Two one-dimensional coordination polymers generated from a new benzimidazole bridging ligand and CdX₂ (X = Br and I)

The novel asymmetric bridging ligand 1-[(pyridin-3-yl)methyl]-2-[4-(pyridin-3-yl)phenyl]-1H-benzimidazole (L) has been used to construct the coordination polymers catena-poly[[[dibromidocadmium(II)]-μ₃-1-[(pyridin-3-yl)methyl]-2-[4-(pyridin-3-yl)phenyl]-1H-benzimidazole] monohydrate], {[CdBr₂(C₂₄H₁₈N₄)]·H₂O}_n, (I), and catena-poly[[diiodidocadmium(II)]-μ₃-1-[(pyridin-3-yl)methyl]-2-[4-(pyridin-3-yl)phenyl]-1H-benzimidazole], [CdI₂(C₂₄H₁₈N₄)]_n, (II). Com­pounds (I) and (II) are closely related one-dimensional polymers based on 16- and 20-membered macrocycles along the chains, but they are not isomorphous. The chains are crosslinked into a two-dimensional network via hydrogen bonds and π–π inter­actions in (I), and into a three-dimensional framework through π–π inter­actions in (II). One well-ordered solvent water mol­ecule per asymmetric unit is included in (I) and forms O...Br hydrogen bonds.

S1. Comment

Coordination polymers assembled from metal nodes and organic ligands have attracted considerable interest over recent decades. Due to their often porous structures and special properties, they may have potential applications in, for example, absorption and separation processes (Gu et al., 2010), gas storage (Stavila et al., 2012) or drug delivery (Horcajada et al., 2008), or as functional materials (Wang et al., 2011), for photophysical applications (Yanai et al., 2012) or as catalysts (Li et al., 2012).

Appropriate ligands doubtless play an important role as building blocks to construct supramolecular complexes. Among the numerous reports concerned with benzimidazole ligands (Kundu et al., 2010; Li et al., 2010; Xiao et al., 2011), no coordination compound generated from 1-[(pyridin-3-yl)methyl]-2-[4-(pyridin-3-yl)phenyl]-1H-benzimidazole (L) has yet been reported. In order to investigate its self-assembly reactions, we have synthesized this novel ligand. The combination of L with CdBr₂ and CdI₂ afforded two one-dimensional coordination complexes, {[CdBr₂(L)].H₂O}_n, (I) (Fig. 1), and [CdI₂(L)]_n, (II) (Fig. 2).

The compounds crystallize in the triclinic system; the asymmetric unit comprises one Cd^II centre, one L ligand and two halide anions in both cases and, only for (I), a solvent water molecule. As a consequence of this solvent content, the unit cell of (I) has a larger volume [1174.7 (5) ų] than that of (II) [1154.4 (5) ų], despite the sterically less demanding halide in the former. The chains in (I) extend in the [101] direction, with the length of this diagonal being 14.153 (3) Å, whereas (II) forms chains along the [001] direction, the lattice parameter c being 13.429 (4) Å.

In (I), each Cd^II centre is five-coordinated by two Br and three N atoms; one N atom belongs to the benzimidazole ring, and the other two originate from the pyridine rings of two different ligands. The distortion parameter τ(I) (Addison et al., 1984) of 0.83 indicates that the coordination environment corresponds to a slightly distorted trigonal bipyramid; expected values are τ = 0 for a square pyramid and τ = 1 for an ideal trigonal bipyramid, with τ = (β - α)/60°, α and β being the two largest angles around the central atom (Addison et al., 1984).

The tridentate ligands and the coordinated Cd^II cations subtend two kinds of macrocycles. In the 20-membered macrocycle of (I) (Fig. 3a), the distance between atoms Cd1 and N1ⁱ is 2.397 (6) Å [symmetry code: (i) -x + 1, -y + 1, -z], similar to the Cd—N distance reported by Ding et al. (2012). Moreover, the dihedral angle between the benzene rings and the neighbouring imidazole rings is 52.0 (2)°, and the dihedral angle between the benzene rings and the neighbouring pyridine rings is 32.1 (3)°. The 16-membered macrocycle is also centrosymmetric (Fig. 3b), with Cd1—N2 = 2.315 (6) Å and Cd1—N4ⁱⁱ = 2.475 (7) Å [symmetry code: (ii) -x + 2, -y + 1, -z + 1], similar to published values (Xu et al., 2011; Lan et al., 2009). The overall chain in (I) extends in the [101] direction and is shown in Fig. 3(c). Adjacent chains are linked to form two-dimensional sheets by hydrogen bonds (Table 1 and Fig. 4). Water molecules are arranged regularly in the voids and play an important role in connecting the chains via O—H···Br interactions.

The Cd^II centre in (II) has a similar coordination environment to that in polymer (I), with two iodide ligands and τ(II) = 0.75. Chains extend along the c axis, with an intrachain geometry similar to that depicted for (I) in Fig. 3. The Cd—N bonds (Table 3) are slightly longer than in the bromide derivative, (I). In the 20-membered macrocycle, the dihedral angle between the benzene rings and the neighbouring imidazole rings is 54.3 (2)°, and the interplanar angle between the benzene ring and the neighbouring pyridine ring is 34.7 (2)°.

Fig. 5 shows, in the direction of the a axis, how neighbouring chains in (II) are linked by π–π interactions between two parallel pyridine rings and by C—H···π interactions C23—H23···Cgⁱ, where Cgⁱ denotes the centroid of the C6—C11 ring at the symmetry-related position (-x + 1, -y + 1, -z + 1). The π–π interactions in (II) are associated with a centroid-to-centroid distance of 3.612 (2) Å; in contrast, the analogous contacts in (I) amount to 4.117 (2) Å and are not relevant. The C—H···π angle of 133° and the H···π distance of 3.00 Å are in close agreement with values reported previously (Goswami et al., 2007) and lead to the formation of two-dimensional sheets in the bc plane. A second kind of π–π interaction between the imidazole rings and benzene rings of the benzimidazoles from adjacent chains, with a centroid-to-centroid distance of 3.723 (2) Å, is shown in Fig. 6 and results in a three-dimensional network. No water molecules reside in the crystal structure of (II), presumably due to the larger ionic radius of the iodide anion. If the water molecule is not taken into account, the `cavity' in (I), with a Br1···Br2ⁱ [symmetry code: (i) -x + 1, -y, -z] distance of 5.092 (2) Å, is much larger than that in (II), where the corresponding distance between two iodides amounts to 4.853 (2) Å.

In summary, a novel asymmetric bridging benzimidazole ligand has been successfully synthesized and used as a tridentate ligand to construct two coordination polymers. In (I), hydrogen bonds between water molecules and bromide anions play an important role in linking the chains to form a two-dimensional motif; in (II), weak π–π interactions generate a three-dimensional framework.

Related literature

For related literature, see: Addison et al. (1984); Ding et al. (2012); Gong & Pauls (2000); Goswami et al. (2007); Gu et al. (2010); Horcajada et al. (2008); Kundu et al. (2010); Lan et al. (2009); Li et al. (2010, 2012); Stavila et al. (2012); Wang et al. (2011); Xiao et al. (2011); Xu et al. (2011); Yanai et al. (2012).

S2. Experimental

4-(Pyridin-3-yl)benzoic acid was obtained according to the method of Gong & Pauls (2000).

For the preparation of 2-[4-(pyridin-3-yl)phenyl]-1H-benzimidazole, polyphosphoric acid (30.0 g) was added to a mixture of 4-(pyridin-3-yl)benzoic acid (2.60 g, 13.07 mmol) and o-phenylenediamine (1.41 g, 13.07 mmol). The reaction mixture was stirred for 5 h at 453 K, and then water was poured into the cooled beaker. After adjusting the pH to 9 with aqueous ammonia, the precipitate was filtered off, washed with water, dried and purified by column chromatography on silica gel with dichloromethane and methanol (15:1 v/v) as the eluent to afford 2-[4-(pyridin-3-yl)phenyl]-1H-benzimidazole as a white solid (yield 2.67 g, 75.4%). Spectroscopic analysis: ¹H NMR (300 MHz, DMSO, 298 K, TMS, δ, p.p.m.): 13.00 (s, 1H, –NH), 9.00 (s, 1H, –C₅H₄N), 8.61–8.59 (d, 1H, –C₅H₄N), 8.32–8.29 (d, 2H, –C₅H₄N), 8.19–8.16 (d, 1H, –C₆H₄), 7.95–7.93 (d, 2H, –C₆H₄), 7.53 (m, 1H, –C₆H₄), 7.51 (t, 2H, –C₆H₄), 7.23–7.21 (s, 2H, –C₆H₄); IR (KBr pellet, ν, cm^-1): 3054 (m), 1621 (w), 1592 (w), 1550 (m), 1501 (s), 1473 (s), 1449 (s), 1417 (s),1316 (s), 1280 (s), 1230 (m), 1187 (w), 1103 (m), 1058 (m), 1027 (s), 1005 (m), 950 (w), 858 (w), 814 (s), 766 (s), 710 (m), 671 (w), 630 (m), 562 (m), 538 (m), 504 (w), 455 (w). Elemental analysis, calculated for C₁₈H₁₈N₃: C 78.23, H 6.57, N 15.21%; found: C 78.25, H 6.55, N 15.20%.

For the preparation of (L), anhydrous dimethylformamide (10 ml) was added with stirring to a mixture of 2-[4-(pyridin-3-yl)phenyl]-1H-benzimidazole (0.90 g, 3.33 mmol), 3-chloromethylpyridine hydrochloride (0.55 g, 3.33 mmol), anhydrous potassium carbonate (4.60 g, 33.3 mmol) and potassium iodide (0.06 g). Stirring was continued for 24 h at 341 K, and the reaction was monitored by thin-layer chromatography (TLC). The resulting mixture was poured into water and the precipitate was filtered off, washed with water, dried and purified by column chromatography on silica gel with dichloromethane and tetrahydrofuran (2:1 v/v) as the eluent to afford L as a white solid (yield 0.82 g, 68.3%). Spectroscopic analysis: ¹H NMR (300 MHz, CDCl₃, 298 K, TMS, δ, p.p.m.): 8.89 (s, 1H, –C₅H₄N), 8.65–8.64 (d, 1H, –C₅H₄N), 8.59 (d, 1H, –C₅H₄N), 8.53 (s, 1H, –C₅H₄N), 7.96–7.94 (d, 2H, –C₆H₄), 7.84–7.83 (d, 2H, –C₅H₄N), 7.74–7.71 (d, 2H, –C₅H₄N), 7.46–7.44 (d, 2H, –C₆H₄), 7.38–7.36 (d, 2H, –C₆H₄), 7.33–7.32 (m, 2H, –C₆H₄); IR (KBr pellet, ν, cm^-1): 3324 (s), 1637 (s), 1457 (s), 1396 (s), 1329 (m), 1283 (m), 1249 (m), 1162 (m), 1124 (w), 1024 (m), 989 (w), 942 (w), 852 (s), 809 (m), 765 (m), 746 (s), 711 (s), 594 (w). Elemental analysis, calculated for C₁₆H₁₁N₃O₄: C 79.54, H 5.01, N 15.46%; found: C79.58, H 4.96, N 15.49%.

For the preparation of (I), a mixture of L (3.62 mg, 0.01 mmol), CdBr₂ (13.8 mg, 0.04 mmol) and water (2 ml) was sealed in a 5 ml test tube, heated to 423 K for 38 h and cooled slowly to room temperature over a period of 50 h. Colourless crystals of (I) were obtained (yield 5.43 mg, 75%). Spectroscopic analysis: IR (KBr pellet, ν, cm^-1): 3485 (s), 1626 (s), 1461 (s), 1440 (m), 1407 (s), 1291 (w), 1257 (w), 1131 (m), 1031 (w), 1008 (w), 989 (w), 856 (m), 816 (m), 752 (s), 701 (s), 491 (w).

For the preparation of (II), a mixture of L (3.62 mg, 0.01 mmol), CdI₂ (14.7 mg, 0.04 mmol) and water (2 ml) was sealed in a 5 ml test tube, heated to 423 K for 38 h and cooled slowly to room temperature over a period of 50 h. Colourless [Yellow in CIF tables - please clarify] crystals of compound (II) were obtained (yield 5.82 mg, 80%). Spectroscopic analysis: IR (KBr pellet, ν, cm^-1): 3439 (s), 1661 (s), 1614 (s), 1509 (w), 1456 (m), 1402 (s), 1293 (w), 1131 (m), 1030 (w), 1007 (w), 989 (w), 854 (m), 807 (w), 749 (m), 699 (s), 528 (w).

S3. Refinement

H atoms attached to C atoms were placed in geometrically idealized positions and included as riding, with C—H = 0.93 (aromatic) or 0.97 Å (methylene). Water H atoms were located in difference maps and constrained to an O—H distance of 0.85 Å. All H atoms were refined with U_iso(H) = 1.2U_eq(parent atom).

Computing details

For both compounds, data collection: SMART (Bruker, 2003); cell refinement: SMART (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. Thesymmetric unit of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The asymmetric unit of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. (a) The 20-membered macrocycle [symmetry code: (i) -x + 1, -y + 1, -z], (b) the 16-membered macrocycle [symmetry code: (ii) -x + 2, -y + 1, -z+1], and (c) the one-dimensional chain in (I).
	Fig. 4. The two-dimensional sheet in (I), linked by two kinds of hydrogen bonds (blue and pink dashed lines in the electronic version of the paper). H atoms not involved in short contacts have been omitted for clarity. [Symmetry code: (i) -x + 1, -y, -z.]
	Fig. 5. π–π interactions (red dashed lines in the electronic version of the paper) and C—H···π interactions (purple dashed lines) between adjacent chains of (II), viewed along the crystallographic a axis. [Symmetry code: (i) -x + 1, -y + 1, -z + 1.]
	Fig. 6. π–π interactions (red and purple dashed lines in the electronic version of the paper) in the stacking motif of complex (II), along the c axis. H atoms have been omitted for clarity.

(I) catena-Poly[[[dibromidocadmium(II)]-µ₃-1-[(pyridin-3-yl)methyl]-2-[4-(pyridin-3-yl)phenyl]-1H-benzimidazole] monohydrate]

Crystal data

[CdBr2(C24H18N4)]·H2O	Z = 2
Mr = 652.66	F(000) = 636
Triclinic, P1	Dx = 1.845 Mg m^−3
Hall symbol: -P1	Mo Kα radiation, λ = 0.71073 Å
a = 9.379 (2) Å	Cell parameters from 3305 reflections
b = 10.023 (2) Å	θ = 2.3–28.1°
c = 13.773 (3) Å	µ = 4.36 mm^−1
α = 101.504 (3)°	T = 298 K
β = 107.424 (3)°	Bar, colourless
γ = 99.561 (3)°	0.28 × 0.16 × 0.12 mm
V = 1174.7 (5) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	4256 independent reflections
Radiation source: fine-focus sealed tube	3348 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
ϕ and ω scans	θmax = 25.5°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −11→10
Tmin = 0.375, Tmax = 0.623	k = −10→12
6132 measured reflections	l = −14→16

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.178	H-atom parameters constrained
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0941P)^2 + 1.6163P] where P = (Fo^2 + 2Fc^2)/3
4256 reflections	(Δ/σ)max < 0.001
289 parameters	Δρmax = 2.03 e Å^−3
0 restraints	Δρmin = −1.63 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Br1	0.72809 (12)	0.13263 (12)	0.08554 (8)	0.0669 (3)
Br2	0.50224 (10)	−0.02270 (10)	0.31475 (8)	0.0564 (3)
C1	0.7284 (9)	0.8361 (9)	−0.1574 (6)	0.0447 (19)
H1	0.7302	0.8830	−0.2090	0.054*
C2	0.8654 (10)	0.8238 (11)	−0.0919 (7)	0.054 (2)
H2	0.9577	0.8601	−0.1000	0.064*
C3	0.8640 (10)	0.7573 (10)	−0.0145 (7)	0.051 (2)
H3	0.9556	0.7473	0.0303	0.061*
C4	0.7246 (8)	0.7048 (8)	−0.0032 (6)	0.0348 (16)
C5	0.5922 (8)	0.7210 (8)	−0.0741 (6)	0.0364 (17)
H5	0.4980	0.6861	−0.0677	0.044*
C6	0.7147 (8)	0.6424 (8)	0.0847 (6)	0.0361 (17)
C7	0.6005 (8)	0.6606 (8)	0.1269 (6)	0.0348 (16)
H7	0.5261	0.7048	0.0961	0.042*
C8	0.5952 (8)	0.6144 (8)	0.2135 (6)	0.0357 (16)
H8	0.5169	0.6271	0.2403	0.043*
C9	0.7062 (8)	0.5486 (7)	0.2616 (6)	0.0345 (16)
C10	0.8169 (9)	0.5250 (8)	0.2178 (6)	0.0431 (19)
H10	0.8881	0.4767	0.2468	0.052*
C11	0.8230 (9)	0.5726 (8)	0.1305 (6)	0.0427 (18)
H11	0.8996	0.5578	0.1025	0.051*
C12	0.7061 (8)	0.5069 (8)	0.3580 (5)	0.0333 (16)
C13	0.7188 (8)	0.3921 (8)	0.4776 (6)	0.0352 (16)
C14	0.7294 (10)	0.2935 (9)	0.5360 (6)	0.047 (2)
H14	0.7313	0.2021	0.5066	0.057*
C15	0.7368 (10)	0.3366 (10)	0.6388 (7)	0.053 (2)
H15	0.7453	0.2728	0.6796	0.064*
C16	0.7322 (10)	0.4709 (10)	0.6838 (7)	0.053 (2)
H16	0.7396	0.4957	0.7542	0.064*
C17	0.7169 (9)	0.5691 (9)	0.6268 (6)	0.047 (2)
H17	0.7104	0.6590	0.6560	0.057*
C18	0.7115 (8)	0.5260 (8)	0.5227 (6)	0.0380 (17)
C19	0.7062 (9)	0.7475 (8)	0.4641 (7)	0.0453 (19)
H19A	0.6173	0.7624	0.4829	0.054*
H19B	0.6970	0.7741	0.3989	0.054*
C20	0.8490 (8)	0.8410 (7)	0.5493 (6)	0.0340 (16)
C21	0.8425 (9)	0.9734 (8)	0.5980 (7)	0.046 (2)
H21	0.7514	1.0026	0.5790	0.056*
C22	0.9733 (11)	1.0613 (10)	0.6751 (9)	0.074 (3)
H22	0.9718	1.1506	0.7094	0.089*
C23	1.1053 (11)	1.0151 (9)	0.7002 (9)	0.068 (3)
H23	1.1935	1.0765	0.7509	0.081*
C24	0.9868 (8)	0.8034 (8)	0.5820 (6)	0.0384 (17)
H24	0.9911	0.7138	0.5503	0.046*
Cd1	0.64339 (6)	0.16969 (6)	0.24849 (4)	0.0364 (2)
N1	0.5924 (7)	0.7835 (7)	−0.1503 (5)	0.0393 (15)
N2	0.7140 (7)	0.3821 (6)	0.3747 (5)	0.0363 (14)
N3	0.7043 (7)	0.5982 (6)	0.4458 (5)	0.0350 (14)
N4	1.1153 (7)	0.8880 (7)	0.6567 (6)	0.0488 (17)
O1	0.7725 (9)	0.2847 (11)	−0.1092 (7)	0.104 (3)
H1A	0.7634	0.2575	−0.0559	0.125*
H1B	0.7134	0.2208	−0.1642	0.125*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0616 (6)	0.0932 (8)	0.0639 (6)	0.0345 (5)	0.0373 (5)	0.0227 (6)
Br2	0.0507 (5)	0.0512 (6)	0.0753 (7)	0.0100 (4)	0.0215 (4)	0.0361 (5)
C1	0.048 (5)	0.048 (5)	0.049 (5)	0.013 (4)	0.026 (4)	0.022 (4)
C2	0.040 (4)	0.075 (6)	0.059 (5)	0.016 (4)	0.027 (4)	0.029 (5)
C3	0.041 (4)	0.066 (6)	0.055 (5)	0.020 (4)	0.018 (4)	0.026 (5)
C4	0.032 (4)	0.038 (4)	0.035 (4)	0.010 (3)	0.013 (3)	0.010 (3)
C5	0.032 (4)	0.042 (4)	0.037 (4)	0.008 (3)	0.013 (3)	0.013 (3)
C6	0.033 (4)	0.034 (4)	0.037 (4)	0.008 (3)	0.005 (3)	0.011 (3)
C7	0.034 (4)	0.037 (4)	0.038 (4)	0.013 (3)	0.012 (3)	0.015 (3)
C8	0.031 (4)	0.040 (4)	0.038 (4)	0.012 (3)	0.009 (3)	0.016 (3)
C9	0.036 (4)	0.029 (4)	0.035 (4)	0.005 (3)	0.008 (3)	0.009 (3)
C10	0.040 (4)	0.041 (4)	0.046 (5)	0.014 (3)	0.006 (3)	0.016 (4)
C11	0.044 (4)	0.043 (4)	0.051 (5)	0.020 (4)	0.020 (4)	0.021 (4)
C12	0.029 (3)	0.034 (4)	0.029 (4)	0.006 (3)	0.003 (3)	0.003 (3)
C13	0.033 (4)	0.032 (4)	0.041 (4)	0.007 (3)	0.012 (3)	0.012 (3)
C14	0.059 (5)	0.041 (5)	0.046 (5)	0.014 (4)	0.018 (4)	0.019 (4)
C15	0.055 (5)	0.051 (5)	0.055 (5)	0.003 (4)	0.018 (4)	0.027 (5)
C16	0.055 (5)	0.063 (6)	0.039 (5)	0.003 (4)	0.019 (4)	0.012 (4)
C17	0.055 (5)	0.044 (5)	0.038 (4)	0.005 (4)	0.019 (4)	0.003 (4)
C18	0.035 (4)	0.037 (4)	0.038 (4)	0.004 (3)	0.009 (3)	0.011 (3)
C19	0.042 (4)	0.035 (4)	0.050 (5)	0.016 (3)	0.003 (4)	0.009 (4)
C20	0.037 (4)	0.026 (4)	0.040 (4)	0.009 (3)	0.011 (3)	0.012 (3)
C21	0.044 (4)	0.040 (4)	0.053 (5)	0.019 (4)	0.010 (4)	0.010 (4)
C22	0.064 (6)	0.036 (5)	0.095 (8)	0.018 (4)	−0.002 (6)	−0.004 (5)
C23	0.048 (5)	0.034 (5)	0.091 (7)	0.011 (4)	−0.006 (5)	−0.003 (5)
C24	0.036 (4)	0.032 (4)	0.045 (4)	0.012 (3)	0.013 (3)	0.004 (3)
Cd1	0.0355 (3)	0.0342 (3)	0.0396 (3)	0.0091 (2)	0.0113 (2)	0.0123 (2)
N1	0.040 (3)	0.044 (4)	0.038 (3)	0.010 (3)	0.015 (3)	0.017 (3)
N2	0.041 (3)	0.033 (3)	0.036 (3)	0.011 (3)	0.010 (3)	0.012 (3)
N3	0.032 (3)	0.036 (3)	0.034 (3)	0.009 (3)	0.007 (2)	0.008 (3)
N4	0.040 (4)	0.033 (4)	0.066 (5)	0.009 (3)	0.007 (3)	0.015 (3)
O1	0.075 (5)	0.151 (9)	0.082 (6)	0.016 (5)	0.021 (4)	0.039 (6)

Geometric parameters (Å, º)

Cd1—Br1	2.5766 (12)	C14—H14	0.9300
Cd1—Br2	2.6233 (10)	C15—C16	1.379 (13)
C1—N1	1.336 (10)	C15—H15	0.9300
C1—C2	1.373 (12)	C16—C17	1.376 (12)
C1—H1	0.9300	C16—H16	0.9300
C2—C3	1.367 (12)	C17—C18	1.396 (11)
C2—H2	0.9300	C17—H17	0.9300
C3—C4	1.392 (11)	C18—N3	1.389 (9)
C3—H3	0.9300	C19—N3	1.463 (9)
C4—C5	1.388 (10)	C19—C20	1.500 (10)
C4—C6	1.488 (10)	C19—H19A	0.9700
C5—N1	1.326 (9)	C19—H19B	0.9700
C5—H5	0.9300	C20—C24	1.377 (10)
C6—C7	1.383 (11)	C20—C21	1.382 (11)
C6—C11	1.396 (10)	C21—C22	1.377 (12)
C7—C8	1.374 (10)	C21—H21	0.9300
C7—H7	0.9300	C22—C23	1.365 (13)
C8—C9	1.396 (10)	C22—H22	0.9300
C8—H8	0.9300	C23—N4	1.327 (11)
C9—C10	1.378 (11)	C23—H23	0.9300
C9—C12	1.470 (10)	C24—N4	1.342 (10)
C10—C11	1.392 (11)	C24—H24	0.9300
C10—H10	0.9300	Cd1—N2	2.315 (6)
C11—H11	0.9300	Cd1—N1^i	2.397 (6)
C12—N2	1.327 (9)	Cd1—N4^ii	2.475 (7)
C12—N3	1.368 (9)	N1—Cd1^i	2.397 (6)
C13—C18	1.384 (10)	N4—Cd1^ii	2.475 (7)
C13—N2	1.387 (9)	O1—H1A	0.8549
C13—C14	1.392 (10)	O1—H1B	0.8530
C14—C15	1.372 (12)
Cd1—Br1—H1A	140.3	C16—C17—H17	122.0
N1—C1—C2	122.9 (7)	C18—C17—H17	122.0
N1—C1—H1	118.6	C13—C18—N3	105.8 (7)
C2—C1—H1	118.6	C13—C18—C17	122.8 (7)
C3—C2—C1	119.0 (8)	N3—C18—C17	131.4 (7)
C3—C2—H2	120.5	N3—C19—C20	113.7 (6)
C1—C2—H2	120.5	N3—C19—H19A	108.8
C2—C3—C4	119.6 (8)	C20—C19—H19A	108.8
C2—C3—H3	120.2	N3—C19—H19B	108.8
C4—C3—H3	120.2	C20—C19—H19B	108.8
C5—C4—C3	117.1 (7)	H19A—C19—H19B	107.7
C5—C4—C6	120.0 (6)	C24—C20—C21	117.7 (7)
C3—C4—C6	122.8 (7)	C24—C20—C19	124.1 (7)
N1—C5—C4	123.6 (7)	C21—C20—C19	118.2 (7)
N1—C5—H5	118.2	C22—C21—C20	118.9 (8)
C4—C5—H5	118.2	C22—C21—H21	120.6
C7—C6—C11	118.5 (7)	C20—C21—H21	120.6
C7—C6—C4	119.5 (6)	C23—C22—C21	118.9 (9)
C11—C6—C4	121.9 (7)	C23—C22—H22	120.6
C8—C7—C6	121.2 (7)	C21—C22—H22	120.6
C8—C7—H7	119.4	N4—C23—C22	124.0 (8)
C6—C7—H7	119.4	N4—C23—H23	118.0
C7—C8—C9	120.5 (7)	C22—C23—H23	118.0
C7—C8—H8	119.7	N4—C24—C20	124.1 (7)
C9—C8—H8	119.7	N4—C24—H24	117.9
C10—C9—C8	118.8 (7)	C20—C24—H24	117.9
C10—C9—C12	120.7 (7)	N2—Cd1—N1^i	92.7 (2)
C8—C9—C12	120.5 (7)	N2—Cd1—N4^ii	89.9 (2)
C9—C10—C11	120.6 (7)	N1^i—Cd1—N4^ii	177.4 (2)
C9—C10—H10	119.7	N2—Cd1—Br1	123.50 (15)
C11—C10—H10	119.7	N1^i—Cd1—Br1	91.39 (15)
C10—C11—C6	120.3 (8)	N4^ii—Cd1—Br1	86.88 (18)
C10—C11—H11	119.9	N2—Cd1—Br2	108.50 (15)
C6—C11—H11	119.9	N1^i—Cd1—Br2	93.21 (15)
N2—C12—N3	111.0 (6)	N4^ii—Cd1—Br2	86.34 (16)
N2—C12—C9	126.3 (7)	Br1—Cd1—Br2	127.48 (4)
N3—C12—C9	122.7 (7)	C5—N1—C1	117.8 (7)
C18—C13—N2	109.3 (6)	C5—N1—Cd1^i	118.4 (5)
C18—C13—C14	119.9 (7)	C1—N1—Cd1^i	123.0 (5)
N2—C13—C14	130.8 (7)	C12—N2—C13	106.6 (6)
C15—C14—C13	117.3 (8)	C12—N2—Cd1	127.1 (5)
C15—C14—H14	121.4	C13—N2—Cd1	122.8 (5)
C13—C14—H14	121.4	C12—N3—C18	107.3 (6)
C14—C15—C16	122.5 (8)	C12—N3—C19	129.1 (6)
C14—C15—H15	118.8	C18—N3—C19	123.4 (6)
C16—C15—H15	118.8	C23—N4—C24	116.4 (7)
C17—C16—C15	121.4 (8)	C23—N4—Cd1^ii	113.1 (5)
C17—C16—H16	119.3	C24—N4—Cd1^ii	129.4 (5)
C15—C16—H16	119.3	H1A—O1—H1B	107.0
C16—C17—C18	116.1 (8)
N1—C1—C2—C3	−1.3 (14)	C21—C20—C24—N4	−1.1 (12)
C1—C2—C3—C4	−0.5 (14)	C19—C20—C24—N4	178.6 (8)
C2—C3—C4—C5	1.3 (13)	H1A—Br1—Cd1—N2	−41.4
C2—C3—C4—C6	−174.5 (8)	H1A—Br1—Cd1—N1^i	52.7
C3—C4—C5—N1	−0.3 (12)	H1A—Br1—Cd1—N4^ii	−129.2
C6—C4—C5—N1	175.6 (7)	H1A—Br1—Cd1—Br2	147.8
C5—C4—C6—C7	−30.2 (10)	C4—C5—N1—C1	−1.4 (12)
C3—C4—C6—C7	145.5 (8)	C4—C5—N1—Cd1^i	−171.4 (6)
C5—C4—C6—C11	153.6 (8)	C2—C1—N1—C5	2.2 (13)
C3—C4—C6—C11	−30.7 (11)	C2—C1—N1—Cd1^i	171.7 (7)
C11—C6—C7—C8	1.6 (11)	N3—C12—N2—C13	−0.4 (8)
C4—C6—C7—C8	−174.7 (7)	C9—C12—N2—C13	176.8 (7)
C6—C7—C8—C9	0.5 (11)	N3—C12—N2—Cd1	158.6 (5)
C7—C8—C9—C10	−3.0 (11)	C9—C12—N2—Cd1	−24.1 (10)
C7—C8—C9—C12	176.3 (7)	C18—C13—N2—C12	0.8 (8)
C8—C9—C10—C11	3.5 (11)	C14—C13—N2—C12	−179.1 (8)
C12—C9—C10—C11	−175.8 (7)	C18—C13—N2—Cd1	−159.4 (5)
C9—C10—C11—C6	−1.4 (12)	C14—C13—N2—Cd1	20.7 (11)
C7—C6—C11—C10	−1.1 (11)	N1^i—Cd1—N2—C12	−44.9 (6)
C4—C6—C11—C10	175.1 (7)	N4^ii—Cd1—N2—C12	134.7 (6)
C10—C9—C12—N2	−50.4 (10)	Br1—Cd1—N2—C12	48.5 (6)
C8—C9—C12—N2	130.3 (8)	Br2—Cd1—N2—C12	−139.2 (5)
C10—C9—C12—N3	126.6 (8)	N1^i—Cd1—N2—C13	111.0 (5)
C8—C9—C12—N3	−52.7 (10)	N4^ii—Cd1—N2—C13	−69.4 (5)
C18—C13—C14—C15	−2.0 (11)	Br1—Cd1—N2—C13	−155.6 (5)
N2—C13—C14—C15	177.9 (8)	Br2—Cd1—N2—C13	16.7 (6)
C13—C14—C15—C16	0.8 (13)	N2—C12—N3—C18	0.0 (8)
C14—C15—C16—C17	1.2 (14)	C9—C12—N3—C18	−177.5 (6)
C15—C16—C17—C18	−2.1 (12)	N2—C12—N3—C19	175.7 (6)
N2—C13—C18—N3	−0.8 (8)	C9—C12—N3—C19	−1.7 (11)
C14—C13—C18—N3	179.1 (7)	C13—C18—N3—C12	0.5 (8)
N2—C13—C18—C17	−178.8 (7)	C17—C18—N3—C12	178.3 (8)
C14—C13—C18—C17	1.1 (11)	C13—C18—N3—C19	−175.5 (6)
C16—C17—C18—C13	0.9 (11)	C17—C18—N3—C19	2.2 (12)
C16—C17—C18—N3	−176.5 (8)	C20—C19—N3—C12	−114.9 (8)
N3—C19—C20—C24	22.1 (12)	C20—C19—N3—C18	60.3 (10)
N3—C19—C20—C21	−158.2 (7)	C22—C23—N4—C24	1.6 (17)
C24—C20—C21—C22	0.9 (13)	C22—C23—N4—Cd1^ii	−167.4 (10)
C19—C20—C21—C22	−178.9 (9)	C20—C24—N4—C23	−0.1 (13)
C20—C21—C22—C23	0.5 (16)	C20—C24—N4—Cd1^ii	166.8 (6)
C21—C22—C23—N4	−1.8 (19)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···Br2^iii	0.85	2.62	3.459 (9)	170
O1—H1A···Br1	0.85	2.59	3.433 (9)	170

Symmetry code: (iii) −x+1, −y, −z.

(II) catena-Poly[[diiodidocadmium (II)]-µ₃-1-[(pyridin-3-yl)methyl]-2-[4-(pyridin-3-yl)phenyl]-1H-benzimidazole]

Crystal data

[CdI2(C24H18N4)]	Z = 2
Mr = 728.62	F(000) = 688
Triclinic, P1	Dx = 2.096 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.128 (2) Å	Cell parameters from 3305 reflections
b = 10.254 (3) Å	θ = 2.3–28.0°
c = 13.429 (4) Å	µ = 3.64 mm^−1
α = 70.065 (3)°	T = 298 K
β = 77.717 (4)°	Bar, yellow
γ = 86.952 (3)°	0.28 × 0.16 × 0.12 mm
V = 1154.4 (5) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	4424 independent reflections
Radiation source: fine-focus sealed tube	3863 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
ϕ and ω scans	θmax = 26.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −11→11
Tmin = 0.502, Tmax = 0.646	k = −10→12
6318 measured reflections	l = −11→16

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.077	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0387P)^2 + 0.214P] where P = (Fo^2 + 2Fc^2)/3
4424 reflections	(Δ/σ)max = 0.001
280 parameters	Δρmax = 0.84 e Å^−3
0 restraints	Δρmin = −0.55 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
Cd1	0.36190 (3)	1.32721 (3)	0.23763 (2)	0.02950 (9)
I1	0.64498 (4)	1.37177 (4)	0.10783 (3)	0.05443 (11)
I2	0.13184 (3)	1.50971 (3)	0.27458 (2)	0.04140 (10)
N1	0.7491 (4)	0.7373 (3)	−0.1127 (3)	0.0330 (8)
N2	0.3074 (4)	1.1119 (3)	0.3762 (2)	0.0272 (7)
N3	0.2289 (4)	0.8917 (3)	0.4570 (3)	0.0268 (7)
N4	0.5115 (4)	0.6109 (3)	0.6357 (3)	0.0354 (8)
C1	0.8846 (5)	0.6977 (5)	−0.0930 (3)	0.0393 (10)
H1	0.9473	0.6579	−0.1386	0.047*
C2	0.9356 (5)	0.7129 (6)	−0.0089 (4)	0.0508 (13)
H2	1.0314	0.6851	0.0017	0.061*
C3	0.8426 (5)	0.7702 (5)	0.0600 (4)	0.0446 (11)
H3	0.8747	0.7793	0.1187	0.053*
C4	0.7029 (5)	0.8138 (4)	0.0419 (3)	0.0318 (9)
C5	0.6607 (5)	0.7932 (4)	−0.0451 (3)	0.0312 (9)
H5	0.5653	0.8198	−0.0573	0.037*
C6	0.5966 (5)	0.8703 (4)	0.1159 (3)	0.0307 (9)
C7	0.6494 (5)	0.9482 (4)	0.1686 (3)	0.0351 (9)
H7	0.7503	0.9741	0.1502	0.042*
C8	0.5542 (5)	0.9875 (4)	0.2477 (3)	0.0328 (9)
H8	0.5920	1.0385	0.2825	0.039*
C9	0.4032 (4)	0.9520 (4)	0.2757 (3)	0.0274 (8)
C10	0.3474 (5)	0.8807 (4)	0.2189 (3)	0.0313 (9)
H10	0.2453	0.8601	0.2339	0.038*
C11	0.4436 (5)	0.8408 (4)	0.1405 (3)	0.0317 (9)
H11	0.4053	0.7933	0.1035	0.038*
C12	0.3096 (4)	0.9876 (4)	0.3660 (3)	0.0267 (8)
C13	0.2237 (4)	1.0964 (4)	0.4795 (3)	0.0253 (8)
C14	0.1860 (4)	1.1918 (4)	0.5325 (3)	0.0306 (9)
H14	0.2162	1.2845	0.4990	0.037*
C15	0.1027 (5)	1.1447 (4)	0.6358 (3)	0.0347 (9)
H15	0.0773	1.2070	0.6731	0.042*
C16	0.0539 (5)	1.0056 (5)	0.6879 (3)	0.0386 (10)
H16	−0.0027	0.9778	0.7582	0.046*
C17	0.0893 (5)	0.9100 (4)	0.6354 (3)	0.0355 (9)
H17	0.0582	0.8175	0.6686	0.043*
C18	0.1736 (4)	0.9588 (4)	0.5304 (3)	0.0272 (8)
C19	0.2048 (4)	0.7445 (4)	0.4788 (3)	0.0311 (9)
H19A	0.2187	0.7284	0.4103	0.037*
H19B	0.1016	0.7197	0.5162	0.037*
C20	0.3062 (4)	0.6507 (4)	0.5452 (3)	0.0259 (8)
C21	0.4219 (4)	0.6962 (4)	0.5774 (3)	0.0306 (9)
H21	0.4382	0.7913	0.5573	0.037*
C22	0.4864 (5)	0.4756 (4)	0.6638 (4)	0.0391 (10)
H22	0.5486	0.4150	0.7041	0.047*
C23	0.3738 (5)	0.4208 (4)	0.6364 (4)	0.0392 (10)
H23	0.3602	0.3252	0.6580	0.047*
C24	0.2816 (5)	0.5083 (4)	0.5770 (3)	0.0338 (9)
H24	0.2037	0.4732	0.5581	0.041*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.03043 (16)	0.02622 (16)	0.03053 (17)	0.00191 (12)	−0.00370 (12)	−0.00968 (12)
I1	0.03719 (18)	0.0559 (2)	0.0597 (2)	−0.00668 (15)	0.00824 (15)	−0.01606 (17)
I2	0.03625 (17)	0.03927 (17)	0.0528 (2)	0.01083 (12)	−0.00949 (14)	−0.02213 (14)
N1	0.0385 (19)	0.0304 (18)	0.0294 (18)	0.0044 (15)	−0.0058 (15)	−0.0105 (14)
N2	0.0313 (17)	0.0228 (16)	0.0280 (17)	0.0005 (13)	−0.0044 (14)	−0.0104 (13)
N3	0.0323 (17)	0.0197 (15)	0.0282 (17)	0.0012 (13)	−0.0093 (14)	−0.0060 (13)
N4	0.0380 (19)	0.0253 (18)	0.046 (2)	0.0016 (15)	−0.0164 (17)	−0.0110 (16)
C1	0.037 (2)	0.044 (3)	0.035 (2)	0.001 (2)	0.0017 (19)	−0.017 (2)
C2	0.036 (2)	0.073 (4)	0.049 (3)	0.018 (2)	−0.010 (2)	−0.030 (3)
C3	0.045 (3)	0.060 (3)	0.039 (3)	0.008 (2)	−0.015 (2)	−0.028 (2)
C4	0.034 (2)	0.031 (2)	0.028 (2)	0.0038 (17)	−0.0037 (17)	−0.0108 (17)
C5	0.036 (2)	0.029 (2)	0.028 (2)	0.0028 (17)	−0.0064 (17)	−0.0088 (17)
C6	0.040 (2)	0.026 (2)	0.026 (2)	0.0064 (17)	−0.0100 (17)	−0.0074 (16)
C7	0.032 (2)	0.035 (2)	0.038 (2)	0.0030 (18)	−0.0060 (18)	−0.0131 (19)
C8	0.038 (2)	0.030 (2)	0.032 (2)	0.0006 (18)	−0.0092 (18)	−0.0124 (18)
C9	0.036 (2)	0.0180 (18)	0.0260 (19)	0.0034 (16)	−0.0074 (17)	−0.0045 (15)
C10	0.031 (2)	0.030 (2)	0.033 (2)	0.0023 (17)	−0.0063 (17)	−0.0104 (17)
C11	0.039 (2)	0.028 (2)	0.033 (2)	0.0051 (17)	−0.0128 (19)	−0.0136 (17)
C12	0.0280 (19)	0.0243 (19)	0.029 (2)	0.0045 (15)	−0.0108 (16)	−0.0080 (16)
C13	0.0262 (19)	0.0231 (19)	0.0259 (19)	0.0011 (15)	−0.0069 (16)	−0.0066 (15)
C14	0.033 (2)	0.026 (2)	0.034 (2)	0.0016 (16)	−0.0080 (18)	−0.0117 (17)
C15	0.036 (2)	0.036 (2)	0.036 (2)	0.0065 (18)	−0.0097 (19)	−0.0178 (19)
C16	0.034 (2)	0.050 (3)	0.027 (2)	0.000 (2)	−0.0009 (18)	−0.012 (2)
C17	0.038 (2)	0.032 (2)	0.034 (2)	0.0013 (18)	−0.0076 (19)	−0.0072 (18)
C18	0.0242 (19)	0.0263 (19)	0.031 (2)	0.0026 (15)	−0.0084 (16)	−0.0087 (16)
C19	0.035 (2)	0.0228 (19)	0.036 (2)	−0.0019 (16)	−0.0112 (18)	−0.0076 (17)
C20	0.032 (2)	0.0208 (18)	0.0246 (19)	−0.0002 (15)	−0.0037 (16)	−0.0085 (15)
C21	0.035 (2)	0.0202 (19)	0.039 (2)	0.0000 (16)	−0.0107 (18)	−0.0116 (17)
C22	0.040 (2)	0.029 (2)	0.048 (3)	0.0063 (19)	−0.015 (2)	−0.0108 (19)
C23	0.048 (3)	0.020 (2)	0.050 (3)	0.0006 (18)	−0.015 (2)	−0.0090 (18)
C24	0.034 (2)	0.026 (2)	0.044 (2)	0.0008 (17)	−0.0084 (19)	−0.0149 (18)

Geometric parameters (Å, º)

Cd1—N2	2.346 (3)	C8—C9	1.383 (5)
Cd1—N1^i	2.415 (3)	C8—H8	0.9300
Cd1—N4^ii	2.507 (3)	C9—C10	1.401 (5)
Cd1—I1	2.7551 (7)	C9—C12	1.470 (5)
Cd1—I2	2.8161 (7)	C10—C11	1.382 (6)
N1—C1	1.334 (5)	C10—H10	0.9300
N1—C5	1.340 (5)	C11—H11	0.9300
N1—Cd1^i	2.415 (3)	C13—C14	1.384 (5)
N2—C12	1.326 (5)	C13—C18	1.394 (5)
N2—C13	1.395 (5)	C14—C15	1.368 (6)
N3—C12	1.370 (5)	C14—H14	0.9300
N3—C18	1.384 (5)	C15—C16	1.406 (6)
N3—C19	1.456 (5)	C15—H15	0.9300
N4—C22	1.326 (5)	C16—C17	1.379 (6)
N4—C21	1.333 (5)	C16—H16	0.9300
N4—Cd1^ii	2.507 (3)	C17—C18	1.389 (6)
C1—C2	1.367 (6)	C17—H17	0.9300
C1—H1	0.9300	C19—C20	1.500 (5)
C2—C3	1.381 (6)	C19—H19A	0.9700
C2—H2	0.9300	C19—H19B	0.9700
C3—C4	1.372 (6)	C20—C21	1.380 (5)
C3—H3	0.9300	C20—C24	1.390 (5)
C4—C5	1.389 (5)	C21—H21	0.9300
C4—C6	1.479 (5)	C22—C23	1.368 (6)
C5—H5	0.9300	C22—H22	0.9300
C6—C11	1.390 (6)	C23—C24	1.367 (6)
C6—C7	1.393 (6)	C23—H23	0.9300
C7—C8	1.382 (6)	C24—H24	0.9300
C7—H7	0.9300
N2—Cd1—N1^i	94.05 (11)	C11—C10—C9	120.1 (4)
N2—Cd1—N4^ii	85.75 (11)	C11—C10—H10	119.9
N1^i—Cd1—N4^ii	177.27 (11)	C9—C10—H10	119.9
N2—Cd1—I1	118.09 (8)	C10—C11—C6	121.3 (4)
N1^i—Cd1—I1	94.54 (9)	C10—C11—H11	119.4
N4^ii—Cd1—I1	83.17 (9)	C6—C11—H11	119.4
N2—Cd1—I2	107.95 (8)	N2—C12—N3	111.4 (3)
N1^i—Cd1—I2	94.30 (8)	N2—C12—C9	124.5 (3)
N4^ii—Cd1—I2	88.35 (8)	N3—C12—C9	123.6 (3)
I1—Cd1—I2	132.223 (19)	C14—C13—C18	120.1 (4)
C1—N1—C5	117.2 (4)	C14—C13—N2	130.9 (3)
C1—N1—Cd1^i	123.5 (3)	C18—C13—N2	109.0 (3)
C5—N1—Cd1^i	118.2 (3)	C15—C14—C13	117.5 (4)
C12—N2—C13	106.3 (3)	C15—C14—H14	121.2
C12—N2—Cd1	127.6 (3)	C13—C14—H14	121.2
C13—N2—Cd1	123.6 (2)	C14—C15—C16	122.5 (4)
C12—N3—C18	107.5 (3)	C14—C15—H15	118.8
C12—N3—C19	128.6 (3)	C16—C15—H15	118.8
C18—N3—C19	123.9 (3)	C17—C16—C15	120.5 (4)
C22—N4—C21	117.5 (4)	C17—C16—H16	119.7
C22—N4—Cd1^ii	113.2 (3)	C15—C16—H16	119.7
C21—N4—Cd1^ii	123.6 (3)	C16—C17—C18	116.6 (4)
N1—C1—C2	123.0 (4)	C16—C17—H17	121.7
N1—C1—H1	118.5	C18—C17—H17	121.7
C2—C1—H1	118.5	N3—C18—C17	131.3 (4)
C1—C2—C3	118.9 (4)	N3—C18—C13	105.9 (3)
C1—C2—H2	120.5	C17—C18—C13	122.8 (4)
C3—C2—H2	120.5	N3—C19—C20	114.5 (3)
C4—C3—C2	119.9 (4)	N3—C19—H19A	108.6
C4—C3—H3	120.0	C20—C19—H19A	108.6
C2—C3—H3	120.0	N3—C19—H19B	108.6
C3—C4—C5	116.9 (4)	C20—C19—H19B	108.6
C3—C4—C6	122.0 (4)	H19A—C19—H19B	107.6
C5—C4—C6	120.9 (4)	C21—C20—C24	117.8 (4)
N1—C5—C4	124.0 (4)	C21—C20—C19	124.4 (3)
N1—C5—H5	118.0	C24—C20—C19	117.8 (3)
C4—C5—H5	118.0	N4—C21—C20	123.4 (4)
C11—C6—C7	118.0 (4)	N4—C21—H21	118.3
C11—C6—C4	121.7 (4)	C20—C21—H21	118.3
C7—C6—C4	120.2 (4)	N4—C22—C23	123.3 (4)
C8—C7—C6	121.1 (4)	N4—C22—H22	118.3
C8—C7—H7	119.5	C23—C22—H22	118.3
C6—C7—H7	119.5	C22—C23—C24	119.2 (4)
C7—C8—C9	120.7 (4)	C22—C23—H23	120.4
C7—C8—H8	119.6	C24—C23—H23	120.4
C9—C8—H8	119.6	C23—C24—C20	118.8 (4)
C8—C9—C10	118.6 (4)	C23—C24—H24	120.6
C8—C9—C12	118.3 (4)	C20—C24—H24	120.6
C10—C9—C12	123.1 (4)
N1^i—Cd1—N2—C12	36.3 (3)	C19—N3—C12—C9	−7.4 (6)
N4^ii—Cd1—N2—C12	−141.0 (3)	C8—C9—C12—N2	49.5 (5)
I1—Cd1—N2—C12	−61.0 (3)	C10—C9—C12—N2	−132.3 (4)
I2—Cd1—N2—C12	132.1 (3)	C8—C9—C12—N3	−121.6 (4)
N1^i—Cd1—N2—C13	−123.2 (3)	C10—C9—C12—N3	56.7 (5)
N4^ii—Cd1—N2—C13	59.6 (3)	C12—N2—C13—C14	179.9 (4)
I1—Cd1—N2—C13	139.5 (3)	Cd1—N2—C13—C14	−17.0 (6)
I2—Cd1—N2—C13	−27.3 (3)	C12—N2—C13—C18	−0.9 (4)
C5—N1—C1—C2	−0.6 (6)	Cd1—N2—C13—C18	162.2 (2)
Cd1^i—N1—C1—C2	−167.8 (4)	C18—C13—C14—C15	1.7 (6)
N1—C1—C2—C3	0.8 (8)	N2—C13—C14—C15	−179.2 (4)
C1—C2—C3—C4	−1.5 (8)	C13—C14—C15—C16	−0.8 (6)
C2—C3—C4—C5	1.9 (7)	C14—C15—C16—C17	0.1 (7)
C2—C3—C4—C6	177.4 (4)	C15—C16—C17—C18	−0.2 (6)
C1—N1—C5—C4	1.1 (6)	C12—N3—C18—C17	−177.9 (4)
Cd1^i—N1—C5—C4	169.0 (3)	C19—N3—C18—C17	0.7 (6)
C3—C4—C5—N1	−1.7 (6)	C12—N3—C18—C13	0.3 (4)
C6—C4—C5—N1	−177.3 (4)	C19—N3—C18—C13	178.9 (3)
C3—C4—C6—C11	−141.7 (4)	C16—C17—C18—N3	179.0 (4)
C5—C4—C6—C11	33.6 (6)	C16—C17—C18—C13	1.1 (6)
C3—C4—C6—C7	34.1 (6)	C14—C13—C18—N3	179.7 (3)
C5—C4—C6—C7	−150.6 (4)	N2—C13—C18—N3	0.4 (4)
C11—C6—C7—C8	3.9 (6)	C14—C13—C18—C17	−1.9 (6)
C4—C6—C7—C8	−172.0 (4)	N2—C13—C18—C17	178.8 (3)
C6—C7—C8—C9	−0.8 (6)	C12—N3—C19—C20	98.4 (5)
C7—C8—C9—C10	−2.9 (6)	C18—N3—C19—C20	−79.9 (5)
C7—C8—C9—C12	175.5 (3)	N3—C19—C20—C21	−5.0 (6)
C8—C9—C10—C11	3.4 (6)	N3—C19—C20—C24	174.8 (4)
C12—C9—C10—C11	−174.9 (3)	C22—N4—C21—C20	−0.1 (6)
C9—C10—C11—C6	−0.2 (6)	Cd1^ii—N4—C21—C20	−151.6 (3)
C7—C6—C11—C10	−3.4 (6)	C24—C20—C21—N4	0.9 (6)
C4—C6—C11—C10	172.5 (4)	C19—C20—C21—N4	−179.4 (4)
C13—N2—C12—N3	1.1 (4)	C21—N4—C22—C23	−0.4 (7)
Cd1—N2—C12—N3	−161.1 (2)	Cd1^ii—N4—C22—C23	153.9 (4)
C13—N2—C12—C9	−170.8 (3)	N4—C22—C23—C24	0.1 (7)
Cd1—N2—C12—C9	26.9 (5)	C22—C23—C24—C20	0.6 (6)
C18—N3—C12—N2	−0.9 (4)	C21—C20—C24—C23	−1.1 (6)
C19—N3—C12—N2	−179.4 (3)	C19—C20—C24—C23	179.2 (4)
C18—N3—C12—C9	171.1 (3)

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