Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615018264/ku3167sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615018264/ku3167Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615018264/ku3167IIsup3.hkl |
CCDC references: 1428595; 1428594
\ Extensive attention has been concentrated on the crystal engineering of new dielectric and ferroelectric materials in recent years, owing to their novel structural characteristics and potential applications, for instance as filters, capacitors, resonators, switchable nonlinear optical devices or solid-state transducer components in microwave communication systems (Vanderah, 2002; Fu et al., 2008; Ye et al., 2013; Shi et al., 2014). In the search for potential ferroelectric materials, molecular-based one-, two- and three-dimensional cadmium(II) organic–inorganic compounds have been of interest as they often display solid–solid phase transitions induced by a variation in temperature (Zhou et al., 2013; Liao & Zhang, 2013). Many reports have been devoted to the formation of infinite polymeric frameworks through carboxylate bridging ligands (Zhang et al., 2012; Wang et al., 2012; Nie & Wang, 2011). According to the literature [References?], carboxylic acid and nitrogen bridging ligands with different coordinating characters are excellent candidates for the construction of novel highly connected topological frameworks. The structural topologies of these polymers are affected by the coordination geometries of the organic ligands and the metal atoms involved. Bridging ligands with N– and O-donor atoms play an instructive role in building coordination polymers. Among the various ligands, the versatile carboxylic acid ligands showing diverse coordination modes, especially for aromatic carboxylic acids, such as benzene- and naphthalene-based carboxylic acids, have been used and well documented in the preparation of numerous carboxylate-containing coordination complexes [References?]. In the present paper, we report two one-dimensional coordination polymers which exhibit interesting structural features. These are catena-poly[[chloridocadmium(II)]-di-µ-chlorido-[chloridocadmium(II)]- bis[µ2-4-(dimethylamino)pyridin-1-ium-1-acetate]-κ3O:O,\ O';κ3O,O':O], (I), and catena-poly[1-cyanomethyl-1,4-diazoniabicyclo[2.2.2]octane [[dichloridocadmium(II)]-µ-oxalato-κ4O1,O2:O1',\ O2'] monohydrate], (II).
4-(Dimethylamino)pyridin-1-ium-1-acetate was prepared according to the literature procedure of Wei et al. (1997). An aqueous solution (15 ml) of 4-(dimethylamino)pyridin-1-ium-1-acetate (0.725 g, 4 mmol) was added slowly to an aqueous solution containing cadmium chloride (0.733 g, 4 mmol), affording a colourless solution. Upon standing at room temperature for several days, suitable colourless single crystals of (I) were obtained by slow solvent evaporation.
1-Cyanomethyl-4-aza-1-azoniabicyclo[2.2.2]octane chloride was prepared according to the literature procedures of Li et al. (2015). An aqueous solution (20 ml) of 1-cyanomethyl-4-aza-1-azoniabicyclo[2.2.2]octane chloride (0.750 g, 4 mmol) was added slowly to an aqueous solution containing cadmium chloride (0.456 g, 2 mmol) and oxalic acid dihydrate (0.252 g, 2 mmol), affording a colourless solution. Upon standing at room temperature for several days, suitable colourless single crystals of (II) were obtained by slow solvent evaporation.
Crystal data, data collection and structure refinement details are summarized in Table 1. C-bound H atoms were included in calculated positions and refined using a riding model, with C—H = 0.93 (pyridine), 0.96 (methyl) or 0.97 Å (methylene), and with Uiso(H) = 1.2Ueq(C) for pyridine and methylene H atoms, and 1.5Ueq(C) for methyl H atoms [Added text OK?]. The water H atoms were located in a difference Fourier synthesis and treated by a mixture of independent and constrained refinement, with O—H and H···H distance restraints of 0.82 (1) and 1.39 (1) Å, respectively.
\ The asymmetric unit of complex (I) contains one CdII cation, two chloride ligands and one 4-(dimethylamino)pyridin-1-ium-1-acetate (L) ligand (Fig. 1). As shown in Fig. 1, the central CdII cation is six-coordinated by three O atoms, O1, O1i and O2i (see Table 2 for geometric parameters and symmetry codes), from two different L carboxylate groups, one terminal Cl2 and two bridging chloride anions (Cl1 and Cl1ii). The CdII centre adopts a distorted CdO3Cl3 octahedral coordination geometry, brought about mainly by the small bite angles [O1—Cd1—O2 = 53.73 (7)°] of the bidentate carboxylate groups (Table 2). The carboxyl O atoms of the L ligands are coordinated to two different CdII cations. Each CdII cation is joined to neighbouring CdII cations through double chloride bridges and monodentate carboxylate groups of L ligands. The Cd—O1/O2 bond lengths range from 2.337 (2) to 2.519 (2) Å and the terminal Cd—Cl2 distance is 2.4621 (9) Å, while the Cd—µ2-Cl1 bond lengths are 2.5476 (8) and 2.6457 (8) Å. Thus, the order of the Cd—Cl distances is clearly differentiated as µ2-Cl > terminal Cl. In general, all the bond lengths and angles are in the normal ranges for those in other CdII compounds (Inomata et al., 2004).
Compound (I) displays a novel coordination architecture compared with the similar compound [CdCl2(Hpipe-4)], (III) (Hpipe-4 is ????; Inomata et al., 2004), in which the central CdII cation is in a distorted octahedral geometry coordinated by two carboxylate O atoms and four bridging Cl atoms, rather than three O atoms of two carboxylate groups, plus one terminal and two bridging chloride anions. It should be pointed out that the structure of (III) consists of a one-dimensional polymer chain bridged only by symmetry-related Cl atoms. This is different from the case of (I), in which the metal atoms are bridged by symmetry-related Cl atoms and O atoms of the carboxylate groups, forming a one-dimensional polymer chain.
In the structure of (I), the corrugated one-dimensional polymer chain has rectangular Cd2(Cl)2 rings and diamond-shaped Cd2(O)2 rings with additional L ligands, extending in the direction of the c axis like a twisted zigzag screen, with a Cd···Cd···Cd bond angle of 155.4 (4)°. The Cd···Cd distance across the bridging Cl atom is 3.821 (9) Å, while the longest Cd···Cd contact across the carboxylate group is 4.125 (1) Å. These twisted zigzag chains are linked into a layer structure in the bc plane via weak π–π interactions between the pyridine rings, with an interplanar distance of 3.888 (5) Å (Fig. 2).
The crystal structure of (I) exhibits two distinct metal-atom coordination modes: one can be described as bidentate chelating and monodentate carboxylate groups, and the other can be described as terminal and bridging chlorides. This is different from what we found in our previous report on catena-poly[1-carboxymethyl-4-(dimethylamino)pyridinium [cadmium(II)-tri-µ-thiocyanato-κ4N:S;κ2S:N] [[[4-(dimethylamino)pyridinium-1-acetate-κ2O,O']cadmium(II)]\ -di-µ-thiocyanato-κ2N:S;κ2S:N]] (Wang & Zhou, 2015), where the carboxylate group exhibits only the bidentate chelating coordination mode. Polymer (I) can thus be considered as the first example of a cadmium–halide/carboxylate complex having various coordination modes. To the best of our knowledge, this distinct type of coordination polymer involving chloride ligands and bidentate chelating and monodentate carboxylate groups has not been reported previously.
In addition to π–π interactions between the pyridine rings, the main intermolecular interactions in (I) are C2—H2···Cl2 and C5—H5···O2 hydrogen-bond interactions linking the L ligands and terminal Cl atoms (Fig. 3 and Table 3). Adjacent coordination polymers are linked together via C2—H2···Cl2? [Please provide missing symmetry code] hydrogen bonds to form a two-dimensional network in the bc plane.
Complex (II) contains one CdII cation, one oxalate ligand, one 1-cyanomethyl-1,4-diazoniabicyclo[2.2.2]octane cation (L'), two chloride ligands and one free water molecule (Fig. 4 and Table 4). As shown in Fig. 4, the central CdII cation is six-coordinated by four O atoms from two oxalate ligands and two terminal Cl ligands, adopting a distorted CdO4Cl2 octahedral coordination geometry. Each CdII cation is joined to neighbouring CdII cations through bridging bis-monodentate oxalate groups, and the organic cation is bonded to the oxalate groups through N1—H1···O2? [Please provide missing symmetry code] hydrogen bonding. The Cd—O and Cd—Cl bond lengths are in good agreement with values found in other CdII complexes with a six-coordinate octahedral geometry (Inomata et al., 2004; Zhou et al., 2013). The tetradentate bridging oxalates chelate to the cadmium centres with different carboxylate groups, forming five-membered CdC2O2 rings composed of atoms Cd1, C9, C9i, O3i and O4 [symmetry code: (i) −x, −y, −z + 1].
In contrast with the structure of (I), in (II) bridging bis-monodentate oxalate groups only exist between adjacent CdII cations to give a chain structure, with a Cd···Cd distance of 5.992 (9) Å. The metal atoms are linked by symmetry-related oxalate groups, forming a one-dimensional zigzag chain, with a Cd···Cd···Cd bond angle of 90.40 (5)°. Additionally, each water molecule is connected to two adjacent coordination polymers by means of O1W—H1A···O4, O1W—H1A···Cl2 and O1W—H1B···Cl1 hydrogen bonds (Fig. 5 and Table 5), forming a network.
Finally, our original interest in (I) and (II) lay mainly in their potential as molecular ferroelectric materials. The variable-temperature dielectric response, especially in the relatively high frequency range, is treated as an effective indicator of a structural phase transition. However, measurement of the dielectric properties of (I) and (II) with varying temperature did not reveal dielectric anomalies over the temperature range 83–393 K. This reveals that the two compounds might not undergo a distinct structural phase transition within this temperature range and so they are not ferroelectric materials like those reported earlier (Ye et al., 2009; Fu et al., 2008). Further phase-transition materials still need to be sought and explored, and related materials are currently being investigated for dielectric properties and ferroelectric activity.
For both compounds, data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
[CdCl2(C9H12N2O2)] | F(000) = 712 |
Mr = 363.51 | Dx = 2.010 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2705 reflections |
a = 10.273 (2) Å | θ = 3.4–27.5° |
b = 15.081 (3) Å | µ = 2.25 mm−1 |
c = 7.7654 (16) Å | T = 293 K |
β = 93.06 (3)° | Block, colourless |
V = 1201.3 (4) Å3 | 0.23 × 0.20 × 0.20 mm |
Z = 4 |
Rigaku SCXmini diffractometer | 2389 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.026 |
Graphite monochromator | θmax = 27.5°, θmin = 3.4° |
ω scans | h = −13→13 |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −19→18 |
Tmin = 0.626, Tmax = 0.662 | l = −9→9 |
8199 measured reflections | 3 standard reflections every 180 reflections |
2705 independent reflections | intensity decay: none |
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)] = 0.027 | H-atom parameters constrained |
wR(F2) = 0.060 | w = 1/[σ2(Fo2) + (0.0255P)2 + 0.4338P] where P = (Fo2 + 2Fc2)/3 |
S = 1.16 | (Δ/σ)max < 0.001 |
2705 reflections | Δρmax = 0.40 e Å−3 |
147 parameters | Δρmin = −0.98 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008) |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0819 (12) |
[CdCl2(C9H12N2O2)] | V = 1201.3 (4) Å3 |
Mr = 363.51 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.273 (2) Å | µ = 2.25 mm−1 |
b = 15.081 (3) Å | T = 293 K |
c = 7.7654 (16) Å | 0.23 × 0.20 × 0.20 mm |
β = 93.06 (3)° |
Rigaku SCXmini diffractometer | 2389 reflections with I > 2σ(I) |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | Rint = 0.026 |
Tmin = 0.626, Tmax = 0.662 | 3 standard reflections every 180 reflections |
8199 measured reflections | intensity decay: none |
2705 independent reflections |
R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
wR(F2) = 0.060 | H-atom parameters constrained |
S = 1.16 | Δρmax = 0.40 e Å−3 |
2705 reflections | Δρmin = −0.98 e Å−3 |
147 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 | 0.031494 (18) | 0.482011 (13) | 0.24224 (2) | 0.02572 (8) | |
Cl2 | 0.27032 (7) | 0.48204 (5) | 0.29061 (11) | 0.03636 (17) | |
Cl1 | −0.02696 (7) | 0.61262 (4) | 0.04490 (9) | 0.03150 (15) | |
O1 | −0.00217 (18) | 0.59393 (13) | 0.4736 (3) | 0.0353 (5) | |
C8 | 0.1001 (2) | 0.62695 (17) | 0.5422 (3) | 0.0247 (6) | |
N1 | 0.2953 (2) | 0.72499 (13) | 0.5061 (3) | 0.0231 (5) | |
C7 | 0.1716 (2) | 0.69114 (17) | 0.4287 (3) | 0.0253 (6) | |
H7A | 0.1888 | 0.6615 | 0.3214 | 0.030* | |
H7B | 0.1148 | 0.7411 | 0.4008 | 0.030* | |
N2 | 0.6425 (2) | 0.82156 (16) | 0.7260 (3) | 0.0326 (5) | |
C4 | 0.4290 (3) | 0.84663 (17) | 0.5900 (4) | 0.0295 (6) | |
H4 | 0.4398 | 0.9078 | 0.5968 | 0.035* | |
C2 | 0.5078 (3) | 0.69823 (18) | 0.6287 (4) | 0.0292 (6) | |
H2 | 0.5721 | 0.6576 | 0.6632 | 0.035* | |
C3 | 0.5311 (2) | 0.79042 (18) | 0.6510 (3) | 0.0248 (6) | |
C5 | 0.3157 (3) | 0.81287 (17) | 0.5217 (4) | 0.0262 (6) | |
H5 | 0.2496 | 0.8516 | 0.4844 | 0.031* | |
C1 | 0.3926 (3) | 0.66909 (17) | 0.5577 (4) | 0.0284 (6) | |
H1 | 0.3799 | 0.6084 | 0.5438 | 0.034* | |
C6 | 0.7460 (3) | 0.7622 (2) | 0.7917 (4) | 0.0420 (8) | |
H6A | 0.7093 | 0.7163 | 0.8597 | 0.063* | |
H6B | 0.8086 | 0.7952 | 0.8619 | 0.063* | |
H6C | 0.7882 | 0.7361 | 0.6967 | 0.063* | |
C9 | 0.6632 (3) | 0.9167 (2) | 0.7448 (5) | 0.0472 (8) | |
H9A | 0.6717 | 0.9428 | 0.6333 | 0.071* | |
H9B | 0.7412 | 0.9272 | 0.8154 | 0.071* | |
H9C | 0.5902 | 0.9427 | 0.7983 | 0.071* | |
O2 | 0.1422 (2) | 0.60966 (14) | 0.6910 (2) | 0.0357 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.02282 (11) | 0.03089 (12) | 0.02344 (12) | −0.00546 (8) | 0.00115 (8) | 0.00155 (8) |
Cl2 | 0.0238 (3) | 0.0330 (4) | 0.0520 (5) | 0.0002 (3) | −0.0009 (3) | 0.0010 (3) |
Cl1 | 0.0374 (4) | 0.0288 (3) | 0.0284 (3) | 0.0005 (3) | 0.0029 (3) | −0.0009 (3) |
O1 | 0.0262 (10) | 0.0400 (12) | 0.0397 (12) | −0.0104 (8) | 0.0014 (9) | 0.0011 (9) |
C8 | 0.0259 (13) | 0.0241 (13) | 0.0244 (14) | 0.0000 (10) | 0.0056 (11) | −0.0020 (11) |
N1 | 0.0204 (10) | 0.0229 (11) | 0.0262 (12) | −0.0030 (9) | 0.0017 (9) | 0.0017 (9) |
C7 | 0.0219 (13) | 0.0285 (14) | 0.0252 (14) | −0.0046 (10) | −0.0031 (11) | 0.0020 (11) |
N2 | 0.0253 (12) | 0.0399 (14) | 0.0324 (13) | −0.0074 (10) | −0.0009 (10) | −0.0053 (11) |
C4 | 0.0299 (14) | 0.0208 (13) | 0.0381 (16) | −0.0019 (11) | 0.0032 (12) | −0.0037 (12) |
C2 | 0.0224 (13) | 0.0291 (14) | 0.0360 (16) | 0.0032 (10) | −0.0008 (12) | 0.0036 (12) |
C3 | 0.0209 (12) | 0.0319 (14) | 0.0221 (13) | −0.0038 (10) | 0.0050 (10) | −0.0014 (11) |
C5 | 0.0238 (13) | 0.0241 (13) | 0.0309 (15) | 0.0029 (10) | 0.0039 (11) | 0.0026 (11) |
C1 | 0.0293 (14) | 0.0212 (13) | 0.0348 (16) | 0.0003 (10) | 0.0022 (12) | 0.0015 (11) |
C6 | 0.0281 (15) | 0.057 (2) | 0.0406 (18) | −0.0053 (14) | −0.0050 (13) | 0.0062 (16) |
C9 | 0.0369 (18) | 0.0455 (19) | 0.059 (2) | −0.0109 (14) | −0.0004 (16) | −0.0155 (17) |
O2 | 0.0401 (12) | 0.0442 (12) | 0.0229 (10) | −0.0109 (9) | 0.0028 (9) | 0.0052 (9) |
Cd1—O2i | 2.337 (2) | N2—C3 | 1.341 (3) |
Cd1—Cl2 | 2.4621 (9) | N2—C9 | 1.456 (4) |
Cd1—O1 | 2.502 (2) | N2—C6 | 1.461 (4) |
Cd1—O1i | 2.519 (2) | C4—C5 | 1.353 (4) |
Cd1—Cl1 | 2.5476 (8) | C4—C3 | 1.410 (4) |
Cd1—Cl1ii | 2.6457 (8) | C4—H4 | 0.9300 |
Cd1—C8i | 2.752 (3) | C2—C1 | 1.352 (4) |
Cl1—Cd1ii | 2.6457 (8) | C2—C3 | 1.420 (4) |
O1—C8 | 1.255 (3) | C2—H2 | 0.9300 |
O1—Cd1i | 2.519 (2) | C5—H5 | 0.9300 |
C8—O2 | 1.240 (3) | C1—H1 | 0.9300 |
C8—C7 | 1.524 (4) | C6—H6A | 0.9600 |
C8—Cd1i | 2.752 (3) | C6—H6B | 0.9600 |
N1—C5 | 1.346 (3) | C6—H6C | 0.9600 |
N1—C1 | 1.352 (3) | C9—H9A | 0.9600 |
N1—C7 | 1.468 (3) | C9—H9B | 0.9600 |
C7—H7A | 0.9700 | C9—H9C | 0.9600 |
C7—H7B | 0.9700 | O2—Cd1i | 2.3372 (19) |
O2i—Cd1—Cl2 | 137.11 (6) | C8—C7—H7A | 108.6 |
O2i—Cd1—O1 | 95.94 (7) | N1—C7—H7B | 108.6 |
Cl2—Cd1—O1 | 93.73 (5) | C8—C7—H7B | 108.6 |
O2i—Cd1—O1i | 53.73 (7) | H7A—C7—H7B | 107.6 |
Cl2—Cd1—O1i | 91.79 (5) | C3—N2—C9 | 120.4 (3) |
O1—Cd1—O1i | 69.52 (8) | C3—N2—C6 | 121.7 (2) |
O2i—Cd1—Cl1 | 115.62 (6) | C9—N2—C6 | 117.9 (2) |
Cl2—Cd1—Cl1 | 107.01 (3) | C5—C4—C3 | 120.9 (2) |
O1—Cd1—Cl1 | 82.71 (5) | C5—C4—H4 | 119.5 |
O1i—Cd1—Cl1 | 147.48 (5) | C3—C4—H4 | 119.5 |
O2i—Cd1—Cl1ii | 83.60 (6) | C1—C2—C3 | 120.4 (3) |
Cl2—Cd1—Cl1ii | 95.81 (4) | C1—C2—H2 | 119.8 |
O1—Cd1—Cl1ii | 166.40 (5) | C3—C2—H2 | 119.8 |
O1i—Cd1—Cl1ii | 119.71 (5) | N2—C3—C4 | 122.5 (3) |
Cl1—Cd1—Cl1ii | 85.25 (3) | N2—C3—C2 | 122.0 (3) |
O2i—Cd1—C8i | 26.65 (7) | C4—C3—C2 | 115.5 (2) |
Cl2—Cd1—C8i | 115.16 (6) | N1—C5—C4 | 122.1 (2) |
O1—Cd1—C8i | 82.81 (7) | N1—C5—H5 | 118.9 |
O1i—Cd1—C8i | 27.10 (7) | C4—C5—H5 | 118.9 |
Cl1—Cd1—C8i | 136.06 (6) | C2—C1—N1 | 122.4 (2) |
Cl1ii—Cd1—C8i | 101.74 (6) | C2—C1—H1 | 118.8 |
Cd1—Cl1—Cd1ii | 94.75 (3) | N1—C1—H1 | 118.8 |
C8—O1—Cd1 | 115.32 (16) | N2—C6—H6A | 109.5 |
C8—O1—Cd1i | 86.85 (16) | N2—C6—H6B | 109.5 |
Cd1—O1—Cd1i | 110.48 (8) | H6A—C6—H6B | 109.5 |
O2—C8—O1 | 123.7 (2) | N2—C6—H6C | 109.5 |
O2—C8—C7 | 121.2 (2) | H6A—C6—H6C | 109.5 |
O1—C8—C7 | 115.1 (2) | H6B—C6—H6C | 109.5 |
O2—C8—Cd1i | 57.69 (13) | N2—C9—H9A | 109.5 |
O1—C8—Cd1i | 66.05 (14) | N2—C9—H9B | 109.5 |
C7—C8—Cd1i | 177.16 (18) | H9A—C9—H9B | 109.5 |
C5—N1—C1 | 118.6 (2) | N2—C9—H9C | 109.5 |
C5—N1—C7 | 120.4 (2) | H9A—C9—H9C | 109.5 |
C1—N1—C7 | 121.0 (2) | H9B—C9—H9C | 109.5 |
N1—C7—C8 | 114.7 (2) | C8—O2—Cd1i | 95.66 (16) |
N1—C7—H7A | 108.6 | ||
O2i—Cd1—Cl1—Cd1ii | −80.56 (6) | Cd1—O1—C8—Cd1i | −111.19 (13) |
Cl2—Cd1—Cl1—Cd1ii | 94.64 (4) | C5—N1—C7—C8 | −124.1 (3) |
O1—Cd1—Cl1—Cd1ii | −173.67 (5) | C1—N1—C7—C8 | 58.2 (3) |
O1i—Cd1—Cl1—Cd1ii | −142.63 (8) | O2—C8—C7—N1 | 3.6 (4) |
Cl1ii—Cd1—Cl1—Cd1ii | 0.0 | O1—C8—C7—N1 | −176.3 (2) |
C8i—Cd1—Cl1—Cd1ii | −102.00 (8) | Cd1i—C8—C7—N1 | 69 (4) |
O2i—Cd1—O1—C8 | 144.06 (18) | C9—N2—C3—C4 | −1.0 (4) |
Cl2—Cd1—O1—C8 | 5.90 (18) | C6—N2—C3—C4 | 178.7 (3) |
O1i—Cd1—O1—C8 | 96.4 (2) | C9—N2—C3—C2 | 179.4 (3) |
Cl1—Cd1—O1—C8 | −100.79 (18) | C6—N2—C3—C2 | −0.9 (4) |
Cl1ii—Cd1—O1—C8 | −128.6 (2) | C5—C4—C3—N2 | −177.1 (3) |
C8i—Cd1—O1—C8 | 120.81 (17) | C5—C4—C3—C2 | 2.5 (4) |
O2i—Cd1—O1—Cd1i | 47.64 (8) | C1—C2—C3—N2 | 177.8 (3) |
Cl2—Cd1—O1—Cd1i | −90.52 (7) | C1—C2—C3—C4 | −1.8 (4) |
O1i—Cd1—O1—Cd1i | 0.0 | C1—N1—C5—C4 | −1.2 (4) |
Cl1—Cd1—O1—Cd1i | 162.79 (7) | C7—N1—C5—C4 | −179.0 (2) |
Cl1ii—Cd1—O1—Cd1i | 134.95 (16) | C3—C4—C5—N1 | −1.1 (4) |
C8i—Cd1—O1—Cd1i | 24.39 (7) | C3—C2—C1—N1 | −0.4 (4) |
Cd1—O1—C8—O2 | −108.2 (3) | C5—N1—C1—C2 | 2.0 (4) |
Cd1i—O1—C8—O2 | 3.0 (3) | C7—N1—C1—C2 | 179.7 (3) |
Cd1—O1—C8—C7 | 71.6 (2) | O1—C8—O2—Cd1i | −3.2 (3) |
Cd1i—O1—C8—C7 | −177.2 (2) | C7—C8—O2—Cd1i | 176.9 (2) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···Cl2iii | 0.93 | 2.67 | 3.582 (3) | 167 |
C5—H5···O2iv | 0.93 | 2.55 | 3.263 (3) | 134 |
Symmetry codes: (iii) −x+1, −y+1, −z+1; (iv) x, −y+3/2, z−1/2. |
(C8H15N3)[CdCl2(C2O4)]·H2O | F(000) = 880 |
Mr = 442.57 | Dx = 1.909 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3518 reflections |
a = 8.4937 (17) Å | θ = 3.1–27.5° |
b = 8.2364 (16) Å | µ = 1.79 mm−1 |
c = 22.015 (4) Å | T = 293 K |
β = 91.57 (3)° | Block, colourless |
V = 1539.5 (5) Å3 | 0.24 × 0.23 × 0.21 mm |
Z = 4 |
Rigaku SCXmini diffractometer | 2866 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.042 |
Graphite monochromator | θmax = 27.5°, θmin = 3.1° |
ω scans | h = −11→10 |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −10→8 |
Tmin = 0.674, Tmax = 0.705 | l = −18→28 |
10055 measured reflections | 3 standard reflections every 180 reflections |
3518 independent reflections | intensity decay: none |
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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.150 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.060P)2 + 9.8P] where P = (Fo2 + 2Fc2)/3 |
3518 reflections | (Δ/σ)max < 0.001 |
193 parameters | Δρmax = 1.02 e Å−3 |
3 restraints | Δρmin = −1.21 e Å−3 |
(C8H15N3)[CdCl2(C2O4)]·H2O | V = 1539.5 (5) Å3 |
Mr = 442.57 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.4937 (17) Å | µ = 1.79 mm−1 |
b = 8.2364 (16) Å | T = 293 K |
c = 22.015 (4) Å | 0.24 × 0.23 × 0.21 mm |
β = 91.57 (3)° |
Rigaku SCXmini diffractometer | 2866 reflections with I > 2σ(I) |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | Rint = 0.042 |
Tmin = 0.674, Tmax = 0.705 | 3 standard reflections every 180 reflections |
10055 measured reflections | intensity decay: none |
3518 independent reflections |
R[F2 > 2σ(F2)] = 0.054 | 3 restraints |
wR(F2) = 0.150 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 1.02 e Å−3 |
3518 reflections | Δρmin = −1.21 e Å−3 |
193 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 | 0.24393 (5) | −0.02846 (6) | 0.40479 (2) | 0.02987 (17) | |
Cl1 | 0.2663 (2) | −0.2561 (3) | 0.33064 (9) | 0.0514 (5) | |
Cl2 | 0.1598 (3) | 0.2020 (3) | 0.33618 (10) | 0.0655 (7) | |
O1 | 0.6200 (6) | 0.1686 (6) | 0.5128 (2) | 0.0452 (13) | |
O2 | 0.4828 (5) | 0.1000 (6) | 0.42967 (19) | 0.0331 (10) | |
O3 | −0.0122 (6) | 0.1356 (7) | 0.5609 (2) | 0.0460 (14) | |
O4 | 0.1657 (6) | 0.1219 (7) | 0.4893 (2) | 0.0485 (14) | |
C9 | 0.0433 (7) | 0.0731 (9) | 0.5142 (3) | 0.0316 (14) | |
C10 | 0.5300 (7) | 0.0788 (8) | 0.4844 (3) | 0.0303 (14) | |
N1 | 0.3777 (7) | 0.6397 (7) | 0.6182 (3) | 0.0331 (12) | |
H1 | 0.431 (9) | 0.717 (10) | 0.606 (3) | 0.040* | |
N2 | 0.2470 (5) | 0.3892 (6) | 0.6574 (2) | 0.0240 (10) | |
N3 | 0.3535 (10) | 0.0014 (8) | 0.6992 (4) | 0.058 (2) | |
C1 | 0.4135 (11) | 0.5004 (10) | 0.5786 (3) | 0.049 (2) | |
H1C | 0.5262 | 0.4812 | 0.5793 | 0.059* | |
H1D | 0.3798 | 0.5244 | 0.5371 | 0.059* | |
C2 | 0.3307 (10) | 0.3528 (9) | 0.6003 (3) | 0.0430 (18) | |
H2A | 0.4064 | 0.2663 | 0.6076 | 0.052* | |
H2B | 0.2554 | 0.3164 | 0.5693 | 0.052* | |
C4 | 0.2050 (9) | 0.6692 (9) | 0.6186 (4) | 0.050 (2) | |
H4B | 0.1645 | 0.6870 | 0.5775 | 0.060* | |
H4C | 0.1826 | 0.7648 | 0.6426 | 0.060* | |
C3 | 0.1266 (8) | 0.5190 (10) | 0.6462 (5) | 0.053 (2) | |
H3A | 0.0786 | 0.5483 | 0.6842 | 0.064* | |
H3B | 0.0445 | 0.4790 | 0.6186 | 0.064* | |
C5 | 0.4386 (8) | 0.6057 (9) | 0.6808 (3) | 0.0374 (16) | |
H5A | 0.4122 | 0.6948 | 0.7074 | 0.045* | |
H5B | 0.5524 | 0.5955 | 0.6807 | 0.045* | |
C6 | 0.3672 (8) | 0.4507 (9) | 0.7036 (3) | 0.0336 (15) | |
H6A | 0.3171 | 0.4704 | 0.7420 | 0.040* | |
H6B | 0.4489 | 0.3698 | 0.7102 | 0.040* | |
C7 | 0.1602 (8) | 0.2427 (8) | 0.6807 (3) | 0.0340 (15) | |
H7A | 0.1085 | 0.2707 | 0.7180 | 0.041* | |
H7B | 0.0800 | 0.2100 | 0.6510 | 0.041* | |
C8 | 0.2695 (9) | 0.1074 (9) | 0.6921 (3) | 0.0392 (16) | |
O1W | 0.1737 (17) | 0.4808 (11) | 0.4612 (5) | 0.148 (5) | |
H1A | 0.1892 | 0.3929 | 0.4448 | 0.222* | |
H1B | 0.2023 | 0.5546 | 0.4390 | 0.222* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.0244 (2) | 0.0393 (3) | 0.0260 (2) | −0.0055 (2) | 0.00296 (16) | −0.0035 (2) |
Cl1 | 0.0379 (9) | 0.0613 (13) | 0.0552 (11) | 0.0046 (8) | 0.0033 (8) | −0.0250 (10) |
Cl2 | 0.0707 (14) | 0.0750 (17) | 0.0516 (12) | 0.0379 (12) | 0.0128 (10) | 0.0201 (11) |
O1 | 0.056 (3) | 0.038 (3) | 0.040 (3) | −0.018 (2) | −0.011 (2) | 0.009 (2) |
O2 | 0.035 (2) | 0.035 (3) | 0.030 (2) | −0.011 (2) | −0.0050 (18) | 0.010 (2) |
O3 | 0.038 (3) | 0.062 (4) | 0.039 (3) | −0.021 (2) | 0.014 (2) | −0.024 (2) |
O4 | 0.046 (3) | 0.054 (4) | 0.047 (3) | −0.024 (3) | 0.019 (2) | −0.023 (3) |
C9 | 0.029 (3) | 0.039 (4) | 0.027 (3) | −0.007 (3) | 0.005 (2) | −0.003 (3) |
C10 | 0.031 (3) | 0.030 (4) | 0.029 (3) | −0.005 (3) | 0.000 (2) | 0.002 (3) |
N1 | 0.035 (3) | 0.024 (3) | 0.039 (3) | −0.009 (2) | −0.001 (2) | 0.010 (2) |
N2 | 0.023 (2) | 0.019 (3) | 0.029 (3) | −0.0006 (19) | −0.0014 (19) | 0.001 (2) |
N3 | 0.079 (5) | 0.029 (4) | 0.064 (5) | 0.003 (3) | −0.013 (4) | 0.009 (3) |
C1 | 0.060 (5) | 0.058 (6) | 0.030 (4) | −0.011 (4) | 0.012 (3) | 0.001 (3) |
C2 | 0.066 (5) | 0.036 (4) | 0.027 (3) | −0.011 (4) | 0.009 (3) | −0.007 (3) |
C4 | 0.038 (4) | 0.030 (4) | 0.082 (6) | −0.005 (3) | −0.007 (4) | 0.015 (4) |
C3 | 0.022 (3) | 0.039 (5) | 0.098 (7) | 0.005 (3) | −0.001 (4) | 0.024 (4) |
C5 | 0.040 (4) | 0.034 (4) | 0.037 (4) | −0.012 (3) | −0.007 (3) | 0.004 (3) |
C6 | 0.037 (3) | 0.037 (4) | 0.027 (3) | −0.013 (3) | −0.004 (3) | 0.000 (3) |
C7 | 0.033 (3) | 0.029 (4) | 0.040 (4) | −0.012 (3) | −0.005 (3) | 0.003 (3) |
C8 | 0.054 (4) | 0.027 (4) | 0.036 (4) | −0.012 (3) | −0.006 (3) | 0.003 (3) |
O1W | 0.222 (14) | 0.077 (7) | 0.139 (10) | −0.029 (7) | −0.085 (9) | 0.010 (6) |
Cd1—O3i | 2.303 (5) | N3—C8 | 1.136 (10) |
Cd1—O2 | 2.340 (4) | C1—C2 | 1.490 (10) |
Cd1—O4 | 2.346 (5) | C1—H1C | 0.9700 |
Cd1—O1ii | 2.418 (5) | C1—H1D | 0.9700 |
Cd1—Cl1 | 2.496 (2) | C2—H2A | 0.9700 |
Cd1—Cl2 | 2.517 (2) | C2—H2B | 0.9700 |
O1—C10 | 1.223 (8) | C4—C3 | 1.538 (10) |
O1—Cd1ii | 2.418 (5) | C4—H4B | 0.9700 |
O2—C10 | 1.271 (7) | C4—H4C | 0.9700 |
O3—C9 | 1.253 (8) | C3—H3A | 0.9700 |
O3—Cd1i | 2.303 (5) | C3—H3B | 0.9700 |
O4—C9 | 1.255 (8) | C5—C6 | 1.506 (9) |
C9—C9i | 1.535 (13) | C5—H5A | 0.9700 |
C10—C10ii | 1.560 (13) | C5—H5B | 0.9700 |
N1—C1 | 1.477 (10) | C6—H6A | 0.9700 |
N1—C5 | 1.484 (8) | C6—H6B | 0.9700 |
N1—C4 | 1.487 (9) | C7—C8 | 1.468 (10) |
N1—H1 | 0.83 (8) | C7—H7A | 0.9700 |
N2—C2 | 1.492 (8) | C7—H7B | 0.9700 |
N2—C3 | 1.496 (8) | O1W—H1A | 0.8207 |
N2—C6 | 1.508 (8) | O1W—H1B | 0.8200 |
N2—C7 | 1.510 (8) | ||
O3i—Cd1—O2 | 147.11 (16) | C2—C1—H1D | 109.7 |
O3i—Cd1—O4 | 71.28 (17) | H1C—C1—H1D | 108.2 |
O2—Cd1—O4 | 80.69 (17) | C1—C2—N2 | 110.2 (6) |
O3i—Cd1—O1ii | 88.05 (19) | C1—C2—H2A | 109.6 |
O2—Cd1—O1ii | 69.31 (16) | N2—C2—H2A | 109.6 |
O4—Cd1—O1ii | 78.3 (2) | C1—C2—H2B | 109.6 |
O3i—Cd1—Cl1 | 90.43 (13) | N2—C2—H2B | 109.6 |
O2—Cd1—Cl1 | 114.32 (13) | H2A—C2—H2B | 108.1 |
O4—Cd1—Cl1 | 160.59 (14) | N1—C4—C3 | 108.0 (6) |
O1ii—Cd1—Cl1 | 95.09 (14) | N1—C4—H4B | 110.1 |
O3i—Cd1—Cl2 | 104.75 (17) | C3—C4—H4B | 110.1 |
O2—Cd1—Cl2 | 91.70 (13) | N1—C4—H4C | 110.1 |
O4—Cd1—Cl2 | 89.76 (17) | C3—C4—H4C | 110.1 |
O1ii—Cd1—Cl2 | 158.82 (14) | H4B—C4—H4C | 108.4 |
Cl1—Cd1—Cl2 | 101.50 (8) | N2—C3—C4 | 109.8 (6) |
C10—O1—Cd1ii | 111.9 (4) | N2—C3—H3A | 109.7 |
C10—O2—Cd1 | 114.1 (4) | C4—C3—H3A | 109.7 |
C9—O3—Cd1i | 117.1 (4) | N2—C3—H3B | 109.7 |
C9—O4—Cd1 | 115.7 (4) | C4—C3—H3B | 109.7 |
O3—C9—O4 | 124.2 (6) | H3A—C3—H3B | 108.2 |
O3—C9—C9i | 118.0 (7) | N1—C5—C6 | 109.7 (5) |
O4—C9—C9i | 117.8 (7) | N1—C5—H5A | 109.7 |
O1—C10—O2 | 125.2 (6) | C6—C5—H5A | 109.7 |
O1—C10—C10ii | 119.0 (7) | N1—C5—H5B | 109.7 |
O2—C10—C10ii | 115.7 (7) | C6—C5—H5B | 109.7 |
C1—N1—C5 | 109.2 (6) | H5A—C5—H5B | 108.2 |
C1—N1—C4 | 110.5 (6) | C5—C6—N2 | 109.3 (5) |
C5—N1—C4 | 110.1 (6) | C5—C6—H6A | 109.8 |
C1—N1—H1 | 106 (5) | N2—C6—H6A | 109.8 |
C5—N1—H1 | 105 (5) | C5—C6—H6B | 109.8 |
C4—N1—H1 | 115 (5) | N2—C6—H6B | 109.8 |
C2—N2—C3 | 110.1 (6) | H6A—C6—H6B | 108.3 |
C2—N2—C6 | 107.9 (5) | C8—C7—N2 | 110.6 (5) |
C3—N2—C6 | 108.5 (6) | C8—C7—H7A | 109.5 |
C2—N2—C7 | 111.9 (5) | N2—C7—H7A | 109.5 |
C3—N2—C7 | 106.8 (5) | C8—C7—H7B | 109.5 |
C6—N2—C7 | 111.5 (5) | N2—C7—H7B | 109.5 |
N1—C1—C2 | 109.8 (6) | H7A—C7—H7B | 108.1 |
N1—C1—H1C | 109.7 | N3—C8—C7 | 178.0 (8) |
C2—C1—H1C | 109.7 | H1A—O1W—H1B | 109.8 |
N1—C1—H1D | 109.7 | ||
O3i—Cd1—O2—C10 | 22.9 (7) | N1—C1—C2—N2 | −4.0 (9) |
O4—Cd1—O2—C10 | 54.4 (5) | C3—N2—C2—C1 | 60.9 (8) |
O1ii—Cd1—O2—C10 | −26.5 (5) | C6—N2—C2—C1 | −57.4 (8) |
Cl1—Cd1—O2—C10 | −112.7 (5) | C7—N2—C2—C1 | 179.5 (6) |
Cl2—Cd1—O2—C10 | 143.9 (5) | C1—N1—C4—C3 | 63.3 (9) |
O3i—Cd1—O4—C9 | 2.5 (5) | C5—N1—C4—C3 | −57.4 (9) |
O2—Cd1—O4—C9 | −160.1 (6) | C2—N2—C3—C4 | −54.8 (9) |
O1ii—Cd1—O4—C9 | −89.5 (6) | C6—N2—C3—C4 | 63.1 (9) |
Cl1—Cd1—O4—C9 | −17.9 (9) | C7—N2—C3—C4 | −176.5 (7) |
Cl2—Cd1—O4—C9 | 108.2 (5) | N1—C4—C3—N2 | −5.6 (10) |
Cd1i—O3—C9—O4 | 177.7 (6) | C1—N1—C5—C6 | −57.3 (8) |
Cd1i—O3—C9—C9i | −2.6 (11) | C4—N1—C5—C6 | 64.1 (8) |
Cd1—O4—C9—O3 | 177.6 (6) | N1—C5—C6—N2 | −4.8 (8) |
Cd1—O4—C9—C9i | −2.1 (10) | C2—N2—C6—C5 | 62.2 (7) |
Cd1ii—O1—C10—O2 | −156.2 (6) | C3—N2—C6—C5 | −57.1 (7) |
Cd1ii—O1—C10—C10ii | 21.6 (10) | C7—N2—C6—C5 | −174.5 (6) |
Cd1—O2—C10—O1 | −156.4 (6) | C2—N2—C7—C8 | 58.6 (7) |
Cd1—O2—C10—C10ii | 25.7 (9) | C3—N2—C7—C8 | 179.1 (6) |
C5—N1—C1—C2 | 62.8 (8) | C6—N2—C7—C8 | −62.4 (7) |
C4—N1—C1—C2 | −58.4 (8) | N2—C7—C8—N3 | −86 (24) |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2iii | 0.83 (8) | 1.86 (8) | 2.679 (7) | 169 (8) |
O1W—H1A···O4 | 0.82 | 2.45 | 3.021 (11) | 128 |
O1W—H1A···Cl2 | 0.82 | 2.87 | 3.583 (11) | 147 |
O1W—H1B···Cl1iv | 0.82 | 2.91 | 3.701 (12) | 162 |
Symmetry codes: (iii) −x+1, −y+1, −z+1; (iv) x, y+1, z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [CdCl2(C9H12N2O2)] | (C8H15N3)[CdCl2(C2O4)]·H2O |
Mr | 363.51 | 442.57 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 10.273 (2), 15.081 (3), 7.7654 (16) | 8.4937 (17), 8.2364 (16), 22.015 (4) |
β (°) | 93.06 (3) | 91.57 (3) |
V (Å3) | 1201.3 (4) | 1539.5 (5) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 2.25 | 1.79 |
Crystal size (mm) | 0.23 × 0.20 × 0.20 | 0.24 × 0.23 × 0.21 |
Data collection | ||
Diffractometer | Rigaku SCXmini diffractometer | Rigaku SCXmini diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2005) | Multi-scan (CrystalClear; Rigaku, 2005) |
Tmin, Tmax | 0.626, 0.662 | 0.674, 0.705 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8199, 2705, 2389 | 10055, 3518, 2866 |
Rint | 0.026 | 0.042 |
(sin θ/λ)max (Å−1) | 0.649 | 0.649 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.060, 1.16 | 0.054, 0.150, 1.08 |
No. of reflections | 2705 | 3518 |
No. of parameters | 147 | 193 |
No. of restraints | 0 | 3 |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.40, −0.98 | 1.02, −1.21 |
Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005).
Cd1—O2i | 2.337 (2) | Cd1—Cl1 | 2.5476 (8) |
Cd1—Cl2 | 2.4621 (9) | Cd1—Cl1ii | 2.6457 (8) |
Cd1—O1 | 2.502 (2) | Cl1—Cd1ii | 2.6457 (8) |
Cd1—O1i | 2.519 (2) | O1—Cd1i | 2.519 (2) |
O2i—Cd1—Cl2 | 137.11 (6) | Cl2—Cd1—Cl1ii | 95.81 (4) |
O2i—Cd1—O1i | 53.73 (7) | O1i—Cd1—Cl1ii | 119.71 (5) |
O2i—Cd1—Cl1ii | 83.60 (6) | Cl1—Cd1—Cl1ii | 85.25 (3) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···Cl2iii | 0.93 | 2.67 | 3.582 (3) | 167.2 |
C5—H5···O2iv | 0.93 | 2.55 | 3.263 (3) | 134.2 |
Symmetry codes: (iii) −x+1, −y+1, −z+1; (iv) x, −y+3/2, z−1/2. |
Cd1—O3i | 2.303 (5) | Cd1—Cl1 | 2.496 (2) |
Cd1—O2 | 2.340 (4) | Cd1—Cl2 | 2.517 (2) |
Cd1—O4 | 2.346 (5) | O1—Cd1ii | 2.418 (5) |
Cd1—O1ii | 2.418 (5) | O3—Cd1i | 2.303 (5) |
O3i—Cd1—O2 | 147.11 (16) | O2—Cd1—Cl1 | 114.32 (13) |
O3i—Cd1—O4 | 71.28 (17) | O4—Cd1—Cl1 | 160.59 (14) |
O2—Cd1—O4 | 80.69 (17) | O2—Cd1—Cl2 | 91.70 (13) |
O4—Cd1—O1ii | 78.3 (2) | Cl1—Cd1—Cl2 | 101.50 (8) |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2iii | 0.83 (8) | 1.86 (8) | 2.679 (7) | 169 (8) |
O1W—H1A···O4 | 0.82 | 2.45 | 3.021 (11) | 127.8 |
O1W—H1A···Cl2 | 0.82 | 2.87 | 3.583 (11) | 146.9 |
O1W—H1B···Cl1iv | 0.82 | 2.91 | 3.701 (12) | 161.5 |
Symmetry codes: (iii) −x+1, −y+1, −z+1; (iv) x, y+1, z. |