O11—Zn1—N11 | 90.47 (11) | N11—C13—N12 | 125.7 (3) |
O13—Zn1—N11 | 157.42 (12) | N11—C13—S11 | 113.5 (3) |
O1—Zn1—N11 | 96.25 (11) | N12—C13—S11 | 120.8 (3) |
N13—Zn1—N11 | 79.29 (11) | C15—C14—N13 | 114.7 (3) |
O2—Zn2—O23 | 100.60 (11) | C15—C14—C11 | 129.3 (3) |
O2—Zn2—O21 | 100.53 (11) | N13—C14—C11 | 116.0 (3) |
O23—Zn2—O21 | 88.22 (10) | C14—C15—S12 | 111.0 (3) |
O2—Zn2—N21 | 100.54 (11) | C14—C15—H15 | 124.5 |
O23—Zn2—N21 | 92.46 (10) | S12—C15—H15 | 124.5 |
O21—Zn2—N21 | 158.42 (12) | N14—C16—N13 | 124.3 (3) |
O2—Zn2—N23 | 104.88 (11) | N14—C16—S12 | 121.9 (3) |
O23—Zn2—N23 | 154.14 (11) | N13—C16—S12 | 113.8 (3) |
O21—Zn2—N23 | 91.35 (11) | O12—C17—O11 | 122.5 (3) |
N21—Zn2—N23 | 78.76 (11) | O12—C17—C18 | 115.9 (3) |
Zn1—O1—H1A | 107.9 | O11—C17—C18 | 121.6 (3) |
Zn1—O1—H1B | 114.0 | C19—C18—C17 | 123.9 (3) |
H1A—O1—H1B | 105.9 | C19—C18—H18A | 106.4 |
Zn2—O2—H2A | 111.8 | C17—C18—H18A | 106.4 |
Zn2—O2—H2B | 122.1 | C19—C18—H18B | 106.4 |
H2A—O2—H2B | 108.8 | C17—C18—H18B | 106.4 |
C17—O11—Zn1 | 131.8 (2) | H18A—C18—H18B | 106.4 |
C19—O13—Zn1 | 131.3 (2) | O14—C19—O13 | 123.0 (3) |
C27—O21—Zn2 | 127.8 (3) | O14—C19—C18 | 115.9 (3) |
C29—O23—Zn2 | 129.8 (2) | O13—C19—C18 | 121.1 (3) |
H1WA—O1W—H1WB | 106.5 | C22—C21—N21 | 114.5 (3) |
H2WA—O2W—H2WB | 110.0 | C22—C21—C24 | 130.0 (3) |
C13—N11—C11 | 111.2 (3) | N21—C21—C24 | 115.5 (3) |
C13—N11—Zn1 | 134.3 (2) | C21—C22—S21 | 111.5 (3) |
C11—N11—Zn1 | 114.4 (2) | C21—C22—H22 | 124.2 |
C13—N12—H12A | 117.3 | S21—C22—H22 | 124.2 |
C13—N12—H12B | 123.1 | N21—C23—N22 | 124.2 (3) |
H12A—N12—H12B | 119.3 | N21—C23—S21 | 113.5 (3) |
C16—N13—C14 | 111.1 (3) | N22—C23—S21 | 122.3 (3) |
C16—N13—Zn1 | 134.4 (2) | C25—C24—N23 | 115.0 (3) |
C14—N13—Zn1 | 114.5 (2) | C25—C24—C21 | 129.5 (3) |
C16—N14—H14A | 123.7 | N23—C24—C21 | 115.5 (3) |
C16—N14—H14B | 114.8 | C24—C25—S22 | 111.0 (3) |
H14A—N14—H14B | 121.5 | C24—C25—H25 | 124.5 |
C23—N21—C21 | 111.3 (3) | S22—C25—H25 | 124.5 |
C23—N21—Zn2 | 133.1 (2) | N23—C26—N24 | 124.5 (3) |
C21—N21—Zn2 | 115.2 (2) | N23—C26—S22 | 113.6 (3) |
C23—N22—H22A | 115.3 | N24—C26—S22 | 121.9 (3) |
C23—N22—H22B | 117.7 | O22—C27—O21 | 122.4 (3) |
H22A—N22—H22B | 124.2 | O22—C27—C28 | 116.4 (3) |
C26—N23—C24 | 111.0 (3) | O21—C27—C28 | 121.1 (3) |
C26—N23—Zn2 | 134.2 (2) | C29—C28—C27 | 124.1 (3) |
C24—N23—Zn2 | 114.8 (2) | C29—C28—H28A | 106.3 |
C26—N24—H24A | 119.6 | C27—C28—H28A | 106.3 |
C26—N24—H24B | 120.1 | C29—C28—H28B | 106.3 |
H24A—N24—H24B | 119.4 | C27—C28—H28B | 106.3 |
C12—S11—C13 | 88.98 (19) | H28A—C28—H28B | 106.4 |
C15—S12—C16 | 89.39 (17) | O24—C29—O23 | 123.1 (3) |
C22—S21—C23 | 89.26 (18) | O24—C29—C28 | 115.8 (3) |
C25—S22—C26 | 89.37 (18) | O23—C29—C28 | 121.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O24i | 0.84 | 1.86 | 2.694 (4) | 173 |
O1—H1B···O1W | 0.83 | 1.80 | 2.619 (4) | 168 |
O2—H2A···O2W | 0.80 | 1.88 | 2.673 (4) | 168 |
O2—H2B···O22i | 0.86 | 1.83 | 2.687 (4) | 175 |
O1W—H1WA···O12ii | 0.85 | 2.06 | 2.855 (4) | 154 |
O1W—H1WB···O12iii | 0.84 | 1.93 | 2.774 (4) | 174 |
O2W—H2WA···O14iii | 0.82 | 2.07 | 2.839 (4) | 156 |
O2W—H2WB···O1 | 0.82 | 2.15 | 2.957 (4) | 173 |
N12—H12A···O22iv | 0.87 | 2.06 | 2.910 (4) | 168 |
N14—H14B···O24v | 0.88 | 2.05 | 2.905 (4) | 163 |
N22—H22B···O14vi | 0.86 | 2.02 | 2.854 (4) | 164 |
N24—H24B···O12ii | 0.87 | 2.06 | 2.880 (4) | 156 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x−1, y, z; (iii) −x+2, −y, −z+1; (iv) x+1, y, z; (v) x, y, z+1; (vi) x, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C3H2O4)(C6H6N4S2)(H2O)]·H2O |
Mr | 401.72 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 295 |
a, b, c (Å) | 8.4695 (11), 12.5509 (15), 14.8615 (19) |
α, β, γ (°) | 68.895 (1), 88.074 (2), 78.337 (2) |
V (Å3) | 1442.1 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.03 |
Crystal size (mm) | 0.25 × 0.22 × 0.15 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.628, 0.735 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7536, 4992, 3768 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.086, 1.08 |
No. of reflections | 4992 |
No. of parameters | 398 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.40 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), PROCESS-AUTO, CrystalStructure (Rigaku/MSC, 2002), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Zn1—O1 | 2.023 (2) | Zn2—O2 | 2.016 (3) |
Zn1—O11 | 2.013 (2) | Zn2—O21 | 2.026 (3) |
Zn1—O13 | 2.016 (2) | Zn2—O23 | 2.023 (2) |
Zn1—N11 | 2.098 (3) | Zn2—N21 | 2.076 (3) |
Zn1—N13 | 2.077 (3) | Zn2—N23 | 2.097 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O24i | 0.84 | 1.86 | 2.694 (4) | 173 |
O1—H1B···O1W | 0.83 | 1.80 | 2.619 (4) | 168 |
O2—H2A···O2W | 0.80 | 1.88 | 2.673 (4) | 168 |
O2—H2B···O22i | 0.86 | 1.83 | 2.687 (4) | 175 |
O1W—H1WA···O12ii | 0.85 | 2.06 | 2.855 (4) | 154 |
O1W—H1WB···O12iii | 0.84 | 1.93 | 2.774 (4) | 174 |
O2W—H2WA···O14iii | 0.82 | 2.07 | 2.839 (4) | 156 |
O2W—H2WB···O1 | 0.82 | 2.15 | 2.957 (4) | 173 |
N12—H12A···O22iv | 0.87 | 2.06 | 2.910 (4) | 168 |
N14—H14B···O24v | 0.88 | 2.05 | 2.905 (4) | 163 |
N22—H22B···O14vi | 0.86 | 2.02 | 2.854 (4) | 164 |
N24—H24B···O12ii | 0.87 | 2.06 | 2.880 (4) | 156 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x−1, y, z; (iii) −x+2, −y, −z+1; (iv) x+1, y, z; (v) x, y, z+1; (vi) x, y, z−1. |
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Transition metal complexes of 2,2'-diamino-4,4'-bi-1,3-thiazole (DABT) have shown potential application in the field of soft magnetic material (Sun et al., 1997). As part of serial structural investigation of metal complexes with DABT (Liu & Xu, 2004; Luo et al., 2004), the title ZnII complex was recently prepared and its X-ray structure is presented here.
Asymmetric unit of the crystal of the title compound contains two independent ZnII complexes (Fig. 1). Each ZnII ion has a distorted square pyramid coordination geometry (Table 1) formed by one of DABT ligand, one of malonate dianion and one water molecules. The O atom of coordinated water lies on the apical position of square pyramid. The The Zn1 and Zn2 atoms are out of the base plane of pyramidal by 0.437 (2) Å and 0.413 (2) Å, respectively.
Within the complex, each DABT moiety is approximately coplanar with a dihedral angles of 3.23 (19)° for Zn1 complex and 2.54 (18)° for Zn1 and Zn2 complex respectively. The average distances of 1.334 (4) Å of C—N(amino) within Zn1 complex and 1.329 (4) Å of C—N(amino) within Zn2 complex imply the existence of electron delocalization between thiazole rings and amino groups. This feature of electron delocalization of DABT agrees with reported CuII complex of DABT (Wu et al., 2003).
The malonate dianion chelates to the ZnII atom with a nearly planar configuration with the maximum atomic deviation of 0.025 (2) Å (C17) to the mean plane defined by O11 O13 C17 C18 C19 and 0.071 (3) Å (C29) to the mean plane defined by O21 O23 C27 C28 C29. The extensive hydrogen bonding between lattice water and complex molecules helps to stabilize the crystal structure (Fig. 1. and Table 2).