Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229616001522/qs3053sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229616001522/qs3053Isup2.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S2053229616001522/qs3053Isup3.pdf |
CCDC reference: 1449574
Photocatalysis is a green technology for the treatment of all kinds of contaminants, which has many advantages over other treatment methods, for instance, the use of the environmentally friendly oxidant (O2 or H2O2), the ambient temperature reaction condition, and the oxidation of the organic compounds, even at low concentrations (Ma et al., 2003; Liu et al., 2010). Recently, considering the novelty of this field in metal–organic frameworks (MOFs), much effort has been devoted to developing new photocatalytic materials based on MOFs in the degradation of many kinds of organic contaminants with up to 90% efficiency (Liu, Ding, Li et al., 2014; Liu, Ding, Huang et al., 2014; Wu et al., 2015). Compared to the traditional semiconductor metal oxide, the advantages of MOFs as photocatalyst lie in the fact that their combination of inorganic and organic moieties can result in different metal–ligand charge-transfer-related tunable photocatalysts (Wen et al., 2012).
Thus, the examination of the photocatalytic properties of MOFs have been productive (Wang et al., 2011, 2015; Dai et al., 2014). In particular, Cd-based MOFs have exhibited efficient photocatalytic activities for the organic dyes (Wen et al., 2012; Liu, Ding, Huang et al., 2014; Dai et al., 2014; Liu, Yu, Ma et al., 2015). For example, Hou and co-workers reported that four polynuclear CdII polymers showed high photocatalytic activity towards the degradation of methylene blue (MB) (Liu, Ding, Huang et al., 2014). Lang et al. utilized tetrakis(pyridin-4-yl)cyclobutane to synthesize a series of CdII coordination polymers, and the results revealed that some coordination polymers may be active photocatalytic materials due to their high catalytic activities for the degradation of methyl orange, methyl blue or rhodamine B in aqueous solution (Li et al., 2014). Aiming to search for more effective photocatalysts, we combined Cd(OAc)2·2H2O with benzene-1,2-dicarboxylic acid (H2L) and 1,4-bis(pyridin-3-ylmethoxy)benzene (bpmb) to produce the title compound, [Cd2(L)2(bpmb)]n, (I), and report the characterization of the material and photocatalytic activity herein.
1,4-Bis(pyridin-3-ylmethoxy)benzene (bpmb) was prepared according to the literature method of Liu, Yu, Li et al. (2015). All other chemicals and reagents were obtained from commercial sources (Sigma–Aldrich) and used as received. A mixture of Cd(OAc)2·2H2O (11 mg, 0.04 mmol; OAc is acetate), benzene-1,2-dicarboxylic acid (3 mg, 0.02 mmol), bpmb (6 mg, 0.02 mmol) and MeOH–H2O (1:1 v/v, 4 ml) was sealed in a 10 ml Pyrex glass tube and heated at 438 K for 4 d, and then cooled to room temperature at a rate of 5 K h−1. Colourless blocks of (I) were collected and dried in air (yield 7 mg, 41%, based on bpmb). Analysis calculated for C34H24Cd2N2O10 (%): H 2.86, C 48.31, N 3.31; found: H 2.59, C 48.14, N 3.60.
Crystal data, data collection, and structure refinement details are summarized in Table 1. A l l H atoms are placed in geometrically idealized positions, with C—H = 0.93 Å for aromatic and 0.97 Å for methylene H atoms, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C,O).
The title compound, (I), crystallizes in the monoclinic space group C2/c, and its asymmetric unit contains half of a [Cd2(L)2(bpmb)] unit. As shown in Fig. 1, each CdII centre is five-coordinated by four carboxylate O atoms [O2, O3, O4i and O1ii; symmetry codes: (i) −x + 1, y, −z + 3/2; (ii) −x + 1, −y + 1, −z + 1] from two L2− ligands and one N atom (N1) from a bpmb ligand, forming a disordered pentagonal pyramidal coordination geometry. Selected bond lengths and angles for (I) are listed in Table 2.
In the structure of (I), each adjoining pair of CdII atoms is connected by two carboxylate groups (µ2-η1:η1) from two L2− ligands to generate a [Cd2(CO2)2] subunit with a Cd···Cd distance of 4.037 (3) Å (Fig. 2). Such subunits are bridged by L2− ligands to form an infinite [Cd2(L)2]n chain extending along the c axis (Fig. 2). Each chain is interlinked to adjacent chains through bpmb linkers, producing a two-dimensional network with parallelogrammic meshes (15.54 × 16.62 Å2) extending along the bc plane (Fig. 3). Furthermore, additional bpmb ligands are employed as pillars to link the two-dimensional networks to afford a three-dimensional framework with one-dimensional rhombic channels along the [001] direction (Fig. 4). These channels are filled by mutual interpenetration of three independent equivalent frameworks, generating a threefold interpenetrating three-dimensional architecture (Fig. 5). Topologically (Wells, 1997), if the CdII centres are regarded as 5-connected nodes, and the L2− and bpmb ligands are considered as linkers, the overall structure of (I) can be specified by a Schläfli symbol of 3342637181 (Fig. 5). Geometric details of the hydrogen-bond interactions are given in Table 3.
Compound (I) was also characterized by powder X-ray diffraction (PXRD) at room temperature. The PXRD pattern of (I) is coincident with the simulated pattern derived from the single-crystal X-ray data (see Fig. S1 in the Supporting information), which implies that the structure of the bulk sample is the same as that of the single-crystal.
The photocatalytic activity of compound (I) was evaluated by the degradation of MB under irradiation of a 350 W Xe lamp. In a catalytic process, 20 mg of compound (I) as photocatalyst was added into 50 ml of MB solution (4 × 10 −5 mol l−1). The solution was stirred for 30 min in the dark before irradiation to reach adsorption equilibrium between the catalyst and solution and was then exposed to UV irradiation. About 4 ml of the suspension was continually taken from the reaction cell and collected by centrifugation at 30 min intervals during the irradiation. The resulting solution was analyzed on a Varian 50 UV/Vis spectrophotometer.
To evaluate the band gaps, the UV–vis absorption spectrum of (I) was measured at room temperature (see Fig. S2 in the Supporting information). The result gives Eg (band-gap energy) value of 3.43 eV for (I) (see Fig. S3 in the Supporting information). As illustrated in Fig. 6, the absorption of MB notably decreased in the presence of (I). The degradation efficiency is defined as C/C0, where C and C0 represent the resultant and initial concentration of MB, respectively. By contrast, the simple photolysis experiment was also completed under the same conditions without any catalyst (Fig. 7). The organic dye concentrations were estimated by the absorbance at 665 nm (MB). Compound (I) shows a relatively good photocatalytic activity towards the degradation ratio of MB reached 96.8% exposed to UV light for 120 min (Fig. 7). Compared with other Cd-based coordination polymer (CP) materials, e.g. {[Cd(tpcb)0.75(OH)(H2O)2]NO3}n [tpcp is tetrakis(pyridin-4-yl)cyclobutane; Li et al., 2014], {[Cd(btbb)0.5(btec)0.5(H2O)]·2H2O}n {btbb is 1,4-bis[2-(thiazol-2-yl)benzimidazole-1-ylmethyl]benzene and H4btec is benzene-1,2,4,5-tetracarboxylate; Liu, Ding, Li et al., 2014} and {[Cd3(bcb)2(H2O)5]·H2O}n [H3bcb is 3,4-bis(4-carboxyphenyl)benzoic acid; Liu, Ding, Huang et al., 2014], as catalysts, ca 82.0, 92.7 and 88.7% of MB was degraded in 120, 140 and 180 min, respectively. These results suggest that compound (I) may be of use as a potential photoactive material.
Photocatalysis is a green technology for the treatment of all kinds of contaminants, which has many advantages over other treatment methods, for instance, the use of the environmentally friendly oxidant (O2 or H2O2), the ambient temperature reaction condition, and the oxidation of the organic compounds, even at low concentrations (Ma et al., 2003; Liu et al., 2010). Recently, considering the novelty of this field in metal–organic frameworks (MOFs), much effort has been devoted to developing new photocatalytic materials based on MOFs in the degradation of many kinds of organic contaminants with up to 90% efficiency (Liu, Ding, Li et al., 2014; Liu, Ding, Huang et al., 2014; Wu et al., 2015). Compared to the traditional semiconductor metal oxide, the advantages of MOFs as photocatalyst lie in the fact that their combination of inorganic and organic moieties can result in different metal–ligand charge-transfer-related tunable photocatalysts (Wen et al., 2012).
Thus, the examination of the photocatalytic properties of MOFs have been productive (Wang et al., 2011, 2015; Dai et al., 2014). In particular, Cd-based MOFs have exhibited efficient photocatalytic activities for the organic dyes (Wen et al., 2012; Liu, Ding, Huang et al., 2014; Dai et al., 2014; Liu, Yu, Ma et al., 2015). For example, Hou and co-workers reported that four polynuclear CdII polymers showed high photocatalytic activity towards the degradation of methylene blue (MB) (Liu, Ding, Huang et al., 2014). Lang et al. utilized tetrakis(pyridin-4-yl)cyclobutane to synthesize a series of CdII coordination polymers, and the results revealed that some coordination polymers may be active photocatalytic materials due to their high catalytic activities for the degradation of methyl orange, methyl blue or rhodamine B in aqueous solution (Li et al., 2014). Aiming to search for more effective photocatalysts, we combined Cd(OAc)2·2H2O with benzene-1,2-dicarboxylic acid (H2L) and 1,4-bis(pyridin-3-ylmethoxy)benzene (bpmb) to produce the title compound, [Cd2(L)2(bpmb)]n, (I), and report the characterization of the material and photocatalytic activity herein.
The title compound, (I), crystallizes in the monoclinic space group C2/c, and its asymmetric unit contains half of a [Cd2(L)2(bpmb)] unit. As shown in Fig. 1, each CdII centre is five-coordinated by four carboxylate O atoms [O2, O3, O4i and O1ii; symmetry codes: (i) −x + 1, y, −z + 3/2; (ii) −x + 1, −y + 1, −z + 1] from two L2− ligands and one N atom (N1) from a bpmb ligand, forming a disordered pentagonal pyramidal coordination geometry. Selected bond lengths and angles for (I) are listed in Table 2.
In the structure of (I), each adjoining pair of CdII atoms is connected by two carboxylate groups (µ2-η1:η1) from two L2− ligands to generate a [Cd2(CO2)2] subunit with a Cd···Cd distance of 4.037 (3) Å (Fig. 2). Such subunits are bridged by L2− ligands to form an infinite [Cd2(L)2]n chain extending along the c axis (Fig. 2). Each chain is interlinked to adjacent chains through bpmb linkers, producing a two-dimensional network with parallelogrammic meshes (15.54 × 16.62 Å2) extending along the bc plane (Fig. 3). Furthermore, additional bpmb ligands are employed as pillars to link the two-dimensional networks to afford a three-dimensional framework with one-dimensional rhombic channels along the [001] direction (Fig. 4). These channels are filled by mutual interpenetration of three independent equivalent frameworks, generating a threefold interpenetrating three-dimensional architecture (Fig. 5). Topologically (Wells, 1997), if the CdII centres are regarded as 5-connected nodes, and the L2− and bpmb ligands are considered as linkers, the overall structure of (I) can be specified by a Schläfli symbol of 3342637181 (Fig. 5). Geometric details of the hydrogen-bond interactions are given in Table 3.
Compound (I) was also characterized by powder X-ray diffraction (PXRD) at room temperature. The PXRD pattern of (I) is coincident with the simulated pattern derived from the single-crystal X-ray data (see Fig. S1 in the Supporting information), which implies that the structure of the bulk sample is the same as that of the single-crystal.
The photocatalytic activity of compound (I) was evaluated by the degradation of MB under irradiation of a 350 W Xe lamp. In a catalytic process, 20 mg of compound (I) as photocatalyst was added into 50 ml of MB solution (4 × 10 −5 mol l−1). The solution was stirred for 30 min in the dark before irradiation to reach adsorption equilibrium between the catalyst and solution and was then exposed to UV irradiation. About 4 ml of the suspension was continually taken from the reaction cell and collected by centrifugation at 30 min intervals during the irradiation. The resulting solution was analyzed on a Varian 50 UV/Vis spectrophotometer.
To evaluate the band gaps, the UV–vis absorption spectrum of (I) was measured at room temperature (see Fig. S2 in the Supporting information). The result gives Eg (band-gap energy) value of 3.43 eV for (I) (see Fig. S3 in the Supporting information). As illustrated in Fig. 6, the absorption of MB notably decreased in the presence of (I). The degradation efficiency is defined as C/C0, where C and C0 represent the resultant and initial concentration of MB, respectively. By contrast, the simple photolysis experiment was also completed under the same conditions without any catalyst (Fig. 7). The organic dye concentrations were estimated by the absorbance at 665 nm (MB). Compound (I) shows a relatively good photocatalytic activity towards the degradation ratio of MB reached 96.8% exposed to UV light for 120 min (Fig. 7). Compared with other Cd-based coordination polymer (CP) materials, e.g. {[Cd(tpcb)0.75(OH)(H2O)2]NO3}n [tpcp is tetrakis(pyridin-4-yl)cyclobutane; Li et al., 2014], {[Cd(btbb)0.5(btec)0.5(H2O)]·2H2O}n {btbb is 1,4-bis[2-(thiazol-2-yl)benzimidazole-1-ylmethyl]benzene and H4btec is benzene-1,2,4,5-tetracarboxylate; Liu, Ding, Li et al., 2014} and {[Cd3(bcb)2(H2O)5]·H2O}n [H3bcb is 3,4-bis(4-carboxyphenyl)benzoic acid; Liu, Ding, Huang et al., 2014], as catalysts, ca 82.0, 92.7 and 88.7% of MB was degraded in 120, 140 and 180 min, respectively. These results suggest that compound (I) may be of use as a potential photoactive material.
1,4-Bis(pyridin-3-ylmethoxy)benzene (bpmb) was prepared according to the literature method of Liu, Yu, Li et al. (2015). All other chemicals and reagents were obtained from commercial sources (Sigma–Aldrich) and used as received. A mixture of Cd(OAc)2·2H2O (11 mg, 0.04 mmol; OAc is acetate), benzene-1,2-dicarboxylic acid (3 mg, 0.02 mmol), bpmb (6 mg, 0.02 mmol) and MeOH–H2O (1:1 v/v, 4 ml) was sealed in a 10 ml Pyrex glass tube and heated at 438 K for 4 d, and then cooled to room temperature at a rate of 5 K h−1. Colourless blocks of (I) were collected and dried in air (yield 7 mg, 41%, based on bpmb). Analysis calculated for C34H24Cd2N2O10 (%): H 2.86, C 48.31, N 3.31; found: H 2.59, C 48.14, N 3.60.
Crystal data, data collection, and structure refinement details are summarized in Table 1. A l l H atoms are placed in geometrically idealized positions, with C—H = 0.93 Å for aromatic and 0.97 Å for methylene H atoms, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C,O).
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
[Cd2(C8H4O4)2(C18H16N2O2)] | F(000) = 1672 |
Mr = 422.68 | Dx = 1.868 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 19.490 (4) Å | Cell parameters from 8901 reflections |
b = 9.985 (2) Å | θ = 2.6–28.4° |
c = 15.540 (3) Å | µ = 1.48 mm−1 |
β = 96.25 (3)° | T = 296 K |
V = 3006.4 (11) Å3 | Block, colourless |
Z = 8 | 0.40 × 0.35 × 0.30 mm |
Bruker APEXII CCD diffractometer | 2575 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.027 |
φ and ω scans | θmax = 25.3°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −23→23 |
Tmin = 0.559, Tmax = 0.641 | k = −11→11 |
10582 measured reflections | l = −17→18 |
2726 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.019 | H-atom parameters constrained |
wR(F2) = 0.050 | w = 1/[σ2(Fo2) + (0.0244P)2 + 2.9124P]
where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.002 |
2726 reflections | Δρmax = 0.49 e Å−3 |
218 parameters | Δρmin = −0.50 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00155 (9) |
[Cd2(C8H4O4)2(C18H16N2O2)] | V = 3006.4 (11) Å3 |
Mr = 422.68 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 19.490 (4) Å | µ = 1.48 mm−1 |
b = 9.985 (2) Å | T = 296 K |
c = 15.540 (3) Å | 0.40 × 0.35 × 0.30 mm |
β = 96.25 (3)° |
Bruker APEXII CCD diffractometer | 2726 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 2575 reflections with I > 2σ(I) |
Tmin = 0.559, Tmax = 0.641 | Rint = 0.027 |
10582 measured reflections |
R[F2 > 2σ(F2)] = 0.019 | 0 restraints |
wR(F2) = 0.050 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.49 e Å−3 |
2726 reflections | Δρmin = −0.50 e Å−3 |
218 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. |
x | y | z | Uiso*/Ueq | ||
Cd1 | 0.47738 (2) | 0.55800 (2) | 0.62009 (2) | 0.02664 (8) | |
C1 | 0.59402 (10) | 0.37244 (19) | 0.54707 (12) | 0.0275 (4) | |
C2 | 0.64743 (9) | 0.31891 (19) | 0.61587 (12) | 0.0268 (4) | |
C3 | 0.69675 (10) | 0.2327 (2) | 0.58786 (14) | 0.0370 (5) | |
H3 | 0.6962 | 0.2155 | 0.5290 | 0.044* | |
C4 | 0.74634 (12) | 0.1724 (3) | 0.64544 (16) | 0.0467 (6) | |
H4 | 0.7785 | 0.1148 | 0.6254 | 0.056* | |
C5 | 0.74781 (11) | 0.1981 (3) | 0.73249 (16) | 0.0462 (6) | |
H5 | 0.7814 | 0.1586 | 0.7715 | 0.055* | |
C6 | 0.69917 (11) | 0.2828 (2) | 0.76203 (14) | 0.0367 (5) | |
H6 | 0.7004 | 0.2994 | 0.8211 | 0.044* | |
C7 | 0.64867 (9) | 0.3434 (2) | 0.70502 (13) | 0.0274 (4) | |
C8 | 0.59964 (10) | 0.43616 (19) | 0.74401 (14) | 0.0302 (5) | |
C9 | 0.56250 (11) | 0.8258 (2) | 0.66987 (16) | 0.0420 (5) | |
H9 | 0.5949 | 0.7621 | 0.6910 | 0.050* | |
C10 | 0.57996 (14) | 0.9592 (2) | 0.6773 (2) | 0.0533 (7) | |
H10 | 0.6231 | 0.9848 | 0.7036 | 0.064* | |
C11 | 0.53318 (13) | 1.0533 (2) | 0.64563 (18) | 0.0467 (6) | |
H11 | 0.5440 | 1.1439 | 0.6506 | 0.056* | |
C12 | 0.46960 (11) | 1.0133 (2) | 0.60610 (15) | 0.0352 (5) | |
C13 | 0.45515 (11) | 0.8783 (2) | 0.60228 (14) | 0.0328 (4) | |
H13 | 0.4120 | 0.8508 | 0.5770 | 0.039* | |
C14 | 0.42123 (11) | 1.1201 (2) | 0.56917 (17) | 0.0439 (6) | |
H14A | 0.4204 | 1.1925 | 0.6106 | 0.053* | |
H14B | 0.4376 | 1.1559 | 0.5171 | 0.053* | |
C15 | 0.30410 (11) | 1.1629 (2) | 0.52356 (14) | 0.0339 (5) | |
C16 | 0.23693 (11) | 1.1207 (2) | 0.52420 (15) | 0.0385 (5) | |
H16 | 0.2280 | 1.0333 | 0.5404 | 0.046* | |
C17 | 0.31735 (11) | 1.2929 (2) | 0.49896 (15) | 0.0379 (5) | |
H17 | 0.3626 | 1.3220 | 0.4981 | 0.045* | |
N1 | 0.50085 (9) | 0.78433 (17) | 0.63354 (11) | 0.0303 (4) | |
O1 | 0.61458 (7) | 0.39855 (16) | 0.47526 (9) | 0.0363 (3) | |
O2 | 0.53142 (7) | 0.38073 (15) | 0.56053 (10) | 0.0349 (3) | |
O3 | 0.58020 (8) | 0.54186 (14) | 0.70469 (12) | 0.0421 (4) | |
O4 | 0.58290 (9) | 0.40550 (18) | 0.81667 (10) | 0.0457 (4) | |
O5 | 0.35474 (9) | 1.06960 (14) | 0.54953 (13) | 0.0479 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.02504 (10) | 0.02343 (11) | 0.03080 (11) | −0.00069 (5) | 0.00017 (6) | 0.00245 (5) |
C1 | 0.0297 (10) | 0.0219 (10) | 0.0298 (11) | −0.0043 (7) | −0.0018 (8) | −0.0003 (8) |
C2 | 0.0223 (9) | 0.0277 (10) | 0.0304 (10) | −0.0025 (7) | 0.0024 (7) | 0.0035 (8) |
C3 | 0.0306 (10) | 0.0498 (13) | 0.0318 (11) | 0.0065 (9) | 0.0086 (8) | 0.0004 (10) |
C4 | 0.0359 (12) | 0.0602 (16) | 0.0452 (14) | 0.0200 (11) | 0.0095 (10) | 0.0016 (12) |
C5 | 0.0353 (12) | 0.0605 (17) | 0.0418 (13) | 0.0211 (11) | 0.0000 (9) | 0.0098 (11) |
C6 | 0.0349 (11) | 0.0446 (13) | 0.0300 (11) | 0.0087 (9) | 0.0007 (8) | 0.0035 (9) |
C7 | 0.0250 (9) | 0.0257 (10) | 0.0311 (10) | 0.0004 (7) | 0.0007 (7) | 0.0035 (8) |
C8 | 0.0268 (10) | 0.0280 (11) | 0.0334 (12) | 0.0016 (8) | −0.0075 (8) | −0.0061 (8) |
C9 | 0.0339 (11) | 0.0343 (12) | 0.0550 (14) | −0.0031 (9) | −0.0082 (10) | 0.0113 (10) |
C10 | 0.0412 (14) | 0.0389 (14) | 0.075 (2) | −0.0137 (10) | −0.0139 (13) | 0.0098 (12) |
C11 | 0.0450 (14) | 0.0288 (13) | 0.0641 (17) | −0.0112 (9) | −0.0038 (12) | 0.0056 (10) |
C12 | 0.0376 (12) | 0.0266 (11) | 0.0414 (12) | 0.0020 (9) | 0.0042 (9) | 0.0015 (9) |
C13 | 0.0298 (10) | 0.0279 (11) | 0.0395 (12) | −0.0004 (8) | −0.0011 (8) | −0.0016 (9) |
C14 | 0.0372 (12) | 0.0289 (12) | 0.0652 (16) | 0.0010 (9) | 0.0042 (11) | 0.0042 (11) |
C15 | 0.0368 (11) | 0.0242 (10) | 0.0396 (12) | 0.0013 (8) | −0.0010 (9) | −0.0005 (9) |
C16 | 0.0419 (12) | 0.0234 (11) | 0.0493 (14) | −0.0025 (9) | 0.0001 (10) | 0.0052 (9) |
C17 | 0.0333 (11) | 0.0311 (12) | 0.0488 (13) | −0.0036 (9) | 0.0019 (9) | 0.0018 (10) |
N1 | 0.0303 (8) | 0.0245 (9) | 0.0352 (9) | −0.0016 (7) | −0.0008 (7) | 0.0028 (7) |
O1 | 0.0343 (8) | 0.0445 (9) | 0.0288 (8) | −0.0061 (7) | −0.0017 (6) | 0.0078 (7) |
O2 | 0.0242 (7) | 0.0363 (8) | 0.0430 (9) | 0.0037 (6) | −0.0018 (6) | −0.0026 (7) |
O3 | 0.0370 (8) | 0.0245 (8) | 0.0606 (11) | 0.0043 (6) | −0.0138 (7) | 0.0014 (7) |
O4 | 0.0544 (10) | 0.0515 (10) | 0.0320 (9) | 0.0226 (8) | 0.0082 (7) | −0.0047 (7) |
O5 | 0.0364 (9) | 0.0246 (8) | 0.0796 (13) | 0.0002 (6) | −0.0079 (8) | 0.0046 (7) |
Cd1—O4i | 2.2173 (16) | C9—C10 | 1.376 (3) |
Cd1—O1ii | 2.2399 (16) | C9—H9 | 0.9300 |
Cd1—O3 | 2.2796 (17) | C10—C11 | 1.364 (4) |
Cd1—O2 | 2.3047 (15) | C10—H10 | 0.9300 |
Cd1—N1 | 2.3108 (17) | C11—C12 | 1.381 (3) |
C1—O1 | 1.254 (2) | C11—H11 | 0.9300 |
C1—O2 | 1.263 (2) | C12—C13 | 1.377 (3) |
C1—C2 | 1.507 (3) | C12—C14 | 1.496 (3) |
C2—C3 | 1.395 (3) | C13—N1 | 1.347 (3) |
C2—C7 | 1.404 (3) | C13—H13 | 0.9300 |
C3—C4 | 1.382 (3) | C14—O5 | 1.393 (3) |
C3—H3 | 0.9300 | C14—H14A | 0.9700 |
C4—C5 | 1.374 (3) | C14—H14B | 0.9700 |
C4—H4 | 0.9300 | C15—C16 | 1.376 (3) |
C5—C6 | 1.386 (3) | C15—O5 | 1.385 (3) |
C5—H5 | 0.9300 | C15—C17 | 1.386 (3) |
C6—C7 | 1.389 (3) | C16—C17iii | 1.382 (3) |
C6—H6 | 0.9300 | C16—H16 | 0.9300 |
C7—C8 | 1.505 (3) | C17—C16iii | 1.382 (3) |
C8—O4 | 1.247 (3) | C17—H17 | 0.9300 |
C8—O3 | 1.257 (2) | O1—Cd1ii | 2.2400 (16) |
C9—N1 | 1.337 (3) | O4—Cd1i | 2.2172 (16) |
O4i—Cd1—O1ii | 90.11 (6) | C10—C9—H9 | 118.7 |
O4i—Cd1—O3 | 99.84 (6) | C11—C10—C9 | 119.2 (2) |
O1ii—Cd1—O3 | 170.06 (6) | C11—C10—H10 | 120.4 |
O4i—Cd1—O2 | 86.44 (7) | C9—C10—H10 | 120.4 |
O1ii—Cd1—O2 | 104.53 (6) | C10—C11—C12 | 119.6 (2) |
O3—Cd1—O2 | 76.45 (5) | C10—C11—H11 | 120.2 |
O4i—Cd1—N1 | 137.80 (6) | C12—C11—H11 | 120.2 |
O1ii—Cd1—N1 | 90.38 (6) | C13—C12—C11 | 118.2 (2) |
O3—Cd1—N1 | 82.19 (6) | C13—C12—C14 | 124.3 (2) |
O2—Cd1—N1 | 133.86 (6) | C11—C12—C14 | 117.5 (2) |
O1—C1—O2 | 122.83 (18) | N1—C13—C12 | 122.83 (19) |
O1—C1—C2 | 116.26 (17) | N1—C13—H13 | 118.6 |
O2—C1—C2 | 120.73 (17) | C12—C13—H13 | 118.6 |
C3—C2—C7 | 118.50 (18) | O5—C14—C12 | 111.02 (18) |
C3—C2—C1 | 116.34 (18) | O5—C14—H14A | 109.4 |
C7—C2—C1 | 125.07 (17) | C12—C14—H14A | 109.4 |
C4—C3—C2 | 121.6 (2) | O5—C14—H14B | 109.4 |
C4—C3—H3 | 119.2 | C12—C14—H14B | 109.4 |
C2—C3—H3 | 119.2 | H14A—C14—H14B | 108.0 |
C5—C4—C3 | 119.6 (2) | C16—C15—O5 | 116.13 (19) |
C5—C4—H4 | 120.2 | C16—C15—C17 | 119.6 (2) |
C3—C4—H4 | 120.2 | O5—C15—C17 | 124.21 (19) |
C4—C5—C6 | 119.9 (2) | C15—C16—C17iii | 120.6 (2) |
C4—C5—H5 | 120.1 | C15—C16—H16 | 119.7 |
C6—C5—H5 | 120.1 | C17iii—C16—H16 | 119.7 |
C5—C6—C7 | 121.2 (2) | C16iii—C17—C15 | 119.8 (2) |
C5—C6—H6 | 119.4 | C16iii—C17—H17 | 120.1 |
C7—C6—H6 | 119.4 | C15—C17—H17 | 120.1 |
C6—C7—C2 | 119.20 (18) | C9—N1—C13 | 117.70 (19) |
C6—C7—C8 | 116.64 (18) | C9—N1—Cd1 | 120.10 (14) |
C2—C7—C8 | 124.13 (17) | C13—N1—Cd1 | 122.14 (14) |
O4—C8—O3 | 123.5 (2) | C1—O1—Cd1ii | 108.59 (12) |
O4—C8—C7 | 116.99 (17) | C1—O2—Cd1 | 127.52 (13) |
O3—C8—C7 | 119.5 (2) | C8—O3—Cd1 | 122.62 (13) |
N1—C9—C10 | 122.6 (2) | C8—O4—Cd1i | 115.86 (14) |
N1—C9—H9 | 118.7 | C15—O5—C14 | 115.92 (16) |
O1—C1—C2—C3 | −36.7 (3) | C11—C12—C13—N1 | −1.6 (3) |
O2—C1—C2—C3 | 138.5 (2) | C14—C12—C13—N1 | 177.6 (2) |
O1—C1—C2—C7 | 146.91 (19) | C13—C12—C14—O5 | 14.3 (3) |
O2—C1—C2—C7 | −37.9 (3) | C11—C12—C14—O5 | −166.5 (2) |
C7—C2—C3—C4 | −0.3 (3) | O5—C15—C16—C17iii | 178.7 (2) |
C1—C2—C3—C4 | −176.9 (2) | C17—C15—C16—C17iii | −0.4 (4) |
C2—C3—C4—C5 | −0.5 (4) | C16—C15—C17—C16iii | 0.4 (4) |
C3—C4—C5—C6 | 0.8 (4) | O5—C15—C17—C16iii | −178.7 (2) |
C4—C5—C6—C7 | −0.3 (4) | C10—C9—N1—C13 | 1.0 (4) |
C5—C6—C7—C2 | −0.5 (3) | C10—C9—N1—Cd1 | 178.1 (2) |
C5—C6—C7—C8 | −178.5 (2) | C12—C13—N1—C9 | 0.3 (3) |
C3—C2—C7—C6 | 0.8 (3) | C12—C13—N1—Cd1 | −176.80 (16) |
C1—C2—C7—C6 | 177.07 (19) | O2—C1—O1—Cd1ii | −4.6 (2) |
C3—C2—C7—C8 | 178.66 (19) | C2—C1—O1—Cd1ii | 170.47 (13) |
C1—C2—C7—C8 | −5.1 (3) | O1—C1—O2—Cd1 | −96.2 (2) |
C6—C7—C8—O4 | −35.2 (3) | C2—C1—O2—Cd1 | 88.9 (2) |
C2—C7—C8—O4 | 146.9 (2) | O4—C8—O3—Cd1 | −85.3 (2) |
C6—C7—C8—O3 | 141.6 (2) | C7—C8—O3—Cd1 | 98.1 (2) |
C2—C7—C8—O3 | −36.3 (3) | O3—C8—O4—Cd1i | −5.0 (3) |
N1—C9—C10—C11 | −0.8 (5) | C7—C8—O4—Cd1i | 171.77 (13) |
C9—C10—C11—C12 | −0.6 (5) | C16—C15—O5—C14 | −164.9 (2) |
C10—C11—C12—C13 | 1.7 (4) | C17—C15—O5—C14 | 14.2 (3) |
C10—C11—C12—C14 | −177.5 (3) | C12—C14—O5—C15 | 173.4 (2) |
Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+1, −y+1, −z+1; (iii) −x+1/2, −y+5/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9···O3 | 0.93 | 2.23 | 2.900 (3) | 128 |
C14—H14A···O4iv | 0.97 | 2.41 | 3.363 (3) | 166 |
Symmetry code: (iv) −x+1, y+1, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Cd2(C8H4O4)2(C18H16N2O2)] |
Mr | 422.68 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 296 |
a, b, c (Å) | 19.490 (4), 9.985 (2), 15.540 (3) |
β (°) | 96.25 (3) |
V (Å3) | 3006.4 (11) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.48 |
Crystal size (mm) | 0.40 × 0.35 × 0.30 |
Data collection | |
Diffractometer | Bruker APEXII CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2003) |
Tmin, Tmax | 0.559, 0.641 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10582, 2726, 2575 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.600 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.019, 0.050, 1.08 |
No. of reflections | 2726 |
No. of parameters | 218 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.49, −0.50 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL2013 (Sheldrick, 2015), XP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
Cd1—O4i | 2.2173 (16) | Cd1—O2 | 2.3047 (15) |
Cd1—O1ii | 2.2399 (16) | Cd1—N1 | 2.3108 (17) |
Cd1—O3 | 2.2796 (17) | ||
O4i—Cd1—O1ii | 90.11 (6) | O3—Cd1—O2 | 76.45 (5) |
O4i—Cd1—O3 | 99.84 (6) | O4i—Cd1—N1 | 137.80 (6) |
O1ii—Cd1—O3 | 170.06 (6) | O1ii—Cd1—N1 | 90.38 (6) |
O4i—Cd1—O2 | 86.44 (7) | O3—Cd1—N1 | 82.19 (6) |
O1ii—Cd1—O2 | 104.53 (6) | O2—Cd1—N1 | 133.86 (6) |
Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9···O3 | 0.93 | 2.23 | 2.900 (3) | 128.3 |
C14—H14A···O4iii | 0.97 | 2.41 | 3.363 (3) | 166.4 |
Symmetry code: (iii) −x+1, y+1, −z+3/2. |
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