[Lambda]-{1,4,7,10-Tetrakis­[(S)-2-hydroxy­propyl-[kappa]O]-1,4,7,10-tetra­aza­cyclo­do­decane-[kappa]⁴N}cadmium(II) bis(2,4,6-tri­nitro­phenolate) aceto­nitrile solvate

Crystallization of [Cd(S-thpc12)](ClO₄)₂·H₂O {S-thpc12 is 1,4,7,10-tetrakis­[(S)-2-hydroxy­propyl]-1,4,7,10-tetra­aza­cyclo­do­decane} in the presence of two equivalents of sodium picrate monohydrate (sodium 2,4,6-tri­nitro­phenolate monohydrate) diastereoselectively produces a neutral receptor complex, viz. the title compound, [Lambda]-[Cd(C₂₀H₄₄N₄O₄)](C₆H₂N₃O₇)₂·CH₃CN. In this complex, two picrate anions hydrogen bond, via their phenolate moieties, to the pendant hydroxyl groups of the receptor which, together with the four N atoms, themselves bond to Cd^II in an approximately cubic arrangement. One picrate anion hydrogen bonds to all four hydroxyl groups, one of which also acts as the sole hydrogen-bond donor to the second picrate anion.

S1. Comment

The ability of optically active pendant hydroxyl-donor macrocyclic ligands based on cyclen (cyclen is 1,4,7,10-tetraazacyclododecane) to coordinate in a diastereoselective manner has been noted previously (Dhillon et al., 1997, 1998). The structures of such complexes generally approximate to that of a distorted cube or square antiprism (Buøen et al., 1982; Chin et al., 1994; Hancock et al., 1988; Luckay et al., 1995) and as such have an inherent helicity which may be described Δ or Λ depending on whether the four hydroxyl donors are displaced anticlockwise or clockwise, with respect to the N atom to which each is attached, when the molecule is viewed from the plane of the hydroxyl groups towards the plane of the four N atoms along the pseudo-C₄ axis (Dhillon et al., 1995). Our recent research has been directed towards attaching aromatic groups to each of the pendant arms in such a way that they will juxtapose to form a cavity suitable for the inclusion of smaller guest molecules, in particular aromatic anions (Smith et al., 1999, 2002). In the present work, the attached group is the smaller methyl group and it was of interest to us to determine if, by using it, association with picrate (2,4,6-trinitrophenolate), which appears to be too large to be included within complexes having more enclosed cavities (Smith et al., 2002), could be induced.

The cation of the title compound, (I), shows the expected approximately cubic coordination geometry about Cd, with Cd—N bond lengths in the range 2.440 (2)–2.525 (3) Å and Cd—O(hydroxyl) bond lengths in the range 2.378 (2)–2.845 (2) Å (Table 1 and Fig. 1). The plane of the four O atoms is rotated clockwise by ca 14°, with respect to the plane of the four N atoms, giving the complex the Λ helicity (left-handed screw form of the N—O chelating arms around the local fourfold axis). One picrate anion is located centrally above the cation, held in place by hydrogen bonds from all four hydroxyl O atoms to O1a, while the other packs in the crystal beside it and is hydrogen bonded only to hydroxyl atom O1 (Table 2 and Fig. 2). The planar regions of the two anions are approximately parallel, with a mean separation of 3.22 Å, and are offset in such a way as to prevent the eclipsing of any of the atoms (Fig. 3). The extra stability conferred on the crystal structure by the stacking of the anions and steric factors involved in the formation of the bifurcated hydrogen bond from O1 to the electron-rich O1b centre apparently combine to weaken the Cd—O1 bond. This bond is 0.219 Å longer than any such bond currently recorded in the Cambridge Structural Database (Version 5.24; Allen, 2002). The Cd^II to phenolate O1a distance is 3.656 (2) Å, eliminating the possibility of significant ionic interaction between these charged centres. No association of the acetonitrile molecule present in the crystal lattice with the complex is apparent.

As judged from the range of hydrogen-bond donor–acceptor distances in (I) (2.840–3.197 Å), the picrate anions are held less strongly than are 4-nitrophenolate anions in similar complexes; corresponding distances are 2.627–2.797 Å in {1,4,7,10-tetrakis[(S)-2-hydroxypropyl-κO]-1,4,7,10- tetraazacyclododecane-κ⁴N}cadmium(II) 4-nitrophenolate perchlorate hydrate (Davies et al., 2000), and 2.546 and 2.630 Å (twice) in {1,4,7,10-tetrakis[(S)-2-hydroxy-3-phenoxypropyl-κO]-1,4,7,10- tetraazacyclododecane-κ⁴N}cadmium(II) di-4-nitrophenolate (Smith et al., 2002). This probably arises for two reasons: (i) the greater delocalization of the negative charge away from the O atom on the picrate corresponding to short C—O1a/O1b bonds (Table 1) compared with corresponding distances in the 4-nitrophenolate anions in the above structures [1.293 (10) and 1.277 (4) Å, respectively], making these picrate O atoms more like neutral hydrogen-bond acceptors, (ii) a steric constraint is possibly more marked when associated with forming four hydrogen bonds to the same acceptor (O1a), rather than two, i.e. if the phenolate O moves any closer to the Cd atom, the hydrogen bonds will shorten, but the O—H.·O angles will deviate further from linearity than they already have.

The crystal structure of (I) shows that both picrates associate with the complex in the solid state. The electrical conductivity for the receptor complex in N,N-dimethylformamide (DMF) solution (128 Ω⁻¹ cm² mol⁻¹), however, is almost in the range normally shown by 1:2 electrolytes in this solvent (130–170 Ω⁻¹ cm² mol⁻¹; Geary, 1971), suggesting that both picrates are substantially dissociated in DMF, and probably more so in solvents of higher dielectric constant.

S2. Experimental

The title compound, (I), was prepared by adding sodium picrate monohydrate (159 mg, 0.6 mmol; Silberrad & Phillips, 1908) to a solution of [Cd(S-thpc12)](ClO₄)₂·H₂O (212 mg, 0.3 mmol; Davies et al., 2000) in dry acetonitrile (15 ml). The solid dissolved quickly and a mass of yellow precipitate filled the flask within 20 min. This precipitate was dissolved in situ by heating the suspension to the boiling point of the solvent. The resulting solution was then allowed to reflux for 2 h. Upon cooling, large yellow prisms of (I), suitable for X-ray diffraction studies, formed. These were filtered off and dried (yield 228 mg, 76%). ¹³C NMR (DMSO-d₆): δ 160.90, 141.96, 125.30, 124.27, 118.16 (CH₃CN), 61.93, 59.36, 49.95, 48.00, 20.94, 1.24 (CH₃CN). Analysis calculated for C₃₄H₅₁CdN₁₁O₁₈: C 40.26, H 5.07, N 15.19%; found: C 40.2, H 5.0, N 15.0%. Conductivity: 128 Ω⁻¹ cm² mol⁻¹ (1 × 10⁻³ M, DMF).

S3. Refinement

Hydroxyl H-atom positions were obtained from the four highest peaks in the penultimate difference map and others were placed in calculated positions.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997) and Xtal3.7 ADDREF SORTRF (Hall et al., 2000); program(s) used to solve structure: SIR97 (Altomare et al., 1994); program(s) used to refine structure: Xtal3.7 CRYLSQ; molecular graphics: Xtal3.7; software used to prepare material for publication: Xtal3.7 BONDLA CIFIO.

Figures

	Fig. 1. View of the title compound showing atom labels. Hydrogen bonds are shown as dashed lines. Displacement ellipsoids are at the 50% probability level and H atoms have been omitted.
	Fig. 2. View of the title compound nearly edge-on to the trinitrophenolate planes. Hydrogen bonds are shown as dashed lines. Atoms are shown as spheres of arbitrary size and H atoms have been omitted.
	Fig. 3. Stacking of the trinitrophenolate planes, viewed strictly normal to the least-squares plane. Displacement ellipsoids are at the 50% probability level. H atoms have been omitted.

(I)

Crystal data

[Cd(C20H44N4O4)]·(C6H2N3O7)2·C2H3N	F(000) = 1048
Mr = 1014.25	Dx = 1.597 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: p 2yb	Cell parameters from 6088 reflections
a = 10.980 (2) Å	θ = 1.2–26.4°
b = 16.575 (3) Å	µ = 0.61 mm^−1
c = 11.640 (2) Å	T = 168 K
β = 95.51 (1)°	Irregular hexagonal plate, yellow
V = 2108.6 (7) Å^3	0.60 × 0.42 × 0.15 mm
Z = 2

Data collection

Bruker P4 diffractometer	8289 independent reflections
Radiation source: sealed tube	4248 reflections with F^2 > 0
Graphite monochromator	Rint = 0.016
ω scans	θmax = 26.4°
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 1997)	h = −13→13
Tmin = 0.779, Tmax = 0.913	k = −20→20
15919 measured reflections	l = −14→14

Refinement

Refinement on F^2	H-atom parameters not refined
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.05Fo^2)^2]^1/2
R[F^2 > 2σ(F^2)] = 0.023	(Δ/σ)max = 0.001
wR(F^2) = 0.057	Δρmax = 0.37 e Å^−3
S = 1.23	Δρmin = −0.31 e Å^−3
8289 reflections	Extinction correction: Zachariasen, Larson (1970), Eq22 p292 "Cryst. Comp." Munksgaard 1970
578 parameters	Extinction coefficient: 13E2 (3)
0 restraints	Absolute structure: Flack (1983), 3983 Friedel pairs
0 constraints	Absolute structure parameter: 0.018 (14)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cd	0.51822 (2)	0.19597	0.751280 (10)	0.01855 (10)
O1	0.6529 (2)	0.33695 (15)	0.8223 (2)	0.0275 (12)
O2	0.7324 (2)	0.17482 (13)	0.73439 (17)	0.0234 (12)
O3	0.5936 (2)	0.07227 (15)	0.8702 (2)	0.0304 (13)
O4	0.5124 (2)	0.22364 (13)	0.95112 (18)	0.0243 (11)
O1a	0.77320 (18)	0.1933 (2)	0.97763 (16)	0.0318 (10)
O2a	0.9408 (3)	0.26278 (19)	0.8568 (2)	0.0434 (15)
O3a	1.0705 (3)	0.33873 (17)	0.9565 (2)	0.0354 (14)
O5a	1.1341 (3)	0.1702 (2)	1.4252 (2)	0.054 (2)
O4a	1.2266 (3)	0.2604 (2)	1.3288 (2)	0.0495 (17)
O7a	0.6641 (3)	0.0977 (3)	1.1182 (3)	0.061 (2)
O6a	0.7553 (5)	0.0623 (3)	1.2757 (4)	0.105 (3)
O1b	0.8145 (3)	0.40135 (17)	1.0135 (2)	0.0346 (13)
O2b	0.9166 (3)	0.55402 (18)	0.9815 (2)	0.0445 (16)
O3b	1.1079 (3)	0.5270 (2)	1.0215 (3)	0.067 (2)
O5b	1.0755 (3)	0.3724 (3)	1.5056 (2)	0.061 (2)
O4b	1.1854 (4)	0.4676 (3)	1.4382 (3)	0.062 (2)
O7b	0.6442 (3)	0.3355 (2)	1.1335 (3)	0.0487 (18)
O6b	0.7062 (3)	0.2844 (2)	1.2962 (3)	0.059 (2)
N1	0.4218 (3)	0.3219 (2)	0.6771 (3)	0.0214 (15)
N2	0.5517 (2)	0.1965 (3)	0.54702 (18)	0.0240 (11)
N3	0.4332 (3)	0.0648 (2)	0.6675 (3)	0.0254 (17)
N4	0.3044 (2)	0.1894 (2)	0.79980 (19)	0.0232 (12)
N1a	0.9943 (3)	0.28350 (19)	0.9494 (2)	0.0286 (14)
N2a	1.1423 (3)	0.2126 (2)	1.3393 (2)	0.038 (2)
N3a	0.7508 (3)	0.1013 (2)	1.1876 (3)	0.0356 (17)
N1b	0.9999 (3)	0.5191 (2)	1.0390 (3)	0.0354 (17)
N2b	1.0972 (3)	0.4214 (2)	1.4301 (3)	0.045 (2)
N3b	0.7211 (3)	0.3288 (2)	1.2140 (3)	0.0349 (17)
N1c	0.7802 (4)	0.4311 (3)	0.5550 (4)	0.052 (2)
C1	0.4054 (4)	0.3114 (2)	0.5498 (3)	0.0278 (17)
C2	0.5185 (4)	0.2792 (2)	0.5015 (3)	0.0282 (18)
C3	0.4724 (4)	0.1356 (2)	0.4854 (3)	0.0295 (18)
C4	0.4727 (4)	0.0559 (2)	0.5499 (3)	0.0315 (18)
C5	0.2973 (3)	0.0724 (2)	0.6619 (3)	0.0295 (18)
C6	0.2557 (3)	0.1065 (2)	0.7728 (3)	0.0285 (17)
C7	0.2335 (3)	0.2503 (2)	0.7286 (3)	0.0270 (17)
C8	0.3022 (3)	0.3299 (2)	0.7236 (3)	0.0261 (17)
C11	0.4931 (4)	0.3975 (2)	0.7052 (4)	0.026 (2)
C12	0.5605 (4)	0.3983 (2)	0.8232 (3)	0.0282 (19)
C13	0.6130 (4)	0.4827 (3)	0.8468 (4)	0.042 (2)
C21	0.6816 (3)	0.1787 (2)	0.5334 (3)	0.0278 (18)
C22	0.7697 (3)	0.2110 (2)	0.6307 (3)	0.0259 (17)
C23	0.8993 (3)	0.1880 (4)	0.6098 (3)	0.0365 (18)
C31	0.4734 (4)	−0.0063 (3)	0.7373 (4)	0.033 (2)
C32	0.6023 (4)	0.0042 (2)	0.7965 (3)	0.030 (2)
C33	0.6444 (5)	−0.0719 (3)	0.8618 (4)	0.047 (3)
C41	0.2989 (3)	0.2065 (3)	0.9242 (3)	0.0257 (16)
C42	0.4146 (3)	0.17944 (19)	0.9965 (3)	0.0254 (17)
C43	0.4047 (3)	0.1968 (3)	1.1227 (2)	0.0323 (15)
C1a	0.8573 (2)	0.1950 (3)	1.0574 (2)	0.0243 (12)
C2a	0.9711 (3)	0.2401 (2)	1.0533 (3)	0.0252 (16)
C3a	1.0606 (3)	0.2465 (2)	1.1437 (3)	0.0279 (17)
C4a	1.0466 (3)	0.2045 (3)	1.2447 (2)	0.0307 (18)
C5a	0.9450 (4)	0.1583 (2)	1.2572 (3)	0.0294 (17)
C6a	0.8538 (3)	0.1528 (2)	1.1672 (3)	0.0277 (17)
C1b	0.8646 (3)	0.4140 (2)	1.1115 (3)	0.0267 (16)
C2b	0.9700 (3)	0.4673 (2)	1.1336 (3)	0.0282 (17)
C3b	1.0466 (4)	0.4701 (3)	1.2334 (3)	0.031 (2)
C4b	1.0156 (4)	0.4219 (2)	1.3256 (3)	0.0331 (18)
C5b	0.9094 (4)	0.3772 (2)	1.3183 (3)	0.0306 (17)
C6b	0.8334 (3)	0.3748 (2)	1.2172 (3)	0.0267 (16)
C1c	0.8500 (4)	0.4391 (3)	0.6320 (4)	0.043 (2)
C2c	0.9406 (6)	0.4490 (4)	0.7329 (5)	0.065 (3)
H2	0.77284	0.19619	0.78824	0.02300*
H3	0.67270	0.07788	0.90123	0.03800*
H4	0.58673	0.20418	1.00000	0.02300*
H1	0.69012	0.33096	0.89241	0.03500*
H1a	0.38577	0.36216	0.51470	0.03400*
H1b	0.34003	0.27471	0.53087	0.03400*
H2a	0.50388	0.27599	0.41945	0.03500*
H2b	0.58490	0.31460	0.52140	0.03500*
H3a	0.50050	0.12611	0.41181	0.03700*
H3b	0.39083	0.15533	0.47554	0.03700*
H4a	0.41842	0.01969	0.50723	0.03900*
H4b	0.55317	0.03444	0.55570	0.03900*
H5a	0.26234	0.02035	0.65036	0.03700*
H5b	0.27012	0.10686	0.60075	0.03700*
H6a	0.16941	0.10861	0.76521	0.03600*
H6b	0.28354	0.07163	0.83475	0.03600*
H7a	0.15880	0.26050	0.76140	0.03400*
H7b	0.21684	0.23053	0.65277	0.03400*
H8a	0.25343	0.36631	0.67685	0.03300*
H8b	0.31594	0.35083	0.80012	0.03300*
H11a	0.43878	0.44163	0.69828	0.03200*
H11b	0.55203	0.40279	0.65024	0.03200*
H12	0.50882	0.38729	0.88247	0.03500*
H13a	0.65535	0.48398	0.92219	0.06300*
H13b	0.54834	0.52104	0.84262	0.06300*
H13c	0.66790	0.49543	0.79158	0.06300*
H21a	0.70185	0.20191	0.46277	0.03500*
H21b	0.69118	0.12174	0.52986	0.03500*
H22	0.76841	0.26827	0.63652	0.03300*
H23a	0.95467	0.20817	0.67069	0.05500*
H23b	0.91848	0.21036	0.53857	0.05500*
H23c	0.90573	0.13088	0.60677	0.05500*
H31a	0.47185	−0.05224	0.68780	0.04100*
H31b	0.41807	−0.01490	0.79422	0.04100*
H32	0.66113	0.01278	0.74353	0.03800*
H33a	0.72470	−0.06375	0.89716	0.07200*
H33b	0.64456	−0.11551	0.80824	0.07200*
H33c	0.59044	−0.08356	0.91783	0.07200*
H41a	0.23067	0.17900	0.94999	0.03200*
H41b	0.28892	0.26301	0.93380	0.03200*
H42	0.42822	0.12296	0.99208	0.03200*
H43a	0.47727	0.18044	1.16699	0.04800*
H43b	0.33644	0.16964	1.14770	0.04800*
H43c	0.39419	0.25393	1.13254	0.04800*
H3a'	1.13114	0.27915	1.13732	0.03500*
H5a'	0.93682	0.12995	1.32692	0.03600*
H3b'	1.11631	0.50376	1.24038	0.03900*
H5b'	0.88891	0.34784	1.38385	0.03900*
H2ca	1.00448	0.48293	0.71438	0.09600*
H2cb	0.97227	0.39750	0.75673	0.09600*
H2cc	0.90101	0.47213	0.79495	0.09600*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd	0.01840 (10)	0.02028 (11)	0.01674 (10)	−0.00020 (16)	0.00043 (6)	0.00156 (10)
O1	0.0318 (14)	0.0258 (13)	0.0236 (11)	0.0078 (11)	−0.0048 (10)	−0.0000 (10)
O2	0.0243 (11)	0.0279 (16)	0.0171 (9)	−0.0030 (8)	−0.0019 (8)	−0.0022 (8)
O3	0.0288 (13)	0.0341 (15)	0.0279 (12)	−0.0007 (11)	0.0001 (10)	0.0004 (10)
O4	0.0248 (12)	0.0277 (13)	0.0197 (10)	−0.0038 (8)	−0.0016 (9)	0.0022 (8)
O1a	0.0279 (10)	0.0398 (13)	0.0259 (9)	−0.006 (2)	−0.0075 (8)	0.0033 (15)
O2a	0.0458 (16)	0.061 (2)	0.0227 (12)	−0.0200 (14)	−0.0021 (11)	−0.0052 (12)
O3a	0.0291 (14)	0.0388 (16)	0.0374 (14)	−0.0035 (12)	−0.0004 (12)	−0.0006 (12)
O5a	0.0490 (17)	0.081 (3)	0.0297 (14)	0.0071 (15)	−0.0132 (12)	0.0057 (13)
O4a	0.0325 (15)	0.080 (2)	0.0339 (14)	−0.0063 (15)	−0.0093 (12)	−0.0111 (14)
O7a	0.0369 (18)	0.097 (3)	0.0484 (17)	−0.0270 (19)	−0.0049 (14)	0.0248 (18)
O6a	0.106 (4)	0.130 (4)	0.070 (2)	−0.076 (3)	−0.034 (2)	0.064 (3)
O1b	0.0368 (15)	0.0372 (15)	0.0277 (12)	−0.0010 (12)	−0.0070 (11)	0.0011 (11)
O2b	0.0512 (18)	0.0401 (16)	0.0407 (15)	0.0043 (13)	−0.0036 (14)	0.0153 (13)
O3b	0.042 (2)	0.069 (2)	0.091 (3)	−0.0084 (17)	0.0092 (18)	0.043 (2)
O5b	0.050 (2)	0.101 (3)	0.0303 (15)	0.0151 (18)	−0.0044 (13)	0.0124 (17)
O4b	0.060 (3)	0.063 (2)	0.057 (2)	0.002 (2)	−0.0301 (18)	−0.0096 (17)
O7b	0.0351 (17)	0.057 (2)	0.0515 (18)	−0.0100 (15)	−0.0057 (15)	−0.0023 (15)
O6b	0.057 (2)	0.070 (2)	0.0542 (18)	−0.0152 (18)	0.0233 (16)	0.0167 (17)
N1	0.0213 (17)	0.0254 (18)	0.0173 (14)	−0.0023 (13)	0.0001 (13)	0.0006 (12)
N2	0.0249 (11)	0.0274 (12)	0.0191 (10)	0.001 (2)	−0.0006 (8)	0.0028 (17)
N3	0.0245 (18)	0.0241 (18)	0.0272 (16)	−0.0037 (14)	0.0005 (14)	−0.0040 (13)
N4	0.0215 (11)	0.0259 (15)	0.0218 (10)	−0.0019 (16)	−0.0005 (8)	0.0000 (15)
N1a	0.0236 (14)	0.0355 (17)	0.0264 (14)	0.0028 (13)	0.0003 (11)	−0.0044 (12)
N2a	0.0353 (16)	0.053 (3)	0.0228 (14)	0.0101 (16)	−0.0063 (12)	−0.0074 (13)
N3a	0.040 (2)	0.039 (2)	0.0273 (15)	−0.0000 (15)	−0.0017 (14)	0.0026 (14)
N1b	0.040 (2)	0.0277 (17)	0.0382 (17)	−0.0033 (14)	0.0027 (15)	0.0076 (13)
N2b	0.045 (2)	0.057 (2)	0.0316 (18)	0.0175 (19)	−0.0085 (16)	−0.0033 (17)
N3b	0.038 (2)	0.0325 (19)	0.0364 (17)	0.0037 (15)	0.0162 (15)	−0.0014 (15)
N1c	0.047 (3)	0.060 (3)	0.048 (2)	0.011 (2)	0.003 (2)	0.0136 (19)
C1	0.032 (2)	0.0287 (19)	0.0210 (15)	0.0001 (15)	−0.0051 (14)	0.0065 (13)
C2	0.032 (2)	0.032 (2)	0.0197 (15)	−0.0008 (16)	−0.0001 (14)	0.0080 (14)
C3	0.031 (2)	0.037 (2)	0.0199 (16)	−0.0035 (16)	0.0011 (14)	−0.0042 (14)
C4	0.035 (2)	0.031 (2)	0.0284 (17)	−0.0023 (16)	0.0030 (15)	−0.0104 (14)
C5	0.0293 (19)	0.030 (2)	0.0284 (18)	−0.0099 (15)	−0.0016 (15)	−0.0029 (15)
C6	0.0253 (18)	0.028 (2)	0.0323 (17)	−0.0088 (15)	0.0021 (15)	0.0010 (15)
C7	0.0205 (16)	0.032 (2)	0.0283 (16)	0.0010 (14)	−0.0006 (13)	0.0014 (15)
C8	0.0241 (17)	0.0267 (19)	0.0268 (17)	0.0050 (14)	−0.0013 (15)	0.0045 (15)
C11	0.025 (2)	0.021 (2)	0.033 (2)	0.0009 (15)	−0.0016 (16)	0.0047 (15)
C12	0.028 (2)	0.022 (2)	0.034 (2)	0.0049 (15)	−0.0009 (16)	−0.0052 (15)
C13	0.039 (2)	0.026 (2)	0.059 (3)	0.0048 (19)	−0.013 (2)	−0.0150 (19)
C21	0.0284 (16)	0.033 (3)	0.0222 (14)	−0.0005 (13)	0.0030 (12)	0.0008 (13)
C22	0.0278 (15)	0.026 (3)	0.0241 (14)	−0.0036 (13)	0.0046 (12)	−0.0002 (12)
C23	0.0272 (15)	0.051 (2)	0.0319 (15)	−0.001 (2)	0.0034 (12)	−0.007 (2)
C31	0.035 (2)	0.022 (2)	0.043 (3)	−0.0037 (17)	0.004 (2)	−0.0034 (16)
C32	0.033 (2)	0.021 (2)	0.037 (2)	0.0040 (17)	0.0030 (17)	0.0038 (15)
C33	0.042 (3)	0.034 (3)	0.064 (3)	0.001 (2)	0.003 (2)	0.016 (2)
C41	0.0254 (14)	0.028 (2)	0.0245 (13)	0.0003 (16)	0.0035 (11)	0.0017 (15)
C42	0.0301 (16)	0.022 (2)	0.0240 (14)	−0.0006 (12)	0.0022 (12)	0.0047 (12)
C43	0.0454 (17)	0.0277 (16)	0.0240 (13)	0.004 (3)	0.0048 (12)	0.001 (2)
C1a	0.0267 (13)	0.0232 (14)	0.0225 (12)	0.001 (2)	−0.0014 (10)	−0.002 (2)
C2a	0.0260 (17)	0.0257 (18)	0.0234 (15)	0.0063 (14)	0.0004 (13)	−0.0048 (13)
C3a	0.0216 (16)	0.034 (2)	0.0274 (16)	0.0062 (14)	−0.0022 (13)	−0.0112 (14)
C4a	0.0280 (15)	0.039 (3)	0.0233 (13)	0.007 (2)	−0.0071 (11)	−0.0066 (17)
C5a	0.037 (2)	0.0305 (18)	0.0197 (15)	0.0111 (16)	−0.0007 (14)	−0.0016 (13)
C6a	0.0292 (18)	0.0276 (19)	0.0259 (16)	0.0024 (14)	0.0006 (14)	−0.0023 (14)
C1b	0.0265 (17)	0.0249 (18)	0.0281 (16)	0.0043 (13)	−0.0010 (14)	0.0013 (13)
C2b	0.0333 (19)	0.0236 (18)	0.0271 (17)	0.0022 (14)	−0.0003 (14)	0.0019 (13)
C3b	0.030 (2)	0.028 (2)	0.036 (2)	0.0001 (16)	0.0005 (16)	−0.0043 (15)
C4b	0.035 (2)	0.035 (2)	0.0282 (17)	0.0097 (16)	−0.0047 (15)	−0.0057 (15)
C5b	0.037 (2)	0.031 (2)	0.0254 (16)	0.0130 (15)	0.0081 (14)	0.0030 (14)
C6b	0.0305 (18)	0.0222 (17)	0.0285 (16)	0.0071 (14)	0.0083 (14)	−0.0017 (13)
C1c	0.051 (3)	0.035 (2)	0.042 (2)	0.0062 (19)	0.009 (2)	0.0105 (18)
C2c	0.076 (4)	0.062 (4)	0.054 (3)	−0.012 (3)	−0.012 (3)	0.005 (3)

Geometric parameters (Å, º)

Cd—O1	2.845 (2)	C5—H5b	0.938
Cd—O2	2.404 (2)	C6—H6a	0.944
Cd—O3	2.566 (2)	C6—H6b	0.951
Cd—O4	2.378 (2)	C7—C8	1.524 (5)
Cd—N1	2.459 (3)	C7—H7a	0.953
Cd—N2	2.440 (2)	C7—H7b	0.943
Cd—N3	2.525 (3)	C8—H8a	0.945
Cd—N4	2.469 (2)	C8—H8b	0.954
O1—C12	1.436 (5)	C11—C12	1.496 (6)
O1—H1	0.882	C11—H11a	0.943
O2—C22	1.442 (4)	C11—H11b	0.957
O2—H2	0.814	C12—C13	1.529 (6)
O3—C32	1.426 (5)	C12—H12	0.952
O3—H3	0.913	C13—H13a	0.953
O4—C42	1.442 (4)	C13—H13b	0.951
O4—H4	1.002	C13—H13c	0.946
O1a—C1a	1.245 (3)	C21—C22	1.515 (4)
O1b—C1b	1.236 (4)	C21—H21a	0.953
O2a—N1a	1.226 (4)	C21—H21b	0.951
O3a—N1a	1.237 (4)	C22—C23	1.515 (5)
O5a—N2a	1.232 (4)	C22—H22	0.952
O4a—N2a	1.233 (5)	C23—H23a	0.950
O7a—N3a	1.190 (4)	C23—H23b	0.950
O6a—N3a	1.209 (6)	C23—H23c	0.951
O2b—N1b	1.226 (4)	C31—C32	1.523 (6)
O3b—N1b	1.229 (5)	C31—H31a	0.954
O5b—N2b	1.236 (5)	C31—H31b	0.952
O4b—N2b	1.231 (6)	C32—C33	1.521 (6)
O7b—N3b	1.205 (4)	C32—H32	0.946
O6b—N3b	1.230 (5)	C33—H33a	0.947
N1—C1	1.486 (4)	C33—H33b	0.955
N1—C8	1.474 (5)	C33—H33c	0.942
N1—C11	1.496 (5)	C41—C42	1.523 (4)
N2—C2	1.502 (5)	C41—H41a	0.950
N2—C3	1.475 (5)	C41—H41b	0.950
N2—C21	1.479 (4)	C42—C43	1.511 (4)
N3—C4	1.482 (5)	C42—H42	0.950
N3—C5	1.493 (5)	C43—H43a	0.946
N3—C31	1.475 (6)	C43—H43b	0.944
N4—C6	1.497 (5)	C43—H43c	0.962
N4—C7	1.479 (5)	C1a—C2a	1.461 (5)
N4—C41	1.483 (4)	C1a—C6a	1.462 (5)
N1a—C2a	1.451 (4)	C2a—C3a	1.373 (4)
N2a—C4a	1.454 (4)	C3a—C4a	1.387 (5)
N3a—C6a	1.454 (5)	C3a—H3a'	0.954
N1b—C2b	1.458 (5)	C4a—C5a	1.373 (6)
N2b—C4b	1.440 (5)	C5a—C6a	1.381 (5)
N3b—C6b	1.448 (5)	C5a—H5a'	0.949
N1c—C1c	1.129 (6)	C1b—C2b	1.459 (5)
C1—C2	1.509 (5)	C1b—C6b	1.461 (5)
C1—H1a	0.951	C2b—C3b	1.367 (5)
C1—H1b	0.950	C3b—C4b	1.404 (6)
C2—H2a	0.954	C3b—H3b'	0.945
C2—H2b	0.947	C4b—C5b	1.378 (5)
C3—C4	1.519 (5)	C5b—C6b	1.376 (5)
C3—H3a	0.951	C5b—H5b'	0.950
C3—H3b	0.950	C1c—C2c	1.474 (7)
C4—H4a	0.951	C2c—H2ca	0.940
C4—H4b	0.949	C2c—H2cb	0.953
C5—C6	1.519 (5)	C2c—H2cc	0.958
C5—H5a	0.948
O1—H1—O1b	137.44	N4—C7—H7a	108.9
O1—H1—O1a	124.22	N4—C7—H7b	109.4
O2—H2—O1a	135.18	C8—C7—H7a	108.1
O3—H3—O1a	129.02	C8—C7—H7b	108.5
O4—H4—O1a	135.13	H7a—C7—H7b	109.8
O2—H2—O2a	149.58	N1—C8—C7	113.5 (3)
O3—H3—O7a	106.28	N1—C8—H8a	108.7
O1—Cd—O2	70.03 (7)	N1—C8—H8b	108.0
O1—Cd—O3	111.57 (7)	C7—C8—H8a	108.7
O1—Cd—O4	67.61 (7)	C7—C8—H8b	108.3
O1—Cd—N1	66.37 (9)	H8a—C8—H8b	109.6
O1—Cd—N2	99.05 (10)	N1—C11—C12	114.3 (3)
O1—Cd—N3	169.13 (10)	N1—C11—H11a	108.6
O1—Cd—N4	116.65 (10)	N1—C11—H11b	107.7
O2—Cd—O3	70.13 (8)	C12—C11—H11a	109.0
O2—Cd—O4	103.08 (7)	C12—C11—H11b	107.8
O2—Cd—N1	119.11 (10)	H11a—C11—H11b	109.5
O2—Cd—N2	71.39 (7)	O1—C12—C11	106.0 (3)
O2—Cd—N3	99.86 (10)	O1—C12—C13	113.3 (3)
O2—Cd—N4	166.22 (9)	O1—C12—H12	109.9
O3—Cd—O4	70.37 (8)	C11—C12—C13	108.5 (3)
O3—Cd—N1	166.74 (10)	C11—C12—H12	112.7
O3—Cd—N2	117.23 (11)	C13—C12—H12	106.6
O3—Cd—N3	66.95 (9)	C12—C13—H13a	109.1
O3—Cd—N4	96.09 (10)	C12—C13—H13b	109.6
O4—Cd—N1	97.41 (9)	C12—C13—H13c	109.6
O4—Cd—N2	166.66 (10)	H13a—C13—H13b	109.2
O4—Cd—N3	120.02 (9)	H13a—C13—H13c	109.6
O4—Cd—N4	70.70 (8)	H13b—C13—H13c	109.8
N1—Cd—N2	75.79 (12)	N2—C21—C22	113.7 (3)
N1—Cd—N3	117.67 (11)	N2—C21—H21a	108.6
N1—Cd—N4	74.40 (12)	N2—C21—H21b	108.4
N2—Cd—N3	73.25 (12)	C22—C21—H21a	108.4
N2—Cd—N4	117.29 (7)	C22—C21—H21b	108.5
N3—Cd—N4	74.10 (12)	H21a—C21—H21b	109.1
Cd—O1—C12	103.6 (2)	O2—C22—C21	105.4 (3)
Cd—O1—H1	110.99	O2—C22—C23	112.1 (3)
C12—O1—H1	109.8	O2—C22—H22	110.4
Cd—O2—C22	111.50 (17)	C21—C22—C23	109.5 (3)
Cd—O2—H2	109.82	C21—C22—H22	113.1
C22—O2—H2	106.6	C23—C22—H22	106.4
Cd—O3—C32	110.1 (2)	C22—C23—H23a	109.6
Cd—O3—H3	112.19	C22—C23—H23b	109.5
C32—O3—H3	101.7	C22—C23—H23c	109.3
Cd—O4—C42	110.57 (16)	H23a—C23—H23b	109.5
Cd—O4—H4	113.37	H23a—C23—H23c	109.4
C42—O4—H4	102.9	H23b—C23—H23c	109.5
Cd—N1—C1	104.9 (2)	N3—C31—C32	112.0 (4)
Cd—N1—C8	108.4 (2)	N3—C31—H31a	108.5
Cd—N1—C11	115.8 (2)	N3—C31—H31b	109.0
C1—N1—C8	110.5 (3)	C32—C31—H31a	109.1
C1—N1—C11	109.1 (3)	C32—C31—H31b	109.3
C8—N1—C11	108.1 (3)	H31a—C31—H31b	109.0
Cd—N2—C2	107.1 (2)	O3—C32—C31	104.5 (3)
Cd—N2—C3	109.5 (2)	O3—C32—C33	112.9 (3)
Cd—N2—C21	109.91 (16)	O3—C32—H32	111.2
C2—N2—C3	110.0 (2)	C31—C32—C33	110.8 (4)
C2—N2—C21	110.4 (3)	C31—C32—H32	112.7
C3—N2—C21	109.9 (3)	C33—C32—H32	104.9
Cd—N3—C4	108.2 (2)	C32—C33—H33a	109.0
Cd—N3—C5	106.0 (2)	C32—C33—H33b	108.8
Cd—N3—C31	113.3 (2)	C32—C33—H33c	109.6
C4—N3—C5	110.3 (3)	H33a—C33—H33b	109.3
C4—N3—C31	109.3 (3)	H33a—C33—H33c	110.4
C5—N3—C31	109.7 (3)	H33b—C33—H33c	109.7
Cd—N4—C6	108.7 (2)	N4—C41—C42	111.9 (3)
Cd—N4—C7	107.6 (2)	N4—C41—H41a	108.9
Cd—N4—C41	110.14 (17)	N4—C41—H41b	108.6
C6—N4—C7	110.5 (2)	C42—C41—H41a	109.0
C6—N4—C41	109.5 (3)	C42—C41—H41b	109.0
C7—N4—C41	110.4 (3)	H41a—C41—H41b	109.5
O2a—N1a—O3a	122.0 (3)	O4—C42—C41	105.0 (2)
O2a—N1a—C2a	119.1 (3)	O4—C42—C43	112.7 (3)
O3a—N1a—C2a	118.8 (3)	O4—C42—H42	110.7
O5a—N2a—O4a	124.1 (3)	C41—C42—C43	110.3 (3)
O5a—N2a—C4a	117.3 (3)	C41—C42—H42	112.8
O4a—N2a—C4a	118.6 (3)	C43—C42—H42	105.5
O7a—N3a—O6a	121.0 (4)	C42—C43—H43a	109.8
O7a—N3a—C6a	120.2 (3)	C42—C43—H43b	110.0
O6a—N3a—C6a	118.9 (4)	C42—C43—H43c	108.9
O2b—N1b—O3b	122.7 (4)	H43a—C43—H43b	110.4
O2b—N1b—C2b	118.7 (3)	H43a—C43—H43c	108.8
O3b—N1b—C2b	118.6 (3)	H43b—C43—H43c	109.0
O5b—N2b—O4b	123.9 (3)	O1a—C1a—C2a	124.3 (3)
O5b—N2b—C4b	117.3 (4)	O1a—C1a—C6a	124.2 (3)
O4b—N2b—C4b	118.8 (4)	C2a—C1a—C6a	111.6 (2)
O7b—N3b—O6b	121.6 (4)	N1a—C2a—C1a	120.0 (3)
O7b—N3b—C6b	120.2 (3)	N1a—C2a—C3a	115.5 (3)
O6b—N3b—C6b	118.2 (3)	C1a—C2a—C3a	124.5 (3)
N1—C1—C2	112.8 (3)	C2a—C3a—C4a	118.8 (3)
N1—C1—H1a	108.9	C2a—C3a—H3a'	120.7
N1—C1—H1b	108.8	C4a—C3a—H3a'	120.5
C2—C1—H1a	108.3	N2a—C4a—C3a	117.7 (3)
C2—C1—H1b	108.6	N2a—C4a—C5a	120.4 (3)
H1a—C1—H1b	109.4	C3a—C4a—C5a	121.8 (3)
N2—C2—C1	111.8 (3)	C4a—C5a—C6a	119.6 (3)
N2—C2—H2a	108.3	C4a—C5a—H5a'	120.8
N2—C2—H2b	108.9	C6a—C5a—H5a'	119.6
C1—C2—H2a	109.1	N3a—C6a—C1a	120.6 (3)
C1—C2—H2b	109.4	N3a—C6a—C5a	115.7 (3)
H2a—C2—H2b	109.4	C1a—C6a—C5a	123.6 (3)
N2—C3—C4	112.5 (3)	O1b—C1b—C2b	122.8 (3)
N2—C3—H3a	108.9	O1b—C1b—C6b	125.6 (3)
N2—C3—H3b	109.1	C2b—C1b—C6b	111.5 (3)
C4—C3—H3a	108.5	N1b—C2b—C1b	117.0 (3)
C4—C3—H3b	108.5	N1b—C2b—C3b	117.2 (3)
H3a—C3—H3b	109.4	C1b—C2b—C3b	125.7 (3)
N3—C4—C3	112.5 (3)	C2b—C3b—C4b	117.1 (4)
N3—C4—H4a	108.7	C2b—C3b—H3b'	121.3
N3—C4—H4b	108.9	C4b—C3b—H3b'	121.6
C3—C4—H4a	108.6	N2b—C4b—C3b	118.2 (3)
C3—C4—H4b	108.6	N2b—C4b—C5b	120.2 (3)
H4a—C4—H4b	109.4	C3b—C4b—C5b	121.6 (3)
N3—C5—C6	112.0 (3)	C4b—C5b—C6b	120.5 (3)
N3—C5—H5a	108.6	C4b—C5b—H5b'	119.4
N3—C5—H5b	109.2	C6b—C5b—H5b'	120.1
C6—C5—H5a	107.9	N3b—C6b—C1b	118.7 (3)
C6—C5—H5b	108.6	N3b—C6b—C5b	118.8 (3)
H5a—C5—H5b	110.6	C1b—C6b—C5b	122.4 (3)
N4—C6—C5	112.9 (3)	N1c—C1c—C2c	179.6 (5)
N4—C6—H6a	108.7	C1c—C2c—H2ca	110.3
N4—C6—H6b	108.4	C1c—C2c—H2cb	109.4
C5—C6—H6a	108.4	C1c—C2c—H2cc	109.0
C5—C6—H6b	108.5	H2ca—C2c—H2cb	110.0
H6a—C6—H6b	109.9	H2ca—C2c—H2cc	109.6
N4—C7—C8	112.1 (3)	H2cb—C2c—H2cc	108.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1a	0.88	2.62	3.197 (4)	124
O1—H1···O1b	0.88	2.20	2.913 (3)	137
O2—H2···O1a	0.81	2.21	2.840 (3)	135
O3—H3···O1a	0.91	2.34	3.000 (4)	129
O4—H4···O1a	1.00	2.10	2.894 (3)	135