[(S)-1-Carbamoylethyl]bis­(dimethyl­glyoximato-κ²N,N′)[(S)-1-phenyl­ethyl­amine]cobalt(III) and bis­(dimethylglyoximato-κ²N,N′)[(R)-1-(N-methyl­carbamoyl)ethyl][(R)-1-phenyl­ethyl­amine]cobalt(III) monohydrate

The title complexes, [Co(C₃H₆NO)(C₄H₇N₂O₂)₂(C₈H₁₁N)] and [Co(C₄H₈NO)(C₄H₇N₂O₂)₂(C₈H₁₁N)]·H₂O, were resolved from [(RS)-1-carbamoylethyl]bis­(dimethyl­glyoxim­ato)[(S)-1-phenyl­ethyl­amine]cobalt(III) and bis­(di­methyl­glyoximato)[(RS)-1-(N-methyl­carbamoyl)­ethyl][(R)-1-phenyl­ethyl­amine]cobalt(III), respectively, and their crystal structures were determined in order to reveal the absolute configuration of the major enantiomer produced in the photoisomerization of each series of 2-carbamoylethyl and 2-(N-methyl­carbamoyl)ethyl cobaloxime complexes.

S1. Comment

Solid-state specific and unidirectional photoisomerization of 2-cyanoethyl, 2-methoxycarbonylethyl, 2-carbamoylethyl, 2-(N-methylcarbamoyl)ethyl and 3-substituted propyl cobaloximes have been reported previously (Ohgo & Takeuchi, 1985; Kurashima et al., 1995; Ohgo et al., 1994, 1996, 2000, 2001). Moreover, asymmetric induction was found to occur in the (β → α) photoisomerization of various 2-substututed ethyl cobaloximes having chiral axial ligands as the chiral handle for forming the chiral lattice (Ohgo et al., 1994, 1996, 2000). However, the absolute configuration of the alkyl moiety of each chiral product has not yet been determined in the cases of the series of 2-carbamoylethyl and 2-(N-methylcarbamoyl)ethyl cobaloximes. The crystal structure analyses of the title complexes were undertaken to reveal the configurational correlation of asymmetric photoisomerization.

The crystal structure of the title 1-carbamoylethyl complex, (I), viewed along the c axis, and a stereoview of the crystal structure of the 1-(N-methylcarbamoyl)ethyl complex, (II), are shown in Figs. 1 and 2, respectively. The molecular structures of (I) and (II) are shown in Figs. 3 and 4, respectively. The absolute configuration (S) of the 1-carbamoylethyl group in (I) was set by reference to the known chirality of the axial base, (S)-1-phenylethylamine. Similarly, the absolute configuration (R) of the 1-(N-methylcarbamoyl)ethyl group in (II) was set by reference to that of the coordinated (R)-1-phenylethylamine. Selected bond distances and angles are given in Tables 1 and 3, respectively. The hydrogen bonds in (I) and (II) are given in Tables 2 and 4, respectively.

The molecular structures of (I) and (II) essentially maintain similar structural features except for their configurations. Each C_alkyl—Co—N_amine moiety is almost linear: the C9—Co—N5 and C9—Co—N6 angles in (I) and (II) are 177.3 (1) and 177.8 (2)°, respectively. Both the carbamoyl group and the phenylethyl group of the axial base of each complex are located on the same side, namely the O2—O3 side in (I) and the O1—O4 side in (II); the C12—N5—C9—C10 and C13—N6—C9—C10 torsion angles in (I) and (II) are −85.3 (2) and 70.7 (6)°, respectively. The N—H bond of each carbamoyl group is directed to one of the O atoms on the planar ligands to form an intramolecular hydrogen bond [N6—H6D···O3 in (I) and N5—H5···O4 in (II)]. The aromatic ring lies parallel with the Co–glyoxime plane, and the dihedral angles between the Co–glyoxime plane, Co/C3/C4/N3/N4, and the aromatic rings, C13–C18 in (I) and C14–C19 in (II), are 8.8 (2) and 12.7 (1)°, respectively.

Adjacent molecules in the structure of (I) are connected by intermolecular N5—H5B···O5ⁱ and N6—H6E···O1ⁱⁱ hydrogen bonds [symmetry codes: (i) 1/2 − x, 1/2 + y, − z; (ii) 1 − x, y − 1/2, − z], forming chains along the b axis. In the structure of (II), adjacent molecules are linked into a three-dimensional network by intermolecular hydrogen bonds involving the solvent water molecule, the coordinated amine group and the amide group in the 1-(N-methylcarbamoyl)ethyl moiety. Thus, the molecules are interconnected, forming chains along the a axis through intermolecular N6—H6E···O5ⁱⁱ hydrogen bonds [symmetry code: (ii) 1/2 + x, 1/2 − y, 1 − z]. Each chain so formed is connected to four neighbouring chains by bridging water molecules via three intermolecular hydrogen bonds, N6—H6D···O6ⁱⁱ, O6—H6G···O5 and O6—H6F···O4ⁱ [symmetry code: (i) 1/2 − x, − y, 1/2 + z], to form a three-dimensional hydrogen-bond network.

The axial base of (II) was displaced by methyldiphenylphosphine to afford bis(dimethylglyoximato-N,N')[(R)-1-(N-methylcarbamoyl)ethyl] (methyldiphenylphosphine)cobalt(III) {optical rotation [α]₅₈₉ = +28.6, [α]₅₇₈ = +23.7, [α]₅₄₆ = +2.0 (c = 0.101, CHCl₃)}, which was analyzed by high-performance liquid chromatography (HPLC) using a chiral column. The powdered sample of bis(dimethylglyoximato)[2-(N-methylcarbamoyl)ethyl] [methyl (S)-phenylalaninate-N]cobalt(III), complex (III) (Ohgo et al., 1996, 2000), was irradiated with a solar simulator (flux density 100 mW cm⁻²) to give a diastereomeric mixture of bis(dimethylglyoximato)[1-(N-methylcarbamoyl)ethyl] [methyl (S)-phenylalaninate-N]cobalt(III), which was also analyzed by HPLC after displacement of the axial ligand with methyldiphenylphosphine. From a comparison of the results of the HPLC analysis of these samples, the absolute configuration of the major enantiomer produced by photoisomerization of complex (III) was determined to be (S). On the other hand, the axial base of (I) was displaced by dimethylphenylphosphine to afford [(S)-1-carbamoylethyl]bis(dimethylglyoximato-N,N') (dimethylphenylphosphine)cobalt(III), complex (IV) {optical rotation [α]₅₈₉ = −47.9, [α]₅₇₈ = −47.9, [α]₅₄₆ = −46.2 (CHCl₃)}. The configuration of the major enantiomer produced by irradiation of the powdered crystals of a series of 2-carbamoylethyl cobaloximes was also revealed from a comparison of the optical rotation of complex (IV) with that of the photoisomerization products treated with dimethylphenylphosphine.

S2. Experimental

Complexes (I) and (II) were prepared according to the literature method of Ohgo et al. (1996). [(RS)-1-carbamoylethyl] bis(dimethylglyoximato-N,N')[(S)-1-phenylethylamine]cobalt(III) was recrystallized five times from dichloromethane–hexane to afford yellow crystals Red below of complex (I), with maximum optical rotation [α]₅₈₉ = +27.6, [α]₅₇₈ = +41.4, [α]₅₄₆ = +100.5 (c = 0.102, CHCl₃). Analysis found: C 47.1, H 6.4, N 17.2%; calculated for C₁₉H₃₁CoN₆O₅: C 47.3, H 6.5, N 17.4%. Bis(dimethylglyoximato-N,N')[(RS)-1-(N-methylcarbamoyl)ethyl] [(R)-1-phenylethylamine]cobalt(III) was recrystallized six times from benzene–hexane and finally from benzene [including 1% (R)-phenylethylamine]–hexane to afford dark-red crystals of complex (II) with maximum optical rotation [α]₅₈₉ = −60.4, [α]₅₇₈ = −82.5, [α]₅₄₆ = −158.2 (c = 0.104, CHCl₃). Analysis found: C 46.9, H 6.8, N 16.3%; calculated for C₂₀H₃₅CoN₆O₆: C 46.7, H 6.9, N 16.3%. Please give ratios of solvents used for both crystals.

S3. Refinement

Water H atoms were located in difference maps; O—H distances were constrained at 0.95 Å and U_iso(H) were set at 1.2U_eq(O). All other H atoms were refined using a riding model, with C—H distances of 0.96 for primary, 0.97 for secondary and 0.93 Å for aromatic, and with U_iso(H) = 1.2U_eq(C) (1.5 for methyl groups). The absolute structures were set by reference to the known chirality of the enantiopure amine coordinated in each complex and the Flack parameter is in agreement with each expected configuration.

Computing details

For both compounds, data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1992). Program(s) used to solve structure: MULTAN88 (Debaerdemaeker, 1988) for (I); SIR92 (Altomare et al., 1993) for (II). For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SV (Nemoto & Ohashi, 1993) and ORTEP (Johnson, 1965); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. Projection of the crystal structure of complex (I), viewed along the c axis. Dotted lines show the hydrogen bonds.
	Fig. 2. A stereoview of the crystal structure of complex (II). Dotted lines show the hydrogen bonds. H atoms bonded to C atoms have been omitted for clarity.
	Fig. 3. The molecular structure of complex (I) with the atomic numbering. Dashed lines show the hydrogen bonds. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 4. The molecular structure of complex (II), with the atomic numbering. Dashed lines show the hydrogen bonds. Displacement ellipsoids are drawn at the 50% probability level.

(I) [(S)-1-Carbamoylethyl]bis(dimethylglyoximato-κ²N,N')[(S)-1- phenylethylamine]cobalt(III)

Crystal data

[Co(C3H6NO)(C4H7N2O2)2(C8H11N)]	F(000) = 508
Mr = 482.43	Dx = 1.458 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: P2yb	Cell parameters from 25 reflections
a = 8.743 (2) Å	θ = 12.6–14.9°
b = 14.696 (3) Å	µ = 0.82 mm^−1
c = 8.565 (3) Å	T = 223 K
β = 93.29 (2)°	Needle, red
V = 1098.7 (5) Å^3	0.23 × 0.18 × 0.17 mm
Z = 2

Data collection

Rigaku AFC-7R diffractometer	2404 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.027
Graphite monochromator	θmax = 27.5°, θmin = 2.7°
ω/2θ scans	h = −6→11
Absorption correction: ψ scan (North et al., 1968)	k = 0→19
Tmin = 0.789, Tmax = 0.869	l = −11→11
3200 measured reflections	3 standard reflections every 100 reflections
2624 independent reflections	intensity decay: 0.7%

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)] = 0.025	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.066	w = 1/[σ^2(Fo^2) + (0.0308P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.21	(Δ/σ)max < 0.001
2624 reflections	Δρmax = 0.22 e Å^−3
299 parameters	Δρmin = −0.23 e Å^−3
1 restraint	Absolute structure: Flack (1983), with how many Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.004 (14)

Special details

Experimental. ¹H NMR (CDCl₃, p.p.m.): 0.32 (3H, d), 1.23 (3H, d), 1.46 (1H, dd), 1.89 (1H, q), 2.20 (12H, d), 2.33 (1H, dd), 3.62 (1H, m), 7.04–7.33 (m).

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
Co1	0.61819 (4)	0.86456 (2)	0.12322 (4)	0.01723 (9)
O1	0.3405 (2)	0.95407 (15)	0.0257 (2)	0.0271 (4)
O2	0.7967 (2)	0.74302 (16)	−0.0571 (3)	0.0341 (5)
H2	0.8510	0.7507	0.0245	0.051*
O3	0.8951 (2)	0.77424 (15)	0.2194 (3)	0.0319 (5)
O4	0.4512 (2)	0.99594 (15)	0.2924 (3)	0.0305 (5)
H4	0.4026	0.9929	0.2064	0.046*
O5	0.4061 (3)	0.64932 (15)	0.0388 (3)	0.0341 (5)
N1	0.4449 (3)	0.89254 (15)	−0.0103 (3)	0.0210 (5)
N2	0.6636 (3)	0.79086 (15)	−0.0487 (3)	0.0224 (5)
N3	0.7875 (3)	0.83271 (17)	0.2599 (3)	0.0231 (5)
N4	0.5724 (3)	0.93830 (16)	0.2935 (3)	0.0219 (5)
N5	0.7316 (3)	0.97004 (16)	0.0171 (3)	0.0204 (4)
H5A	0.7149	0.9620	−0.0878	0.024*
H5B	0.6820	1.0221	0.0414	0.024*
N6	0.6284 (3)	0.62084 (19)	0.1761 (4)	0.0336 (6)
H6D	0.693 (5)	0.651 (3)	0.228 (5)	0.051 (13)*
H6E	0.643 (5)	0.570 (4)	0.115 (5)	0.067 (15)*
C1	0.4327 (3)	0.84861 (19)	−0.1424 (3)	0.0252 (7)
C2	0.5623 (3)	0.7880 (2)	−0.1649 (3)	0.0253 (6)
C3	0.7924 (3)	0.8704 (3)	0.3982 (3)	0.0259 (5)
C4	0.6636 (3)	0.9328 (2)	0.4177 (3)	0.0243 (5)
C5	0.2974 (4)	0.8593 (3)	−0.2565 (4)	0.0419 (8)
H5C	0.2223	0.8988	−0.2120	0.063*
H5D	0.2518	0.8002	−0.2786	0.063*
H5E	0.3303	0.8859	−0.3526	0.063*
C6	0.5761 (4)	0.7291 (2)	−0.3049 (4)	0.0398 (8)
H6A	0.6804	0.7068	−0.3075	0.060*
H6B	0.5504	0.7641	−0.3988	0.060*
H6C	0.5065	0.6779	−0.2997	0.060*
C7	0.9182 (4)	0.8545 (3)	0.5213 (4)	0.0370 (8)
H7A	1.0093	0.8337	0.4725	0.056*
H7B	0.8861	0.8087	0.5941	0.056*
H7C	0.9407	0.9108	0.5771	0.056*
C8	0.6414 (4)	0.9862 (2)	0.5636 (3)	0.0380 (8)
H8A	0.5498	1.0232	0.5492	0.057*
H8B	0.7294	1.0252	0.5858	0.057*
H8C	0.6304	0.9447	0.6504	0.057*
C9	0.4943 (3)	0.76118 (19)	0.2266 (3)	0.0224 (5)
H9	0.5448	0.7505	0.3314	0.027*
C10	0.5059 (3)	0.67391 (19)	0.1379 (3)	0.0234 (5)
C11	0.3274 (3)	0.7848 (2)	0.2526 (4)	0.0335 (7)
H11A	0.3234	0.8405	0.3132	0.050*
H11B	0.2809	0.7357	0.3088	0.050*
H11C	0.2719	0.7934	0.1524	0.050*
C12	0.8995 (3)	0.98892 (19)	0.0453 (3)	0.0233 (5)
H12	0.9545	0.9301	0.0439	0.028*
C13	0.9367 (3)	1.03343 (19)	0.2019 (3)	0.0225 (5)
C14	0.8454 (3)	1.1009 (2)	0.2623 (3)	0.0293 (6)
H14	0.7545	1.1188	0.2068	0.035*
C15	0.8879 (4)	1.1416 (2)	0.4038 (4)	0.0352 (7)
H15	0.8237	1.1858	0.4452	0.042*
C16	1.0243 (4)	1.1182 (3)	0.4855 (4)	0.0349 (8)
H16	1.0524	1.1463	0.5816	0.042*
C17	1.1172 (4)	1.0538 (2)	0.4245 (4)	0.0367 (7)
H17	1.2106	1.0383	0.4776	0.044*
C18	1.0728 (3)	1.0111 (2)	0.2829 (3)	0.0290 (6)
H18	1.1366	0.9665	0.2423	0.035*
C19	0.9574 (4)	1.0485 (3)	−0.0862 (3)	0.0363 (7)
H19A	0.9412	1.0171	−0.1854	0.054*
H19B	1.0658	1.0605	−0.0661	0.054*
H19C	0.9016	1.1056	−0.0902	0.054*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.02021 (15)	0.01547 (14)	0.01575 (14)	0.00054 (15)	−0.00113 (10)	−0.00037 (13)
O1	0.0223 (9)	0.0268 (11)	0.0318 (10)	0.0049 (8)	−0.0024 (8)	0.0025 (8)
O2	0.0336 (11)	0.0317 (12)	0.0378 (12)	0.0095 (10)	0.0078 (9)	−0.0055 (10)
O3	0.0268 (10)	0.0277 (11)	0.0404 (12)	0.0101 (9)	−0.0049 (9)	0.0021 (9)
O4	0.0279 (10)	0.0310 (12)	0.0325 (11)	0.0093 (9)	0.0004 (9)	−0.0061 (9)
O5	0.0360 (12)	0.0285 (11)	0.0365 (12)	−0.0066 (9)	−0.0090 (9)	−0.0054 (9)
N1	0.0241 (10)	0.0178 (11)	0.0210 (10)	−0.0022 (8)	0.0000 (8)	0.0028 (8)
N2	0.0293 (12)	0.0172 (11)	0.0210 (11)	0.0006 (9)	0.0056 (9)	−0.0005 (9)
N3	0.0221 (11)	0.0186 (10)	0.0280 (12)	0.0014 (9)	−0.0020 (9)	0.0024 (9)
N4	0.0240 (11)	0.0203 (11)	0.0215 (11)	−0.0004 (9)	0.0008 (8)	−0.0016 (9)
N5	0.0220 (10)	0.0176 (10)	0.0212 (11)	−0.0025 (9)	−0.0019 (9)	0.0005 (9)
N6	0.0376 (14)	0.0234 (13)	0.0391 (15)	0.0028 (11)	−0.0037 (12)	−0.0011 (11)
C1	0.0321 (13)	0.0232 (19)	0.0196 (12)	−0.0071 (11)	−0.0054 (10)	0.0026 (10)
C2	0.0362 (15)	0.0210 (14)	0.0188 (12)	−0.0080 (12)	0.0029 (11)	−0.0013 (10)
C3	0.0318 (12)	0.0229 (13)	0.0223 (11)	−0.0043 (15)	−0.0058 (9)	0.0035 (14)
C4	0.0327 (14)	0.0235 (13)	0.0166 (11)	−0.0066 (12)	−0.0005 (10)	−0.0005 (10)
C5	0.0457 (17)	0.045 (2)	0.0327 (15)	−0.001 (2)	−0.0192 (12)	0.0008 (19)
C6	0.060 (2)	0.0346 (18)	0.0248 (15)	−0.0071 (16)	0.0065 (14)	−0.0118 (13)
C7	0.0427 (16)	0.0307 (19)	0.0356 (15)	−0.0060 (16)	−0.0160 (12)	0.0048 (15)
C8	0.053 (2)	0.041 (2)	0.0201 (14)	−0.0085 (16)	0.0027 (13)	−0.0089 (13)
C9	0.0276 (13)	0.0198 (13)	0.0197 (12)	−0.0033 (11)	0.0000 (10)	0.0012 (10)
C10	0.0270 (13)	0.0186 (12)	0.0248 (12)	−0.0041 (11)	0.0022 (10)	0.0045 (10)
C11	0.0314 (15)	0.0307 (16)	0.0396 (16)	−0.0023 (13)	0.0133 (13)	0.0040 (13)
C12	0.0220 (12)	0.0229 (14)	0.0252 (13)	0.0014 (10)	0.0022 (10)	−0.0016 (10)
C13	0.0208 (12)	0.0218 (13)	0.0248 (13)	−0.0033 (10)	0.0010 (10)	0.0005 (10)
C14	0.0286 (14)	0.0258 (15)	0.0327 (15)	0.0041 (12)	−0.0048 (12)	−0.0050 (12)
C15	0.0414 (17)	0.0274 (15)	0.0365 (16)	0.0024 (13)	−0.0015 (13)	−0.0071 (13)
C16	0.046 (2)	0.0319 (15)	0.0254 (15)	−0.0088 (15)	−0.0075 (14)	0.0002 (12)
C17	0.0321 (15)	0.0403 (18)	0.0358 (16)	−0.0049 (14)	−0.0134 (12)	0.0049 (14)
C18	0.0231 (13)	0.0315 (15)	0.0319 (14)	−0.0002 (12)	−0.0024 (11)	0.0003 (12)
C19	0.0323 (15)	0.0474 (19)	0.0293 (14)	−0.0093 (14)	0.0039 (12)	0.0002 (14)

Geometric parameters (Å, º)

Co1—N4	1.879 (2)	C6—H6A	0.9700
Co1—N2	1.888 (2)	C6—H6B	0.9700
Co1—N1	1.890 (2)	C6—H6C	0.9700
Co1—N3	1.892 (2)	C7—H7A	0.9700
Co1—N5	2.077 (2)	C7—H7B	0.9700
Co1—C9	2.092 (3)	C7—H7C	0.9700
O1—N1	1.334 (3)	C8—H8A	0.9700
O2—N2	1.365 (3)	C8—H8B	0.9700
O2—H2	0.8300	C8—H8C	0.9700
O3—N3	1.334 (3)	C9—C10	1.497 (4)
O4—N4	1.356 (3)	C9—C11	1.529 (4)
O4—H4	0.8300	C9—H9	0.9900
O5—C10	1.236 (3)	C11—H11A	0.9700
N1—C1	1.301 (4)	C11—H11B	0.9700
N2—C2	1.294 (4)	C11—H11C	0.9700
N3—C3	1.306 (4)	C12—C13	1.511 (4)
N4—C4	1.294 (3)	C12—C19	1.535 (4)
N5—C12	1.500 (3)	C12—H12	0.9900
N5—H5A	0.9100	C13—C18	1.382 (4)
N5—H5B	0.9100	C13—C14	1.391 (4)
N6—C10	1.350 (4)	C14—C15	1.383 (4)
N6—H6D	0.83 (5)	C14—H14	0.9400
N6—H6E	0.92 (5)	C15—C16	1.391 (5)
C1—C2	1.463 (4)	C15—H15	0.9400
C1—C5	1.499 (4)	C16—C17	1.371 (5)
C2—C6	1.490 (4)	C16—H16	0.9400
C3—C4	1.469 (5)	C17—C18	1.400 (4)
C3—C7	1.498 (4)	C17—H17	0.9400
C4—C8	1.498 (4)	C18—H18	0.9400
C5—H5C	0.9700	C19—H19A	0.9700
C5—H5D	0.9700	C19—H19B	0.9700
C5—H5E	0.9700	C19—H19C	0.9700
N4—Co1—N2	179.7 (1)	H6A—C6—H6C	109.5
N4—Co1—N1	98.4 (1)	H6B—C6—H6C	109.5
N2—Co1—N1	81.4 (1)	C3—C7—H7A	109.5
N4—Co1—N3	81.7 (1)	C3—C7—H7B	109.5
N2—Co1—N3	98.6 (1)	H7A—C7—H7B	109.5
N1—Co1—N3	177.8 (1)	C3—C7—H7C	109.5
N4—Co1—N5	92.2 (1)	H7A—C7—H7C	109.5
N2—Co1—N5	87.7 (1)	H7B—C7—H7C	109.5
N1—Co1—N5	87.64 (9)	C4—C8—H8A	109.5
N3—Co1—N5	94.5 (1)	C4—C8—H8B	109.5
N4—Co1—C9	87.2 (1)	H8A—C8—H8B	109.5
N2—Co1—C9	92.9 (1)	C4—C8—H8C	109.5
N1—Co1—C9	89.9 (1)	H8A—C8—H8C	109.5
N3—Co1—C9	88.0 (1)	H8B—C8—H8C	109.5
N5—Co1—C9	177.3 (1)	C10—C9—C11	111.2 (2)
N2—O2—H2	109.5	C10—C9—Co1	110.8 (2)
N4—O4—H4	109.5	C11—C9—Co1	114.7 (2)
C1—N1—O1	121.0 (2)	C10—C9—H9	106.5
C1—N1—Co1	116.2 (2)	C11—C9—H9	106.5
O1—N1—Co1	122.9 (2)	Co1—C9—H9	106.5
C2—N2—O2	119.3 (2)	O5—C10—N6	121.1 (3)
C2—N2—Co1	117.0 (2)	O5—C10—C9	122.2 (3)
O2—N2—Co1	123.7 (2)	N6—C10—C9	116.6 (3)
C3—N3—O3	121.4 (2)	C9—C11—H11A	109.5
C3—N3—Co1	116.1 (2)	C9—C11—H11B	109.5
O3—N3—Co1	122.4 (2)	H11A—C11—H11B	109.5
C4—N4—O4	119.3 (2)	C9—C11—H11C	109.5
C4—N4—Co1	116.9 (2)	H11A—C11—H11C	109.5
O4—N4—Co1	123.8 (2)	H11B—C11—H11C	109.5
C12—N5—Co1	123.7 (2)	N5—C12—C13	112.4 (2)
C12—N5—H5A	106.4	N5—C12—C19	110.4 (2)
Co1—N5—H5A	106.4	C13—C12—C19	109.9 (2)
C12—N5—H5B	106.4	N5—C12—H12	108.0
Co1—N5—H5B	106.4	C13—C12—H12	108.0
H5A—N5—H5B	106.5	C19—C12—H12	108.0
C10—N6—H6D	109 (3)	C18—C13—C14	118.6 (3)
C10—N6—H6E	118 (3)	C18—C13—C12	118.6 (3)
H6D—N6—H6E	128 (4)	C14—C13—C12	122.7 (2)
N1—C1—C2	113.0 (2)	C15—C14—C13	120.2 (3)
N1—C1—C5	122.4 (3)	C15—C14—H14	119.9
C2—C1—C5	124.5 (3)	C13—C14—H14	119.9
N2—C2—C1	112.3 (2)	C14—C15—C16	120.9 (3)
N2—C2—C6	123.7 (3)	C14—C15—H15	119.6
C1—C2—C6	124.0 (3)	C16—C15—H15	119.6
N3—C3—C4	112.5 (2)	C17—C16—C15	119.2 (3)
N3—C3—C7	123.8 (3)	C17—C16—H16	120.4
C4—C3—C7	123.7 (3)	C15—C16—H16	120.4
N4—C4—C3	112.7 (2)	C16—C17—C18	120.0 (3)
N4—C4—C8	123.3 (3)	C16—C17—H17	120.0
C3—C4—C8	124.0 (2)	C18—C17—H17	120.0
C1—C5—H5C	109.5	C13—C18—C17	121.1 (3)
C1—C5—H5D	109.5	C13—C18—H18	119.5
H5C—C5—H5D	109.5	C17—C18—H18	119.5
C1—C5—H5E	109.5	C12—C19—H19A	109.5
H5C—C5—H5E	109.5	C12—C19—H19B	109.5
H5D—C5—H5E	109.5	H19A—C19—H19B	109.5
C2—C6—H6A	109.5	C12—C19—H19C	109.5
C2—C6—H6B	109.5	H19A—C19—H19C	109.5
H6A—C6—H6B	109.5	H19B—C19—H19C	109.5
C2—C6—H6C	109.5
N4—Co1—N1—C1	−176.5 (2)	Co1—N2—C2—C6	−176.2 (2)
N2—Co1—N1—C1	3.6 (2)	N1—C1—C2—N2	−0.4 (4)
N5—Co1—N1—C1	91.6 (2)	C5—C1—C2—N2	−179.5 (3)
C9—Co1—N1—C1	−89.4 (2)	N1—C1—C2—C6	179.2 (3)
N4—Co1—N1—O1	4.0 (2)	C5—C1—C2—C6	0.1 (5)
N2—Co1—N1—O1	−175.8 (2)	O3—N3—C3—C4	179.6 (2)
N5—Co1—N1—O1	−87.8 (2)	Co1—N3—C3—C4	−1.3 (4)
C9—Co1—N1—O1	91.2 (2)	O3—N3—C3—C7	1.7 (5)
N1—Co1—N2—C2	−3.9 (2)	Co1—N3—C3—C7	−179.2 (3)
N3—Co1—N2—C2	173.9 (2)	O4—N4—C4—C3	−177.6 (2)
N5—Co1—N2—C2	−91.8 (2)	Co1—N4—C4—C3	2.2 (3)
C9—Co1—N2—C2	85.5 (2)	O4—N4—C4—C8	1.0 (4)
N1—Co1—N2—O2	174.8 (2)	Co1—N4—C4—C8	−179.2 (2)
N3—Co1—N2—O2	−7.5 (2)	N3—C3—C4—N4	−0.6 (4)
N5—Co1—N2—O2	86.8 (2)	C7—C3—C4—N4	177.4 (3)
C9—Co1—N2—O2	−95.8 (2)	N3—C3—C4—C8	−179.2 (3)
N4—Co1—N3—C3	1.9 (2)	C7—C3—C4—C8	−1.3 (5)
N2—Co1—N3—C3	−178.2 (2)	N4—Co1—C9—C10	−174.4 (2)
N5—Co1—N3—C3	93.4 (2)	N2—Co1—C9—C10	5.9 (2)
C9—Co1—N3—C3	−85.6 (2)	N1—Co1—C9—C10	87.3 (2)
N4—Co1—N3—O3	−179.0 (2)	N3—Co1—C9—C10	−92.5 (2)
N2—Co1—N3—O3	0.9 (2)	N4—Co1—C9—C11	58.7 (2)
N5—Co1—N3—O3	−87.5 (2)	N2—Co1—C9—C11	−121.1 (2)
C9—Co1—N3—O3	93.5 (2)	N1—Co1—C9—C11	−39.7 (2)
N1—Co1—N4—C4	175.5 (2)	N3—Co1—C9—C11	140.5 (2)
N3—Co1—N4—C4	−2.3 (2)	C11—C9—C10—O5	32.0 (4)
N5—Co1—N4—C4	−96.6 (2)	Co1—C9—C10—O5	−96.9 (3)
C9—Co1—N4—C4	86.0 (2)	C11—C9—C10—N6	−145.2 (3)
N1—Co1—N4—O4	−4.7 (2)	Co1—C9—C10—N6	85.9 (3)
N3—Co1—N4—O4	177.5 (2)	Co1—N5—C12—C13	−75.4 (3)
N5—Co1—N4—O4	83.2 (2)	Co1—N5—C12—C19	161.4 (2)
C9—Co1—N4—O4	−94.1 (2)	N5—C12—C13—C18	144.5 (3)
N4—Co1—N5—C12	89.8 (2)	C19—C12—C13—C18	−92.1 (3)
N2—Co1—N5—C12	−90.4 (2)	N5—C12—C13—C14	−40.5 (4)
N1—Co1—N5—C12	−171.9 (2)	C19—C12—C13—C14	82.9 (3)
N3—Co1—N5—C12	8.0 (2)	C18—C13—C14—C15	−2.6 (5)
O1—N1—C1—C2	176.7 (2)	C12—C13—C14—C15	−177.6 (3)
Co1—N1—C1—C2	−2.7 (3)	C13—C14—C15—C16	2.1 (5)
O1—N1—C1—C5	−4.2 (4)	C14—C15—C16—C17	−0.1 (5)
Co1—N1—C1—C5	176.4 (3)	C15—C16—C17—C18	−1.3 (5)
O2—N2—C2—C1	−175.3 (2)	C14—C13—C18—C17	1.3 (4)
Co1—N2—C2—C1	3.4 (3)	C12—C13—C18—C17	176.5 (3)
O2—N2—C2—C6	5.1 (4)	C16—C17—C18—C13	0.6 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3	0.83	1.73	2.515 (3)	158
O4—H4···O1	0.83	1.71	2.506 (3)	160
N5—H5B···O5^i	0.91	2.12	2.925 (3)	147
N6—H6D···O3	0.83 (5)	2.53 (5)	3.249 (4)	145 (4)
N6—H6E···O1^ii	0.92 (5)	2.10 (5)	3.021 (4)	176 (4)

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

(II) bis(dimethylglyoximato-κ²N,N')[(R)-1-(N-methylcarbamoyl)ethyl][(R)- 1-phenylethylamine]cobalt(III) monohydrate

Crystal data

[Co(C4H8NO)(C4H7N2O2)2(C8H11N)]·H2O	F(000) = 1088
Mr = 514.47	Dx = 1.380 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: P2ac2ab	Cell parameters from 25 reflections
a = 14.1206 (19) Å	θ = 12.8–14.7°
b = 14.169 (2) Å	µ = 0.74 mm^−1
c = 12.372 (2) Å	T = 293 K
V = 2475.3 (6) Å^3	Needle, red
Z = 4	0.25 × 0.15 × 0.12 mm

Data collection

Rigaku AFC-7R diffractometer	1749 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.039
Graphite monochromator	θmax = 27.5°, θmin = 2.6°
ω/2θ scans	h = −10→18
Absorption correction: ψ scan (North et al., 1968)	k = 0→18
Tmin = 0.838, Tmax = 0.917	l = −9→16
4662 measured reflections	3 standard reflections every 100 reflections
3581 independent reflections	intensity decay: −0.8%

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)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.105	w = 1/[σ^2(Fo^2) + (0.029P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.98	(Δ/σ)max < 0.001
3581 reflections	Δρmax = 0.43 e Å^−3
317 parameters	Δρmin = −0.80 e Å^−3
2 restraints	Absolute structure: Flack (1983), with how many Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (3)

Special details

Experimental. ¹H NMR (CDCl₃, p.p.m.): 0.33 (3H, d), 1.23 (3H, d), 1.44 (1H, dd), 1.85 (1H, q), 2.17 (12H, d), 2.25 (1H, dd), 2.52 (3H, d), 3.62 (1H, m), 5.32 (1H, q), 7.05–7.37 (m).

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
Co1	0.42129 (6)	0.26852 (6)	0.32901 (7)	0.0319 (2)
O1	0.4301 (4)	0.0758 (3)	0.4031 (3)	0.0452 (12)
H1	0.4232	0.0704	0.3376	0.068*
O2	0.4526 (3)	0.4341 (3)	0.4552 (4)	0.0550 (15)
O3	0.4225 (4)	0.4594 (3)	0.2582 (4)	0.0550 (13)
H3	0.4349	0.4633	0.3228	0.082*
O4	0.4000 (3)	0.1035 (3)	0.2035 (3)	0.0431 (13)
O5	0.2098 (3)	0.1949 (3)	0.4989 (4)	0.0516 (14)
O6	0.2008 (4)	0.0629 (3)	0.6684 (5)	0.0693 (15)
H6F	0.156 (4)	0.014 (4)	0.650 (6)	0.083*
H6G	0.201 (5)	0.096 (5)	0.601 (4)	0.083*
N1	0.4319 (4)	0.1690 (4)	0.4298 (4)	0.0372 (14)
N2	0.4416 (4)	0.3403 (4)	0.4557 (4)	0.0397 (16)
N3	0.4104 (4)	0.3685 (4)	0.2313 (4)	0.0362 (15)
N4	0.3993 (3)	0.1970 (4)	0.2021 (4)	0.0315 (14)
N5	0.2240 (4)	0.1159 (4)	0.3431 (5)	0.0411 (13)
H5	0.2360	0.1189	0.2750	0.049*
N6	0.5669 (3)	0.2641 (3)	0.3100 (3)	0.0360 (12)
H6D	0.5851	0.3226	0.2910	0.043*
H6E	0.5915	0.2532	0.3760	0.043*
C1	0.4424 (5)	0.1925 (5)	0.5307 (6)	0.0374 (17)
C2	0.4483 (5)	0.2935 (5)	0.5466 (5)	0.0405 (19)
C3	0.3893 (5)	0.3468 (5)	0.1328 (5)	0.0375 (18)
C4	0.3844 (4)	0.2456 (4)	0.1147 (5)	0.0316 (16)
C5	0.4486 (5)	0.1210 (5)	0.6200 (5)	0.059 (2)
H5A	0.4794	0.0652	0.5938	0.089*
H5B	0.3860	0.1053	0.6443	0.089*
H5C	0.4843	0.1469	0.6791	0.089*
C6	0.4635 (5)	0.3421 (5)	0.6533 (5)	0.058 (2)
H6A	0.4367	0.4043	0.6505	0.087*
H6B	0.5301	0.3465	0.6678	0.087*
H6C	0.4333	0.3065	0.7096	0.087*
C7	0.3748 (5)	0.4193 (5)	0.0462 (5)	0.057 (2)
H7A	0.4120	0.4742	0.0623	0.085*
H7B	0.3091	0.4362	0.0429	0.085*
H7C	0.3942	0.3937	−0.0222	0.085*
C8	0.3672 (5)	0.2002 (5)	0.0070 (5)	0.055 (2)
H8A	0.3379	0.1398	0.0174	0.082*
H8B	0.4265	0.1921	−0.0299	0.082*
H8C	0.3263	0.2397	−0.0354	0.082*
C9	0.2752 (4)	0.2786 (4)	0.3471 (5)	0.0377 (16)
H9	0.2489	0.2781	0.2738	0.045*
C10	0.2342 (5)	0.1939 (5)	0.4035 (6)	0.0358 (17)
C11	0.1930 (5)	0.0255 (5)	0.3894 (5)	0.056 (2)
H11A	0.1710	−0.0151	0.3325	0.084*
H11B	0.1426	0.0365	0.4399	0.084*
H11C	0.2452	−0.0039	0.4259	0.084*
C12	0.2403 (5)	0.3703 (5)	0.3996 (6)	0.058 (2)
H12A	0.2723	0.4231	0.3676	0.087*
H12B	0.2533	0.3687	0.4757	0.087*
H12C	0.1733	0.3766	0.3884	0.087*
C13	0.6150 (4)	0.1976 (5)	0.2341 (5)	0.0374 (18)
H13	0.5831	0.1362	0.2384	0.045*
C14	0.6111 (4)	0.2314 (5)	0.1186 (5)	0.0352 (16)
C15	0.6140 (5)	0.3244 (5)	0.0864 (6)	0.0416 (19)
H15	0.6153	0.3717	0.1386	0.050*
C16	0.6151 (5)	0.3490 (6)	−0.0212 (7)	0.060 (2)
H16	0.6152	0.4123	−0.0412	0.073*
C17	0.6160 (5)	0.2807 (8)	−0.0981 (6)	0.069 (3)
H17	0.6166	0.2977	−0.1708	0.082*
C18	0.6161 (6)	0.1875 (7)	−0.0704 (7)	0.067 (3)
H18	0.6183	0.1411	−0.1235	0.081*
C19	0.6129 (5)	0.1629 (5)	0.0371 (6)	0.054 (2)
H19	0.6120	0.0994	0.0560	0.065*
C20	0.7181 (5)	0.1843 (6)	0.2658 (6)	0.069 (3)
H20A	0.7214	0.1567	0.3365	0.103*
H20B	0.7494	0.2444	0.2662	0.103*
H20C	0.7485	0.1433	0.2146	0.103*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0353 (4)	0.0307 (4)	0.0296 (4)	−0.0015 (4)	−0.0001 (5)	0.0016 (4)
O1	0.055 (3)	0.031 (2)	0.050 (3)	0.003 (3)	0.003 (3)	−0.001 (2)
O2	0.067 (4)	0.038 (3)	0.060 (3)	−0.011 (3)	−0.006 (3)	−0.008 (2)
O3	0.080 (4)	0.030 (3)	0.055 (3)	−0.007 (3)	−0.002 (3)	0.005 (2)
O4	0.056 (3)	0.031 (3)	0.042 (3)	0.001 (2)	0.007 (2)	−0.006 (2)
O5	0.068 (4)	0.052 (3)	0.036 (3)	−0.006 (3)	0.017 (3)	0.000 (3)
O6	0.093 (4)	0.062 (4)	0.053 (3)	−0.017 (3)	−0.006 (4)	0.014 (3)
N1	0.032 (4)	0.035 (3)	0.044 (3)	0.000 (3)	−0.008 (3)	0.003 (3)
N2	0.042 (4)	0.045 (4)	0.032 (3)	−0.004 (3)	0.004 (3)	−0.002 (3)
N3	0.041 (4)	0.030 (3)	0.038 (4)	−0.003 (3)	−0.001 (3)	0.007 (3)
N4	0.026 (3)	0.028 (3)	0.041 (3)	−0.002 (2)	0.000 (2)	−0.007 (2)
N5	0.041 (3)	0.047 (3)	0.035 (3)	0.000 (3)	0.005 (3)	0.006 (3)
N6	0.037 (3)	0.040 (3)	0.031 (3)	0.000 (3)	−0.002 (3)	0.005 (3)
C1	0.024 (4)	0.048 (4)	0.041 (4)	−0.002 (3)	0.003 (3)	0.010 (3)
C2	0.037 (5)	0.059 (5)	0.026 (4)	−0.010 (4)	0.002 (3)	0.001 (4)
C3	0.033 (4)	0.049 (5)	0.030 (4)	−0.001 (4)	−0.003 (3)	0.010 (3)
C4	0.028 (3)	0.042 (5)	0.024 (3)	−0.004 (3)	−0.002 (3)	0.000 (3)
C5	0.072 (6)	0.060 (5)	0.046 (5)	−0.005 (4)	−0.010 (4)	0.019 (4)
C6	0.052 (5)	0.095 (6)	0.026 (4)	−0.015 (4)	−0.008 (4)	−0.007 (4)
C7	0.058 (5)	0.058 (5)	0.053 (5)	−0.008 (4)	−0.011 (4)	0.021 (4)
C8	0.045 (4)	0.082 (6)	0.038 (4)	−0.013 (4)	−0.005 (3)	−0.019 (4)
C9	0.027 (3)	0.040 (4)	0.046 (4)	0.004 (3)	0.006 (3)	0.004 (4)
C10	0.028 (4)	0.044 (4)	0.035 (4)	−0.004 (3)	−0.004 (3)	0.002 (4)
C11	0.059 (5)	0.046 (5)	0.063 (5)	−0.005 (4)	0.009 (4)	0.007 (4)
C12	0.045 (5)	0.047 (5)	0.082 (6)	0.016 (4)	0.016 (5)	0.005 (4)
C13	0.033 (4)	0.036 (4)	0.044 (4)	0.007 (3)	−0.002 (3)	−0.003 (3)
C14	0.027 (3)	0.046 (4)	0.032 (3)	−0.004 (4)	0.005 (3)	−0.007 (4)
C15	0.044 (5)	0.042 (5)	0.039 (4)	−0.002 (4)	0.002 (3)	0.003 (3)
C16	0.045 (5)	0.072 (6)	0.064 (6)	0.001 (4)	0.010 (4)	0.023 (5)
C17	0.053 (5)	0.119 (8)	0.033 (4)	−0.009 (6)	0.000 (4)	0.012 (6)
C18	0.053 (6)	0.101 (7)	0.047 (5)	−0.013 (5)	0.007 (4)	−0.015 (5)
C19	0.062 (6)	0.050 (5)	0.052 (5)	0.000 (4)	−0.001 (4)	−0.004 (4)
C20	0.053 (5)	0.104 (7)	0.049 (5)	0.026 (5)	−0.002 (4)	−0.002 (5)

Geometric parameters (Å, º)

Co1—N3	1.868 (5)	C6—H6B	0.9600
Co1—N1	1.889 (5)	C6—H6C	0.9600
Co1—N2	1.890 (5)	C7—H7A	0.9600
Co1—N4	1.894 (5)	C7—H7B	0.9600
Co1—N6	2.070 (4)	C7—H7C	0.9600
Co1—C9	2.080 (5)	C8—H8A	0.9600
O1—N1	1.362 (6)	C8—H8B	0.9600
O1—H1	0.8200	C8—H8C	0.9600
O2—N2	1.339 (6)	C9—C10	1.504 (8)
O3—N3	1.342 (6)	C9—C12	1.534 (8)
O3—H3	0.8200	C9—H9	0.9800
O4—N4	1.326 (6)	C11—H11A	0.9600
O5—C10	1.229 (7)	C11—H11B	0.9600
O6—H6F	0.97 (3)	C11—H11C	0.9600
O6—H6G	0.96 (3)	C12—H12A	0.9600
N1—C1	1.300 (8)	C12—H12B	0.9600
N2—C2	1.310 (8)	C12—H12C	0.9600
N3—C3	1.292 (7)	C13—C14	1.508 (8)
N4—C4	1.298 (7)	C13—C20	1.519 (8)
N5—C10	1.342 (8)	C13—H13	0.9800
N5—C11	1.470 (8)	C14—C15	1.377 (9)
N5—H5	0.8600	C14—C19	1.400 (8)
N6—C13	1.494 (7)	C15—C16	1.376 (9)
N6—H6D	0.9000	C15—H15	0.9300
N6—H6E	0.9000	C16—C17	1.357 (10)
C1—C2	1.447 (9)	C16—H16	0.9300
C1—C5	1.501 (8)	C17—C18	1.365 (11)
C2—C6	1.504 (8)	C17—H17	0.9300
C3—C4	1.453 (9)	C18—C19	1.375 (10)
C3—C7	1.498 (8)	C18—H18	0.9300
C4—C8	1.500 (8)	C19—H19	0.9300
C5—H5A	0.9600	C20—H20A	0.9600
C5—H5B	0.9600	C20—H20B	0.9600
C5—H5C	0.9600	C20—H20C	0.9600
C6—H6A	0.9600
N3—Co1—N1	179.0 (3)	C3—C7—H7A	109.5
N3—Co1—N2	98.1 (2)	C3—C7—H7B	109.5
N1—Co1—N2	80.9 (2)	H7A—C7—H7B	109.5
N3—Co1—N4	81.7 (2)	C3—C7—H7C	109.5
N1—Co1—N4	99.3 (2)	H7A—C7—H7C	109.5
N2—Co1—N4	179.3 (2)	H7B—C7—H7C	109.5
N3—Co1—N6	91.8 (2)	C4—C8—H8A	109.5
N1—Co1—N6	88.5 (2)	C4—C8—H8B	109.5
N2—Co1—N6	87.7 (2)	H8A—C8—H8B	109.5
N4—Co1—N6	93.0 (2)	C4—C8—H8C	109.5
N3—Co1—C9	86.3 (3)	H8A—C8—H8C	109.5
N1—Co1—C9	93.4 (3)	H8B—C8—H8C	109.5
N2—Co1—C9	91.4 (3)	C10—C9—C12	110.8 (5)
N4—Co1—C9	87.9 (2)	C10—C9—Co1	112.1 (4)
N6—Co1—C9	177.8 (2)	C12—C9—Co1	115.0 (4)
N1—O1—H1	109.5	C10—C9—H9	106.0
N3—O3—H3	109.5	C12—C9—H9	106.0
H6F—O6—H6G	99 (6)	Co1—C9—H9	106.0
C1—N1—O1	118.9 (5)	O5—C10—N5	120.9 (6)
C1—N1—Co1	116.9 (5)	O5—C10—C9	123.0 (7)
O1—N1—Co1	124.2 (4)	N5—C10—C9	116.1 (6)
C2—N2—O2	119.9 (6)	N5—C11—H11A	109.5
C2—N2—Co1	116.8 (5)	N5—C11—H11B	109.5
O2—N2—Co1	123.2 (4)	H11A—C11—H11B	109.5
C3—N3—O3	119.5 (6)	N5—C11—H11C	109.5
C3—N3—Co1	116.7 (5)	H11A—C11—H11C	109.5
O3—N3—Co1	123.8 (4)	H11B—C11—H11C	109.5
C4—N4—O4	122.8 (5)	C9—C12—H12A	109.5
C4—N4—Co1	115.7 (4)	C9—C12—H12B	109.5
O4—N4—Co1	121.5 (4)	H12A—C12—H12B	109.5
C10—N5—C11	122.2 (5)	C9—C12—H12C	109.5
C10—N5—H5	118.9	H12A—C12—H12C	109.5
C11—N5—H5	118.9	H12B—C12—H12C	109.5
C13—N6—Co1	122.8 (4)	N6—C13—C14	112.2 (5)
C13—N6—H6D	106.6	N6—C13—C20	110.6 (5)
Co1—N6—H6D	106.6	C14—C13—C20	108.6 (5)
C13—N6—H6E	106.6	N6—C13—H13	108.4
Co1—N6—H6E	106.6	C14—C13—H13	108.4
H6D—N6—H6E	106.6	C20—C13—H13	108.4
N1—C1—C2	112.9 (6)	C15—C14—C19	117.1 (6)
N1—C1—C5	122.7 (7)	C15—C14—C13	125.3 (6)
C2—C1—C5	124.3 (7)	C19—C14—C13	117.4 (7)
N2—C2—C1	112.3 (6)	C16—C15—C14	121.5 (7)
N2—C2—C6	122.1 (6)	C16—C15—H15	119.3
C1—C2—C6	125.5 (7)	C14—C15—H15	119.3
N3—C3—C4	113.0 (6)	C17—C16—C15	119.9 (8)
N3—C3—C7	122.9 (7)	C17—C16—H16	120.1
C4—C3—C7	124.1 (6)	C15—C16—H16	120.1
N4—C4—C3	112.8 (6)	C16—C17—C18	120.9 (8)
N4—C4—C8	122.6 (6)	C16—C17—H17	119.6
C3—C4—C8	124.6 (6)	C18—C17—H17	119.6
C1—C5—H5A	109.5	C17—C18—C19	119.2 (8)
C1—C5—H5B	109.5	C17—C18—H18	120.4
H5A—C5—H5B	109.5	C19—C18—H18	120.4
C1—C5—H5C	109.5	C18—C19—C14	121.4 (7)
H5A—C5—H5C	109.5	C18—C19—H19	119.3
H5B—C5—H5C	109.5	C14—C19—H19	119.3
C2—C6—H6A	109.5	C13—C20—H20A	109.5
C2—C6—H6B	109.5	C13—C20—H20B	109.5
H6A—C6—H6B	109.5	H20A—C20—H20B	109.5
C2—C6—H6C	109.5	C13—C20—H20C	109.5
H6A—C6—H6C	109.5	H20A—C20—H20C	109.5
H6B—C6—H6C	109.5	H20B—C20—H20C	109.5
N2—Co1—N1—C1	3.1 (5)	N1—C1—C2—N2	0.1 (10)
N4—Co1—N1—C1	−176.2 (5)	C5—C1—C2—N2	179.6 (6)
N6—Co1—N1—C1	91.0 (5)	N1—C1—C2—C6	−178.0 (6)
C9—Co1—N1—C1	−87.8 (6)	C5—C1—C2—C6	1.5 (12)
N2—Co1—N1—O1	−176.2 (6)	O3—N3—C3—C4	176.4 (6)
N4—Co1—N1—O1	4.5 (6)	Co1—N3—C3—C4	−4.1 (8)
N6—Co1—N1—O1	−88.3 (6)	O3—N3—C3—C7	−1.7 (11)
C9—Co1—N1—O1	92.9 (6)	Co1—N3—C3—C7	177.8 (5)
N3—Co1—N2—C2	176.7 (5)	O4—N4—C4—C3	−178.6 (5)
N1—Co1—N2—C2	−3.0 (5)	Co1—N4—C4—C3	1.0 (7)
N6—Co1—N2—C2	−91.8 (5)	O4—N4—C4—C8	−0.5 (9)
C9—Co1—N2—C2	90.2 (5)	Co1—N4—C4—C8	179.1 (4)
N3—Co1—N2—O2	−5.8 (5)	N3—C3—C4—N4	2.0 (9)
N1—Co1—N2—O2	174.5 (6)	C7—C3—C4—N4	−180.0 (6)
N6—Co1—N2—O2	85.6 (5)	N3—C3—C4—C8	−176.0 (6)
C9—Co1—N2—O2	−92.3 (5)	C7—C3—C4—C8	2.0 (10)
N2—Co1—N3—C3	−175.6 (6)	N3—Co1—C9—C10	166.1 (5)
N4—Co1—N3—C3	3.7 (5)	N1—Co1—C9—C10	−14.8 (5)
N6—Co1—N3—C3	96.5 (6)	N2—Co1—C9—C10	−95.8 (5)
C9—Co1—N3—C3	−84.7 (6)	N4—Co1—C9—C10	84.3 (5)
N2—Co1—N3—O3	3.9 (6)	N3—Co1—C9—C12	−66.0 (5)
N4—Co1—N3—O3	−176.8 (6)	N1—Co1—C9—C12	113.0 (5)
N6—Co1—N3—O3	−84.1 (6)	N2—Co1—C9—C12	32.0 (5)
C9—Co1—N3—O3	94.7 (6)	N4—Co1—C9—C12	−147.8 (5)
N3—Co1—N4—C4	−2.5 (4)	C11—N5—C10—O5	−6.5 (10)
N1—Co1—N4—C4	177.2 (5)	C11—N5—C10—C9	174.4 (5)
N6—Co1—N4—C4	−93.9 (5)	C12—C9—C10—O5	−26.9 (8)
C9—Co1—N4—C4	84.1 (5)	Co1—C9—C10—O5	103.2 (7)
N3—Co1—N4—O4	177.1 (5)	C12—C9—C10—N5	152.2 (6)
N1—Co1—N4—O4	−3.2 (5)	Co1—C9—C10—N5	−77.8 (6)
N6—Co1—N4—O4	85.7 (4)	Co1—N6—C13—C14	79.4 (6)
C9—Co1—N4—O4	−96.3 (4)	Co1—N6—C13—C20	−159.2 (4)
N3—Co1—N6—C13	−96.2 (4)	N6—C13—C14—C15	34.0 (9)
N1—Co1—N6—C13	84.7 (5)	C20—C13—C14—C15	−88.5 (8)
N2—Co1—N6—C13	165.7 (5)	N6—C13—C14—C19	−151.9 (6)
N4—Co1—N6—C13	−14.5 (5)	C20—C13—C14—C19	85.5 (8)
O1—N1—C1—C2	176.8 (6)	C19—C14—C15—C16	2.4 (10)
Co1—N1—C1—C2	−2.6 (8)	C13—C14—C15—C16	176.5 (6)
O1—N1—C1—C5	−2.7 (11)	C14—C15—C16—C17	−1.9 (11)
Co1—N1—C1—C5	177.9 (5)	C15—C16—C17—C18	−0.2 (12)
O2—N2—C2—C1	−175.1 (6)	C16—C17—C18—C19	1.6 (13)
Co1—N2—C2—C1	2.5 (8)	C17—C18—C19—C14	−1.0 (13)
O2—N2—C2—C6	3.0 (10)	C15—C14—C19—C18	−1.0 (11)
Co1—N2—C2—C6	−179.4 (5)	C13—C14—C19—C18	−175.5 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4	0.82	1.75	2.536 (6)	159
O3—H3···O2	0.82	1.71	2.499 (6)	162
O6—H6F···O4^i	0.97 (3)	1.96 (5)	2.787 (6)	143 (6)
O6—H6G···O5	0.96 (3)	1.89 (4)	2.813 (7)	162 (7)
N5—H5···O4	0.86	2.49	3.030 (7)	122
N6—H6D···O6^ii	0.90	2.36	3.108 (7)	141
N6—H6E···O5^ii	0.90	2.39	3.163 (6)	143

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