Poly[([mu]₃-benzene-1,4-dicarboxyl­ato)di-[mu]-chlorido-(triethanol­amine)­dicadmium(II)]: a cadmium-halide coordination polymer with a hydrogen-bonded three-dimensional framework

The structure of the title compound, [Cd₂(C₈H₄O₄)Cl₂(C₆H₁₅NO₃)]_n, consists of one-dimensional chains in which each centrosymmetric tetra­nuclear Cd₄Cl₄O₂ cluster is terminated by two chelating triethanol­amine (teaH₃) ligands but linked to two adjacent clusters through four bridging benzene-1,4-dicarboxyl­ate (bdc) ligands. The tetra­nuclear Cd₄Cl₄O₂ clusters are held together via bridging Cl and O atoms. Three directional hydrogen bonds from the multi-podal hy­droxy groups of the teaH₃ ligand stabilize and extend the one-dimensional chains into a three-dimensional framework. All three hy­droxy groups of the teaH₃ ligand form hydrogen bonds, illustrating the fact that the teaH₃ ligand can serve as an excellent hydrogen-bond donor.

S1. Comment

Recent advances in supramolecular assembly of coordination polymers have led to many organic–inorganic hybrid materials with interesting structures and desirable functions (Desiraju, 2007). It is now well established that the combination of coordination bonds and hydrogen bonds presents an ideal synthetic paradigm for the crystal engineering of crystalline materials (MacDonald et al., 2000). Triethanolamine (teaH₃) is one member of the alkoxide family containing both amine and alcohol groups, and can serve as a versatile ligand that readily forms coordination complexes with almost all metal ions (Sen & Dotson, 1970). The multi-podal capabilities of the three ethanolic arms suggest that the teaH₃ molecule is indeed an excellent candidate for hydrogen-bond donation, and endow the resultant complexes with great potential in supramolecular chemistry (Chen et al., 2009). Alternatively, the hydroxy H atoms of the teaH₃ molecule may be deprotonated to give the triethanolaminate anion, which can act as both a bridging and a chelating ligand for synthesizing polynuclear species (Liu et al., 2008). The teaH₃ molecule can also behave as a tri- (N,O,O') or tetradentate (N,O,O',O'') neutral ligand to chelate one metal ion, especially for metal ions with large ionic radii. It is known that the ability of the Cd^II ion to extend its coordination number to 7 enables the synthesis of seven-coordinated Cd^II complexes of teaH₃ (Andac et al., 2001). Among Cd-containing complexes, polynuclear cadmium halides have been found to exhibit interesting photoluminescent properties (Dai et al., 2002) and to form a wide range of coordination complexes with variations promoted not only by the ligand characteristics, but also by the variable coordination number of the Cd^II centres. However, the successful incorporation of two types of ligand into such cadmium halides is rare (Liu et al., 2010, 2007). The analogous complexes based on the collaborative use of linear terephthalic acid (bdcH₂) and multi-podal triethanolamine(teaH₃) have not hitherto received any attention. Here, we have chosen the bdcH₂ molecule as a bridging ligand and teaH₃ as a terminal ligand to explore the crystal structure of the novel title coordination polymer, [Cd₂(bdc)Cl₂(teaH₃)]_n, (I), with an unusual hydrogen-bonded three-dimensional framework.

Single-crystal X-ray diffraction reveals that two independent Cd^II cations and Cl^- anions, one teaH₃ molecule and one bdc dianion are present in the asymmetric unit of (I). As shown in Figs. 1 and 2, (I) consists of a one-dimensional chain in which each tetranuclear Cd₄Cl₄O₂ cluster is terminated by two chelating teaH₃ molecules but linked to two adjacent clusters through four bridging bdc dianions. The tetranuclear Cd₄Cl₄O₂ entity has an inversion centre and is held together via µ₂-bridging Cl and O atoms. The Cd^II cations in the tetranuclear Cd₄Cl₄O₂ cluster can are of two types. Each Cd1 centre [and its symmetry-related Cd1ⁱⁱ centre; symmetry code: (ii) -x + 1/2, -y + 1/2, -z] is seven-coordinate with a distorted monocapped trigonal prismatic coordination geometry, surrounded by three O atoms and one N atom from one teaH₃ molecule, two O atoms from one carboxylate group and one µ-Cl^- ion, while each Cd2 centre (and its symmetry-related equivalent) is bonded to three O atoms from two bdc dianions and three µ₂-Cl^- anions, displaying a distorted octahedral configuration. In the Cd1 coordination polyhedron, the three O atoms of the teaH₃ ligand and one Cl^- anion form the equatorial plane (O5—O6—O7—Cl1) of the Cd1 centre, while two O atoms from one carboxylate group are located in pseudo-axial positions and atom N1 occupies the axial position. For the Cd2 centre, atoms Cl2, Cl2ⁱⁱ and O2 are meridional, as are three other atoms [Cl1, O3ⁱ and O4ⁱ; symmetry code: (i) -x + 1, -y, -z].

The Cd—O distances are comparable with those observed for [Cd(bdc)(bpdo)(H₂O)]_n (bpdo is 4,4'-bipyridine N,N'-dioxide; Xu & Xie, 2010). It should be noted that the Cd—O bond distances [2.4045 (16) and 2.5792 (16) Å] involved in the µ₂-O bridging interactions are somewhat longer than the other Cd—O bonds. The Cd—Cl bond lengths range from 2.5343 (8) to 2.6726 (13) Å and are in the normal range for cadmium halide complexes (Zhou et al., 2004). The bond angles around the two Cd^II centres have a very large range [53.49 (5)–169.31 (4)° for Cd1 and 55.79 (6)—165.31 (4)° for Cd2], indicating their significantly distorted coordination geometry. The closest Cd···Cd contact of 3.815 Å is much longer than in the metal (2.98 Å; Reference?).

The overall binding mode of the bdc ligand in the title complex can be assigned as unsymmetrical µ₃-η²η¹ connections to three metal centres. One carboxylate end is chelated to one metal centre in a bidentate chelating mode but the other end is coordinated to two Cd^II cations in a chelating-bridging manner. The two inversion-related bdc dianions are anti-parallel and link adjacent tetranuclear Cd₄Cl₄O₂ clusters into a one-dimensional chain. It is noteworthy that the interplanar distance (3.474 Å) between parallel phenyl rings suggests the presence of π–π interaction between each pair of bdc dianions. This particular arrangement necessitates a bent conformation of the bdc linkers (mean deviation from the C1–C8 plane = 0.0409 Å) and a significant rotation of the two COO^- groups (dihedral angles between the COO^- and benzene planes = 27.9 and 15.1°).

The most interesting structural feature of (I) is the hydrogen-bonding performance of the three ethanolic arms of teaH₃ in stabilizing the open three-dimensional framework. Although the teaH₃ molecules serve as a tetradentate (N,O,O',O'') neutral ligand in the endo conformation, all hydroxy groups of the teaH₃ ligand are involved in the formation of classical hydrogen bonds. One hydroxy group within the tetranuclear cluster and the Cl^- anions form strong intrachain hydrogen bonds [O5···Cl2ⁱⁱ = 3.096 (2) Å] which further consolidate the tetranuclear Cd₄Cl₄O₂ cluster (Fig. 2). The second hydrogen bond between one of the outer hydroxy groups and the carboxylate O atoms [O6···O4ⁱⁱⁱ = 2.666 (2) Å; symmetry code: (iii) -x + 1, -y + 1, -z] extends the one-dimensional chains into two-dimensional layers (Fig. 3). Finally, the third hydroxy group is engaged in interlayer hydrogen bonding with the carboxylate O atoms [O7···O1^iv = 2.667 (2) Å; symmetry code: (iv) -x + 1, y, -z + 1/2] to link each such layer into an open three-dimensional framework in a crossed manner (Fig. 4). It is interesting that, viewed down the crystallographic a axis, the alternate packing of one-dimensional chains displays beautiful sinusoidal ruffles with a period of 38.4 Å (= 2c) (Fig. 5).

The crystal structure of (I) thus clearly illustrates the important role of the teaH₃ ligand in directing supramolecular assembly via directional hydrogen bonds from its multi-podal hydroxy groups.

Related literature

For related literature, see: Andac et al. (2001); Chen et al. (2009); Dai et al. (2002); Desiraju (2007); Liu et al. (2007, 2008, 2010); MacDonald et al. (2000); Sen & Dotson (1970); Xu & Xie (2010); Zhou et al. (2004).

S2. Experimental

A mixture of CdCl₂.2.5H₂O (0.0297 g, 0.13 mmol) and bdcH₂ (0.0221 g, 0.13 mmol) in methanol (10 ml) was stirred for 10 min, and then 4 drops of teaH₃ was added to the mixture with further stirring for 20 min. The resulting solution was transferred to a 17 ml Teflon-lined stainless steel container and heated at 393 K for 24 h. After cooling to room temperature, yellow block-shaped crystals of (I) were collected in 86.5% yield, based on the initial quantity of CdCl₂.2.5H₂O.

S3. Refinement

All C-bound H atoms were refined using a riding model, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) for aromatic H atoms, and with C—H = 0.97 Å and U_iso(H) = 1.2U_eq(C) for CH₂ groups. The hydroxy H atoms were located in a difference Fourier map and their positions were refined under the application of an O—H bond-length restraint of 0.90 (1) Å, with U_iso(H) = 1.5U_eq(O).

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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 environment of the Cd^II ions in (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) -x + 1, -y, -z; (ii) -x + 1/2, -y + 1/2, -z.]
	Fig. 2. A view of the one-dimensional chain of (I), showing the strong intrachain O—H···Cl interactions (dashed lines) consolidating the tetranuclear Cd4Cl4O2 clusters. [Symmetry code: (ii) -x + 1/2, -y + 1/2, -z.]
	Fig. 3. The two-dimensional layer of (I) formed by strong interchain O—H···O interactions (dashed lines). [Symmetry code: (iii) -x + 1, -y + 1, -z.]
	Fig. 4. A packing diagram for (I), showing the unusual three-dimensional framework formed via strong O—H···O interactions (dashed lines) between crossed layers. (In the electronic version of the paper, three colours are used to show the different hydrogen bonds: blue for intrachain, red for interchain and yellow for interlayer.) [Symmetry codes: (ii) -x + 1/2, -y + 1/2, -z; (iv) -x + 1, y, -z + 1/2; (v) x, -y + 1, z + 1/2.]
	Fig. 5. A packing diagram for (I) with metallic polyhedra

Poly[(µ₃-benzene-1,4-dicarboxylato)di-µ-chlorido- (triethanolamine)dicadmium(II)]

Crystal data

[Cd2(C8H4O4)Cl2(C6H15NO3)]	F(000) = 2368
Mr = 609.00	Dx = 2.071 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -c 2yc	Cell parameters from 14198 reflections
a = 23.251 (5) Å	θ = 1.8–28.5°
b = 8.907 (5) Å	µ = 2.49 mm^−1
c = 19.233 (5) Å	T = 293 K
β = 101.221 (5)°	Block, yellow
V = 3907 (3) Å^3	0.40 × 0.40 × 0.20 mm
Z = 8

Data collection

Bruker APEXII CCD area-detector diffractometer	4821 independent reflections
Radiation source: fine-focus sealed tube	4261 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
ω scans	θmax = 28.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −27→30
Tmin = 0.436, Tmax = 0.636	k = −11→11
13547 measured reflections	l = −25→25

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)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.047	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0231P)^2 + 1.6009P] where P = (Fo^2 + 2Fc^2)/3
4821 reflections	(Δ/σ)max = 0.001
244 parameters	Δρmax = 0.31 e Å^−3
3 restraints	Δρmin = −0.62 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	0.45636 (9)	0.4129 (2)	0.09660 (11)	0.0287 (4)
C2	0.49931 (8)	0.3117 (2)	0.07158 (11)	0.0269 (4)
C3	0.49185 (9)	0.2775 (3)	−0.00011 (11)	0.0330 (5)
H3	0.4615	0.3218	−0.0321	0.040*
C4	0.52900 (9)	0.1788 (3)	−0.02399 (11)	0.0344 (5)
H4	0.5242	0.1584	−0.0722	0.041*
C5	0.57364 (9)	0.1094 (2)	0.02336 (11)	0.0294 (4)
C6	0.58157 (10)	0.1443 (3)	0.09514 (11)	0.0363 (5)
H6	0.6117	0.0987	0.1271	0.044*
C7	0.54511 (10)	0.2459 (3)	0.11914 (12)	0.0360 (5)
H7	0.5511	0.2703	0.1670	0.043*
C8	0.61093 (9)	−0.0088 (3)	−0.00113 (12)	0.0317 (5)
C9	0.25792 (13)	0.7131 (3)	0.10179 (14)	0.0562 (8)
H9A	0.2222	0.6727	0.0733	0.067*
H9B	0.2576	0.8210	0.0950	0.067*
C10	0.25932 (10)	0.6789 (3)	0.17824 (13)	0.0459 (6)
H10A	0.2301	0.7400	0.1948	0.055*
H10B	0.2488	0.5744	0.1827	0.055*
C11	0.39632 (12)	0.9000 (3)	0.22971 (13)	0.0456 (6)
H11A	0.4018	1.0074	0.2259	0.055*
H11B	0.4199	0.8666	0.2743	0.055*
C12	0.33243 (12)	0.8679 (3)	0.22959 (14)	0.0451 (6)
H12A	0.3228	0.9071	0.2730	0.054*
H12B	0.3085	0.9207	0.1902	0.054*
C13	0.38053 (11)	0.6198 (3)	0.33519 (12)	0.0468 (6)
H13A	0.3944	0.7167	0.3546	0.056*
H13B	0.3810	0.5507	0.3743	0.056*
C14	0.31975 (10)	0.6344 (3)	0.29337 (12)	0.0451 (6)
H14A	0.3023	0.5353	0.2859	0.054*
H14B	0.2965	0.6925	0.3205	0.054*
N1	0.31739 (8)	0.7071 (2)	0.22393 (9)	0.0313 (4)
O1	0.47267 (6)	0.48765 (19)	0.15310 (8)	0.0379 (4)
O2	0.40496 (6)	0.42171 (17)	0.06169 (8)	0.0324 (3)
O3	0.64129 (7)	−0.09341 (19)	0.04325 (9)	0.0436 (4)
O4	0.60972 (7)	−0.02424 (19)	−0.06708 (8)	0.0395 (4)
O5	0.30721 (8)	0.6506 (2)	0.07873 (8)	0.0456 (4)
O6	0.41577 (8)	0.82625 (19)	0.17254 (9)	0.0406 (4)
O7	0.41747 (7)	0.5658 (2)	0.29025 (8)	0.0434 (4)
Cl1	0.33344 (3)	0.30705 (6)	0.17663 (3)	0.03921 (13)
Cl2	0.22968 (2)	0.08518 (6)	0.03986 (3)	0.03193 (11)
Cd1	0.384088 (6)	0.574018 (17)	0.168115 (7)	0.02777 (5)
Cd2	0.329506 (6)	0.233430 (17)	0.048503 (8)	0.02788 (5)
HO1	0.2938 (11)	0.584 (2)	0.0450 (10)	0.042*
HO2	0.4077 (11)	0.891 (2)	0.1369 (10)	0.042*
HO3	0.4533 (6)	0.537 (3)	0.3112 (12)	0.042*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0236 (9)	0.0291 (11)	0.0343 (10)	0.0017 (9)	0.0081 (8)	−0.0018 (9)
C2	0.0216 (9)	0.0274 (10)	0.0318 (10)	0.0037 (8)	0.0055 (8)	−0.0043 (9)
C3	0.0267 (10)	0.0403 (13)	0.0312 (10)	0.0083 (10)	0.0033 (8)	−0.0003 (10)
C4	0.0337 (11)	0.0420 (13)	0.0281 (10)	0.0060 (10)	0.0072 (8)	−0.0057 (10)
C5	0.0268 (10)	0.0274 (10)	0.0355 (10)	0.0039 (9)	0.0099 (8)	−0.0046 (9)
C6	0.0341 (11)	0.0387 (13)	0.0337 (11)	0.0148 (10)	0.0006 (9)	−0.0014 (10)
C7	0.0340 (11)	0.0439 (13)	0.0286 (10)	0.0105 (10)	0.0022 (8)	−0.0083 (10)
C8	0.0288 (10)	0.0282 (11)	0.0398 (11)	0.0029 (9)	0.0107 (9)	−0.0055 (10)
C9	0.0562 (16)	0.0578 (17)	0.0465 (14)	0.0282 (15)	−0.0102 (12)	−0.0070 (13)
C10	0.0265 (11)	0.0573 (17)	0.0531 (14)	0.0097 (12)	0.0056 (10)	−0.0026 (13)
C11	0.0612 (16)	0.0334 (13)	0.0439 (13)	−0.0064 (12)	0.0139 (12)	−0.0088 (11)
C12	0.0533 (15)	0.0359 (13)	0.0489 (14)	0.0137 (12)	0.0167 (12)	−0.0091 (11)
C13	0.0517 (14)	0.0645 (17)	0.0247 (10)	0.0131 (14)	0.0082 (10)	0.0039 (11)
C14	0.0409 (13)	0.0638 (17)	0.0352 (11)	0.0103 (13)	0.0187 (10)	0.0098 (12)
N1	0.0293 (9)	0.0368 (10)	0.0288 (8)	0.0093 (8)	0.0082 (7)	0.0005 (8)
O1	0.0260 (7)	0.0455 (10)	0.0419 (8)	0.0050 (7)	0.0062 (6)	−0.0191 (8)
O2	0.0209 (7)	0.0360 (9)	0.0397 (8)	0.0055 (6)	0.0046 (6)	−0.0034 (7)
O3	0.0460 (9)	0.0427 (10)	0.0427 (9)	0.0215 (8)	0.0100 (7)	−0.0013 (8)
O4	0.0452 (9)	0.0371 (9)	0.0386 (8)	0.0155 (8)	0.0143 (7)	−0.0023 (7)
O5	0.0589 (11)	0.0416 (10)	0.0317 (8)	0.0106 (9)	−0.0026 (8)	−0.0072 (7)
O6	0.0503 (10)	0.0324 (9)	0.0431 (9)	0.0014 (8)	0.0192 (8)	0.0027 (7)
O7	0.0328 (8)	0.0629 (12)	0.0319 (8)	0.0153 (8)	−0.0003 (6)	0.0011 (8)
Cl1	0.0552 (3)	0.0327 (3)	0.0318 (2)	−0.0063 (3)	0.0136 (2)	−0.0047 (2)
Cl2	0.0323 (2)	0.0292 (3)	0.0321 (2)	0.0000 (2)	0.00093 (19)	0.0031 (2)
Cd1	0.02718 (8)	0.02890 (9)	0.02827 (8)	0.00649 (6)	0.00795 (6)	−0.00384 (6)
Cd2	0.02610 (8)	0.02670 (8)	0.02976 (8)	0.00607 (6)	0.00277 (6)	−0.00477 (6)

Geometric parameters (Å, º)

C1—O2	1.254 (2)	C12—H12A	0.9700
C1—O1	1.268 (2)	C12—H12B	0.9700
C1—C2	1.493 (3)	C13—O7	1.416 (3)
C2—C3	1.390 (3)	C13—C14	1.490 (3)
C2—C7	1.391 (3)	C13—H13A	0.9700
C3—C4	1.372 (3)	C13—H13B	0.9700
C3—H3	0.9300	C14—N1	1.476 (3)
C4—C5	1.386 (3)	C14—H14A	0.9700
C4—H4	0.9300	C14—H14B	0.9700
C5—C6	1.392 (3)	N1—Cd1	2.3686 (17)
C5—C8	1.497 (3)	O1—Cd1	2.2691 (15)
C6—C7	1.379 (3)	O2—Cd2	2.4045 (16)
C6—H6	0.9300	O2—Cd1	2.5792 (16)
C7—H7	0.9300	O3—Cd2^i	2.3657 (17)
C8—O3	1.249 (3)	O4—Cd2^i	2.3237 (18)
C8—O4	1.271 (3)	O5—Cd1	2.3280 (17)
C9—O5	1.421 (3)	O5—HO1	0.890 (10)
C9—C10	1.496 (4)	O6—Cd1	2.361 (2)
C9—H9A	0.9700	O6—HO2	0.887 (10)
C9—H9B	0.9700	O7—Cd1	2.3273 (16)
C10—N1	1.482 (3)	O7—HO3	0.889 (10)
C10—H10A	0.9700	Cl1—Cd2	2.5343 (8)
C10—H10B	0.9700	Cl1—Cd1	2.6726 (13)
C11—O6	1.428 (3)	Cl2—Cd2^ii	2.5460 (8)
C11—C12	1.512 (4)	Cl2—Cd2	2.6473 (8)
C11—H11A	0.9700	Cd2—O4^i	2.3236 (18)
C11—H11B	0.9700	Cd2—O3^i	2.3657 (17)
C12—N1	1.473 (3)	Cd2—Cl2^ii	2.5460 (8)
O2—C1—O1	121.39 (18)	C12—N1—C10	112.6 (2)
O2—C1—C2	119.52 (18)	C14—N1—C10	109.35 (19)
O1—C1—C2	119.09 (18)	C12—N1—Cd1	110.67 (13)
C3—C2—C7	119.46 (19)	C14—N1—Cd1	106.16 (13)
C3—C2—C1	119.34 (18)	C10—N1—Cd1	104.35 (13)
C7—C2—C1	121.14 (18)	C1—O1—Cd1	99.18 (12)
C4—C3—C2	120.5 (2)	C1—O2—Cd2	127.77 (14)
C4—C3—H3	119.8	C1—O2—Cd1	85.12 (12)
C2—C3—H3	119.8	Cd2—O2—Cd1	101.80 (6)
C3—C4—C5	120.35 (19)	C8—O3—Cd2^i	90.83 (13)
C3—C4—H4	119.8	C8—O4—Cd2^i	92.22 (13)
C5—C4—H4	119.8	C9—O5—Cd1	115.75 (14)
C4—C5—C6	119.34 (19)	C9—O5—HO1	107.4 (17)
C4—C5—C8	120.83 (19)	Cd1—O5—HO1	117.0 (16)
C6—C5—C8	119.73 (19)	C11—O6—Cd1	108.79 (14)
C7—C6—C5	120.5 (2)	C11—O6—HO2	104.1 (17)
C7—C6—H6	119.8	Cd1—O6—HO2	124.9 (17)
C5—C6—H6	119.8	C13—O7—Cd1	118.85 (13)
C6—C7—C2	119.9 (2)	C13—O7—HO3	116.5 (17)
C6—C7—H7	120.1	Cd1—O7—HO3	124.5 (16)
C2—C7—H7	120.1	Cd2—Cl1—Cd1	95.95 (2)
O3—C8—O4	121.09 (19)	Cd2^ii—Cl2—Cd2	94.52 (3)
O3—C8—C5	119.62 (19)	O1—Cd1—O7	89.14 (6)
O4—C8—C5	119.3 (2)	O1—Cd1—O5	126.22 (6)
O3—C8—Cd2^i	61.52 (11)	O7—Cd1—O5	144.29 (6)
O4—C8—Cd2^i	59.63 (11)	O1—Cd1—O6	92.44 (6)
C5—C8—Cd2^i	175.65 (15)	O7—Cd1—O6	87.32 (6)
O5—C9—C10	111.2 (2)	O5—Cd1—O6	86.40 (7)
O5—C9—H9A	109.4	O1—Cd1—N1	156.62 (6)
C10—C9—H9A	109.4	O7—Cd1—N1	71.19 (6)
O5—C9—H9B	109.4	O5—Cd1—N1	73.25 (6)
C10—C9—H9B	109.4	O6—Cd1—N1	74.61 (6)
H9A—C9—H9B	108.0	O1—Cd1—O2	53.49 (5)
N1—C10—C9	113.0 (2)	O7—Cd1—O2	135.00 (6)
N1—C10—H10A	109.0	O5—Cd1—O2	78.70 (6)
C9—C10—H10A	109.0	O6—Cd1—O2	115.06 (5)
N1—C10—H10B	109.0	N1—Cd1—O2	149.75 (5)
C9—C10—H10B	109.0	O1—Cd1—Cl1	97.34 (5)
H10A—C10—H10B	107.8	O7—Cd1—Cl1	88.54 (5)
O6—C11—C12	111.7 (2)	O5—Cd1—Cl1	91.24 (5)
O6—C11—H11A	109.3	O6—Cd1—Cl1	169.31 (4)
C12—C11—H11A	109.3	N1—Cd1—Cl1	94.72 (6)
O6—C11—H11B	109.3	O2—Cd1—Cl1	74.56 (4)
C12—C11—H11B	109.3	O4^i—Cd2—O3^i	55.79 (6)
H11A—C11—H11B	107.9	O4^i—Cd2—O2	97.68 (6)
N1—C12—C11	113.8 (2)	O3^i—Cd2—O2	97.87 (6)
N1—C12—H12A	108.8	O4^i—Cd2—Cl1	98.75 (4)
C11—C12—H12A	108.8	O3^i—Cd2—Cl1	154.21 (4)
N1—C12—H12B	108.8	O2—Cd2—Cl1	80.18 (4)
C11—C12—H12B	108.8	O4^i—Cd2—Cl2^ii	147.67 (4)
H12A—C12—H12B	107.7	O3^i—Cd2—Cl2^ii	91.89 (5)
O7—C13—C14	108.94 (19)	O2—Cd2—Cl2^ii	85.20 (5)
O7—C13—H13A	109.9	Cl1—Cd2—Cl2^ii	113.42 (3)
C14—C13—H13A	109.9	O4^i—Cd2—Cl2	96.27 (5)
O7—C13—H13B	109.9	O3^i—Cd2—Cl2	93.76 (5)
C14—C13—H13B	109.9	O2—Cd2—Cl2	165.31 (4)
H13A—C13—H13B	108.3	Cl1—Cd2—Cl2	93.18 (2)
N1—C14—C13	113.02 (19)	Cl2^ii—Cd2—Cl2	85.48 (3)
N1—C14—H14A	109.0	O4^i—Cd2—C8^i	28.15 (6)
C13—C14—H14A	109.0	O3^i—Cd2—C8^i	27.66 (6)
N1—C14—H14B	109.0	O2—Cd2—C8^i	98.12 (6)
C13—C14—H14B	109.0	Cl1—Cd2—C8^i	126.72 (5)
H14A—C14—H14B	107.8	Cl2^ii—Cd2—C8^i	119.52 (5)
C12—N1—C14	113.16 (19)	Cl2—Cd2—C8^i	96.34 (6)
O2—C1—C2—C3	26.2 (3)	C11—O6—Cd1—O5	98.61 (16)
O1—C1—C2—C3	−154.2 (2)	C11—O6—Cd1—N1	25.00 (15)
O2—C1—C2—C7	−151.0 (2)	C11—O6—Cd1—O2	174.36 (14)
O1—C1—C2—C7	28.6 (3)	C11—O6—Cd1—Cl1	21.1 (3)
C7—C2—C3—C4	0.5 (3)	C12—N1—Cd1—O1	58.6 (2)
C1—C2—C3—C4	−176.7 (2)	C14—N1—Cd1—O1	−64.5 (2)
C2—C3—C4—C5	1.5 (4)	C10—N1—Cd1—O1	179.98 (17)
C3—C4—C5—C6	−2.0 (3)	C12—N1—Cd1—O7	92.73 (15)
C3—C4—C5—C8	174.3 (2)	C14—N1—Cd1—O7	−30.43 (15)
C4—C5—C6—C7	0.6 (4)	C10—N1—Cd1—O7	−145.91 (16)
C8—C5—C6—C7	−175.8 (2)	C12—N1—Cd1—O5	−90.56 (15)
C5—C6—C7—C2	1.4 (4)	C14—N1—Cd1—O5	146.28 (16)
C3—C2—C7—C6	−1.9 (4)	C10—N1—Cd1—O5	30.80 (15)
C1—C2—C7—C6	175.3 (2)	C12—N1—Cd1—O6	0.30 (14)
C4—C5—C8—O3	−163.6 (2)	C14—N1—Cd1—O6	−122.86 (16)
C6—C5—C8—O3	12.7 (3)	C10—N1—Cd1—O6	121.65 (16)
C4—C5—C8—O4	14.2 (3)	C12—N1—Cd1—O2	−113.29 (16)
C6—C5—C8—O4	−169.5 (2)	C14—N1—Cd1—O2	123.54 (16)
C4—C5—C8—Cd2^i	−60 (2)	C10—N1—Cd1—O2	8.1 (2)
C6—C5—C8—Cd2^i	117 (2)	C12—N1—Cd1—Cl1	179.57 (14)
O5—C9—C10—N1	46.8 (3)	C14—N1—Cd1—Cl1	56.41 (15)
O6—C11—C12—N1	50.0 (3)	C10—N1—Cd1—Cl1	−59.07 (15)
O7—C13—C14—N1	−45.5 (3)	C1—O2—Cd1—O1	5.09 (12)
C11—C12—N1—C14	94.1 (2)	Cd2—O2—Cd1—O1	132.69 (9)
C11—C12—N1—C10	−141.3 (2)	C1—O2—Cd1—O7	−34.86 (15)
C11—C12—N1—Cd1	−24.9 (2)	Cd2—O2—Cd1—O7	92.74 (8)
C13—C14—N1—C12	−69.5 (3)	C1—O2—Cd1—O5	158.93 (13)
C13—C14—N1—C10	164.1 (2)	Cd2—O2—Cd1—O5	−73.46 (7)
C13—C14—N1—Cd1	52.0 (3)	C1—O2—Cd1—O6	78.38 (13)
C9—C10—N1—C12	68.1 (3)	Cd2—O2—Cd1—O6	−154.02 (6)
C9—C10—N1—C14	−165.2 (2)	C1—O2—Cd1—N1	−178.89 (13)
C9—C10—N1—Cd1	−51.9 (2)	Cd2—O2—Cd1—N1	−51.29 (13)
O2—C1—O1—Cd1	9.9 (2)	C1—O2—Cd1—Cl1	−106.59 (12)
C2—C1—O1—Cd1	−169.72 (16)	Cd2—O2—Cd1—Cl1	21.01 (4)
O1—C1—O2—Cd2	−109.7 (2)	Cd2—Cl1—Cd1—O1	−68.42 (4)
C2—C1—O2—Cd2	69.8 (2)	Cd2—Cl1—Cd1—O7	−157.37 (4)
O1—C1—O2—Cd1	−8.6 (2)	Cd2—Cl1—Cd1—O5	58.35 (5)
C2—C1—O2—Cd1	170.99 (18)	Cd2—Cl1—Cd1—O6	135.4 (2)
O4—C8—O3—Cd2^i	−2.6 (2)	Cd2—Cl1—Cd1—N1	131.64 (5)
C5—C8—O3—Cd2^i	175.19 (18)	Cd2—Cl1—Cd1—O2	−19.56 (3)
O3—C8—O4—Cd2^i	2.6 (2)	C1—O2—Cd2—O4^i	−26.35 (17)
C5—C8—O4—Cd2^i	−175.15 (17)	Cd1—O2—Cd2—O4^i	−119.33 (5)
C10—C9—O5—Cd1	−15.3 (3)	C1—O2—Cd2—O3^i	−82.70 (17)
C12—C11—O6—Cd1	−47.1 (2)	Cd1—O2—Cd2—O3^i	−175.68 (5)
C14—C13—O7—Cd1	15.2 (3)	C1—O2—Cd2—Cl1	71.26 (16)
C1—O1—Cd1—O7	147.92 (14)	Cd1—O2—Cd2—Cl1	−21.71 (4)
C1—O1—Cd1—O5	−37.48 (16)	C1—O2—Cd2—Cl2^ii	−173.95 (16)
C1—O1—Cd1—O6	−124.81 (14)	Cd1—O2—Cd2—Cl2^ii	93.08 (5)
C1—O1—Cd1—N1	179.98 (15)	C1—O2—Cd2—Cl2	135.26 (16)
C1—O1—Cd1—O2	−5.08 (12)	Cd1—O2—Cd2—Cl2	42.28 (17)
C1—O1—Cd1—Cl1	59.50 (13)	C1—O2—Cd2—C8^i	−54.77 (17)
C13—O7—Cd1—O1	175.87 (19)	Cd1—O2—Cd2—C8^i	−147.75 (6)
C13—O7—Cd1—O5	3.3 (2)	Cd1—Cl1—Cd2—O4^i	116.92 (5)
C13—O7—Cd1—O6	83.38 (19)	Cd1—Cl1—Cd2—O3^i	108.35 (11)
C13—O7—Cd1—N1	8.72 (18)	Cd1—Cl1—Cd2—O2	20.57 (4)
C13—O7—Cd1—O2	−153.06 (17)	Cd1—Cl1—Cd2—Cl2^ii	−59.78 (4)
C13—O7—Cd1—Cl1	−86.76 (19)	Cd1—Cl1—Cd2—Cl2	−146.234 (19)
C9—O5—Cd1—O1	−174.51 (17)	Cd1—Cl1—Cd2—C8^i	113.43 (7)
C9—O5—Cd1—O7	−3.8 (2)	Cd2^ii—Cl2—Cd2—O4^i	−147.57 (4)
C9—O5—Cd1—O6	−84.12 (19)	Cd2^ii—Cl2—Cd2—O3^i	−91.60 (5)
C9—O5—Cd1—N1	−9.11 (18)	Cd2^ii—Cl2—Cd2—O2	50.76 (15)
C9—O5—Cd1—O2	159.43 (19)	Cd2^ii—Cl2—Cd2—Cl1	113.26 (3)
C9—O5—Cd1—Cl1	85.44 (19)	Cd2^ii—Cl2—Cd2—Cl2^ii	0.0
C11—O6—Cd1—O1	−135.24 (15)	Cd2^ii—Cl2—Cd2—C8^i	−119.25 (6)
C11—O6—Cd1—O7	−46.21 (16)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—HO1···Cl2^ii	0.89 (1)	2.21 (1)	3.096 (2)	174 (2)
O6—HO2···O4^iii	0.89 (1)	1.78 (1)	2.666 (2)	178 (3)
O7—HO3···O1^iv	0.89 (1)	1.78 (1)	2.667 (2)	175 (2)

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