Diaqua-bis[1-hydroxy-2-(imidazol-3-ium-1-yl)-1,1'-ethyl-idenediphophonato-κO,O']zinc(II).

In the title complex, [Zn(C(5)H(9)NO(7)P(2))(2)(H(2)O)(2)], the zinc atom is coordinated by two bidentate zoledronate [zoledronate = (2-(1-imidazole)-1-hydr-oxy-1,1'-ethyl-idenediphophonate)] ligands and two water mol-ecules. The coordination number is 6. There is one half-mol-ecule in the asymmetric unit with the zinc atom located on a crystallographic inversion centre. The anion exists as a zwitterion with an overall charge of -1; the protonated nitro-gen in the ring has a positive charge and the two phospho-nates groups each have a single negative charge. There are two intra-molecular O-H⋯O hydrogen bonds. The mol-ecules are linked into a chain by inter-molecular O-H⋯O hydrogen bonds. Adjacent chains are further linked by O-H⋯O hydrogen bonds involving the aqua ligands. An N-H⋯O inter-action is also observed.

Related literature

For general background to bis­phospho­nates, see: Fleisch et al. (1968 ▶); Green et al. (1994 ▶); Fleisch (2000 ▶); Ross et al. (2004 ▶); Smith (2005 ▶); Ralston et al. (1989 ▶); Reid et al. (2005 ▶); Rauch & Glorieux (2005 ▶); Chesnut et al. (2004 ▶). For structures of transition metal (Ni, Co and Cu) complexes with the zoledronate anion, see: Cao et al. (2007, 2008). For metal complexes of other bis­phospho­nates (Etidronate and Pamidronate), see: Fernández et al. (2002 ▶); Li et al. (2008 ▶); Chen et al. (2008 ▶); Uchtman (1972 ▶). For a penta­coordinated zinc(II)–zoledronate complex, see: Freire & Vega (2009 ▶). For bond distances and angles in related structures, see: Coiro & Lamba (1989 ▶); Vega et al. (1996 ▶, 1998 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

[Zn(C5H9N2O7P2)2(H2O)2]

M = 643.57

Triclinic,

a = 7.457 (1) Å

b = 8.408 (2) Å

c = 9.843 (2) Å

α = 105.06 (3)°

β = 112.23 (3)°

γ = 97.05 (3)°

V = 534.5 (2) Å3

Z = 1

Mo Kα radiation

μ = 1.54 mm−1

T = 293 K

0.18 × 0.11 × 0.05 mm

Data collection

Rigaku AFC6 diffractometer diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.82, T max = 0.92

2426 measured reflections

1990 independent reflections

1236 reflections with I > 2σ(I)

R int = 0.050

3 standard reflections every 150 reflections intensity decay: <3%

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.152

S = 1.04

1990 reflections

160 parameters

H-atom parameters constrained

Δρmax = 0.84 e Å−3

Δρmin = −0.94 e Å−3

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988 ▶); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: MSC/AFC Diffractometer Control Software; 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: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809042858/bq2165sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809042858/bq2165Isup2.hkl

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

[Zn(C5H9N2O7P2)2(H2O)2]	Z = 1
Mr = 643.57	F(000) = 328
Triclinic, P1	Dx = 1.999 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.457 (1) Å	Cell parameters from 42 reflections
b = 8.408 (2) Å	θ = 8–18°
c = 9.843 (2) Å	µ = 1.54 mm−1
α = 105.06 (3)°	T = 293 K
β = 112.23 (3)°	Prism, colorless
γ = 97.05 (3)°	0.18 × 0.11 × 0.05 mm
V = 534.5 (2) Å3

Rigaku AFC6 Difractometer diffractometer	1236 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.050
graphite	θmax = 25.5°, θmin = 2.4°
ω/2θ scans	h = −9→9
Absorption correction: ψ scan (North et al., 1968)	k = −1→10
Tmin = 0.82, Tmax = 0.92	l = −11→11
2426 measured reflections	3 standard reflections every 150 reflections
1990 independent reflections	intensity decay: <3%

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.152	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0781P)2] where P = (Fo2 + 2Fc2)/3
1990 reflections	(Δ/σ)max < 0.001
160 parameters	Δρmax = 0.84 e Å−3
0 restraints	Δρmin = −0.94 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.

	x	y	z	Uiso*/Ueq
Zn1	0.5000	0.5000	0.5000	0.0266 (4)
P1	0.8731 (2)	0.77240 (19)	0.52403 (17)	0.0172 (4)
P2	0.8422 (2)	0.77671 (19)	0.82873 (17)	0.0186 (4)
O11	0.7109 (6)	0.6106 (5)	0.4453 (4)	0.0211 (9)
O12	0.7749 (6)	0.9268 (5)	0.5228 (5)	0.0242 (10)
H12	0.8403	1.0149	0.5264	0.036*
O13	1.0242 (6)	0.7849 (5)	0.4574 (5)	0.0217 (9)
O21	0.6875 (6)	0.6116 (5)	0.7361 (5)	0.0253 (10)
O22	0.7342 (6)	0.9253 (5)	0.8129 (5)	0.0254 (10)
H22	0.8021	1.0216	0.8691	0.038*
O23	0.9654 (7)	0.8002 (5)	0.9969 (5)	0.0249 (10)
O1	1.1578 (6)	0.9545 (5)	0.8097 (5)	0.0261 (10)
H1	1.1019	1.0326	0.8140	0.039*
N1	1.2533 (8)	0.6520 (6)	0.8864 (6)	0.0224 (11)
N2	1.3599 (9)	0.5904 (8)	1.0957 (7)	0.0372 (15)
H2	1.3678	0.5388	1.1618	0.045*
C1	1.0088 (9)	0.7937 (7)	0.7310 (6)	0.0183 (13)
C2	1.1243 (10)	0.6535 (8)	0.7302 (7)	0.0271 (15)
H2A	1.0288	0.5439	0.6719	0.032*
H2B	1.2067	0.6680	0.6759	0.032*
C3	1.2149 (10)	0.5438 (9)	0.9533 (8)	0.0315 (16)
H3	1.1052	0.4509	0.9084	0.038*
C5	1.4298 (10)	0.7711 (8)	0.9896 (8)	0.0319 (16)
H5	1.4929	0.8611	0.9722	0.038*
C4	1.4926 (12)	0.7303 (10)	1.1212 (8)	0.042 (2)
H4	1.6068	0.7885	1.2127	0.051*
O1W	0.3851 (6)	0.7142 (6)	0.4904 (6)	0.0349 (12)
H1WA	0.4645	0.8074	0.5273	0.052*
H1WB	0.2703	0.7245	0.4668	0.052*

	U11	U22	U33	U12	U13	U23
Zn1	0.0278 (7)	0.0212 (6)	0.0247 (6)	0.0057 (5)	0.0079 (5)	0.0030 (5)
P1	0.0177 (8)	0.0145 (8)	0.0173 (8)	0.0054 (6)	0.0056 (7)	0.0043 (6)
P2	0.0194 (8)	0.0157 (8)	0.0150 (8)	0.0029 (7)	0.0048 (7)	0.0008 (6)
O11	0.020 (2)	0.024 (2)	0.014 (2)	0.0010 (19)	0.0059 (18)	0.0015 (17)
O12	0.026 (2)	0.020 (2)	0.035 (3)	0.0118 (19)	0.016 (2)	0.015 (2)
O13	0.022 (2)	0.019 (2)	0.025 (2)	0.0082 (18)	0.0116 (19)	0.0051 (18)
O21	0.029 (3)	0.021 (2)	0.017 (2)	0.000 (2)	0.006 (2)	0.0027 (18)
O22	0.028 (2)	0.020 (2)	0.024 (2)	0.0100 (19)	0.009 (2)	0.0019 (19)
O23	0.035 (3)	0.021 (2)	0.015 (2)	0.005 (2)	0.007 (2)	0.0037 (18)
O1	0.021 (2)	0.018 (2)	0.030 (2)	0.0008 (19)	0.007 (2)	0.0003 (19)
N1	0.023 (3)	0.022 (3)	0.021 (3)	0.010 (2)	0.006 (2)	0.008 (2)
N2	0.052 (4)	0.039 (4)	0.032 (3)	0.018 (3)	0.020 (3)	0.025 (3)
C1	0.023 (3)	0.017 (3)	0.017 (3)	0.010 (3)	0.007 (3)	0.007 (2)
C2	0.029 (4)	0.023 (3)	0.019 (3)	0.010 (3)	0.002 (3)	0.004 (3)
C3	0.027 (4)	0.031 (4)	0.044 (4)	0.013 (3)	0.016 (3)	0.022 (3)
C5	0.027 (4)	0.026 (4)	0.037 (4)	0.008 (3)	0.007 (3)	0.012 (3)
C4	0.048 (5)	0.042 (5)	0.025 (4)	0.020 (4)	0.000 (3)	0.013 (3)
O1W	0.018 (2)	0.022 (2)	0.059 (3)	0.007 (2)	0.013 (2)	0.011 (2)

Zn1—O11i	2.042 (4)	O1—H1	0.8201
Zn1—O11	2.042 (4)	N1—C3	1.317 (8)
Zn1—O21	2.079 (4)	N1—C5	1.379 (8)
Zn1—O21i	2.079 (4)	N1—C2	1.478 (7)
Zn1—O1Wi	2.096 (4)	N2—C3	1.323 (9)
Zn1—O1W	2.096 (4)	N2—C4	1.341 (9)
P1—O11	1.501 (4)	N2—H2	0.8600
P1—O13	1.509 (4)	C1—C2	1.543 (8)
P1—O12	1.567 (4)	C2—H2A	0.9700
P1—C1	1.847 (6)	C2—H2B	0.9700
P2—O21	1.498 (4)	C3—H3	0.9300
P2—O23	1.502 (4)	C5—C4	1.352 (9)
P2—O22	1.578 (4)	C5—H5	0.9300
P2—C1	1.850 (6)	C4—H4	0.9300
O12—H12	0.8200	O1W—H1WA	0.8200
O22—H22	0.8200	O1W—H1WB	0.8200
O1—C1	1.448 (7)
O11i—Zn1—O11	180.0	C1—O1—H1	109.4
O11i—Zn1—O21	89.35 (16)	C3—N1—C5	108.8 (6)
O11—Zn1—O21	90.65 (16)	C3—N1—C2	126.2 (6)
O11i—Zn1—O21i	90.65 (16)	C5—N1—C2	125.0 (5)
O11—Zn1—O21i	89.35 (16)	C3—N2—C4	109.7 (6)
O21—Zn1—O21i	180.0	C3—N2—H2	125.1
O11i—Zn1—O1Wi	86.18 (18)	C4—N2—H2	125.1
O11—Zn1—O1Wi	93.82 (18)	O1—C1—C2	106.5 (5)
O21—Zn1—O1Wi	87.37 (18)	O1—C1—P1	108.5 (4)
O21i—Zn1—O1Wi	92.63 (18)	C2—C1—P1	105.0 (4)
O11i—Zn1—O1W	93.82 (18)	O1—C1—P2	110.8 (4)
O11—Zn1—O1W	86.18 (18)	C2—C1—P2	112.6 (4)
O21—Zn1—O1W	92.63 (18)	P1—C1—P2	113.1 (3)
O21i—Zn1—O1W	87.37 (18)	N1—C2—C1	114.5 (5)
O1Wi—Zn1—O1W	180.000 (1)	N1—C2—H2A	108.6
O11—P1—O13	115.5 (2)	C1—C2—H2A	108.6
O11—P1—O12	108.9 (2)	N1—C2—H2B	108.6
O13—P1—O12	109.9 (2)	C1—C2—H2B	108.6
O11—P1—C1	108.2 (3)	H2A—C2—H2B	107.6
O13—P1—C1	107.9 (3)	N1—C3—N2	108.0 (6)
O12—P1—C1	106.0 (3)	N1—C3—H3	126.0
O21—P2—O23	115.7 (2)	N2—C3—H3	126.0
O21—P2—O22	108.0 (3)	C4—C5—N1	106.1 (6)
O23—P2—O22	110.9 (2)	C4—C5—H5	127.0
O21—P2—C1	107.4 (3)	N1—C5—H5	127.0
O23—P2—C1	109.4 (3)	N2—C4—C5	107.4 (6)
O22—P2—C1	104.9 (3)	N2—C4—H4	126.3
P1—O11—Zn1	134.2 (2)	C5—C4—H4	126.3
P1—O12—H12	117.6	Zn1—O1W—H1WA	118.1
P2—O21—Zn1	132.6 (3)	Zn1—O1W—H1WB	130.4
P2—O22—H22	116.2	H1WA—O1W—H1WB	110.8
O13—P1—O11—Zn1	167.0 (3)	O12—P1—C1—P2	63.4 (3)
O12—P1—O11—Zn1	−68.8 (4)	O21—P2—C1—O1	177.3 (4)
C1—P1—O11—Zn1	46.0 (4)	O23—P2—C1—O1	−56.4 (4)
O21—Zn1—O11—P1	−30.0 (4)	O22—P2—C1—O1	62.6 (4)
O21i—Zn1—O11—P1	150.0 (4)	O21—P2—C1—C2	−63.6 (5)
O1Wi—Zn1—O11—P1	−117.4 (4)	O23—P2—C1—C2	62.7 (5)
O1W—Zn1—O11—P1	62.6 (4)	O22—P2—C1—C2	−178.3 (4)
O23—P2—O21—Zn1	−172.3 (3)	O21—P2—C1—P1	55.2 (4)
O22—P2—O21—Zn1	62.8 (4)	O23—P2—C1—P1	−178.5 (3)
C1—P2—O21—Zn1	−49.8 (4)	O22—P2—C1—P1	−59.5 (3)
O11i—Zn1—O21—P2	−147.8 (4)	C3—N1—C2—C1	104.1 (7)
O11—Zn1—O21—P2	32.2 (4)	C5—N1—C2—C1	−72.1 (8)
O1Wi—Zn1—O21—P2	126.0 (4)	O1—C1—C2—N1	62.2 (6)
O1W—Zn1—O21—P2	−54.0 (4)	P1—C1—C2—N1	177.1 (4)
O11—P1—C1—O1	−176.6 (3)	P2—C1—C2—N1	−59.4 (6)
O13—P1—C1—O1	57.8 (4)	C5—N1—C3—N2	0.4 (8)
O12—P1—C1—O1	−59.9 (4)	C2—N1—C3—N2	−176.3 (6)
O11—P1—C1—C2	69.9 (4)	C4—N2—C3—N1	0.3 (8)
O13—P1—C1—C2	−55.8 (4)	C3—N1—C5—C4	−0.9 (8)
O12—P1—C1—C2	−173.4 (4)	C2—N1—C5—C4	175.8 (6)
O11—P1—C1—P2	−53.3 (4)	C3—N2—C4—C5	−0.9 (9)
O13—P1—C1—P2	−178.9 (3)	N1—C5—C4—N2	1.1 (8)

D—H···A	D—H	H···A	D···A	D—H···A
O22—H22···O23ii	0.82	1.90	2.676 (6)	159
O12—H12···O13iii	0.82	1.79	2.607 (6)	176
O1—H1···O23ii	0.82	2.28	2.910 (6)	134
O1W—H1WA···O12	0.82	2.43	3.078 (6)	137
O1W—H1WB···O13iv	0.82	1.94	2.745 (6)	167
N2—H2···O21v	0.86	1.90	2.740 (7)	164

Zn1—O11	2.042 (4)
Zn1—O21	2.079 (4)
Zn1—O1W	2.096 (4)

O11—Zn1—O21	90.65 (16)
O11—Zn1—O1W	86.18 (18)
O21—Zn1—O1W	92.63 (18)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O22—H22⋯O23i	0.82	1.90	2.676 (6)	159
O12—H12⋯O13ii	0.82	1.79	2.607 (6)	176
O1—H1⋯O23i	0.82	2.28	2.910 (6)	134
O1W—H1WA⋯O12	0.82	2.43	3.078 (6)	137
O1W—H1WB⋯O13iii	0.82	1.94	2.745 (6)	167
N2—H2⋯O21iv	0.86	1.90	2.740 (7)	164

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