A novel penta­coordinated cadmium compound: catena-poly[benzyl­triethyl­ammonium [[chlorido­cadmate(II)]-di-μ-chlorido]]

The structure of the title one-dimensional ABX₃-type organic–inorganic hybrid complex, {(C₁₃H₂₂N)[CdCl₃]}_n, con­sists of benzyl­tri­ethyl­ammonium cations and one-dimensional anionic {[CdCl₃]⁻}_n chains, in which the Cd^II centres are in an unusual two-layer five-coordinated arrangement. The Cd^II atom is penta­coordinated by four bridging and one terminal chloride ligand, forming a slightly distorted trigonal bipy­rami­dal ClCd(μ-Cl)₄ arrangement. The trigonal bipy­ramid is linked by two opposite shared faces, giving rise to a zigzag linear anionic {[CdCl₃]⁻}_n chain. The benzyl­tri­ethyl­ammo­nium cations are located in the inter-space of the inorganic network. There are C—H...Cl hydrogen bonds present and these play a crucial role in linking the organic cations and inorganic layers, and also help assemble the components into a three-dimensional network.

S1. Introduction

With the development of the electronics and information industries, studies of new ferroelectric materials have attracted increasing inter­est in recent years (Fu et al., 2007; Ye et al., 2009; Zhang et al., 2008). Much attention has been paid to quaternary ammonium salts which often have a paraelectric–ferroelectric phase transition due to the dynamics of the quaternary cations. For instance, in the case of [(CH₃)₄N]₂[ZnI₄], the [(CH₃)₄N]⁺ cation is disordered in the paraelectric phase and ordered in the ferroelectric phase (Gesi et al., 1988). We have reported recently two benzyl­tri­ethyl­ammonium (BnEt₃N⁺) compounds, viz. (BnEt₃)₂[CoCl₄] and BnEt₃N⁺.ClO₄^-, which undergo variable-temperature structural phase transitions, the former due to rotation of the ethyl groups between a propeller-like configuration and a butterfly-like configuration, and the latter owing to an order–disorder transformation of the ClO₄^- anion (Wu et al., 2012, 2013). In our search for potential ferroelectric materials, we have paid much attention to the ABX₃-type compounds, which have been extensively studied because many of these compounds exhibit phase transitions related to the dynamics of the organic cations and inorganic anions (Doudin & Chapuis, 1992; Morosin et al., 1972; Puget et al., 1991; Waśkowska et al., 1990). For example, (Me₄N)[CdBr₃] undergoes a ferroelectric phase transition which may not be a simple order–disorder type but which contains some displacive-type features (Hang et al., 2011). [(CH₃)₃NH][CdCl₃ ] undergoes a phase transition due to the order–disorder of the tri­methyl­ammonium cations (Chapuis & Zuñiga, 1988). With these ideas in mind, we reacted BnEt₃N⁺.Cl^- with CdCl₂ and obtained a new one-dimensional ABX₃ compound catena-poly[benzyl­tri­ethyl­ammonium [di-µ-chlorido-chloridocadmate(II)]], (BnEt₃N)[CdCl₃] (see Scheme), which contains a novel {[CdCl₃]^-}_n architecture with Cd^II centres in a new five-coordinated environment when compared with other similar {[CdCl₃]^-}_n structures (Wu et al., 2013; Jian et al., 2006; Chapuis et al., 1988). We report herein the synthesis and structure of (I).

S2. Experimental

S2.1. Synthesis and crystallization

Benzyl­tri­ethyl­ammonium chloride and CdCl₂ were purchased from Aldrich Chemicals and were used without further purification. To a water solution (10 ml) of CdCl₂ (0.37 g, 2 mmol), a solution of BnEt₃N⁺ (0.455 g, 2 mmol) in water (5 ml) was added slowly with stirring. A large amount of precipitate appeared immediately and was collected. Small needle-shaped colourless single crystals suitable for X-ray structure analysis were obtained from slow evaporation of the filtrate over a period of about 5 d.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms on C atoms were included in calculated positions and were refined using a riding model, with C—H = 0.93 (aromatic), 0.96 (methyl) or 0.97 Å (methyl­ene) and with U_iso(H) = 1.5U_eq(C) for the methyl groups and U_iso(H) = 1.2U_eq(C) otherwise.

S3. Results and discussion

The title compound, (I), crystallizes in the space group P2₁/c. The asymmetric unit contains one BnEt₃N⁺ cation and one [CdCl₃]^- anion (Fig. 1). There is only one type of coordination environment around the Cd^II atoms. Each Cd1 center is bonded to one terminal (Cl1) and four bridging chloride ligands [Cl2, Cl2ⁱ, Cl3 and Cl3ⁱⁱ; symmetry codes: (i) -x+1, -y+2, -z+1; (ii) -x, -y+2, -z+1]. In order to determine whether the description of the geometry for the Cd^II atom is either distorted square-pyramidal or distorted trigonal–bipyramidal, an analysis of the shape-determining bond angles was carried out using the approach of Reedijk and co-workers (Addison et al., 1984). The trigonality index, τ, is 0 or 1 if the geometry is perfect square–pyramidal or trigonal–bipyramidal, respectively. The value obtained for (I) (τ = 0.81) indicates that the coordination geometry around the Cd1 atom can be described as a slightly distorted trigonal bipyramid. Atoms Cl1, Cl2 and Cl3 lie in equatorial positions, with Cl—Cd—Cl angles ranging from 117.51 (3) to 122.16 (3)°, and atoms Cl2ⁱ and Cl3ⁱⁱ are in axial positions, with a Cl2ⁱ—Cd—Cl3ⁱⁱ angle of 170.54 (2)°. Both sets on angles deviate slightly from those expected for an ideal trigonal bipyramid (120 and 180°). The Cd—Cl bond lengths in the equatorial positions are in the range 2.4424 (9)–2.5189 (9) Å, whereas the axial bond lengths are in the range 2.6987 (10)–2.7677 (11) Å. This phenomenon can also be found in other Cd^II compounds, where Cd^II is penta­coordinated (Chesnut et al., 1999; Jin et al., 2010; Matsunaga et al., 2005; Xia et al., 2005). The trigonal–bipyramids are linked togther by two opposite shared faces and give rise to a novel zigzag linear anionic {[CdCl₃]^-}_n chain.

There are several noteworthy features with respect to the {[CdCl₃]^-}_n chain. Firstly, the Cd1 and Cd1ⁱ atoms are linked together by Cl2 and Cl2ⁱ ligands and the Cd1 and Cd1ⁱⁱ atoms are linked together by Cl3 and Cl3ⁱⁱ ligands, the Cd1···Cd1ⁱ and Cd1···Cd1ⁱⁱ distances being 3.924 (8) and 3.878 (8) Å, respectively, much shorter than those reported in other one-dimensional cadmium polymers bridged by chloride ligands (average ca 4.14 Å; Huang et al., 1998; Hu et al., 2003; Laskar et al.,2002). There are two layers for the arrangement of the Cd atoms in the inorganic chain, with the average layer distance being 1.435 (4) Å. In each layer, the Cd^II centre lies above the mid-point of the two Cd^II atoms in the next layer. Further, there are two kinds of rings (R_a and R_b) in the chain created by the binuclear [Cd₂Cl₂] units, which result in these rings forming an uncommon distorted re­cta­ngular shape. The R_a and R_b rings are both centrosymmetric with the inversion points I₁ and I₂, respectively. The dihedral angle between the planes of the two rings is 57.928 (3)° and the Cd1ⁱⁱ···Cd1···Cd1ⁱ angle within the chains is 136.84 (6)°. Thus, the atoms generated by these symmetry points assemble the [CdCl₃]^- units into an extended centrosymmetric zigzag chain of corner-sharing Cd-centred trigonal bipyramids along the a axis (Fig. 2).

The zigzag anionic chain in (I) displays a different coordination architecture to a similar compound, [(CdCl₂)₂CdCl₂(15-crown-5)]_n (Rogers et al., 1996), which consists of chloride-bridged polymers propagating along the unit-cell a axis, with the polymeric chains linked together by µ-Cl inter­actions. Because of the 15-crown-5 ether ligand, the axial Cd—C1 bond lengths range from 2.651 to 2.691 (1) Å and the equatorial Cd—C1 bond lengths range from 2.508 (1) to 2.535 (1) Å. There are no terminal chloride ligands and the Cl1 and Cl6 atoms are coordinated to the Cd3 center, so that the compound displays a two-dimensional network, which is different to (I). It is inter­esting that even though there are many chloridocadmates characterized every year, it is rare to see a compound with the Cd^II centre penta­coordinated. Given these facts, the study of penta­coordinated ABX₃ compounds may not only be meaningful to the structure–property relationships, but also very important for exploring some unexpected physical properties. For example, [(CH₃)₂NH₂][CuCl₃] has a similar one-dimensional inorganic chain to (I), but has magnetic behavior and displays a structural phase transition (Willet et al., 2006).

The BnEt₃N⁺ cation in the structure of (I) is ordered. The C—C—N—C torsion angles range from 51.5 (3) to 179.4 (3)°, giving the cation a butterfly-like configuration. Other configurations have been reported for the BnEt₃N⁺ cation and the ratio of the different configurations is a cause for the phase transition of (C₁₃H₂₂N)₂[CoCl₄] (Wu et al., 2012).

The presence of organic cations as spacers between the inorganic anions can affect the distances between chains or layers and can have distinctive hydrogen-bonding features which influences the structural packing (Xiao et al., 2010). In (I), the chains run along the a axis and are well separated by BnEt₃N⁺ cations. There are inter­molecular hydrogen-bonding inter­actions between the organic and inorganic layers. Between adjacent anionic layers, the organic cations pack with an ABAB sequence as a multilayer (Fig. 3), The A layers are composed of organic cations, while the B layers are composed of {[CdCl₃]^-}_n anions. As is shown in Fig. 4, a [Cd₂Cl₆]^2- unit has four BnEt₃N⁺ cations around it forming an impervious quadrilateral with the [Cd₂Cl₆]^2- unit located at the centre. This quadrilateral is strengthened by intra­molecular C13—H13B···Cl3 and inter­molecular C10—H10B···Cl1ⁱⁱⁱ [symmetry code: (iii) x-1/2, -y+1.5, z-1/2] hydrogen bonds, which assemble the BnEt₃N⁺ cations and the anionic chains into a three-dimensional network, together with other noncovalent inter­actions and static attracting forces, like Coulombic and van der Waals forces (Fig. 4).

Our inter­est in one-dimensional ABX₃-type chloridocadmates is based mainly on their potential solid–solid phase transition. The title compound crystallizes in a centrosymmetric space group at room temperature. It would transform to a ferroelectric phase if it had a crystallographic phase transition to a polar space group at low temperature (Hang et al., 2011). When we measured the variation of its dielectric properties with temperature, however, we were unable to detect any dielectric anomaly within the temperature range 93–293 K, implying that the compound may not have ferroelectric properties (Ye et al., 2009; Fu et al., 2007).

Related literature

For related literature, see: Addison et al. (1984); Chapuis & Zuñiga (1988); Chesnut et al. (1999); Doudin & Chapuis (1992); Fu et al. (2007); Gesi & Perret (1988); Hang et al. (2011); Hu et al. (2003); Huang et al. (1998); Jian et al. (2006); Jin & Wang (2010); Laskar et al. (2002); Matsunaga et al. (2005); Morosin (1972); Puget et al. (1991); Rogers & Bond (1996); Waśkowska et al. (1990); Willet et al. (2006); Wu & Jin (2012, 2013); Xia et al. (2005); Xiao (2010); Ye et al. (2009); Zhang et al. (2008).

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms have been omitted for clarity.

Fig. 2. A segment of the neutral chain in (I) along the a axis, showing the coordination environment of the Cd^II cations. [Symmetry code: (i) -x+1, -y+2, -z+1; (ii) -x, -y+2, -z+1.]

Fig. 3. A view of two-dimensional network of (I). The chloridocadmate(II) chains, formed by corner-shared linear [CdCl₃]^- anions running along the a axis, are separated by BnEt₃N⁺ cations. Dashed lines indicate hydrogen bonds and H atoms have been omitted for clarity.

Fig. 4. A view of the packing of (I) along the a axis. Dashed lines indicate hydrogen bonds and H atoms have been omitted for clarity.

catena-Poly[benzyltriethylammonium [[chloridocadmate(II)]-di-µ-chlorido]]

Crystal data

(C13H22N)[CdCl3]	F(000) = 824
Mr = 411.07	Dx = 1.664 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.2555 (15) Å	Cell parameters from 16586 reflections
b = 13.931 (3) Å	θ = 3.2–27.5°
c = 16.326 (3) Å	µ = 1.80 mm^−1
β = 96.07 (3)°	T = 293 K
V = 1641.0 (6) Å^3	Block, colourless
Z = 4	0.2 × 0.2 × 0.2 mm

Data collection

Rigaku Mercury2 diffractometer	3760 independent reflections
Radiation source: fine-focus sealed tube	3525 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
CCD_Profile_fitting scans	θmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −9→9
Tmin = 0.697, Tmax = 0.704	k = −18→18
16586 measured reflections	l = −21→21

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.030	H-atom parameters constrained
wR(F^2) = 0.076	w = 1/[σ^2(Fo^2) + (0.0298P)^2 + 0.6883P] where P = (Fo^2 + 2Fc^2)/3
S = 1.26	(Δ/σ)max = 0.002
3760 reflections	Δρmax = 0.43 e Å^−3
167 parameters	Δρmin = −1.28 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.168 (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	0.25032 (2)	0.949501 (13)	0.508673 (12)	0.03036 (11)
Cl2	0.47646 (9)	1.05236 (5)	0.59749 (4)	0.03700 (16)
Cl3	0.02711 (8)	1.01891 (5)	0.39683 (4)	0.03594 (16)
Cl1	0.24142 (9)	0.77618 (5)	0.53023 (4)	0.03782 (17)
C7	−0.0843 (3)	0.64407 (17)	0.25518 (15)	0.0306 (5)
H7A	−0.1773	0.6755	0.2173	0.037*
H7B	−0.0579	0.5822	0.2317	0.037*
C12	0.0533 (4)	0.80734 (18)	0.28662 (16)	0.0346 (5)
H12A	0.0080	0.8063	0.3404	0.042*
H12B	0.1690	0.8428	0.2918	0.042*
C5	−0.3325 (4)	0.6809 (3)	0.44712 (19)	0.0509 (8)
H5	−0.3942	0.7295	0.4723	0.061*
C10	0.1644 (4)	0.7020 (2)	0.17739 (15)	0.0360 (6)
H10A	0.1849	0.6356	0.1628	0.043*
H10B	0.0696	0.7278	0.1370	0.043*
C2	−0.1464 (4)	0.5383 (2)	0.3737 (2)	0.0424 (6)
H2	−0.0837	0.4895	0.3494	0.051*
C1	−0.1641 (3)	0.62764 (18)	0.33602 (15)	0.0317 (5)
C11	0.3418 (5)	0.7574 (2)	0.1722 (2)	0.0525 (8)
H11A	0.3230	0.8234	0.1862	0.079*
H11B	0.3766	0.7536	0.1172	0.079*
H11C	0.4384	0.7306	0.2100	0.079*
C13	−0.0846 (5)	0.86045 (19)	0.2281 (2)	0.0471 (7)
H13A	−0.0379	0.8657	0.1754	0.071*
H13B	−0.1040	0.9235	0.2493	0.071*
H13C	−0.1999	0.8261	0.2221	0.071*
C8	0.2345 (3)	0.6651 (2)	0.32796 (15)	0.0339 (5)
H8A	0.3382	0.7093	0.3354	0.041*
H8B	0.1793	0.6625	0.3795	0.041*
C3	−0.2210 (4)	0.5209 (3)	0.4472 (2)	0.0552 (8)
H3	−0.2089	0.4607	0.4717	0.066*
C9	0.3074 (4)	0.5668 (2)	0.31023 (19)	0.0449 (7)
H9A	0.2053	0.5234	0.2981	0.067*
H9B	0.3851	0.5440	0.3575	0.067*
H9C	0.3781	0.5702	0.2638	0.067*
C4	−0.3128 (5)	0.5931 (3)	0.4836 (2)	0.0577 (9)
H4	−0.3614	0.5819	0.5331	0.069*
C6	−0.2622 (4)	0.6987 (2)	0.37330 (17)	0.0385 (6)
H6	−0.2802	0.7584	0.3482	0.046*
N1	0.0925 (3)	0.70459 (14)	0.26193 (12)	0.0273 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.02568 (14)	0.03392 (15)	0.03131 (14)	0.00147 (6)	0.00226 (8)	0.00155 (6)
Cl2	0.0300 (3)	0.0457 (4)	0.0362 (3)	−0.0052 (2)	0.0078 (3)	−0.0058 (2)
Cl3	0.0304 (3)	0.0527 (4)	0.0256 (3)	0.0089 (3)	0.0069 (2)	0.0053 (3)
Cl1	0.0416 (4)	0.0338 (3)	0.0386 (3)	0.0028 (2)	0.0066 (3)	−0.0001 (2)
C7	0.0269 (12)	0.0341 (12)	0.0300 (12)	−0.0018 (9)	−0.0007 (9)	−0.0067 (9)
C12	0.0328 (13)	0.0326 (12)	0.0377 (13)	−0.0010 (10)	−0.0001 (10)	−0.0076 (10)
C5	0.0389 (15)	0.072 (2)	0.0428 (16)	−0.0011 (15)	0.0111 (13)	−0.0099 (15)
C10	0.0369 (13)	0.0466 (15)	0.0249 (12)	0.0054 (11)	0.0058 (10)	−0.0004 (10)
C2	0.0305 (14)	0.0420 (15)	0.0540 (18)	−0.0038 (11)	0.0007 (12)	0.0042 (12)
C1	0.0233 (11)	0.0392 (13)	0.0319 (12)	−0.0033 (10)	−0.0007 (9)	−0.0031 (10)
C11	0.0482 (17)	0.064 (2)	0.0477 (17)	−0.0026 (15)	0.0161 (14)	0.0059 (15)
C13	0.0551 (18)	0.0348 (14)	0.0495 (17)	0.0059 (12)	−0.0032 (14)	0.0017 (12)
C8	0.0251 (11)	0.0479 (14)	0.0271 (11)	0.0044 (10)	−0.0040 (9)	−0.0001 (10)
C3	0.0421 (16)	0.064 (2)	0.057 (2)	−0.0149 (15)	−0.0076 (14)	0.0260 (17)
C9	0.0401 (15)	0.0532 (17)	0.0407 (15)	0.0156 (13)	0.0013 (12)	0.0024 (12)
C4	0.0450 (17)	0.092 (3)	0.0367 (16)	−0.0109 (18)	0.0058 (13)	0.0080 (17)
C6	0.0291 (13)	0.0479 (15)	0.0385 (14)	0.0026 (11)	0.0045 (11)	−0.0027 (12)
N1	0.0246 (9)	0.0330 (10)	0.0241 (9)	0.0015 (8)	0.0007 (7)	−0.0039 (8)

Geometric parameters (Å, º)

Cd1—Cl1	2.4419 (8)	C2—C1	1.388 (4)
Cd1—Cl3	2.5034 (9)	C2—C3	1.389 (4)
Cd1—Cl2	2.5190 (9)	C2—H2	0.9300
Cd1—Cl3^i	2.6984 (9)	C1—C6	1.396 (4)
Cd1—Cl2^ii	2.7678 (10)	C11—H11A	0.9600
Cl2—Cd1^ii	2.7678 (10)	C11—H11B	0.9600
Cl3—Cd1^i	2.6984 (9)	C11—H11C	0.9600
C7—C1	1.514 (3)	C13—H13A	0.9600
C7—N1	1.529 (3)	C13—H13B	0.9600
C7—H7A	0.9700	C13—H13C	0.9600
C7—H7B	0.9700	C8—C9	1.507 (4)
C12—C13	1.503 (4)	C8—N1	1.514 (3)
C12—N1	1.522 (3)	C8—H8A	0.9700
C12—H12A	0.9700	C8—H8B	0.9700
C12—H12B	0.9700	C3—C4	1.375 (5)
C5—C4	1.362 (5)	C3—H3	0.9300
C5—C6	1.380 (4)	C9—H9A	0.9600
C5—H5	0.9300	C9—H9B	0.9600
C10—C11	1.511 (4)	C9—H9C	0.9600
C10—N1	1.527 (3)	C4—H4	0.9300
C10—H10A	0.9700	C6—H6	0.9300
C10—H10B	0.9700
Cl1—Cd1—Cl3	117.53 (3)	C10—C11—H11A	109.5
Cl1—Cd1—Cl2	120.33 (3)	C10—C11—H11B	109.5
Cl3—Cd1—Cl2	122.14 (3)	H11A—C11—H11B	109.5
Cl1—Cd1—Cl3^i	92.65 (2)	C10—C11—H11C	109.5
Cl3—Cd1—Cl3^i	83.68 (3)	H11A—C11—H11C	109.5
Cl2—Cd1—Cl3^i	93.32 (2)	H11B—C11—H11C	109.5
Cl1—Cd1—Cl2^ii	96.46 (2)	C12—C13—H13A	109.5
Cl3—Cd1—Cl2^ii	89.87 (3)	C12—C13—H13B	109.5
Cl2—Cd1—Cl2^ii	84.25 (3)	H13A—C13—H13B	109.5
Cl3^i—Cd1—Cl2^ii	170.55 (2)	C12—C13—H13C	109.5
Cd1—Cl2—Cd1^ii	95.75 (3)	H13A—C13—H13C	109.5
Cd1—Cl3—Cd1^i	96.32 (3)	H13B—C13—H13C	109.5
C1—C7—N1	114.57 (19)	C9—C8—N1	114.8 (2)
C1—C7—H7A	108.6	C9—C8—H8A	108.6
N1—C7—H7A	108.6	N1—C8—H8A	108.6
C1—C7—H7B	108.6	C9—C8—H8B	108.6
N1—C7—H7B	108.6	N1—C8—H8B	108.6
H7A—C7—H7B	107.6	H8A—C8—H8B	107.5
C13—C12—N1	115.1 (2)	C4—C3—C2	119.7 (3)
C13—C12—H12A	108.5	C4—C3—H3	120.1
N1—C12—H12A	108.5	C2—C3—H3	120.1
C13—C12—H12B	108.5	C8—C9—H9A	109.5
N1—C12—H12B	108.5	C8—C9—H9B	109.5
H12A—C12—H12B	107.5	H9A—C9—H9B	109.5
C4—C5—C6	120.7 (3)	C8—C9—H9C	109.5
C4—C5—H5	119.6	H9A—C9—H9C	109.5
C6—C5—H5	119.6	H9B—C9—H9C	109.5
C11—C10—N1	114.4 (2)	C5—C4—C3	120.2 (3)
C11—C10—H10A	108.7	C5—C4—H4	119.9
N1—C10—H10A	108.7	C3—C4—H4	119.9
C11—C10—H10B	108.7	C5—C6—C1	120.4 (3)
N1—C10—H10B	108.7	C5—C6—H6	119.8
H10A—C10—H10B	107.6	C1—C6—H6	119.8
C1—C2—C3	120.8 (3)	C8—N1—C12	106.58 (18)
C1—C2—H2	119.6	C8—N1—C10	111.29 (18)
C3—C2—H2	119.6	C12—N1—C10	110.66 (19)
C2—C1—C6	118.1 (3)	C8—N1—C7	110.72 (19)
C2—C1—C7	119.7 (2)	C12—N1—C7	111.02 (18)
C6—C1—C7	122.2 (2)	C10—N1—C7	106.63 (18)
Cl1—Cd1—Cl2—Cd1^ii	94.14 (3)	C4—C5—C6—C1	−2.1 (4)
Cl3—Cd1—Cl2—Cd1^ii	−86.22 (3)	C2—C1—C6—C5	2.5 (4)
Cl3^i—Cd1—Cl2—Cd1^ii	−170.84 (2)	C7—C1—C6—C5	−179.9 (3)
Cl2^ii—Cd1—Cl2—Cd1^ii	0.0	C9—C8—N1—C12	−173.9 (2)
Cl1—Cd1—Cl3—Cd1^i	89.69 (3)	C9—C8—N1—C10	−53.1 (3)
Cl2—Cd1—Cl3—Cd1^i	−89.96 (3)	C9—C8—N1—C7	65.3 (3)
Cl3^i—Cd1—Cl3—Cd1^i	0.0	C13—C12—N1—C8	179.4 (2)
Cl2^ii—Cd1—Cl3—Cd1^i	−173.08 (2)	C13—C12—N1—C10	58.3 (3)
C3—C2—C1—C6	−1.3 (4)	C13—C12—N1—C7	−59.9 (3)
C3—C2—C1—C7	−179.0 (2)	C11—C10—N1—C8	−58.4 (3)
N1—C7—C1—C2	−106.0 (3)	C11—C10—N1—C12	59.9 (3)
N1—C7—C1—C6	76.3 (3)	C11—C10—N1—C7	−179.3 (2)
C1—C2—C3—C4	−0.4 (5)	C1—C7—N1—C8	51.6 (3)
C6—C5—C4—C3	0.4 (5)	C1—C7—N1—C12	−66.6 (3)
C2—C3—C4—C5	0.8 (5)	C1—C7—N1—C10	172.8 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13B···Cl3	0.96	2.83	3.557 (3)	134
C10—H10B···Cl1^iii	0.97	2.80	3.705 (3)	156

Symmetry code: (iii) x−1/2, −y+3/2, z−1/2.