metal-organic compounds
Bis(tetraphenylarsonium) di-μ-hydroxido-bis[(nitrilotriacetato)cobalt(III)] octahydrate
aDepartment of Chemistry, University of the Free State, PO Box 339, Bloemfontein 9300, South Africa, and bDepartment of Chemistry, University of Cambridge, Lensfield Rd, Cambridge CB2 1EW, England
*Correspondence e-mail: visserhg.sci@mail.uovs.ac.za
In the title compound, (C24H20As)2[Co2(C6H6NO6)2(OH)2]·8H2O, the CoIII atom in the binuclear centrosymmetric anion is octahedrally surrounded by one N atom and three O atoms of the tetradentate nitrilotriacetate ligand and two μ-hydroxide ligands. The crystal packing is controlled by C—H⋯O and O—H⋯O hydrogen-bonding interactions. The crystal employed in this study proved to be a two-component twin around (01).
Related literature
For synthetic background, related structures and kinetics, see: Mori et al. (1958); Visser et al. (1997, 1999, 2001, 2002, 2003). For which was resolved using the program ROTAX, see: Cooper et al. (2002).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2005); cell SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 1999).
Supporting information
https://doi.org/10.1107/S160053681003895X/kj2157sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681003895X/kj2157Isup2.hkl
The title compound was prepared similar to the method described by Mori et al. (1958). CoCl2.6H2O (5 g, 21 mmol) and nitrilotriacetic acid (4 g, 21 mmol) was added to a KHCO3 solution (25 cm3, 2.5 M). H2O2 (1 ml, 30%) was added to this solution and the mixture was placed on an ice bath. After 5 h a purple precipitate separated out. The precipitate was filtered and washed several times with cold water. The product was then redissolved in hot water after which an excess of tetraphenylarsonium was added. Purple crystals of the title compound were obtained after several days.
The methyl and aromatic H atoms were placed in geometrically idealized positions (C—H = 0.93–0.96 Å) and constrained to ride on their parent atoms, with Uiso(H) = 1.5Ueq(C) and 1.2Ueq(C), respectively. The hydrogen atoms of the aqua solvent molecules were obtained from the difference Fourier map. Despite appearing (at least visually) to be single, the crystal employed in this study proved to be a two-component twin around (0 -1 1).
which was resolved using the programs ROTAX (Cooper et al., 2002) and Make HKLF5 (Farrugia, 1999) with a final minor component of 0.0712 (4).The title complex, (AsC24H20)2[Co(C6H6N)(µ-OH)]2.8(H2O), forms a part of an ongoing investigation of the structural and kinetic behaviour of CoIII-nitrilotriacetato compounds (Visser et al., (1997, 1999, 2001, 2002, 2003). The CoIII atom is octahedrally surrounded by one N atom and three O atoms of the tetradentate nitrilotriacetato ligand and two µ-hydroxo ligands (Fig. 1). The Co–O bond distances which vary between 1.8806 (11) and 1.9027 (11) Å and the Co–N1 distance of 1.9312 (13) Å fall well within the normal range (Table 1). The octahedron around the Co atom is only slighlty distorted. The crystal packing is controlled by C—H–O and O—H–O hydrogen bonding interactions (Table 2), creating a three dimensional network.
For synthetic background, related structures and kinetics, see: Mori et al. (1958); Visser et al. (1997, 1999, 2001, 2002, 2003).
which was resolved using the programs ROTAX, see: Cooper et al. (2002).Data collection: APEX2 (Bruker, 2005); cell
SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXL97 (Sheldrick, 2008); program(s) used to refine structure: SIR97 (Altomare et al., 1999); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 1999).Fig. 1. View of the title compund (50% probability displacement ellipsoids). Hydrogen atoms and solvent water molecules omitted for clarity. |
(C24H20As)2[Co2(C6H6NO6)2(OH)2]·8H2O | Z = 1 |
Mr = 1438.88 | F(000) = 740 |
Triclinic, P1 | Dx = 1.549 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.328 (5) Å | Cell parameters from 9875 reflections |
b = 14.491 (5) Å | θ = 2.5–28.3° |
c = 16.564 (5) Å | µ = 1.68 mm−1 |
α = 113.555 (5)° | T = 100 K |
β = 97.040 (5)° | Plate, purple |
γ = 101.152 (5)° | 0.44 × 0.19 × 0.03 mm |
V = 1542.4 (13) Å3 |
Bruker X8 APEXII 4K KappaCCD diffractometer | 23223 independent reflections |
Radiation source: sealed tube | 20726 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
Detector resolution: 0 pixels mm-1 | θmax = 25.0°, θmin = 1.6° |
phi and ω scans | h = −8→8 |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | k = −17→17 |
Tmin = 0.687, Tmax = 0.950 | l = −19→19 |
23209 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.93 | w = 1/[σ2(Fo2) + (0.0699P)2 + 0.5465P] where P = (Fo2 + 2Fc2)/3 |
23223 reflections | (Δ/σ)max = 0.001 |
430 parameters | Δρmax = 0.41 e Å−3 |
10 restraints | Δρmin = −0.36 e Å−3 |
(C24H20As)2[Co2(C6H6NO6)2(OH)2]·8H2O | γ = 101.152 (5)° |
Mr = 1438.88 | V = 1542.4 (13) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.328 (5) Å | Mo Kα radiation |
b = 14.491 (5) Å | µ = 1.68 mm−1 |
c = 16.564 (5) Å | T = 100 K |
α = 113.555 (5)° | 0.44 × 0.19 × 0.03 mm |
β = 97.040 (5)° |
Bruker X8 APEXII 4K KappaCCD diffractometer | 23223 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 20726 reflections with I > 2σ(I) |
Tmin = 0.687, Tmax = 0.950 | Rint = 0.030 |
23209 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 10 restraints |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.93 | Δρmax = 0.41 e Å−3 |
23223 reflections | Δρmin = −0.36 e Å−3 |
430 parameters |
Experimental. The crystal was coated in Exxon Paratone N hydrocarbon oil and mounted on a thin mohair fibre attached to a copper pin. Upon mounting on the diffractometer, the crystal was quenched to 100(K) under a cold nitrogen gas stream supplied by an Oxford Cryosystems Cryostream and data were collected at this temperature. |
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. |
x | y | z | Uiso*/Ueq | ||
As | 0.39743 (2) | 0.447716 (10) | 0.212481 (9) | 0.01293 (5) | |
Co1 | 0.52032 (3) | 0.909913 (13) | 0.511641 (11) | 0.00933 (6) | |
O5 | 0.37750 (13) | 0.76948 (7) | 0.46088 (6) | 0.0136 (2) | |
O6 | 0.37392 (15) | 0.61846 (7) | 0.46771 (7) | 0.0226 (2) | |
O3 | 0.67319 (13) | 0.87442 (7) | 0.42572 (6) | 0.0118 (2) | |
O7 | 0.35509 (14) | 0.94527 (7) | 0.43838 (6) | 0.0103 (2) | |
C25 | −0.0013 (2) | 0.57427 (12) | 0.12621 (10) | 0.0239 (4) | |
H25 | −0.1144 | 0.5486 | 0.0827 | 0.029* | |
C22 | 0.3389 (2) | 0.65222 (11) | 0.25432 (9) | 0.0183 (3) | |
H22 | 0.4537 | 0.6783 | 0.2969 | 0.022* | |
C24 | 0.0660 (2) | 0.68072 (12) | 0.18135 (10) | 0.0249 (4) | |
H24 | −0.0029 | 0.7261 | 0.1754 | 0.030* | |
N1 | 0.69776 (16) | 0.87921 (8) | 0.58731 (7) | 0.0111 (2) | |
C44 | 0.6324 (2) | 0.27716 (12) | −0.04076 (10) | 0.0270 (4) | |
H44 | 0.6776 | 0.2413 | −0.0912 | 0.032* | |
C54 | −0.0652 (2) | 0.19678 (11) | 0.24101 (10) | 0.0223 (4) | |
H4 | −0.1589 | 0.1472 | 0.2459 | 0.027* | |
C13 | 0.7874 (2) | 0.53345 (10) | 0.45190 (9) | 0.0159 (3) | |
H13 | 0.7972 | 0.5165 | 0.5005 | 0.019* | |
C11 | 0.6130 (2) | 0.51328 (10) | 0.31153 (9) | 0.0141 (3) | |
C16 | 0.7629 (2) | 0.58563 (10) | 0.30779 (9) | 0.0171 (3) | |
H36 | 0.7538 | 0.6028 | 0.2593 | 0.021* | |
C12 | 0.6230 (2) | 0.48623 (10) | 0.38328 (9) | 0.0145 (3) | |
H12 | 0.5222 | 0.4378 | 0.3854 | 0.017* | |
C3 | 0.8420 (2) | 0.87705 (10) | 0.45975 (9) | 0.0114 (3) | |
C55 | −0.0350 (2) | 0.30323 (11) | 0.29762 (9) | 0.0189 (3) | |
H5 | −0.1083 | 0.3244 | 0.3403 | 0.023* | |
C6 | 0.6159 (2) | 0.76932 (10) | 0.57216 (9) | 0.0168 (3) | |
H6B | 0.5795 | 0.7698 | 0.6267 | 0.020* | |
H6A | 0.7129 | 0.7317 | 0.5603 | 0.020* | |
C23 | 0.2356 (2) | 0.71896 (12) | 0.24507 (10) | 0.0241 (4) | |
H23 | 0.2805 | 0.7903 | 0.2820 | 0.029* | |
C5 | 0.4429 (2) | 0.71259 (11) | 0.49372 (9) | 0.0150 (3) | |
C4 | 0.8820 (2) | 0.89285 (11) | 0.55782 (9) | 0.0136 (3) | |
H4B | 0.9468 | 0.8425 | 0.5631 | 0.016* | |
H4A | 0.9641 | 0.9624 | 0.5962 | 0.016* | |
C51 | 0.2135 (2) | 0.34422 (10) | 0.22566 (9) | 0.0141 (3) | |
C21 | 0.2698 (2) | 0.54575 (11) | 0.19945 (9) | 0.0155 (3) | |
C46 | 0.6374 (2) | 0.33354 (11) | 0.11640 (10) | 0.0209 (3) | |
H46 | 0.6868 | 0.3365 | 0.1721 | 0.025* | |
C14 | 0.9360 (2) | 0.60521 (11) | 0.44813 (9) | 0.0169 (3) | |
H14 | 1.0451 | 0.6362 | 0.4945 | 0.020* | |
C53 | 0.0440 (2) | 0.16579 (11) | 0.17818 (10) | 0.0229 (4) | |
H3 | 0.0234 | 0.0951 | 0.1410 | 0.028* | |
C45 | 0.7061 (2) | 0.28103 (11) | 0.04135 (10) | 0.0258 (4) | |
H45 | 0.8017 | 0.2485 | 0.0465 | 0.031* | |
C15 | 0.9256 (2) | 0.63202 (10) | 0.37639 (9) | 0.0170 (3) | |
H15 | 1.0266 | 0.6805 | 0.3745 | 0.020* | |
C52 | 0.1852 (2) | 0.23883 (11) | 0.16938 (9) | 0.0190 (3) | |
H2 | 0.2587 | 0.2175 | 0.1269 | 0.023* | |
C56 | 0.1045 (2) | 0.37675 (11) | 0.28960 (9) | 0.0163 (3) | |
H21 | 0.1252 | 0.4475 | 0.3268 | 0.020* | |
C41 | 0.4944 (2) | 0.38168 (10) | 0.10790 (9) | 0.0165 (3) | |
C42 | 0.4214 (2) | 0.37872 (12) | 0.02556 (10) | 0.0243 (4) | |
H42 | 0.3265 | 0.4115 | 0.0201 | 0.029* | |
C26 | 0.0983 (2) | 0.50630 (11) | 0.13542 (10) | 0.0195 (3) | |
H27 | 0.0516 | 0.4348 | 0.0993 | 0.023* | |
C43 | 0.4924 (3) | 0.32580 (12) | −0.04900 (10) | 0.0322 (4) | |
H43 | 0.4448 | 0.3233 | −0.1047 | 0.039* | |
O1 | 0.38813 (13) | 0.94103 (7) | 0.60717 (6) | 0.0128 (2) | |
O4 | 0.97100 (13) | 0.86981 (7) | 0.41750 (6) | 0.0142 (2) | |
O2 | 0.45349 (15) | 1.00672 (8) | 0.75721 (6) | 0.0219 (2) | |
C1 | 0.4993 (2) | 0.96884 (10) | 0.68350 (9) | 0.0144 (3) | |
C2 | 0.7004 (2) | 0.95505 (11) | 0.68087 (9) | 0.0143 (3) | |
H2A | 0.7902 | 1.0216 | 0.6967 | 0.017* | |
H2B | 0.7395 | 0.9288 | 0.7238 | 0.017* | |
O8 | 0.68108 (17) | 1.03630 (9) | 0.91382 (8) | 0.0247 (3) | |
O11 | 0.17288 (17) | 0.12264 (9) | 0.75373 (7) | 0.0268 (3) | |
O9 | 0.33579 (19) | 1.08138 (10) | 0.99202 (9) | 0.0304 (3) | |
O10 | 0.04230 (18) | 0.13286 (10) | 0.91136 (8) | 0.0327 (3) | |
H9B | 0.315 (4) | 1.0439 (17) | 1.0176 (15) | 0.079 (9)* | |
H8B | 0.616 (3) | 1.0211 (15) | 0.8671 (13) | 0.056 (5)* | |
H8A | 0.789 (3) | 1.0632 (15) | 0.9127 (13) | 0.056 (5)* | |
H9A | 0.430 (3) | 1.0771 (13) | 0.9721 (12) | 0.035 (4)* | |
H10B | 0.069 (3) | 0.1294 (14) | 0.8674 (12) | 0.047 (4)* | |
H11A | 0.157 (3) | 0.1295 (14) | 0.7106 (12) | 0.044 (4)* | |
H11B | 0.265 (3) | 0.0912 (13) | 0.7531 (12) | 0.044 (4)* | |
H7 | 0.254 (3) | 0.9294 (13) | 0.4445 (11) | 0.035 (4)* | |
H10C | 0.126 (3) | 0.1179 (14) | 0.9378 (12) | 0.047 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
As | 0.01200 (8) | 0.01345 (9) | 0.01245 (8) | 0.00238 (6) | 0.00164 (6) | 0.00552 (6) |
Co1 | 0.00692 (10) | 0.01049 (10) | 0.01102 (10) | 0.00240 (8) | 0.00233 (8) | 0.00496 (8) |
O5 | 0.0106 (5) | 0.0127 (5) | 0.0169 (5) | 0.0017 (4) | 0.0024 (4) | 0.0068 (4) |
O6 | 0.0148 (6) | 0.0148 (5) | 0.0392 (6) | 0.0025 (5) | 0.0063 (5) | 0.0133 (5) |
O3 | 0.0095 (5) | 0.0139 (5) | 0.0123 (5) | 0.0044 (4) | 0.0034 (4) | 0.0051 (4) |
O7 | 0.0070 (5) | 0.0105 (5) | 0.0128 (5) | 0.0014 (4) | 0.0021 (4) | 0.0049 (4) |
C25 | 0.0205 (9) | 0.0330 (9) | 0.0250 (8) | 0.0095 (8) | 0.0061 (7) | 0.0180 (7) |
C22 | 0.0254 (9) | 0.0190 (8) | 0.0117 (7) | 0.0051 (7) | 0.0077 (7) | 0.0071 (6) |
C24 | 0.0349 (10) | 0.0310 (9) | 0.0272 (9) | 0.0213 (8) | 0.0195 (8) | 0.0217 (8) |
N1 | 0.0099 (6) | 0.0112 (6) | 0.0125 (6) | 0.0030 (5) | 0.0024 (5) | 0.0055 (5) |
C44 | 0.0320 (10) | 0.0193 (8) | 0.0241 (9) | 0.0003 (7) | 0.0169 (8) | 0.0040 (7) |
C54 | 0.0172 (8) | 0.0223 (8) | 0.0296 (9) | −0.0005 (7) | 0.0019 (7) | 0.0170 (7) |
C13 | 0.0173 (8) | 0.0187 (8) | 0.0146 (7) | 0.0092 (7) | 0.0038 (6) | 0.0081 (6) |
C11 | 0.0154 (8) | 0.0130 (7) | 0.0114 (7) | 0.0048 (6) | 0.0026 (6) | 0.0025 (6) |
C16 | 0.0192 (8) | 0.0176 (8) | 0.0157 (7) | 0.0060 (7) | 0.0055 (6) | 0.0073 (6) |
C12 | 0.0121 (7) | 0.0133 (7) | 0.0180 (7) | 0.0038 (6) | 0.0040 (6) | 0.0061 (6) |
C3 | 0.0112 (7) | 0.0058 (7) | 0.0145 (7) | 0.0004 (6) | 0.0017 (6) | 0.0029 (6) |
C55 | 0.0159 (8) | 0.0254 (8) | 0.0187 (8) | 0.0059 (7) | 0.0042 (6) | 0.0126 (7) |
C6 | 0.0175 (8) | 0.0154 (7) | 0.0226 (8) | 0.0044 (6) | 0.0054 (7) | 0.0130 (6) |
C23 | 0.0397 (11) | 0.0175 (8) | 0.0191 (8) | 0.0104 (8) | 0.0139 (8) | 0.0087 (7) |
C5 | 0.0123 (8) | 0.0153 (8) | 0.0208 (8) | 0.0049 (6) | 0.0104 (6) | 0.0086 (6) |
C4 | 0.0095 (7) | 0.0154 (7) | 0.0174 (7) | 0.0045 (6) | 0.0034 (6) | 0.0079 (6) |
C51 | 0.0119 (7) | 0.0157 (7) | 0.0143 (7) | 0.0012 (6) | −0.0009 (6) | 0.0084 (6) |
C21 | 0.0170 (8) | 0.0178 (7) | 0.0153 (7) | 0.0051 (6) | 0.0065 (6) | 0.0097 (6) |
C46 | 0.0171 (8) | 0.0211 (8) | 0.0179 (8) | 0.0033 (7) | 0.0000 (7) | 0.0040 (6) |
C14 | 0.0126 (8) | 0.0173 (8) | 0.0159 (7) | 0.0052 (6) | 0.0007 (6) | 0.0025 (6) |
C53 | 0.0237 (9) | 0.0139 (8) | 0.0257 (8) | 0.0011 (7) | 0.0013 (7) | 0.0061 (7) |
C45 | 0.0191 (9) | 0.0192 (8) | 0.0321 (9) | 0.0040 (7) | 0.0078 (7) | 0.0042 (7) |
C15 | 0.0145 (8) | 0.0152 (7) | 0.0211 (8) | 0.0043 (6) | 0.0079 (6) | 0.0066 (6) |
C52 | 0.0184 (8) | 0.0189 (8) | 0.0190 (8) | 0.0069 (7) | 0.0052 (7) | 0.0064 (6) |
C56 | 0.0182 (8) | 0.0139 (7) | 0.0144 (7) | 0.0053 (6) | 0.0014 (6) | 0.0040 (6) |
C41 | 0.0154 (8) | 0.0140 (7) | 0.0164 (7) | −0.0001 (6) | 0.0046 (6) | 0.0046 (6) |
C42 | 0.0298 (10) | 0.0277 (9) | 0.0204 (8) | 0.0116 (8) | 0.0080 (7) | 0.0131 (7) |
C26 | 0.0191 (8) | 0.0184 (8) | 0.0212 (8) | 0.0043 (7) | 0.0049 (7) | 0.0091 (6) |
C43 | 0.0478 (12) | 0.0314 (9) | 0.0189 (8) | 0.0078 (9) | 0.0119 (8) | 0.0125 (7) |
O1 | 0.0102 (5) | 0.0159 (5) | 0.0142 (5) | 0.0039 (4) | 0.0042 (4) | 0.0078 (4) |
O4 | 0.0097 (5) | 0.0163 (5) | 0.0160 (5) | 0.0031 (4) | 0.0051 (4) | 0.0058 (4) |
O2 | 0.0205 (6) | 0.0339 (6) | 0.0144 (5) | 0.0131 (5) | 0.0085 (5) | 0.0096 (5) |
C1 | 0.0147 (8) | 0.0144 (7) | 0.0164 (8) | 0.0031 (6) | 0.0041 (6) | 0.0092 (6) |
C2 | 0.0142 (8) | 0.0177 (7) | 0.0119 (7) | 0.0054 (6) | 0.0034 (6) | 0.0065 (6) |
O8 | 0.0244 (7) | 0.0317 (7) | 0.0205 (6) | 0.0069 (6) | 0.0048 (5) | 0.0142 (5) |
O11 | 0.0276 (7) | 0.0400 (7) | 0.0196 (6) | 0.0191 (6) | 0.0096 (5) | 0.0141 (6) |
O9 | 0.0297 (7) | 0.0379 (7) | 0.0403 (7) | 0.0168 (6) | 0.0195 (6) | 0.0267 (6) |
O10 | 0.0264 (7) | 0.0510 (8) | 0.0320 (7) | 0.0129 (6) | 0.0107 (6) | 0.0267 (7) |
As—C11 | 1.9049 (15) | C3—O3 | 1.2816 (18) |
As—C21 | 1.9102 (15) | C3—C4 | 1.5288 (19) |
As—C51 | 1.9145 (15) | C55—C56 | 1.387 (2) |
As—C41 | 1.9134 (15) | C55—H5 | 0.9300 |
Co1—O5 | 1.8806 (11) | C6—C5 | 1.520 (2) |
Co1—O1 | 1.9027 (11) | C6—H6B | 0.9700 |
Co1—O3 | 1.8903 (11) | C6—H6A | 0.9700 |
Co1—O5 | 1.8806 (11) | C23—H23 | 0.9300 |
Co1—O3 | 1.8903 (11) | C5—O6 | 1.2295 (16) |
Co1—O7 | 1.8915 (11) | C5—O5 | 1.2855 (17) |
Co1—O7 | 1.8915 (11) | C4—H4B | 0.9700 |
Co1—O7i | 1.8994 (11) | C4—H4A | 0.9700 |
Co1—N1 | 1.9312 (13) | C51—C56 | 1.391 (2) |
Co1—Co1i | 2.8516 (10) | C51—C52 | 1.3916 (19) |
O5—C5 | 1.2855 (17) | C21—C26 | 1.394 (2) |
O6—C5 | 1.2295 (16) | C46—C41 | 1.389 (2) |
O3—C3 | 1.2816 (18) | C46—C45 | 1.387 (2) |
O7—Co1i | 1.8994 (11) | C46—H46 | 0.9300 |
O7—H7 | 0.765 (18) | C14—C15 | 1.3881 (19) |
C25—C26 | 1.377 (2) | C14—H14 | 0.9300 |
C25—C24 | 1.388 (2) | C53—C52 | 1.396 (2) |
C25—H25 | 0.9300 | C53—H3 | 0.9300 |
C22—C23 | 1.381 (2) | C45—H45 | 0.9300 |
C22—C21 | 1.388 (2) | C15—H15 | 0.9300 |
C22—H22 | 0.9300 | C52—H2 | 0.9300 |
C24—C23 | 1.382 (2) | C56—H21 | 0.9300 |
C24—H24 | 0.9300 | C41—C42 | 1.383 (2) |
N1—C4 | 1.4956 (19) | C42—C43 | 1.392 (2) |
N1—C6 | 1.4943 (17) | C42—H42 | 0.9300 |
N1—C2 | 1.4941 (17) | C26—H27 | 0.9300 |
C44—C43 | 1.375 (3) | C43—H43 | 0.9300 |
C44—C45 | 1.375 (2) | O1—C1 | 1.2799 (16) |
C44—H44 | 0.9300 | O2—C1 | 1.2415 (17) |
C54—C53 | 1.376 (2) | C1—O2 | 1.2415 (17) |
C54—C55 | 1.403 (2) | C1—C2 | 1.528 (2) |
C54—H4 | 0.9300 | C2—H2A | 0.9700 |
C13—C14 | 1.379 (2) | C2—H2B | 0.9700 |
C13—C12 | 1.391 (2) | O8—H8B | 0.780 (19) |
C13—H13 | 0.9300 | O8—H8A | 0.82 (2) |
C11—C12 | 1.3906 (19) | O11—H11A | 0.758 (17) |
C11—C16 | 1.390 (2) | O11—H11B | 0.886 (19) |
C16—C15 | 1.383 (2) | O9—H9B | 0.82 (2) |
C16—H36 | 0.9300 | O9—H9A | 0.800 (19) |
C12—H12 | 0.9300 | O10—H10B | 0.762 (18) |
C3—O4 | 1.2396 (18) | O10—H10C | 0.822 (18) |
C3—O4 | 1.2396 (18) | ||
C11—As—C21 | 112.01 (6) | O4—C3—O3 | 122.95 (13) |
C11—As—C51 | 111.91 (6) | O4—C3—O3 | 122.95 (13) |
C21—As—C51 | 107.22 (7) | O4—C3—O3 | 122.95 (13) |
C11—As—C41 | 105.75 (7) | O4—C3—C4 | 120.09 (12) |
C21—As—C41 | 110.79 (6) | O4—C3—C4 | 120.09 (12) |
C51—As—C41 | 109.18 (6) | O3—C3—C4 | 116.94 (12) |
O5—Co1—O3 | 89.83 (5) | O3—C3—C4 | 116.94 (12) |
O5—Co1—O3 | 89.83 (5) | C56—C55—C54 | 119.66 (15) |
O5—Co1—O3 | 89.83 (5) | C56—C55—H5 | 120.2 |
O5—Co1—O3 | 89.83 (5) | C54—C55—H5 | 120.2 |
O5—Co1—O7 | 93.60 (5) | N1—C6—C5 | 112.41 (11) |
O5—Co1—O7 | 93.60 (5) | N1—C6—H6B | 109.1 |
O3—Co1—O7 | 92.04 (5) | C5—C6—H6B | 109.1 |
O3—Co1—O7 | 92.04 (5) | N1—C6—H6A | 109.1 |
O5—Co1—O7 | 93.60 (5) | C5—C6—H6A | 109.1 |
O5—Co1—O7 | 93.60 (5) | H6B—C6—H6A | 107.9 |
O3—Co1—O7 | 92.04 (5) | C24—C23—C22 | 120.60 (14) |
O3—Co1—O7 | 92.04 (5) | C24—C23—H23 | 119.7 |
O7—Co1—O7 | 0.00 (5) | C22—C23—H23 | 119.7 |
O5—Co1—O7i | 175.18 (4) | O6—C5—O5 | 125.03 (13) |
O5—Co1—O7i | 175.18 (4) | O6—C5—O5 | 125.03 (13) |
O3—Co1—O7i | 93.03 (5) | O6—C5—O5 | 125.03 (13) |
O3—Co1—O7i | 93.03 (5) | O6—C5—O5 | 125.03 (13) |
O7—Co1—O7i | 82.43 (5) | O6—C5—C6 | 119.13 (12) |
O7—Co1—O7i | 82.43 (5) | O6—C5—C6 | 119.13 (12) |
O5—Co1—O1 | 89.72 (5) | O5—C5—C6 | 115.82 (12) |
O5—Co1—O1 | 89.72 (5) | O5—C5—C6 | 115.82 (12) |
O3—Co1—O1 | 172.72 (4) | N1—C4—C3 | 109.35 (11) |
O3—Co1—O1 | 172.72 (4) | N1—C4—H4B | 109.8 |
O7—Co1—O1 | 95.25 (6) | C3—C4—H4B | 109.8 |
O7—Co1—O1 | 95.25 (6) | N1—C4—H4A | 109.8 |
O7i—Co1—O1 | 87.93 (4) | C3—C4—H4A | 109.8 |
O5—Co1—N1 | 88.78 (5) | H4B—C4—H4A | 108.3 |
O5—Co1—N1 | 88.78 (5) | C56—C51—C52 | 121.13 (13) |
O3—Co1—N1 | 87.07 (6) | C56—C51—As | 118.76 (10) |
O3—Co1—N1 | 87.07 (6) | C52—C51—As | 120.06 (11) |
O7—Co1—N1 | 177.45 (4) | C22—C21—C26 | 120.58 (14) |
O7—Co1—N1 | 177.45 (4) | C22—C21—As | 121.78 (11) |
O7i—Co1—N1 | 95.23 (5) | C26—C21—As | 117.57 (11) |
O1—Co1—N1 | 85.65 (6) | C41—C46—C45 | 119.64 (14) |
O5—Co1—Co1i | 134.86 (4) | C41—C46—H46 | 120.2 |
O5—Co1—Co1i | 134.86 (4) | C45—C46—H46 | 120.2 |
O3—Co1—Co1i | 93.37 (3) | C13—C14—C15 | 121.14 (13) |
O3—Co1—Co1i | 93.37 (3) | C13—C14—H14 | 119.4 |
O7—Co1—Co1i | 41.32 (3) | C15—C14—H14 | 119.4 |
O7—Co1—Co1i | 41.32 (3) | C54—C53—C52 | 121.04 (14) |
O7i—Co1—Co1i | 41.11 (4) | C54—C53—H3 | 119.5 |
O1—Co1—Co1i | 92.10 (3) | C52—C53—H3 | 119.5 |
N1—Co1—Co1i | 136.33 (3) | C44—C45—C46 | 119.77 (16) |
C5—O5—Co1 | 115.09 (9) | C44—C45—H45 | 120.1 |
C3—O3—Co1 | 113.20 (9) | C46—C45—H45 | 120.1 |
Co1—O7—Co1i | 97.57 (5) | C16—C15—C14 | 119.09 (14) |
Co1—O7—H7 | 108.2 (13) | C16—C15—H15 | 120.5 |
Co1i—O7—H7 | 117.9 (13) | C14—C15—H15 | 120.5 |
C26—C25—C24 | 120.49 (15) | C53—C52—C51 | 118.51 (15) |
C26—C25—H25 | 119.8 | C53—C52—H2 | 120.7 |
C24—C25—H25 | 119.8 | C51—C52—H2 | 120.7 |
C23—C22—C21 | 119.29 (14) | C55—C56—C51 | 119.68 (13) |
C23—C22—H22 | 120.4 | C55—C56—H21 | 120.2 |
C21—C22—H22 | 120.4 | C51—C56—H21 | 120.2 |
C23—C24—C25 | 119.74 (14) | C46—C41—C42 | 120.64 (14) |
C23—C24—H24 | 120.1 | C46—C41—As | 117.79 (11) |
C25—C24—H24 | 120.1 | C42—C41—As | 121.54 (12) |
C4—N1—C6 | 112.32 (10) | C41—C42—C43 | 118.91 (16) |
C4—N1—C2 | 115.56 (11) | C41—C42—H42 | 120.5 |
C6—N1—C2 | 111.17 (10) | C43—C42—H42 | 120.5 |
C4—N1—Co1 | 106.22 (8) | C25—C26—C21 | 119.29 (14) |
C6—N1—Co1 | 107.09 (8) | C25—C26—H27 | 120.4 |
C2—N1—Co1 | 103.62 (9) | C21—C26—H27 | 120.4 |
C43—C44—C45 | 120.61 (15) | C44—C43—C42 | 120.42 (15) |
C43—C44—H44 | 119.7 | C44—C43—H43 | 119.8 |
C45—C44—H44 | 119.7 | C42—C43—H43 | 119.8 |
C53—C54—C55 | 119.99 (14) | C1—O1—Co1 | 111.85 (10) |
C53—C54—H4 | 120.0 | O2—C1—O1 | 123.92 (14) |
C55—C54—H4 | 120.0 | O2—C1—O1 | 123.92 (14) |
C14—C13—C12 | 120.32 (13) | O2—C1—C2 | 119.79 (12) |
C14—C13—H13 | 119.8 | O2—C1—C2 | 119.79 (12) |
C12—C13—H13 | 119.8 | O1—C1—C2 | 116.28 (12) |
C12—C11—C16 | 121.26 (13) | N1—C2—C1 | 108.05 (11) |
C12—C11—As | 120.89 (11) | N1—C2—H2A | 110.1 |
C16—C11—As | 117.79 (10) | C1—C2—H2A | 110.1 |
C15—C16—C11 | 119.81 (13) | N1—C2—H2B | 110.1 |
C15—C16—H36 | 120.1 | C1—C2—H2B | 110.1 |
C11—C16—H36 | 120.1 | H2A—C2—H2B | 108.4 |
C13—C12—C11 | 118.38 (13) | H8B—O8—H8A | 107 (2) |
C13—C12—H12 | 120.8 | H11A—O11—H11B | 108 (2) |
C11—C12—H12 | 120.8 | H9B—O9—H9A | 112 (2) |
O4—C3—O3 | 122.95 (13) | H10B—O10—H10C | 107 (2) |
O3—Co1—O5—C5 | 88.39 (10) | N1—C6—C5—O5 | −9.19 (18) |
O3—Co1—O5—C5 | 88.39 (10) | N1—C6—C5—O5 | −9.19 (18) |
O7—Co1—O5—C5 | −179.58 (10) | C6—N1—C4—C3 | 91.91 (12) |
O7—Co1—O5—C5 | −179.58 (10) | C2—N1—C4—C3 | −139.11 (11) |
O1—Co1—O5—C5 | −84.34 (10) | Co1—N1—C4—C3 | −24.85 (12) |
N1—Co1—O5—C5 | 1.32 (10) | O4—C3—C4—N1 | −169.55 (11) |
Co1i—Co1—O5—C5 | −177.02 (8) | O4—C3—C4—N1 | −169.55 (11) |
O5—Co1—O3—C3 | −107.97 (9) | O3—C3—C4—N1 | 12.06 (16) |
O5—Co1—O3—C3 | −107.97 (9) | O3—C3—C4—N1 | 12.06 (16) |
O7—Co1—O3—C3 | 158.44 (9) | C11—As—C51—C56 | 72.54 (12) |
O7—Co1—O3—C3 | 158.44 (9) | C21—As—C51—C56 | −50.66 (12) |
O7i—Co1—O3—C3 | 75.91 (9) | C41—As—C51—C56 | −170.74 (11) |
N1—Co1—O3—C3 | −19.18 (9) | C11—As—C51—C52 | −110.07 (12) |
Co1i—Co1—O3—C3 | 117.09 (8) | C21—As—C51—C52 | 126.73 (11) |
O5—Co1—O7—Co1i | 177.26 (4) | C41—As—C51—C52 | 6.65 (13) |
O5—Co1—O7—Co1i | 177.26 (4) | C23—C22—C21—C26 | 0.2 (2) |
O3—Co1—O7—Co1i | −92.78 (5) | C23—C22—C21—As | −176.62 (11) |
O3—Co1—O7—Co1i | −92.78 (5) | C11—As—C21—C22 | 3.51 (14) |
O1—Co1—O7—Co1i | 87.20 (5) | C51—As—C21—C22 | 126.65 (12) |
O5—Co1—N1—C4 | 114.14 (8) | C41—As—C21—C22 | −114.30 (12) |
O5—Co1—N1—C4 | 114.14 (8) | C11—As—C21—C26 | −173.39 (11) |
O3—Co1—N1—C4 | 24.25 (8) | C51—As—C21—C26 | −50.25 (13) |
O3—Co1—N1—C4 | 24.25 (8) | C41—As—C21—C26 | 68.80 (13) |
O7i—Co1—N1—C4 | −68.53 (8) | C55—C54—C53—C52 | −0.2 (2) |
O1—Co1—N1—C4 | −156.04 (8) | C43—C44—C45—C46 | 0.7 (2) |
Co1i—Co1—N1—C4 | −67.56 (9) | C41—C46—C45—C44 | 0.1 (2) |
O5—Co1—N1—C6 | −6.07 (8) | C56—C51—C52—C53 | 0.2 (2) |
O5—Co1—N1—C6 | −6.07 (8) | As—C51—C52—C53 | −177.17 (11) |
O3—Co1—N1—C6 | −95.97 (9) | C54—C55—C56—C51 | −0.1 (2) |
O3—Co1—N1—C6 | −95.97 (9) | C52—C51—C56—C55 | −0.1 (2) |
O7i—Co1—N1—C6 | 171.26 (8) | As—C51—C56—C55 | 177.30 (10) |
O1—Co1—N1—C6 | 83.74 (9) | C45—C46—C41—C42 | −0.7 (2) |
Co1i—Co1—N1—C6 | 172.23 (7) | C45—C46—C41—As | 177.33 (11) |
O5—Co1—N1—C2 | −123.66 (9) | C11—As—C41—C46 | 39.24 (12) |
O5—Co1—N1—C2 | −123.66 (9) | C21—As—C41—C46 | 160.81 (11) |
O3—Co1—N1—C2 | 146.44 (8) | C51—As—C41—C46 | −81.33 (12) |
O3—Co1—N1—C2 | 146.44 (8) | C11—As—C41—C42 | −142.74 (12) |
O7i—Co1—N1—C2 | 53.67 (9) | C21—As—C41—C42 | −21.17 (13) |
O1—Co1—N1—C2 | −33.85 (8) | C51—As—C41—C42 | 96.69 (13) |
Co1i—Co1—N1—C2 | 54.64 (10) | C46—C41—C42—C43 | 0.6 (2) |
C21—As—C11—C12 | 119.23 (12) | As—C41—C42—C43 | −177.37 (12) |
C51—As—C11—C12 | −1.21 (14) | C24—C25—C26—C21 | −1.4 (2) |
C41—As—C11—C12 | −119.99 (12) | C22—C21—C26—C25 | 0.8 (2) |
C21—As—C11—C16 | −63.40 (13) | As—C21—C26—C25 | 177.78 (11) |
C51—As—C11—C16 | 176.16 (11) | C45—C44—C43—C42 | −0.8 (2) |
C41—As—C11—C16 | 57.38 (13) | C41—C42—C43—C44 | 0.1 (2) |
As—C11—C16—C15 | −177.37 (11) | O5—Co1—O1—C1 | 114.55 (9) |
As—C11—C12—C13 | 177.29 (10) | O5—Co1—O1—C1 | 114.55 (9) |
Co1—O3—C3—O4 | −170.26 (10) | O7—Co1—O1—C1 | −151.86 (9) |
Co1—O3—C3—O4 | −170.26 (10) | O7—Co1—O1—C1 | −151.86 (9) |
Co1—O3—C3—C4 | 8.08 (14) | O7i—Co1—O1—C1 | −69.66 (9) |
C53—C54—C55—C56 | 0.3 (2) | N1—Co1—O1—C1 | 25.75 (9) |
C4—N1—C6—C5 | −106.93 (13) | Co1i—Co1—O1—C1 | −110.57 (8) |
C2—N1—C6—C5 | 121.84 (13) | Co1—O1—C1—O2 | 169.64 (11) |
Co1—N1—C6—C5 | 9.30 (13) | Co1—O1—C1—O2 | 169.64 (11) |
C25—C24—C23—C22 | 0.1 (2) | Co1—O1—C1—C2 | −9.27 (14) |
C21—C22—C23—C24 | −0.6 (2) | C4—N1—C2—C1 | 151.43 (11) |
Co1—O5—C5—O6 | −177.51 (11) | C6—N1—C2—C1 | −79.03 (13) |
Co1—O5—C5—O6 | −177.51 (11) | Co1—N1—C2—C1 | 35.68 (12) |
Co1—O5—C5—C6 | 4.07 (15) | O2—C1—C2—N1 | 162.19 (12) |
N1—C6—C5—O6 | 172.29 (12) | O2—C1—C2—N1 | 162.19 (12) |
N1—C6—C5—O6 | 172.29 (12) | O1—C1—C2—N1 | −18.86 (16) |
Symmetry code: (i) −x+1, −y+2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4A···O4ii | 0.97 | 2.49 | 3.239 (2) | 134 |
C13—H13···O6iii | 0.93 | 2.39 | 3.1207 (19) | 135 |
C14—H14···O6iv | 0.93 | 2.55 | 3.146 (3) | 123 |
C15—H15···O5iv | 0.93 | 2.58 | 3.313 (3) | 136 |
C23—H23···O7 | 0.93 | 2.56 | 3.4034 (19) | 150 |
C52—H2···O9v | 0.93 | 2.53 | 3.386 (2) | 153 |
O7—H7···O4vi | 0.77 (2) | 2.00 (2) | 2.740 (2) | 162 (2) |
O8—H8A···O10vii | 0.82 (2) | 1.94 (2) | 2.758 (2) | 178 (2) |
O8—H8B···O2 | 0.78 (2) | 1.96 (2) | 2.7329 (17) | 171 (2) |
O9—H9A···O8 | 0.80 (2) | 2.25 (2) | 3.045 (2) | 170 (2) |
O9—H9B···O8viii | 0.82 (2) | 1.92 (2) | 2.7290 (19) | 169 (3) |
O10—H10B···O11 | 0.76 (2) | 2.09 (2) | 2.8483 (18) | 174 (2) |
O10—H10C···O9ix | 0.82 (2) | 1.95 (2) | 2.771 (2) | 175 (2) |
O11—H11A···O4iii | 0.76 (2) | 2.22 (2) | 2.9542 (16) | 164 (2) |
O11—H11B···O2ix | 0.89 (2) | 2.02 (2) | 2.905 (2) | 172 (2) |
Symmetry codes: (ii) −x+2, −y+2, −z+1; (iii) −x+1, −y+1, −z+1; (iv) x+1, y, z; (v) x, y−1, z−1; (vi) x−1, y, z; (vii) x+1, y+1, z; (viii) −x+1, −y+2, −z+2; (ix) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | (C24H20As)2[Co2(C6H6NO6)2(OH)2]·8H2O |
Mr | 1438.88 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 7.328 (5), 14.491 (5), 16.564 (5) |
α, β, γ (°) | 113.555 (5), 97.040 (5), 101.152 (5) |
V (Å3) | 1542.4 (13) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.68 |
Crystal size (mm) | 0.44 × 0.19 × 0.03 |
Data collection | |
Diffractometer | Bruker X8 APEXII 4K KappaCCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.687, 0.950 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23209, 23223, 20726 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.098, 0.93 |
No. of reflections | 23223 |
No. of parameters | 430 |
No. of restraints | 10 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.41, −0.36 |
Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2004), SAINT-Plus and XPREP (Bruker, 2004), SHELXL97 (Sheldrick, 2008), SIR97 (Altomare et al., 1999), DIAMOND (Brandenburg & Putz, 2005), WinGX (Farrugia, 1999).
Co1—O1 | 1.9027 (11) | Co1—O7 | 1.8915 (11) |
Co1—O3 | 1.8903 (11) | Co1—O7i | 1.8994 (11) |
Co1—O5 | 1.8806 (11) | Co1—N1 | 1.9312 (13) |
Symmetry code: (i) −x+1, −y+2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4A···O4ii | 0.97 | 2.49 | 3.239 (2) | 133.6 |
C13—H13···O6iii | 0.93 | 2.39 | 3.1207 (19) | 135.4 |
C14—H14···O6iv | 0.93 | 2.55 | 3.146 (3) | 122.6 |
C15—H15···O5iv | 0.93 | 2.58 | 3.313 (3) | 135.9 |
C23—H23···O7 | 0.93 | 2.56 | 3.4034 (19) | 150.2 |
C52—H2···O9v | 0.93 | 2.53 | 3.386 (2) | 152.6 |
O7—H7···O4vi | 0.765 (18) | 2.003 (18) | 2.740 (2) | 161.7 (18) |
O8—H8A···O10vii | 0.82 (2) | 1.94 (2) | 2.758 (2) | 178 (2) |
O8—H8B···O2 | 0.780 (19) | 1.960 (19) | 2.7329 (17) | 171 (2) |
O9—H9A···O8 | 0.800 (19) | 2.254 (19) | 3.045 (2) | 170.0 (17) |
O9—H9B···O8viii | 0.82 (2) | 1.92 (2) | 2.7290 (19) | 169 (3) |
O10—H10B···O11 | 0.762 (18) | 2.090 (18) | 2.8483 (18) | 174 (2) |
O10—H10C···O9ix | 0.822 (18) | 1.952 (19) | 2.771 (2) | 175 (2) |
O11—H11A···O4iii | 0.758 (17) | 2.218 (17) | 2.9542 (16) | 164 (2) |
O11—H11B···O2ix | 0.886 (19) | 2.024 (19) | 2.905 (2) | 172.1 (17) |
Symmetry codes: (ii) −x+2, −y+2, −z+1; (iii) −x+1, −y+1, −z+1; (iv) x+1, y, z; (v) x, y−1, z−1; (vi) x−1, y, z; (vii) x+1, y+1, z; (viii) −x+1, −y+2, −z+2; (ix) x, y−1, z. |
Acknowledgements
The UFS is gratefully acknowledged for funding. JKC acknowledges the Marie Curie IIF scheme of the 7th EU Framework Program
References
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The title complex, (AsC24H20)2[Co(C6H6N)(µ-OH)]2.8(H2O), forms a part of an ongoing investigation of the structural and kinetic behaviour of CoIII-nitrilotriacetato compounds (Visser et al., (1997, 1999, 2001, 2002, 2003). The CoIII atom is octahedrally surrounded by one N atom and three O atoms of the tetradentate nitrilotriacetato ligand and two µ-hydroxo ligands (Fig. 1). The Co–O bond distances which vary between 1.8806 (11) and 1.9027 (11) Å and the Co–N1 distance of 1.9312 (13) Å fall well within the normal range (Table 1). The octahedron around the Co atom is only slighlty distorted. The crystal packing is controlled by C—H–O and O—H–O hydrogen bonding interactions (Table 2), creating a three dimensional network.