Acta Cryst. (2008). E64, m585 [ doi:10.1107/S1600536808007836 ]
In the title compound, [Ni(H2O)6](C11H7ClNO3S)2·2H2O, the NiII atom lies on an inversion center and is six-coordinate in an octahedral environment of water molecules. The cation and anion are linked through O-H
O hydrogen bonding involving the coordinated and uncoordinated water molecules into a three-dimensional network.
4-[(2-Chloro-5-thiazolyl)methoxy]benzoic acid was prepared by substitute reaction of 4-hydroxybenzoic acid and 2-chloro-5-chloromethoxythiazol under basic conditions(stephen et al.,2000). Nickel nitrate hexahydrate(0.582 g, 2 mmol) and 4-[(2-Chloro-5-thiazolyl)methoxy]benzoic acid(0.538 g, 2 mmol) were dissolved in water(15 ml) and the pH was adjusted to 7 with 0.01 mol/L sodium hydroxide. Jade-green crystals separated from filtered after several days.
H atoms bound to C atoms were placed in calculated positions and treated as riding on their parent atoms, with C—H = 0.93 Å (aromatic C), C—H = 0.97 Å (methylene C), and with Uiso(H) = 1.2Ueq(C). Water H atoms were initially located in a difference Fourier map but they were treated as riding on their parent atoms with O—H=0.85 Å, Uiso(H) = 1.5Ueq(O).
Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); 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: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./ng2435fig1thm.gif)
| Fig. 1. The molecular structure of (I) with the atom labeling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. A dashed line indicates the intermolecular O—H···O hydrogen-bonding interaction. [Symmetry code: (i) 2 - x, -y, 1 - z] |
![[Figure 2]](./ng2435fig2thm.gif)
| Fig. 2. A partial packing view, showing the three-dimensional network. Dashed lines indicate the hydrogen-bonding interactions. The H atoms have been omitted for clarity. |
| [Ni(H2O)6](C11H7ClNO3S)2·2H2O | Z = 1 |
| Mr = 740.21 | F000 = 382 |
| Triclinic, P1 | Dx = 1.647 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation λ = 0.71073 Å |
| a = 7.1844 (4) Å | Cell parameters from 4613 reflections |
| b = 7.2084 (4) Å | θ = 2.7–28.2º |
| c = 15.5621 (8) Å | µ = 1.04 mm−1 |
| α = 78.388 (1)º | T = 291 (2) K |
| β = 81.285 (1)º | Block, green |
| γ = 71.734 (1)º | 0.20 × 0.18 × 0.08 mm |
| V = 746.26 (7) Å3 |
| Rigaku R-AXIS RAPID diffractometer | 2862 independent reflections |
| Radiation source: fine-focus sealed tube | 2496 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.012 |
| T = 291(2) K | θmax = 26.0º |
| ω scan | θmin = 2.7º |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −8→8 |
| Tmin = 0.819, Tmax = 0.922 | k = −4→8 |
| 4613 measured reflections | l = −19→19 |
| 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)] = 0.030 | H-atom parameters constrained |
| wR(F2) = 0.076 | w = 1/[σ2(Fo2) + (0.0324P)2 + 0.4113P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.06 | (Δ/σ)max < 0.001 |
| 2862 reflections | Δρmax = 0.36 e Å−3 |
| 196 parameters | Δρmin = −0.22 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| [Ni(H2O)6](C11H7ClNO3S)2·2H2O | γ = 71.734 (1)º |
| Mr = 740.21 | V = 746.26 (7) Å3 |
| Triclinic, P1 | Z = 1 |
| a = 7.1844 (4) Å | Mo Kα |
| b = 7.2084 (4) Å | µ = 1.04 mm−1 |
| c = 15.5621 (8) Å | T = 291 (2) K |
| α = 78.388 (1)º | 0.20 × 0.18 × 0.08 mm |
| β = 81.285 (1)º |
| Rigaku R-AXIS RAPID diffractometer | 2862 independent reflections |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 2496 reflections with I > 2σ(I) |
| Tmin = 0.819, Tmax = 0.922 | Rint = 0.012 |
| 4613 measured reflections |
| R[F2 > 2σ(F2)] = 0.030 | 196 parameters |
| wR(F2) = 0.076 | H-atom parameters constrained |
| S = 1.06 | Δρmax = 0.36 e Å−3 |
| 2862 reflections | Δρmin = −0.22 e Å−3 |
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 | ||
| C1 | 0.4407 (3) | 0.4075 (3) | 0.34973 (14) | 0.0299 (5) | |
| C2 | 0.5199 (3) | 0.3065 (3) | 0.27064 (14) | 0.0290 (4) | |
| C3 | 0.5491 (3) | 0.4165 (3) | 0.18875 (14) | 0.0341 (5) | |
| H1 | 0.5231 | 0.5528 | 0.1836 | 0.041* | |
| C4 | 0.6166 (3) | 0.3275 (3) | 0.11385 (15) | 0.0377 (5) | |
| H2 | 0.6367 | 0.4031 | 0.0593 | 0.045* | |
| C5 | 0.6532 (3) | 0.1257 (3) | 0.12194 (14) | 0.0357 (5) | |
| C6 | 0.6261 (4) | 0.0128 (3) | 0.20322 (15) | 0.0454 (6) | |
| H3 | 0.6515 | −0.1234 | 0.2081 | 0.055* | |
| C7 | 0.5612 (4) | 0.1027 (3) | 0.27714 (15) | 0.0414 (6) | |
| H4 | 0.5450 | 0.0260 | 0.3318 | 0.050* | |
| C8 | 0.7285 (4) | 0.1271 (3) | −0.03345 (14) | 0.0404 (5) | |
| H6 | 0.8182 | 0.2060 | −0.0388 | 0.048* | |
| H5 | 0.5999 | 0.2151 | −0.0474 | 0.048* | |
| C9 | 0.8018 (3) | −0.0208 (3) | −0.09460 (14) | 0.0336 (5) | |
| C10 | 0.8419 (4) | 0.0072 (4) | −0.18299 (15) | 0.0444 (6) | |
| H7 | 0.8252 | 0.1330 | −0.2162 | 0.053* | |
| C11 | 0.9178 (3) | −0.3136 (3) | −0.16161 (15) | 0.0369 (5) | |
| Cl1 | 0.99611 (11) | −0.54983 (9) | −0.18443 (5) | 0.05607 (19) | |
| N1 | 0.9093 (3) | −0.1615 (3) | −0.22133 (13) | 0.0431 (5) | |
| Ni1 | 1.0000 | 0.0000 | 0.5000 | 0.02618 (11) | |
| O1 | 0.4168 (2) | 0.2996 (2) | 0.42325 (10) | 0.0360 (4) | |
| O2 | 0.4022 (2) | 0.5919 (2) | 0.33923 (10) | 0.0420 (4) | |
| O3 | 0.7165 (3) | 0.0213 (2) | 0.05258 (10) | 0.0521 (5) | |
| O4 | 1.0411 (2) | −0.1930 (2) | 0.41173 (11) | 0.0435 (4) | |
| H8 | 0.9563 | −0.2515 | 0.4097 | 0.065* | |
| H9 | 1.1530 | −0.2663 | 0.3946 | 0.065* | |
| O5 | 0.9559 (3) | 0.2269 (2) | 0.39824 (11) | 0.0519 (5) | |
| H10 | 1.0058 | 0.2093 | 0.3463 | 0.078* | |
| H11 | 0.8994 | 0.3483 | 0.4014 | 0.078* | |
| O6 | 0.7076 (2) | 0.0327 (2) | 0.52300 (11) | 0.0403 (4) | |
| H12 | 0.6286 | 0.1176 | 0.4888 | 0.061* | |
| H13 | 0.6671 | −0.0686 | 0.5411 | 0.061* | |
| O7 | 0.2566 (2) | 0.3897 (2) | 0.58489 (11) | 0.0418 (4) | |
| H15 | 0.3537 | 0.3765 | 0.6131 | 0.063* | |
| H14 | 0.3016 | 0.3778 | 0.5319 | 0.063* | |
| S1 | 0.84843 (10) | −0.26984 (9) | −0.05532 (4) | 0.04168 (16) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0288 (10) | 0.0311 (12) | 0.0304 (11) | −0.0066 (9) | −0.0005 (8) | −0.0112 (9) |
| C2 | 0.0305 (10) | 0.0267 (11) | 0.0279 (11) | −0.0039 (8) | −0.0003 (8) | −0.0090 (9) |
| C3 | 0.0447 (12) | 0.0248 (11) | 0.0319 (12) | −0.0084 (9) | 0.0001 (9) | −0.0082 (9) |
| C4 | 0.0515 (13) | 0.0326 (12) | 0.0258 (11) | −0.0108 (10) | 0.0030 (10) | −0.0049 (9) |
| C5 | 0.0450 (12) | 0.0313 (12) | 0.0270 (11) | −0.0040 (10) | 0.0032 (9) | −0.0126 (9) |
| C6 | 0.0708 (17) | 0.0232 (12) | 0.0336 (13) | −0.0049 (11) | 0.0067 (12) | −0.0080 (10) |
| C7 | 0.0600 (15) | 0.0301 (12) | 0.0268 (11) | −0.0074 (11) | 0.0080 (10) | −0.0065 (10) |
| C8 | 0.0577 (14) | 0.0332 (13) | 0.0272 (12) | −0.0087 (11) | 0.0025 (10) | −0.0104 (10) |
| C9 | 0.0417 (12) | 0.0282 (11) | 0.0291 (11) | −0.0076 (9) | 0.0003 (9) | −0.0075 (9) |
| C10 | 0.0702 (16) | 0.0297 (12) | 0.0284 (12) | −0.0098 (11) | 0.0028 (11) | −0.0071 (10) |
| C11 | 0.0434 (12) | 0.0328 (12) | 0.0327 (12) | −0.0067 (10) | 0.0022 (10) | −0.0126 (10) |
| Cl1 | 0.0756 (5) | 0.0341 (3) | 0.0554 (4) | −0.0099 (3) | 0.0077 (3) | −0.0205 (3) |
| N1 | 0.0622 (13) | 0.0352 (11) | 0.0283 (10) | −0.0085 (9) | 0.0044 (9) | −0.0130 (9) |
| Ni1 | 0.0301 (2) | 0.0224 (2) | 0.0240 (2) | −0.00492 (15) | 0.00206 (14) | −0.00691 (15) |
| O1 | 0.0464 (9) | 0.0331 (8) | 0.0274 (8) | −0.0104 (7) | 0.0037 (7) | −0.0098 (7) |
| O2 | 0.0575 (10) | 0.0278 (8) | 0.0362 (9) | −0.0050 (7) | 0.0040 (7) | −0.0130 (7) |
| O3 | 0.0902 (14) | 0.0318 (9) | 0.0255 (8) | −0.0070 (9) | 0.0071 (8) | −0.0114 (7) |
| O4 | 0.0432 (9) | 0.0421 (10) | 0.0493 (10) | −0.0121 (7) | 0.0064 (7) | −0.0255 (8) |
| O5 | 0.0836 (13) | 0.0268 (9) | 0.0277 (8) | 0.0023 (8) | 0.0087 (8) | −0.0048 (7) |
| O6 | 0.0340 (8) | 0.0358 (9) | 0.0482 (10) | −0.0101 (7) | 0.0004 (7) | −0.0035 (7) |
| O7 | 0.0494 (9) | 0.0378 (9) | 0.0371 (9) | −0.0085 (7) | 0.0032 (7) | −0.0159 (7) |
| S1 | 0.0599 (4) | 0.0318 (3) | 0.0279 (3) | −0.0089 (3) | 0.0050 (3) | −0.0064 (2) |
| C1—O2 | 1.251 (3) | C10—N1 | 1.380 (3) |
| C1—O1 | 1.269 (3) | C10—H7 | 0.9300 |
| C1—C2 | 1.503 (3) | C11—N1 | 1.279 (3) |
| C2—C3 | 1.383 (3) | C11—Cl1 | 1.710 (2) |
| C2—C7 | 1.390 (3) | C11—S1 | 1.716 (2) |
| C3—C4 | 1.393 (3) | Ni1—O5 | 2.0167 (16) |
| C3—H1 | 0.9300 | Ni1—O5i | 2.0167 (16) |
| C4—C5 | 1.378 (3) | Ni1—O6i | 2.0230 (15) |
| C4—H2 | 0.9300 | Ni1—O6 | 2.0230 (15) |
| C5—O3 | 1.379 (3) | Ni1—O4i | 2.0732 (15) |
| C5—C6 | 1.382 (3) | Ni1—O4 | 2.0732 (15) |
| C6—C7 | 1.381 (3) | O4—H8 | 0.8499 |
| C6—H3 | 0.9300 | O4—H9 | 0.8500 |
| C7—H4 | 0.9300 | O5—H10 | 0.8500 |
| C8—O3 | 1.406 (3) | O5—H11 | 0.8500 |
| C8—C9 | 1.492 (3) | O6—H12 | 0.8499 |
| C8—H6 | 0.9700 | O6—H13 | 0.8500 |
| C8—H5 | 0.9700 | O7—H15 | 0.8499 |
| C9—C10 | 1.349 (3) | O7—H14 | 0.8501 |
| C9—S1 | 1.718 (2) | ||
| O2—C1—O1 | 124.10 (19) | N1—C10—H7 | 121.9 |
| O2—C1—C2 | 118.33 (19) | N1—C11—Cl1 | 122.70 (17) |
| O1—C1—C2 | 117.58 (19) | N1—C11—S1 | 116.45 (17) |
| C3—C2—C7 | 118.43 (19) | Cl1—C11—S1 | 120.85 (14) |
| C3—C2—C1 | 120.19 (19) | C11—N1—C10 | 109.39 (19) |
| C7—C2—C1 | 121.36 (19) | O5—Ni1—O5i | 180.000 (1) |
| C2—C3—C4 | 121.4 (2) | O5—Ni1—O6i | 88.79 (7) |
| C2—C3—H1 | 119.3 | O5i—Ni1—O6i | 91.21 (7) |
| C4—C3—H1 | 119.3 | O5—Ni1—O6 | 91.21 (7) |
| C5—C4—C3 | 118.9 (2) | O5i—Ni1—O6 | 88.79 (7) |
| C5—C4—H2 | 120.5 | O6i—Ni1—O6 | 180.00 (9) |
| C3—C4—H2 | 120.5 | O5—Ni1—O4i | 91.14 (7) |
| C4—C5—O3 | 124.3 (2) | O5i—Ni1—O4i | 88.86 (7) |
| C4—C5—C6 | 120.6 (2) | O6i—Ni1—O4i | 92.92 (6) |
| O3—C5—C6 | 115.1 (2) | O6—Ni1—O4i | 87.08 (6) |
| C7—C6—C5 | 119.9 (2) | O5—Ni1—O4 | 88.86 (7) |
| C7—C6—H3 | 120.0 | O5i—Ni1—O4 | 91.14 (7) |
| C5—C6—H3 | 120.0 | O6i—Ni1—O4 | 87.08 (6) |
| C6—C7—C2 | 120.7 (2) | O6—Ni1—O4 | 92.92 (6) |
| C6—C7—H4 | 119.6 | O4i—Ni1—O4 | 180.0 |
| C2—C7—H4 | 119.6 | C5—O3—C8 | 118.64 (18) |
| O3—C8—C9 | 107.34 (18) | Ni1—O4—H8 | 121.8 |
| O3—C8—H6 | 110.2 | Ni1—O4—H9 | 123.8 |
| C9—C8—H6 | 110.2 | H8—O4—H9 | 107.5 |
| O3—C8—H5 | 110.2 | Ni1—O5—H10 | 121.0 |
| C9—C8—H5 | 110.2 | Ni1—O5—H11 | 126.5 |
| H6—C8—H5 | 108.5 | H10—O5—H11 | 112.2 |
| C10—C9—C8 | 129.8 (2) | Ni1—O6—H12 | 120.0 |
| C10—C9—S1 | 109.38 (17) | Ni1—O6—H13 | 119.8 |
| C8—C9—S1 | 120.84 (16) | H12—O6—H13 | 109.8 |
| C9—C10—N1 | 116.1 (2) | H15—O7—H14 | 107.2 |
| C9—C10—H7 | 121.9 | C11—S1—C9 | 88.63 (11) |
| Symmetry codes: (i) −x+2, −y, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O4—H8···O7ii | 0.85 | 2.05 | 2.903 (2) | 175 |
| O4—H9···O2iii | 0.85 | 1.93 | 2.776 (2) | 172 |
| O5—H10···N1iv | 0.85 | 2.01 | 2.858 (2) | 173 |
| O5—H11···O7v | 0.85 | 1.91 | 2.750 (2) | 173 |
| O6—H12···O1 | 0.85 | 1.94 | 2.781 (2) | 171 |
| O6—H13···O1ii | 0.85 | 1.90 | 2.747 (2) | 177 |
| O7—H14···O1 | 0.85 | 1.88 | 2.718 (2) | 169 |
| Symmetry codes: (ii) −x+1, −y, −z+1; (iii) x+1, y−1, z; (iv) −x+2, −y, −z; (v) −x+1, −y+1, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O4—H8···O7i | 0.85 | 2.05 | 2.903 (2) | 175 |
| O4—H9···O2ii | 0.85 | 1.93 | 2.776 (2) | 172 |
| O5—H10···N1iii | 0.85 | 2.01 | 2.858 (2) | 173 |
| O5—H11···O7iv | 0.85 | 1.91 | 2.750 (2) | 173 |
| O6—H12···O1 | 0.85 | 1.94 | 2.781 (2) | 171 |
| O6—H13···O1i | 0.85 | 1.90 | 2.747 (2) | 177 |
| O7—H14···O1 | 0.85 | 1.88 | 2.718 (2) | 169 |
| Symmetry codes: (i) −x+1, −y, −z+1; (ii) x+1, y−1, z; (iii) −x+2, −y, −z; (iv) −x+1, −y+1, −z+1. |
The authors gratefully acknowledge financial support from the China West Normal University and Heilongjiang University.
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.
Mirci, L. E. (1990). Rom. Patent No. 0 743 205.
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Simple carboxylic acids exhibit a variety of superamolecular aggregation patterns. Recenttly,our attention has been focused on 4-[(2-Chloro-5-thiazolyl)methoxy]Benzoic acid, it is a intermediate used in the synthesis of pesticide. In this paper, we reprot a new complex, (I), synthesized by the reaction of 4-[(2-chloro-5-thiazolyl)methoxy]benzoic acid and nickel(II) nitrate hexahydrate in an aqueous solution.
The asymmetric unit of (I) consists of a hexaaquanickel(II) cation, two 4-[(2-chloro-5-thiazolyl)methoxy]benzoate anions and noe uncoordinated water molecules(Fig. 1). The Ni(II) atom lies on an inversion and is coordinated by six water molecules in an octahedral environment. The anion is almost planar,the largest deviation being 0.136 (5) Å for atom Cl1.
All cations, anions and uncoordinated water molecules are linked through O—H···O hydrogen bonds,resulting in a three-dimensional supramolecular network(Fig. 2; Table 1).