metal-organic compounds
Diaquabis(1H-imidazole-κN3)bis(4-nitrobenzoato-κO1)cadmium
aCenter of Applied Solid State Chemistry Research, Ningbo University, Ningbo, Zhejiang 315211, People's Republic of China
*Correspondence e-mail: linjianli@nbu.edu.cn
In the centrosymmetric title compound, [Cd(C7H4NO4)2(C3H4N2)2(H2O)2], the CdII atom, located on an inversion center, is coordinated by two N atoms and four O atoms in an octahedral geometry. The internal cohesion of the molecule is enhanced by an intramolecular O—H⋯O hydrogen bond. Intermolecular O—H⋯O and C—H⋯O hydrogen bonds and π–π contacts [centroid–centroid distance = 3.6549 (2) Å] define two-dimensional networks parallel to (001), which are further connected by weaker C—H⋯O interactions into a weakly connected three-dimensional supramolecular framework.
Related literature
For general background to aromatic carboxyl acid complexes, see: Kuang et al. (2007); Hsu et al. (2011). For related structures, see: Zheng et al. (2008).
Experimental
Crystal data
|
Refinement
|
Data collection: RAPID-AUTO (Rigaku, 1998); cell RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004); 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.
Supporting information
10.1107/S1600536812033739/bg2473sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812033739/bg2473Isup2.hkl
Dropwise addition of 1.0 ml (1 M) of K2CO3 to a stirred aqueous solution of Cd(CH3COO)2.2H2O (0.266 g, 1.0 mmol) in 10.0 ml of H2O yielded a fine white precipitate, which was separated by centrifugation and washed with water until no CH3COO- anions were detectable in the supernatant. The fresh precipitate was then added to a stirred aqueous solution of 4-nitrobenzoic acid (0.167 g, 1.0 mmol) in C2H5OH/H2O (1:1, 20.0 ml), producing a white suspension, to which imidazole (0.137 g, 2.0 mmol) was added. The mixture was further stirred vigorously for about 0.5 h. After filtration, the white filtrate (pH = 6.59) was maintained at room temperature and colorless crystals were grown.
H atoms bonded to C atoms were palced in geometrically calculated positions and were refined using a riding model. H atoms attached to O atoms were found in a difference Fourier synthesis and were refined with restrained O—H = 0.84 (1)Å. In all cases, Uiso(H) values were set at 1.2 Ueq(host).
Data collection: RAPID-AUTO (Rigaku, 1998); cell
RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); 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).[Cd(C7H4NO4)2(C3H4N2)2(H2O)2] | Z = 1 |
Mr = 614.80 | F(000) = 308 |
Triclinic, P1 | Dx = 1.747 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.8017 (12) Å | Cell parameters from 5719 reflections |
b = 8.0253 (16) Å | θ = 3.2–27.5° |
c = 12.879 (3) Å | µ = 1.00 mm−1 |
α = 77.99 (3)° | T = 293 K |
β = 88.42 (3)° | Plate, colorless |
γ = 85.16 (3)° | 0.33 × 0.14 × 0.09 mm |
V = 584.4 (2) Å3 |
Rigaku R-AXIS RAPID diffractometer | 2627 independent reflections |
Radiation source: fine-focus sealed tube | 2511 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
ω scans | θmax = 27.5°, θmin = 3.2° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −6→7 |
Tmin = 0.989, Tmax = 0.989 | k = −10→10 |
5719 measured reflections | l = −16→16 |
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)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.076 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.24 | w = 1/[σ2(Fo2) + (0.0208P)2 + 0.3927P] where P = (Fo2 + 2Fc2)/3 |
2627 reflections | (Δ/σ)max < 0.001 |
175 parameters | Δρmax = 0.54 e Å−3 |
3 restraints | Δρmin = −0.80 e Å−3 |
[Cd(C7H4NO4)2(C3H4N2)2(H2O)2] | γ = 85.16 (3)° |
Mr = 614.80 | V = 584.4 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 5.8017 (12) Å | Mo Kα radiation |
b = 8.0253 (16) Å | µ = 1.00 mm−1 |
c = 12.879 (3) Å | T = 293 K |
α = 77.99 (3)° | 0.33 × 0.14 × 0.09 mm |
β = 88.42 (3)° |
Rigaku R-AXIS RAPID diffractometer | 2627 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 2511 reflections with I > 2σ(I) |
Tmin = 0.989, Tmax = 0.989 | Rint = 0.031 |
5719 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 3 restraints |
wR(F2) = 0.076 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.24 | Δρmax = 0.54 e Å−3 |
2627 reflections | Δρmin = −0.80 e Å−3 |
175 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cd | 0.5000 | 1.0000 | 0.0000 | 0.03040 (10) | |
N1 | 0.4161 (4) | 0.7310 (3) | 0.07261 (18) | 0.0351 (5) | |
C1 | 0.5412 (6) | 0.6131 (4) | 0.1376 (3) | 0.0497 (8) | |
H1A | 0.6844 | 0.6290 | 0.1632 | 0.060* | |
C2 | 0.2360 (6) | 0.4946 (4) | 0.1116 (3) | 0.0518 (8) | |
H2A | 0.1261 | 0.4160 | 0.1136 | 0.062* | |
N2 | 0.4388 (5) | 0.4676 (3) | 0.1627 (2) | 0.0500 (7) | |
C3 | 0.2227 (6) | 0.6573 (4) | 0.0569 (3) | 0.0510 (8) | |
H3A | 0.0992 | 0.7108 | 0.0147 | 0.061* | |
O1 | 0.7532 (3) | 0.9739 (3) | 0.14420 (15) | 0.0384 (5) | |
O2 | 0.4950 (4) | 1.0755 (3) | 0.25118 (18) | 0.0553 (6) | |
C4 | 0.6746 (5) | 0.9881 (4) | 0.2347 (2) | 0.0336 (6) | |
C5 | 0.8110 (5) | 0.8918 (4) | 0.3301 (2) | 0.0343 (6) | |
C6 | 1.0191 (5) | 0.7974 (4) | 0.3212 (2) | 0.0398 (7) | |
H6A | 1.0781 | 0.7893 | 0.2544 | 0.048* | |
C7 | 1.1397 (5) | 0.7150 (4) | 0.4110 (2) | 0.0451 (7) | |
H7A | 1.2798 | 0.6518 | 0.4054 | 0.054* | |
C8 | 1.0480 (5) | 0.7285 (4) | 0.5088 (2) | 0.0421 (7) | |
C9 | 0.8406 (6) | 0.8178 (5) | 0.5205 (3) | 0.0581 (10) | |
H9A | 0.7807 | 0.8235 | 0.5875 | 0.070* | |
C10 | 0.7234 (6) | 0.8990 (5) | 0.4301 (3) | 0.0568 (9) | |
H10A | 0.5821 | 0.9601 | 0.4365 | 0.068* | |
N3 | 1.1799 (5) | 0.6471 (4) | 0.6046 (2) | 0.0548 (7) | |
O3 | 1.3619 (6) | 0.5690 (5) | 0.5945 (3) | 0.1018 (13) | |
O4 | 1.1007 (6) | 0.6639 (5) | 0.6907 (2) | 0.0890 (10) | |
O5 | 0.1847 (3) | 1.1006 (3) | 0.09734 (16) | 0.0385 (5) | |
H5A | 0.252 (5) | 1.088 (4) | 0.1559 (14) | 0.046* | |
H5B | 0.069 (4) | 1.043 (4) | 0.112 (2) | 0.046* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd | 0.03111 (16) | 0.02902 (15) | 0.02818 (15) | −0.00363 (11) | −0.00305 (10) | 0.00151 (10) |
N1 | 0.0371 (12) | 0.0309 (11) | 0.0343 (12) | −0.0032 (10) | −0.0033 (10) | 0.0009 (9) |
C1 | 0.0417 (17) | 0.0403 (16) | 0.060 (2) | −0.0052 (14) | −0.0155 (15) | 0.0081 (14) |
C2 | 0.057 (2) | 0.0329 (15) | 0.063 (2) | −0.0156 (15) | −0.0132 (17) | 0.0023 (14) |
N2 | 0.0605 (17) | 0.0342 (13) | 0.0488 (16) | −0.0008 (13) | −0.0064 (13) | 0.0059 (11) |
C3 | 0.0523 (19) | 0.0360 (15) | 0.061 (2) | −0.0116 (15) | −0.0226 (16) | 0.0051 (14) |
O1 | 0.0343 (10) | 0.0508 (12) | 0.0283 (10) | −0.0078 (9) | −0.0042 (8) | −0.0022 (8) |
O2 | 0.0432 (12) | 0.0741 (16) | 0.0449 (13) | 0.0183 (12) | −0.0127 (10) | −0.0115 (11) |
C4 | 0.0287 (13) | 0.0375 (14) | 0.0339 (14) | −0.0045 (12) | −0.0064 (11) | −0.0045 (11) |
C5 | 0.0330 (14) | 0.0394 (14) | 0.0291 (14) | −0.0040 (12) | −0.0038 (11) | −0.0031 (11) |
C6 | 0.0398 (15) | 0.0456 (16) | 0.0306 (14) | 0.0047 (13) | −0.0003 (12) | −0.0034 (12) |
C7 | 0.0398 (16) | 0.0488 (17) | 0.0413 (17) | 0.0117 (14) | −0.0032 (13) | −0.0023 (13) |
C8 | 0.0430 (16) | 0.0457 (16) | 0.0331 (15) | −0.0038 (14) | −0.0107 (12) | 0.0036 (12) |
C9 | 0.052 (2) | 0.090 (3) | 0.0283 (16) | 0.0104 (19) | 0.0000 (14) | −0.0078 (16) |
C10 | 0.0446 (18) | 0.087 (3) | 0.0346 (17) | 0.0216 (18) | −0.0033 (14) | −0.0120 (16) |
N3 | 0.0543 (18) | 0.0620 (18) | 0.0407 (16) | −0.0015 (15) | −0.0138 (13) | 0.0067 (13) |
O3 | 0.079 (2) | 0.147 (3) | 0.0583 (19) | 0.052 (2) | −0.0207 (16) | 0.0044 (19) |
O4 | 0.090 (2) | 0.131 (3) | 0.0339 (15) | 0.017 (2) | −0.0135 (14) | 0.0035 (16) |
O5 | 0.0283 (10) | 0.0424 (11) | 0.0415 (12) | −0.0039 (9) | −0.0024 (8) | −0.0005 (9) |
Cd—N1i | 2.254 (2) | C4—C5 | 1.513 (4) |
Cd—N1 | 2.254 (2) | C5—C10 | 1.383 (4) |
Cd—O1i | 2.364 (2) | C5—C6 | 1.385 (4) |
Cd—O1 | 2.364 (2) | C6—C7 | 1.383 (4) |
Cd—O5i | 2.370 (2) | C6—H6A | 0.9300 |
Cd—O5 | 2.370 (2) | C7—C8 | 1.375 (4) |
N1—C1 | 1.308 (4) | C7—H7A | 0.9300 |
N1—C3 | 1.351 (4) | C8—C9 | 1.369 (5) |
C1—N2 | 1.330 (4) | C8—N3 | 1.471 (4) |
C1—H1A | 0.9300 | C9—C10 | 1.377 (5) |
C2—N2 | 1.343 (4) | C9—H9A | 0.9300 |
C2—C3 | 1.345 (4) | C10—H10A | 0.9300 |
C2—H2A | 0.9300 | N3—O3 | 1.199 (4) |
C3—H3A | 0.9300 | N3—O4 | 1.218 (4) |
O1—C4 | 1.263 (3) | O5—H5A | 0.842 (10) |
O2—C4 | 1.245 (4) | O5—H5B | 0.842 (10) |
Cg1···Cg1ii | 3.6549 (2) | ||
N1i—Cd—N1 | 180.0 | C4—O1—Cd | 120.39 (17) |
N1i—Cd—O1i | 86.19 (8) | O2—C4—O1 | 125.1 (3) |
N1—Cd—O1i | 93.81 (8) | O2—C4—C5 | 117.7 (3) |
N1i—Cd—O1 | 93.81 (8) | O1—C4—C5 | 117.2 (2) |
N1—Cd—O1 | 86.19 (8) | C10—C5—C6 | 118.9 (3) |
O1i—Cd—O1 | 180.0 | C10—C5—C4 | 118.3 (3) |
N1i—Cd—O5i | 88.39 (8) | C6—C5—C4 | 122.8 (3) |
N1—Cd—O5i | 91.61 (8) | C7—C6—C5 | 120.5 (3) |
O1i—Cd—O5i | 91.85 (7) | C7—C6—H6A | 119.8 |
O1—Cd—O5i | 88.15 (7) | C5—C6—H6A | 119.8 |
N1i—Cd—O5 | 91.61 (8) | C8—C7—C6 | 118.5 (3) |
N1—Cd—O5 | 88.39 (8) | C8—C7—H7A | 120.7 |
O1i—Cd—O5 | 88.15 (7) | C6—C7—H7A | 120.7 |
O1—Cd—O5 | 91.85 (7) | C9—C8—C7 | 122.5 (3) |
O5i—Cd—O5 | 180.0 | C9—C8—N3 | 118.7 (3) |
C1—N1—C3 | 105.2 (2) | C7—C8—N3 | 118.8 (3) |
C1—N1—Cd | 128.3 (2) | C8—C9—C10 | 118.0 (3) |
C3—N1—Cd | 126.52 (19) | C8—C9—H9A | 121.0 |
N1—C1—N2 | 111.8 (3) | C10—C9—H9A | 121.0 |
N1—C1—H1A | 124.1 | C9—C10—C5 | 121.5 (3) |
N2—C1—H1A | 124.1 | C9—C10—H10A | 119.2 |
N2—C2—C3 | 106.7 (3) | C5—C10—H10A | 119.2 |
N2—C2—H2A | 126.6 | O3—N3—O4 | 122.8 (3) |
C3—C2—H2A | 126.6 | O3—N3—C8 | 118.8 (3) |
C1—N2—C2 | 106.7 (3) | O4—N3—C8 | 118.4 (3) |
C2—C3—N1 | 109.6 (3) | Cd—O5—H5A | 98 (2) |
C2—C3—H3A | 125.2 | Cd—O5—H5B | 120 (2) |
N1—C3—H3A | 125.2 | H5A—O5—H5B | 104 (2) |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5A···O2 | 0.84 (1) | 1.88 (1) | 2.679 (1) | 159 |
O5—H5B···O1iii | 0.84 (1) | 1.97 (1) | 2.785 (1) | 164 |
C2—H2A···O5iv | 0.93 | 2.58 | 3.244 (1) | 129 |
C3—H3A···O5v | 0.93 | 2.43 | 3.344 (1) | 169 |
C10—H10A···O2 | 0.93 | 2.42 | 2.751 (4) | 101 |
Symmetry codes: (iii) x−1, y, z; (iv) x, y−1, z; (v) −x, −y+2, −z. |
Experimental details
Crystal data | |
Chemical formula | [Cd(C7H4NO4)2(C3H4N2)2(H2O)2] |
Mr | 614.80 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 5.8017 (12), 8.0253 (16), 12.879 (3) |
α, β, γ (°) | 77.99 (3), 88.42 (3), 85.16 (3) |
V (Å3) | 584.4 (2) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.00 |
Crystal size (mm) | 0.33 × 0.14 × 0.09 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.989, 0.989 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5719, 2627, 2511 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.076, 1.24 |
No. of reflections | 2627 |
No. of parameters | 175 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.54, −0.80 |
Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5A···O2 | 0.84 (1) | 1.88 (1) | 2.679 (1) | 159.0 |
O5—H5B···O1i | 0.84 (1) | 1.97 (1) | 2.785 (1) | 164.0 |
C2—H2A···O5ii | 0.93 | 2.58 | 3.244 (1) | 129.0 |
C3—H3A···O5iii | 0.93 | 2.43 | 3.344 (1) | 169.0 |
C10—H10A···O2 | 0.93 | 2.42 | 2.751 (4) | 101.0 |
Symmetry codes: (i) x−1, y, z; (ii) x, y−1, z; (iii) −x, −y+2, −z. |
Acknowledgements
This project was supported by the Scientific Research Fund of Ningbo University (grant No. XKL069). Sincere thanks are also extended to the K. C. Wong Magna Fund in Ningbo University.
References
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Hsu, S.-C., Lo, S.-H., Kao, C.-C. & Lin, C.-H. (2011). Acta Cryst. E67, m65. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kuang, Y.-F., Li, C.-H., Li, W. & Yang, Y.-Q. (2007). Chin. J. Struct. Chem. 26, 749–752. CAS Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2004). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zheng, Y.-Q., Cheng, D.-Y., Lin, J.-L., Li, Z.-F. & Wang, X.-W. (2008). Eur. J. Inorg. Chem. pp. 4453–4461. Web of Science CSD CrossRef Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Aromatic carboxyl acid complexes have been paid great attention these years for their potential applications in gas storage, separation, catalysis, magnetism, luminescence, and drug delivery (Kuang et al., 2007). As a N-containing aromatic carboxyl acid, nitrobenzoic acid has been widely used in dye intermediate, organic synthesis, sensitization material, functional pigment (Hsu et al., 2011). So far, to our knowledge, cadmium complexes constructed from 4-nitrobenzoato and imidazole have not been reported. In order to get new CdII complexes with novel functions and discover their structure-property relationship, a new complex [Cd(C7H4NO4)(C3H4N2)(H2O)] was synthesized.
The asymmetric unit of [Cd(C7H4NO4)(C3H4N2)(H2O)] consists of a Cd2+ ion lying on an inversion centre, a 4-NBA- ion (4-HNBA = 4-nitrobenzoic acid), one imidazole ligand and one lattice water as illustrated in Fig. 1. The Cd2+ cation is octahedrally coordinated by two N atoms of imidazole ligands, two O atoms from two 4-NBA- ions and two O atoms from two lattice water molecules; it takes a (4 + 2) octahedral geometry, with the oxygen atoms located in the equatorial plane (Cd—O1 = 2.364 (2) Å, Cd—O5 = 2.367 (2) Å, and the two nitrogen atoms occupying the axial position (Cd—N1 = 2.255 (2) Å). Table 1 presents the \p···\p contact information involving the C3N2 ring (centroid, Cg1) and Table 2, the more meaningful H-bonds in the structure; the most important ones are those involving water H's. The one described in the first entry in Table 2 is intramolecular; the seocnd one, instead defines chains along a (Figure 2, vertical arrays). The weak one involving C2—H2A (Table 2, third entry) and the π–π contact (Table 1) link chains into a two-dimensional supramolecular network parallel to (001) as illustrated in Figure 2. Finaly, the remaining weak H-bonds link these 2D structures into a 3D supramolecular architecture (Figure 3).