PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 April 1; 66(Pt 4): m483–m484.
Published online 2010 March 31. doi:  10.1107/S1600536810010998
PMCID: PMC2984083

Penta­aqua­tri-μ3-hydroxido-tris­(imino­diacetato)-μ3-oxido-tetra­hedro-calcium(II)tricobalt(III) 2.54-hydrate

Abstract

In the title compound, [CaCo3(C4H5NO4)3(OH)3O(H2O)5]·2.54H2O, the Co atom is octa­hedrally coordinated by one imino­diacetate (ida) dianion as a facial O,N,O′-tridentate ligand, two μ3-OH groups and one μ3-O ligand, forming an partial Co3O4 cubane cluster. This unit coordinates to a CaII cation in an O,O′,O′′-tridentate fashion, generating a distorted CaCo3O4 cubane-type cluster. The Ca—μ3-O distances [2.429 (5)–2.572 (6) Å] are much longer than the Co—μ3—O bonds [1.895 (5)–1.941 (5) Å]. The CaII cation is also coord­inated by five water mol­ecules with Ca—O distances in the range 2.355 (6)–2.543 (6) Å. There are three additional uncoordinated water mol­ecules in the asymmetric unit, the occupancy of which refined to 0.54 (3). In H2O (or D2O), the title complex hydrolyses to Ca2+ aq cations and [Co3(ida)32-OH)33-O)]2− anions.

Related literature

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

An external file that holds a picture, illustration, etc.
Object name is e-66-0m483-scheme1.jpg

Experimental

Crystal data

  • [CaCo3(C4H5NO4)3(OH)3O(H2O)5]·2.54H2O
  • M r = 812.92
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m483-efi1.jpg
  • 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 [triangle]) 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 [triangle]); cell refinement: WinAFC; data reduction: CrystalStructure (Rigaku/MSC, 2007 [triangle]); program(s) used to solve structure: DIRDIF99 (Beurskens et al., 1999 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2007 [triangle]).

Table 1
Selected bond lengths (Å)

Supplementary Material

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

Acknowledgments

The authors are grateful to Kochi University for financial support.

supplementary crystallographic information

Comment

We have previously reported on the structures of some [Co3(L)32-OH)33-O)]n+ (L: tridentate ligand) complexes which form incomplete cubane Co3O4 clusters (Ama et al., 1997, 2000,2001, 2006). While many such cationic [Co3(L)32-OH)33-O)]n+ complexes are known, we could find no mention of an anionic complex in our survey of the literature. The title compound was formed during an attempt to prepare the anionic complex [Co3(ida)32-OH)33-O)]2-.

Investigations of the CaMn3O4 cluster are important to gain an understanding of the chemistry of O2 evolution centers (OEC) in plants (Yocum, 2008; Sauer et al., 2008; Barber & Murray, 2008; Rappaport & Diner, 2008). The Mn clusters in the OEC are of interest due to their unique structure, photoreaction mechanisms, and redox chemistry. Moreover, as the covalent radius of Co (1.33 Å) is similar to that of Mn (1.35 Å), we were interested in the preparation of the cobalt analogue, CaCo3O4, as a model of OEC.

In the title complex, each Co atom is coordinated by one ida (iminodiacetato) molecule which acts as a facial tridentate (O,N,O') ligand, two µ2-OH groups and one µ3-O ligand, forming a Co3O4 cluster. This cluster further coordinates to CaII in a tridentate manner generating a distorted CaCo3O4 cubane-type cluster. The µ2-O—Co distances are 1.895 (5) - 1.941 (5)Å and the Co—µ2-O—Co' angles are 94.5 (2) – 95.8 (2)°. In the T1 isomer (Ama et al., 1995) of [Co3(edma)32-OH)33-O)]+ (edma: ethylenediaminemonoacetato), the corresponding distances and angles are 1.899 (3) -1.923 (2)Å and 95.0 (1) - 96.2 (1)°. Hence the structure of the Co3O4 cluster in the title compound resembles that of [Co3(edma)32-OH)33-O)]+ cation. As the Ca2+ cation is coordinated by the three µ3-OH ligands of the Co3O4 cluster, the CaCo3O4 cluster can be considered to be a distorted cubane cluster. The Ca—µ3-O distances (2.429 (5) – 2.572 (6) Å) are much longer than Co—µ3-O (1.895 (5) - 1.921 (5) Å). The µ3-O—Ca—µ3-O' angles (59.84 (16) - 63.09 (16)) are smaller than those involving cobalt, µ3-O—Co—µ3-O' (84.0 (2) - 85.6 (2)°) and Co—µ3-O—Co' (94.5 (2) - 95.8 (2)) in the Co3O4 cluster. There are three additional uncoordinated water molecules in the asymmetric unit, the occupancy of one of these solvates that has the largest Ueq value refines to 0.54 (3).

Experimental

To a suspension of 7.0 g of KHCO3 in 10 cm3 of water, a solution 2.38 g of cobalt(II) chloride hexahydrate and 4 cm3 of 30% H2O2 in 10 cm3 of water was added dropwise with stirring at below 0° C. After the solution was stirred for 15 min, 10 cm3 of H2O containing 1.3 g of H2ida was added and then stirred overnight. The solution was acidified to pH 1.0 with 30% HClO4, stirred for 30 min, pH adjusted to 8.3 with 2 mol dm-3 KOH aqueous solution and then stirred for 2.5 h at 45°C. Filtering off the insoluble white-brown precipitate, the filtrate was loaded onto a QAE-Sephadex column (Cl- form). The adsorbed band was developed with 0.2 mol dm-3 KCl Solution. The eluate from the fifth brown band was collected and concentrated to a small volume and then methanol was added to deposit KCl. After removing the KCl by filtration, potassium salt (K2[Co3(ida)32-OH)33-O)] 3.25 H2O) was obtained by standing the filtrate in a refrigerator. Yield: 76 mg. (Anal. Found: C, 18.45; H, 3.21; N, 5.34%. Calcd for C12H24.5N3O19.25K2Co3 (K2[Co3(ida)32-OH)(µ3-O)] 3.25 H2O): C, 18.62; H, 3.19; N, 5.43%. This potassium salt was dissolved in a small amount of water, which was loaded to a QAE-Sephadex column (Cl- form; ø 6.5 cm × 3.5 cm) and then eluted with 500 cm3 of water to remove the K+ ion in the solution. The adsorbed brown band was eluted out with 0.5 mol dm-3 of CaCl2. The eluted solution was concentrated to a few cm3 and then ethanol and diethylether were added. As the solution was separated into a brown and an uncolored layers, the colorless layer was removed by decantation. After these procedures were repeated several times, a large amount of ethanol was added and the solution allowed to stand overnight at room temperature. The resulting brown precipitate was collected and washed with ethanol. This crude solid was recrystallized from water by adding ethanol. Anal. Found: C, 17.84; H, 4.04; N, 5.11%. Calcd for C12H33.08N3O23.54CaCo3 ([Ca(H2O)5Co3(ida)3(µ-OH)33-O)] 2.54 H2O): C, 17.73; H, 4.09; N, 5.17%. 1H NMR: (δ=4.22 and 3.24ppm; Jgem=17.6 Hz) and (δ=4.03 and 3.24ppm; Jgem=17.2 Hz).

Refinement

All H atoms of the fragment containing CaCo3O4 cluster were positioned geometrically (C—H = 0.95 Å, N—H = 0.91 Å and O—H = 0.84 Å) and refined as riding, with Uiso(H)= 1.2 Ueq of the parent atom. The H atoms of the solvate water molecules were found in the difference Fourier synthesis, constrained to O—H = 0.84Å and then refined as riding.

Figures

Fig. 1.
The asymmetric unit of the title compound showing the atom-labeling scheme and with 50% probability displacement ellipsoids.

Crystal data

[CaCo3(C4H5NO4)3(OH)3O(H2O)5]·2.54H2OZ = 2
Mr = 812.92F(000) = 830.80
Triclinic, P1Dx = 1.948 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71069 Å
a = 10.474 (3) ÅCell parameters from 12 reflections
b = 11.303 (7) Åθ = 15.1–15.8°
c = 12.588 (5) ŵ = 2.06 mm1
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

Data collection

Rigaku AFC-7S diffractometerRint = 0.076
ω–2θ scansθmax = 27.5°
Absorption correction: ψ scan (North et al., 1968)h = 0→13
Tmin = 0.673, Tmax = 0.902k = −14→14
6713 measured reflectionsl = −16→16
6360 independent reflections3 standard reflections every 150 reflections
3290 reflections with F2 > 2σ(F2) intensity decay: 4.8%

Refinement

Refinement on F2H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.060w = 1/[σ2(Fo2) + (0.1052P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.207(Δ/σ)max < 0.0001
S = 1.00Δρmax = 1.17 e Å3
6360 reflectionsΔρmin = −1.13 e Å3
389 parameters

Special details

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).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/UeqOcc. (<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)0.79470.90791.00480.020*
H(2)0.54521.01720.64760.018*
H(3)0.40150.58890.88640.020*
H(4)0.88590.78411.18670.033*
H(5)0.97020.86231.09440.033*
H(6)0.60910.87111.06370.030*
H(7)0.69040.81831.17380.030*
H(8)0.70571.23400.62070.037*
H(9)0.64231.15670.53030.037*
H(10)0.51171.04790.80140.026*
H(11)0.57321.18440.74780.026*
H(12)0.19620.58970.72940.030*
H(13)0.25510.47490.79230.030*
H(14)0.36320.76420.90710.028*
H(15)0.22370.70090.85580.028*
H(16)0.91660.84980.85860.021*
H(17)0.64080.85540.59400.018*
H(18)0.61070.55000.84130.019*
H(19)0.93470.91790.62580.060*
H(20)1.01150.86820.57100.060*
H(21)0.68030.58620.50780.043*
H(22)0.58060.59970.55770.043*
H(23)0.78390.40560.79910.042*
H(24)0.66260.41300.73650.042*
H(25)0.94100.56900.90480.038*
H(26)1.02090.56660.83100.038*
H(27)0.89770.53870.56770.047*
H(28)0.98230.65400.55140.047*
H(29)0.13830.87070.94020.038*
H(30)0.13400.89160.84780.038*
H(31)0.66830.83790.42290.049*
H(32)0.67650.95000.39520.049*
H(33)0.81620.71090.38780.079*0.54
H(34)0.87080.82150.39780.079*0.54

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
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)

Geometric parameters (Å, °)

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

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O(2)—H(16)···O(22)i0.841.882.707 (7)168
O(3)—H(17)···O(23)0.841.882.677 (7)159
O(4)—H(18)···O(8)ii0.842.072.870 (7)158
O(17)—H(19)···O(9)0.841.922.744 (11)168
O(17)—H(20)···O(10)iii0.842.102.850 (13)148
O(18)—H(21)···O(14)iv0.841.872.699 (12)168
O(18)—H(22)···O(13)0.842.002.708 (9)141
O(19)—H(23)···O(6)v0.842.212.829 (9)131
O(19)—H(24)···O(8)ii0.842.142.863 (9)145
O(20)—H(25)···O(5)0.842.172.787 (9)130
O(20)—H(26)···O(6)v0.842.152.765 (10)130
O(21)—H(27)···O(14)iv0.842.343.043 (9)142
O(21)—H(28)···O(10)iii0.841.992.801 (9)164
O(22)—H(29)···O(12)vi0.842.042.800 (9)152
O(22)—H(30)···O(16)0.842.072.840 (10)153
O(23)—H(31)···O(18)0.842.402.909 (10)120
O(23)—H(31)···O(24)0.842.243.01 (2)153
O(23)—H(32)···O(16)vii0.841.972.802 (8)172
O(24)—H(33)···O(14)iv0.782.192.912 (18)156
O(24)—H(34)···O(10)iii0.812.533.054 (18)124
N(1)—H(1)···O(11)0.912.032.857 (7)150
N(1)—H(1)···O(22)vi0.912.553.121 (9)122
N(2)—H(2)···O(15)0.912.182.917 (7)138
N(2)—H(2)···O(23)vii0.912.362.977 (9)125
N(3)—H(3)···O(7)0.912.363.038 (7)132
N(3)—H(3)···O(7)ii0.912.493.259 (8)143

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SJ2753).

References

  • Ama, T., Miyazaki, J., Hamada, K., Okamoto, K., Yonemura, T., Kawaguchi, H. & Yasui, T. (1995). Chem. Lett. pp. 267–268.
  • Ama, T., Rashid, Md. M., Sarker, A. K., Miyakawa, H., Yonemura, T., Kawaguchi, H. & Yasui, T. (2001). Bull. Chem. Soc. Jpn, 74, 2327–2333.
  • Ama, T., Rashid, Md. M., Yonemura, T., Kawaguchi, H. & Yasui, T. (2000). Coord. Chem. Rev.198, 101–116.
  • Ama, T., Shiro, M., Takeuchi, A., Yonemura, T., Kawaguchi, H. & Yasui, T. (1997). Bull. Chem. Soc. Jpn, 70, 2685–1692.
  • Ama, T., Yonemura, T. & Yamaguchi, M. (2006). Bull. Chem. Soc. Jpn, 79, 1063–1065.
  • Barber, J. & Murray, J. W. (2008). Coord. Chem. Rev.252, 233–243.
  • Beurskens, P. T., Admiraal, G., Beurskens, G., Bosman, W. P., Garcia-Granda, S., Gould, R. O., Smits, J. M. M. & Smykalla, C. (1999). DIRDIF99. University of Nijmegen, The Netherlands.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Rappaport, F. & Diner, B. A. (2008). Coord. Chem. Rev.252, 259–272.
  • Rigaku/MSC (2000). WinAFC Rigaku/MSC, The Woodlands,Texas, USA.
  • Rigaku/MSC (2007). CrystalStructure Rigaku Americas, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan.
  • Sauer, K., Yano, J. & Yachandra, V. K. (2008). Coord. Chem. Rev.252, 318–335. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Yocum, C. F. (2008). Coord. Chem. Rev.252, 296–305.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography