Aquabis[1-hydroxy-2-(imidazol-3-ium-1-yl)-1,1′-ethylidenediphophonato-κ2O,O′]zinc(II) dihydrate

Freire, E.; Vega, D.R.

doi:10.1107/S160053680904286X

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Pages m1430-m1431

https://doi.org/10.1107/S160053680904286X

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Aquabis[1-hydroxy-2-(imidazol-3-ium-1-yl)-1,1′-ethylidenediphophonato-κ²O,O′]zinc(II) dihydrate

Eleonora Freire ^a ^*‡ and Daniel R. Vega ^a

^aGerencia de Investigación y Aplicaciones, Centro Atómico Constituyentes, Comisión Nacional de Energía Atómica and, Escuela de Ciencia y Tecnología, Universidad Nacional General San Martín, Buenos Aires, Argentina
^*Correspondence e-mail: freire@tandar.cnea.gov.ar

(Received 5 October 2009; accepted 19 October 2009; online 23 October 2009)

In the title complex, [Zn(C₅H₉NO₇P₂)₂(H₂O)]·2H₂O, the zinc atom is coordinated by two zoledronate anions [zoledronate = (2-(1-imidazole)-1-hydroxy-1,1′-ethylidenediphophonate)] and one water molecule. The coordination number is 5. There is one half-molecule 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 nitrogen in the ring has a positive charge and the two phosphonates groups each have a single negative charge. Intermolecular O—H⋯O hydrogen bonds link the molecules. An N—H⋯O interaction 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_r = 661.58
Monoclinic, C 2/c
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[F² > 2σ(F²)] = 0.032
wR(F²) = 0.096
S = 1.00
2208 reflections
167 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.87 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

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) $[-x+1, y, -z+{\script{3\over 2}}]$ .

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⋯O13^iv	0.82	1.94	2.758 (4)	173
N2—H2⋯O12^v	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) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x, -y+1, z-{\script{1\over 2}}]$ ; (iv) $[-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (v) $[-x+{\script{3\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988 $[Molecular Structure Corporation (1988). MSC/AFC Diffractometer Control Software. MSC, The Woodlands, Texas, USA.]$ ); 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S160053680904286X/bq2166sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053680904286X/bq2166Isup2.hkl

checkCIF report

Comment top

The following work is part of a project directed to the preparation and characterization of coordination complexes obtained by the interaction among metals and organic molecules of relevant pharmacological interest like bisphosphonates. An informative introduction on bisphosphonates has been made in the previous paper (Freire & Vega, 2009). Although few metal derivatives of Zoledronic acid have been reported in CSD (Allen, 2002), an isostructural compound of copper has been synthesized (Cao et al., 2008).

So, we present herein the crystal structure of a Zinc-Zoledronate complex: monozinc dizoledronate trihydrate, (I), Zn.(H₂O).2(P₂O₇N₂C₅H₉).2H₂O. In (I), as in the similar hexacoordinated compound (Freire & Vega, 2009), the zoledronate anion exists as a zwitterion with an overall charge of -1; the protonated nitrogen in the ring has a positive charge and the two phosphonates groups each have a single negative charge.

The coordination number of Zn is 5 (Fig. 1) and the resulting coordination polyhedron is a trigonal bipiramid defined by O21, O21A, O11, O11A and O1W. Atoms O11A and O21A are generated by the symmetry operation (1 - x, y, 3/2 - z). The equatorial plane is defined by O11, O11A and O1W, the apexes are defined by and O21 and O21A. The apical Zn—O distance is 2.041 (2) Å while in the equatorial plane the mean value for the Zn—O distance is 2.004 (4) Å. The coordination angles in the equatorial plane are a little turned aside from the expected 120 ° theoretically due to the "bite" of the ligand: O11—Zn—O11A 134.08 (15)°, O11—Zn—O1W and O11A—Zn—O1W are 112.96 (8) °. The angle between the line defined by O21 and O21A with the normal to the equatorial plane (O11, O11A, O1W and Zn1) is 2.3 °.

Considering the bisphosphonates groups, there are two distinct types of P—O bonds, as shown by the mean value in the following bond distances and angles: P—OH 1,576 (8), P - O 1.505 (5) Å, O—P—OH 109.4° (11), O—P—O 116.4° (14). The staggered conformation of PO3 groups in compound (II) is more prominent than in the hexacoordinated complex (Freire & Vega, 2009), the non bonded torsion angle O12—P1···P2 O22 is -16.1°. In (I), the imidazol ring is planar, maximum deviation from the L. S. mean plane is 0.0026 Å for C3, and it is not coplanar with C2, between the plane of the ring and the bond N1—C2 is 3.4 ° and C2 is 0.0837 Å far from the ring. The torsion angle C1—C2—N1—C3 is of -78.62 ° and it is possible to describe it like - Syn-Clinal (-sc).

Five hydrogen bonds, involving, H22, H1W, H1, H2WA and H2WB, provide intermolecular cohesion, defining a two-dimensional arrangement, while the three-dimensional net completes with two more hydrogen bonds, involving H2 from the aromatic ring and H12 from the bisphosphonate group (Fig. 2 and Table 2).

Related literature top

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 et al. (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).

Experimental top

Zoledronic Acid was obtained from Gador S. A. laboratory. Compound (II) was obtained by direct mix of a water solution of Zoledronic Acid and a water solution of ZnCl₂. Colorless prismatic crystals were grown after a few days.

Structure description top

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 et al. (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).

Computing details top

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); cell refinement: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); data reduction: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); 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 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. : Molecular view of (I), showing the labeling scheme used. Hydrogen bonding is shown in dashed lines.
	Fig. 2. : Full packing diagram of (I).

Aquabis[1-hydroxy-2-(imidazol-3-ium-1-yl)-1,1'-ethylidenediphophonato- κ²O,O']zinc(II) dihydrate top

Crystal data top

[Zn(C₅H₉N₂O₇P₂)₂(H₂O)]·2H₂O	F(000) = 1352
M_r = 661.58	D_x = 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

Data collection top

Rigaku AFC6 diffractometer	1528 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.054
Graphite monochromator	θ_max = 26.0°, θ_min = 2.2°
ω/2θ scans	h = −1→14
Absorption correction: ψ scan (North et al., 1968)	k = −1→12
T_min = 0.75, T_max = 0.87	l = −23→23
2847 measured reflections	3 standard reflections every 150 reflections
2208 independent reflections	intensity decay: <3%

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) = 0.096	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0521P)² + 1.3378P] where P = (F_o² + 2F_c²)/3
2208 reflections	(Δ/σ)_max = 0.001
167 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.87 e Å⁻³

Crystal data top

[Zn(C₅H₉N₂O₇P₂)₂(H₂O)]·2H₂O	V = 2235.3 (8) Å³
M_r = 661.58	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 12.089 (2) Å	µ = 1.48 mm⁻¹
b = 9.858 (2) Å	T = 293 K
c = 18.831 (4) Å	0.20 × 0.18 × 0.09 mm
β = 95.09 (3)°

Data collection top

Rigaku AFC6 diffractometer	1528 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.054
T_min = 0.75, T_max = 0.87	3 standard reflections every 150 reflections
2847 measured reflections	intensity decay: <3%
2208 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 1.00	Δρ_max = 0.35 e Å⁻³
2208 reflections	Δρ_min = −0.87 e Å⁻³
167 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

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···O13^iv	0.82	1.94	2.758 (4)	173
N2—H2···O12^v	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) −x+3/2, y+1/2, −z+3/2; (iii) x, −y+1, z−1/2; (iv) −x+3/2, −y+1/2, −z+1; (v) −x+3/2, −y+3/2, −z+1.

Experimental details

Crystal data
Chemical formula	[Zn(C₅H₉N₂O₇P₂)₂(H₂O)]·2H₂O
M_r	661.58
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	12.089 (2), 9.858 (2), 18.831 (4)
β (°)	95.09 (3)
V (Å³)	2235.3 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.48
Crystal size (mm)	0.20 × 0.18 × 0.09

Data collection
Diffractometer	Rigaku AFC6 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.75, 0.87
No. of measured, independent and observed [I > 2σ(I)] reflections	2847, 2208, 1528
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.096, 1.00
No. of reflections	2208
No. of parameters	167
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.87

Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Selected geometric parameters (Å, º) top

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

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

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O12—H12···O2W	0.82	1.75	2.566 (3)	170.8
O22—H22···O13ⁱⁱ	0.82	1.84	2.645 (3)	166.7
O2W—H2WA···O21ⁱⁱⁱ	0.82	2.38	2.990 (3)	132.2
O2W—H2WB···O13^iv	0.82	1.94	2.758 (4)	172.6
N2—H2···O12^v	0.86	2.11	2.917 (4)	157.2
O1W—H1W···O23ⁱⁱ	0.82	1.81	2.632 (3)	176.8
O1—H1···O23ⁱⁱ	0.82	1.80	2.581 (3)	159.7

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

Footnotes

‡Member of Consejo Nacional de Ciencia y Técnica, Conicet.

Acknowledgements

We acknowledge PICT 25409, the Spanish Research Council (CSIC) for providing us with a free-of-charge licence to use the CSD system (Allen, 2002 ) and Professor Judith Howard for the donation of a Rigaku AFC6S four-circle diffractometer. EF is a member of the research staff of Conicet. The authors are grateful to Laboratorios Gador for providing the zoledronic acid.

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