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Acta Cryst. (2012). E68, m1149    [ doi:10.1107/S1600536812033739 ]

Diaquabis(1H-imidazole-[kappa]N3)bis(4-nitrobenzoato-[kappa]O1)cadmium

Y.-L. Mao, X.-K. Yu and J.-L. Lin

Abstract top

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 [pi]-[pi] 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.

Comment top

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 ππ 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).

Related literature top

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 top

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.

Refinement top

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).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: 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).

Figures top
[Figure 1] Fig. 1. Figure 1. ORTEP view of the title compound, The dispalcement ellipsoidsare drawn at 45% probability dispalcement ellipsoids. Symmetry code: (v)1-x, 2-y, -z.
[Figure 2] Fig. 2. The two-dimensional supramolecular networks parallel to (001). In order to observe how the complex moleculars form two-dimensional layers clearly, nitrobenzene on 4-nitrobenzoato molecules which are not engaged in link the components into a two-dimensional layers were omitted.
[Figure 3] Fig. 3. The three-dimensional framework of title complex.
Diaquabis(1H-imidazole-κN3)bis(4-nitrobenzoato- κO1)cadmium top
Crystal data top
[Cd(C7H4NO4)2(C3H4N2)2(H2O)2]Z = 1
Mr = 614.80F(000) = 308
Triclinic, P1Dx = 1.747 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.8017 (12) ÅCell parameters from 5719 reflections
b = 8.0253 (16) Åθ = 3.2–27.5°
c = 12.879 (3) ŵ = 1.00 mm1
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
Data collection top
Rigaku R-AXIS RAPID
diffractometer
2627 independent reflections
Radiation source: fine-focus sealed tube2511 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
ω scansθmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
h = 67
Tmin = 0.989, Tmax = 0.989k = 1010
5719 measured reflectionsl = 1616
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.026Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.076H 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 parametersΔρmax = 0.54 e Å3
3 restraintsΔρmin = 0.80 e Å3
Crystal data top
[Cd(C7H4NO4)2(C3H4N2)2(H2O)2]γ = 85.16 (3)°
Mr = 614.80V = 584.4 (2) Å3
Triclinic, P1Z = 1
a = 5.8017 (12) ÅMo Kα radiation
b = 8.0253 (16) ŵ = 1.00 mm1
c = 12.879 (3) ÅT = 293 K
α = 77.99 (3)°0.33 × 0.14 × 0.09 mm
β = 88.42 (3)°
Data collection top
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 = 0.989Rint = 0.031
5719 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.026H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.076Δρmax = 0.54 e Å3
S = 1.24Δρmin = 0.80 e Å3
2627 reflectionsAbsolute structure: ?
175 parametersFlack parameter: ?
3 restraintsRogers parameter: ?
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cd0.50001.00000.00000.03040 (10)
N10.4161 (4)0.7310 (3)0.07261 (18)0.0351 (5)
C10.5412 (6)0.6131 (4)0.1376 (3)0.0497 (8)
H1A0.68440.62900.16320.060*
C20.2360 (6)0.4946 (4)0.1116 (3)0.0518 (8)
H2A0.12610.41600.11360.062*
N20.4388 (5)0.4676 (3)0.1627 (2)0.0500 (7)
C30.2227 (6)0.6573 (4)0.0569 (3)0.0510 (8)
H3A0.09920.71080.01470.061*
O10.7532 (3)0.9739 (3)0.14420 (15)0.0384 (5)
O20.4950 (4)1.0755 (3)0.25118 (18)0.0553 (6)
C40.6746 (5)0.9881 (4)0.2347 (2)0.0336 (6)
C50.8110 (5)0.8918 (4)0.3301 (2)0.0343 (6)
C61.0191 (5)0.7974 (4)0.3212 (2)0.0398 (7)
H6A1.07810.78930.25440.048*
C71.1397 (5)0.7150 (4)0.4110 (2)0.0451 (7)
H7A1.27980.65180.40540.054*
C81.0480 (5)0.7285 (4)0.5088 (2)0.0421 (7)
C90.8406 (6)0.8178 (5)0.5205 (3)0.0581 (10)
H9A0.78070.82350.58750.070*
C100.7234 (6)0.8990 (5)0.4301 (3)0.0568 (9)
H10A0.58210.96010.43650.068*
N31.1799 (5)0.6471 (4)0.6046 (2)0.0548 (7)
O31.3619 (6)0.5690 (5)0.5945 (3)0.1018 (13)
O41.1007 (6)0.6639 (5)0.6907 (2)0.0890 (10)
O50.1847 (3)1.1006 (3)0.09734 (16)0.0385 (5)
H5A0.252 (5)1.088 (4)0.1559 (14)0.046*
H5B0.069 (4)1.043 (4)0.112 (2)0.046*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd0.03111 (16)0.02902 (15)0.02818 (15)0.00363 (11)0.00305 (10)0.00151 (10)
N10.0371 (12)0.0309 (11)0.0343 (12)0.0032 (10)0.0033 (10)0.0009 (9)
C10.0417 (17)0.0403 (16)0.060 (2)0.0052 (14)0.0155 (15)0.0081 (14)
C20.057 (2)0.0329 (15)0.063 (2)0.0156 (15)0.0132 (17)0.0023 (14)
N20.0605 (17)0.0342 (13)0.0488 (16)0.0008 (13)0.0064 (13)0.0059 (11)
C30.0523 (19)0.0360 (15)0.061 (2)0.0116 (15)0.0226 (16)0.0051 (14)
O10.0343 (10)0.0508 (12)0.0283 (10)0.0078 (9)0.0042 (8)0.0022 (8)
O20.0432 (12)0.0741 (16)0.0449 (13)0.0183 (12)0.0127 (10)0.0115 (11)
C40.0287 (13)0.0375 (14)0.0339 (14)0.0045 (12)0.0064 (11)0.0045 (11)
C50.0330 (14)0.0394 (14)0.0291 (14)0.0040 (12)0.0038 (11)0.0031 (11)
C60.0398 (15)0.0456 (16)0.0306 (14)0.0047 (13)0.0003 (12)0.0034 (12)
C70.0398 (16)0.0488 (17)0.0413 (17)0.0117 (14)0.0032 (13)0.0023 (13)
C80.0430 (16)0.0457 (16)0.0331 (15)0.0038 (14)0.0107 (12)0.0036 (12)
C90.052 (2)0.090 (3)0.0283 (16)0.0104 (19)0.0000 (14)0.0078 (16)
C100.0446 (18)0.087 (3)0.0346 (17)0.0216 (18)0.0033 (14)0.0120 (16)
N30.0543 (18)0.0620 (18)0.0407 (16)0.0015 (15)0.0138 (13)0.0067 (13)
O30.079 (2)0.147 (3)0.0583 (19)0.052 (2)0.0207 (16)0.0044 (19)
O40.090 (2)0.131 (3)0.0339 (15)0.017 (2)0.0135 (14)0.0035 (16)
O50.0283 (10)0.0424 (11)0.0415 (12)0.0039 (9)0.0024 (8)0.0005 (9)
Geometric parameters (Å, º) top
Cd—N1i2.254 (2)C4—C51.513 (4)
Cd—N12.254 (2)C5—C101.383 (4)
Cd—O1i2.364 (2)C5—C61.385 (4)
Cd—O12.364 (2)C6—C71.383 (4)
Cd—O5i2.370 (2)C6—H6A0.9300
Cd—O52.370 (2)C7—C81.375 (4)
N1—C11.308 (4)C7—H7A0.9300
N1—C31.351 (4)C8—C91.369 (5)
C1—N21.330 (4)C8—N31.471 (4)
C1—H1A0.9300C9—C101.377 (5)
C2—N21.343 (4)C9—H9A0.9300
C2—C31.345 (4)C10—H10A0.9300
C2—H2A0.9300N3—O31.199 (4)
C3—H3A0.9300N3—O41.218 (4)
O1—C41.263 (3)O5—H5A0.842 (10)
O2—C41.245 (4)O5—H5B0.842 (10)
Cg1···Cg1ii3.6549 (2)
N1i—Cd—N1180.0C4—O1—Cd120.39 (17)
N1i—Cd—O1i86.19 (8)O2—C4—O1125.1 (3)
N1—Cd—O1i93.81 (8)O2—C4—C5117.7 (3)
N1i—Cd—O193.81 (8)O1—C4—C5117.2 (2)
N1—Cd—O186.19 (8)C10—C5—C6118.9 (3)
O1i—Cd—O1180.0C10—C5—C4118.3 (3)
N1i—Cd—O5i88.39 (8)C6—C5—C4122.8 (3)
N1—Cd—O5i91.61 (8)C7—C6—C5120.5 (3)
O1i—Cd—O5i91.85 (7)C7—C6—H6A119.8
O1—Cd—O5i88.15 (7)C5—C6—H6A119.8
N1i—Cd—O591.61 (8)C8—C7—C6118.5 (3)
N1—Cd—O588.39 (8)C8—C7—H7A120.7
O1i—Cd—O588.15 (7)C6—C7—H7A120.7
O1—Cd—O591.85 (7)C9—C8—C7122.5 (3)
O5i—Cd—O5180.0C9—C8—N3118.7 (3)
C1—N1—C3105.2 (2)C7—C8—N3118.8 (3)
C1—N1—Cd128.3 (2)C8—C9—C10118.0 (3)
C3—N1—Cd126.52 (19)C8—C9—H9A121.0
N1—C1—N2111.8 (3)C10—C9—H9A121.0
N1—C1—H1A124.1C9—C10—C5121.5 (3)
N2—C1—H1A124.1C9—C10—H10A119.2
N2—C2—C3106.7 (3)C5—C10—H10A119.2
N2—C2—H2A126.6O3—N3—O4122.8 (3)
C3—C2—H2A126.6O3—N3—C8118.8 (3)
C1—N2—C2106.7 (3)O4—N3—C8118.4 (3)
C2—C3—N1109.6 (3)Cd—O5—H5A98 (2)
C2—C3—H3A125.2Cd—O5—H5B120 (2)
N1—C3—H3A125.2H5A—O5—H5B104 (2)
Symmetry codes: (i) x+1, y+2, z; (ii) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H5A···O20.84 (1)1.88 (1)2.679 (1)159
O5—H5B···O1iii0.84 (1)1.97 (1)2.785 (1)164
C2—H2A···O5iv0.932.583.244 (1)129
C3—H3A···O5v0.932.433.344 (1)169
C10—H10A···O20.932.422.751 (4)101
Symmetry codes: (iii) x1, y, z; (iv) x, y1, z; (v) x, y+2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H5A···O20.84 (1)1.88 (1)2.679 (1)159.0
O5—H5B···O1i0.84 (1)1.97 (1)2.785 (1)164.0
C2—H2A···O5ii0.932.583.244 (1)129.0
C3—H3A···O5iii0.932.433.344 (1)169.0
C10—H10A···O20.932.422.751 (4)101.0
Symmetry codes: (i) x1, y, z; (ii) x, y1, z; (iii) x, y+2, z.
Acknowledgements top

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
References top

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.

Hsu, S.-C., Lo, S.-H., Kao, C.-C. & Lin, C.-H. (2011). Acta Cryst. E67, m65.

Kuang, Y.-F., Li, C.-H., Li, W. & Yang, Y.-Q. (2007). Chin. J. Struct. Chem. 26, 749–752.

Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.

Rigaku/MSC (2004). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Zheng, Y.-Q., Cheng, D.-Y., Lin, J.-L., Li, Z.-F. & Wang, X.-W. (2008). Eur. J. Inorg. Chem. pp. 4453–4461.