Diastereoisomeric β-ethyl aspartate–cobalt(III) complexes: Λ(+)₅₇₈- and Δ(−)₅₇₈-bis­(ethane-1,2-diamine)[β-ethyl (S)-aspartato]cobalt(III) bis­(perchlorate) monohydrate

The structures of the diastereoisomers Λ(+)₅₇₈-, (I), and Δ(−)₅₇₈-bis­(ethane-1,2-diamine)[β-ethyl (S)-aspartato-κ²N,O¹]cobalt(III) bis­(perchlorate) monohydrate, (II), both [Co(C₆H₁₀N₂O₄)(C₂H₈N₂)₂](ClO₄)₂·H₂O, are compared. In both structures, the ester group of the amino acid side chain is engaged only in intra­molecular hydrogen bonding to coordinated amine groups. This inter­action is stronger in (I) and correlates with previously observed diastereoisomeric equilibrium ratios for related metal complex systems in aqueous media. The two perchlorate anions of (II) are located on twofold axes. Both perchlorates in (I) and one of the perchlorates in (II) are affected by disorder. Both structures exhibit extensive three-dimensional hydrogen-bonding net­works.

S1. Comment

Octahedral Δ/Λ-bis(ethane-1,2-diamine)[(R/S)-α-amino acidato-N,O]cobalt(III) complexes typically comprise two stereogenic centres, the metal and the α-C atom of the amino acid. The diastereoisomeric equilibrium ratio, K_c = [(Δ-S,Λ-R)]/[(Δ-R,Λ-S)], has been determined in 0.010 M NaOH at 298 K for a number of such systems, and values vary with the coordinated amino acid: 0.67 (3) for Asp, 0.77 (2) (A₂pr), 0.85 (3) (Glu), 1.00 (2) (Ala), 1.2 (1) (Phe), 1.9 (1) (Val) (A₂pr is 2,3-diaminopropanoic acid; Buckingham et al., 1990; Barfod et al., 1999). Even though these values evince modest levels of selectivity, it is notable that K_c < 1 only for those systems which carry side chains with potential hydrogen-bond acceptor sites. Thus, in these instances the (Δ-R,Λ-S) diastereoisomer is preferred over the (Δ-S,Λ-R) diastereoisomer, whereas the opposite preference applies for systems with bulky apolar side chains. Clearly, such preferences (in solution) are governed to a large extent by a number of intramolecular interactions, but at present it is unclear which interactions are decisive in determining these preferences. Crystal structures of relevant complexes, for example Λ(+)₄₉₅-[Co(en)₂{S-Glu(O^-)O}]ClO₄ (Gillard et al., 1970), Λ(+)₅₇₈-[Co(en)₂{S-Asp(OH)O}](ClO₄)₂ (Barfod et al., 1999) and rac-(Δ-R,Λ-S)-\[Co(en)₂{O₂CCH(CH[CO₂Et]₂)NH₂}](ClO₄)₂ (Bendahl et al., 2002), reveal firm intramolecular hydrogen-bonding interactions from coordinated ligand amine groups to side-chain acceptor sites. However, in the structure of the asparagine complex, Λ-[Co(en)₂(S-AsnO)]I_1.6(NO₃)_0.4, the amino acid side chain is not engaged in intramolecular hydrogen bonding with coordinated ethane-1,2-diamine (Keyes et al., 1976). These structures each represent only one of two possible diastereoisomers and, incidentally, this is the thermodynamically favoured diastereoisomer (Δ-R,Λ-S) in all four instances. Investigations aimed at elucidating the origins of the stability preferences observed in solution for such systems through structural comparison of both diastereoisomers have not yet been published.

The title β-ethyl-(S)-aspartate complexes, (I), Λ-form, and (II), Δ-form, constitute such a diastereoisomeric pair. The crystals of (I) and (II) are constitutionally identical, thus providing an optimal basis for comparison. The two structures are illustrated in Figs. 1 and 2, respectively, and selected interatomic distances are given in Tables 1 and 3.

Both structures are characterized by extensive three-dimensional hydrogen-bonding networks (Tables 2 and 4), the only hydrogen-bond donors being the coordinated primary amine groups and the water molecules. The amino acid side chain carries only one hydrogen-bond acceptor, namely the ester carbonyl-O atom, but this is not engaged in intermolecular hydrogen bonding. Thus, it is noteworthy that in both structures the ester carbonyl-O atoms are only intramolecularly hydrogen-bonded to the amine group of the amino acid ligand and to the nearest amine group of one ethane-1,2-diamine ligand (Fig. 3). The interaction of the ester carbonyl with the amine of the amino acid ligand results in similar N1···O3 distances in both structures, but the two structures differ with respect to the intramolecular hydrogen-bonding to the nearest ethane-1,2-diamine ligand. Whereas the N11···O3(carbonyl) distances are identical in the two structures, the associated H11···O3 distances are notably different [in (I), H11B···O3 = 2.15 Å; in (II), H11A···O3 = 2.48 Å]. From Fig. 3(a) it is evident that the ethane-1,2-diamine chelate is optimally positioned relative to the amino acid ligand, pointing the N11—H11B bond almost directly towards the ester carbonyl atom O3, allowing the shorter, almost linear, hydrogen bond, consistent with a stronger interaction (Jeffrey, 1997). This is a consequence of the (Λ-S) relative absolute configuration of the complex of this structure. By contrast, in (II), the (Δ-S) relative configuration (Fig. 3b), neither of the relevant ethane-1,2-diamine N11—H11 bonds points directly towards the ester carbonyl-O atom in a manner similar to the situation for (I). This supports the notion that (I) displays the stronger interaction.

Even though the diastereoisomeric equilibrium ratio has not been determined in water for the two molecular diastereoisomers of this study (the ester would hydrolyse in the basic conditions required for attaining equilibrium), the observed structural features implying (I) to be the more stable diastereoisomer correlate with the stereochemical preferences observed in aqueous equilibrium studies of complexes bearing polar side chains, as outlined in the introduction (Buckingham et al., 1990; Barfod et al., 1999). The decisive hydrogen-bonding interactions of the amino acid side chains of (I) and (II) are all intramolecular and evidently not much governed by the `intermolecular' situation within the crystal structure. Thus, the present structures may serve to identify the likely decisive interaction governing the generally observed preferences in solution in the case of similar amino acid complexes with hydrogen-bond accepting side chains. The fact that amino acid complexes with nonpolar side chains display the opposite diastereoisomer stability preference remains unexplained, but since they lack hydrogen-bond acceptors in the side chains, weaker interactions must apply in these instances.

The insight provided by the present study is important for future application of the cis-bis(ethane-1,2-diamine)cobalt(III) moiety as a `chiral handle' in stereoselective syntheses of amino acids (Hammershøi et al., 1984; Curtis et al., 1987; Drok et al., 1993; Bendahl et al., 1996, 2002; Laval et al., 2002).

S2. Experimental

Complexes (I) and (II) were synthesized as described by Barfod et al. (1999). Caution! Although we experienced no difficulty with the perchlorate salts described here, these should be treated as potentially explosive and handled accordingly. [Crystallization from which solvent?]

S3. Refinement

The data set of (I) obtained at 298 K was chosen for refinement, since crystals of (I) disintegrated upon cooling to ~253 K and a tentative data set collected at 273 K showed signs of deterioration, evidenced by data of poor quality.

For both structures, H atoms were located in difference Fourier maps and were included in the refinement as constrained idealized H atoms riding the parent atom, with C—H = 0.96 (CH₃), 0.97 (CH₂) or 0.98 Å (CH) and N—H = 0.90 Å in (I), and C—H = 0.98 (CH₃), 0.99 (CH₂) or 1.00 Å (CH) and N—H = 0.92 Å in (II), and with U_iso(H) = 1.2U_eq(C,N). In the final refinement, the coordinates of the H atoms of the solvent water molecule in (I) had to be fixed, with O—H = 0.85 and 0.86 Å, and with U_iso(H) = 1.2U_eq(O). The H atoms of the solvent water molecule in (II) were refined as semi-free with a distance restraint, and with U_iso(H) = 1.2U_eq(O).

Both perchlorate anions of (I) are disordered. The disorder was resolved by refining two of the O atoms on Cl1 in two positions, with site-occupancy factors of 0.546 (9) and 0.454 (9). In the case of the second perchlorate ion, the entire anion was refined in two positions, with site-occupancy factors of 0.596 (9) and 0.404 (9) and with equal anisotropic displacement parameters for all O atoms. Furthermore, the perchlorates were restrained in an approximate tetrahedral geometry.

In (II), the Cl1 perchlorate anion is in a general position, but the other two, centred at Cl2 and Cl3, are located on the crystallographic twofold axis. [Please check rephrasing] Furthermore, one of these perchlorates is disordered. This disorder was resolved by refining the O atoms on Cl3 in two positions, with site-occupancy factors of 0.565 (13) and 0.435 (13).

Computing details

For both compounds, data collection: COLLECT (Nonius, 1999); cell refinement: COLLECT (Nonius, 1999); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. A view of the molecular structure of (I), with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. The disordered parts of the anions have been omitted for clarity. Dotted lines illustrate the intramolecular hydrogen bonds.
	Fig. 2. A view of the molecular structure of (II), with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. The disordered parts of the anions have been omitted for clarity. Dotted lines illustrate the intramolecular hydrogen bonds. [Symmetry code: (i) y, x, -z.]
	Fig. 3. Highlighted views of the hydrogen bond between the ester carbonyl and the amine of the amino acid ligand in (a) (I) and (b) (II).

(I) Λ(+)₅₇₈-bis(ethane-1,2-diamine)[β-ethyl (S)-aspartato- κ²N,O¹]cobalt(III) bis(perchlorate) monohydrate

Crystal data

[Co(C6H10N2O4)(C2H8N2)2](ClO4)2·H2O	F(000) = 576
Mr = 556.20	Dx = 1.685 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 12384 reflections
a = 11.6507 (4) Å	θ = 1.9–27.5°
b = 8.7600 (5) Å	µ = 1.10 mm^−1
c = 11.7169 (6) Å	T = 298 K
β = 113.572 (4)°	Prism, orange
V = 1096.04 (9) Å^3	0.35 × 0.14 × 0.13 mm
Z = 2

Data collection

Nonius KappaCCD area-detector diffractometer	4996 independent reflections
Radiation source: fine-focus sealed tube	4684 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ω and ϕ scans	θmax = 27.5°, θmin = 1.9°
Absorption correction: integration (Gaussian integration; Coppens, 1970)	h = −15→15
Tmin = 0.675, Tmax = 0.898	k = −11→11
31975 measured reflections	l = −15→15

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)] = 0.045	H-atom parameters constrained
wR(F^2) = 0.139	w = 1/[σ^2(Fo^2) + (0.0895P)^2 + 0.7174P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.016
4996 reflections	Δρmax = 0.57 e Å^−3
285 parameters	Δρmin = −0.36 e Å^−3
161 restraints	Absolute structure: Flack (1983), 2329 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (2)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co1	0.38979 (4)	0.09231 (6)	0.75245 (4)	0.03511 (14)
N1	0.2259 (3)	0.1929 (4)	0.6896 (3)	0.0442 (7)
H1A	0.1924	0.1922	0.6058	0.053*
H1B	0.1738	0.1425	0.7161	0.053*
O1	0.4469 (2)	0.2621 (3)	0.8588 (2)	0.0385 (5)
O2	0.3829 (3)	0.4753 (4)	0.9194 (3)	0.0492 (7)
O3	0.1704 (5)	0.2077 (6)	0.9104 (4)	0.0808 (13)
C1	0.2417 (4)	0.3527 (5)	0.7357 (4)	0.0403 (8)
H1	0.2469	0.4184	0.6703	0.048*
C2	0.3641 (4)	0.3658 (5)	0.8484 (4)	0.0374 (8)
C3	0.1317 (4)	0.4078 (6)	0.7641 (5)	0.0531 (10)
H3A	0.1405	0.5164	0.7816	0.064*
H3B	0.0544	0.3920	0.6915	0.064*
C4	0.1243 (5)	0.3265 (8)	0.8718 (6)	0.0632 (13)
O4	0.0557 (7)	0.4030 (8)	0.9200 (6)	0.115 (2)
C5	0.0527 (8)	0.3507 (18)	1.0389 (11)	0.143 (5)
H5A	0.0812	0.4305	1.1014	0.171*
H5B	0.1048	0.2611	1.0701	0.171*
C6	−0.0840 (9)	0.313 (2)	1.0054 (15)	0.160 (6)
H6A	−0.0959	0.2873	1.0795	0.192*
H6B	−0.1082	0.2286	0.9487	0.192*
H6C	−0.1346	0.4005	0.9667	0.192*
N11	0.3570 (3)	−0.0125 (4)	0.8841 (3)	0.0447 (7)
H11A	0.4248	−0.0062	0.9565	0.054*
H11B	0.2923	0.0322	0.8945	0.054*
C12	0.3274 (7)	−0.1741 (7)	0.8490 (7)	0.0721 (17)
H12A	0.4041	−0.2333	0.8761	0.087*
H12B	0.2757	−0.2150	0.8892	0.087*
C13	0.2610 (7)	−0.1850 (8)	0.7137 (8)	0.0796 (19)
H13A	0.2592	−0.2905	0.6878	0.095*
H13B	0.1752	−0.1508	0.6892	0.095*
N14	0.3232 (4)	−0.0914 (5)	0.6529 (4)	0.0538 (9)
H14A	0.2684	−0.0652	0.5762	0.065*
H14B	0.3859	−0.1446	0.6454	0.065*
N15	0.5623 (3)	0.0169 (4)	0.8201 (3)	0.0423 (7)
H15A	0.5956	0.0245	0.9037	0.051*
H15B	0.5638	−0.0819	0.7996	0.051*
C16	0.6357 (4)	0.1103 (8)	0.7673 (5)	0.0570 (12)
H16A	0.7129	0.0585	0.7780	0.068*
H16B	0.6564	0.2084	0.8090	0.068*
C17	0.5562 (5)	0.1317 (6)	0.6326 (4)	0.0553 (11)
H17A	0.5456	0.0354	0.5887	0.066*
H17B	0.5949	0.2041	0.5962	0.066*
N18	0.4328 (4)	0.1904 (5)	0.6235 (3)	0.0460 (8)
H18A	0.3734	0.1697	0.5476	0.055*
H18B	0.4366	0.2923	0.6342	0.055*
Cl1	0.41478 (12)	0.0984 (2)	0.27769 (12)	0.0647 (3)
O11	0.4149 (6)	0.2379 (5)	0.3358 (6)	0.0981 (17)
O12	0.5408 (5)	0.0408 (7)	0.3286 (6)	0.1060 (19)
O13	0.3969 (12)	0.1455 (15)	0.1491 (8)	0.115 (2)	0.549 (10)
O14	0.3244 (12)	−0.0029 (13)	0.2696 (11)	0.115 (2)	0.549 (10)
O13A	0.3642 (16)	0.062 (2)	0.1538 (12)	0.115 (2)	0.451 (10)
O14A	0.3617 (16)	−0.004 (2)	0.3452 (13)	0.115 (2)	0.451 (10)
Cl2	−0.1103 (7)	0.0471 (14)	0.5991 (7)	0.085 (2)	0.602 (9)
O21	−0.0653 (14)	0.060 (3)	0.5078 (11)	0.180 (3)	0.602 (9)
O22	−0.0066 (10)	0.040 (2)	0.7161 (10)	0.180 (3)	0.602 (9)
O23	−0.1975 (15)	−0.074 (2)	0.5713 (14)	0.180 (3)	0.602 (9)
O24	−0.1681 (13)	0.1870 (19)	0.6051 (13)	0.180 (3)	0.602 (9)
Cl2A	−0.0974 (11)	0.005 (2)	0.6039 (11)	0.089 (4)	0.398 (9)
O21A	−0.043 (2)	0.074 (4)	0.5342 (18)	0.180 (3)	0.398 (9)
O22A	−0.0333 (17)	−0.120 (3)	0.6786 (17)	0.180 (3)	0.398 (9)
O23A	−0.2246 (16)	−0.026 (4)	0.5256 (18)	0.180 (3)	0.398 (9)
O24A	−0.1168 (17)	0.100 (3)	0.6964 (16)	0.180 (3)	0.398 (9)
O10	0.1670 (5)	0.0841 (12)	0.4106 (5)	0.127 (2)
H10A	0.2168	0.0579	0.3764	0.152*
H10B	0.1789	0.1801	0.4228	0.152*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0371 (2)	0.0355 (2)	0.0305 (2)	−0.0014 (2)	0.01125 (15)	−0.0046 (2)
N1	0.0375 (15)	0.0494 (19)	0.0387 (15)	−0.0014 (14)	0.0078 (13)	−0.0043 (14)
O1	0.0386 (13)	0.0380 (13)	0.0337 (12)	0.0008 (11)	0.0091 (10)	−0.0054 (10)
O2	0.0606 (17)	0.0422 (15)	0.0437 (15)	0.0026 (13)	0.0196 (13)	−0.0089 (12)
O3	0.097 (3)	0.088 (3)	0.080 (3)	0.031 (3)	0.059 (3)	0.027 (2)
C1	0.0403 (19)	0.043 (2)	0.0369 (18)	0.0036 (16)	0.0145 (15)	0.0008 (15)
C2	0.0416 (19)	0.0361 (18)	0.0338 (17)	−0.0035 (15)	0.0143 (15)	−0.0011 (14)
C3	0.044 (2)	0.058 (3)	0.058 (2)	0.0091 (19)	0.0215 (19)	0.002 (2)
C4	0.049 (2)	0.080 (4)	0.068 (3)	0.005 (2)	0.031 (2)	0.002 (3)
O4	0.142 (5)	0.128 (5)	0.124 (5)	0.055 (4)	0.104 (4)	0.028 (4)
C5	0.091 (6)	0.229 (16)	0.132 (9)	−0.010 (8)	0.070 (6)	−0.026 (10)
C6	0.135 (10)	0.157 (11)	0.184 (15)	−0.035 (8)	0.061 (10)	0.023 (10)
N11	0.0488 (18)	0.0401 (17)	0.0473 (18)	0.0017 (14)	0.0216 (15)	0.0027 (14)
C12	0.095 (5)	0.046 (3)	0.082 (4)	−0.019 (3)	0.042 (4)	−0.004 (3)
C13	0.083 (4)	0.060 (3)	0.101 (5)	−0.030 (3)	0.042 (4)	−0.029 (3)
N14	0.059 (2)	0.046 (2)	0.051 (2)	−0.0029 (17)	0.0155 (17)	−0.0162 (17)
N15	0.0442 (16)	0.0424 (17)	0.0405 (16)	0.0044 (14)	0.0171 (13)	−0.0025 (14)
C16	0.0453 (19)	0.065 (4)	0.064 (2)	0.004 (2)	0.0257 (18)	0.002 (3)
C17	0.066 (3)	0.058 (3)	0.056 (2)	0.0075 (19)	0.039 (2)	0.0037 (18)
N18	0.0554 (19)	0.0492 (19)	0.0339 (15)	0.0003 (15)	0.0182 (14)	0.0002 (14)
Cl1	0.0729 (6)	0.0564 (6)	0.0657 (6)	0.0045 (9)	0.0286 (5)	−0.0010 (8)
O11	0.138 (5)	0.059 (3)	0.114 (4)	0.013 (3)	0.067 (4)	0.002 (3)
O12	0.094 (3)	0.110 (5)	0.102 (4)	0.034 (3)	0.027 (3)	−0.006 (3)
O13	0.132 (5)	0.118 (5)	0.086 (3)	−0.037 (4)	0.035 (4)	−0.008 (5)
O14	0.132 (5)	0.118 (5)	0.086 (3)	−0.037 (4)	0.035 (4)	−0.008 (5)
O13A	0.132 (5)	0.118 (5)	0.086 (3)	−0.037 (4)	0.035 (4)	−0.008 (5)
O14A	0.132 (5)	0.118 (5)	0.086 (3)	−0.037 (4)	0.035 (4)	−0.008 (5)
Cl2	0.0484 (17)	0.151 (7)	0.0582 (19)	−0.014 (3)	0.0236 (14)	−0.007 (3)
O21	0.122 (4)	0.315 (10)	0.101 (4)	−0.078 (6)	0.042 (3)	−0.042 (5)
O22	0.122 (4)	0.315 (10)	0.101 (4)	−0.078 (6)	0.042 (3)	−0.042 (5)
O23	0.122 (4)	0.315 (10)	0.101 (4)	−0.078 (6)	0.042 (3)	−0.042 (5)
O24	0.122 (4)	0.315 (10)	0.101 (4)	−0.078 (6)	0.042 (3)	−0.042 (5)
Cl2A	0.057 (4)	0.131 (8)	0.063 (4)	−0.017 (4)	0.008 (3)	−0.031 (4)
O21A	0.122 (4)	0.315 (10)	0.101 (4)	−0.078 (6)	0.042 (3)	−0.042 (5)
O22A	0.122 (4)	0.315 (10)	0.101 (4)	−0.078 (6)	0.042 (3)	−0.042 (5)
O23A	0.122 (4)	0.315 (10)	0.101 (4)	−0.078 (6)	0.042 (3)	−0.042 (5)
O24A	0.122 (4)	0.315 (10)	0.101 (4)	−0.078 (6)	0.042 (3)	−0.042 (5)
O10	0.105 (4)	0.188 (7)	0.072 (3)	−0.030 (6)	0.019 (3)	−0.002 (5)

Geometric parameters (Å, º)

Co1—O1	1.883 (3)	C13—N14	1.455 (8)
Co1—N1	1.960 (3)	C13—H13A	0.9700
Co1—N11	1.959 (4)	C13—H13B	0.9700
Co1—N14	1.957 (4)	N14—H14A	0.9000
Co1—N15	1.957 (3)	N14—H14B	0.9000
Co1—N18	1.969 (3)	N15—C16	1.486 (6)
N1—C1	1.485 (6)	N15—H15A	0.9000
N1—H1A	0.9000	N15—H15B	0.9000
N1—H1B	0.9000	C16—C17	1.488 (7)
O1—C2	1.294 (5)	C16—H16A	0.9700
O2—C2	1.231 (5)	C16—H16B	0.9700
O3—C4	1.176 (8)	C17—N18	1.491 (6)
C1—C2	1.511 (6)	C17—H17A	0.9700
C1—C3	1.525 (6)	C17—H17B	0.9700
C1—H1	0.9800	N18—H18A	0.9000
C3—C4	1.481 (7)	N18—H18B	0.9000
C3—H3A	0.9700	Cl1—O14	1.351 (9)
C3—H3B	0.9700	Cl1—O13A	1.369 (13)
C4—O4	1.330 (7)	Cl1—O11	1.398 (5)
O4—C5	1.480 (13)	Cl1—O12	1.437 (5)
C5—C6	1.516 (5)	Cl1—O14A	1.484 (14)
C5—H5A	0.9700	Cl1—O13	1.494 (9)
C5—H5B	0.9700	Cl2—O21	1.371 (11)
C6—H6A	0.9600	Cl2—O24	1.414 (13)
C6—H6B	0.9600	Cl2—O23	1.416 (12)
C6—H6C	0.9600	Cl2—O22	1.421 (11)
N11—C12	1.477 (7)	Cl2A—O21A	1.362 (13)
N11—H11A	0.9000	Cl2A—O22A	1.418 (14)
N11—H11B	0.9000	Cl2A—O23A	1.423 (13)
C12—C13	1.463 (11)	Cl2A—O24A	1.454 (14)
C12—H12A	0.9700	O10—H10A	0.860
C12—H12B	0.9700	O10—H10B	0.860
O1—Co1—N15	87.98 (13)	H12A—C12—H12B	108.3
O1—Co1—N14	174.39 (16)	N14—C13—C12	110.0 (5)
N15—Co1—N14	93.56 (16)	N14—C13—H13A	109.7
O1—Co1—N11	88.69 (14)	C12—C13—H13A	109.7
N15—Co1—N11	90.84 (15)	N14—C13—H13B	109.7
N14—Co1—N11	85.89 (17)	C12—C13—H13B	109.7
O1—Co1—N1	85.79 (13)	H13A—C13—H13B	108.2
N15—Co1—N1	172.98 (16)	C13—N14—Co1	109.2 (3)
N14—Co1—N1	92.95 (16)	C13—N14—H14A	109.8
N11—Co1—N1	92.24 (16)	Co1—N14—H14A	109.8
O1—Co1—N18	91.85 (14)	C13—N14—H14B	109.8
N15—Co1—N18	85.60 (15)	Co1—N14—H14B	109.8
N14—Co1—N18	93.65 (17)	H14A—N14—H14B	108.3
N11—Co1—N18	176.37 (17)	C16—N15—Co1	108.3 (3)
N1—Co1—N18	91.38 (16)	C16—N15—H15A	110.0
C1—N1—Co1	109.1 (2)	Co1—N15—H15A	110.0
C1—N1—H1A	109.9	C16—N15—H15B	110.0
Co1—N1—H1A	109.9	Co1—N15—H15B	110.0
C1—N1—H1B	109.9	H15A—N15—H15B	108.4
Co1—N1—H1B	109.9	N15—C16—C17	107.1 (4)
H1A—N1—H1B	108.3	N15—C16—H16A	110.3
C2—O1—Co1	116.1 (2)	C17—C16—H16A	110.3
N1—C1—C2	109.0 (3)	N15—C16—H16B	110.3
N1—C1—C3	112.6 (4)	C17—C16—H16B	110.3
C2—C1—C3	111.6 (4)	H16A—C16—H16B	108.6
N1—C1—H1	107.8	C16—C17—N18	107.0 (3)
C2—C1—H1	107.8	C16—C17—H17A	110.3
C3—C1—H1	107.8	N18—C17—H17A	110.3
O2—C2—O1	124.0 (4)	C16—C17—H17B	110.3
O2—C2—C1	120.0 (4)	N18—C17—H17B	110.3
O1—C2—C1	115.9 (3)	H17A—C17—H17B	108.6
C4—C3—C1	111.9 (4)	C17—N18—Co1	109.2 (3)
C4—C3—H3A	109.2	C17—N18—H18A	109.8
C1—C3—H3A	109.2	Co1—N18—H18A	109.8
C4—C3—H3B	109.2	C17—N18—H18B	109.8
C1—C3—H3B	109.2	Co1—N18—H18B	109.8
H3A—C3—H3B	107.9	H18A—N18—H18B	108.3
O3—C4—O4	122.8 (6)	O14—Cl1—O13A	77.1 (7)
O3—C4—C3	125.5 (5)	O14—Cl1—O11	117.2 (6)
O4—C4—C3	111.7 (5)	O13A—Cl1—O11	129.7 (8)
C4—O4—C5	119.3 (7)	O14—Cl1—O12	115.8 (7)
O4—C5—C6	103.9 (9)	O13A—Cl1—O12	107.0 (8)
O4—C5—H5A	111.0	O11—Cl1—O12	107.7 (4)
C6—C5—H5A	111.0	O13A—Cl1—O14A	109.2 (8)
O4—C5—H5B	111.0	O11—Cl1—O14A	100.8 (7)
C6—C5—H5B	111.0	O12—Cl1—O14A	98.1 (8)
H5A—C5—H5B	109.0	O14—Cl1—O13	108.7 (6)
C5—C6—H6A	109.5	O11—Cl1—O13	102.9 (5)
C5—C6—H6B	109.5	O12—Cl1—O13	102.9 (6)
H6A—C6—H6B	109.5	O14A—Cl1—O13	141.7 (7)
C5—C6—H6C	109.5	O21—Cl2—O24	107.8 (13)
H6A—C6—H6C	109.5	O21—Cl2—O23	110.2 (11)
H6B—C6—H6C	109.5	O24—Cl2—O23	110.5 (10)
C12—N11—Co1	109.1 (3)	O21—Cl2—O22	108.3 (9)
C12—N11—H11A	109.9	O24—Cl2—O22	103.2 (11)
Co1—N11—H11A	109.9	O23—Cl2—O22	116.3 (11)
C12—N11—H11B	109.9	O21A—Cl2A—O22A	117.1 (17)
Co1—N11—H11B	109.9	O21A—Cl2A—O23A	108.4 (14)
H11A—N11—H11B	108.3	O22A—Cl2A—O23A	113.8 (15)
C13—C12—N11	109.2 (5)	O21A—Cl2A—O24A	116.4 (17)
C13—C12—H12A	109.8	O22A—Cl2A—O24A	100.6 (14)
N11—C12—H12A	109.8	O23A—Cl2A—O24A	99.2 (13)
C13—C12—H12B	109.8	H10A—O10—H10B	104.0
N11—C12—H12B	109.8

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O3	0.90	2.36	2.909 (5)	119
N1—H1A···O10	0.90	2.38	3.205 (7)	152
N1—H1B···O22	0.90	2.29	3.147 (14)	160
N1—H1B···O21A	0.90	2.64	3.10 (2)	113
N11—H11A···O2^i	0.90	2.13	2.985 (5)	158
N11—H11B···O3	0.90	2.15	3.013 (6)	160
N14—H14A···O10	0.90	2.24	3.099 (8)	159
N15—H15A···O2^i	0.90	2.03	2.880 (5)	157
N15—H15B···O11^ii	0.90	2.32	3.127 (6)	149
N18—H18B···O12^iii	0.90	2.21	3.113 (7)	176
O10—H10A···O14	0.86	2.17	3.017 (15)	173
O10—H10A···O14A	0.86	1.95	2.778 (19)	165
O10—H10B···O23^iv	0.86	2.16	3.01 (2)	173
O10—H10B···O22A^iv	0.86	2.40	2.99 (2)	127

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

(II) Δ(-)₅₇₈-bis(ethane-1,2-diamine)[β-ethyl (S)-aspartato- κ²N,O¹]cobalt(III) bis(perchlorate) monohydrate

Crystal data

[Co(C6H10N2O4)(C2H8N2)2](ClO4)2·H2O	Dx = 1.748 Mg m^−3
Mr = 556.20	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P43212	Cell parameters from 32707 reflections
Hall symbol: P 4nw 2abw	θ = 1.7–27.5°
a = 9.2898 (3) Å	µ = 1.14 mm^−1
c = 48.9696 (14) Å	T = 122 K
V = 4226.1 (2) Å^3	Prism, orange
Z = 8	0.20 × 0.19 × 0.07 mm
F(000) = 2304

Data collection

Nonius KappaCCD area-detector diffractometer	4818 independent reflections
Radiation source: fine-focus sealed tube	4583 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.055
ω and ϕ scans	θmax = 27.5°, θmin = 2.2°
Absorption correction: integration (Gaussian integration; Coppens, 1970)	h = −12→12
Tmin = 0.810, Tmax = 0.924	k = −12→12
84126 measured reflections	l = −63→63

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)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.064	w = 1/[σ^2(Fo^2) + (0.0298P)^2 + 3.6785P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
4818 reflections	Δρmax = 0.55 e Å^−3
302 parameters	Δρmin = −0.87 e Å^−3
5 restraints	Absolute structure: Flack (1983), with 1893 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.017 (11)

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)
Co1	0.23045 (3)	0.56261 (3)	0.085906 (5)	0.00832 (6)
N1	0.09632 (18)	0.54275 (18)	0.11644 (3)	0.0103 (3)
H1A	0.0035	0.5560	0.1104	0.012*
H1B	0.1033	0.4518	0.1237	0.012*
O1	0.33189 (15)	0.69449 (15)	0.10829 (3)	0.0098 (3)
O2	0.34389 (16)	0.78129 (16)	0.15067 (3)	0.0131 (3)
O3	0.27508 (19)	0.41040 (18)	0.15997 (3)	0.0220 (4)
O4	0.16021 (17)	0.43102 (18)	0.20028 (3)	0.0191 (3)
C1	0.1315 (2)	0.6519 (2)	0.13766 (4)	0.0090 (4)
H1	0.0636	0.7338	0.1345	0.011*
C2	0.2815 (2)	0.7120 (2)	0.13273 (4)	0.0095 (4)
C3	0.1033 (2)	0.6007 (2)	0.16663 (4)	0.0124 (4)
H3A	0.1252	0.6802	0.1794	0.015*
H3B	−0.0002	0.5774	0.1685	0.015*
C4	0.1903 (2)	0.4709 (2)	0.17465 (4)	0.0132 (4)
C5	0.2501 (3)	0.3192 (3)	0.21218 (5)	0.0253 (5)
H5A	0.2745	0.2469	0.1981	0.030*
H5B	0.1967	0.2698	0.2270	0.030*
C6	0.3853 (3)	0.3835 (3)	0.22345 (6)	0.0365 (7)
H6A	0.4447	0.3075	0.2315	0.044*
H6B	0.3608	0.4546	0.2375	0.044*
H6C	0.4389	0.4307	0.2087	0.044*
N11	0.35455 (18)	0.41039 (19)	0.10045 (3)	0.0120 (3)
H11A	0.4016	0.4433	0.1158	0.014*
H11B	0.2993	0.3324	0.1054	0.014*
C12	0.4613 (2)	0.3662 (2)	0.07960 (4)	0.0167 (4)
H12A	0.4164	0.3016	0.0660	0.020*
H12B	0.5430	0.3151	0.0882	0.020*
C13	0.5120 (2)	0.5037 (2)	0.06626 (5)	0.0160 (4)
H13A	0.5701	0.5611	0.0793	0.019*
H13B	0.5720	0.4817	0.0501	0.019*
N14	0.38064 (18)	0.5852 (2)	0.05796 (3)	0.0133 (3)
H14A	0.3476	0.5513	0.0415	0.016*
H14B	0.4028	0.6812	0.0559	0.016*
N15	0.11508 (18)	0.4312 (2)	0.06352 (3)	0.0134 (3)
H15A	0.1711	0.3930	0.0498	0.016*
H15B	0.0815	0.3566	0.0741	0.016*
C16	−0.0088 (2)	0.5115 (3)	0.05141 (5)	0.0200 (5)
H16A	−0.0893	0.5163	0.0646	0.024*
H16B	−0.0431	0.4623	0.0347	0.024*
C17	0.0432 (2)	0.6613 (2)	0.04456 (4)	0.0177 (4)
H17A	0.1108	0.6582	0.0289	0.021*
H17B	−0.0391	0.7238	0.0396	0.021*
N18	0.11710 (19)	0.71749 (19)	0.06940 (3)	0.0123 (3)
H18A	0.0500	0.7506	0.0817	0.015*
H18B	0.1764	0.7929	0.0647	0.015*
Cl1	0.17332 (5)	0.07588 (6)	0.103024 (11)	0.01638 (11)
O11	0.09154 (17)	−0.04003 (16)	0.11450 (3)	0.0192 (3)
O12	0.3110 (2)	0.0861 (2)	0.11591 (5)	0.0457 (6)
O13	0.09670 (17)	0.20982 (16)	0.10747 (3)	0.0203 (3)
O14	0.1915 (3)	0.0541 (2)	0.07447 (4)	0.0501 (6)
Cl2	0.2925	0.2925	0.0000	0.01723 (15)
O21	0.2552 (2)	0.2067 (2)	0.02326 (3)	0.0304 (4)
O22	0.2681 (2)	0.4413 (2)	0.00661 (4)	0.0345 (5)
Cl3	0.6703	0.6703	0.0000	0.01984 (15)
O31	0.7031 (4)	0.7125 (8)	0.02820 (12)	0.0405 (19)	0.565 (13)
O32	0.5347 (8)	0.7266 (10)	−0.00668 (14)	0.060 (2)	0.565 (13)
O31X	0.7162 (9)	0.7846 (10)	0.0157 (2)	0.069 (3)	0.435 (13)
O32X	0.5181 (8)	0.6563 (15)	0.00084 (16)	0.066 (3)	0.435 (13)
O10	0.3470 (2)	0.8751 (2)	0.03275 (4)	0.0290 (4)
H10A	0.416 (3)	0.868 (3)	0.0229 (5)	0.035*
H10B	0.330 (4)	0.961 (2)	0.0329 (6)	0.035*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.00788 (13)	0.00886 (13)	0.00820 (11)	−0.00048 (10)	0.00033 (10)	−0.00106 (10)
N1	0.0077 (8)	0.0118 (8)	0.0115 (7)	−0.0008 (6)	0.0001 (6)	−0.0004 (6)
O1	0.0092 (6)	0.0099 (7)	0.0104 (6)	−0.0006 (5)	0.0013 (5)	−0.0006 (5)
O2	0.0120 (7)	0.0145 (7)	0.0128 (7)	−0.0010 (6)	−0.0011 (6)	−0.0029 (6)
O3	0.0286 (9)	0.0228 (8)	0.0147 (7)	0.0125 (7)	0.0034 (7)	0.0017 (6)
O4	0.0224 (8)	0.0223 (8)	0.0126 (7)	0.0034 (7)	0.0018 (6)	0.0051 (6)
C1	0.0087 (9)	0.0087 (9)	0.0094 (8)	0.0002 (7)	−0.0001 (7)	−0.0003 (7)
C2	0.0098 (9)	0.0075 (8)	0.0112 (9)	0.0036 (7)	−0.0013 (7)	0.0007 (7)
C3	0.0135 (10)	0.0129 (10)	0.0107 (9)	0.0000 (8)	0.0018 (8)	−0.0009 (8)
C4	0.0150 (10)	0.0132 (10)	0.0114 (9)	−0.0031 (7)	−0.0009 (8)	0.0001 (8)
C5	0.0339 (14)	0.0236 (12)	0.0183 (11)	0.0052 (11)	−0.0017 (10)	0.0104 (9)
C6	0.0318 (15)	0.0465 (18)	0.0312 (14)	0.0028 (12)	−0.0121 (12)	0.0090 (13)
N11	0.0123 (8)	0.0110 (8)	0.0127 (8)	−0.0002 (6)	0.0011 (6)	−0.0008 (6)
C12	0.0158 (11)	0.0169 (10)	0.0175 (10)	0.0064 (8)	0.0020 (8)	−0.0026 (8)
C13	0.0108 (10)	0.0210 (11)	0.0161 (10)	0.0039 (8)	0.0032 (8)	−0.0010 (9)
N14	0.0133 (8)	0.0155 (9)	0.0111 (8)	−0.0003 (7)	0.0018 (6)	−0.0013 (7)
N15	0.0126 (8)	0.0149 (9)	0.0126 (8)	−0.0018 (7)	0.0009 (7)	−0.0034 (7)
C16	0.0149 (11)	0.0231 (12)	0.0220 (11)	−0.0001 (9)	−0.0065 (9)	−0.0060 (9)
C17	0.0196 (11)	0.0199 (11)	0.0136 (10)	0.0019 (9)	−0.0053 (8)	−0.0012 (8)
N18	0.0131 (8)	0.0133 (8)	0.0105 (8)	0.0006 (7)	−0.0005 (6)	−0.0011 (7)
Cl1	0.0154 (2)	0.0104 (2)	0.0233 (3)	−0.00101 (19)	0.00586 (19)	0.00234 (19)
O11	0.0191 (8)	0.0100 (7)	0.0283 (8)	−0.0009 (6)	0.0085 (7)	0.0057 (6)
O12	0.0190 (9)	0.0234 (10)	0.0948 (18)	−0.0020 (8)	−0.0185 (11)	0.0094 (11)
O13	0.0187 (8)	0.0093 (7)	0.0330 (9)	0.0012 (6)	0.0018 (7)	0.0033 (7)
O14	0.0891 (18)	0.0352 (12)	0.0260 (10)	−0.0043 (12)	0.0296 (11)	−0.0001 (9)
Cl2	0.0197 (4)	0.022	0.0102 (3)	−0.0020 (3)	0.000	0.000
O21	0.0380 (11)	0.0336 (10)	0.0196 (8)	−0.0037 (9)	0.0089 (8)	0.0074 (7)
O22	0.0552 (13)	0.0237 (9)	0.0246 (9)	0.0050 (9)	−0.0024 (8)	−0.0099 (7)
Cl3	0.0192 (4)	0.023	0.0175 (3)	0.0026 (3)	0.000	0.000
O31	0.037 (2)	0.052 (4)	0.033 (3)	0.006 (2)	−0.0103 (18)	−0.023 (3)
O32	0.048 (4)	0.094 (5)	0.039 (3)	0.048 (4)	−0.019 (3)	−0.020 (3)
O31X	0.125 (7)	0.037 (4)	0.044 (5)	−0.011 (4)	−0.019 (4)	−0.028 (4)
O32X	0.022 (3)	0.140 (9)	0.037 (3)	−0.005 (4)	0.003 (2)	0.034 (4)
O10	0.0335 (11)	0.0249 (9)	0.0287 (9)	0.0027 (8)	−0.0006 (8)	0.0042 (8)

Geometric parameters (Å, º)

Co1—O1	1.8948 (14)	C13—H13B	0.9900
Co1—N1	1.9552 (16)	N14—H14A	0.9200
Co1—N11	1.9586 (17)	N14—H14B	0.9200
Co1—N14	1.9655 (17)	N15—C16	1.494 (3)
Co1—N15	1.9600 (17)	N15—H15A	0.9200
Co1—N18	1.9575 (18)	N15—H15B	0.9200
N1—C1	1.488 (2)	C16—C17	1.510 (3)
N1—H1A	0.9200	C16—H16A	0.9900
N1—H1B	0.9200	C16—H16B	0.9900
O1—C2	1.296 (2)	C17—N18	1.491 (3)
O2—C2	1.234 (2)	C17—H17A	0.9900
O3—C4	1.206 (3)	C17—H17B	0.9900
C1—C2	1.521 (3)	N18—H18A	0.9200
C1—C3	1.519 (3)	N18—H18B	0.9200
C1—H1	1.0000	Cl1—O14	1.4230 (19)
C3—C4	1.503 (3)	Cl1—O12	1.429 (2)
O4—C4	1.338 (2)	Cl1—O11	1.4327 (15)
O4—C5	1.455 (3)	Cl1—O13	1.4499 (16)
C3—H3A	0.9900	Cl2—O21	1.4331 (17)
C3—H3B	0.9900	Cl2—O21^i	1.4332 (17)
C5—C6	1.496 (4)	Cl2—O22	1.4375 (18)
C5—H5A	0.9900	Cl2—O22^i	1.4375 (18)
C5—H5B	0.9900	Cl3—O31X	1.379 (5)
C6—H6A	0.9800	Cl3—O31X^i	1.379 (5)
C6—H6B	0.9800	Cl3—O32^i	1.403 (5)
C6—H6C	0.9800	Cl3—O32	1.403 (5)
N11—C12	1.481 (3)	Cl3—O32X^i	1.421 (7)
N11—H11A	0.9200	Cl3—O32X	1.421 (7)
N11—H11B	0.9200	Cl3—O31	1.468 (4)
C12—C13	1.510 (3)	Cl3—O31^i	1.468 (4)
C12—H12A	0.9900	O31X—O31X^i	1.784 (16)
C12—H12B	0.9900	O32X—O32X^i	1.82 (2)
C13—N14	1.493 (3)	O10—H10A	0.802 (18)
C13—H13A	0.9900	O10—H10B	0.814 (18)
O1—Co1—N1	86.31 (6)	H13A—C13—H13B	108.6
O1—Co1—N18	91.78 (7)	C13—N14—Co1	109.68 (13)
N1—Co1—N18	92.43 (7)	C13—N14—H14A	109.7
O1—Co1—N11	87.92 (7)	Co1—N14—H14A	109.7
N1—Co1—N11	91.66 (7)	C13—N14—H14B	109.7
N18—Co1—N11	175.88 (7)	Co1—N14—H14B	109.7
O1—Co1—N15	176.67 (7)	H14A—N14—H14B	108.2
N1—Co1—N15	91.18 (7)	C16—N15—Co1	109.39 (14)
N18—Co1—N15	86.14 (8)	C16—N15—H15A	109.8
N11—Co1—N15	94.33 (8)	Co1—N15—H15A	109.8
O1—Co1—N14	88.88 (7)	C16—N15—H15B	109.8
N1—Co1—N14	174.23 (7)	Co1—N15—H15B	109.8
N18—Co1—N14	90.91 (8)	H15A—N15—H15B	108.2
N11—Co1—N14	84.98 (7)	N15—C16—C17	107.57 (18)
N15—Co1—N14	93.75 (7)	N15—C16—H16A	110.2
C1—N1—Co1	109.27 (12)	C17—C16—H16A	110.2
C1—N1—H1A	109.8	N15—C16—H16B	110.2
Co1—N1—H1A	109.8	C17—C16—H16B	110.2
C1—N1—H1B	109.8	H16A—C16—H16B	108.5
Co1—N1—H1B	109.8	N18—C17—C16	106.78 (17)
H1A—N1—H1B	108.3	N18—C17—H17A	110.4
C2—O1—Co1	115.84 (13)	C16—C17—H17A	110.4
C4—O4—C5	116.99 (17)	N18—C17—H17B	110.4
N1—C1—C3	113.65 (16)	C16—C17—H17B	110.4
N1—C1—C2	109.90 (15)	H17A—C17—H17B	108.6
C3—C1—C2	114.89 (16)	C17—N18—Co1	109.09 (13)
N1—C1—H1	105.9	C17—N18—H18A	109.9
C3—C1—H1	105.9	Co1—N18—H18A	109.9
C2—C1—H1	105.9	C17—N18—H18B	109.9
O2—C2—O1	123.61 (19)	Co1—N18—H18B	109.9
O2—C2—C1	120.62 (17)	H18A—N18—H18B	108.3
O1—C2—C1	115.57 (17)	O14—Cl1—O12	109.68 (16)
C4—C3—C1	113.76 (16)	O14—Cl1—O11	109.97 (12)
C4—C3—H3A	108.8	O12—Cl1—O11	110.55 (11)
C1—C3—H3A	108.8	O14—Cl1—O13	109.15 (12)
C4—C3—H3B	108.8	O12—Cl1—O13	108.43 (11)
C1—C3—H3B	108.8	O11—Cl1—O13	109.01 (9)
H3A—C3—H3B	107.7	O21—Cl2—O21^i	111.27 (16)
O3—C4—O4	124.49 (19)	O21—Cl2—O22	108.51 (11)
O3—C4—C3	124.70 (18)	O21^i—Cl2—O22	108.89 (11)
O4—C4—C3	110.81 (17)	O21—Cl2—O22^i	108.89 (11)
O4—C5—C6	110.1 (2)	O21^i—Cl2—O22^i	108.51 (11)
O4—C5—H5A	109.6	O22—Cl2—O22^i	110.78 (17)
C6—C5—H5A	109.6	O31X—Cl3—O31X^i	80.6 (9)
O4—C5—H5B	109.6	O31X—Cl3—O32^i	116.5 (8)
C6—C5—H5B	109.6	O31X^i—Cl3—O32^i	96.9 (4)
H5A—C5—H5B	108.2	O31X—Cl3—O32	96.9 (4)
C5—C6—H6A	109.5	O31X^i—Cl3—O32	116.5 (8)
C5—C6—H6B	109.5	O32^i—Cl3—O32	136.4 (9)
H6A—C6—H6B	109.5	O31X—Cl3—O32X^i	144.2 (8)
C5—C6—H6C	109.5	O31X^i—Cl3—O32X^i	111.2 (6)
H6A—C6—H6C	109.5	O32—Cl3—O32X^i	106.4 (9)
H6B—C6—H6C	109.5	O31X—Cl3—O32X	111.2 (6)
C12—N11—Co1	110.10 (13)	O31X^i—Cl3—O32X	144.2 (8)
C12—N11—H11A	109.6	O32^i—Cl3—O32X	106.4 (9)
Co1—N11—H11A	109.6	O32—Cl3—O32X	31.5 (3)
C12—N11—H11B	109.6	O32X^i—Cl3—O32X	79.5 (11)
Co1—N11—H11B	109.6	O31X^i—Cl3—O31	106.5 (7)
H11A—N11—H11B	108.2	O32^i—Cl3—O31	86.7 (6)
N11—C12—C13	105.81 (17)	O32—Cl3—O31	107.8 (3)
N11—C12—H12A	110.6	O32X^i—Cl3—O31	108.2 (6)
C13—C12—H12A	110.6	O32X—Cl3—O31	101.8 (4)
N11—C12—H12B	110.6	O31X—Cl3—O31^i	106.5 (7)
C13—C12—H12B	110.6	O32^i—Cl3—O31^i	107.8 (3)
H12A—C12—H12B	108.7	O32—Cl3—O31^i	86.7 (6)
N14—C13—C12	106.97 (17)	O32X^i—Cl3—O31^i	101.8 (4)
N14—C13—H13A	110.3	O32X—Cl3—O31^i	108.2 (6)
C12—C13—H13A	110.3	O31—Cl3—O31^i	140.8 (6)
N14—C13—H13B	110.3	H10A—O10—H10B	104 (3)
C12—C13—H13B	110.3

Symmetry code: (i) y, x, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2^ii	0.92	2.19	2.979 (2)	144
N1—H1A···O12^iii	0.92	2.51	3.034 (3)	117
N1—H1B···O13	0.92	2.39	3.124 (2)	137
N1—H1B···O3	0.92	2.42	2.969 (2)	119
N11—H11A···O11^iv	0.92	2.20	3.040 (2)	151
N11—H11A···O3	0.92	2.48	3.007 (2)	117
N11—H11B···O13	0.92	2.20	3.054 (2)	154
N11—H11B···O12	0.92	2.35	3.133 (3)	143
N14—H14A···O22	0.92	2.12	3.034 (2)	171
N14—H14B···O10	0.92	2.19	2.979 (3)	143
N15—H15A···O21	0.92	2.30	3.151 (3)	153
N15—H15A···O22	0.92	2.34	3.129 (3)	143
N15—H15B···O13	0.92	2.13	2.982 (2)	153
N18—H18A···O2^ii	0.92	2.12	2.931 (2)	146
N18—H18A···O11^v	0.92	2.55	3.164 (2)	124
N18—H18B···O10	0.92	2.36	3.151 (3)	145
O10—H10A···O32	0.80 (2)	2.25 (2)	2.944 (6)	146 (3)
O10—H10B···O14^v	0.81 (2)	2.56 (3)	3.004 (3)	116 (3)

Symmetry codes: (ii) x−1/2, −y+3/2, −z+1/4; (iii) x−1/2, −y+1/2, −z+1/4; (iv) x+1/2, −y+1/2, −z+1/4; (v) x, y+1, z.