A novel cadmium(II) coordination polymer containing two kinds of independent one-dimensional chain

The structure of the title compound, catena-poly[[cad­mium(II)-di-[mu]-chlorido-[mu]-(1,4-diazonia­bicyclo­[2.2.2]oc­tane-1-carboxyl­ato)] [[aquachlorido­cadmium(II)]-di-[mu]-chlorido] dihydrate], {[Cd(C₈H₁₅N₂O₂)Cl₂][CdCl₃(H₂O)]·2H₂O}_n, con­tains two kinds of independent one-dimensional chain, viz. {[Cd(C₈H₁₅N₂O₂)Cl₂]⁺}_n and {[CdCl₃(H₂O)]^-}_n, and uncoordinated water mol­ecules. Each Cd^II cation in the {[Cd(C₈H₁₅N₂O₂)Cl₂]⁺}_n chain is octa­hedrally coordinated by two pairs of bridging chloride ligands and two O atoms from different bridging carboxyl­ate groups. Cd^II cations in the {[CdCl₃(H₂O)]^-}_n chain are also octa­hedrally surrounded by four bridging chloride ligands, one terminal chloride ligand and one coordinated water mol­ecule. Hydrogen bonds between solvent water mol­ecules and these two independent chains generate a three-dimensional framework containing two-dimensional zigzag layers.

S1. Introduction

The design and synthesis of coordination polymers are of great inter­est due to their intriguing structural diversity and potential applications as functional materials (Kitagawa & Kondo, 1998; Hagrman et al., 1999; Moulton & Zaworotko, 2001). As part of this inter­est in coordination polymers, attention has been devoted to one-, two- and three-dimensional chloridocadmate(II) compounds. Among the one-dimensional polymeric chloridocadmates, a great variety of architectures, such as linear chains (Schroder et al., 1983; Corradi et al., 1997), zigzag chains (Charles et al., 1984; Corradi et al., 1997) and ribbon-like chains (Rolies & De Ranter, 1978; Bats et al., 1979; Corradi et al., 1993; Thorn et al., 2006), have been reported in recent decades. However, chloridocadmates containing two kinds of independent one-dimensional chain have rarely been explored. Additionally, coordination polymers constructed with double betaine ligands, such as 1,4-diazo­niabi­cyclo­[2.2.2]o­ctane-l,4-di­acetate (Wei et al., 1997, 1998), 1,4-bis­(2-picolyloxyl)benzene-N,N'-di­acetate (Zhang et al., 2004) and 1,3-bis­(pyridinio-4-acetato)­propane (Wu et al., 2006), have been widely studied, but reports of coordination polymers based on mono-betaine ligands, like 1,4-di­aza­bicyclo­[2.2.2]o­ctane-1-acetate (DABCO mono-betaine), are rare. Against this background, we present here the title compound, {[CdCl₂(DABCO mono-betaine)][CdCl₃(H₂O)].2H₂O}_n, (I), containing two kinds of independent one-dimensional chain.

S2. Synthesis and crystallization

Experimental details are summarized in Table 1.

DABCO mono-betaine tri­hydro­chloride dihydrate was prepared according to the literature method of Barczyński et al. (2009). The title compound was synthesized by adding a solution of cadmium chloride (1.141 g, 5 mmol) to a solution of DABCO mono-betaine tri­hydro­chloride dihydrate (2.429 g, 5 mmol) in water (50 ml). Colourless crystals of (I) were obtained by slow evaporation of the solvent over a period of a few weeks.

S3. Refinement

Considering the difficulty of finding H atoms in a difference Fourier map derived from room-temperature data in a crystal containing heavy atoms such as Cd, all N- and C-bound H atoms were generated geometrically and refined using a riding model, with N—H = 0.91 Å or C—H = 0.96 Å, and with U_iso(H) = 1.2U_eq(N,C). All water H atoms were found in a difference Fourier map. However, they were then placed in ideal positions and refined using a rotating model, with U_iso(H) = 1.5U_eq(O), and with restraints for the O—H and H···H distances of 0.85 (2) and 1.38 (2) Å, respectively.

S4. Comment

Compound (I) crystallizes in the orthorhombic space group Pbca. The structure consists of one-dimensional cationic {[CdCl₂(DABCO mono-betaine)]⁺}_n chains, one-dimensional anionic {[CdCl₃(H₂O)]^-}_n chains and uncoordinated water molecules (Fig. 1). These two kinds of one-dimensional chain are totally different. In the {[CdCl₂(DABCO mono-betaine)]⁺}_n chain, atom Cd1 is o­cta­hedrally surrounded by two pairs of bridging chloride ligands [Cl1/Cl1ⁱⁱ and Cl2/Cl2ⁱ; symmetry codes: (i) x + 1/2, -y + 1/2, -z; (ii) x - 1/2, -y + 1/2, -z] and two O atoms (O1 and O2) from different bridging carboxyl­ate groups. The four chloride ligands form a square plane, which extends into a zigzag in the direction of the a axis like an infinite folding screen, sharing opposite edges (Fig. 2). The carboxyl­ate group is coordinated in a fork-like manner to two Cd^II cations. A similar metal–ligand coordination to that observed in this chain is common in cadmium complexes with amino acids and their derivatives (Yukawa et al., 1982, 1983; Schaffers & Keszler, 1993; Kobayashi et al., 1997) but unusual in cadmium complexes constructed with betaine ligands. The mean Cd1—Cl distance [2.6530 (14) Å] is longer, while the average Cd1—O bond length [2.2715 (4) Å] is shorter, than those found in cadmium complexes with amino acids (Table 2). The carboxyl­ate groups in this chain show a bridging bidentate coordination mode, different from that in the one-dimensional polymeric chloridocadmate based on DABCO dibetaine (Wu & Mak, 1996), in which only one of the two carboxyl­ate O atoms is coordinated to a Cd^II cation. The coordination geometry about atom Cd1 is distorted o­cta­hedral and the most distorted angle of the o­cta­hedron is O2—Cd1—Cl1ⁱⁱ [85.27 (11)°]. In contrast, atom Cd2 in the {[CdCl₃(H₂O)]^-}_n chain is o­cta­hedrally coordinated to four bridging chloride ligands [Cl3, Cl3^iv, Cl5 and Cl5ⁱⁱⁱ; symmetry codes: (iii) x + 1/2, y, -z + 1/2; (iv) x - 1/2, y, -z + 1/2], one terminal chloride ligand (Cl4) and one coordinated water molecule (O1W). The water molecules and the terminal chloride ligands are in trans positions with respect to one another, giving rise to a linear polymeric chain of edge-sharing o­cta­hedra running along the a axis (Fig. 2). The Cd2—Cl bond lengths have expected values (Leligny & Monier, 1974, 1975) and the nonbridging Cd2—Cl distance is shorter than the others, in agreement with literature results (Yu et al., 2009). The Cd2—O1W bond length [2.357 4) Å] is comparable with corresponding bond lengths in other compounds containing {[CdCl₃(H₂O)]^-}_n chains (Charles et al., 1984; Corradi et al., 1997; Adams et al., 2010). The o­cta­hedral geometry around the Cd2 atom is also distorted, with the O1W—Cd2—Cl5ⁱⁱⁱ angle being 83.96 (10)° (Table 2). Therefore, two kinds of independent one-dimensional chain can be discerned in (I).

A structural configuration with two kinds of independent one-dimensional chain is rarely seen among one-dimensional polymeric chloridocadmates. To the best of our knowledge, only one chloridocadmate compound, {[Cd₄(bet)₄Cl₆(H₂O)₄][Cd₂Cl₆]}_n [bet = (CH₃)₃NCH₂CO₂; Che et al., 2007], containing such a structural configuration has been reported to date. The [Cd₂Cl₆]_n chain of that compound contains two independent Cd^II cations, which are linked by three µ₂-chloride ligands. The [Cd₄(bet)₄Cl₆(H₂O)₄]_n chain there consists of three independent Cd^II cations, which are six-coordinated by Cl and O atoms and bridged by µ³- and µ²-chloride ligands. Hence, the coordination architectures of both chains in that compound are completely different from those in complex (I). In addition, Cai (2011) has reported a simple cadmium(II) complex based on DABCO mono-betaine, [Cd₂Br₄(C₈H₁₅N₂O₂)₂(NO₂)₂].2H₂O, in which each Cd^II cation is coordinated by two O atoms from a bidentate nitrite anion, three bromide anions and one N atom from an organic ligand. However, a coordination polymer of DABCO mono-betaine has never been studied. Thus, complex (I) contains a novel structural configuration and is the first example of a coordination polymer constructed with DABCO mono-betaine.

The presence of solvent molecules can modulate the distances between chains or layers and give rise to distinctive hydrogen-bonding features. Two kinds of free water atom (O2W and O3W) can be found in (I). Atom O2W acts as a fourfold hydrogen-bond donor in O2W—H2WA···Cl1, O2W—H2WB···Cl4ⁱⁱⁱ, O2W—H2WB···Cl5^x and O2W—H2WA···Cl2^x hydrogen bonds, and also as a twofold hydrogen-bond acceptor in O1W—H1WB···O2W^v and N1—H1···O2W^vi hydrogen bonds [symmetry codes: (v) x - 1, y, z; (vi) -x + 5/2, y + 1/2, z; (x) x + 1, y, z] (Table 3). Atom O3W acts as a hydrogen-bond donor to atom Cl3^viii via atom H3WB, and also as a hydrogen-bond acceptor in the N1—H1···O3W^vii hydrogen bond [symmetry codes: (vii) -x + 5/2, y - 1/2, z; (viii) -x + 3/2, y + 1/2, z]. There is also an O1W—H1WA···Cl4ⁱⁱⁱ hydrogen bond (Table 3). The hydrogen-bonding inter­actions between the solvent water molecules and these two independent chains generate a one-dimensional hydrogen-bonded chain in which the {[CdCl₂(DABCO mono-betaine)]⁺}_n chain is sandwiched between two {[CdCl₃(H₂O)]^-}_n chains (Fig. 2). These hydrogen-bonded chains extend in a zigzag in the direction of the c axis, giving rise to two-dimensional zigzag layers, which are further linked into a three-dimensional framework through O3W—H3WA···Cl5^ix [symmetry code: (ix) x + 1, y + 1, z] hydrogen bonds (Fig. 3).

In summary, we report here a novel cadmium coordination polymer containing two kinds of independent one-dimensional chain. The complex is also the first example of a coordination polymer based on DABCO mono-betaine. Chloridocadamates(II) represent a potential class of materials with unusual structural archetypes and, with suitable ligands, chloridocadmate(II) can form many intriguing coordination polymers. On the other hand, DABCO mono-betaine, being less flexible than double betaine ligands, can also construct novel coordination polymers.

Related literature

For related literature, see: Adams et al. (2010); Barczyński et al. (2009); Bats et al. (1979); Cai (2011); Charles et al. (1984); Che et al. (2007); Corradi et al. (1993, 1997); Hagrman et al. (1999); Kitagawa & Kondo (1998); Kobayashi et al. (1997); Leligny & Monier (1974, 1975); Moulton & Zaworotko (2001); Rolies & De Ranter (1978); Schaffers & Keszler (1993); Schroder et al. (1983); Thorn et al. (2006); Wei et al. (1997, 1998); Wu & Mak (1996); Wu et al. (2006); Yu et al. (2009); Yukawa et al. (1982, 1983); Zhang et al. (2004).

Computing details

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).

Figures

	Fig. 1. The two independent coordination polymers in (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) x + 1/2, -y + 1/2, -z; (ii) x - 1/2, -y + 1/2, -z; (iii) x + 1/2, y, -z + 1/2; (iv) x - 1/2, y, -z + 1/2.]
	Fig. 2. A view of the packing of (I). Dashed lines indicate hydrogen bonds. H atoms not involved in these interactions or bonded to C atoms have been omitted for clarity.
	Fig. 3. A packing diagram for (I), showing the hydrogen bond-derived (dashed lines) three-dimensional supramolecular network with two-dimensional zigzag layers. H atoms not involved in these interactions or bonded to C atoms have been omitted for clarity.

catena-Poly[[cadmium(II)-di-µ-chlorido-µ-(4-azonia-1-azabicyclo[2.2.2]octane-1-carboxylato)] [aquadi-µ-chlorido-chloridocadmium(II)] dihydrate]

Crystal data

[CdCl2(C8H15N2O2)][CdCl3(H2O)]·2H2O	F(000) = 2432
Mr = 627.34	Dx = 2.246 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 12903 reflections
a = 7.4502 (15) Å	θ = 3.1–27.5°
b = 16.337 (3) Å	µ = 3.03 mm^−1
c = 30.484 (6) Å	T = 298 K
V = 3710.3 (12) Å^3	Block, colourless
Z = 8	0.36 × 0.32 × 0.28 mm

Data collection

Rigaku SCXmini diffractometer	4251 independent reflections
Radiation source: fine-focus sealed tube	3076 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.087
Detector resolution: 13.6612 pixels mm^-1	θmax = 27.5°, θmin = 2.8°
ω scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −21→21
Tmin = 0.349, Tmax = 0.428	l = −39→39
33275 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.099	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0356P)^2 + 6.3607P] where P = (Fo^2 + 2Fc^2)/3
4251 reflections	(Δ/σ)max = 0.001
199 parameters	Δρmax = 0.64 e Å^−3
0 restraints	Δρmin = −1.13 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.7747 (8)	0.3800 (3)	0.05341 (17)	0.0234 (12)
C2	0.7963 (7)	0.4517 (3)	0.08524 (19)	0.0226 (12)
H2A	0.7504	0.5006	0.0712	0.027*
H2B	0.7221	0.4412	0.1108	0.027*
C3	0.9738 (7)	0.5385 (3)	0.1331 (2)	0.0305 (14)
H3A	0.9120	0.5205	0.1594	0.037*
H3B	0.9065	0.5835	0.1204	0.037*
C4	1.1619 (7)	0.5668 (4)	0.14463 (19)	0.0302 (14)
H4A	1.1876	0.6185	0.1302	0.036*
H4B	1.1722	0.5747	0.1761	0.036*
C5	1.1074 (7)	0.4951 (3)	0.06417 (17)	0.0239 (13)
H5A	1.0686	0.5477	0.0528	0.029*
H5B	1.1024	0.4556	0.0405	0.029*
C6	1.3006 (7)	0.5019 (4)	0.08117 (19)	0.0278 (14)
H6A	1.3713	0.4557	0.0711	0.033*
H6B	1.3559	0.5519	0.0705	0.033*
C7	1.0644 (7)	0.3958 (3)	0.12398 (19)	0.0270 (13)
H7A	1.0895	0.3526	0.1031	0.032*
H7B	0.9799	0.3750	0.1455	0.032*
C8	1.2366 (9)	0.4218 (4)	0.1466 (2)	0.0375 (16)
H8A	1.2176	0.4248	0.1780	0.045*
H8B	1.3302	0.3819	0.1410	0.045*
Cd1	0.51895 (5)	0.25781 (2)	0.004663 (13)	0.02062 (12)
Cd2	0.15774 (6)	0.25813 (2)	0.257302 (14)	0.02571 (13)
Cl1	0.76339 (19)	0.15082 (9)	0.03319 (5)	0.0302 (3)
Cl2	0.25908 (18)	0.21954 (9)	0.05834 (4)	0.0276 (3)
Cl3	0.41295 (19)	0.37021 (8)	0.25836 (5)	0.0275 (3)
Cl4	0.1115 (2)	0.26059 (10)	0.34011 (5)	0.0365 (4)
Cl5	−0.09139 (19)	0.14587 (8)	0.24397 (5)	0.0290 (3)
N2	0.9849 (6)	0.4687 (3)	0.10063 (14)	0.0184 (9)
N1	1.2919 (5)	0.5028 (3)	0.12966 (16)	0.0252 (11)
H1	1.4026	0.5150	0.1404	0.030*
O1	0.6146 (5)	0.3649 (2)	0.04458 (13)	0.0299 (10)
O2	0.4115 (5)	0.1537 (2)	−0.03861 (14)	0.0368 (11)
O1W	0.1928 (5)	0.2558 (2)	0.18047 (12)	0.0288 (9)
H1WB	0.1521	0.2147	0.1666	0.043*
H1WA	0.3050	0.2592	0.1757	0.043*
O2W	0.9571 (5)	0.1538 (3)	0.13180 (13)	0.0388 (11)
H2WB	0.8779	0.1756	0.1481	0.058*
H2WA	0.9698	0.1832	0.1090	0.058*
O3W	0.9076 (5)	0.9902 (2)	0.18192 (13)	0.0345 (10)
H3WA	0.8968	1.0325	0.1979	0.052*
H3WB	0.9121	0.9483	0.1984	0.052*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.023 (3)	0.028 (3)	0.020 (3)	0.002 (2)	−0.004 (2)	−0.007 (2)
C2	0.010 (3)	0.022 (3)	0.036 (3)	0.000 (2)	0.001 (2)	−0.011 (2)
C3	0.025 (3)	0.028 (3)	0.038 (4)	−0.001 (3)	0.000 (3)	−0.021 (3)
C4	0.028 (3)	0.033 (3)	0.029 (3)	0.001 (3)	0.001 (3)	−0.018 (3)
C5	0.030 (3)	0.025 (3)	0.016 (3)	−0.004 (3)	−0.003 (2)	0.001 (2)
C6	0.019 (3)	0.037 (3)	0.028 (3)	−0.001 (3)	0.003 (2)	−0.009 (3)
C7	0.029 (3)	0.022 (3)	0.030 (3)	−0.003 (3)	−0.007 (3)	0.004 (2)
C8	0.035 (4)	0.032 (3)	0.046 (4)	−0.008 (3)	−0.023 (3)	0.016 (3)
Cd1	0.0160 (2)	0.0205 (2)	0.0253 (2)	−0.00166 (16)	−0.00067 (15)	−0.00487 (17)
Cd2	0.0205 (2)	0.0301 (2)	0.0265 (2)	0.00083 (19)	0.00013 (16)	0.00076 (18)
Cl1	0.0234 (8)	0.0301 (8)	0.0370 (8)	−0.0011 (6)	0.0007 (6)	0.0114 (6)
Cl2	0.0217 (7)	0.0368 (8)	0.0242 (7)	0.0015 (6)	0.0013 (6)	0.0068 (6)
Cl3	0.0222 (8)	0.0272 (7)	0.0331 (8)	0.0012 (6)	0.0002 (6)	−0.0014 (6)
Cl4	0.0285 (8)	0.0550 (10)	0.0261 (8)	0.0071 (7)	0.0002 (6)	0.0013 (7)
Cl5	0.0241 (8)	0.0281 (7)	0.0349 (8)	0.0010 (6)	0.0027 (6)	−0.0028 (6)
N2	0.012 (2)	0.023 (2)	0.021 (2)	−0.0014 (19)	−0.0004 (18)	−0.0065 (19)
N1	0.011 (3)	0.034 (3)	0.030 (3)	−0.002 (2)	−0.0089 (19)	0.000 (2)
O1	0.020 (2)	0.031 (2)	0.039 (3)	0.0019 (18)	−0.0081 (18)	−0.0191 (19)
O2	0.022 (2)	0.040 (2)	0.048 (3)	−0.004 (2)	0.002 (2)	−0.024 (2)
O1W	0.024 (2)	0.032 (2)	0.030 (2)	−0.0023 (18)	0.0001 (17)	0.0000 (18)
O2W	0.032 (2)	0.054 (3)	0.030 (2)	0.006 (2)	0.006 (2)	0.000 (2)
O3W	0.040 (3)	0.033 (2)	0.030 (2)	0.004 (2)	0.004 (2)	0.0061 (19)

Geometric parameters (Å, º)

C1—O2^i	1.243 (6)	C8—H8B	0.9700
C1—O1	1.248 (6)	Cd1—O1	2.247 (4)
C1—C2	1.529 (7)	Cd1—O2	2.296 (4)
C2—N2	1.508 (6)	Cd1—Cl2	2.6109 (14)
C2—H2A	0.9700	Cd1—Cl2^i	2.6507 (14)
C2—H2B	0.9700	Cd1—Cl1	2.6699 (15)
C3—N2	1.512 (6)	Cd1—Cl1^ii	2.6805 (15)
C3—C4	1.517 (8)	Cd2—O1W	2.357 (4)
C3—H3A	0.9700	Cd2—Cl4	2.5482 (16)
C3—H3B	0.9700	Cd2—Cl5^iii	2.6188 (15)
C4—N1	1.497 (7)	Cd2—Cl3^iv	2.6280 (15)
C4—H4A	0.9700	Cd2—Cl3	2.6398 (15)
C4—H4B	0.9700	Cd2—Cl5	2.6408 (15)
C5—N2	1.502 (7)	Cl1—Cd1^i	2.6805 (15)
C5—C6	1.534 (7)	Cl2—Cd1^ii	2.6507 (14)
C5—H5A	0.9700	Cl3—Cd2^iii	2.6281 (15)
C5—H5B	0.9700	Cl5—Cd2^iv	2.6188 (15)
C6—N1	1.480 (7)	N1—H1	0.9100
C6—H6A	0.9700	O2—C1^ii	1.243 (6)
C6—H6B	0.9700	O1W—H1WB	0.8501
C7—N2	1.509 (7)	O1W—H1WA	0.8500
C7—C8	1.517 (7)	O2W—H2WB	0.8500
C7—H7A	0.9700	O2W—H2WA	0.8503
C7—H7B	0.9700	O3W—H3WA	0.8500
C8—N1	1.479 (7)	O3W—H3WB	0.8500
C8—H8A	0.9700
O2^i—C1—O1	128.2 (5)	O2—Cd1—Cl2^i	85.54 (11)
O2^i—C1—C2	118.9 (5)	Cl2—Cd1—Cl2^i	171.12 (3)
O1—C1—C2	112.9 (5)	O1—Cd1—Cl1	96.73 (10)
N2—C2—C1	115.9 (4)	O2—Cd1—Cl1	86.56 (11)
N2—C2—H2A	108.3	Cl2—Cd1—Cl1	98.33 (5)
C1—C2—H2A	108.3	Cl2^i—Cd1—Cl1	82.36 (5)
N2—C2—H2B	108.3	O1—Cd1—Cl1^ii	91.42 (10)
C1—C2—H2B	108.3	O2—Cd1—Cl1^ii	85.27 (11)
H2A—C2—H2B	107.4	Cl2—Cd1—Cl1^ii	82.90 (5)
N2—C3—C4	109.3 (4)	Cl2^i—Cd1—Cl1^ii	95.15 (5)
N2—C3—H3A	109.8	Cl1—Cd1—Cl1^ii	171.62 (2)
C4—C3—H3A	109.8	O1W—Cd2—Cl4	178.58 (10)
N2—C3—H3B	109.8	O1W—Cd2—Cl5^iii	83.96 (10)
C4—C3—H3B	109.8	Cl4—Cd2—Cl5^iii	97.02 (5)
H3A—C3—H3B	108.3	O1W—Cd2—Cl3^iv	84.70 (10)
N1—C4—C3	108.3 (4)	Cl4—Cd2—Cl3^iv	94.31 (5)
N1—C4—H4A	110.0	Cl5^iii—Cd2—Cl3^iv	168.67 (5)
C3—C4—H4A	110.0	O1W—Cd2—Cl3	86.77 (10)
N1—C4—H4B	110.0	Cl4—Cd2—Cl3	94.27 (5)
C3—C4—H4B	110.0	Cl5^iii—Cd2—Cl3	88.39 (5)
H4A—C4—H4B	108.4	Cl3^iv—Cd2—Cl3	91.08 (5)
N2—C5—C6	109.9 (4)	O1W—Cd2—Cl5	85.04 (10)
N2—C5—H5A	109.7	Cl4—Cd2—Cl5	93.92 (5)
C6—C5—H5A	109.7	Cl5^iii—Cd2—Cl5	90.74 (5)
N2—C5—H5B	109.7	Cl3^iv—Cd2—Cl5	88.18 (5)
C6—C5—H5B	109.7	Cl3—Cd2—Cl5	171.81 (5)
H5A—C5—H5B	108.2	Cd1—Cl1—Cd1^i	88.84 (4)
N1—C6—C5	107.3 (4)	Cd1—Cl2—Cd1^ii	90.74 (4)
N1—C6—H6A	110.3	Cd2^iii—Cl3—Cd2	90.82 (5)
C5—C6—H6A	110.3	Cd2^iv—Cl5—Cd2	91.00 (5)
N1—C6—H6B	110.3	C5—N2—C2	112.9 (4)
C5—C6—H6B	110.3	C5—N2—C7	109.7 (4)
H6A—C6—H6B	108.5	C2—N2—C7	111.5 (4)
N2—C7—C8	109.0 (4)	C5—N2—C3	107.5 (4)
N2—C7—H7A	109.9	C2—N2—C3	107.0 (4)
C8—C7—H7A	109.9	C7—N2—C3	107.9 (4)
N2—C7—H7B	109.9	C6—N1—C8	110.7 (4)
C8—C7—H7B	109.9	C6—N1—C4	109.8 (4)
H7A—C7—H7B	108.3	C8—N1—C4	109.8 (5)
N1—C8—C7	109.1 (4)	C6—N1—H1	108.8
N1—C8—H8A	109.9	C8—N1—H1	108.8
C7—C8—H8A	109.9	C4—N1—H1	108.8
N1—C8—H8B	109.9	C1—O1—Cd1	125.0 (3)
C7—C8—H8B	109.9	C1^ii—O2—Cd1	145.3 (4)
H8A—C8—H8B	108.3	Cd2—O1W—H1WB	118.0
O1—Cd1—O2	176.60 (15)	Cd2—O1W—H1WA	106.1
O1—Cd1—Cl2	94.71 (11)	H1WB—O1W—H1WA	108.5
O2—Cd1—Cl2	85.66 (11)	H2WB—O2W—H2WA	108.5
O1—Cd1—Cl2^i	94.00 (11)	H3WA—O3W—H3WB	108.5
O2^i—C1—C2—N2	−7.6 (8)	C1—C2—N2—C5	64.6 (6)
O1—C1—C2—N2	174.7 (5)	C1—C2—N2—C7	−59.5 (6)
N2—C3—C4—N1	−14.9 (7)	C1—C2—N2—C3	−177.3 (5)
N2—C5—C6—N1	−15.5 (6)	C8—C7—N2—C5	65.6 (6)
N2—C7—C8—N1	−13.6 (7)	C8—C7—N2—C2	−168.5 (5)
O1—Cd1—Cl1—Cd1^i	−64.77 (11)	C8—C7—N2—C3	−51.3 (6)
O2—Cd1—Cl1—Cd1^i	114.34 (11)	C4—C3—N2—C5	−50.1 (6)
Cl2—Cd1—Cl1—Cd1^i	−160.56 (5)	C4—C3—N2—C2	−171.7 (5)
Cl2^i—Cd1—Cl1—Cd1^i	28.39 (4)	C4—C3—N2—C7	68.2 (6)
Cl1^ii—Cd1—Cl1—Cd1^i	101.6 (3)	C5—C6—N1—C8	69.5 (6)
O1—Cd1—Cl2—Cd1^ii	119.89 (10)	C5—C6—N1—C4	−51.9 (6)
O2—Cd1—Cl2—Cd1^ii	−56.72 (11)	C7—C8—N1—C6	−52.8 (7)
Cl2^i—Cd1—Cl2—Cd1^ii	−48.8 (2)	C7—C8—N1—C4	68.6 (6)
Cl1—Cd1—Cl2—Cd1^ii	−142.59 (5)	C3—C4—N1—C6	70.3 (6)
Cl1^ii—Cd1—Cl2—Cd1^ii	29.05 (4)	C3—C4—N1—C8	−51.6 (6)
O1W—Cd2—Cl3—Cd2^iii	−74.44 (10)	O2^i—C1—O1—Cd1	8.8 (9)
Cl4—Cd2—Cl3—Cd2^iii	106.53 (5)	C2—C1—O1—Cd1	−173.8 (3)
Cl5^iii—Cd2—Cl3—Cd2^iii	9.61 (4)	O2—Cd1—O1—C1	−129 (2)
Cl3^iv—Cd2—Cl3—Cd2^iii	−159.07 (7)	Cl2—Cd1—O1—C1	134.7 (4)
Cl5—Cd2—Cl3—Cd2^iii	−74.4 (3)	Cl2^i—Cd1—O1—C1	−47.1 (5)
O1W—Cd2—Cl5—Cd2^iv	−94.44 (10)	Cl1—Cd1—O1—C1	35.7 (5)
Cl4—Cd2—Cl5—Cd2^iv	84.59 (5)	Cl1^ii—Cd1—O1—C1	−142.3 (4)
Cl5^iii—Cd2—Cl5—Cd2^iv	−178.32 (7)	O1—Cd1—O2—C1^ii	−55 (3)
Cl3^iv—Cd2—Cl5—Cd2^iv	−9.60 (4)	Cl2—Cd1—O2—C1^ii	41.6 (7)
Cl3—Cd2—Cl5—Cd2^iv	−94.5 (3)	Cl2^i—Cd1—O2—C1^ii	−137.1 (7)
C6—C5—N2—C2	−173.6 (4)	Cl1—Cd1—O2—C1^ii	140.3 (7)
C6—C5—N2—C7	−48.6 (6)	Cl1^ii—Cd1—O2—C1^ii	−41.6 (7)
C6—C5—N2—C3	68.6 (5)

Symmetry codes: (i) x+1/2, −y+1/2, −z; (ii) x−1/2, −y+1/2, −z; (iii) x+1/2, y, −z+1/2; (iv) x−1/2, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2W—H2WB···Cl4^iii	0.85	2.45	3.226 (4)	153
O1W—H1WA···Cl4^iii	0.85	2.33	3.183 (4)	176
O1W—H1WB···O2W^v	0.85	2.06	2.839 (5)	153
N1—H1···O2W^vi	0.91	2.51	3.096 (6)	123
N1—H1···O3W^vii	0.91	1.94	2.755 (6)	148
O3W—H3WB···Cl3^viii	0.85	2.58	3.325 (4)	147
O3W—H3WA···Cl5^ix	0.85	2.33	3.170 (4)	172
O2W—H2WB···Cl5^x	0.85	2.97	3.441 (4)	117
O2W—H2WA···Cl2^x	0.85	2.72	3.351 (4)	133
O2W—H2WA···Cl1	0.85	2.83	3.335 (4)	120

Symmetry codes: (iii) x+1/2, y, −z+1/2; (v) x−1, y, z; (vi) −x+5/2, y+1/2, z; (vii) −x+5/2, y−1/2, z; (viii) −x+3/2, y+1/2, z; (ix) x+1, y+1, z; (x) x+1, y, z.