Aquabis[1-hydroxy-2-(imidazol-3-ium-1-yl)-1,1'-ethylidenediphophonato-κO,O']zinc(II) dihydrate.

In the title complex, [Zn(C(5)H(9)NO(7)P(2))(2)(H(2)O)]·2H(2)O, the zinc atom is coordinated by two zoledronate anions [zoledronate = (2-(1-imidazole)-1-hydr-oxy-1,1'-ethyl-idenediphophonate)] and one water mol-ecule. The coordination number is 5. There is one half-mol-ecule in the asymmetric unit, the zinc atom being located on a twofold rotation axis passing through the metal centre and the coordinating water O atom. 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. Inter-molecular O-H⋯O hydrogen bonds link the mol-ecules. An N-H⋯O inter-action is also present.

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 hexa­coordinated zinc(II)–zoledronate complex, see: Freire & Vega (2009 ▶).

Experimental

Crystal data

[Zn(C5H9N2O7P2)2(H2O)]·2H2O

M = 661.58

Monoclinic,

a = 12.089 (2) Å

b = 9.858 (2) Å

c = 18.831 (4) Å

β = 95.09 (3)°

V = 2235.3 (8) Å3

Z = 4

Mo Kα radiation

μ = 1.48 mm−1

T = 293 K

0.20 × 0.18 × 0.09 mm

Data collection

Rigaku AFC6 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.75, T max = 0.87

2847 measured reflections

2208 independent reflections

1528 reflections with I > 2σ(I)

R int = 0.054

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

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.096

S = 1.00

2208 reflections

167 parameters

H-atom parameters constrained

Δρmax = 0.35 e Å−3

Δρmin = −0.87 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/S160053680904286X/bq2166sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680904286X/bq2166Isup2.hkl

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

[Zn(C5H9N2O7P2)2(H2O)]·2H2O	F(000) = 1352
Mr = 661.58	Dx = 1.966 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 42 reflections
a = 12.089 (2) Å	θ = 8–25°
b = 9.858 (2) Å	µ = 1.48 mm−1
c = 18.831 (4) Å	T = 293 K
β = 95.09 (3)°	Prism, colorless
V = 2235.3 (8) Å3	0.20 × 0.18 × 0.09 mm
Z = 4

Rigaku AFC6 diffractometer	1528 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.054
graphite	θmax = 26.0°, θmin = 2.2°
ω/2θ scans	h = −1→14
Absorption correction: ψ scan (North et al., 1968)	k = −1→12
Tmin = 0.75, Tmax = 0.87	l = −23→23
2847 measured reflections	3 standard reflections every 150 reflections
2208 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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.096	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0521P)2 + 1.3378P] where P = (Fo2 + 2Fc2)/3
2208 reflections	(Δ/σ)max = 0.001
167 parameters	Δρmax = 0.35 e Å−3
0 restraints	Δρmin = −0.87 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
Zn1	0.5000	0.50532 (5)	0.7500	0.02015 (15)
P1	0.64482 (6)	0.41327 (8)	0.61862 (4)	0.01916 (19)
P2	0.76934 (6)	0.48891 (8)	0.75923 (4)	0.01749 (19)
O1	0.71512 (19)	0.6590 (2)	0.64590 (11)	0.0237 (5)
H1	0.7154	0.7093	0.6806	0.043 (12)*
O11	0.54208 (18)	0.4259 (3)	0.65807 (12)	0.0299 (5)
O12	0.6205 (2)	0.4826 (2)	0.54319 (13)	0.0288 (5)
H12	0.6271	0.4369	0.5075	0.050 (14)*
O13	0.68721 (19)	0.2707 (2)	0.61059 (12)	0.0277 (5)
O21	0.66152 (17)	0.5108 (2)	0.79201 (11)	0.0253 (5)
O22	0.85809 (18)	0.5945 (2)	0.79009 (12)	0.0269 (5)
H22	0.8339	0.6491	0.8177	0.051 (14)*
O23	0.81904 (19)	0.3498 (2)	0.76479 (12)	0.0280 (5)
O1W	0.5000	0.7080 (4)	0.7500	0.0727 (17)
H1W	0.5565	0.7530	0.7470	0.109*
O2W	0.6191 (2)	0.3463 (3)	0.42704 (13)	0.0394 (6)
H2WA	0.5899	0.3910	0.3937	0.059*
H2WB	0.6790	0.3124	0.4196	0.059*
N1	0.8788 (2)	0.5706 (3)	0.56618 (13)	0.0218 (5)
N2	0.8895 (2)	0.7275 (3)	0.48801 (15)	0.0328 (7)
H2	0.8972	0.8060	0.4691	0.039*
C1	0.7536 (2)	0.5248 (3)	0.66243 (16)	0.0183 (6)
C2	0.8707 (2)	0.5064 (3)	0.63530 (16)	0.0216 (6)
H2A	0.9262	0.5453	0.6698	0.026*
H2B	0.8865	0.4103	0.6315	0.026*
C3	0.8930 (3)	0.7035 (3)	0.55705 (18)	0.0278 (7)
H3	0.9034	0.7680	0.5931	0.033*
C4	0.8718 (3)	0.6092 (4)	0.45095 (19)	0.0351 (8)
H4	0.8657	0.5991	0.4017	0.042*
C5	0.8649 (3)	0.5096 (4)	0.49990 (17)	0.0282 (7)
H5	0.8530	0.4178	0.4907	0.034*

	U11	U22	U33	U12	U13	U23
Zn1	0.0189 (2)	0.0212 (3)	0.0206 (3)	0.000	0.00281 (18)	0.000
P1	0.0201 (4)	0.0188 (4)	0.0187 (4)	−0.0007 (3)	0.0023 (3)	−0.0026 (3)
P2	0.0181 (4)	0.0171 (4)	0.0172 (4)	0.0010 (3)	0.0010 (3)	0.0012 (3)
O1	0.0348 (12)	0.0148 (10)	0.0211 (11)	0.0063 (9)	−0.0003 (9)	0.0005 (9)
O11	0.0207 (11)	0.0397 (14)	0.0304 (13)	−0.0072 (10)	0.0080 (9)	−0.0142 (11)
O12	0.0363 (13)	0.0275 (12)	0.0217 (11)	0.0036 (10)	−0.0033 (10)	−0.0023 (10)
O13	0.0378 (13)	0.0175 (11)	0.0282 (11)	0.0015 (10)	0.0044 (10)	−0.0035 (10)
O21	0.0190 (10)	0.0362 (13)	0.0208 (11)	0.0021 (9)	0.0029 (8)	−0.0011 (10)
O22	0.0231 (11)	0.0291 (13)	0.0284 (12)	−0.0052 (9)	0.0019 (9)	−0.0081 (11)
O23	0.0360 (13)	0.0193 (11)	0.0296 (12)	0.0064 (9)	0.0072 (10)	0.0062 (9)
O1W	0.025 (2)	0.0195 (19)	0.177 (6)	0.000	0.027 (3)	0.000
O2W	0.0535 (17)	0.0414 (15)	0.0233 (12)	0.0094 (13)	0.0041 (11)	−0.0019 (11)
N1	0.0212 (12)	0.0244 (13)	0.0203 (13)	−0.0008 (10)	0.0051 (10)	−0.0006 (12)
N2	0.0363 (16)	0.0302 (15)	0.0324 (15)	−0.0009 (12)	0.0062 (13)	0.0132 (14)
C1	0.0207 (14)	0.0144 (13)	0.0197 (14)	0.0035 (11)	0.0020 (11)	0.0013 (11)
C2	0.0193 (14)	0.0239 (16)	0.0217 (15)	−0.0002 (12)	0.0025 (12)	0.0034 (13)
C3	0.0288 (17)	0.0252 (16)	0.0304 (18)	−0.0040 (13)	0.0073 (13)	0.0004 (14)
C4	0.0333 (19)	0.049 (2)	0.0230 (17)	0.0047 (16)	0.0012 (14)	0.0041 (17)
C5	0.0291 (17)	0.0322 (18)	0.0237 (16)	−0.0001 (14)	0.0044 (13)	−0.0070 (15)

Zn1—O1W	1.999 (4)	O1W—H1W	0.8200
Zn1—O11	2.006 (2)	O2W—H2WA	0.8200
Zn1—O11i	2.006 (2)	O2W—H2WB	0.8200
Zn1—O21i	2.041 (2)	N1—C3	1.335 (4)
Zn1—O21	2.041 (2)	N1—C5	1.382 (4)
P1—O13	1.508 (2)	N1—C2	1.458 (4)
P1—O11	1.508 (2)	N2—C3	1.318 (4)
P1—O12	1.580 (2)	N2—C4	1.366 (5)
P1—C1	1.851 (3)	N2—H2	0.8600
P2—O23	1.497 (2)	C1—C2	1.558 (4)
P2—O21	1.506 (2)	C2—H2A	0.9700
P2—O22	1.569 (2)	C2—H2B	0.9700
P2—C1	1.850 (3)	C3—H3	0.9300
O1—C1	1.427 (3)	C4—C5	1.355 (5)
O1—H1	0.8200	C4—H4	0.9300
O12—H12	0.8200	C5—H5	0.9300
O22—H22	0.8200
O1W—Zn1—O11	112.97 (8)	H2WA—O2W—H2WB	114.6
O1W—Zn1—O11i	112.97 (7)	C3—N1—C5	108.5 (3)
O11—Zn1—O11i	134.06 (15)	C3—N1—C2	124.1 (3)
O1W—Zn1—O21i	88.48 (7)	C5—N1—C2	127.2 (3)
O11—Zn1—O21i	89.03 (9)	C3—N2—C4	109.9 (3)
O11i—Zn1—O21i	92.16 (9)	C3—N2—H2	125.0
O1W—Zn1—O21	88.48 (7)	C4—N2—H2	125.0
O11—Zn1—O21	92.16 (9)	O1—C1—C2	108.9 (2)
O11i—Zn1—O21	89.03 (9)	O1—C1—P2	113.3 (2)
O21i—Zn1—O21	176.96 (14)	C2—C1—P2	106.45 (19)
O13—P1—O11	115.37 (14)	O1—C1—P1	104.41 (18)
O13—P1—O12	110.54 (13)	C2—C1—P1	114.5 (2)
O11—P1—O12	108.12 (14)	P2—C1—P1	109.42 (15)
O13—P1—C1	111.36 (13)	N1—C2—C1	112.1 (2)
O11—P1—C1	108.35 (13)	N1—C2—H2A	109.2
O12—P1—C1	102.23 (13)	C1—C2—H2A	109.2
O23—P2—O21	117.33 (14)	N1—C2—H2B	109.2
O23—P2—O22	108.95 (14)	C1—C2—H2B	109.2
O21—P2—O22	109.95 (13)	H2A—C2—H2B	107.9
O23—P2—C1	104.47 (13)	N2—C3—N1	108.1 (3)
O21—P2—C1	111.03 (13)	N2—C3—H3	126.0
O22—P2—C1	104.20 (13)	N1—C3—H3	126.0
C1—O1—H1	114.1	C5—C4—N2	106.7 (3)
P1—O11—Zn1	137.76 (14)	C5—C4—H4	126.6
P1—O12—H12	118.4	N2—C4—H4	126.6
P2—O21—Zn1	132.07 (13)	C4—C5—N1	106.8 (3)
P2—O22—H22	113.5	C4—C5—H5	126.6
Zn1—O1W—H1W	122.7	N1—C5—H5	126.6
O13—P1—O11—Zn1	114.0 (2)	O13—P1—C1—O1	162.06 (18)
O12—P1—O11—Zn1	−121.6 (2)	O11—P1—C1—O1	−70.0 (2)
C1—P1—O11—Zn1	−11.6 (3)	O12—P1—C1—O1	44.0 (2)
O1W—Zn1—O11—P1	70.5 (2)	O13—P1—C1—C2	43.0 (2)
O11i—Zn1—O11—P1	−109.5 (2)	O11—P1—C1—C2	170.9 (2)
O21i—Zn1—O11—P1	158.5 (2)	O12—P1—C1—C2	−75.0 (2)
O21—Zn1—O11—P1	−18.7 (2)	O13—P1—C1—P2	−76.38 (17)
O23—P2—O21—Zn1	−95.2 (2)	O11—P1—C1—P2	51.53 (18)
O22—P2—O21—Zn1	139.62 (18)	O12—P1—C1—P2	165.57 (14)
C1—P2—O21—Zn1	24.8 (2)	C3—N1—C2—C1	78.5 (4)
O1W—Zn1—O21—P2	−102.54 (19)	C5—N1—C2—C1	−96.1 (3)
O11—Zn1—O21—P2	10.4 (2)	O1—C1—C2—N1	−39.8 (3)
O11i—Zn1—O21—P2	144.5 (2)	P2—C1—C2—N1	−162.3 (2)
O23—P2—C1—O1	−175.2 (2)	P1—C1—C2—N1	76.6 (3)
O21—P2—C1—O1	57.4 (2)	C4—N2—C3—N1	0.6 (4)
O22—P2—C1—O1	−60.9 (2)	C5—N1—C3—N2	−0.6 (4)
O23—P2—C1—C2	−55.5 (2)	C2—N1—C3—N2	−176.1 (3)
O21—P2—C1—C2	177.09 (19)	C3—N2—C4—C5	−0.3 (4)
O22—P2—C1—C2	58.8 (2)	N2—C4—C5—N1	0.0 (4)
O23—P2—C1—P1	68.72 (17)	C3—N1—C5—C4	0.4 (4)
O21—P2—C1—P1	−58.67 (18)	C2—N1—C5—C4	175.7 (3)
O22—P2—C1—P1	−176.99 (13)

D—H···A	D—H	H···A	D···A	D—H···A
O12—H12···O2W	0.82	1.75	2.566 (3)	171
O22—H22···O13ii	0.82	1.84	2.645 (3)	167
O2W—H2WA···O21iii	0.82	2.38	2.990 (3)	132
O2W—H2WB···O13iv	0.82	1.94	2.758 (4)	173
N2—H2···O12v	0.86	2.11	2.917 (4)	157
O1W—H1W···O23ii	0.82	1.81	2.632 (3)	177
O1—H1···O23ii	0.82	1.80	2.581 (3)	160

Zn1—O1W	1.999 (4)
Zn1—O11	2.006 (2)
Zn1—O21	2.041 (2)

O1W—Zn1—O11	112.97 (8)
O11—Zn1—O11i	134.06 (15)
O11—Zn1—O21i	89.03 (9)
O1W—Zn1—O21	88.48 (7)
O11—Zn1—O21	92.16 (9)
O21i—Zn1—O21	176.96 (14)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O12—H12⋯O2W	0.82	1.75	2.566 (3)	171
O22—H22⋯O13ii	0.82	1.84	2.645 (3)	167
O2W—H2WA⋯O21iii	0.82	2.38	2.990 (3)	132
O2W—H2WB⋯O13iv	0.82	1.94	2.758 (4)	173
N2—H2⋯O12v	0.86	2.11	2.917 (4)	157
O1W—H1W⋯O23ii	0.82	1.81	2.632 (3)	177
O1—H1⋯O23ii	0.82	1.80	2.581 (3)	160

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