catena-Poly[[(2-phenyl-1H-1,3,7,8-tetra­azacyclo­penta­[l]phenanthrene-κ²N⁷,N⁸)cadmium(II)]-di-μ-chlorido-[(2-phenyl-1H-1,3,7,8-tetra­azacyclo­penta­[l]phenanthrene-κ²N⁷,N⁸)cadmium(II)]-μ-fumarato-κ⁴O¹,O^1′:O⁴,O^4′]: a coordination polymer with a two-dimensional supra­molecular architecture

The title cadmium(II) coordination polymer, [Cd₂(C₄H₂O₄)Cl₂(C₁₉H₁₂N₄)₂]_n, (I), was obtained by the reaction of CdCl₂·2.5H₂O, fumaric acid (H₂fum) and 2-phenyl-1H-1,3,7,8-tetra­azacyclo­penta­[l]phenanthrene (L) under hydro­thermal conditions. The fum dianion is situated across an inversion centre in the space group . The Cd^II atom is six-coordinated by two L N atoms, two fum O atoms and two Cl atoms in a distorted octa­hedral geometry. The μ₂-Cl atoms and the bis-chelating fum dianions bridge neighbouring Cd^II centres, yielding a coordination polymer chain structure along the c axis. N—H...O hydrogen bonds between the N atoms of L and the carboxyl­ate O atoms of fum lead to a sheet structure in the bc plane. Compound (I) represents a rare example of a supra­molecular structure constructed by a chloride anion, a dicarboxyl­ate anion and a 1,10-phenanthroline derivative. This work may further the development of the coordination chemistry of 1,10-phenanthroline derivatives.

S1. Comment

Generally, two different types of interactions (covalent bonds and non-covalent intermolecular forces) can be used to construct varied supramolecular architectures. The π–π interaction, as one of the most powerful non-covalent intermolecular interactions, is operative in determining supramolecular architectures (Chen & Liu, 2002). On this basis, a number of coordination polymers have been prepared from one-dimensional covalently bonded chains or layers, yielding extended two- or three-dimensional supramolecular structures through these interactions (Zhang et al., 2005; Wang et al., 2007).

To date, 1,10-phenanthroline (phen) and 2,2-bipyridyl have been widely used to build supramolecular architectures, due to their excellent coordinating ability and large conjugated systems that can easily form π–π interactions (Wang et al., 2008; Tong et al., 2000; Zheng et al., 2001). However, far less attention has been given to their derivatives (Yang, Li et al., 2007; Yang, Ma et al., 2007). For example, the rare phen derivative 2-phenyl-1H-1,3,7,8,-tetraazacyclopenta[l]phenanthrene (L) possesses a promising aromatic system and is a good candidate for the construction of metal–organic supramolecular architectures (Wang et al., 2007). In this contribution, we selected fumaric acid (H₂fum) as a linker and L as a secondary ligand, generating the title new Cd^II coordination polymer, (I), which displays a two-dimensional supramolecular architecture interlinked through hydrogen bonds.

As shown in Fig. 1, the asymmetric unit of (I) contains one unique Cd^II cation, one unique Cl^- anion and one-half of a fum dianionic ligand. The fum dianion is situated across an inversion centre. Each Cd^II atom is six-coordinated by two N atoms (N1 and N2) from one L ligand, two O atoms (O1 and O2) from one fum ligand and two Cl^- anions [Cl1 and Cl1ⁱ; symmetry code: (i) 1 - x, 1 - y, -z Please check added symop] in a distorted octahedral geometry. The average Cd—O and Cd—N distances in (I) (Table 1) are comparable twith those observed for [Cd₄(OH)₂(H₂O)₂(sip)₂(4,4'-bpy)₄].H₂O (sip = 5-sulfoisophthalate and 4,4'-bpy = 4,4'-bipyridyl; Li et al., 2005).

As depicted in Fig. 2, two µ₂-Cl atoms bridge two Cd^II centres to yield a [Cd₂Cl₂]^2- unit. The fum dianions link neighbouring [Cd₂Cl₂]^2- units in a bis-chelating mode, to give a one-dimensional chain structure along the c axis. The L ligands are extended on both sides of the chain, and the planes of adjacent L ligands are nearly parallel [Dihedral angle between the best planes?]. The secondary L ligand plays an important role in the formation of the chain structure. Two N atoms from the secondary L ligand occupy two coordination positions of the Cd^II atom, while the remaining coordination positions are available for fum ligands, allowing the formation of the chain structure. N—H···O hydrogen bonds between the N atoms of L and the carboxylate O atoms of fum lead to a sheet structure of (I) in the bc plane (Table 2, Fig. 3).

It is noteworthy that the structure of (I) presented here is clearly different from that of the previously reported compound [Pb(ndc)(L)].0.5H₂O (ndc = 1,4-naphthalenedicarboxylate; Yang, Li et al., 2007). In the latter compound, the ndc ligand links the Pb^II atoms to yield a single chain. The L ligands extend solely on one side of the chain in a slanted fashion, and π–π interactions between the L ligands result in a final wavy layer structure. The structure of (I) is also entirely different from that of [Pb(fum)(dpdp)].H₂O (dpdp = dipyrido[3,2-a:2',3'-c]phenazine; Yang, Ma et al., 2007). In that structure, each fum ligand bridges four Pb^II centres in a tetradentate mode, generating a novel layer structure. These layers are decorated with dpdp ligands alternating on the two sides of each layer. π–π interactions between the dpdp ligands lead to a unique three-dimensional supramolecular structure.

It should be pointed out that the complex structure of (I) is not sensitive to the Cd^II:L ratio. The same compound (I), with a Cd^II:L ratio of 1:1, can always be isolated using Cd^II:L reaction stoichiometries of 1, 2, or 3. We have also tried to investigate the effects of different cadmium(II) salts on the structure of the complex through reaction with Cd(NO₃)₂, Cd(CH₃COOH)₂ or CdSO₄, but single crystals of their products have not been obtained. Therefore, the Cl^- anion probably plays an important role in the formation of complex (I). To the best of our knowledge, compound (I), featuring a fascinating two-dimensional superamolecular structure, is the first solid entity constructed by a Cl^- anion, a dicarboxylate anion and a phen derivative.

Related literature

For related literature, see: Chen & Liu (2002); Hiort et al. (1993); Li et al. (2005); Tong et al. (2000); Wang et al. (2007, 2008); Yang, Li, Cao, Yue, Li & Chen (2007); Yang, Ma, Liu, Ma & Batten (2007); Zhang et al. (2005); Zheng et al. (2001).

S2. Experimental

1,10-Phenanthroline was oxidized to 1,10-phenanthroline-5,6-dione according to the reported procedure of Hiort et al. (1993). For the preparation of L, a mixture of 1,10-phenanthroline-5,6-dione (2 mmol), benzaldehyde (2.2 mmol), glacial acetic acid (15 ml) and ammonium acetate (3.2 g) was heated under reflux for 2 h, resulting in a yellow precipitate. After cooling, the mixture was diluted with water (25 ml) and the pH value of the solution was adjusted with concentrated aqueous ammonia to 5.5. The yellow product was filtered off from the mixture, washed with water and acetone, and oven-dried at 333 K. For the preparation of (I), CdCl₂.2.5H₂O (0.114 g, 0.5 mmol), H₂fum (0.058 g, 0.5 mmol) and L (0.148 g, 0.5 mmol) were dissolved in distilled water (12 ml), followed by addition of triethylamine until the pH of the system was about 5.3. The resulting solution was stirred for about 3 h at room temperature, sealed in a 23 ml Teflon-lined stainless steel autoclave and heated at 463 K for 7 d under autogenous pressure. The reaction system was then cooled slowly to room temperature. Pale-yellow block crystals of (I) suitable for single-crystal X-ray diffraction analysis were collected from the final reaction system by filtration, washed several times with distilled water and dried in air at ambient temperature (yield: 39% based on Cd^II). Spectroscopic analysis: IR (ν, cm^-1, KBr): 3115 (s), 3056 (s), 2914 (vs), 1611 (vs), 1389 (s), 1340 (s), 1113 (s), 753 (s), 654 (s).

S3. Refinement

All H atoms were positioned geometrically (N—H = 0.86 Å and C—H = 0.93 Å) and refined as riding, with U_iso(H)=1.2U_eq(C,N).

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: PROCESS-AUTO (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. A view of the local coordination of the Cd^II cation in (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry codes: (i) 1 - x, 1 - y, -z; (ii) 1 - x, 1 - y, 1 - z.]
	Fig. 2. A view of the coordination polymer chain structure of (I), along the c axis.
	Fig. 3. A view of the sheet formed by the linking of the coordination polymer chains by N—H···O hydrogen bonds.

catena-Poly[[(2-phenyl-1H-1,3,7,8- tetraazacyclopenteno[l]phenanthrene- κ²N⁷,N⁸)cadmium(II)]-di-µ-chlorido-[(2-phenyl-1H- 1,3,7,8-tetraazacyclopenteno[l]phenanthrene- κ²N⁷,N⁸)cadmium(II)]-µ-fumarato- κ⁴O¹,O^1':O⁴,O^4']

Crystal data

[Cd2(C4H2O4)Cl2(C19H12N4)2]	Z = 1
Mr = 1002.40	F(000) = 496
Triclinic, P1	Dx = 1.726 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.069 (3) Å	Cell parameters from 8106 reflections
b = 10.480 (2) Å	θ = 3.0–27.5°
c = 10.749 (4) Å	µ = 1.30 mm^−1
α = 88.59 (3)°	T = 293 K
β = 63.20 (3)°	Block, pale yellow
γ = 73.59 (5)°	0.33 × 0.25 × 0.21 mm
V = 964.2 (6) Å^3

Data collection

Rigaku R-AXIS RAPID diffractometer	4365 independent reflections
Radiation source: rotating anode	3755 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: 10.0 pixels mm^-1	θmax = 27.5°, θmin = 3.4°
ω scans	h = −13→12
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −13→13
Tmin = 0.642, Tmax = 0.760	l = −13→13
9502 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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.062	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0229P)^2 + 0.382P] where P = (Fo^2 + 2Fc^2)/3
4365 reflections	(Δ/σ)max = 0.001
262 parameters	Δρmax = 0.42 e Å^−3
0 restraints	Δρmin = −0.39 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	0.4231 (3)	0.8318 (3)	−0.1039 (3)	0.0378 (6)
H1	0.3451	0.7905	−0.0735	0.045*
C2	0.4198 (3)	0.9327 (3)	−0.1904 (3)	0.0425 (6)
H2	0.3400	0.9589	−0.2158	0.051*
C3	0.5351 (3)	0.9927 (3)	−0.2373 (3)	0.0375 (6)
H3A	0.5342	1.0605	−0.2946	0.045*
C4	0.6547 (3)	0.9514 (2)	−0.1986 (2)	0.0303 (5)
C5	0.6497 (3)	0.8491 (2)	−0.1100 (2)	0.0277 (5)
C6	0.7708 (3)	0.8012 (2)	−0.0661 (3)	0.0320 (5)
C7	0.8617 (4)	0.6646 (3)	0.0682 (4)	0.0513 (7)
H7	0.8500	0.6001	0.1300	0.062*
C8	0.9882 (4)	0.7125 (4)	0.0284 (4)	0.0687 (10)
H8	1.0592	0.6817	0.0635	0.082*
C9	1.0061 (4)	0.8062 (3)	−0.0637 (4)	0.0598 (9)
H9	1.0915	0.8383	−0.0935	0.072*
C10	0.8972 (3)	0.8537 (3)	−0.1130 (3)	0.0386 (6)
C11	0.9021 (3)	0.9548 (3)	−0.2042 (3)	0.0367 (6)
C12	0.7848 (3)	1.0020 (2)	−0.2416 (3)	0.0327 (5)
C13	0.9654 (3)	1.1033 (3)	−0.3384 (3)	0.0410 (6)
C14	1.0505 (3)	1.1930 (3)	−0.4231 (3)	0.0453 (7)
C15	1.1828 (4)	1.1979 (4)	−0.4166 (4)	0.0636 (10)
H15	1.2147	1.1461	−0.3579	0.076*
C16	1.2683 (5)	1.2790 (4)	−0.4964 (4)	0.0785 (13)
H16	1.3574	1.2813	−0.4914	0.094*
C17	1.2217 (5)	1.3556 (4)	−0.5827 (4)	0.0749 (13)
H17	1.2792	1.4103	−0.6361	0.090*
C18	1.0911 (5)	1.3522 (3)	−0.5908 (3)	0.0671 (11)
H18	1.0599	1.4045	−0.6497	0.081*
C19	1.0043 (4)	1.2701 (3)	−0.5105 (3)	0.0545 (8)
H19	0.9156	1.2676	−0.5162	0.065*
C20	0.4984 (3)	0.5876 (3)	0.3413 (3)	0.0379 (6)
C21	0.4637 (3)	0.5568 (3)	0.4866 (3)	0.0402 (6)
H21	0.3874	0.6208	0.5614	0.048*
N1	0.7562 (3)	0.7065 (2)	0.0221 (2)	0.0364 (5)
N2	0.5331 (2)	0.79241 (19)	−0.0635 (2)	0.0304 (4)
N3	0.8268 (3)	1.0978 (2)	−0.3281 (2)	0.0378 (5)
H3	0.7757	1.1452	−0.3681	0.045*
N4	1.0148 (3)	1.0182 (2)	−0.2652 (3)	0.0447 (6)
O1	0.4310 (2)	0.70323 (19)	0.3250 (2)	0.0463 (5)
O2	0.5921 (3)	0.4988 (2)	0.2410 (2)	0.0497 (5)
Cd1	0.55367 (2)	0.618432 (18)	0.072732 (19)	0.03153 (7)
Cl1	0.70589 (7)	0.41956 (6)	−0.12379 (7)	0.03761 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0372 (14)	0.0411 (14)	0.0454 (15)	−0.0189 (12)	−0.0241 (12)	0.0146 (12)
C2	0.0439 (15)	0.0424 (14)	0.0547 (17)	−0.0143 (13)	−0.0339 (14)	0.0175 (13)
C3	0.0457 (15)	0.0337 (13)	0.0396 (14)	−0.0135 (12)	−0.0248 (12)	0.0140 (11)
C4	0.0346 (12)	0.0274 (11)	0.0269 (12)	−0.0099 (10)	−0.0123 (10)	0.0044 (10)
C5	0.0296 (12)	0.0269 (11)	0.0273 (12)	−0.0092 (10)	−0.0133 (10)	0.0038 (9)
C6	0.0338 (13)	0.0318 (12)	0.0315 (13)	−0.0115 (11)	−0.0154 (10)	0.0068 (10)
C7	0.0559 (18)	0.0568 (17)	0.065 (2)	−0.0268 (15)	−0.0439 (16)	0.0305 (16)
C8	0.060 (2)	0.082 (2)	0.101 (3)	−0.0333 (19)	−0.062 (2)	0.043 (2)
C9	0.0485 (17)	0.070 (2)	0.090 (3)	−0.0356 (17)	−0.0477 (18)	0.0377 (19)
C10	0.0341 (13)	0.0407 (14)	0.0476 (16)	−0.0165 (12)	−0.0217 (12)	0.0106 (12)
C11	0.0322 (13)	0.0345 (13)	0.0414 (15)	−0.0152 (11)	−0.0127 (11)	0.0080 (11)
C12	0.0362 (13)	0.0274 (11)	0.0310 (13)	−0.0124 (11)	−0.0110 (10)	0.0056 (10)
C13	0.0419 (15)	0.0348 (13)	0.0389 (15)	−0.0190 (12)	−0.0081 (12)	0.0023 (12)
C14	0.0475 (16)	0.0360 (14)	0.0361 (15)	−0.0213 (13)	−0.0005 (12)	0.0009 (12)
C15	0.067 (2)	0.066 (2)	0.057 (2)	−0.0416 (19)	−0.0156 (17)	0.0102 (17)
C16	0.085 (3)	0.081 (3)	0.069 (3)	−0.063 (2)	−0.013 (2)	0.007 (2)
C17	0.085 (3)	0.055 (2)	0.056 (2)	−0.046 (2)	0.005 (2)	0.0013 (18)
C18	0.085 (3)	0.0380 (16)	0.0434 (18)	−0.0201 (17)	0.0007 (17)	0.0036 (14)
C19	0.0556 (18)	0.0404 (15)	0.0443 (17)	−0.0161 (14)	−0.0028 (14)	0.0033 (14)
C20	0.0488 (15)	0.0463 (15)	0.0387 (15)	−0.0280 (13)	−0.0301 (13)	0.0234 (13)
C21	0.0515 (16)	0.0483 (15)	0.0355 (14)	−0.0254 (14)	−0.0272 (13)	0.0207 (12)
N1	0.0413 (12)	0.0372 (11)	0.0405 (12)	−0.0138 (10)	−0.0264 (10)	0.0131 (10)
N2	0.0320 (10)	0.0329 (10)	0.0313 (11)	−0.0138 (9)	−0.0169 (9)	0.0095 (9)
N3	0.0454 (13)	0.0309 (10)	0.0354 (12)	−0.0159 (10)	−0.0151 (10)	0.0111 (9)
N4	0.0394 (12)	0.0424 (12)	0.0513 (14)	−0.0230 (11)	−0.0142 (11)	0.0117 (11)
O1	0.0621 (12)	0.0440 (11)	0.0438 (11)	−0.0197 (10)	−0.0325 (10)	0.0215 (9)
O2	0.0626 (13)	0.0510 (12)	0.0382 (11)	−0.0149 (11)	−0.0276 (10)	0.0179 (10)
Cd1	0.03937 (11)	0.03465 (10)	0.03032 (10)	−0.01762 (8)	−0.02106 (8)	0.01408 (7)
Cl1	0.0315 (3)	0.0424 (3)	0.0385 (3)	−0.0118 (3)	−0.0155 (3)	0.0031 (3)

Geometric parameters (Å, º)

C1—N2	1.323 (3)	C13—C14	1.468 (4)
C1—C2	1.394 (4)	C14—C19	1.377 (5)
C1—H1	0.9300	C14—C15	1.380 (5)
C2—C3	1.367 (4)	C15—C16	1.382 (5)
C2—H2	0.9300	C15—H15	0.9300
C3—C4	1.400 (4)	C16—C17	1.366 (6)
C3—H3A	0.9300	C16—H16	0.9300
C4—C5	1.413 (3)	C17—C18	1.368 (6)
C4—C12	1.430 (4)	C17—H17	0.9300
C5—N2	1.354 (3)	C18—C19	1.399 (4)
C5—C6	1.457 (3)	C18—H18	0.9300
C6—N1	1.347 (3)	C19—H19	0.9300
C6—C10	1.407 (4)	C20—O2	1.247 (3)
C7—N1	1.328 (4)	C20—O1	1.261 (3)
C7—C8	1.384 (5)	C20—C21	1.487 (4)
C7—H7	0.9300	C20—Cd1	2.712 (3)
C8—C9	1.366 (5)	C21—C21^i	1.311 (5)
C8—H8	0.9300	C21—H21	0.9300
C9—C10	1.390 (4)	N3—H3	0.8600
C9—H9	0.9300	Cd1—N1	2.312 (2)
C10—C11	1.422 (4)	Cd1—N2	2.333 (2)
C11—C12	1.373 (4)	Cd1—O1	2.479 (2)
C11—N4	1.376 (3)	Cd1—O2	2.289 (2)
C12—N3	1.376 (3)	Cd1—Cl1^ii	2.5640 (9)
C13—N4	1.315 (4)	Cd1—Cl1	2.5782 (14)
C13—N3	1.367 (4)
N2—C1—C2	122.5 (3)	C18—C17—H17	119.9
N2—C1—H1	118.7	C17—C18—C19	120.0 (4)
C2—C1—H1	118.7	C17—C18—H18	120.0
C3—C2—C1	119.2 (3)	C19—C18—H18	120.0
C3—C2—H2	120.4	C14—C19—C18	119.9 (4)
C1—C2—H2	120.4	C14—C19—H19	120.0
C2—C3—C4	119.6 (2)	C18—C19—H19	120.0
C2—C3—H3A	120.2	O2—C20—O1	122.7 (3)
C4—C3—H3A	120.2	O2—C20—C21	119.0 (2)
C3—C4—C5	118.0 (2)	O1—C20—C21	118.2 (3)
C3—C4—C12	126.2 (2)	O2—C20—Cd1	57.13 (14)
C5—C4—C12	115.9 (2)	O1—C20—Cd1	65.85 (15)
N2—C5—C4	121.3 (2)	C21—C20—Cd1	173.51 (19)
N2—C5—C6	118.0 (2)	C21^i—C21—C20	122.7 (3)
C4—C5—C6	120.8 (2)	C21^i—C21—H21	118.7
N1—C6—C10	121.4 (2)	C20—C21—H21	118.7
N1—C6—C5	117.7 (2)	C7—N1—C6	119.0 (2)
C10—C6—C5	120.9 (2)	C7—N1—Cd1	124.2 (2)
N1—C7—C8	123.0 (3)	C6—N1—Cd1	116.66 (17)
N1—C7—H7	118.5	C1—N2—C5	119.4 (2)
C8—C7—H7	118.5	C1—N2—Cd1	124.78 (18)
C9—C8—C7	118.4 (3)	C5—N2—Cd1	115.66 (16)
C9—C8—H8	120.8	C13—N3—C12	106.8 (2)
C7—C8—H8	120.8	C13—N3—H3	126.6
C8—C9—C10	120.3 (3)	C12—N3—H3	126.6
C8—C9—H9	119.9	C13—N4—C11	104.5 (2)
C10—C9—H9	119.9	C20—O1—Cd1	86.49 (17)
C9—C10—C6	117.8 (3)	C20—O2—Cd1	95.63 (16)
C9—C10—C11	124.5 (3)	O2—Cd1—N1	93.76 (8)
C6—C10—C11	117.6 (2)	O2—Cd1—N2	160.78 (7)
C12—C11—N4	111.2 (2)	N1—Cd1—N2	71.64 (8)
C12—C11—C10	120.9 (2)	O2—Cd1—O1	54.83 (7)
N4—C11—C10	127.9 (3)	N1—Cd1—O1	91.37 (8)
C11—C12—N3	105.1 (2)	N2—Cd1—O1	111.63 (7)
C11—C12—C4	123.9 (2)	O2—Cd1—Cl1^ii	96.92 (6)
N3—C12—C4	131.0 (2)	N1—Cd1—Cl1^ii	165.67 (5)
N4—C13—N3	112.4 (2)	N2—Cd1—Cl1^ii	95.72 (6)
N4—C13—C14	123.8 (3)	O1—Cd1—Cl1^ii	87.03 (6)
N3—C13—C14	123.7 (3)	O2—Cd1—Cl1	95.16 (6)
C19—C14—C15	119.1 (3)	N1—Cd1—Cl1	97.60 (6)
C19—C14—C13	122.2 (3)	N2—Cd1—Cl1	99.06 (6)
C15—C14—C13	118.7 (3)	O1—Cd1—Cl1	149.30 (5)
C14—C15—C16	120.7 (4)	Cl1^ii—Cd1—Cl1	90.93 (4)
C14—C15—H15	119.6	O2—Cd1—C20	27.24 (8)
C16—C15—H15	119.6	N1—Cd1—C20	94.33 (8)
C17—C16—C15	119.9 (4)	N2—Cd1—C20	138.40 (8)
C17—C16—H16	120.0	O1—Cd1—C20	27.66 (7)
C15—C16—H16	120.0	Cl1^ii—Cd1—C20	90.86 (7)
C16—C17—C18	120.3 (3)	Cl1—Cd1—C20	121.92 (7)
C16—C17—H17	119.9	Cd1^ii—Cl1—Cd1	89.07 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1^iii	0.86	2.09	2.820 (3)	142

Symmetry code: (iii) −x+1, −y+2, −z.