Penta-aqua-tri-μ(3)-hydroxido-tris-(imino-diacetato)-μ(3)-oxido-tetra-hedro-calcium(II)tricobalt(III) 2.54-hydrate.

In the title compound, [CaCo(3)(C(4)H(5)NO(4))(3)(OH)(3)O(H(2)O)(5)]·2.54H(2)O, the Co atom is octa-hedrally coordinated by one imino-diacetate (ida) dianion as a facial O,N,O'-tridentate ligand, two μ(3)-OH groups and one μ(3)-O ligand, forming an partial Co(3)O(4) cubane cluster. This unit coordinates to a Ca(II) cation in an O,O',O''-tridentate fashion, generating a distorted CaCo(3)O(4) cubane-type cluster. The Ca-μ(3)-O distances [2.429 (5)-2.572 (6) Å] are much longer than the Co-μ(3)-O bonds [1.895 (5)-1.941 (5) Å]. The Ca(II) cation is also coord-inated by five water mol-ecules with Ca-O distances in the range 2.355 (6)-2.543 (6) Å. There are three additional uncoordinated water mol-ecules in the asymmetric unit, the occupancy of which refined to 0.54 (3). In H(2)O (or D(2)O), the title complex hydrolyses to Ca(2+) (aq) cations and [Co(3)(ida)(3)(μ(2)-OH)(3)(μ(3)-O)](2-) anions.

Related literature

For the synthesis and chemistry of partial Co3O4 cubane clusters, see: Ama et al. (1997 ▶, 2000 ▶, 2001 ▶, 2006 ▶). For the chemistry and structure of CaMn4O4 clusters in the OEC (oxygen evolution center) of plants, see: Barber & Murray (2008 ▶); Rappaport & Diner (2008 ▶); Sauer et al. (2008 ▶); Yocum (2008 ▶). For a related structure, see: Ama et al. (1995 ▶).

Experimental

Crystal data

[CaCo3(C4H5NO4)3(OH)3O(H2O)5]·2.54H2O

M = 812.92

Triclinic,

a = 10.474 (3) Å

b = 11.303 (7) Å

c = 12.588 (5) Å

α = 75.88 (4)°

β = 100.92 (3)°

γ = 104.58 (3)°

V = 1385.6 (10) Å3

Z = 2

Mo Kα radiation

μ = 2.06 mm−1

T = 296 K

0.40 × 0.40 × 0.05 mm

Data collection

Rigaku AFC-7S diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.673, T max = 0.902

6713 measured reflections

6360 independent reflections

3290 reflections with F 2 > 2σ(F 2)

R int = 0.076

3 standard reflections every 150 reflections intensity decay: 4.8%

Refinement

R[F 2 > 2σ(F 2)] = 0.060

wR(F 2) = 0.207

S = 1.00

6360 reflections

389 parameters

H-atom parameters constrained

Δρmax = 1.17 e Å−3

Δρmin = −1.13 e Å−3

Data collection: WinAFC (Rigaku/MSC, 2000 ▶); cell refinement: WinAFC; data reduction: CrystalStructure (Rigaku/MSC, 2007 ▶); program(s) used to solve structure: DIRDIF99 (Beurskens et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2007 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810010998/sj2753sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810010998/sj2753Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[CaCo3(C4H5NO4)3(OH)3O(H2O)5]·2.54H2O	Z = 2
Mr = 812.92	F(000) = 830.80
Triclinic, P1	Dx = 1.948 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 10.474 (3) Å	Cell parameters from 12 reflections
b = 11.303 (7) Å	θ = 15.1–15.8°
c = 12.588 (5) Å	µ = 2.06 mm−1
α = 75.88 (4)°	T = 296 K
β = 100.92 (3)°	Plate, brown
γ = 104.58 (3)°	0.40 × 0.40 × 0.05 mm
V = 1385.6 (10) Å3

Rigaku AFC-7S diffractometer	Rint = 0.076
ω–2θ scans	θmax = 27.5°
Absorption correction: ψ scan (North et al., 1968)	h = 0→13
Tmin = 0.673, Tmax = 0.902	k = −14→14
6713 measured reflections	l = −16→16
6360 independent reflections	3 standard reflections every 150 reflections
3290 reflections with F2 > 2σ(F2)	intensity decay: 4.8%

Refinement on F2	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.060	w = 1/[σ2(Fo2) + (0.1052P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.207	(Δ/σ)max < 0.0001
S = 1.00	Δρmax = 1.17 e Å−3
6360 reflections	Δρmin = −1.13 e Å−3
389 parameters

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt).

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co(1)	0.71696 (10)	0.72533 (9)	0.93041 (8)	0.0137 (2)
Co(2)	0.73172 (10)	0.93813 (9)	0.75658 (8)	0.0141 (2)
Co(3)	0.51954 (10)	0.72856 (9)	0.74180 (8)	0.0140 (2)
Ca(1)	0.81420 (15)	0.67221 (15)	0.69882 (13)	0.0190 (3)
O(1)	0.6046 (4)	0.8286 (4)	0.8436 (4)	0.0141 (10)
O(2)	0.8387 (5)	0.8207 (4)	0.8306 (4)	0.0176 (11)
O(3)	0.6625 (5)	0.8240 (4)	0.6610 (4)	0.0154 (10)
O(4)	0.6435 (5)	0.6261 (4)	0.8183 (4)	0.0160 (10)
O(5)	0.8438 (5)	0.6279 (5)	1.0143 (4)	0.0224 (12)
O(6)	1.0147 (6)	0.6325 (6)	1.1499 (5)	0.0377 (16)
O(7)	0.5867 (5)	0.6299 (5)	1.0215 (4)	0.0227 (12)
O(8)	0.4950 (6)	0.6300 (6)	1.1655 (5)	0.0327 (14)
O(9)	0.8615 (5)	1.0388 (5)	0.6638 (4)	0.0256 (12)
O(10)	0.8934 (7)	1.2014 (6)	0.5255 (6)	0.052 (2)
O(11)	0.7888 (5)	1.0409 (4)	0.8634 (4)	0.0176 (11)
O(12)	0.7064 (8)	1.1589 (7)	0.9394 (5)	0.051 (2)
O(13)	0.4431 (5)	0.6281 (5)	0.6339 (4)	0.0228 (12)
O(14)	0.2633 (7)	0.4911 (7)	0.5851 (6)	0.051 (2)
O(15)	0.4032 (5)	0.8393 (5)	0.6783 (4)	0.0203 (11)
O(16)	0.2518 (6)	0.9176 (6)	0.7259 (5)	0.0399 (16)
O(17)	0.9506 (7)	0.8551 (6)	0.6103 (6)	0.050 (2)
O(18)	0.6561 (6)	0.6337 (6)	0.5383 (5)	0.0358 (16)
O(19)	0.7455 (5)	0.4350 (6)	0.7370 (5)	0.0348 (15)
O(20)	0.9788 (6)	0.6105 (6)	0.8499 (5)	0.0313 (14)
O(21)	0.9474 (6)	0.5947 (6)	0.5991 (5)	0.0395 (16)
O(22)	0.0992 (5)	0.9178 (6)	0.8899 (5)	0.0315 (14)
O(23)	0.6372 (6)	0.8910 (6)	0.4401 (5)	0.0411 (17)
O(24)	0.8213 (16)	0.7798 (16)	0.3566 (14)	0.068 (4)	0.54 (3)
N(1)	0.7746 (6)	0.8266 (5)	1.0404 (5)	0.0168 (12)
N(2)	0.6218 (5)	1.0576 (5)	0.6830 (5)	0.0149 (12)
N(3)	0.3720 (6)	0.6372 (5)	0.8218 (5)	0.0167 (12)
C(1)	0.9207 (8)	0.6772 (7)	1.0912 (6)	0.0236 (17)
C(2)	0.5724 (7)	0.6812 (7)	1.0984 (6)	0.0195 (15)
C(3)	0.8963 (8)	0.7956 (8)	1.1112 (7)	0.0279 (18)
C(4)	0.6595 (8)	0.8098 (7)	1.0997 (7)	0.0251 (17)
C(5)	0.8276 (9)	1.1327 (8)	0.5968 (7)	0.0300 (19)
C(6)	0.7038 (9)	1.1044 (7)	0.8667 (6)	0.0253 (17)
C(7)	0.6939 (9)	1.1555 (8)	0.6011 (7)	0.031 (2)
C(8)	0.5893 (8)	1.1025 (7)	0.7744 (6)	0.0213 (16)
C(9)	0.3283 (8)	0.5566 (8)	0.6488 (7)	0.0266 (18)
C(10)	0.3213 (7)	0.8398 (7)	0.7426 (6)	0.0217 (16)
C(11)	0.2752 (8)	0.5578 (7)	0.7508 (7)	0.0246 (17)
C(12)	0.3138 (8)	0.7343 (7)	0.8439 (6)	0.0237 (17)
H(1)	0.7947	0.9079	1.0048	0.020*
H(2)	0.5452	1.0172	0.6476	0.018*
H(3)	0.4015	0.5889	0.8864	0.020*
H(4)	0.8859	0.7841	1.1867	0.033*
H(5)	0.9702	0.8623	1.0944	0.033*
H(6)	0.6091	0.8711	1.0637	0.030*
H(7)	0.6904	0.8183	1.1738	0.030*
H(8)	0.7057	1.2340	0.6207	0.037*
H(9)	0.6423	1.1567	0.5303	0.037*
H(10)	0.5117	1.0479	0.8014	0.026*
H(11)	0.5732	1.1844	0.7478	0.026*
H(12)	0.1962	0.5897	0.7294	0.030*
H(13)	0.2551	0.4749	0.7923	0.030*
H(14)	0.3632	0.7642	0.9071	0.028*
H(15)	0.2237	0.7009	0.8558	0.028*
H(16)	0.9166	0.8498	0.8586	0.021*
H(17)	0.6408	0.8554	0.5940	0.018*
H(18)	0.6107	0.5500	0.8413	0.019*
H(19)	0.9347	0.9179	0.6258	0.060*
H(20)	1.0115	0.8682	0.5710	0.060*
H(21)	0.6803	0.5862	0.5078	0.043*
H(22)	0.5806	0.5997	0.5577	0.043*
H(23)	0.7839	0.4056	0.7991	0.042*
H(24)	0.6626	0.4130	0.7365	0.042*
H(25)	0.9410	0.5690	0.9048	0.038*
H(26)	1.0209	0.5666	0.8310	0.038*
H(27)	0.8977	0.5387	0.5677	0.047*
H(28)	0.9823	0.6540	0.5514	0.047*
H(29)	0.1383	0.8707	0.9402	0.038*
H(30)	0.1340	0.8916	0.8478	0.038*
H(31)	0.6683	0.8379	0.4229	0.049*
H(32)	0.6765	0.9500	0.3952	0.049*
H(33)	0.8162	0.7109	0.3878	0.079*	0.54
H(34)	0.8708	0.8215	0.3978	0.079*	0.54

	U11	U22	U33	U12	U13	U23
Co(1)	0.0127 (4)	0.0144 (5)	0.0121 (4)	0.0010 (3)	0.0026 (3)	−0.0006 (3)
Co(2)	0.0116 (4)	0.0139 (5)	0.0152 (4)	0.0011 (3)	0.0034 (3)	−0.0007 (3)
Co(3)	0.0110 (4)	0.0161 (5)	0.0135 (4)	0.0006 (3)	0.0026 (3)	−0.0024 (3)
Ca(1)	0.0147 (7)	0.0214 (8)	0.0208 (7)	0.0042 (6)	0.0039 (6)	−0.0027 (6)
O(1)	0.012 (2)	0.014 (2)	0.018 (2)	0.003 (2)	−0.0010 (19)	−0.008 (2)
O(2)	0.013 (2)	0.016 (2)	0.020 (2)	0.002 (2)	0.000 (2)	−0.001 (2)
O(3)	0.018 (2)	0.015 (2)	0.013 (2)	0.003 (2)	0.004 (2)	−0.001 (2)
O(4)	0.018 (2)	0.012 (2)	0.018 (2)	0.004 (2)	0.005 (2)	−0.003 (2)
O(5)	0.025 (2)	0.018 (2)	0.023 (2)	0.008 (2)	0.001 (2)	0.000 (2)
O(6)	0.032 (3)	0.039 (3)	0.038 (3)	0.019 (3)	−0.007 (2)	0.001 (3)
O(7)	0.020 (2)	0.018 (2)	0.024 (2)	−0.004 (2)	0.007 (2)	0.001 (2)
O(8)	0.029 (3)	0.034 (3)	0.032 (3)	−0.003 (2)	0.017 (2)	−0.002 (2)
O(9)	0.020 (2)	0.021 (2)	0.034 (3)	0.001 (2)	0.015 (2)	0.002 (2)
O(10)	0.058 (4)	0.040 (4)	0.057 (4)	0.018 (3)	0.039 (4)	0.025 (3)
O(11)	0.020 (2)	0.017 (2)	0.015 (2)	0.000 (2)	−0.002 (2)	−0.009 (2)
O(12)	0.067 (5)	0.073 (5)	0.033 (3)	0.046 (4)	−0.014 (3)	−0.033 (3)
O(13)	0.015 (2)	0.031 (3)	0.019 (2)	−0.007 (2)	0.009 (2)	−0.006 (2)
O(14)	0.035 (3)	0.069 (5)	0.052 (4)	−0.022 (3)	0.012 (3)	−0.045 (4)
O(15)	0.016 (2)	0.023 (2)	0.021 (2)	0.007 (2)	0.002 (2)	−0.001 (2)
O(16)	0.034 (3)	0.038 (3)	0.050 (4)	0.019 (3)	0.020 (3)	0.008 (3)
O(17)	0.041 (4)	0.034 (3)	0.083 (5)	0.003 (3)	0.043 (4)	−0.005 (3)
O(18)	0.028 (3)	0.048 (4)	0.045 (3)	0.006 (3)	0.010 (2)	−0.033 (3)
O(19)	0.020 (3)	0.033 (3)	0.047 (3)	0.002 (2)	0.006 (2)	−0.002 (3)
O(20)	0.030 (3)	0.036 (3)	0.030 (3)	0.009 (2)	0.004 (2)	−0.009 (2)
O(21)	0.040 (3)	0.029 (3)	0.051 (4)	−0.003 (2)	0.025 (3)	−0.007 (3)
O(22)	0.020 (2)	0.039 (3)	0.037 (3)	0.002 (2)	0.002 (2)	−0.016 (2)
O(23)	0.039 (3)	0.053 (4)	0.029 (3)	0.020 (3)	0.009 (3)	0.010 (3)
O(24)	0.063 (10)	0.071 (11)	0.066 (10)	0.016 (9)	0.003 (8)	−0.009 (9)
N(1)	0.021 (3)	0.015 (3)	0.015 (3)	0.003 (2)	0.006 (2)	−0.004 (2)
N(2)	0.013 (2)	0.013 (2)	0.017 (3)	−0.001 (2)	0.003 (2)	−0.001 (2)
N(3)	0.015 (3)	0.017 (3)	0.016 (3)	0.004 (2)	0.000 (2)	−0.001 (2)
C(1)	0.023 (4)	0.018 (4)	0.029 (4)	0.004 (3)	0.010 (3)	0.001 (3)
C(2)	0.015 (3)	0.019 (3)	0.023 (3)	0.003 (2)	0.001 (3)	−0.002 (3)
C(3)	0.026 (4)	0.034 (4)	0.028 (4)	0.008 (3)	0.002 (3)	−0.014 (3)
C(4)	0.024 (4)	0.022 (4)	0.027 (4)	−0.004 (3)	0.009 (3)	−0.006 (3)
C(5)	0.028 (4)	0.025 (4)	0.037 (5)	−0.002 (3)	0.014 (3)	−0.008 (3)
C(6)	0.038 (4)	0.021 (4)	0.023 (4)	0.014 (3)	0.005 (3)	−0.008 (3)
C(7)	0.036 (4)	0.023 (4)	0.034 (4)	0.018 (3)	0.012 (4)	0.013 (3)
C(8)	0.029 (4)	0.025 (4)	0.015 (3)	0.010 (3)	0.005 (3)	−0.007 (3)
C(9)	0.019 (3)	0.029 (4)	0.031 (4)	0.000 (3)	0.005 (3)	−0.009 (3)
C(10)	0.016 (3)	0.021 (4)	0.025 (4)	0.003 (3)	−0.001 (3)	−0.003 (3)
C(11)	0.019 (3)	0.023 (4)	0.035 (4)	−0.005 (3)	0.009 (3)	−0.016 (3)
C(12)	0.022 (4)	0.022 (4)	0.027 (4)	0.004 (3)	0.011 (3)	0.000 (3)

Co(1)—O(1)	1.877 (5)	N(3)—C(11)	1.491 (10)
Co(1)—O(2)	1.903 (5)	N(3)—C(12)	1.484 (12)
Co(1)—O(4)	1.941 (5)	C(1)—C(3)	1.511 (14)
Co(1)—O(5)	1.932 (5)	C(2)—C(4)	1.511 (10)
Co(1)—O(7)	1.894 (5)	C(5)—C(7)	1.499 (14)
Co(1)—N(1)	1.923 (6)	C(6)—C(8)	1.503 (11)
Co(2)—O(1)	1.888 (4)	C(9)—C(11)	1.498 (14)
Co(2)—O(2)	1.907 (5)	C(10)—C(12)	1.518 (10)
Co(2)—O(3)	1.895 (5)	O(2)—H(16)	0.842
Co(2)—O(9)	1.918 (5)	O(3)—H(17)	0.843
Co(2)—O(11)	1.904 (5)	O(4)—H(18)	0.842
Co(2)—N(2)	1.943 (6)	O(17)—H(19)	0.841
Co(3)—Ca(1)	3.466 (2)	O(17)—H(20)	0.844
Co(3)—O(1)	1.866 (5)	O(18)—H(21)	0.840
Co(3)—O(3)	1.915 (5)	O(18)—H(22)	0.840
Co(3)—O(4)	1.921 (5)	O(19)—H(23)	0.840
Co(3)—O(13)	1.913 (6)	O(19)—H(24)	0.839
Co(3)—O(15)	1.897 (5)	O(20)—H(25)	0.840
Co(3)—N(3)	1.936 (6)	O(20)—H(26)	0.840
Ca(1)—O(2)	2.572 (6)	O(21)—H(27)	0.840
Ca(1)—O(3)	2.527 (6)	O(21)—H(28)	0.840
Ca(1)—O(4)	2.429 (5)	O(22)—H(29)	0.837
Ca(1)—O(17)	2.355 (6)	O(22)—H(30)	0.839
Ca(1)—O(18)	2.411 (6)	O(23)—H(31)	0.837
Ca(1)—O(19)	2.543 (6)	O(23)—H(32)	0.836
Ca(1)—O(20)	2.406 (6)	O(24)—H(33)	0.775
Ca(1)—O(21)	2.471 (8)	O(24)—H(34)	0.809
O(5)—C(1)	1.280 (9)	N(1)—H(1)	0.910
O(6)—C(1)	1.249 (10)	N(2)—H(2)	0.910
O(7)—C(2)	1.292 (11)	N(3)—H(3)	0.910
O(8)—C(2)	1.220 (10)	C(3)—H(4)	0.951
O(9)—C(5)	1.267 (10)	C(3)—H(5)	0.951
O(10)—C(5)	1.227 (11)	C(4)—H(6)	0.951
O(11)—C(6)	1.288 (12)	C(4)—H(7)	0.947
O(12)—C(6)	1.215 (13)	C(7)—H(8)	0.951
O(13)—C(9)	1.287 (9)	C(7)—H(9)	0.950
O(14)—C(9)	1.219 (12)	C(8)—H(10)	0.952
O(15)—C(10)	1.288 (11)	C(8)—H(11)	0.950
O(16)—C(10)	1.234 (12)	C(11)—H(12)	0.951
N(1)—C(3)	1.477 (10)	C(11)—H(13)	0.948
N(1)—C(4)	1.485 (12)	C(12)—H(14)	0.951
N(2)—C(7)	1.475 (10)	C(12)—H(15)	0.951
N(2)—C(8)	1.489 (12)
O(1)—Co(1)—O(2)	83.4 (2)	Co(2)—O(11)—C(6)	113.5 (4)
O(1)—Co(1)—O(4)	82.8 (2)	Co(3)—O(13)—C(9)	115.3 (6)
O(1)—Co(1)—O(5)	175.6 (2)	Co(3)—O(15)—C(10)	113.6 (4)
O(1)—Co(1)—O(7)	93.8 (2)	Co(1)—N(1)—C(3)	110.3 (6)
O(1)—Co(1)—N(1)	93.2 (2)	Co(1)—N(1)—C(4)	107.1 (4)
O(2)—Co(1)—O(4)	85.6 (2)	C(3)—N(1)—C(4)	115.2 (6)
O(2)—Co(1)—O(5)	92.3 (2)	Co(2)—N(2)—C(7)	109.6 (5)
O(2)—Co(1)—O(7)	176.1 (2)	Co(2)—N(2)—C(8)	104.6 (4)
O(2)—Co(1)—N(1)	97.0 (2)	C(7)—N(2)—C(8)	115.1 (6)
O(4)—Co(1)—O(5)	97.9 (2)	Co(3)—N(3)—C(11)	108.5 (5)
O(4)—Co(1)—O(7)	91.4 (2)	Co(3)—N(3)—C(12)	105.2 (4)
O(4)—Co(1)—N(1)	175.0 (2)	C(11)—N(3)—C(12)	111.8 (6)
O(5)—Co(1)—O(7)	90.5 (2)	O(5)—C(1)—O(6)	123.4 (8)
O(5)—Co(1)—N(1)	86.3 (2)	O(5)—C(1)—C(3)	117.9 (7)
O(7)—Co(1)—N(1)	85.8 (2)	O(6)—C(1)—C(3)	118.7 (7)
O(1)—Co(2)—O(2)	82.9 (2)	O(7)—C(2)—O(8)	122.9 (7)
O(1)—Co(2)—O(3)	82.7 (2)	O(7)—C(2)—C(4)	114.9 (6)
O(1)—Co(2)—O(9)	175.7 (2)	O(8)—C(2)—C(4)	122.2 (8)
O(1)—Co(2)—O(11)	91.0 (2)	N(1)—C(3)—C(1)	110.2 (7)
O(1)—Co(2)—N(2)	96.5 (2)	N(1)—C(4)—C(2)	109.2 (7)
O(2)—Co(2)—O(3)	84.0 (2)	O(9)—C(5)—O(10)	124.4 (9)
O(2)—Co(2)—O(9)	94.7 (2)	O(9)—C(5)—C(7)	117.0 (7)
O(2)—Co(2)—O(11)	94.9 (2)	O(10)—C(5)—C(7)	118.4 (8)
O(2)—Co(2)—N(2)	179.2 (2)	O(11)—C(6)—O(12)	125.5 (8)
O(3)—Co(2)—O(9)	93.4 (2)	O(11)—C(6)—C(8)	115.3 (8)
O(3)—Co(2)—O(11)	173.8 (2)	O(12)—C(6)—C(8)	119.1 (9)
O(3)—Co(2)—N(2)	96.4 (2)	N(2)—C(7)—C(5)	111.7 (7)
O(9)—Co(2)—O(11)	92.8 (2)	N(2)—C(8)—C(6)	109.6 (7)
O(9)—Co(2)—N(2)	86.0 (2)	O(13)—C(9)—O(14)	123.7 (9)
O(11)—Co(2)—N(2)	84.6 (2)	O(13)—C(9)—C(11)	116.2 (7)
Ca(1)—Co(3)—O(1)	93.60 (17)	O(14)—C(9)—C(11)	120.2 (7)
Ca(1)—Co(3)—O(3)	45.55 (17)	O(15)—C(10)—O(16)	124.6 (7)
Ca(1)—Co(3)—O(4)	42.59 (16)	O(15)—C(10)—C(12)	114.8 (7)
Ca(1)—Co(3)—O(13)	82.93 (19)	O(16)—C(10)—C(12)	120.6 (8)
Ca(1)—Co(3)—O(15)	139.35 (16)	N(3)—C(11)—C(9)	112.4 (6)
Ca(1)—Co(3)—N(3)	136.5 (2)	N(3)—C(12)—C(10)	107.0 (7)
O(1)—Co(3)—O(3)	82.8 (2)	Co(1)—O(2)—H(16)	117.0
O(1)—Co(3)—O(4)	83.6 (2)	Co(2)—O(2)—H(16)	116.9
O(1)—Co(3)—O(13)	176.3 (2)	Ca(1)—O(2)—H(16)	117.0
O(1)—Co(3)—O(15)	90.4 (2)	Co(2)—O(3)—H(17)	116.3
O(1)—Co(3)—N(3)	96.7 (2)	Co(3)—O(3)—H(17)	116.2
O(3)—Co(3)—O(4)	85.1 (2)	Ca(1)—O(3)—H(17)	116.2
O(3)—Co(3)—O(13)	93.8 (2)	Co(1)—O(4)—H(18)	116.3
O(3)—Co(3)—O(15)	95.2 (2)	Co(3)—O(4)—H(18)	116.3
O(3)—Co(3)—N(3)	177.9 (2)	Ca(1)—O(4)—H(18)	116.4
O(4)—Co(3)—O(13)	94.6 (2)	Ca(1)—O(17)—H(19)	109.5
O(4)—Co(3)—O(15)	174.0 (2)	Ca(1)—O(17)—H(20)	133.3
O(4)—Co(3)—N(3)	96.9 (2)	H(19)—O(17)—H(20)	117.1
O(13)—Co(3)—O(15)	91.3 (2)	Ca(1)—O(18)—H(21)	109.5
O(13)—Co(3)—N(3)	86.8 (2)	Ca(1)—O(18)—H(22)	109.5
O(15)—Co(3)—N(3)	82.8 (2)	H(21)—O(18)—H(22)	109.4
Co(3)—Ca(1)—O(2)	64.34 (12)	Ca(1)—O(19)—H(23)	109.4
Co(3)—Ca(1)—O(3)	32.76 (10)	Ca(1)—O(19)—H(24)	109.4
Co(3)—Ca(1)—O(4)	32.37 (12)	H(23)—O(19)—H(24)	109.6
Co(3)—Ca(1)—O(17)	111.7 (2)	Ca(1)—O(20)—H(25)	109.5
Co(3)—Ca(1)—O(18)	74.12 (19)	Ca(1)—O(20)—H(26)	109.5
Co(3)—Ca(1)—O(19)	97.28 (16)	H(25)—O(20)—H(26)	109.5
Co(3)—Ca(1)—O(20)	121.95 (18)	Ca(1)—O(21)—H(27)	109.4
Co(3)—Ca(1)—O(21)	153.06 (16)	Ca(1)—O(21)—H(28)	109.4
O(2)—Ca(1)—O(3)	59.84 (16)	H(27)—O(21)—H(28)	109.5
O(2)—Ca(1)—O(4)	62.91 (17)	H(29)—O(22)—H(30)	84.2
O(2)—Ca(1)—O(17)	78.2 (2)	H(31)—O(23)—H(32)	93.0
O(2)—Ca(1)—O(18)	132.2 (2)	H(33)—O(24)—H(34)	105.7
O(2)—Ca(1)—O(19)	128.8 (2)	Co(1)—N(1)—H(1)	108.0
O(2)—Ca(1)—O(20)	75.0 (2)	C(3)—N(1)—H(1)	108.1
O(2)—Ca(1)—O(21)	141.50 (19)	C(4)—N(1)—H(1)	107.9
O(3)—Ca(1)—O(4)	63.09 (16)	Co(2)—N(2)—H(2)	109.1
O(3)—Ca(1)—O(17)	79.3 (2)	C(7)—N(2)—H(2)	109.1
O(3)—Ca(1)—O(18)	72.5 (2)	C(8)—N(2)—H(2)	109.2
O(3)—Ca(1)—O(19)	126.86 (18)	Co(3)—N(3)—H(3)	110.4
O(3)—Ca(1)—O(20)	134.5 (2)	C(11)—N(3)—H(3)	110.3
O(3)—Ca(1)—O(21)	139.57 (19)	C(12)—N(3)—H(3)	110.5
O(4)—Ca(1)—O(17)	135.4 (2)	N(1)—C(3)—H(4)	109.3
O(4)—Ca(1)—O(18)	93.7 (2)	N(1)—C(3)—H(5)	109.3
O(4)—Ca(1)—O(19)	76.6 (2)	C(1)—C(3)—H(4)	109.3
O(4)—Ca(1)—O(20)	92.9 (2)	C(1)—C(3)—H(5)	109.3
O(4)—Ca(1)—O(21)	148.6 (2)	H(4)—C(3)—H(5)	109.4
O(17)—Ca(1)—O(18)	97.1 (2)	N(1)—C(4)—H(6)	109.5
O(17)—Ca(1)—O(19)	148.0 (2)	N(1)—C(4)—H(7)	109.7
O(17)—Ca(1)—O(20)	97.6 (2)	C(2)—C(4)—H(6)	109.3
O(17)—Ca(1)—O(21)	76.0 (2)	C(2)—C(4)—H(7)	109.5
O(18)—Ca(1)—O(19)	77.4 (2)	H(6)—C(4)—H(7)	109.6
O(18)—Ca(1)—O(20)	151.5 (2)	N(2)—C(7)—H(8)	108.7
O(18)—Ca(1)—O(21)	79.4 (2)	N(2)—C(7)—H(9)	108.8
O(19)—Ca(1)—O(20)	77.2 (2)	C(5)—C(7)—H(8)	109.0
O(19)—Ca(1)—O(21)	72.0 (2)	C(5)—C(7)—H(9)	109.1
O(20)—Ca(1)—O(21)	80.6 (2)	H(8)—C(7)—H(9)	109.4
Co(1)—O(1)—Co(2)	97.1 (2)	N(2)—C(8)—H(10)	109.5
Co(1)—O(1)—Co(3)	98.6 (2)	N(2)—C(8)—H(11)	109.6
Co(2)—O(1)—Co(3)	97.7 (2)	C(6)—C(8)—H(10)	109.4
Co(1)—O(2)—Co(2)	95.6 (2)	C(6)—C(8)—H(11)	109.5
Co(1)—O(2)—Ca(1)	101.5 (2)	H(10)—C(8)—H(11)	109.3
Co(2)—O(2)—Ca(1)	105.8 (2)	N(3)—C(11)—H(12)	108.6
Co(2)—O(3)—Co(3)	95.8 (2)	N(3)—C(11)—H(13)	108.8
Co(2)—O(3)—Ca(1)	107.9 (2)	C(9)—C(11)—H(12)	108.7
Co(3)—O(3)—Ca(1)	101.7 (2)	C(9)—C(11)—H(13)	108.8
Co(1)—O(4)—Co(3)	94.5 (2)	H(12)—C(11)—H(13)	109.6
Co(1)—O(4)—Ca(1)	105.5 (2)	N(3)—C(12)—H(14)	110.2
Co(3)—O(4)—Ca(1)	105.0 (2)	N(3)—C(12)—H(15)	110.3
Co(1)—O(5)—C(1)	113.7 (5)	C(10)—C(12)—H(14)	110.0
Co(1)—O(7)—C(2)	115.1 (4)	C(10)—C(12)—H(15)	110.0
Co(2)—O(9)—C(5)	115.6 (6)	H(14)—C(12)—H(15)	109.4

D—H···A	D—H	H···A	D···A	D—H···A
O(2)—H(16)···O(22)i	0.84	1.88	2.707 (7)	168
O(3)—H(17)···O(23)	0.84	1.88	2.677 (7)	159
O(4)—H(18)···O(8)ii	0.84	2.07	2.870 (7)	158
O(17)—H(19)···O(9)	0.84	1.92	2.744 (11)	168
O(17)—H(20)···O(10)iii	0.84	2.10	2.850 (13)	148
O(18)—H(21)···O(14)iv	0.84	1.87	2.699 (12)	168
O(18)—H(22)···O(13)	0.84	2.00	2.708 (9)	141
O(19)—H(23)···O(6)v	0.84	2.21	2.829 (9)	131
O(19)—H(24)···O(8)ii	0.84	2.14	2.863 (9)	145
O(20)—H(25)···O(5)	0.84	2.17	2.787 (9)	130
O(20)—H(26)···O(6)v	0.84	2.15	2.765 (10)	130
O(21)—H(27)···O(14)iv	0.84	2.34	3.043 (9)	142
O(21)—H(28)···O(10)iii	0.84	1.99	2.801 (9)	164
O(22)—H(29)···O(12)vi	0.84	2.04	2.800 (9)	152
O(22)—H(30)···O(16)	0.84	2.07	2.840 (10)	153
O(23)—H(31)···O(18)	0.84	2.40	2.909 (10)	120
O(23)—H(31)···O(24)	0.84	2.24	3.01 (2)	153
O(23)—H(32)···O(16)vii	0.84	1.97	2.802 (8)	172
O(24)—H(33)···O(14)iv	0.78	2.19	2.912 (18)	156
O(24)—H(34)···O(10)iii	0.81	2.53	3.054 (18)	124
N(1)—H(1)···O(11)	0.91	2.03	2.857 (7)	150
N(1)—H(1)···O(22)vi	0.91	2.55	3.121 (9)	122
N(2)—H(2)···O(15)	0.91	2.18	2.917 (7)	138
N(2)—H(2)···O(23)vii	0.91	2.36	2.977 (9)	125
N(3)—H(3)···O(7)	0.91	2.36	3.038 (7)	132
N(3)—H(3)···O(7)ii	0.91	2.49	3.259 (8)	143

Table 1

Selected bond lengths (Å)

Co1—O1	1.877 (5)
Co1—O2	1.903 (5)
Co1—O4	1.941 (5)
Co2—O1	1.888 (4)
Co2—O2	1.907 (5)
Co2—O3	1.895 (5)
Co3—O1	1.866 (5)
Co3—O3	1.915 (5)
Co3—O4	1.921 (5)
Ca1—O2	2.572 (6)
Ca1—O3	2.527 (6)
Ca1—O4	2.429 (5)
Ca1—O17	2.355 (6)
Ca1—O18	2.411 (6)
Ca1—O19	2.543 (6)
Ca1—O20	2.406 (6)
Ca1—O21	2.471 (8)