A capped trigonal prismatic cadmium complex with tetra- and tridentate ligands: bis­(tri­ethanol­amine)-κ³N,O,O′;κ⁴N,O,O′,O′′-cadmium(II) squarate monohydrate

In the crystal structure of the title compound, [Cd(C₆H₁₅NO₃)₂](C₄O₄)·H₂O, a supramolecular structure is observed. The asymmetric unit consists of one unit of the cationic Cd complex, one water mol­ecule and two half-squarate anions, each sitting on a crystallographic inversion center. The different coordinations of the two triethanolamine (TEA) ligands results in an unusual example of coordination number seven for the Cd^II ion. Both TEA ligands coordinate to the Cd^II ion, forming a distorted monocapped trigonal prismatic geometry with approximate C_2v symmetry. One of the TEA ligands acts as an N,O,O′-tridentate ligand, whereas the other behaves as an N,O,O′,O′′-tetradentate donor. The anions and cations are linked to one another by hydrogen bonds between hydroxy H atoms of the TEA ligands and squarate O atoms. The crystal structure is stabilized by O—H...O hydrogen bonds between the unligated water mol­ecule and a squarate O atom, together with a weak π–ring interaction between the ethyl­ene group of a TEA ligand and a squarate anion.

S1. Comment

Supramolecular structures containing metal ions have attracted many workers from a variety of scientific disciplines for different kinds of applications, such as zeolite-like materials (Venkataraman et al., 1995), catalysts (Fujita et al., 1994) and magnetic materials (Kahn, 1993). In order to understand the properties of supramolecular architectures, detailed structural information is required. In this context, we have synthesized bis(triethanolamine) cadmium(II) squarate monohydrate. Squaric acid was selected because of its utility in building cocrystals (Bouma et al., 1999; Bertollasi et al., 2001; Bulut et al., 2003). The triethanolamine (TEA) molecule is also used as a ligand since it contains four donor atoms – three hydroxy O atoms and one amine N atom. The TEA ligand usually acts as an N,O,O'-tridentate ligand in transition metal complexes (Sen & Dotson, 1970; Icbudak et al., 1995; Ucar et al., 2004). Although such behaviour is not common, TEA may also act as an N,O,O',O''-tetradentate ligand when geometrical demands enforce high coordination numbers or the metal ions have large ionic radii (Naiini et al., 1995; Naiini et al., 1996; Topcu et al., 2002; Starynowicz & Gatner, 2003). Coordination number seven is rare because of increased ligand–ligand repulsion, weaker bonds and, usually, reduced CF (crystal field) stabilization in comparison to those of octahedral complexes. Seven-coordination is most commonly found in discrete complexes of second- and third-row transition metals, such as lanthanides and actinides (Arndt et al., 2002; Han et al., 1999). The three known coordination geometries for coordination number seven are (i) pentagonal bipyramidal, (ii) capped octahedral with a seventh ligand added to a rectangular face and (iii) capped trigonal prismatic with a seventh ligand added to a rectangular face. These geometries are considered to have approximately equal a priori probabilities (Park et al., 1970). The third coordination geometry is observed in the title complex.

An ORTEPIII (Burnet & Johnson., 1996) view of (I) and its atom-labelling scheme are shown in Fig. 1. The crystal structure contains a complex [Cd(TEA)₂]²⁺ cation and an uncoordinated squarate anion, C₄O₄²⁻. The structure of the complex cation reveals a heptacoordinated Cd^II ion with a coordination polyhedron best described as a distorted monocapped trigonal prism with approximate C_2v symmetry. In the complex cation, in which the Cd^II ion is coordinated by two TEA ligands and is seven coordinate, both tri- and tetradentate TEA molecules are present. The coordination modes of the two TEA molecules are different. One molecule coordinates to Cd^II with all donor atoms, behaving as an N,O,O',O''-tetradentate ligand, while the other coordinates through two hydroxy O atoms and the amine group, acting as an N,O,O'-tridentate ligand and leaving the other hydroxy group free. The C and O atoms of the free hydroxy group, C22 and O22, are disordered over two positions, with occupancies of 0.7 for O22a/C22a and 0.3 for O22b/C22b.

In the monocapped trigonal prism, the triangles O1/O4/O5 and O2/O3/N2 form the bases; these planes are nearly parallel to one another, with a dihedral angle of 6.08 (3)°. The rectangular faces [O3/O4/N2/O5 (plane 1), O1/O2/O3/O4 (plane 2) and O1/O2/N2/O5 (plane 3)] are almost planar, with r.m.s. deviations of 0.0679, 0.0884 and 0.1223 Å, and the maximum deviations from these planes are 0.071 (2) Å for atom N2, 0.092 (2) Å for atom O3 and 0.131 (2) Å for atom N2, respectively. The dihedral angles between these least-squares planes are 77.07 (11)° between planes 1 and 3, 51.14 (9)° between planes 2 and 3, and 51.86 (11)° between planes 1 and 2. The dihedral angles between the rectangular face (plane 1) and the nearly parallel triangular bases are 86.03 (12) and 82.51 (13)°. In the monocapped trigonal prism, atom N1 is located at the axial position, while atoms N2 and O5 are in pseudo-axial positions. When the capping atom N1 (additional ligand) is added on top of a face of the trigonal prism, a slight distortion occurs. The Cd—O bond distances are in the range 2.310 (4)–2.457 (4) Å, while the Cd—N bond distances are 2.389 (4) and 2.404 (4) Å. It was seen that, in the tetradentate and tridentate TEA ligands, the Cd—O and Cd—N bond distances are different, so the two TEA ligands are not equivalent. All the O—Cd—O angles deviate significantly from 90 and 180°. The central Cd^II ion is located 0.2498 (16) Å below the least-squares plane (O1/O2/O3/O4). These values are comparable to those observed for another Cd^II TEA complex (Andac et al., 2001; Naiini et al., 1995). The values also indicate that the coordination geometry around the Cd^II ion is irregular, presumably as a result of the steric constraints arising from the shape of the polydentate ligands.

The uncoordinated squarate anions are almost coplanar and play an important role in the supramolecular architecture. The O—C bond distances are in the range of 1.246 (6)–1.256 (6) Å in the squarate anion, while the unique C—C bond distances are 1.451 (6) and 1.463 (7) Å. These bond lengths accord with the fact that the squarate anion, C₄O₄²⁻, which possesses a pronounced degree of delocalization, is considered to be aromatic. Each squarate anion is surrounded by four [Cd(TEA)₂]²⁺ cations. As shown in Fig. 2, the squarate O atoms participate in hydrogen bonds with the hydroxy H atoms (O atoms lie on the equatorial plane) of the TEA ligands. The lattice water molecules link the complex cation to the squarate ion through hydrogen-bonding interactions (see table 2 for details). In the extended structure (Fig. 2), there is also a weak C—H···π interaction between atoms C5 and H5B of the tetradentate TEA ligand and a squarate anion. For the C—H···Cg contact (Cg is the center of the squarate ion containing atoms C14 and C15), the distance between the squarate centroid and the nearest methylene H atom is 2.99 Å. The perpendicular distance between atom H5B and the center of the squarate ion is 2.862 Å and the C—H···Cg angle is 143.61°. An extensive network of hydrogen bonds and C—H···π intermolecular interactions embeds the complex in an infinite three-dimensional lattice.

S2. Experimental

Squaric acid (0.57 g, 5 mmol), dissolved in water (25 ml), was neutralized with NaOH (0.40 g, 10 mmol) and was added to a hot solution of CdCl₂·H₂O(0.201 g, 5 mmol) dissolved in water (50 ml). The mixture was stirred at 333 K for 12 h and then cooled to room temperature. The resulting yellow crystals were filtered, washed with water and alcohol, and dried in a vacuum. A solution of triethanolamine (0.298 g, 2 mmol) in methanol (50 ml) was added dropwise with stirring to a suspension of CdSq·2H₂O (0.26 g, 1 mmol) in water (50 ml). The mixture was heated to 323 K for 12 h and then left to cool to room temperature. A few days later, well formed crystals were selected for X-ray studies.

S3. Refinement

The hydroxy and water H atoms were located from a difference map and then restrained to an O—H distance of 0.84 (3) Å. Other H atoms were placed at calculated positions (C—H = 0.97 Å) and were allowed to ride on their parent atoms [U_iso(H)= 1.2U_eq(C)]. The disordered hydroxymethyl moiety (site-occupancy factors are 0.7 for O22a/C22a and 0.3 for O22b/C22b) was refined anisotropically, with constraints and restraints imposed on the C—C and O—C distances, the N—C—C and C—C—O angles, and the anisotropic displacement parameters of the O and C atoms. The highest peak and deepest hole are located 0.05 and 0.11 Å from atoms O2 and O22b, respectively, and are thus related to disorder in the O atoms.

Computing details

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2001); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. ORTEP-3 view of the ionic moeities of (I) together with the hydrogen bonds. H atoms of hydroxyl groups are shown as small circles and hydrogen bonds are indicated by dashed lines. The methylene H atoms are omitted. Symmetry codes: i) x, y, 1 + z ii) 1 + x, 1 + y, 2 + z
	Fig. 2. : The three-dimensional structure of the co-crystal. Dashed lines illustrate the hydrogen bonds and π-ring interactions.

(I)

Crystal data

[Cd(C6H15NO3)2](C4O4)·H2O	Z = 2
Mr = 539.83	F(000) = 554
Triclinic, P1	Dx = 1.678 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 9.135 (5) Å	Cell parameters from 16158 reflections
b = 10.972 (5) Å	θ = 1.9–25.9°
c = 11.968 (5) Å	µ = 1.08 mm^−1
α = 71.537 (5)°	T = 293 K
β = 70.118 (5)°	Prism, colorless
γ = 86.582 (5)°	0.4 × 0.3 × 0.2 mm
V = 1068.4 (9) Å^3

Data collection

Stoe IPDS-II diffractometer	4123 independent reflections
Radiation source: fine-focus sealed tube	3368 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.000
Detector resolution: 6.67 pixels mm^-1	θmax = 25.9°, θmin = 1.9°
rotation method scans	h = −10→11
Absorption correction: integration X-RED32 (Stoe & Cie, 2002)	k = −12→13
Tmin = 0.480, Tmax = 0.819	l = 0→14
4123 measured reflections

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)] = 0.044	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.118	w = 1/[σ^2(Fo^2) + (0.0878P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.97	(Δ/σ)max < 0.001
4123 reflections	Δρmax = 1.17 e Å^−3
277 parameters	Δρmin = −2.53 e Å^−3
192 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.023 (2)

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	Occ. (<1)
Cd1	0.22532 (4)	0.28813 (3)	0.72935 (3)	0.02810 (15)
O1	0.2512 (5)	0.2761 (4)	0.5343 (4)	0.0501 (6)
O2	0.0902 (5)	0.0773 (4)	0.7933 (4)	0.0501 (6)
O3	0.2163 (4)	0.2490 (4)	0.9375 (3)	0.0407 (8)
O4	0.4230 (4)	0.4433 (3)	0.6900 (3)	0.0368 (8)
O5	0.1398 (4)	0.4937 (3)	0.6345 (3)	0.0400 (8)
O6	0.1266 (5)	−0.0639 (4)	0.6425 (4)	0.0493 (10)
O7	0.0006 (5)	−0.2045 (3)	0.4908 (4)	0.0508 (10)
O8	0.6041 (5)	0.4212 (4)	1.1553 (4)	0.0495 (10)
O9	0.4516 (5)	0.2954 (4)	1.0075 (4)	0.0500 (10)
O10	0.1873 (6)	−0.3195 (4)	0.7214 (4)	0.0520 (10)
N1	0.4703 (5)	0.1970 (4)	0.6580 (4)	0.0339 (9)
N2	−0.0425 (5)	0.2951 (4)	0.8537 (4)	0.0327 (9)
C1	−0.0737 (8)	0.0711 (6)	0.8552 (6)	0.0546 (9)
H1A	−0.0975	0.0287	0.9443	0.065*
H1B	−0.1246	0.0205	0.8241	0.065*
C2	−0.1355 (6)	0.2040 (5)	0.8338 (5)	0.0403 (11)
H2A	−0.1367	0.2368	0.7487	0.048*
H2B	−0.2421	0.1984	0.8901	0.048*
C3	−0.0555 (6)	0.2591 (6)	0.9875 (5)	0.0453 (13)
H3A	−0.0689	0.1663	1.0240	0.054*
H3B	−0.1473	0.2957	1.0321	0.054*
C4	0.0845 (7)	0.3049 (6)	1.0036 (5)	0.0470 (13)
H4A	0.0973	0.3980	0.9704	0.056*
H4B	0.0729	0.2789	1.0917	0.056*
C5	−0.0950 (6)	0.4262 (5)	0.8113 (5)	0.0438 (12)
H5A	−0.0664	0.4791	0.8527	0.053*
H5B	−0.2078	0.4223	0.8354	0.053*
C6	−0.0256 (6)	0.4877 (5)	0.6722 (5)	0.0445 (12)
H6A	−0.0589	0.4381	0.6300	0.053*
H6B	−0.0619	0.5738	0.6485	0.053*
C7	0.5754 (6)	0.3984 (5)	0.6620 (5)	0.0384 (11)
H7A	0.5969	0.3553	0.7388	0.046*
H7B	0.6514	0.4700	0.6123	0.046*
C8	0.5854 (6)	0.3069 (6)	0.5908 (6)	0.0447 (12)
H8A	0.5705	0.3532	0.5120	0.054*
H8B	0.6891	0.2745	0.5716	0.054*
C9	0.3846 (7)	0.2144 (6)	0.4770 (5)	0.0429 (12)
H9A	0.4621	0.2793	0.4129	0.052*
H9B	0.3545	0.1610	0.4367	0.052*
C10	0.4561 (7)	0.1314 (6)	0.5720 (5)	0.0468 (13)
H10A	0.3919	0.0525	0.6203	0.056*
H10B	0.5587	0.1085	0.5277	0.056*
C11	0.5240 (8)	0.1089 (6)	0.7575 (6)	0.0546 (9)
H11A	0.6275	0.0842	0.7173	0.065*	0.694 (6)
H11B	0.5344	0.1575	0.8097	0.065*	0.694 (6)
H11C	0.5992	0.1641	0.7623	0.065*	0.306 (6)
H11D	0.4337	0.1014	0.8318	0.065*	0.306 (6)
C12	−0.0002 (6)	−0.0929 (5)	0.4962 (5)	0.0361 (11)
C13	0.0567 (6)	−0.0290 (5)	0.5645 (5)	0.0359 (11)
C14	0.4775 (6)	0.4077 (5)	1.0040 (5)	0.0329 (10)
C15	0.5461 (6)	0.4637 (5)	1.0708 (4)	0.0323 (10)
H1	0.175 (6)	0.253 (7)	0.529 (7)	0.07 (2)*
H2	0.105 (7)	0.039 (5)	0.747 (4)	0.039 (15)*
H3	0.288 (5)	0.263 (6)	0.957 (5)	0.040 (16)*
H4	0.403 (8)	0.479 (6)	0.744 (5)	0.06 (2)*
H5	0.163 (10)	0.542 (7)	0.671 (7)	0.09 (3)*
H6	0.169 (9)	−0.243 (3)	0.690 (6)	0.07 (2)*
H7	0.270 (7)	−0.325 (11)	0.736 (10)	0.12 (4)*
C22A	0.4306 (11)	−0.0067 (8)	0.8384 (8)	0.0546 (9)	0.694 (6)
H22A	0.4483	−0.0323	0.9179	0.065*	0.694 (6)
H22B	0.3215	0.0113	0.8543	0.065*	0.694 (6)
O22A	0.4631 (7)	−0.1110 (5)	0.7881 (6)	0.0501 (6)	0.694 (6)
C22B	0.5252	−0.0132	0.7790	0.0546 (9)	0.306 (6)
H22C	0.6127	−0.0363	0.7174	0.065*	0.306 (6)
H22D	0.4291	−0.0473	0.7799	0.065*	0.306 (6)
O22B	0.5390	−0.0548	0.8922	0.0501 (6)	0.306 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.0268 (2)	0.0295 (2)	0.0308 (2)	0.00259 (12)	−0.01022 (13)	−0.01297 (13)
O1	0.0629 (17)	0.0414 (14)	0.0572 (15)	0.0048 (12)	−0.0281 (13)	−0.0222 (12)
O2	0.0629 (17)	0.0414 (14)	0.0572 (15)	0.0048 (12)	−0.0281 (13)	−0.0222 (12)
O3	0.037 (2)	0.055 (2)	0.0372 (19)	0.0018 (17)	−0.0155 (16)	−0.0218 (17)
O4	0.0325 (18)	0.0362 (19)	0.049 (2)	0.0066 (14)	−0.0161 (15)	−0.0215 (16)
O5	0.0389 (19)	0.0318 (19)	0.046 (2)	0.0046 (15)	−0.0139 (16)	−0.0095 (16)
O6	0.072 (3)	0.034 (2)	0.067 (2)	0.0156 (19)	−0.053 (2)	−0.0215 (18)
O7	0.067 (3)	0.0293 (19)	0.081 (3)	0.0163 (18)	−0.051 (2)	−0.0266 (19)
O8	0.072 (3)	0.045 (2)	0.054 (2)	0.022 (2)	−0.046 (2)	−0.0223 (18)
O9	0.069 (3)	0.031 (2)	0.068 (3)	0.0077 (18)	−0.044 (2)	−0.0185 (18)
O10	0.069 (3)	0.041 (2)	0.064 (3)	0.022 (2)	−0.042 (2)	−0.024 (2)
N1	0.036 (2)	0.029 (2)	0.041 (2)	0.0091 (17)	−0.0168 (18)	−0.0140 (17)
N2	0.032 (2)	0.032 (2)	0.035 (2)	0.0022 (16)	−0.0112 (16)	−0.0113 (17)
C1	0.063 (2)	0.0429 (19)	0.060 (2)	0.0056 (18)	−0.0284 (19)	−0.0119 (17)
C2	0.031 (3)	0.043 (3)	0.050 (3)	0.002 (2)	−0.017 (2)	−0.014 (2)
C3	0.038 (3)	0.059 (4)	0.036 (3)	0.005 (2)	−0.008 (2)	−0.016 (2)
C4	0.047 (3)	0.064 (4)	0.036 (3)	0.005 (3)	−0.012 (2)	−0.026 (3)
C5	0.032 (3)	0.038 (3)	0.058 (3)	0.011 (2)	−0.011 (2)	−0.017 (2)
C6	0.038 (3)	0.038 (3)	0.051 (3)	0.007 (2)	−0.019 (2)	−0.003 (2)
C7	0.029 (2)	0.037 (3)	0.052 (3)	0.000 (2)	−0.015 (2)	−0.016 (2)
C8	0.032 (3)	0.045 (3)	0.057 (3)	0.006 (2)	−0.011 (2)	−0.023 (3)
C9	0.050 (3)	0.046 (3)	0.037 (3)	0.003 (2)	−0.014 (2)	−0.019 (2)
C10	0.053 (3)	0.044 (3)	0.051 (3)	0.011 (3)	−0.017 (3)	−0.027 (3)
C11	0.063 (2)	0.0429 (19)	0.060 (2)	0.0056 (18)	−0.0284 (19)	−0.0119 (17)
C12	0.040 (3)	0.031 (3)	0.048 (3)	0.007 (2)	−0.025 (2)	−0.016 (2)
C13	0.042 (3)	0.030 (3)	0.046 (3)	0.006 (2)	−0.024 (2)	−0.017 (2)
C14	0.033 (2)	0.032 (3)	0.038 (2)	0.006 (2)	−0.017 (2)	−0.014 (2)
C15	0.033 (2)	0.034 (3)	0.035 (2)	0.011 (2)	−0.0154 (19)	−0.014 (2)
C22A	0.063 (2)	0.0429 (19)	0.060 (2)	0.0056 (18)	−0.0284 (19)	−0.0119 (17)
O22A	0.0629 (17)	0.0414 (14)	0.0572 (15)	0.0048 (12)	−0.0281 (13)	−0.0222 (12)
C22B	0.063 (2)	0.0429 (19)	0.060 (2)	0.0056 (18)	−0.0284 (19)	−0.0119 (17)
O22B	0.0629 (17)	0.0414 (14)	0.0572 (15)	0.0048 (12)	−0.0281 (13)	−0.0222 (12)

Geometric parameters (Å, º)

Cd1—O1	2.310 (4)	C3—H3A	0.9700
Cd1—O3	2.363 (4)	C3—H3B	0.9700
Cd1—O4	2.379 (4)	C4—H4A	0.9700
Cd1—N1	2.390 (4)	C4—H4B	0.9700
Cd1—O5	2.399 (4)	C5—C6	1.500 (8)
Cd1—N2	2.404 (4)	C5—H5A	0.9700
Cd1—O2	2.457 (4)	C5—H5B	0.9700
O1—C9	1.428 (7)	C6—H6A	0.9700
O1—H1	0.78 (3)	C6—H6B	0.9700
O2—C1	1.421 (8)	C7—C8	1.490 (7)
O2—H2	0.77 (3)	C7—H7A	0.9700
O3—C4	1.422 (7)	C7—H7B	0.9700
O3—H3	0.81 (3)	C8—H8A	0.9700
O4—C7	1.414 (6)	C8—H8B	0.9700
O4—H4	0.82 (3)	C9—C10	1.526 (8)
O5—C6	1.422 (6)	C9—H9A	0.9700
O5—H5	0.86 (9)	C9—H9B	0.9700
O6—C13	1.256 (6)	C10—H10A	0.9700
O7—C12	1.246 (6)	C10—H10B	0.9700
O8—C15	1.248 (6)	C11—C22B	1.282 (6)
O9—C14	1.253 (6)	C11—C22A	1.437 (10)
O10—H6	0.83 (3)	C11—H11A	0.9700
O10—H7	0.83 (8)	C11—H11B	0.9700
N1—C10	1.471 (7)	C11—H11C	0.9701
N1—C8	1.473 (7)	C11—H11D	0.9700
N1—C11	1.485 (7)	C12—C13	1.458 (7)
N2—C2	1.472 (6)	C14—C15	1.451 (6)
N2—C5	1.475 (7)	C22A—O22A	1.426 (9)
N2—C3	1.486 (6)	C22A—H11D	1.1645
C1—C2	1.509 (8)	C22A—H22A	0.9700
C1—H1A	0.9700	C22A—H22B	0.9700
C1—H1B	0.9700	C22B—O22B	1.3333 (5)
C2—H2A	0.9700	C22B—H22C	0.9700
C2—H2B	0.9700	C22B—H22D	0.9700
C3—C4	1.494 (8)
O1—Cd1—O3	166.28 (14)	O3—C4—H4B	110.2
O1—Cd1—O4	104.74 (14)	C3—C4—H4B	110.2
O3—Cd1—O4	81.38 (13)	H4A—C4—H4B	108.5
O1—Cd1—N1	73.67 (15)	N2—C5—C6	112.4 (4)
O3—Cd1—N1	96.99 (13)	N2—C5—H5A	109.1
O4—Cd1—N1	72.97 (13)	C6—C5—H5A	109.1
O1—Cd1—O5	78.40 (14)	N2—C5—H5B	109.1
O3—Cd1—O5	115.27 (13)	C6—C5—H5B	109.1
O4—Cd1—O5	73.66 (13)	H5A—C5—H5B	107.9
N1—Cd1—O5	128.56 (13)	O5—C6—C5	110.1 (4)
O1—Cd1—N2	112.22 (15)	O5—C6—H6A	109.6
O3—Cd1—N2	72.78 (13)	C5—C6—H6A	109.6
O4—Cd1—N2	123.19 (13)	O5—C6—H6B	109.6
N1—Cd1—N2	157.68 (14)	C5—C6—H6B	109.6
O5—Cd1—N2	73.42 (13)	H6A—C6—H6B	108.2
O1—Cd1—O2	80.65 (15)	O4—C7—C8	107.8 (4)
O3—Cd1—O2	89.51 (14)	O4—C7—H7A	110.1
O4—Cd1—O2	159.51 (14)	C8—C7—H7A	110.1
N1—Cd1—O2	90.13 (15)	O4—C7—H7B	110.1
O5—Cd1—O2	126.77 (14)	C8—C7—H7B	110.1
N2—Cd1—O2	70.41 (14)	H7A—C7—H7B	108.5
C9—O1—Cd1	116.4 (3)	N1—C8—C7	113.8 (4)
C9—O1—H1	112 (6)	N1—C8—H8A	108.8
Cd1—O1—H1	115 (6)	C7—C8—H8A	108.8
C1—O2—Cd1	115.9 (3)	N1—C8—H8B	108.8
C1—O2—H2	107 (4)	C7—C8—H8B	108.8
Cd1—O2—H2	121 (4)	H8A—C8—H8B	107.7
C4—O3—Cd1	110.3 (3)	O1—C9—C10	111.9 (4)
C4—O3—H3	107 (4)	O1—C9—H9A	109.2
Cd1—O3—H3	125 (4)	C10—C9—H9A	109.2
C7—O4—Cd1	114.3 (3)	O1—C9—H9B	109.2
C7—O4—H4	113 (5)	C10—C9—H9B	109.2
Cd1—O4—H4	113 (5)	H9A—C9—H9B	107.9
C6—O5—Cd1	109.3 (3)	N1—C10—C9	112.6 (4)
C6—O5—H5	106 (6)	N1—C10—H10A	109.1
Cd1—O5—H5	103 (6)	C9—C10—H10A	109.1
H6—O10—H7	111 (9)	N1—C10—H10B	109.1
C10—N1—C8	110.9 (4)	C9—C10—H10B	109.1
C10—N1—C11	111.2 (4)	H10A—C10—H10B	107.8
C8—N1—C11	107.0 (4)	C22B—C11—N1	122.7 (5)
C10—N1—Cd1	106.4 (3)	C22A—C11—N1	118.3 (6)
C8—N1—Cd1	105.5 (3)	C22A—C11—H11A	107.7
C11—N1—Cd1	115.7 (3)	N1—C11—H11A	107.7
C2—N2—C5	109.2 (4)	C22B—C11—H11B	128.3
C2—N2—C3	111.1 (4)	C22A—C11—H11B	107.7
C5—N2—C3	110.6 (4)	N1—C11—H11B	107.7
C2—N2—Cd1	107.8 (3)	H11A—C11—H11B	107.1
C5—N2—Cd1	109.1 (3)	C22B—C11—H11C	127.6
C3—N2—Cd1	109.0 (3)	C22A—C11—H11C	136.4
O2—C1—C2	110.9 (5)	N1—C11—H11C	101.9
O2—C1—H1A	109.5	N1—C11—H11D	101.6
C2—C1—H1A	109.5	H11A—C11—H11D	150.5
O2—C1—H1B	109.5	H11C—C11—H11D	104.7
C2—C1—H1B	109.5	O7—C12—C13	135.2 (5)
H1A—C1—H1B	108.1	O6—C13—C12	134.9 (5)
N2—C2—C1	113.0 (4)	O9—C14—C15	135.0 (4)
N2—C2—H2A	109.0	O8—C15—C14	135.6 (5)
C1—C2—H2A	109.0	O22A—C22A—C11	113.4 (7)
N2—C2—H2B	109.0	O22A—C22A—H11D	154.0
C1—C2—H2B	109.0	O22A—C22A—H22A	108.9
H2A—C2—H2B	107.8	C11—C22A—H22A	108.9
N2—C3—C4	112.3 (4)	O22A—C22A—H22B	108.9
N2—C3—H3A	109.1	C11—C22A—H22B	108.9
C4—C3—H3A	109.1	H22A—C22A—H22B	107.7
N2—C3—H3B	109.1	C11—C22B—O22B	102.0 (3)
C4—C3—H3B	109.1	C11—C22B—H22C	111.4
H3A—C3—H3B	107.9	O22B—C22B—H22C	111.4
O3—C4—C3	107.5 (4)	C11—C22B—H22D	111.4
O3—C4—H4A	110.2	O22B—C22B—H22D	111.4
C3—C4—H4A	110.2	H22C—C22B—H22D	109.2
O3—Cd1—O1—C9	−43.3 (8)	O5—Cd1—N2—C2	110.2 (3)
O4—Cd1—O1—C9	71.8 (4)	O2—Cd1—N2—C2	−30.0 (3)
N1—Cd1—O1—C9	4.9 (4)	O1—Cd1—N2—C5	−77.9 (4)
O5—Cd1—O1—C9	141.2 (4)	O3—Cd1—N2—C5	115.7 (4)
N2—Cd1—O1—C9	−152.3 (4)	O4—Cd1—N2—C5	48.7 (4)
O2—Cd1—O1—C9	−88.0 (4)	N1—Cd1—N2—C5	−179.1 (4)
O1—Cd1—O2—C1	−110.7 (4)	O5—Cd1—N2—C5	−8.2 (3)
O3—Cd1—O2—C1	78.9 (4)	O2—Cd1—N2—C5	−148.5 (4)
O4—Cd1—O2—C1	142.1 (4)	O1—Cd1—N2—C3	161.3 (3)
N1—Cd1—O2—C1	175.9 (4)	O3—Cd1—N2—C3	−5.1 (3)
O5—Cd1—O2—C1	−42.8 (4)	O4—Cd1—N2—C3	−72.1 (4)
N2—Cd1—O2—C1	7.1 (4)	N1—Cd1—N2—C3	60.1 (5)
O1—Cd1—O3—C4	−139.1 (6)	O5—Cd1—N2—C3	−129.1 (4)
O4—Cd1—O3—C4	103.3 (4)	O2—Cd1—N2—C3	90.7 (3)
N1—Cd1—O3—C4	174.8 (4)	Cd1—O2—C1—C2	17.1 (6)
O5—Cd1—O3—C4	36.0 (4)	C5—N2—C2—C1	170.9 (5)
N2—Cd1—O3—C4	−25.6 (3)	C3—N2—C2—C1	−66.9 (6)
O2—Cd1—O3—C4	−95.2 (4)	Cd1—N2—C2—C1	52.5 (5)
O1—Cd1—O4—C7	−75.0 (3)	O2—C1—C2—N2	−47.1 (7)
O3—Cd1—O4—C7	92.5 (3)	C2—N2—C3—C4	153.2 (5)
N1—Cd1—O4—C7	−7.6 (3)	C5—N2—C3—C4	−85.4 (6)
O5—Cd1—O4—C7	−147.9 (3)	Cd1—N2—C3—C4	34.6 (5)
N2—Cd1—O4—C7	155.3 (3)	Cd1—O3—C4—C3	52.0 (5)
O2—Cd1—O4—C7	28.0 (6)	N2—C3—C4—O3	−59.1 (6)
O1—Cd1—O5—C6	96.5 (4)	C2—N2—C5—C6	−81.3 (5)
O3—Cd1—O5—C6	−82.3 (4)	C3—N2—C5—C6	156.2 (5)
O4—Cd1—O5—C6	−154.2 (4)	Cd1—N2—C5—C6	36.3 (5)
N1—Cd1—O5—C6	154.5 (3)	Cd1—O5—C6—C5	47.7 (5)
N2—Cd1—O5—C6	−21.1 (3)	N2—C5—C6—O5	−58.5 (6)
O2—Cd1—O5—C6	27.6 (4)	Cd1—O4—C7—C8	34.4 (5)
O1—Cd1—N1—C10	−27.2 (3)	C10—N1—C8—C7	164.2 (4)
O3—Cd1—N1—C10	142.5 (3)	C11—N1—C8—C7	−74.4 (6)
O4—Cd1—N1—C10	−138.8 (3)	Cd1—N1—C8—C7	49.3 (5)
O5—Cd1—N1—C10	−87.1 (4)	O4—C7—C8—N1	−57.9 (6)
N2—Cd1—N1—C10	81.7 (5)	Cd1—O1—C9—C10	18.2 (6)
O2—Cd1—N1—C10	53.0 (3)	C8—N1—C10—C9	−67.2 (6)
O1—Cd1—N1—C8	90.7 (3)	C11—N1—C10—C9	173.9 (5)
O3—Cd1—N1—C8	−99.6 (3)	Cd1—N1—C10—C9	47.1 (5)
O4—Cd1—N1—C8	−20.9 (3)	O1—C9—C10—N1	−45.1 (7)
O5—Cd1—N1—C8	30.8 (4)	C10—N1—C11—C22B	−13.5 (8)
N2—Cd1—N1—C8	−160.4 (4)	C8—N1—C11—C22B	−134.7 (5)
O2—Cd1—N1—C8	170.9 (3)	Cd1—N1—C11—C22B	108.1 (5)
O1—Cd1—N1—C11	−151.2 (4)	C10—N1—C11—C22A	−59.4 (8)
O3—Cd1—N1—C11	18.5 (4)	C8—N1—C11—C22A	179.4 (6)
O4—Cd1—N1—C11	97.2 (4)	Cd1—N1—C11—C22A	62.2 (7)
O5—Cd1—N1—C11	148.9 (3)	O7—C12—C13—O6	−0.2 (12)
N2—Cd1—N1—C11	−42.4 (6)	O9—C14—C15—O8	0.0 (11)
O2—Cd1—N1—C11	−71.0 (4)	C22B—C11—C22A—O22A	−23.0 (4)
O1—Cd1—N2—C2	40.6 (3)	N1—C11—C22A—O22A	85.2 (8)
O3—Cd1—N2—C2	−125.8 (3)	C22A—C11—C22B—O22B	−67.6 (6)
O4—Cd1—N2—C2	167.2 (3)	N1—C11—C22B—O22B	−163.8 (5)
N1—Cd1—N2—C2	−60.6 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O10—H7···O8^i	0.83 (8)	2.03 (6)	2.770 (5)	148 (10)
O10—H6···O6	0.83 (3)	1.92 (3)	2.749 (6)	171 (7)
O3—H3···O9	0.81 (3)	1.88 (3)	2.685 (5)	179 (6)
O4—H4···O8^ii	0.82 (3)	1.86 (3)	2.662 (5)	168 (7)
O5—H5···O10^iii	0.86 (9)	1.85 (4)	2.690 (6)	164 (9)
O1—H1···O7^iv	0.78 (3)	1.83 (7)	2.614 (6)	177 (8)
O2—H2···O6	0.77 (3)	1.89 (3)	2.658 (6)	176 (6)

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