Diaqua-bis-(dihydrogen 3-aza-niumyl-1-hy-droxy-propyl-idene-1,1-di-phos-phon-ato-κO,O')cobalt(II).

The asymmetric unit of title compound, [Co(C(3)H(10)NO(7)P(2))(2)(H(2)O)(2)], contains one half-mol-ecule of the complex. The Co(II) atom is located on an inversion centre and displays a distorted octa-hedral coordination geometry defined by four O atoms of two 3-aza-niumyl-1-hy-droxy-propyl-idene-1,1-bis-phospho-nato ligands in the equatorial plane and two water mol-ecules located in axial positions. The ligand mol-ecules, which exist in a zwitterionic state, form two six-membered chelate rings with chair conformations. In the crystal, mol-ecules are inter-linked by O-H⋯O and N-H⋯O hydrogen bonds, forming a three-dimensional supra-molecular structure.

Related literature

For general background to organic diphospho­nic acids and their applications, see: Matczak-Jon & Videnova-Adrabinska (2005 ▶). For applications of bis­phospho­nate metal complexes in medicine, see: Matkovskaya et al. (2001 ▶). For a related structure, see: Bon et al. (2010 ▶). For bond-length data, see: Allen et al. (2004 ▶).

Experimental

Crystal data

[Co(C3H10NO7P2)2(H2O)2]

M = 563.08

Monoclinic,

a = 7.3292 (2) Å

b = 10.8172 (3) Å

c = 12.6403 (3) Å

β = 120.801 (1)°

V = 860.79 (4) Å3

Z = 2

Mo Kα radiation

μ = 1.46 mm−1

T = 100 K

0.50 × 0.25 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.528, T max = 0.811

6688 measured reflections

2613 independent reflections

2273 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.080

S = 1.04

2613 reflections

157 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.70 e Å−3

Δρmin = −0.41 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2010 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811045120/ez2263sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811045120/ez2263Isup2.hkl

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

[Co(C3H10NO7P2)2(H2O)2]	F(000) = 578
Mr = 563.08	Dx = 2.172 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3543 reflections
a = 7.3292 (2) Å	θ = 2.7–30.6°
b = 10.8172 (3) Å	µ = 1.46 mm−1
c = 12.6403 (3) Å	T = 100 K
β = 120.801 (1)°	Block, pink
V = 860.79 (4) Å3	0.50 × 0.25 × 0.15 mm
Z = 2

Bruker APEXII CCD diffractometer	2613 independent reflections
Radiation source: fine-focus sealed tube	2273 reflections with I > 2σ(I)
graphite	Rint = 0.020
φ and ω scans	θmax = 30.6°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −10→9
Tmin = 0.528, Tmax = 0.811	k = −12→15
6688 measured reflections	l = −18→12

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0452P)2 + 0.4224P] where P = (Fo2 + 2Fc2)/3
2613 reflections	(Δ/σ)max = 0.003
157 parameters	Δρmax = 0.70 e Å−3
1 restraint	Δρmin = −0.41 e Å−3

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
Co1	0.0000	0.5000	0.0000	0.01045 (9)
P1	0.25936 (6)	0.70145 (4)	−0.05843 (4)	0.00902 (10)
P2	−0.12574 (6)	0.58120 (4)	−0.28208 (4)	0.00964 (10)
O1	0.1630 (2)	0.72770 (13)	−0.29229 (12)	0.0156 (3)
H1O	0.127 (4)	0.802 (3)	−0.289 (2)	0.023*
O2	0.25165 (18)	0.60515 (12)	0.02492 (11)	0.0124 (2)
O3	0.1139 (2)	0.81197 (12)	−0.07370 (12)	0.0145 (3)
H3O	0.154 (4)	0.874 (3)	−0.079 (2)	0.022*
O4	0.48210 (18)	0.74524 (13)	−0.01964 (11)	0.0137 (3)
O5	−0.1323 (2)	0.49001 (12)	−0.19349 (11)	0.0143 (3)
O6	−0.2632 (2)	0.69798 (12)	−0.29892 (12)	0.0151 (3)
H6O	−0.334 (4)	0.712 (2)	−0.365 (2)	0.023*
O7	−0.1968 (2)	0.52889 (12)	−0.40857 (11)	0.0137 (3)
O8	0.1663 (2)	0.33228 (13)	0.02254 (13)	0.0158 (3)
H81	0.270 (4)	0.320 (2)	0.007 (2)	0.024*
H82	0.082 (4)	0.283 (2)	−0.014 (2)	0.024*
N1	0.4212 (3)	0.38826 (17)	−0.30480 (17)	0.0192 (3)
H2N	0.356 (4)	0.323 (3)	−0.297 (2)	0.029*
H3N	0.553 (5)	0.394 (2)	−0.237 (3)	0.029*
H1N	0.439 (4)	0.383 (3)	−0.3675 (19)	0.029*
C1	0.1504 (2)	0.63551 (16)	−0.21320 (15)	0.0108 (3)
C2	0.2914 (3)	0.52507 (17)	−0.20331 (16)	0.0140 (3)
H2A	0.4370	0.5391	−0.1330	0.017*
H2B	0.2357	0.4493	−0.1858	0.017*
C3	0.3018 (3)	0.50443 (17)	−0.31959 (18)	0.0164 (4)
H3A	0.1565	0.4980	−0.3922	0.020*
H3B	0.3743	0.5750	−0.3325	0.020*

	U11	U22	U33	U12	U13	U23
Co1	0.01100 (15)	0.00938 (17)	0.00988 (16)	−0.00047 (11)	0.00457 (12)	0.00097 (12)
P1	0.00920 (18)	0.0085 (2)	0.00885 (19)	−0.00167 (14)	0.00423 (15)	−0.00129 (15)
P2	0.01040 (19)	0.0090 (2)	0.00774 (18)	−0.00077 (14)	0.00333 (15)	−0.00018 (15)
O1	0.0225 (6)	0.0115 (6)	0.0157 (6)	0.0003 (5)	0.0118 (5)	0.0027 (5)
O2	0.0120 (5)	0.0124 (6)	0.0107 (5)	−0.0017 (4)	0.0042 (4)	0.0020 (5)
O3	0.0171 (6)	0.0076 (6)	0.0190 (6)	−0.0005 (5)	0.0094 (5)	−0.0013 (5)
O4	0.0110 (5)	0.0168 (7)	0.0133 (6)	−0.0049 (4)	0.0063 (5)	−0.0040 (5)
O5	0.0163 (6)	0.0141 (6)	0.0103 (6)	−0.0043 (5)	0.0052 (5)	0.0014 (5)
O6	0.0148 (6)	0.0147 (6)	0.0109 (6)	0.0051 (5)	0.0031 (5)	0.0004 (5)
O7	0.0162 (6)	0.0125 (6)	0.0092 (5)	−0.0015 (5)	0.0041 (5)	−0.0030 (5)
O8	0.0139 (6)	0.0134 (6)	0.0210 (6)	−0.0007 (5)	0.0096 (5)	−0.0009 (5)
N1	0.0186 (7)	0.0182 (8)	0.0237 (8)	−0.0020 (6)	0.0129 (7)	−0.0071 (7)
C1	0.0114 (7)	0.0099 (8)	0.0103 (7)	−0.0005 (6)	0.0050 (6)	0.0001 (6)
C2	0.0155 (7)	0.0125 (8)	0.0125 (7)	0.0038 (6)	0.0061 (6)	−0.0007 (7)
C3	0.0181 (8)	0.0156 (9)	0.0180 (9)	0.0017 (6)	0.0111 (7)	−0.0008 (7)

Co1—O2i	2.0494 (12)	O1—H1O	0.85 (3)
Co1—O2	2.0494 (12)	O3—H3O	0.76 (3)
Co1—O8i	2.1221 (14)	O6—H6O	0.74 (3)
Co1—O8	2.1221 (14)	O8—H81	0.89 (3)
Co1—O5i	2.1225 (13)	O8—H82	0.77 (3)
Co1—O5	2.1225 (13)	N1—C3	1.487 (3)
P1—O2	1.5031 (13)	N1—H2N	0.88 (3)
P1—O4	1.5199 (12)	N1—H3N	0.91 (3)
P1—O3	1.5469 (14)	N1—H1N	0.870 (17)
P1—C1	1.8367 (17)	C1—C2	1.542 (2)
P2—O5	1.5115 (13)	C2—C3	1.527 (3)
P2—O7	1.5149 (13)	C2—H2A	0.9900
P2—O6	1.5609 (14)	C2—H2B	0.9900
P2—C1	1.8422 (16)	C3—H3A	0.9900
O1—C1	1.448 (2)	C3—H3B	0.9900
O2i—Co1—O2	180.0	P2—O5—Co1	130.65 (7)
O2i—Co1—O8i	92.52 (5)	P2—O6—H6O	111 (2)
O2—Co1—O8i	87.48 (5)	Co1—O8—H81	126.4 (17)
O2i—Co1—O8	87.48 (5)	Co1—O8—H82	107 (2)
O2—Co1—O8	92.52 (5)	H81—O8—H82	107 (2)
O8i—Co1—O8	180.0	C3—N1—H2N	111.7 (18)
O2i—Co1—O5i	92.85 (5)	C3—N1—H3N	109.5 (17)
O2—Co1—O5i	87.15 (5)	H2N—N1—H3N	109 (2)
O8i—Co1—O5i	90.19 (5)	C3—N1—H1N	107.2 (19)
O8—Co1—O5i	89.81 (5)	H2N—N1—H1N	113 (2)
O2i—Co1—O5	87.15 (5)	H3N—N1—H1N	106 (2)
O2—Co1—O5	92.85 (5)	O1—C1—C2	108.19 (14)
O8i—Co1—O5	89.81 (5)	O1—C1—P1	108.73 (11)
O8—Co1—O5	90.19 (5)	C2—C1—P1	107.85 (11)
O5i—Co1—O5	180.00 (7)	O1—C1—P2	109.67 (11)
O2—P1—O4	114.17 (7)	C2—C1—P2	108.63 (12)
O2—P1—O3	110.62 (8)	P1—C1—P2	113.62 (9)
O4—P1—O3	110.93 (8)	C3—C2—C1	113.39 (14)
O2—P1—C1	109.00 (8)	C3—C2—H2A	108.9
O4—P1—C1	105.91 (8)	C1—C2—H2A	108.9
O3—P1—C1	105.73 (8)	C3—C2—H2B	108.9
O5—P2—O7	114.46 (8)	C1—C2—H2B	108.9
O5—P2—O6	111.46 (8)	H2A—C2—H2B	107.7
O7—P2—O6	108.02 (7)	N1—C3—C2	108.60 (15)
O5—P2—C1	107.58 (7)	N1—C3—H3A	110.0
O7—P2—C1	108.58 (8)	C2—C3—H3A	110.0
O6—P2—C1	106.40 (8)	N1—C3—H3B	110.0
C1—O1—H1O	119.0 (17)	C2—C3—H3B	110.0
P1—O2—Co1	129.11 (7)	H3A—C3—H3B	108.4
P1—O3—H3O	115 (2)
O4—P1—O2—Co1	−170.27 (9)	O4—P1—C1—C2	61.76 (13)
O3—P1—O2—Co1	63.77 (11)	O3—P1—C1—C2	179.55 (12)
C1—P1—O2—Co1	−52.07 (12)	O2—P1—C1—P2	58.97 (11)
O8i—Co1—O2—P1	−55.98 (10)	O4—P1—C1—P2	−177.76 (9)
O8—Co1—O2—P1	124.02 (10)	O3—P1—C1—P2	−59.97 (11)
O5i—Co1—O2—P1	−146.30 (11)	O5—P2—C1—O1	−177.36 (11)
O5—Co1—O2—P1	33.70 (11)	O7—P2—C1—O1	58.25 (13)
O7—P2—O5—Co1	166.92 (9)	O6—P2—C1—O1	−57.80 (13)
O6—P2—O5—Co1	−70.11 (12)	O5—P2—C1—C2	64.58 (13)
C1—P2—O5—Co1	46.17 (13)	O7—P2—C1—C2	−59.81 (13)
O2i—Co1—O5—P2	148.83 (11)	O6—P2—C1—C2	−175.86 (11)
O2—Co1—O5—P2	−31.17 (11)	O5—P2—C1—P1	−55.46 (11)
O8i—Co1—O5—P2	56.30 (11)	O7—P2—C1—P1	−179.85 (8)
O8—Co1—O5—P2	−123.70 (11)	O6—P2—C1—P1	64.10 (11)
O2—P1—C1—O1	−178.61 (10)	O1—C1—C2—C3	−31.88 (19)
O4—P1—C1—O1	−55.34 (13)	P1—C1—C2—C3	−149.34 (13)
O3—P1—C1—O1	62.45 (12)	P2—C1—C2—C3	87.10 (16)
O2—P1—C1—C2	−61.51 (13)	C1—C2—C3—N1	−173.76 (14)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O5ii	0.85 (3)	2.05 (3)	2.845 (2)	155 (2)
O3—H3O···O7ii	0.76 (3)	1.72 (3)	2.4627 (19)	167 (3)
O6—H6O···O4iii	0.74 (3)	1.78 (3)	2.5124 (18)	175 (3)
O8—H81···O4iv	0.89 (3)	1.88 (3)	2.7277 (18)	160 (2)
O8—H82···O1v	0.77 (3)	2.25 (3)	2.8953 (19)	142 (3)
N1—H2N···O6v	0.88 (3)	2.15 (3)	2.975 (2)	156 (2)
N1—H3N···O2iv	0.91 (3)	2.30 (3)	3.096 (2)	146 (2)
N1—H3N···O5vi	0.91 (3)	2.32 (3)	3.030 (2)	134 (2)
N1—H1N···O4vii	0.87 (2)	2.33 (2)	3.071 (2)	143 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯O5i	0.85 (3)	2.05 (3)	2.845 (2)	155 (2)
O3—H3O⋯O7i	0.76 (3)	1.72 (3)	2.4627 (19)	167 (3)
O6—H6O⋯O4ii	0.74 (3)	1.78 (3)	2.5124 (18)	175 (3)
O8—H81⋯O4iii	0.89 (3)	1.88 (3)	2.7277 (18)	160 (2)
O8—H82⋯O1iv	0.77 (3)	2.25 (3)	2.8953 (19)	142 (3)
N1—H2N⋯O6iv	0.88 (3)	2.15 (3)	2.975 (2)	156 (2)
N1—H3N⋯O2iii	0.91 (3)	2.30 (3)	3.096 (2)	146 (2)
N1—H3N⋯O5v	0.91 (3)	2.32 (3)	3.030 (2)	134 (2)
N1—H1N⋯O4vi	0.87 (2)	2.33 (2)	3.071 (2)	143 (2)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .