Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615005823/ly3010sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615005823/ly3010Isup2.hkl | |
Microsoft Word (DOC) file https://doi.org/10.1107/S2053229615005823/ly3010Isup3.doc |
CCDC reference: 1055478
Metal-organic frameworks (MOFs) have attracted extensive attention owing to their versatile architectures and potential applications in optical, biochemical, electronic, magnetic and porous materials (Wu et al., 2011; Kang et al., 2015; Zhao et al., 2015). A large number of MOFs based on mixed ligands have subsequently been reported (Jiang et al., 2011; Ju et al., 2014). The assembly of MOFs is mainly affected by a combination of a few factors, including the metal ion, organic ligand and auxiliary ligand, the metal-to-ligand ratio, the solvent and the reaction temperature (Ma, Abney & Lin, 2009 OR Ma, Wang et al., 2009 ?; Li et al., 2010; Zhang et al., 2012; Luo et al., 2014). The organic ligands are the key to obtaining such intriguing topologies and functional materials. Flexible ligands can adopt additional different conformations according to the geometric requirements of different metal ions, and may afford unpredictable and interesting supramolecular networks (Fang et al., 2010; Zhu et al., 2011; Li et al., 2012). Self-assembly between metal ions and flexible ligands has been proven to be a most effective synthetic design to achieve chiral or helical frameworks and high-nuclear complexes (Zhu et al., 2010) or single helices (Wang et al., 2007), with potential applications in selective catalysis, separation and so on (Ma, Abney & Lin, 2009 OR Ma, Wang et al., 2009 ?; Zhang et al., 2010). Cyclohexanedicarboxylic acid is a flexible ditopic ligand which possesses three possible conformations of its two carboxylate groups: a,a-trans-chdcH2, e,e-trans-chdcH2 and e,a-cis-chdcH2 (Scheme 1 in the Supporting information) and has been reported to be a good candidate for the self-assenbly of coordination polymers due to its superior bridging ability and different coordination modes (Yoon et al., 2012; Su et al., 2012; Chen et al., 2013 OR 2014 ?; Hao et al., 2014; Wang et al., 2014). It is a good strategy to select mixed ligands for the construction of coordination polymers. Pyridylbenzimidazoles have been employed as auxiliary ligands to obtain many novel frameworks with particular structures and properties (Zhang et al., 2011; Chen et al., 2013 OR 2014 ?; Abed et al., 2014). However, polymers constructed from cyclohexanedicarboxylic acid and pyridylbenzimidazole have rarely been reported. Based on these considerations, we chose cyclohexane-1,4-dicarboxylic acid as the primary ligand and introduced 2-(4-pyridyl)benzimidazole as the auxiliary ligand. As expected, a new CdII compound, (I), with a two-dimensional polymeric framework was obtained.
A mixture of Cd(CH3COO)2·2H2O (0.053 g, 0.2 mmol), 4-PyBIm (0.037 g, 0.2 mmol) and H2chdc (0.034 g, 0.2 mmol) in H2O (9 ml) was sealed in a 23 ml Teflon-lined stainless steel reactor. The mixture was kept at 433 K for 72 h and then cooled to room temperature at a rate of 5 K h-1. Colourless block crystals of (I) suitable for X-ray analysis were obtained, and these were washed with distilled water and dried in air (yield 25% based on Cd). Elemental analysis, calculated for C96H96Cd6N12O28 (%): C 50.35, H 2.83, N 4.90; found (%): C 50.31, H 2.80, N 4.89.
Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms attached to C and N atoms were fixed geometrically and treated as riding, with C—H = 0.98 Å (methine), 0.97 Å (methylene) and 0.93 Å (aromatic), and N—H = 0.86 Å, and with Uiso(H) = 1.2Ueq(C,N). The H atoms of the water molecules were located in a difference Fourier map and included in the refinement using the restraints O—H = 0.82 (1) Å and H···H = 1.39 (2) Å, and with Uiso(H) = 1.5Ueq(O).
As shown in Fig. 1, the asymmetric unit contains one and a half of CdII ions, one 4-PyBIm ligand, one and a half 1,4-chdc2- ligands and one coordinated water molecule. The 1,4-chdc2- ligands possess two conformations, e,e-trans-chdc2-, and e,a-cis-chdc2-, in (I). The Cd1 and Cd2 centres adopt different coordination geometries. The Cd2 cation, sitting on a crystallographic two-fold rotation axis, is ligated to six carboxylate O atoms from four distinct e,a-cis-1,4-chdc2- ligands and two different e,e-trans-1,4-chdc2- ligands to furnish a distorted octahedral coordination geometry. The Cd2—O distances range from 2.217 (3) to 2.299 (2) Å. However, the Cd1 centre shows a distorted pentagonal–bipyramidal geometry, coordinated by one N atom from 4-PyBIm and six O atoms from two different e,e-trans-1,4-chdc2- ligands, one cis-1,4-chdc2- ligand and one aqua molecule. The N atom from 4-PyBIm and one O atom from one of the cis-1,4-chdc2- ligands occupy the axial sites, with the other O atoms forming the equatorial plane. Atoms O3i, O4i, O5, O6 and O7 on the equatorial plane are almost coplanar [symmetry code: ???]. The average deviation from the plane is 0.019 Å. The Cd1—O bond lengths vary from 2.229 (2) to 2.803 (3) Å and the Cd1—N bond length is 2.341 (3) Å. The Cd—O and Cd—N distances are comparable with those reported previously (Clegg et al., 1995; Liu et al., 2011; Wang et al., 2011). The crystallographically independent chdc2- ligand exhibits an e,a-cis-conformation and adopts a pentadentate coordination mode: one carboxylate group, acting in a bis-monodentate coordination mode, coordinates to an adjacent CdII centre, while the other carboxylate group adopts a chelate/bridging tridentate coordination mode connecting two CdII ions. The crystallographically symmetric chdc2- ligand shows an e,e-trans-1,4-chdc2- conformation and its carboxylate groups all display a chelate/bridging tridentate coordination mode. Two adjacent CdII ions are joined by one carboxylate group with bis-monodentate coordination modes and two carboxylate groups with chelate/bridging coordination modes, with a Cd···Cd separation of 3.808 Å.
Complex (I) exhibits a two-dimensional polymeric framework based on [Cd3(chdc2-)3(4-PyBIm)2(H2O)2] units. Three neighbouring CdII centres are joined by four carboxylate groups from two cis-1,4-chdc2- ligands, resulting in a trinuclear {Cd3(COO)4} cluster. These {Cd3(COO)4} clusters are connected by the cyclohexyl groups of cis-1,4-chdc2- ligands to form a one-dimensional loop-like chain. Adjacent chains are further linked by trans-1,4-chdc2- ligands, leading to an interesting two-dimensional network, which is similar to that in the complex [Cd3(L)2(cis-1,4-chdc)2(trans-1,4-chdc)] [L = 2-(4-fluoropheny1)-1H-imidazo[4,5-f][1,10] phenanthroline and 1,4-H2chdc = l,4-cyclohexanedicarboxylic acid; Xu et al., 2010]. From a topological point of view, the trinuclear CdII cluster can be defined as a four-connected node. Thus, the overall topology of the two-dimensional framework is best described as a four-connected (4,4) network (Fig.4).
Hydrogen bonds [O7—H2···N2(-x + 1, -y - 1, -z) and N3—H3A···O6(x, y + 1, z)] and π–π stacking interactions are present in the structure of (I). The 4-PyBIm ligand is a hydrogen-bond donor through its imidazolyl NH group to a carboxylate O atom (O6) of an e,a-trans-chdc2- ligand within the layer. It is also a hydrogen-bond acceptor from a coordinated water molecule (O7) of another adjacent layer through the other imidazolyl N atom, forming a three-dimensional network structure, as illustrated in Fig. 5. The π–π stacking interaction exists between the pyridyl ring of one 4-PyBIm ligand and the benzene ring of a 4-PyBIm ligand in a neighbouring layer, with a centroid-to-centroid distance of 3.7727 Å.
A thermogravimetric (TG) study of (I) was performed to evaluate its thermal stability, and the resulting curve is shown in Fig. 6. The TG curve exhibits a three-step weight loss. The first weight loss of 3.09% (calculated 2.83%) at 483–528 K corresponds to the release of solvent water, while the next two weight losses of about 69.80% (calculated 70.70%) between 543 and 873 K are attributed to decomposition of the 4-PyBIm and chdc2- ligands.
The photoluminescent properties of (I) were investigated in the solid state at room temperature. Compound (I) exhibits photoluminescence under light excitation at 300 nm (Fig. 7). It gives a strong emission peak maximum at 420 nm at room temperature, and no obvious emission band is detected for free H2chdc ligands. It has been reported that the ligand 4-PyBIm has a weak emission band centred at 492 nm (Xia et al., 2005). Generally, metal-to-ligand charge transfer (MLCT) is the most common assignment for the luminescence of d10 transition metal complexes (Colacio et al., 2002). Most of the CdII–PyBIm complexes exhibit luminescence in the range 350–600 nm (Liang et al., 2006; Yang et al., 2009; Li et al., 2011). So the photoluminescence of (I) may be assigned to MLCT between CdII cations and 4-PyBIm ligands.
The IR spectrum of complex (I) shows characteristic bands of carboxylate groups at 1610 and 1570 cm-1 for antisymmetric stretching, and at 1380 cm-1 for symmetric strectching. According to the Deacon–Phillips model (Deacon et al., 1980), the separation is >200 cm-1 for monodentate carboxylate groups, whereas it is <200 cm-1 in bidentate groups. So the separation has often been used to diagnose the coordination modes of carboxylate groups. Here, the separations between νas (COO-) and νs (COO-) are 230 cm-1 and 150 cm-1 for (I), indicating monodentate and bidentate coordination modes, respectively, for the coordinated carboxylate groups. These IR results are in agreement with the crystallographic structural analysis.
Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
[Cd3(C8H10O4)3(C12H9N3)2(H2O)2] | Z = 2 |
Mr = 1274.19 | F(000) = 1276 |
Monoclinic, P2/c | Dx = 1.754 Mg m−3 |
Hall symbol: -P 2yc | Mo Kα radiation, λ = 0.71073 Å |
a = 10.366 (3) Å | θ = 2.0–27.5° |
b = 8.774 (3) Å | µ = 1.38 mm−1 |
c = 27.071 (7) Å | T = 293 K |
β = 101.48 (1)° | Prism, colourless |
V = 2412.9 (12) Å3 | 0.30 × 0.20 × 0.15 mm |
Rigaku Mercury CCD area-detector diffractometer | 5500 independent reflections |
Radiation source: fine-focus sealed tube | 4825 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5°, θmin = 2.8° |
CCD Profile fitting scans | h = −13→12 |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007) | k = −11→11 |
Tmin = 0.569, Tmax = 1.000 | l = −33→35 |
18383 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)] = 0.038 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.109 | w = 1/[σ2(Fo2) + (0.0523P)2 + 0.539P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.001 |
5500 reflections | Δρmax = 1.63 e Å−3 |
327 parameters | Δρmin = −0.99 e Å−3 |
9 restraints | Extinction correction: SHELXL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0027 (4) |
[Cd3(C8H10O4)3(C12H9N3)2(H2O)2] | V = 2412.9 (12) Å3 |
Mr = 1274.19 | Z = 2 |
Monoclinic, P2/c | Mo Kα radiation |
a = 10.366 (3) Å | µ = 1.38 mm−1 |
b = 8.774 (3) Å | T = 293 K |
c = 27.071 (7) Å | 0.30 × 0.20 × 0.15 mm |
β = 101.48 (1)° |
Rigaku Mercury CCD area-detector diffractometer | 5500 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007) | 4825 reflections with I > 2σ(I) |
Tmin = 0.569, Tmax = 1.000 | Rint = 0.041 |
18383 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 9 restraints |
wR(F2) = 0.109 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | Δρmax = 1.63 e Å−3 |
5500 reflections | Δρmin = −0.99 e Å−3 |
327 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 | ||
Cd1 | 0.13470 (2) | −0.64177 (2) | −0.120948 (8) | 0.03391 (11) | |
Cd2 | 0.0000 | −0.63992 (3) | −0.2500 | 0.03055 (12) | |
O1 | −0.0825 (3) | −0.7998 (4) | −0.20075 (13) | 0.0793 (9) | |
O2 | 0.0280 (3) | −0.8637 (3) | −0.12597 (11) | 0.0547 (7) | |
O3 | −0.0232 (3) | −1.4593 (3) | −0.19379 (11) | 0.0669 (8) | |
O4 | −0.0374 (3) | −1.4894 (3) | −0.11496 (10) | 0.0548 (6) | |
O5 | 0.2014 (2) | −0.6516 (3) | −0.19613 (9) | 0.0451 (6) | |
O6 | 0.3426 (2) | −0.7911 (3) | −0.14465 (9) | 0.0518 (6) | |
O7 | 0.1793 (3) | −0.7005 (3) | −0.03492 (9) | 0.0539 (6) | |
H2 | 0.2403 | −0.7263 | −0.0113 | 0.14 (3)* | |
N1 | 0.2861 (3) | −0.4416 (3) | −0.10222 (10) | 0.0416 (6) | |
N2 | 0.6552 (3) | −0.0846 (3) | −0.01933 (9) | 0.0385 (6) | |
N3 | 0.5460 (3) | 0.0642 (3) | −0.08077 (10) | 0.0397 (6) | |
H3A | 0.4870 | 0.0927 | −0.1061 | 0.048* | |
C1 | 0.3996 (4) | −0.4602 (4) | −0.07008 (14) | 0.0536 (9) | |
H1A | 0.4206 | −0.5572 | −0.0571 | 0.064* | |
C2 | 0.4881 (4) | −0.3445 (4) | −0.05478 (15) | 0.0531 (10) | |
H2B | 0.5660 | −0.3638 | −0.0319 | 0.064* | |
C3 | 0.4601 (3) | −0.1983 (4) | −0.07386 (11) | 0.0359 (6) | |
C4 | 0.3441 (4) | −0.1799 (4) | −0.10875 (14) | 0.0487 (8) | |
H4A | 0.3219 | −0.0850 | −0.1233 | 0.058* | |
C5 | 0.2612 (4) | −0.3032 (4) | −0.12193 (14) | 0.0515 (9) | |
H5A | 0.1842 | −0.2886 | −0.1458 | 0.062* | |
C6 | 0.5528 (3) | −0.0740 (3) | −0.05707 (11) | 0.0355 (6) | |
C7 | 0.7182 (3) | 0.0558 (4) | −0.01779 (11) | 0.0374 (6) | |
C8 | 0.8309 (4) | 0.1081 (4) | 0.01465 (12) | 0.0462 (8) | |
H8A | 0.8763 | 0.0470 | 0.0404 | 0.055* | |
C9 | 0.8729 (4) | 0.2547 (4) | 0.00711 (14) | 0.0537 (9) | |
H9A | 0.9467 | 0.2932 | 0.0287 | 0.064* | |
C10 | 0.8070 (4) | 0.3458 (4) | −0.03219 (15) | 0.0566 (10) | |
H10A | 0.8392 | 0.4428 | −0.0366 | 0.068* | |
C11 | 0.6947 (4) | 0.2953 (4) | −0.06482 (14) | 0.0522 (8) | |
H11A | 0.6506 | 0.3560 | −0.0910 | 0.063* | |
C12 | 0.6514 (3) | 0.1492 (3) | −0.05641 (12) | 0.0380 (7) | |
C13 | −0.1496 (3) | −1.0227 (3) | −0.16560 (12) | 0.0372 (7) | |
H13A | −0.2398 | −0.9834 | −0.1703 | 0.045* | |
C14 | −0.1261 (3) | −1.1182 (3) | −0.11790 (12) | 0.0385 (7) | |
H14A | −0.1354 | −1.0553 | −0.0898 | 0.046* | |
H14B | −0.0376 | −1.1567 | −0.1118 | 0.046* | |
C15 | −0.2225 (3) | −1.2510 (4) | −0.12229 (13) | 0.0443 (7) | |
H15A | −0.3105 | −1.2120 | −0.1260 | 0.053* | |
H15B | −0.2039 | −1.3101 | −0.0919 | 0.053* | |
C16 | −0.2128 (3) | −1.3525 (3) | −0.16716 (13) | 0.0400 (7) | |
H16A | −0.2842 | −1.4274 | −0.1705 | 0.048* | |
C17 | −0.2353 (4) | −1.2593 (4) | −0.21560 (14) | 0.0561 (10) | |
H17A | −0.3246 | −1.2236 | −0.2233 | 0.067* | |
H17B | −0.2217 | −1.3233 | −0.2429 | 0.067* | |
C18 | −0.1429 (4) | −1.1228 (4) | −0.21160 (13) | 0.0473 (8) | |
H18A | −0.0542 | −1.1589 | −0.2085 | 0.057* | |
H18B | −0.1640 | −1.0624 | −0.2417 | 0.057* | |
C19 | −0.0595 (3) | −0.8861 (4) | −0.16403 (14) | 0.0440 (8) | |
C20 | −0.0837 (3) | −1.4405 (3) | −0.15805 (13) | 0.0413 (7) | |
C21 | 0.3046 (3) | −0.7338 (4) | −0.18682 (12) | 0.0393 (7) | |
C22 | 0.3805 (3) | −0.7461 (4) | −0.22900 (12) | 0.0426 (7) | |
H22A | 0.3158 | −0.7480 | −0.2608 | 0.051* | |
C23 | 0.4634 (4) | −0.8859 (4) | −0.22785 (16) | 0.0518 (9) | |
H23B | 0.5292 | −0.8853 | −0.1974 | 0.062* | |
H23A | 0.4088 | −0.9746 | −0.2286 | 0.078* | |
C24 | 0.4610 (4) | −0.6021 (4) | −0.22902 (17) | 0.0581 (10) | |
H24C | 0.5196 | −0.5936 | −0.1969 | 0.070* | |
H24B | 0.4033 | −0.5154 | −0.2340 | 0.087* | |
H1 | 0.107 (5) | −0.752 (10) | −0.040 (3) | 0.30 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.03658 (17) | 0.03115 (16) | 0.03223 (16) | −0.00112 (8) | 0.00261 (11) | 0.00013 (7) |
Cd2 | 0.0334 (2) | 0.02769 (18) | 0.02850 (18) | 0.000 | 0.00107 (13) | 0.000 |
O1 | 0.0741 (16) | 0.0734 (15) | 0.0846 (16) | −0.0193 (13) | 0.0015 (13) | 0.0403 (13) |
O2 | 0.0577 (16) | 0.0423 (14) | 0.0586 (15) | −0.0175 (11) | −0.0020 (13) | 0.0041 (11) |
O3 | 0.079 (2) | 0.0548 (16) | 0.0767 (18) | 0.0056 (14) | 0.0395 (16) | −0.0204 (14) |
O4 | 0.0506 (14) | 0.0497 (14) | 0.0618 (16) | 0.0121 (12) | 0.0055 (12) | 0.0045 (12) |
O5 | 0.0307 (12) | 0.0641 (16) | 0.0384 (12) | 0.0088 (10) | 0.0019 (9) | −0.0062 (10) |
O6 | 0.0474 (14) | 0.0568 (15) | 0.0515 (14) | 0.0082 (11) | 0.0107 (11) | 0.0115 (12) |
O7 | 0.0687 (17) | 0.0504 (14) | 0.0384 (12) | 0.0048 (13) | 0.0004 (12) | 0.0083 (11) |
N1 | 0.0435 (15) | 0.0386 (14) | 0.0409 (13) | −0.0067 (12) | 0.0038 (12) | −0.0002 (11) |
N2 | 0.0443 (15) | 0.0348 (13) | 0.0338 (12) | −0.0028 (11) | 0.0015 (11) | 0.0016 (11) |
N3 | 0.0376 (14) | 0.0377 (14) | 0.0399 (13) | 0.0010 (11) | −0.0017 (11) | 0.0025 (11) |
C1 | 0.051 (2) | 0.0403 (17) | 0.061 (2) | −0.0056 (16) | −0.0081 (17) | 0.0100 (16) |
C2 | 0.051 (2) | 0.0428 (18) | 0.056 (2) | −0.0059 (15) | −0.0140 (17) | 0.0087 (15) |
C3 | 0.0353 (15) | 0.0380 (16) | 0.0349 (14) | −0.0017 (12) | 0.0081 (12) | −0.0021 (12) |
C4 | 0.0449 (19) | 0.0396 (17) | 0.055 (2) | −0.0041 (15) | −0.0052 (16) | 0.0081 (16) |
C5 | 0.0425 (19) | 0.0467 (19) | 0.059 (2) | −0.0070 (15) | −0.0050 (16) | 0.0059 (17) |
C6 | 0.0367 (15) | 0.0359 (15) | 0.0340 (14) | 0.0006 (12) | 0.0072 (12) | −0.0019 (12) |
C7 | 0.0429 (17) | 0.0360 (15) | 0.0337 (14) | −0.0038 (12) | 0.0082 (13) | −0.0035 (12) |
C8 | 0.050 (2) | 0.0486 (18) | 0.0370 (16) | −0.0075 (15) | 0.0019 (15) | −0.0010 (14) |
C9 | 0.057 (2) | 0.052 (2) | 0.0481 (19) | −0.0174 (17) | 0.0019 (17) | −0.0041 (16) |
C10 | 0.068 (3) | 0.0419 (19) | 0.059 (2) | −0.0161 (17) | 0.010 (2) | 0.0016 (16) |
C11 | 0.063 (2) | 0.0398 (17) | 0.0523 (19) | −0.0040 (17) | 0.0072 (17) | 0.0073 (16) |
C12 | 0.0421 (17) | 0.0340 (15) | 0.0376 (15) | −0.0016 (12) | 0.0071 (14) | −0.0004 (12) |
C13 | 0.0288 (14) | 0.0318 (14) | 0.0492 (16) | −0.0003 (11) | 0.0032 (12) | 0.0099 (13) |
C14 | 0.0495 (19) | 0.0304 (14) | 0.0388 (16) | 0.0001 (13) | 0.0166 (14) | 0.0000 (12) |
C15 | 0.0467 (18) | 0.0337 (15) | 0.060 (2) | 0.0038 (13) | 0.0295 (16) | 0.0070 (14) |
C16 | 0.0332 (16) | 0.0311 (15) | 0.0547 (19) | −0.0060 (11) | 0.0066 (14) | 0.0005 (13) |
C17 | 0.060 (2) | 0.050 (2) | 0.0492 (19) | −0.0122 (17) | −0.0111 (17) | 0.0028 (16) |
C18 | 0.054 (2) | 0.0486 (19) | 0.0372 (16) | −0.0090 (15) | 0.0033 (15) | 0.0105 (14) |
C19 | 0.0363 (17) | 0.0328 (15) | 0.060 (2) | −0.0002 (13) | 0.0033 (15) | 0.0129 (15) |
C20 | 0.0426 (17) | 0.0267 (14) | 0.0558 (18) | −0.0037 (12) | 0.0127 (15) | −0.0094 (13) |
C21 | 0.0308 (15) | 0.0436 (17) | 0.0427 (16) | −0.0010 (13) | 0.0052 (13) | −0.0049 (13) |
C22 | 0.0349 (16) | 0.0493 (18) | 0.0430 (16) | 0.0021 (14) | 0.0067 (13) | −0.0018 (14) |
C23 | 0.057 (2) | 0.0398 (17) | 0.067 (2) | 0.0004 (15) | 0.033 (2) | 0.0041 (17) |
C24 | 0.065 (3) | 0.0413 (17) | 0.076 (3) | −0.0023 (17) | 0.033 (2) | −0.0056 (19) |
Cd1—O2 | 2.230 (2) | C4—C5 | 1.383 (5) |
Cd1—O4i | 2.261 (3) | C4—H4A | 0.9300 |
Cd1—O5 | 2.278 (2) | C5—H5A | 0.9300 |
Cd1—O7 | 2.340 (2) | C7—C8 | 1.392 (4) |
Cd1—N1 | 2.342 (3) | C7—C12 | 1.398 (4) |
Cd1—O6 | 2.706 (3) | C8—C9 | 1.386 (5) |
Cd1—O3i | 2.801 (3) | C8—H8A | 0.9300 |
Cd1—C21 | 2.861 (3) | C9—C10 | 1.396 (5) |
Cd1—Cd2 | 3.4947 (9) | C9—H9A | 0.9300 |
Cd1—H1 | 2.47 (6) | C10—C11 | 1.386 (5) |
Cd2—O1 | 2.221 (3) | C10—H10A | 0.9300 |
Cd2—O1ii | 2.221 (3) | C11—C12 | 1.392 (4) |
Cd2—O3i | 2.243 (3) | C11—H11A | 0.9300 |
Cd2—O3iii | 2.243 (3) | C13—C19 | 1.515 (4) |
Cd2—O5 | 2.299 (2) | C13—C14 | 1.518 (4) |
Cd2—O5ii | 2.299 (2) | C13—C18 | 1.537 (5) |
Cd2—Cd1ii | 3.4947 (9) | C13—H13A | 0.9800 |
O1—C19 | 1.234 (4) | C14—C15 | 1.525 (4) |
O2—C19 | 1.246 (4) | C14—H14A | 0.9602 |
O3—C20 | 1.264 (4) | C14—H14B | 0.9601 |
O3—Cd2iv | 2.243 (3) | C15—C16 | 1.525 (5) |
O3—Cd1iv | 2.801 (3) | C15—H15A | 0.9601 |
O4—C20 | 1.246 (4) | C15—H15B | 0.9597 |
O4—Cd1iv | 2.261 (3) | C16—C20 | 1.522 (5) |
O5—C21 | 1.273 (4) | C16—C17 | 1.524 (5) |
O6—C21 | 1.238 (4) | C16—H16A | 0.9800 |
O7—H2 | 0.8357 | C17—C18 | 1.524 (5) |
O7—H1 | 0.859 (11) | C17—H17A | 0.9598 |
N1—C1 | 1.327 (4) | C17—H17B | 0.9603 |
N1—C5 | 1.331 (4) | C18—H18A | 0.9600 |
N2—C6 | 1.322 (4) | C18—H18B | 0.9595 |
N2—C7 | 1.391 (4) | C21—C22 | 1.514 (5) |
N3—C6 | 1.367 (4) | C22—C23 | 1.494 (5) |
N3—C12 | 1.378 (4) | C22—C24 | 1.515 (5) |
N3—H3A | 0.8600 | C22—H22A | 0.9800 |
C1—C2 | 1.376 (5) | C23—C23v | 1.541 (7) |
C1—H1A | 0.9300 | C23—H23B | 0.9600 |
C2—C3 | 1.392 (4) | C23—H23A | 0.9600 |
C2—H2B | 0.9300 | C24—C24v | 1.520 (8) |
C3—C4 | 1.382 (4) | C24—H24C | 0.9597 |
C3—C6 | 1.465 (4) | C24—H24B | 0.9602 |
O2—Cd1—O4i | 97.59 (10) | C3—C2—H2B | 120.3 |
O2—Cd1—O5 | 98.49 (10) | C4—C3—C2 | 116.7 (3) |
O4i—Cd1—O5 | 118.07 (9) | C4—C3—C6 | 123.6 (3) |
O2—Cd1—O7 | 82.28 (10) | C2—C3—C6 | 119.7 (3) |
O4i—Cd1—O7 | 93.50 (10) | C3—C4—C5 | 119.7 (3) |
O5—Cd1—O7 | 147.80 (9) | C3—C4—H4A | 120.1 |
O2—Cd1—N1 | 166.06 (10) | C5—C4—H4A | 120.1 |
O4i—Cd1—N1 | 92.59 (10) | N1—C5—C4 | 123.3 (3) |
O5—Cd1—N1 | 84.97 (9) | N1—C5—H5A | 118.3 |
O7—Cd1—N1 | 87.62 (10) | C4—C5—H5A | 118.3 |
O2—Cd1—O6 | 88.37 (10) | N2—C6—N3 | 112.6 (3) |
O4i—Cd1—O6 | 168.61 (9) | N2—C6—C3 | 124.4 (3) |
O5—Cd1—O6 | 51.11 (8) | N3—C6—C3 | 123.0 (3) |
O7—Cd1—O6 | 96.93 (9) | N2—C7—C8 | 129.8 (3) |
N1—Cd1—O6 | 83.31 (9) | N2—C7—C12 | 109.7 (3) |
O2—Cd1—O3i | 104.05 (9) | C8—C7—C12 | 120.5 (3) |
O4i—Cd1—O3i | 49.72 (9) | C9—C8—C7 | 117.5 (3) |
O5—Cd1—O3i | 68.37 (8) | C9—C8—H8A | 121.3 |
O7—Cd1—O3i | 142.98 (9) | C7—C8—H8A | 121.3 |
N1—Cd1—O3i | 89.79 (9) | C8—C9—C10 | 121.6 (3) |
O6—Cd1—O3i | 119.42 (7) | C8—C9—H9A | 119.2 |
O2—Cd1—C21 | 94.30 (10) | C10—C9—H9A | 119.2 |
O4i—Cd1—C21 | 143.52 (9) | C11—C10—C9 | 121.6 (3) |
O5—Cd1—C21 | 25.62 (8) | C11—C10—H10A | 119.2 |
O7—Cd1—C21 | 122.29 (10) | C9—C10—H10A | 119.2 |
N1—Cd1—C21 | 82.96 (10) | C10—C11—C12 | 116.6 (3) |
O6—Cd1—C21 | 25.50 (8) | C10—C11—H11A | 121.7 |
O3i—Cd1—C21 | 93.94 (9) | C12—C11—H11A | 121.7 |
O2—Cd1—Cd2 | 81.29 (7) | N3—C12—C11 | 132.1 (3) |
O4i—Cd1—Cd2 | 84.55 (7) | N3—C12—C7 | 105.6 (3) |
O5—Cd1—Cd2 | 40.44 (6) | C11—C12—C7 | 122.3 (3) |
O7—Cd1—Cd2 | 163.04 (8) | C19—C13—C14 | 114.8 (3) |
N1—Cd1—Cd2 | 109.27 (7) | C19—C13—C18 | 110.3 (3) |
O6—Cd1—Cd2 | 86.78 (5) | C14—C13—C18 | 110.4 (2) |
O3i—Cd1—Cd2 | 39.86 (5) | C19—C13—H13A | 107.0 |
C21—Cd1—Cd2 | 63.34 (6) | C14—C13—H13A | 107.0 |
O2—Cd1—H1 | 64.5 (18) | C18—C13—H13A | 107.0 |
O4i—Cd1—H1 | 86 (2) | C13—C14—C15 | 111.3 (3) |
O5—Cd1—H1 | 153 (3) | C13—C14—H14A | 109.4 |
O7—Cd1—H1 | 20.4 (5) | C15—C14—H14A | 109.5 |
N1—Cd1—H1 | 107.0 (13) | C13—C14—H14B | 109.0 |
O6—Cd1—H1 | 105 (2) | C15—C14—H14B | 109.5 |
O3i—Cd1—H1 | 134 (2) | H14A—C14—H14B | 108.0 |
C21—Cd1—H1 | 130 (3) | C14—C15—C16 | 111.2 (3) |
Cd2—Cd1—H1 | 142.9 (8) | C14—C15—H15A | 109.3 |
O1—Cd2—O1ii | 101.6 (2) | C16—C15—H15A | 109.6 |
O1—Cd2—O3i | 86.15 (13) | C14—C15—H15B | 109.2 |
O1ii—Cd2—O3i | 163.72 (12) | C16—C15—H15B | 109.5 |
O1—Cd2—O3iii | 163.72 (12) | H15A—C15—H15B | 107.9 |
O1ii—Cd2—O3iii | 86.15 (13) | C20—C16—C17 | 113.0 (3) |
O3i—Cd2—O3iii | 90.09 (16) | C20—C16—C15 | 111.2 (3) |
O1—Cd2—O5 | 90.04 (11) | C17—C16—C15 | 110.4 (3) |
O1ii—Cd2—O5 | 86.74 (10) | C20—C16—H16A | 107.3 |
O3i—Cd2—O5 | 78.91 (10) | C17—C16—H16A | 107.3 |
O3iii—Cd2—O5 | 104.78 (10) | C15—C16—H16A | 107.3 |
O1—Cd2—O5ii | 86.74 (10) | C16—C17—C18 | 112.0 (3) |
O1ii—Cd2—O5ii | 90.04 (11) | C16—C17—H17A | 109.7 |
O3i—Cd2—O5ii | 104.78 (10) | C18—C17—H17A | 109.0 |
O3iii—Cd2—O5ii | 78.91 (10) | C16—C17—H17B | 109.1 |
O5—Cd2—O5ii | 174.90 (12) | C18—C17—H17B | 109.1 |
O1—Cd2—Cd1ii | 118.18 (9) | H17A—C17—H17B | 108.0 |
O1ii—Cd2—Cd1ii | 61.44 (9) | C17—C18—C13 | 112.2 (3) |
O3i—Cd2—Cd1ii | 127.30 (8) | C17—C18—H18A | 109.0 |
O3iii—Cd2—Cd1ii | 53.17 (8) | C13—C18—H18A | 108.4 |
O5—Cd2—Cd1ii | 139.97 (6) | C17—C18—H18B | 109.9 |
O5ii—Cd2—Cd1ii | 39.99 (6) | C13—C18—H18B | 109.4 |
O1—Cd2—Cd1 | 61.44 (9) | H18A—C18—H18B | 108.0 |
O1ii—Cd2—Cd1 | 118.18 (9) | O1—C19—O2 | 124.1 (3) |
O3i—Cd2—Cd1 | 53.17 (8) | O1—C19—C13 | 116.3 (3) |
O3iii—Cd2—Cd1 | 127.30 (8) | O2—C19—C13 | 119.5 (3) |
O5—Cd2—Cd1 | 39.99 (6) | O4—C20—O3 | 120.9 (3) |
O5ii—Cd2—Cd1 | 139.97 (6) | O4—C20—C16 | 119.3 (3) |
Cd1ii—Cd2—Cd1 | 179.468 (10) | O3—C20—C16 | 119.7 (3) |
C19—O1—Cd2 | 146.6 (3) | O6—C21—O5 | 120.9 (3) |
C19—O2—Cd1 | 117.3 (2) | O6—C21—C22 | 123.3 (3) |
C20—O3—Cd2iv | 138.4 (2) | O5—C21—C22 | 115.7 (3) |
C20—O3—Cd1iv | 81.1 (2) | O6—C21—Cd1 | 70.26 (18) |
Cd2iv—O3—Cd1iv | 86.97 (9) | O5—C21—Cd1 | 50.66 (16) |
C20—O4—Cd1iv | 107.4 (2) | C22—C21—Cd1 | 165.3 (2) |
C21—O5—Cd1 | 103.7 (2) | C23—C22—C21 | 115.2 (3) |
C21—O5—Cd2 | 140.5 (2) | C23—C22—C24 | 111.8 (3) |
Cd1—O5—Cd2 | 99.57 (9) | C21—C22—C24 | 108.0 (3) |
C21—O6—Cd1 | 84.24 (19) | C23—C22—H22A | 107.2 |
Cd1—O7—H2 | 142.1 | C21—C22—H22A | 107.2 |
Cd1—O7—H1 | 88 (4) | C24—C22—H22A | 107.2 |
H2—O7—H1 | 118.6 | C22—C23—C23v | 110.7 (3) |
C1—N1—C5 | 116.8 (3) | C22—C23—H23B | 108.7 |
C1—N1—Cd1 | 121.2 (2) | C23v—C23—H23B | 107.0 |
C5—N1—Cd1 | 122.0 (2) | C22—C23—H23A | 109.3 |
C6—N2—C7 | 105.1 (2) | C23v—C23—H23A | 111.2 |
C6—N3—C12 | 107.0 (2) | H23B—C23—H23A | 109.8 |
C6—N3—H3A | 126.5 | C22—C24—C24v | 112.0 (3) |
C12—N3—H3A | 126.5 | C22—C24—H24C | 108.3 |
N1—C1—C2 | 123.9 (3) | C24v—C24—H24C | 110.0 |
N1—C1—H1A | 118.0 | C22—C24—H24B | 109.4 |
C2—C1—H1A | 118.0 | C24v—C24—H24B | 107.8 |
C1—C2—C3 | 119.4 (3) | H24C—C24—H24B | 109.3 |
C1—C2—H2B | 120.3 |
Symmetry codes: (i) x, y+1, z; (ii) −x, y, −z−1/2; (iii) −x, y+1, −z−1/2; (iv) x, y−1, z; (v) −x+1, y, −z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H2···N2vi | 0.84 | 2.06 | 2.767 (4) | 142 |
N3—H3A···O6i | 0.86 | 1.94 | 2.755 (4) | 159 |
Symmetry codes: (i) x, y+1, z; (vi) −x+1, −y−1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Cd3(C8H10O4)3(C12H9N3)2(H2O)2] |
Mr | 1274.19 |
Crystal system, space group | Monoclinic, P2/c |
Temperature (K) | 293 |
a, b, c (Å) | 10.366 (3), 8.774 (3), 27.071 (7) |
β (°) | 101.48 (1) |
V (Å3) | 2412.9 (12) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.38 |
Crystal size (mm) | 0.30 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Rigaku Mercury CCD area-detector diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2007) |
Tmin, Tmax | 0.569, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18383, 5500, 4825 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.109, 1.09 |
No. of reflections | 5500 |
No. of parameters | 327 |
No. of restraints | 9 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.63, −0.99 |
Computer programs: CrystalClear (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999).
Cd1—O2 | 2.230 (2) | Cd2—O1 | 2.221 (3) |
Cd1—O4i | 2.261 (3) | Cd2—O1ii | 2.221 (3) |
Cd1—O5 | 2.278 (2) | Cd2—O3i | 2.243 (3) |
Cd1—O7 | 2.340 (2) | Cd2—O3iii | 2.243 (3) |
Cd1—N1 | 2.342 (3) | Cd2—O5 | 2.299 (2) |
Cd1—O6 | 2.706 (3) | Cd2—O5ii | 2.299 (2) |
Cd1—O3i | 2.801 (3) | ||
O2—Cd1—O4i | 97.59 (10) | O7—Cd1—O3i | 142.98 (9) |
O2—Cd1—O5 | 98.49 (10) | N1—Cd1—O3i | 89.79 (9) |
O4i—Cd1—O5 | 118.07 (9) | O6—Cd1—O3i | 119.42 (7) |
O2—Cd1—O7 | 82.28 (10) | O1—Cd2—O1ii | 101.6 (2) |
O4i—Cd1—O7 | 93.50 (10) | O1—Cd2—O3i | 86.15 (13) |
O5—Cd1—O7 | 147.80 (9) | O1ii—Cd2—O3i | 163.72 (12) |
O2—Cd1—N1 | 166.06 (10) | O1—Cd2—O3iii | 163.72 (12) |
O4i—Cd1—N1 | 92.59 (10) | O1ii—Cd2—O3iii | 86.15 (13) |
O5—Cd1—N1 | 84.97 (9) | O3i—Cd2—O3iii | 90.09 (16) |
O7—Cd1—N1 | 87.62 (10) | O1—Cd2—O5 | 90.04 (11) |
O2—Cd1—O6 | 88.37 (10) | O1ii—Cd2—O5 | 86.74 (10) |
O4i—Cd1—O6 | 168.61 (9) | O3i—Cd2—O5 | 78.91 (10) |
O5—Cd1—O6 | 51.11 (8) | O3iii—Cd2—O5 | 104.78 (10) |
O7—Cd1—O6 | 96.93 (9) | O1—Cd2—O5ii | 86.74 (10) |
N1—Cd1—O6 | 83.31 (9) | O1ii—Cd2—O5ii | 90.04 (11) |
O2—Cd1—O3i | 104.05 (9) | O3i—Cd2—O5ii | 104.78 (10) |
O4i—Cd1—O3i | 49.72 (9) | O3iii—Cd2—O5ii | 78.91 (10) |
O5—Cd1—O3i | 68.37 (8) | O5—Cd2—O5ii | 174.90 (12) |
Symmetry codes: (i) x, y+1, z; (ii) −x, y, −z−1/2; (iii) −x, y+1, −z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H2···N2iv | 0.84 | 2.06 | 2.767 (4) | 141.5 |
N3—H3A···O6i | 0.86 | 1.94 | 2.755 (4) | 159.0 |
Symmetry codes: (i) x, y+1, z; (iv) −x+1, −y−1, −z. |