Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103027847/ob1153sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103027847/ob1153Isup2.hkl |
CCDC reference: 233099
CdCl2·2H2O (0.11 g, 0.5 mmol) was added to an aqueous solution (20 ml) containing succinic acid (0.06 g, 0.5 mmol) and NaOH (0.04 g, 1 mmol). After refluxing the mixture for 1 h, an aqueous solution (10 ml) of benzimidazole (0.12 g, 1 mmol) was added. The solution was refluxed for 3 h and filtered. After cooling to room temperature, the solution was filtered once more. Single crystals of (I) were obtained from the filtrate after 40 d.
H atoms on methylene and that of the water molecule were located in difference Fourier maps and included in the structure factor calculations in fixed positions, with Uiso(H) = 0.05 Å2. The H atoms of the benzimidazole ligand were placed in calculated positions, with C—H = 0.93 and N—H = 0.86 Å, and included in the final cycles of refinement using a riding model, with Uiso(H) = 1.2Ueq of the carrier atom.
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Molecular Structure Corporation and Rigaku, 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).
[Cd(C4H4O4)(C7H6N2)2(H2O)] | F(000) = 968 |
Mr = 482.76 | Dx = 1.788 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 6608 reflections |
a = 13.1406 (11) Å | θ = 2.8–26.0° |
b = 14.0664 (12) Å | µ = 1.26 mm−1 |
c = 9.7823 (10) Å | T = 295 K |
β = 97.415 (19)° | Prism, colourless |
V = 1793.0 (3) Å3 | 0.32 × 0.24 × 0.16 mm |
Z = 4 |
Rigaku R-AXIS RAPID diffractometer | 2061 independent reflections |
Radiation source: fine-focus sealed tube | 1922 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
Detector resolution: 10.00 pixels mm-1 | θmax = 27.5°, θmin = 2.1° |
ω scans | h = −17→17 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −18→18 |
Tmin = 0.660, Tmax = 0.818 | l = −12→12 |
8568 measured reflections |
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)] = 0.023 | H-atom parameters constrained |
wR(F2) = 0.072 | w = 1/[σ2(Fo2) + (0.041P)2 + 0.6321P] where P = (Fo2 + 2Fc2)/3 |
S = 1.34 | (Δ/σ)max = 0.002 |
2061 reflections | Δρmax = 0.64 e Å−3 |
130 parameters | Δρmin = −0.56 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0097 (6) |
[Cd(C4H4O4)(C7H6N2)2(H2O)] | V = 1793.0 (3) Å3 |
Mr = 482.76 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 13.1406 (11) Å | µ = 1.26 mm−1 |
b = 14.0664 (12) Å | T = 295 K |
c = 9.7823 (10) Å | 0.32 × 0.24 × 0.16 mm |
β = 97.415 (19)° |
Rigaku R-AXIS RAPID diffractometer | 2061 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 1922 reflections with I > 2σ(I) |
Tmin = 0.660, Tmax = 0.818 | Rint = 0.015 |
8568 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | 0 restraints |
wR(F2) = 0.072 | H-atom parameters constrained |
S = 1.34 | Δρmax = 0.64 e Å−3 |
2061 reflections | Δρmin = −0.56 e Å−3 |
130 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 | ||
Cd | 0.5000 | 0.0000 | 0.5000 | 0.02326 (11) | |
O1 | 0.41795 (10) | 0.13344 (9) | 0.54720 (13) | 0.0325 (3) | |
O2 | 0.36730 (12) | 0.17604 (12) | 0.32953 (15) | 0.0401 (4) | |
O3 | 0.5000 | 0.04827 (13) | 0.2500 | 0.0260 (4) | |
N1 | 0.75909 (13) | 0.18721 (12) | 0.66107 (16) | 0.0353 (4) | |
H1 | 0.7829 | 0.2301 | 0.7192 | 0.042* | |
N3 | 0.64934 (11) | 0.08462 (11) | 0.55024 (15) | 0.0288 (3) | |
C2 | 0.66391 (16) | 0.15018 (16) | 0.6472 (2) | 0.0323 (4) | |
H2 | 0.6137 | 0.1688 | 0.7004 | 0.039* | |
C4 | 0.77069 (17) | 0.02604 (18) | 0.3868 (3) | 0.0382 (4) | |
H4 | 0.7252 | −0.0165 | 0.3385 | 0.046* | |
C5 | 0.86832 (19) | 0.0381 (2) | 0.3535 (3) | 0.0522 (6) | |
H5 | 0.8889 | 0.0033 | 0.2811 | 0.063* | |
C6 | 0.93754 (18) | 0.1017 (2) | 0.4260 (3) | 0.0540 (6) | |
H6 | 1.0032 | 0.1076 | 0.4011 | 0.065* | |
C7 | 0.91057 (16) | 0.15537 (17) | 0.5330 (2) | 0.0451 (5) | |
H7 | 0.9565 | 0.1974 | 0.5815 | 0.054* | |
C8 | 0.81125 (14) | 0.14387 (14) | 0.56519 (19) | 0.0317 (4) | |
C9 | 0.74218 (13) | 0.07969 (13) | 0.49521 (19) | 0.0281 (4) | |
C10 | 0.37000 (13) | 0.18563 (12) | 0.45745 (19) | 0.0254 (4) | |
C11 | 0.30641 (13) | 0.26530 (13) | 0.50791 (19) | 0.0272 (4) | |
H3 | 0.4528 | 0.0907 | 0.2641 | 0.050* | |
H11A | 0.3154 | 0.3222 | 0.4585 | 0.050* | |
H11B | 0.3291 | 0.2805 | 0.5953 | 0.050* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd | 0.01888 (14) | 0.02134 (15) | 0.02911 (15) | 0.00152 (5) | 0.00142 (8) | −0.00038 (5) |
O1 | 0.0324 (7) | 0.0298 (7) | 0.0353 (7) | 0.0115 (5) | 0.0046 (5) | 0.0036 (6) |
O2 | 0.0446 (9) | 0.0444 (9) | 0.0321 (7) | 0.0204 (7) | 0.0078 (6) | 0.0018 (6) |
O3 | 0.0246 (8) | 0.0263 (9) | 0.0274 (8) | 0.000 | 0.0041 (7) | 0.000 |
N1 | 0.0384 (9) | 0.0352 (9) | 0.0312 (8) | −0.0114 (7) | 0.0002 (7) | −0.0057 (7) |
N3 | 0.0252 (7) | 0.0302 (8) | 0.0302 (7) | −0.0037 (6) | 0.0010 (6) | −0.0015 (6) |
C2 | 0.0334 (10) | 0.0342 (10) | 0.0292 (9) | −0.0057 (8) | 0.0037 (8) | −0.0019 (8) |
C4 | 0.0329 (11) | 0.0364 (10) | 0.0450 (11) | −0.0023 (10) | 0.0035 (9) | −0.0085 (11) |
C5 | 0.0421 (13) | 0.0580 (16) | 0.0602 (15) | −0.0013 (12) | 0.0203 (11) | −0.0122 (13) |
C6 | 0.0326 (11) | 0.0623 (16) | 0.0696 (16) | −0.0079 (11) | 0.0162 (11) | −0.0034 (13) |
C7 | 0.0297 (10) | 0.0476 (13) | 0.0569 (13) | −0.0148 (9) | 0.0013 (9) | 0.0014 (11) |
C8 | 0.0303 (9) | 0.0320 (9) | 0.0314 (9) | −0.0056 (7) | −0.0018 (7) | 0.0025 (7) |
C9 | 0.0228 (8) | 0.0282 (9) | 0.0324 (8) | −0.0024 (7) | 0.0004 (7) | 0.0023 (7) |
C10 | 0.0194 (7) | 0.0233 (8) | 0.0343 (9) | 0.0023 (6) | 0.0062 (7) | 0.0014 (7) |
C11 | 0.0247 (8) | 0.0239 (9) | 0.0334 (8) | 0.0048 (7) | 0.0050 (7) | −0.0006 (7) |
Cd—O1 | 2.2421 (13) | C4—C9 | 1.392 (3) |
Cd—N3 | 2.2936 (15) | C4—H4 | 0.9300 |
Cd—O3 | 2.5381 (5) | C5—C6 | 1.401 (4) |
O1—C10 | 1.251 (2) | C5—H5 | 0.9300 |
O2—C10 | 1.255 (2) | C6—C7 | 1.374 (4) |
O3—H3 | 0.884 | C6—H6 | 0.9300 |
N1—C2 | 1.345 (3) | C7—C8 | 1.391 (3) |
N1—C8 | 1.374 (3) | C7—H7 | 0.9300 |
N1—H1 | 0.8600 | C8—C9 | 1.395 (3) |
N3—C2 | 1.319 (3) | C10—C11 | 1.518 (2) |
N3—C9 | 1.397 (2) | C11—C11i | 1.532 (3) |
C2—H2 | 0.9300 | C11—H11A | 0.950 |
C4—C5 | 1.374 (3) | C11—H11B | 0.894 |
O1—Cd—N3 | 86.69 (5) | C7—C6—C5 | 121.5 (2) |
O1—Cd—O3 | 91.96 (5) | C7—C6—H6 | 119.3 |
N3—Cd—O3 | 87.78 (5) | C5—C6—H6 | 119.3 |
C10—O1—Cd | 123.99 (12) | C6—C7—C8 | 116.8 (2) |
Cdii—O3—Cd | 148.96 (8) | C6—C7—H7 | 121.6 |
Cdii—O3—H3 | 114.7 | C8—C7—H7 | 121.6 |
Cd—O3—H3 | 86.7 | N1—C8—C7 | 131.95 (19) |
C2—N1—C8 | 107.38 (16) | N1—C8—C9 | 105.77 (16) |
C2—N1—H1 | 126.3 | C7—C8—C9 | 122.28 (19) |
C8—N1—H1 | 126.3 | C4—C9—C8 | 120.17 (18) |
C2—N3—C9 | 105.00 (15) | C4—C9—N3 | 130.90 (17) |
C2—N3—Cd | 123.89 (13) | C8—C9—N3 | 108.89 (16) |
C9—N3—Cd | 131.08 (12) | O1—C10—O2 | 125.72 (16) |
N3—C2—N1 | 112.94 (18) | O1—C10—C11 | 116.99 (16) |
N3—C2—H2 | 123.5 | O2—C10—C11 | 117.25 (16) |
N1—C2—H2 | 123.5 | C10—C11—C11i | 109.02 (18) |
C5—C4—C9 | 117.7 (2) | C10—C11—H11A | 110.3 |
C5—C4—H4 | 121.2 | C11i—C11—H11A | 111.6 |
C9—C4—H4 | 121.2 | C10—C11—H11B | 111.0 |
C4—C5—C6 | 121.6 (2) | C11i—C11—H11B | 111.3 |
C4—C5—H5 | 119.2 | H11A—C11—H11B | 103.7 |
C6—C5—H5 | 119.2 | H3—O3—H3ii | 95.1 |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x+1, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2iii | 0.86 | 1.96 | 2.799 (2) | 166 |
O3—H3···O2 | 0.88 | 1.82 | 2.688 (2) | 168 |
Symmetry code: (iii) x+1/2, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cd(C4H4O4)(C7H6N2)2(H2O)] |
Mr | 482.76 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 295 |
a, b, c (Å) | 13.1406 (11), 14.0664 (12), 9.7823 (10) |
β (°) | 97.415 (19) |
V (Å3) | 1793.0 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.26 |
Crystal size (mm) | 0.32 × 0.24 × 0.16 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.660, 0.818 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8568, 2061, 1922 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.072, 1.34 |
No. of reflections | 2061 |
No. of parameters | 130 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.64, −0.56 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), PROCESS-AUTO, CrystalStructure (Molecular Structure Corporation and Rigaku, 2002), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Cd—O1 | 2.2421 (13) | C10—C11 | 1.518 (2) |
Cd—N3 | 2.2936 (15) | C11—C11i | 1.532 (3) |
Cd—O3 | 2.5381 (5) | ||
O1—Cd—N3 | 86.69 (5) | C10—O1—Cd | 123.99 (12) |
O1—Cd—O3 | 91.96 (5) | Cdii—O3—Cd | 148.96 (8) |
N3—Cd—O3 | 87.78 (5) |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x+1, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2iii | 0.86 | 1.96 | 2.799 (2) | 166 |
O3—H3···O2 | 0.88 | 1.82 | 2.688 (2) | 168 |
Symmetry code: (iii) x+1/2, −y+1/2, z+1/2. |
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In carboxylate-bridging metal complexes, a variety of bridging modes, such as µ2, µ3 and µ4 bridges, have been found (Ng, 1998; Rastsvetaeva et al., 1996; Ng & Kumar Das, 1993). Some recent structure determinations have shown that the coordination mode of the carboxylate anion is related to the hydrogen bonding between carboxylate and imidazole ligands (Liu et al., 2003). In order to study the effect of this hydrogen bonding between carboxylate and neighbouring ligands on the coordination mode of the carboxylate, a series of metal complexes with both dicarboxylate and benzimidazole ligands has been prepared in this laboratory. The title compound, (I), is one of these and its crystal stucture is presented here. \sch
The structure of (I) is shown in Fig. 1. This CdII complex is polymeric, and the repeat unit contains a CdII atom, a water molecule, a succinate dianion and two benzimidazole molecules. The Cd atom is located on an inversion centre. The coordination geometry is an elongated octahedron, formed by succinate dianions, benzimidazole ligands and water molecules, with a normal Cd—O1 bond length of 2.2421 (13) Å and a longer Cd—O3 bond distance (discussed below).
The succinate dianion is located on an inversion centre. The planar carbon skeleton is approximately perpendicular to the carboxyl group, with a dihedral angle of 78.56 (17)°. Each succinate dianion bridges two adjacent Cd atoms via both terminal carboxyl groups, to form the succinate-bridged polymeric chain shown in Fig. 1. The carboxyl group coordinates to the Cd atom in a monodentate mode, and the uncoordinated carboxyl atom O2 is hydrogen-bonded to the neighbouring coordinated water molecule (Fig. 1) and benzimidazole ligand (Fig. 2 and Table 2).
The coordinated water atom O3 is located on a twofold axis and links adjacent succinate-bridged chains to form water-bridged polymeric chains along the [001] direction (Fig. 2). Two succinate-bridged chains linked by the water molecule extend along the [110] and [110] directions, respectively, separated by 4.8912 (10) Å, a half of the c length. Thus, these polymeric chains are nearly perpendicular to each other and form the three-dimensional polymeric structure (Fig. 3). O—H.·O and N—H.·O hydrogen bonds (Table 2) stabilize the three-dimensional polymeric structure of (I).
The Cd—O3 bond distance of 2.5381 (5) Å is significantly longer than the Cd—O(water) bonds found in analogous reported structures, for example 2.373 (3) Å in aqua-nicotinato-cadmium(II) (Zhang et al., 1996) and 2.364–2.279 Å in diaqua-succinato-cadmium(II) (Griffith et al., 1982). However, it is comparable with the Cd—O(µ2-H2O) bond distances found in some µ2-aqua-cadmium(II) complexes, for example 2.537 Å in catena[bis(µ2-aqua)-hexakis(µ2-cyano)-aqua-di-cadmium(II)-di-copper(I)] (Nishikiori, 1996) and 2.619 Å in bis(µ2-aqua)bis[triaqua(µ2-phenylenediamine-tetraacetato)dicadmium(II)] (Nakasuka et al., 1986). The Cd—O3—Cdii bond angle in (I) is 148.96 (8)°, which is much larger than the values of 113.8 and 104.8°, respectively, in the µ2-aqua-cadmium(II) complexes cited above [symmetry code: (ii) 1 − x, y, 1/2 − z]. However, the Cd—O(µ2-H2O) bond distances are essentially the same in these complexes. This fact may suggest an electrostatic bonding interaction between the Cd atom and the bridging water molecule.
The benzimidazole ligand displays normal geometry in (I). A π–π stacking interaction is usually found in the structures of metal complexes with benzimidazole ligands, but no π–π stacking between the benzimidazole rings was observed in the present three-dimensional polymeric structure.