Potassium cis-[(R)-aspartato(2–)][(S)-aspartato(2–)]cobaltate(III) 3.5-hydrate at 120 K

The title compound, K[Co(C₄H₄NO₄)₂]3.5H₂O, is a by-product resulting from adventitious oxidation, in the presence of racemic aspartic acid, of cobalt(II) in a cobaltous starting material. The presence of both enanti­omeric forms of the tridentate aspartate ligand in the cobaltate anion is significant in eliminating the possibility of the existence of isomeric forms of the cis(N) isomer.

Comment

As part of our continuing study of transition metal complexes with amino acids (Felcman & de Miranda, 1997; de Miranda & Felcman, 2001; de Miranda et al., 2002; Felcman et al., 2003), we have isolated and characterized the title compound, (I), from an aqueous reaction mixture containing DL-aspartic acid (asp), guanidinoacetic acid (gaa) and Co^II (1:1:1). Crystals of (I) were obtained after several months. No crystalline complex containing gaa, either alone or in a mixed complex with asp, appeared in a similar time.

The asymmetric unit in the structure of (I) is shown in Fig. 1, and selected bond lengths and angles are given in Table 1. In the anion, an enanti­omeric pair of asp dianions, with identical numbering of the atoms and distinguished by the suffixes A and B, act as tridentate ligands, creating octa­hedral coordination of atom Co1. The enantiomeric relationship of the asp dianions in the complex anion is evident in the torsion angles given in Table 1 and significant in later discussion of the isomerism of such complexes.

The K⁺ cation caps one face of the coordination octa­hedron of the anion to give a Co1⋯K1 distance of 3.6502 (14) Å. Its sevenfold coordination (Fig. 2) is completed by two non-coordinating O atoms associated with two further cobaltate anions and by two water mol­ecules. A complex arrangement of K—O bonds connects the ions in layers parallel to (100), as shown schematically in Fig. 3. The connectivity creates, as the sub-unit, rings of four anions with four bridging K⁺ ions, two of which are seen in the case of the eight octa­hedra nearest the horizontal mid-line of Fig. 3. When the layer is seen edge-on, as in Fig. 4, it is clear that the distribution of the anions creates grooves running in the direction of c in which the K⁺ cations lie.

Also shown in Fig. 4 are the water mol­ecules which, for the choice of origin used in the refinement of the structure, occur in layers centred on x = and alternate with layers of anions centred on x = 0, the whole arrangement being replicated by cell translation in the direction of a. As shown in Table 2, a large number of N—H⋯O and O—H⋯O hydrogen bonds are present in the structure of (I). Only those hydrogen bonds involving the O5 water mol­ecule, which is the only water mol­ecule not contributing to the immediate coordination of the K⁺ ion, provide connectivity between adjacent layers of ions. The O5—H5A⋯O4B hydrogen bond is directed to one of the neighbouring layers and the other three, of the form N1B—H11B⋯O5^iv, O6—H6A⋯O5^v and O5—H5B⋯O2B^v [symmetry codes: (iv) −x + 1, −y + 1, −z; (v) −x + 1, y + , −z + ], to the other. Also given in Table 2 are details of two weak C—H⋯O hydrogen bonds.

The asp ligands can be considered to have three distinct atom types available for bonding to the central metal atom because, on the basis of the labelling scheme used in this report, atom O1 is part of the carboxylate group directly attached to the asymmetric centre (C2) of the ligand and is distinguishable, therefore, from atom O3, which is part of a carboxylate group which is β to the asymmetric centre. When the octa­hedral complex is formed with one asp in each of its two enantiomeric forms, as is the case in (I), only one cis(N) isomer is possible in which cis(O1) and cis(O3) also occur. If, however, both asp ligands in the complex have the same enanti­omeric form, say L, as in the cobaltate(III) compounds described by Oonish et al. (1973, 1975), the cis(N) arrangement is found in two isomeric forms, one with trans(O1) and the other with trans(O3), as is clearly demonstrated by Oonish et al. (1973).

The presence of Co^III in (I), determined by the application of charge-balance considerations to the structural model, is at variance with the nature of the Co^II salt starting material. However, the bond lengths and angles within the cobaltate anion in (I) are in good agreement with those found in other structures containing this type of anion such as, for example, those described by Oonish et al. (1973, 1975) and several other related structures. In contrast, recourse to the Cambridge Structural Database (Version 5.26; Allen, 2002) by means of the Chemical Database Service of the EPSRC (Fletcher et al., 1996) has revealed only one example of a cobaltous aspartate species, namely cobaltous aspartate trihydrate, (II) (Doyne et al., 1957), which is polymeric, has a Co:asp ratio of 1:1 [as distinct from 1:2 in (I)] and displays different (slightly longer) Co—N and C—O bond distances from those observed in the cobaltate anion in (I). It seems reasonable to suggest that, had not oxidation of the Co^II of the starting material to Co^III taken place resulting in the formation of (I), then (II) might well have been the product of the reaction.

Figure 1 The asymmetric unit of (I). Displacement ellipsoids are drawn at the 20% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate hydrogen bonds.

Figure 2 The coordination of the K^+ cation in (I). Displacement ellipsoids are drawn at the 10% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry codes: (i) x, −y + , z + ; (ii) −x + 2, −y + 1, −z + 1.]

Figure 3 A schematic view of a layer of ions in (I). The cobaltate anions are represented by coordination octa­hedra. Circles of arbitrary radii represent other atoms, large and black for K and lighter and decreasing in size for O and C in that order. H atoms and water mol­ecules have been omitted for clarity.

Figure 4 A schematic representation of the unit cell contents of (I), viewed along [001]. The cobaltate anions are represented by coordination octa­hedra. Circles of arbitrary radii represent other atoms, large and black for K and lighter and decreasing in size for O, C and H in that order. Dashed lines represent hydrogen bonds.

Experimental

To a hot solution (333 K) of guanidinoacetic acid (0.3513 g, 3 mmol) and DL-aspartic acid (0.3993 g, 3 mmol) in deionized water (100 ml) was slowly added a solution of cobalt(II) nitrate hexa­hydrate (0.8732 g, 3 mmol) in deionized water (5 ml). The reaction mixture was stirred at 333 K for 8 h, slowly cooled to 277 K, and the pH adjusted to 6.0 with KOH (3 M). The initial white precipitate which formed was filtered off and the filtrate was stored in a covered, but not sealed, vessel. Dark-blue crystals began to form after the fifth month and were collected after six months, washed with absolute ethanol and dried at 323 K. Although electron paramagnetic resonance spectroscopy indicated the presence of at least some Co^II in the bulk product, it is clear that the sample crystal, containing Co^III, is a by-product of this reaction, arising from Co^III either present as an impurity or created by oxidation of the initial Co^II by oxygen in the air.

Crystal data

• K[Co(C₄H₅NO₄)₂]·3.5H₂O

• M_r = 423.27

• Monoclinic, P 2₁ /c

• a = 12.4853 (13) Å

• b = 12.4689 (13) Å

• c = 9.6914 (8) Å

• β = 92.952 (7)°

• V = 1506.7 (3) ų

• Z = 4

• D_x = 1.866 Mg m⁻³

• Mo Kα radiation

• Cell parameters from 3129 reflections

• θ = 2.9–27.5°

• μ = 1.48 mm⁻¹

• T = 120 (2) K

• Block, dark blue

• 0.40 × 0.30 × 0.08 mm

Data collection

• Nonius KappaCCD area-detector diffractometer

• φ and ω scans

• Absorption correction: multi-scan(SADABS; Sheldrick, 2003)T_min = 0.517, T_max = 0.891

• 16788 measured reflections

• 3330 independent reflections

• 2568 reflections with I > 2σ(I)

• R_int = 0.045

• θ_max = 27.5°

• h = −16 → 15

• k = −16 → 16

• l = −12 → 12

Refinement

• Refinement on F²

• R[F² > 2σ(F²)] = 0.065

• wR(F²) = 0.175

• S = 1.09

• 3330 reflections

• 208 parameters

• H-atom parameters constrained

• w = 1/[σ²(F_o²) + (0.0839P)² + 4.5102P] where P = (F_o² + 2F_c²)/3

• (Δ/σ)_max < 0.001

• Δρ_max = 1.24 e Å⁻³

• Δρ_min = −0.64 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Co1—O1B	1.886 (3)
Co1—O3A	1.899 (3)
Co1—N1A	1.902 (4)
Co1—N1B	1.909 (4)
Co1—O3B	1.917 (3)
Co1—O1A	1.921 (3)
K1—O3B	2.759 (3)
K1—O6	2.766 (4)
K1—O7	2.799 (6)
K1—O2A^i	2.821 (4)
K1—O2B^ii	2.862 (4)
K1—O3A	3.078 (4)
K1—O1A	3.092 (3)

O1B—Co1—O3A	177.34 (14)
O1B—Co1—N1A	89.62 (16)
O3A—Co1—N1A	91.48 (16)
O1B—Co1—N1B	86.38 (15)
O3A—Co1—N1B	91.08 (15)
N1A—Co1—N1B	97.02 (18)
O1B—Co1—O3B	92.85 (15)
O3A—Co1—O3B	86.27 (14)
N1A—Co1—O3B	174.29 (15)
N1B—Co1—O3B	88.27 (16)
O1B—Co1—O1A	90.54 (13)
O3A—Co1—O1A	91.97 (13)
N1A—Co1—O1A	84.57 (15)
N1B—Co1—O1A	176.52 (15)
O3B—Co1—O1A	90.26 (14)

N1A—C2A—C3A—C4A	50.6 (6)
C1A—C2A—C3A—C4A	−67.7 (5)
N1B—C2B—C3B—C4B	−45.0 (7)
C1B—C2B—C3B—C4B	72.8 (7)
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H11A⋯O2A^iii	0.92	2.29	2.930 (5)	126
N1A—H11A⋯O4A^iv	0.92	2.32	3.011 (5)	131
N1A—H12A⋯O4A^v	0.92	2.06	2.981 (5)	177
N1B—H11B⋯O5^vi	0.92	2.04	2.942 (6)	168
N1B—H12B⋯O1B^iii	0.92	2.34	2.925 (5)	121
N1B—H12B⋯O1A^iii	0.92	2.49	3.166 (5)	130
O5—H5A⋯O4B	0.84	1.87	2.685 (6)	163
O5—H5B⋯O2B^vii	0.84	1.94	2.777 (6)	169
O6—H6A⋯O5^vii	0.84	2.07	2.826 (6)	149
O6—H6B⋯O4A^viii	0.84	2.08	2.914 (6)	174
O7—H7A⋯O6^ix	0.84	2.23	3.074 (11)	17
O7—H7B⋯O4B	0.84	2.20	3.038 (10)	179
C2B—H21B⋯O3B^iii	1.00	2.48	3.419 (7)	156
C3A—H32A⋯O5^x	0.99	2.59	3.328 (7)	132
Symmetry codes: (iii) ; (iv) ; (v) -x+2, -y+1, -z; (vi) -x+1, -y+1, -z; (vii) ; (viii) ; (ix) ; (x) x+1, y, z.

As indicated by PLATON (Spek, 2003), the structural model used here sustains two symmetry-related [at (, 0, 0) and (, , )] solvent-accessible regions, each of volume 19 ų, per unit cell. Excluded from each of these regions of the structural model were two low electron density (approximately 2 e Å⁻³) features. This was accompanied by the supression, by means of the SQUEEZE option of PLATON, of their contribution to the intensity data. These features, less than 3 Å from the K⁺ ion, less than 1 Å apart and with site occupancy factors estimated to be of the order of 0.25, are perceived as representing additional highly disordered water mol­ecules solvating the K⁺ ion and present in total to the extent of 0.5H₂O per formula unit. The additional half-mol­ecule of water has been included in the mol­ecular formula but is, of course, absent from the structural model. In the final stages of refinement, H atoms attached to C and N atoms were placed in calculated positions, with C—H distances for tertiary and secondary C atoms of 1.00 and 0.99 Å, respectively, and for N, treated as secondary C, with N—H distance 0.92 Å. These H atoms were then refined with a riding model, with U_iso(H) = 1.2U_eq(C,N). Approximate positions for the H atoms of the water mol­ecules were obtained from difference maps, the geometry of the water mol­ecules idealized to give O—H distances of 0.84 Å and H—O—H angles in the range 101–105°, and the H atoms then refined with a riding model, with U_iso(H) = 1.5U_eq(O). In the final difference map, the largest peak is 1.01 Å from atom C2B.

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and ATOMS for Windows (Dowty, 1998); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

Supporting information

S1. Comment

As part of our continuing study of transition metal complexes with amino acids (Felcman & de Miranda, 1997; de Miranda & Felcman, 2001; de Miranda et al., 2002; Felcman et al., 2003), we have isolated and characterized the title compound, (I), from an aqueous reaction mixture containing DL-aspartic acid (asp), guanidineacetic acid (gaa) and Co^II (1:1:1). Crystals of (I) were obtained after several months. No crystalline complex containing gaa, either alone or in a mixed complex with asp, appeared in a similar time.

The asymmetric unit in the structure of (I) is shown in Fig. 1, and selected bond lengths and angles are given in Table 1. In the anion, an enantiomeric pair of asp dianions, with identical labelling of the atoms and distinguished by the suffixes A and B, act as tridentate ligands, creating octahedral coordination of atom Co1. The enantiomeric relationship of the asp dianions in the complex anion is evident in the torsion angles given in Table 1 and significant in later discussion of the isomerism of such complexes.

The K atom caps one face of the coordination octahedron of the anion to give a Co1···K1 distance of 3.6502 (14) Å. Its sevenfold coordination (Fig. 2) is completed by two non-coordinating O atoms associated with two further cobaltate anions and by two water molecules. A complex arrangement of K—O bonds connects the ions in layers parallel to (100), as shown schematically in Fig. 3. The connectivity creates, as the sub-unit, rings of four anions with four bridging K atoms, two of which are seen in the case of the eight octahedra nearest the horizontal mid-line of Fig. 3. When the layer is seen edge-on, as in Fig. 4, it is clear that the distribution of the anions creates grooves running in the direction of c in which the K cations lie.

Also shown in Fig. 4 are the water molecules which, for the choice of origin used in the refinement of the structure, occur in layers centred on x = 1/2 and alternate with layers of anions centred on x = 0, the whole arrangement being replicated by cell translation in the direction of a. As shown in Table 2, a large number of N—H···O and O—H···O hydrogen bonds are present in the structure of (I). Only those hydrogen bonds involving the O5 water molecule, which is the only water molecule not contributing to the immediate coordination of the K atom, provide connectivity between adjacent layers of ions. The O5—H5A···O4B hydrogen bond is directed to one of the neighbouring layers and the other three, of the form N1B—H11B···O5^iv, O6—H6A···O5^v and O5—H5B···O2B^v [symmetry codes: (iv) −x + 1, −y + 1, −z; (v) −x + 1, y + 1/2, −z + 1/2], to the other. Also given in Table 2 are details of two weak C—H···O hydrogen bonds.

The asp ligands can be considered to have three distinct atom types available for bonding to the central metal atom because, on the basis of the labelling scheme used in this report, atom O1 is part of the carboxyl group directly attached to the asymmetric centre (C2) of the ligand and is distinguishable, therefore, from atom O3, which is part of a carboxyl group which is β to the asymmetric centre. When the octahedral complex is formed with one asp in each of its two enantiomeric forms, as is the case in (I), only one cis(N) isomer is possible in which cis(O1) and cis(O3) also occur. If, however, both asp ligands in the complex have the same enantiomeric form, say L, as in the cobaltate(III) compounds described by Oonish et al. (1973, 1975), the cis(N) arrangement is found in two isomeric forms, one with trans(O1) and the other with trans(O3), as is clearly demonstrated by Oonish et al. (1973).

The presence of Co^III in (I), determined by the application of charge-balance considerations to the structural model, is at variance with the nature of the Co^II salt starting material. However, the bond lengths and angles within the cobaltate anion in (I) are in good agreement with those found in other structures containing this type of anion such as, for example, those described by Oonish et al. (1973, 1975) and several other related structures. In contrast, recourse to the Cambridge Structural Database (Version?; Allen, 2002) by means the Chemical Database Service of the EPSRC (Fletcher et al., 1996) has revealed only one example of a cobaltous aspartate species, namely cobaltous aspartate trihydrate, (II) (Doyne et al., 1957), which is polymeric, has a Co:asp ratio of 1:1 [as distinct from 1:2 in (I)] and displays different (slightly longer) Co—N and C—O bond distances from those observed in the cobaltate anion in (I). It seems reasonable to suggest that, had not oxidation of the Co^II of the starting material to Co^III taken place resulting in the formation of (I), then (II) might well have been the product of the reaction.

S2. Experimental

To a hot solution (333 K) of guanidinoacetic acid (0.3513 g, 3 mmol) and DL-aspartic acid (0.3993 g, 3 mmol) in deionized water (Volume?) was slowly added a solution of cobalt(II) nitrate hexahydrate (0.8732 g, 3 mmol) in deionized water (5 ml). The reaction mixture was stirred at 333 K for 8 h, slowly cooled to 277 K, and the pH adjusted to 6.0 with KOH (3 M). The initial white precipitate which formed was filtered off and the filtrate was stored in a covered, but not sealed, vessel. Dark-blue crystals began to form after the fifth month and were collected after six months, washed with absolute alcohol [ethanol?] and dried at 323 K. Although electron paramagnetic resonance spectroscopy indicated the presence of at least some Co^II in the bulk product, it is clear that the sample crystal, containing Co^III, is a by-product of this reaction, arising from Co^III either present as an impurity or created by oxidation of the initial Co^II by oxygen of the air.

S3. Refinement

As indicated by PLATON (Spek, 2003), the structural model used here sustains two symmetry-related [at (1/2,0,0) and (1/2,1/2,1/2)] solvent-accessible regions, each of volume 19 ų, per unit cell. Excluded from each of these regions of the structural model were two low electron density (approximately 2 e Å⁻³) features. This was accompanied by the supression, by means of the SQUEEZE option of PLATON, of their contribution to the intensity data. These features, less than 3 Å from the K atom, less than 1 Å apart and with site occupancy factors estimated to be of the order of 1/4, are perceived as representing additional highly disordered water molecules solvating the K atom and present in total to the extent of 0.5 H₂O per formula unit. The additional half-molecule of water has been included in the molecular formula but is, of course, absent from the structural model. In the final stages of refinement, H atoms attached to C and N atoms were placed in calculated positions, with C—H distances for tertiary and secondary C atoms of 1.00 and 0.99 Å, respectively, and for N, treated as secondary C, with N—H distance 0.92 Å. These H atoms were then refined with a riding model, with U_iso(H) = 1.2U_eq(C,N). Approximate positions for the H atoms of the water molecules were obtained from difference maps, the geometry of the water molecules idealized to give O—H distances of 0.84 Å and H—O—H angles in the range 100.9–104.8°, and the H atoms then refined with a riding model, with U_iso(H) = 1.5U_eq(O). In the final difference map, the largest peak is 1.01 Å from atom C2B.

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and ATOMS for Windows (Dowty, 1998); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

Figures

	Fig. 1. The asymmetric unit in (I). Displacement ellipsoids are drawn at the 20% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate hydrogen bonds.
	Fig. 2. The coordination of the K atom in (I). Displacement ellipsoids are drawn at the 10% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry codes: (i) x, −y + 1/2, z + 1/2; (ii) −x + 2, −y + 1, −z + 1.]
	Fig. 3. A schematic view of a layer of ions in (I). The cobaltate anions are represented by coordination octahedra. Circles of arbitrary radii represent other atoms, large and black for K and lighter and decreasing in size for O and C in that order. H atoms and water molecules have been omitted for clarity.
	Fig. 4. A schematic representation of the unit cell of (I), viewed along [001]. The cobaltate anions are represented by coordination octahedra. Circles of arbitrary radii represent other atoms, large and black for K and lighter and decreasing in size for O, C and H in that order. Dashed lines represent hydrogen bonds.

Potassium cis-[(R)-aspartato(2-)][(S)-aspartato(2-)]cobaltate(III) 3.5-hydrate

Crystal data

K[Co(C4H5NO4)2]·3.5H2O	F(000) = 868
Mr = 423.27	Dx = 1.866 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3129 reflections
a = 12.4853 (13) Å	θ = 2.9–27.5°
b = 12.4689 (13) Å	µ = 1.48 mm^−1
c = 9.6914 (8) Å	T = 120 K
β = 92.952 (7)°	Block, dark blue
V = 1506.7 (3) Å^3	0.40 × 0.30 × 0.08 mm
Z = 4

Data collection

Nonius KappaCCD area-detector diffractometer	3330 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	2568 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.2°
ϕ and ω scans	h = −16→15
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −16→16
Tmin = 0.517, Tmax = 0.891	l = −12→12
16788 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.065	Hydrogen site location: geom and difmap
wR(F^2) = 0.175	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0839P)^2 + 4.5102P] where P = (Fo^2 + 2Fc^2)/3
3330 reflections	(Δ/σ)max < 0.001
208 parameters	Δρmax = 1.24 e Å^−3
0 restraints	Δρmin = −0.64 e Å^−3

Special details

Experimental. Unit cell determined with DIRAX (Duisenberg, 1992; Duisenberg et al. 2000) but refined with the DENZO/COLLECT HKL package.

Refs as: Duisenberg, A. J. M. (1992). J. Appl. Cryst. 25, 92–96. Duisenberg, A. J. M., Hooft, R. W. W., Schreurs, A. M. M. & Kroon, J. (2000). J. Appl. Cryst. 33, 893–898.

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	0.83110 (5)	0.35774 (5)	0.19420 (6)	0.0229 (2)
K1	0.75090 (11)	0.57375 (9)	0.42121 (13)	0.0439 (3)
O1A	0.8801 (3)	0.3649 (2)	0.3852 (3)	0.0261 (7)
O2A	1.0300 (3)	0.3831 (3)	0.5172 (3)	0.0317 (8)
C1A	0.9823 (4)	0.3742 (3)	0.4046 (5)	0.0267 (10)
C2A	1.0420 (4)	0.3720 (4)	0.2685 (5)	0.0295 (10)
H21A	1.1123	0.3343	0.2841	0.035*
N1A	0.9735 (3)	0.3124 (3)	0.1647 (4)	0.0264 (8)
H11A	0.9804	0.2396	0.1777	0.032*
H12A	0.9920	0.3289	0.0765	0.032*
C3A	1.0608 (4)	0.4847 (4)	0.2154 (5)	0.0326 (11)
H31A	1.0981	0.5265	0.2902	0.039*
H32A	1.1096	0.4801	0.1382	0.039*
C4A	0.9615 (4)	0.5457 (4)	0.1658 (5)	0.0274 (10)
O3A	0.8679 (3)	0.5034 (2)	0.1644 (3)	0.0264 (7)
O4A	0.9747 (3)	0.6394 (2)	0.1257 (3)	0.0330 (8)
O1B	0.7903 (3)	0.2133 (2)	0.2163 (3)	0.0270 (7)
O2B	0.6924 (4)	0.0825 (3)	0.1201 (4)	0.0545 (12)
C1B	0.7245 (4)	0.1754 (4)	0.1234 (5)	0.0354 (12)
C2B	0.6882 (5)	0.2621 (5)	0.0140 (6)	0.0491 (15)
H21B	0.6743	0.2280	−0.0785	0.059*
N1B	0.7764 (3)	0.3441 (3)	0.0074 (4)	0.0304 (9)
H11B	0.7499	0.4085	−0.0257	0.036*
H12B	0.8290	0.3208	−0.0486	0.036*
C3B	0.5928 (6)	0.3219 (5)	0.0535 (6)	0.0525 (16)
H31B	0.5632	0.3603	−0.0293	0.063*
H32B	0.5381	0.2692	0.0797	0.063*
C4B	0.6066 (5)	0.3995 (5)	0.1653 (6)	0.0420 (13)
O3B	0.6932 (3)	0.4104 (3)	0.2403 (3)	0.0284 (7)
O4B	0.5292 (4)	0.4599 (5)	0.1905 (6)	0.0818 (17)
O5	0.3163 (3)	0.4669 (3)	0.1357 (5)	0.0475 (10)
H5A	0.3821	0.4518	0.1469	0.071*
H5B	0.3056	0.4986	0.2107	0.071*
O6	0.7698 (4)	0.7853 (3)	0.5047 (6)	0.0744 (17)
H6A	0.7598	0.8298	0.4404	0.112*
H6B	0.8282	0.8038	0.5449	0.112*
O7	0.6130 (6)	0.6865 (6)	0.2363 (8)	0.117 (3)
H7A	0.6556	0.6947	0.1728	0.175*
H7B	0.5893	0.6240	0.2237	0.175*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0306 (4)	0.0164 (3)	0.0212 (3)	0.0002 (2)	−0.0019 (2)	−0.0009 (2)
K1	0.0616 (9)	0.0277 (6)	0.0415 (7)	−0.0043 (5)	−0.0062 (6)	−0.0053 (5)
O1A	0.035 (2)	0.0226 (16)	0.0199 (16)	0.0018 (13)	−0.0024 (13)	−0.0001 (12)
O2A	0.042 (2)	0.0193 (16)	0.0327 (19)	−0.0008 (14)	−0.0092 (15)	0.0028 (13)
C1A	0.032 (3)	0.015 (2)	0.032 (3)	−0.0003 (17)	−0.002 (2)	0.0051 (17)
C2A	0.031 (3)	0.024 (2)	0.033 (3)	0.0026 (19)	−0.002 (2)	0.0043 (19)
N1A	0.032 (2)	0.0168 (18)	0.030 (2)	0.0001 (15)	−0.0011 (16)	−0.0032 (15)
C3A	0.039 (3)	0.027 (3)	0.032 (3)	−0.004 (2)	0.004 (2)	0.0046 (19)
C4A	0.038 (3)	0.024 (2)	0.020 (2)	0.0022 (19)	−0.0010 (19)	0.0003 (17)
O3A	0.0326 (18)	0.0143 (15)	0.0314 (17)	0.0007 (13)	−0.0054 (13)	0.0015 (12)
O4A	0.050 (2)	0.0215 (17)	0.0269 (17)	−0.0100 (14)	−0.0040 (15)	0.0047 (13)
O1B	0.0363 (19)	0.0179 (15)	0.0264 (17)	−0.0028 (13)	−0.0012 (14)	0.0012 (12)
O2B	0.067 (3)	0.049 (3)	0.048 (2)	−0.031 (2)	0.010 (2)	−0.0141 (19)
C1B	0.036 (3)	0.043 (3)	0.027 (3)	−0.001 (2)	0.003 (2)	−0.006 (2)
C2B	0.053 (4)	0.060 (4)	0.034 (3)	0.004 (3)	−0.003 (3)	−0.007 (3)
N1B	0.034 (2)	0.034 (2)	0.023 (2)	−0.0099 (17)	0.0005 (17)	0.0001 (16)
C3B	0.065 (4)	0.044 (3)	0.046 (4)	−0.001 (3)	−0.024 (3)	0.001 (3)
C4B	0.032 (3)	0.055 (3)	0.039 (3)	0.000 (3)	−0.004 (2)	0.004 (3)
O3B	0.0293 (18)	0.0288 (18)	0.0268 (17)	0.0038 (14)	−0.0012 (14)	−0.0045 (13)
O4B	0.040 (3)	0.123 (5)	0.081 (4)	0.019 (3)	−0.007 (2)	−0.016 (3)
O5	0.035 (2)	0.055 (3)	0.051 (2)	0.0017 (18)	−0.0079 (18)	0.0020 (19)
O6	0.066 (3)	0.035 (2)	0.116 (4)	0.007 (2)	−0.046 (3)	−0.018 (3)
O7	0.117 (6)	0.103 (5)	0.124 (6)	0.045 (4)	−0.050 (5)	−0.035 (4)

Geometric parameters (Å, º)

Co1—O1B	1.886 (3)	C3A—H32A	0.9900
Co1—O3A	1.899 (3)	C4A—O4A	1.245 (6)
Co1—N1A	1.902 (4)	C4A—O3A	1.282 (6)
Co1—N1B	1.909 (4)	O1B—C1B	1.278 (6)
Co1—O3B	1.917 (3)	O2B—C1B	1.226 (7)
Co1—O1A	1.921 (3)	O2B—K1^iii	2.862 (4)
K1—O3B	2.759 (3)	C1B—C2B	1.565 (8)
K1—O6	2.766 (4)	C2B—C3B	1.472 (9)
K1—O7	2.799 (6)	C2B—N1B	1.506 (8)
K1—O2A^i	2.821 (4)	C2B—H21B	1.0000
K1—O2B^ii	2.862 (4)	N1B—H11B	0.9200
K1—O3A	3.078 (4)	N1B—H12B	0.9200
K1—O1A	3.092 (3)	C3B—C4B	1.456 (8)
O1A—C1A	1.286 (6)	C3B—H31B	0.9900
O2A—C1A	1.221 (6)	C3B—H32B	0.9900
O2A—K1^i	2.821 (4)	C4B—O4B	1.258 (8)
C1A—C2A	1.549 (7)	C4B—O3B	1.279 (6)
C2A—N1A	1.486 (6)	O5—H5A	0.8434
C2A—C3A	1.518 (6)	O5—H5B	0.8445
C2A—H21A	1.0000	O6—H6A	0.8397
N1A—H11A	0.9200	O6—H6B	0.8406
N1A—H12A	0.9200	O7—H7A	0.8400
C3A—C4A	1.512 (7)	O7—H7B	0.8400
C3A—H31A	0.9900	Co1—K1	3.6502 (14)
O1B—Co1—O3A	177.34 (14)	C2A—N1A—H12A	110.7
O1B—Co1—N1A	89.62 (16)	Co1—N1A—H12A	110.7
O3A—Co1—N1A	91.48 (16)	H11A—N1A—H12A	108.8
O1B—Co1—N1B	86.38 (15)	C4A—C3A—C2A	115.8 (4)
O3A—Co1—N1B	91.08 (15)	C4A—C3A—H31A	108.3
N1A—Co1—N1B	97.02 (18)	C2A—C3A—H31A	108.3
O1B—Co1—O3B	92.85 (15)	C4A—C3A—H32A	108.3
O3A—Co1—O3B	86.27 (14)	C2A—C3A—H32A	108.3
N1A—Co1—O3B	174.29 (15)	H31A—C3A—H32A	107.4
N1B—Co1—O3B	88.27 (16)	O4A—C4A—O3A	121.2 (4)
O1B—Co1—O1A	90.54 (13)	O4A—C4A—C3A	116.9 (4)
O3A—Co1—O1A	91.97 (13)	O3A—C4A—C3A	121.9 (4)
N1A—Co1—O1A	84.57 (15)	C4A—O3A—Co1	128.3 (3)
N1B—Co1—O1A	176.52 (15)	C4A—O3A—K1	110.2 (3)
O3B—Co1—O1A	90.26 (14)	Co1—O3A—K1	91.21 (12)
O3B—K1—O6	154.90 (14)	C1B—O1B—Co1	116.2 (3)
O3B—K1—O7	80.32 (15)	C1B—O2B—K1^iii	124.5 (3)
O6—K1—O7	75.45 (17)	O2B—C1B—O1B	124.4 (5)
O3B—K1—O2A^i	119.60 (11)	O2B—C1B—C2B	123.5 (5)
O6—K1—O2A^i	71.88 (12)	O1B—C1B—C2B	112.0 (5)
O7—K1—O2A^i	126.7 (2)	C3B—C2B—N1B	105.7 (5)
O3B—K1—O2B^ii	81.86 (12)	C3B—C2B—C1B	112.6 (5)
O6—K1—O2B^ii	118.22 (16)	N1B—C2B—C1B	108.1 (4)
O7—K1—O2B^ii	127.1 (2)	C3B—C2B—H21B	110.1
O2A^i—K1—O2B^ii	105.39 (12)	N1B—C2B—H21B	110.1
O3B—K1—O3A	52.76 (9)	C1B—C2B—H21B	110.1
O6—K1—O3A	118.15 (15)	C2B—N1B—Co1	104.3 (3)
O7—K1—O3A	85.84 (18)	C2B—N1B—H11B	110.9
O2A^i—K1—O3A	74.34 (10)	Co1—N1B—H11B	110.9
O2B^ii—K1—O3A	119.93 (11)	C2B—N1B—H12B	110.9
O3B—K1—O1A	55.06 (9)	Co1—N1B—H12B	110.9
O6—K1—O1A	143.04 (13)	H11B—N1B—H12B	108.9
O7—K1—O1A	131.14 (15)	C4B—C3B—C2B	117.6 (5)
O2A^i—K1—O1A	71.27 (9)	C4B—C3B—H31B	107.9
O2B^ii—K1—O1A	69.84 (10)	C2B—C3B—H31B	107.9
O3A—K1—O1A	52.89 (8)	C4B—C3B—H32B	107.9
C1A—O1A—Co1	114.1 (3)	C2B—C3B—H32B	107.9
C1A—O1A—K1	115.3 (3)	H31B—C3B—H32B	107.2
Co1—O1A—K1	90.35 (11)	O4B—C4B—O3B	117.5 (5)
C1A—O2A—K1^i	129.0 (3)	O4B—C4B—C3B	118.6 (5)
O2A—C1A—O1A	125.0 (5)	O3B—C4B—C3B	123.9 (5)
O2A—C1A—C2A	121.9 (4)	C4B—O3B—Co1	125.1 (3)
O1A—C1A—C2A	113.1 (4)	C4B—O3B—K1	128.7 (3)
N1A—C2A—C3A	109.1 (4)	Co1—O3B—K1	101.11 (13)
N1A—C2A—C1A	107.4 (4)	H5A—O5—H5B	100.9
C3A—C2A—C1A	111.2 (4)	K1—O6—H6A	114.0
N1A—C2A—H21A	109.7	K1—O6—H6B	117.1
C3A—C2A—H21A	109.7	H6A—O6—H6B	104.8
C1A—C2A—H21A	109.7	K1—O7—H7A	98.0
C2A—N1A—Co1	105.1 (3)	K1—O7—H7B	80.1
C2A—N1A—H11A	110.7	H7A—O7—H7B	103.8
Co1—N1A—H11A	110.7
O2A—C1A—C2A—N1A	154.3 (4)	O2B—C1B—C2B—N1B	−153.2 (5)
O1A—C1A—C2A—N1A	−25.2 (5)	O1B—C1B—C2B—N1B	27.4 (6)
O2A—C1A—C2A—C3A	−86.4 (5)	O2B—C1B—C2B—C3B	90.5 (7)
O1A—C1A—C2A—C3A	94.1 (5)	O1B—C1B—C2B—C3B	−89.0 (6)
N1A—C2A—C3A—C4A	50.6 (6)	N1B—C2B—C3B—C4B	−45.0 (7)
C1A—C2A—C3A—C4A	−67.7 (5)	C1B—C2B—C3B—C4B	72.8 (7)
C2A—C3A—C4A—O4A	177.9 (4)	C2B—C3B—C4B—O4B	172.2 (6)
C2A—C3A—C4A—O3A	−2.3 (7)	C2B—C3B—C4B—O3B	−7.7 (9)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H11A···O2A^iii	0.92	2.29	2.930 (5)	126
N1A—H11A···O4A^iv	0.92	2.32	3.011 (5)	131
N1A—H12A···O4A^v	0.92	2.06	2.981 (5)	177
N1B—H11B···O5^vi	0.92	2.04	2.942 (6)	168
N1B—H12B···O1B^iii	0.92	2.34	2.925 (5)	121
N1B—H12B···O1A^iii	0.92	2.49	3.166 (5)	130
O5—H5A···O4B	0.84	1.87	2.685 (6)	163
O5—H5B···O2B^vii	0.84	1.94	2.777 (6)	169
O6—H6A···O5^vii	0.84	2.07	2.826 (6)	149
O6—H6B···O4A^viii	0.84	2.08	2.914 (6)	174
O7—H7A···O6^ix	0.84	2.23	3.074 (11)	17
O7—H7B···O4B	0.84	2.20	3.038 (10)	179
C2B—H21B···O3B^iii	1.00	2.48	3.419 (7)	156
C3A—H32A···O5^x	0.99	2.59	3.328 (7)	132

Symmetry codes: (iii) x, −y+1/2, z−1/2; (iv) −x+2, y−1/2, −z+1/2; (v) −x+2, −y+1, −z; (vi) −x+1, −y+1, −z; (vii) −x+1, y+1/2, −z+1/2; (viii) x, −y+3/2, z+1/2; (ix) x, −y+3/2, z−1/2; (x) x+1, y, z.