Bis(1-ammonio­ethane-1,1-diyl­diphos­phonato-κ2O,O′)diaqua­cobalt(II) nona­hydrate

Bon, V.V.; Dudko, A.V.; Kozachkova, A.N.; Pekhnyo, V.I.; Tsaryk, N.V.

doi:10.1107/S1600536810013681

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 5| May 2010| Pages m537-m538

https://doi.org/10.1107/S1600536810013681

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Bis(1-ammonioethane-1,1-diyldiphosphonato-κ²O,O′)diaquacobalt(II) nonahydrate

Vladimir V. Bon,^a Anatolij V. Dudko,^a Alexandra N. Kozachkova,^a Vasily I. Pekhnyo ^a and Natalia V. Tsaryk ^a ^*

^aInstitute of General and Inorganic Chemistry, NAS Ukraine, Kyiv, prosp. Palladina 32/34, 03680, Ukraine
^*Correspondence e-mail: complex@ionc.kiev.ua

(Received 6 April 2010; accepted 13 April 2010; online 17 April 2010)

In the title compound, [Co(C₂H₈NO₆P₂)₂(H₂O)₂]·9H₂O, the Co^II atom has a slightly distorted octahedral coordination environment consisting of four deprotonated phosphonate O atoms of two independent 1-aminoethylidendiphosphonate anions and complemented by the O atoms of two water molecules in cis positions. The anions exists in the zwitterionic form (protonated amino group and two deprotonated phosphonate O atoms) and constitute two six-membered chelate rings. The crystal structure also contains nine partly disordered uncoordinated water molecules, which create an extensive three-dimensional network of strong O—H⋯O and N—H⋯O hydrogen bonds.

Related literature

For general background to organic diphosphonic acids, see: Matczak-Jon & Videnova-Adrabinska (2005 ). For applications of transition metal bisphosphonates, see: Eberhardt et al. (2005 ). For related structures, see: Xiang et al. (2007 ); Yin et al. (2005 ); Dudko et al. (2009 ).

Experimental

Crystal data

[Co(C₂H₈NO₆P₂)₂(H₂O)₂]·9H₂O
M_r = 665.17
Monoclinic, P 2₁ /c
a = 15.1925 (3) Å
b = 13.2046 (2) Å
c = 12.9688 (2) Å
β = 106.0866 (11)°
V = 2499.81 (7) Å³
Z = 4
Mo Kα radiation
μ = 1.04 mm⁻¹
T = 173 K
0.30 × 0.24 × 0.20 mm

Data collection

Bruker APEX-II CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.749, T_max = 0.820
51914 measured reflections
6273 independent reflections
5626 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.090
S = 1.12
6273 reflections
401 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.73 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—O7	2.0697 (14)
Co1—O13	2.0747 (17)
Co1—O10	2.0771 (15)
Co1—O14	2.0837 (16)
Co1—O1	2.1007 (15)
Co1—O4	2.1201 (15)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H11N⋯O17	0.86 (3)	2.00 (3)	2.836 (3)	165 (3)
N1—H12N⋯O7	0.81 (3)	1.98 (3)	2.785 (2)	175 (3)
N1—H13N⋯O15ⁱ	0.85 (3)	1.98 (3)	2.810 (2)	165 (3)
N2—H21N⋯O23A	0.91 (3)	1.94 (3)	2.808 (4)	159 (3)
N2—H22N⋯O4	0.90 (3)	2.05 (3)	2.944 (2)	173 (3)
N2—H23N⋯O16	0.90 (3)	1.90 (3)	2.783 (3)	164 (3)
O3—H3O⋯O6ⁱⁱ	0.66 (3)	1.92 (3)	2.570 (2)	169 (4)
O5—H5O⋯O2ⁱ	0.76 (3)	1.84 (3)	2.592 (2)	170 (3)
O8—H8O⋯O11ⁱⁱⁱ	0.70 (3)	1.81 (3)	2.508 (2)	169 (3)
O12—H12O⋯O9^iv	0.83 (3)	1.71 (3)	2.517 (2)	165 (3)
O13—H131⋯O6ⁱⁱ	0.79 (3)	1.92 (3)	2.691 (2)	166 (3)
O13—H132⋯O20A	0.77 (3)	1.92 (3)	2.671 (3)	165 (3)
O14—H141⋯O18A^v	0.82 (3)	1.91 (3)	2.697 (3)	163 (3)
O14—H142⋯O9^iv	0.74 (3)	1.95 (3)	2.688 (2)	172 (3)
O15—H151⋯O1	0.80 (3)	2.01 (3)	2.803 (2)	177 (3)
O15—H152⋯O14	0.66 (3)	2.50 (3)	2.946 (2)	127 (3)
O15—H152⋯O12^iv	0.66 (3)	2.54 (3)	3.049 (2)	136 (3)
O16—H161⋯O15ⁱ	0.85 (4)	1.94 (4)	2.788 (3)	176 (3)
O16—H162⋯O17ⁱ	0.89 (4)	1.97 (4)	2.844 (3)	170 (3)
O17—H171⋯O21^vi	0.75 (3)	2.14 (4)	2.795 (3)	147 (3)
O17—H172⋯O18A^vii	0.73 (4)	2.13 (4)	2.845 (3)	167 (4)
O19—H191⋯O13	0.84 (4)	2.27 (4)	3.063 (3)	158 (3)
O19—H192⋯O2^v	0.75 (4)	2.04 (4)	2.773 (3)	166 (4)
O21—H211⋯O19	0.80 (4)	2.05 (4)	2.815 (3)	162 (4)
O21—H212⋯O19^viii	1.00 (4)	1.93 (4)	2.914 (3)	169 (3)
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1; (iii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) -x, -y+1, -z+1; (v) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (vi) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (vii) -x+1, -y+2, -z+1; (viii) -x+1, -y+1, -z+2.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810013681/wm2322sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810013681/wm2322Isup2.hkl

checkCIF report

Comment top

Organic diphosphonic acids are potentially very powerful chelating agents used in metal extractions and are tested by the pharmaceutical industry for use as efficient drugs preventing calcification and inhibiting bone resorption (Matczak-Jon et al., 2005). There is evidence that application of transition metal bisphosphonates can improve fixation of cementless metal implants by enhancing the extent of osseointegration (Eberhardt et al., 2005). In this respect, a detailed structure-correlated study of the individual properties and the complex-forming driving factors is desired in order to sufficiently understand bisphosphonate physiological activities.

Several structures of Co^II aminoethylidenediphosphonates have been reported previously (Xiang et al. 2007; Yin et al. 2005). The main difference between these structures and the title compound is the presence of two water molecules instead of a 1,10-phenanthroline ligand in the coordination environment of the transition metal ion (Xiang et al. 2007), leading also to a different symmetry.

The asymmetric unit of the title compound contains one molecule of the complex (Fig.1). Two 1-aminoethylidendiphosphonate anions chelate the central metal ion via two oxygen atoms from phosphonate groups forming six-membered non-planar metalla rings. Two water molecules complement the slightly distorted octahedral coordination environment of Co in cis-position. The Co—O bond lengths have expected values and conform with the previously reported related structures (Xiang et al., 2007). The values of the O—Co—O angles are in the range from 89.23 (7)° to 91.54 (5)°. The Co1—O1—P1—C1—P2—O4 and Co1—O7—P3—C3—P4—O10 metalla cycles have an envelope conformation with the C1 and C3 atoms out of plane by 0.850 (2) Å and 0.795 (2) Å, respectively. The dihedral angle between the planar fragments Co1—O1—P1—P2—O4 and Co1—O7—P3—P4—O10 is 84.20 (3)°. The coordinated ligand molecules exists in the zwitterionic form with a proton transfer from one of the phosphonic groups to the amino group which is representative for all 1-aminodiphosphonic acids. In addition, the amino group does also not participate in coordination (Dudko et al. 2009).

In the crystal structure of the title compound, nine solvent water molecules are present. Such an amount of solvent molecules could be explained by the presence of two coordinated water molecules in addition to the more hydrophilic phosphonate groups. As a result, a 3-D network of mostly strong O—H···O and N—H···O hydrogen bonds is observed in the structure (Fig. 2; Table 1). Several H-bonds can not be unambiguously derived from the model because some of the crystal lattice water molecules are disordered.

Related literature top

For general background to organic diphosphonic acids, see: Matczak-Jon & Videnova-Adrabinska (2005). For applications of transition metal bisphosphonates, see: Eberhardt et al. (2005). For related structures, see: Xiang et al. (2007); Yin et al. (2005); Dudko et al. (2009).

Experimental top

Light pink crystals of the title compound were obtained from the mixture of 10 ml (10 ^-2 mol/l) water solution of Co(NO₃)₂ with 20 ml (10 ^-2 mol/l) solution of 1-aminoethylidendiphosphonic acid. The combined solution was stored in a dark place for slow evaporation. After 20 days of staying, suitable crystals for X-ray data collection were obtained.

Structure description top

For general background to organic diphosphonic acids, see: Matczak-Jon & Videnova-Adrabinska (2005). For applications of transition metal bisphosphonates, see: Eberhardt et al. (2005). For related structures, see: Xiang et al. (2007); Yin et al. (2005); Dudko et al. (2009).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

	Fig. 1. The molecular structure of title compound showing 50% probability displacement ellipsoids for the non-hydrogen atoms. Solvent water molecules are omitted for clarity.
	Fig. 2. Crystal packing of title compound, in a projection along the c axis. Dashed lines indicate hydrogen bonds.

Bis(1-ammonioethane-1,1-diyldiphosphonato- κ²O,O')diaquacobalt(II) nonahydrate top

Crystal data top

[Co(C₂H₈NO₆P₂)₂(H₂O)₂]·9H₂O	F(000) = 1388
M_r = 665.17	D_x = 1.767 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9983 reflections
a = 15.1925 (3) Å	θ = 2.3–28.4°
b = 13.2046 (2) Å	µ = 1.04 mm⁻¹
c = 12.9688 (2) Å	T = 173 K
β = 106.0866 (11)°	Block, light pink
V = 2499.81 (7) Å³	0.30 × 0.24 × 0.20 mm
Z = 4

Data collection top

Bruker APEX-II CCD diffractometer	6273 independent reflections
Radiation source: fine-focus sealed tube	5626 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
Detector resolution: 8.33 pixels mm^-1	θ_max = 28.4°, θ_min = 1.4°
φ and ω scans	h = −19→20
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −17→17
T_min = 0.749, T_max = 0.820	l = −17→17
51914 measured reflections

Refinement top

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ²(F_o²) + (0.0396P)² + 3.3375P] where P = (F_o² + 2F_c²)/3
6273 reflections	(Δ/σ)_max = 0.001
401 parameters	Δρ_max = 0.73 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

[Co(C₂H₈NO₆P₂)₂(H₂O)₂]·9H₂O	V = 2499.81 (7) Å³
M_r = 665.17	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.1925 (3) Å	µ = 1.04 mm⁻¹
b = 13.2046 (2) Å	T = 173 K
c = 12.9688 (2) Å	0.30 × 0.24 × 0.20 mm
β = 106.0866 (11)°

Data collection top

Bruker APEX-II CCD diffractometer	6273 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	5626 reflections with I > 2σ(I)
T_min = 0.749, T_max = 0.820	R_int = 0.030
51914 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	Δρ_max = 0.73 e Å⁻³
6273 reflections	Δρ_min = −0.29 e Å⁻³
401 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Co1	0.255576 (18)	0.49258 (2)	0.52538 (2)	0.01238 (8)
P1	0.40125 (3)	0.68696 (4)	0.57579 (4)	0.01281 (11)
P2	0.37271 (3)	0.58209 (4)	0.35868 (4)	0.01196 (11)
P3	0.06525 (3)	0.58713 (4)	0.36181 (4)	0.01226 (11)
P4	0.08900 (3)	0.35638 (4)	0.36325 (4)	0.01415 (11)
C1	0.36957 (13)	0.70306 (15)	0.42887 (16)	0.0131 (4)
C2	0.43053 (15)	0.78295 (17)	0.39660 (17)	0.0188 (4)
H21C	0.4116	0.7914	0.3185	0.028*
H22C	0.4946	0.7608	0.4198	0.028*
H23C	0.4243	0.8477	0.4309	0.028*
C3	0.06352 (13)	0.47197 (16)	0.28100 (16)	0.0141 (4)
C4	−0.02844 (14)	0.46254 (19)	0.19417 (17)	0.0204 (4)
H41C	−0.0374	0.5219	0.1470	0.031*
H42C	−0.0784	0.4586	0.2283	0.031*
H43C	−0.0282	0.4011	0.1518	0.031*
N1	0.27212 (12)	0.74065 (14)	0.39596 (15)	0.0142 (3)
H11N	0.2720 (19)	0.799 (2)	0.426 (2)	0.021*
H12N	0.237 (2)	0.701 (2)	0.412 (2)	0.021*
H13N	0.2560 (19)	0.749 (2)	0.328 (2)	0.021*
N2	0.13796 (12)	0.48190 (15)	0.22493 (15)	0.0165 (3)
H21N	0.1347 (19)	0.429 (2)	0.179 (2)	0.025*
H22N	0.193 (2)	0.486 (2)	0.273 (2)	0.025*
H23N	0.128 (2)	0.538 (2)	0.183 (2)	0.025*
O1	0.33239 (10)	0.61709 (12)	0.60220 (11)	0.0160 (3)
O2	0.40782 (10)	0.79109 (11)	0.62352 (12)	0.0181 (3)
O3	0.49936 (10)	0.64009 (13)	0.60579 (13)	0.0188 (3)
H3O	0.502 (2)	0.590 (2)	0.605 (2)	0.023*
O4	0.31168 (10)	0.50763 (11)	0.39358 (12)	0.0154 (3)
O5	0.32357 (10)	0.60670 (12)	0.23804 (12)	0.0171 (3)
H5O	0.3517 (19)	0.640 (2)	0.211 (2)	0.020*
O6	0.47085 (10)	0.55160 (12)	0.37641 (12)	0.0178 (3)
O7	0.15729 (9)	0.59446 (11)	0.44381 (11)	0.0151 (3)
O8	0.06089 (11)	0.67523 (12)	0.28140 (13)	0.0191 (3)
H8O	0.017 (2)	0.695 (2)	0.258 (2)	0.023*
O9	−0.01614 (10)	0.58374 (12)	0.40569 (12)	0.0179 (3)
O10	0.17939 (10)	0.37086 (11)	0.44643 (12)	0.0179 (3)
O11	0.08724 (10)	0.26901 (12)	0.28832 (12)	0.0195 (3)
O12	0.00608 (11)	0.34512 (13)	0.41132 (13)	0.0199 (3)
H12O	0.0100 (19)	0.378 (2)	0.467 (2)	0.024*
O13	0.35601 (12)	0.39698 (14)	0.61576 (15)	0.0238 (4)
H131	0.407 (2)	0.403 (2)	0.614 (2)	0.029*
H132	0.340 (2)	0.341 (3)	0.611 (2)	0.029*
O14	0.18902 (11)	0.48630 (13)	0.64577 (13)	0.0198 (3)
H141	0.210 (2)	0.456 (2)	0.702 (3)	0.024*
H142	0.140 (2)	0.472 (2)	0.630 (2)	0.024*
O15	0.19611 (13)	0.70714 (14)	0.67947 (14)	0.0234 (4)
H151	0.235 (2)	0.680 (2)	0.660 (2)	0.028*
H152	0.165 (2)	0.671 (3)	0.674 (3)	0.028*
O16	0.10482 (14)	0.62776 (16)	0.06388 (15)	0.0310 (4)
H161	0.130 (2)	0.679 (3)	0.099 (3)	0.037*
H162	0.143 (2)	0.610 (3)	0.026 (3)	0.037*
O17	0.24161 (13)	0.93732 (14)	0.46692 (16)	0.0265 (4)
H171	0.287 (2)	0.949 (3)	0.506 (3)	0.032*
H172	0.229 (2)	0.979 (3)	0.429 (3)	0.032*
O19	0.44927 (14)	0.42724 (16)	0.85539 (17)	0.0329 (4)
H191	0.415 (2)	0.433 (3)	0.793 (3)	0.039*
H192	0.483 (3)	0.385 (3)	0.866 (3)	0.039*
O21	0.60125 (14)	0.55256 (16)	0.94457 (19)	0.0359 (4)
H211	0.559 (3)	0.523 (3)	0.907 (3)	0.043*
H212	0.590 (2)	0.567 (3)	1.015 (3)	0.043*
O18A	0.77849 (14)	0.88751 (17)	0.66533 (16)	0.0234 (8)	0.873 (11)
O20A	0.3072 (2)	0.20567 (19)	0.6380 (3)	0.0415 (11)	0.869 (14)
O22A	0.67469 (18)	0.7176 (2)	0.6366 (4)	0.0409 (12)	0.876 (13)
O23A	0.1129 (3)	0.3552 (6)	0.0452 (6)	0.0420 (16)	0.71 (3)
O18B	0.747 (3)	0.840 (3)	0.668 (3)	0.101 (12)*	0.127 (11)
O20B	0.350 (3)	0.197 (2)	0.684 (3)	0.076 (10)*	0.131 (14)
O22B	0.6582 (15)	0.7397 (17)	0.579 (3)	0.042 (6)*	0.124 (13)
O23B	0.1074 (8)	0.3242 (16)	0.0717 (14)	0.048 (3)*	0.29 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.01106 (13)	0.01304 (14)	0.01351 (13)	−0.00105 (9)	0.00416 (10)	0.00019 (10)
P1	0.0123 (2)	0.0130 (2)	0.0135 (2)	−0.00120 (18)	0.00427 (18)	−0.00135 (18)
P2	0.0114 (2)	0.0119 (2)	0.0137 (2)	−0.00023 (17)	0.00541 (17)	−0.00051 (18)
P3	0.0101 (2)	0.0140 (2)	0.0133 (2)	0.00027 (17)	0.00432 (17)	0.00080 (18)
P4	0.0142 (2)	0.0133 (2)	0.0157 (2)	−0.00344 (18)	0.00540 (18)	−0.00208 (19)
C1	0.0119 (8)	0.0131 (9)	0.0154 (9)	−0.0009 (7)	0.0056 (7)	−0.0006 (7)
C2	0.0221 (10)	0.0161 (10)	0.0206 (10)	−0.0057 (8)	0.0102 (8)	−0.0005 (8)
C3	0.0121 (8)	0.0177 (10)	0.0135 (8)	−0.0022 (7)	0.0053 (7)	−0.0013 (7)
C4	0.0162 (9)	0.0272 (12)	0.0164 (9)	−0.0025 (8)	0.0020 (8)	−0.0024 (9)
N1	0.0146 (8)	0.0126 (9)	0.0157 (8)	0.0005 (6)	0.0049 (6)	0.0004 (7)
N2	0.0154 (8)	0.0186 (9)	0.0169 (8)	−0.0017 (7)	0.0064 (7)	−0.0012 (7)
O1	0.0161 (7)	0.0180 (7)	0.0150 (7)	−0.0036 (6)	0.0062 (5)	−0.0009 (6)
O2	0.0222 (7)	0.0143 (7)	0.0193 (7)	−0.0018 (6)	0.0083 (6)	−0.0045 (6)
O3	0.0143 (7)	0.0166 (7)	0.0246 (8)	0.0010 (6)	0.0038 (6)	−0.0001 (7)
O4	0.0170 (7)	0.0132 (7)	0.0189 (7)	−0.0030 (5)	0.0095 (6)	−0.0016 (5)
O5	0.0183 (7)	0.0189 (8)	0.0143 (7)	−0.0020 (6)	0.0050 (5)	0.0013 (6)
O6	0.0125 (6)	0.0175 (7)	0.0249 (7)	0.0006 (6)	0.0078 (6)	−0.0010 (6)
O7	0.0119 (6)	0.0145 (7)	0.0177 (7)	0.0005 (5)	0.0020 (5)	−0.0005 (6)
O8	0.0159 (7)	0.0200 (8)	0.0223 (8)	0.0043 (6)	0.0068 (6)	0.0073 (6)
O9	0.0135 (7)	0.0236 (8)	0.0192 (7)	−0.0022 (6)	0.0088 (6)	−0.0036 (6)
O10	0.0184 (7)	0.0147 (7)	0.0188 (7)	−0.0015 (6)	0.0024 (6)	−0.0002 (6)
O11	0.0185 (7)	0.0187 (8)	0.0221 (7)	−0.0035 (6)	0.0070 (6)	−0.0068 (6)
O12	0.0206 (7)	0.0221 (8)	0.0204 (7)	−0.0081 (6)	0.0112 (6)	−0.0056 (6)
O13	0.0156 (7)	0.0193 (8)	0.0364 (9)	−0.0003 (6)	0.0071 (7)	0.0082 (7)
O14	0.0145 (7)	0.0269 (9)	0.0186 (8)	−0.0058 (6)	0.0054 (6)	0.0001 (6)
O15	0.0258 (9)	0.0214 (9)	0.0252 (8)	−0.0049 (7)	0.0108 (7)	−0.0066 (7)
O16	0.0389 (10)	0.0333 (10)	0.0234 (8)	−0.0088 (8)	0.0127 (8)	−0.0040 (8)
O17	0.0268 (9)	0.0222 (9)	0.0283 (9)	0.0019 (7)	0.0036 (7)	−0.0002 (7)
O19	0.0286 (9)	0.0351 (11)	0.0330 (10)	0.0094 (8)	0.0052 (8)	−0.0034 (8)
O21	0.0277 (10)	0.0321 (11)	0.0470 (12)	0.0015 (8)	0.0086 (9)	−0.0061 (9)
O18A	0.0236 (11)	0.0192 (12)	0.0270 (11)	−0.0037 (8)	0.0064 (8)	−0.0031 (8)
O20A	0.0413 (19)	0.0277 (14)	0.055 (2)	−0.0005 (10)	0.0119 (15)	0.0096 (11)
O22A	0.0299 (13)	0.0307 (14)	0.064 (3)	−0.0050 (10)	0.0168 (13)	−0.0156 (15)
O23A	0.063 (2)	0.034 (3)	0.032 (2)	−0.0083 (17)	0.0194 (16)	−0.0152 (19)

Geometric parameters (Å, º) top

Co1—O7	2.0697 (14)	C3—C4	1.537 (3)
Co1—O13	2.0747 (17)	C4—H41C	0.9800
Co1—O10	2.0771 (15)	C4—H42C	0.9800
Co1—O14	2.0837 (16)	C4—H43C	0.9800
Co1—O1	2.1007 (15)	N1—H11N	0.86 (3)
Co1—O4	2.1201 (15)	N1—H12N	0.81 (3)
P1—O2	1.4999 (15)	N1—H13N	0.85 (3)
P1—O1	1.5039 (15)	N2—H21N	0.91 (3)
P1—O3	1.5604 (16)	N2—H22N	0.90 (3)
P1—C1	1.844 (2)	N2—H23N	0.90 (3)
P2—O6	1.4993 (15)	O3—H3O	0.66 (3)
P2—O4	1.5047 (15)	O5—H5O	0.76 (3)
P2—O5	1.5696 (15)	O8—H8O	0.70 (3)
P2—C1	1.846 (2)	O12—H12O	0.83 (3)
P3—O9	1.4982 (15)	O13—H131	0.79 (3)
P3—O7	1.5071 (14)	O13—H132	0.77 (3)
P3—O8	1.5515 (16)	O14—H141	0.82 (3)
P3—C3	1.843 (2)	O14—H142	0.74 (3)
P4—O11	1.5038 (16)	O15—H151	0.80 (3)
P4—O10	1.5050 (15)	O15—H152	0.66 (3)
P4—O12	1.5599 (16)	O16—H161	0.85 (4)
P4—C3	1.841 (2)	O16—H162	0.89 (4)
C1—N1	1.507 (3)	O17—H171	0.75 (3)
C1—C2	1.536 (3)	O17—H172	0.73 (4)
C2—H21C	0.9800	O19—H191	0.84 (4)
C2—H22C	0.9800	O19—H192	0.75 (4)
C2—H23C	0.9800	O21—H211	0.80 (4)
C3—N2	1.510 (3)	O21—H212	1.00 (4)

O7—Co1—O13	176.20 (7)	H21C—C2—H22C	109.5
O7—Co1—O10	91.52 (6)	C1—C2—H23C	109.5
O13—Co1—O10	91.71 (7)	H21C—C2—H23C	109.5
O7—Co1—O14	88.73 (6)	H22C—C2—H23C	109.5
O13—Co1—O14	89.20 (7)	N2—C3—C4	107.71 (16)
O10—Co1—O14	91.08 (6)	N2—C3—P4	106.60 (14)
O7—Co1—O1	87.76 (6)	C4—C3—P4	111.09 (15)
O13—Co1—O1	89.05 (7)	N2—C3—P3	107.91 (14)
O10—Co1—O1	178.83 (6)	C4—C3—P3	110.50 (15)
O14—Co1—O1	89.83 (6)	P4—C3—P3	112.77 (10)
O7—Co1—O4	85.48 (6)	C3—C4—H41C	109.5
O13—Co1—O4	96.63 (7)	C3—C4—H42C	109.5
O10—Co1—O4	88.21 (6)	H41C—C4—H42C	109.5
O14—Co1—O4	174.14 (6)	C3—C4—H43C	109.5
O1—Co1—O4	90.82 (6)	H41C—C4—H43C	109.5
O2—P1—O1	116.06 (9)	H42C—C4—H43C	109.5
O2—P1—O3	108.12 (9)	C1—N1—H11N	106.9 (18)
O1—P1—O3	112.13 (9)	C1—N1—H12N	112 (2)
O2—P1—C1	106.81 (9)	H11N—N1—H12N	112 (3)
O1—P1—C1	107.89 (9)	C1—N1—H13N	108.4 (19)
O3—P1—C1	105.14 (9)	H11N—N1—H13N	108 (3)
O6—P2—O4	116.61 (9)	H12N—N1—H13N	109 (3)
O6—P2—O5	112.75 (9)	C3—N2—H21N	109.5 (18)
O4—P2—O5	105.82 (9)	C3—N2—H22N	110.4 (19)
O6—P2—C1	108.50 (9)	H21N—N2—H22N	112 (3)
O4—P2—C1	108.35 (9)	C3—N2—H23N	110.0 (18)
O5—P2—C1	104.02 (9)	H21N—N2—H23N	106 (3)
O9—P3—O7	115.85 (9)	H22N—N2—H23N	109 (3)
O9—P3—O8	113.06 (9)	P1—O1—Co1	134.61 (9)
O7—P3—O8	106.53 (9)	P1—O3—H3O	116 (3)
O9—P3—C3	107.95 (9)	P2—O4—Co1	136.28 (9)
O7—P3—C3	108.57 (9)	P2—O5—H5O	114 (2)
O8—P3—C3	104.19 (9)	P3—O7—Co1	135.71 (9)
O11—P4—O10	114.20 (9)	P3—O8—H8O	115 (3)
O11—P4—O12	108.26 (9)	P4—O10—Co1	136.45 (10)
O10—P4—O12	113.78 (9)	P4—O12—H12O	115 (2)
O11—P4—C3	107.37 (9)	Co1—O13—H131	120 (2)
O10—P4—C3	108.28 (9)	Co1—O13—H132	112 (2)
O12—P4—C3	104.31 (9)	H131—O13—H132	112 (3)
N1—C1—C2	108.41 (17)	Co1—O14—H141	123 (2)
N1—C1—P1	106.58 (13)	Co1—O14—H142	117 (2)
C2—C1—P1	110.87 (14)	H141—O14—H142	104 (3)
N1—C1—P2	107.64 (13)	H151—O15—H152	102 (4)
C2—C1—P2	111.10 (14)	H161—O16—H162	104 (3)
P1—C1—P2	112.02 (11)	H171—O17—H172	109 (4)
C1—C2—H21C	109.5	H191—O19—H192	117 (4)
C1—C2—H22C	109.5	H211—O21—H212	110 (3)

O2—P1—C1—N1	−69.60 (15)	O8—P3—C3—C4	−65.37 (16)
O1—P1—C1—N1	55.84 (15)	O9—P3—C3—P4	−69.94 (12)
O3—P1—C1—N1	175.67 (13)	O7—P3—C3—P4	56.38 (12)
O2—P1—C1—C2	48.19 (16)	O8—P3—C3—P4	169.62 (10)
O1—P1—C1—C2	173.63 (14)	O2—P1—O1—Co1	152.91 (11)
O3—P1—C1—C2	−66.54 (16)	O3—P1—O1—Co1	−82.16 (14)
O2—P1—C1—P2	172.92 (9)	C1—P1—O1—Co1	33.15 (15)
O1—P1—C1—P2	−61.64 (12)	O7—Co1—O1—P1	−86.87 (13)
O3—P1—C1—P2	58.19 (12)	O13—Co1—O1—P1	95.20 (13)
O6—P2—C1—N1	171.19 (13)	O14—Co1—O1—P1	−175.60 (13)
O4—P2—C1—N1	−61.33 (15)	O4—Co1—O1—P1	−1.42 (13)
O5—P2—C1—N1	50.94 (15)	O6—P2—O4—Co1	102.36 (14)
O6—P2—C1—C2	52.64 (16)	O5—P2—O4—Co1	−131.38 (13)
O4—P2—C1—C2	−179.87 (14)	C1—P2—O4—Co1	−20.33 (16)
O5—P2—C1—C2	−67.61 (15)	O7—Co1—O4—P2	81.31 (13)
O6—P2—C1—P1	−71.96 (12)	O13—Co1—O4—P2	−95.52 (14)
O4—P2—C1—P1	55.52 (12)	O10—Co1—O4—P2	172.97 (14)
O5—P2—C1—P1	167.78 (10)	O1—Co1—O4—P2	−6.38 (14)
O11—P4—C3—N2	−60.67 (15)	O9—P3—O7—Co1	92.63 (14)
O10—P4—C3—N2	63.09 (15)	O8—P3—O7—Co1	−140.66 (12)
O12—P4—C3—N2	−175.41 (13)	C3—P3—O7—Co1	−28.97 (15)
O11—P4—C3—C4	56.41 (16)	O10—Co1—O7—P3	1.53 (13)
O10—P4—C3—C4	−179.83 (14)	O14—Co1—O7—P3	−89.51 (13)
O12—P4—C3—C4	−58.34 (16)	O1—Co1—O7—P3	−179.38 (13)
O11—P4—C3—P3	−178.91 (10)	O4—Co1—O7—P3	89.61 (13)
O10—P4—C3—P3	−55.15 (12)	O11—P4—O10—Co1	146.29 (12)
O12—P4—C3—P3	66.35 (12)	O12—P4—O10—Co1	−88.72 (15)
O9—P3—C3—N2	172.59 (13)	C3—P4—O10—Co1	26.74 (16)
O7—P3—C3—N2	−61.09 (15)	O7—Co1—O10—P4	−0.20 (14)
O8—P3—C3—N2	52.15 (15)	O13—Co1—O10—P4	177.79 (14)
O9—P3—C3—C4	55.06 (16)	O14—Co1—O10—P4	88.55 (14)
O7—P3—C3—C4	−178.61 (14)	O4—Co1—O10—P4	−85.63 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11N···O17	0.86 (3)	2.00 (3)	2.836 (3)	165 (3)
N1—H12N···O7	0.81 (3)	1.98 (3)	2.785 (2)	175 (3)
N1—H13N···O15ⁱ	0.85 (3)	1.98 (3)	2.810 (2)	165 (3)
N2—H21N···O23A	0.91 (3)	1.94 (3)	2.808 (4)	159 (3)
N2—H22N···O4	0.90 (3)	2.05 (3)	2.944 (2)	173 (3)
N2—H23N···O16	0.90 (3)	1.90 (3)	2.783 (3)	164 (3)
O3—H3O···O6ⁱⁱ	0.66 (3)	1.92 (3)	2.570 (2)	169 (4)
O5—H5O···O2ⁱ	0.76 (3)	1.84 (3)	2.592 (2)	170 (3)
O8—H8O···O11ⁱⁱⁱ	0.70 (3)	1.81 (3)	2.508 (2)	169 (3)
O12—H12O···O9^iv	0.83 (3)	1.71 (3)	2.517 (2)	165 (3)
O13—H131···O6ⁱⁱ	0.79 (3)	1.92 (3)	2.691 (2)	166 (3)
O13—H132···O20A	0.77 (3)	1.92 (3)	2.671 (3)	165 (3)
O14—H141···O18A^v	0.82 (3)	1.91 (3)	2.697 (3)	163 (3)
O14—H142···O9^iv	0.74 (3)	1.95 (3)	2.688 (2)	172 (3)
O15—H151···O1	0.80 (3)	2.01 (3)	2.803 (2)	177 (3)
O15—H152···O14	0.66 (3)	2.50 (3)	2.946 (2)	127 (3)
O15—H152···O12^iv	0.66 (3)	2.54 (3)	3.049 (2)	136 (3)
O16—H161···O15ⁱ	0.85 (4)	1.94 (4)	2.788 (3)	176 (3)
O16—H162···O17ⁱ	0.89 (4)	1.97 (4)	2.844 (3)	170 (3)
O17—H171···O21^vi	0.75 (3)	2.14 (4)	2.795 (3)	147 (3)
O17—H172···O18A^vii	0.73 (4)	2.13 (4)	2.845 (3)	167 (4)
O19—H191···O13	0.84 (4)	2.27 (4)	3.063 (3)	158 (3)
O19—H192···O2^v	0.75 (4)	2.04 (4)	2.773 (3)	166 (4)
O21—H211···O19	0.80 (4)	2.05 (4)	2.815 (3)	162 (4)
O21—H212···O19^viii	1.00 (4)	1.93 (4)	2.914 (3)	169 (3)

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

Experimental details

Crystal data
Chemical formula	[Co(C₂H₈NO₆P₂)₂(H₂O)₂]·9H₂O
M_r	665.17
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	15.1925 (3), 13.2046 (2), 12.9688 (2)
β (°)	106.0866 (11)
V (Å³)	2499.81 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.04
Crystal size (mm)	0.30 × 0.24 × 0.20

Data collection
Diffractometer	Bruker APEX-II CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.749, 0.820
No. of measured, independent and observed [I > 2σ(I)] reflections	51914, 6273, 5626
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.090, 1.12
No. of reflections	6273
No. of parameters	401
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.73, −0.29

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2009).

Selected bond lengths (Å) top

Co1—O7	2.0697 (14)	Co1—O14	2.0837 (16)
Co1—O13	2.0747 (17)	Co1—O1	2.1007 (15)
Co1—O10	2.0771 (15)	Co1—O4	2.1201 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11N···O17	0.86 (3)	2.00 (3)	2.836 (3)	165 (3)
N1—H12N···O7	0.81 (3)	1.98 (3)	2.785 (2)	175 (3)
N1—H13N···O15ⁱ	0.85 (3)	1.98 (3)	2.810 (2)	165 (3)
N2—H21N···O23A	0.91 (3)	1.94 (3)	2.808 (4)	159 (3)
N2—H22N···O4	0.90 (3)	2.05 (3)	2.944 (2)	173 (3)
N2—H23N···O16	0.90 (3)	1.90 (3)	2.783 (3)	164 (3)
O3—H3O···O6ⁱⁱ	0.66 (3)	1.92 (3)	2.570 (2)	169 (4)
O5—H5O···O2ⁱ	0.76 (3)	1.84 (3)	2.592 (2)	170 (3)
O8—H8O···O11ⁱⁱⁱ	0.70 (3)	1.81 (3)	2.508 (2)	169 (3)
O12—H12O···O9^iv	0.83 (3)	1.71 (3)	2.517 (2)	165 (3)
O13—H131···O6ⁱⁱ	0.79 (3)	1.92 (3)	2.691 (2)	166 (3)
O13—H132···O20A	0.77 (3)	1.92 (3)	2.671 (3)	165 (3)
O14—H141···O18A^v	0.82 (3)	1.91 (3)	2.697 (3)	163 (3)
O14—H142···O9^iv	0.74 (3)	1.95 (3)	2.688 (2)	172 (3)
O15—H151···O1	0.80 (3)	2.01 (3)	2.803 (2)	177 (3)
O15—H152···O14	0.66 (3)	2.50 (3)	2.946 (2)	127 (3)
O15—H152···O12^iv	0.66 (3)	2.54 (3)	3.049 (2)	136 (3)
O16—H161···O15ⁱ	0.85 (4)	1.94 (4)	2.788 (3)	176 (3)
O16—H162···O17ⁱ	0.89 (4)	1.97 (4)	2.844 (3)	170 (3)
O17—H171···O21^vi	0.75 (3)	2.14 (4)	2.795 (3)	147 (3)
O17—H172···O18A^vii	0.73 (4)	2.13 (4)	2.845 (3)	167 (4)
O19—H191···O13	0.84 (4)	2.27 (4)	3.063 (3)	158 (3)
O19—H192···O2^v	0.75 (4)	2.04 (4)	2.773 (3)	166 (4)
O21—H211···O19	0.80 (4)	2.05 (4)	2.815 (3)	162 (4)
O21—H212···O19^viii	1.00 (4)	1.93 (4)	2.914 (3)	169 (3)

References

Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dudko, A., Bon, V., Kozachkova, A. & Pekhnyo, V. (2009). Acta Cryst. E65, m459. Web of Science CSD CrossRef IUCr Journals Google Scholar
Eberhardt, C., Schwarz, M. & Kurth, A. H. (2005). J. Orthop. Sci. 10, 622–626. Web of Science CrossRef PubMed CAS Google Scholar
Matczak-Jon, E. & Videnova-Adrabinska, V. (2005). Coord. Chem. Rev. 249, 2458–2488. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2009). publCIF. In preparation. Google Scholar
Xiang, J., Li, M., Wu, S., Yuan, L.-J. & Sun, J. (2007). J. Mol. Struct. 826, 143–149. Web of Science CSD CrossRef CAS Google Scholar
Yin, P., Wang, X.-C., Gao, S. & Zheng, L.-M. (2005). J. Solid State Chem. 178, 1049–1053. Web of Science CSD CrossRef CAS Google Scholar

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Volume 66| Part 5| May 2010| Pages m537-m538

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