Decaaqua­dioxidobis[μ3-N-(phospho­n­atometh­yl)imino­diacetato]­dizinc(II)­divanadium(IV) dihydrate

Cunha-Silva, L.; Shi, F.-N.; Klinowski, J.; Trindade, T.; Rocha, J.; Almeida Paz, F.A.

doi:10.1107/S1600536807062253

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Pages m39-m40

https://doi.org/10.1107/S1600536807062253

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Decaaquadioxidobis[μ₃-N-(phosphonatomethyl)iminodiacetato]dizinc(II)divanadium(IV) dihydrate

Luís Cunha-Silva,^a Fa-Nian Shi,^a Jacek Klinowski,^b Tito Trindade,^a João Rocha ^a and Filipe A. Almeida Paz ^a ^*

^aDepartment of Chemistry, University of Aveiro, CICECO, 3810-193 Aveiro, Portugal, and ^bDepartment of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, England
^*Correspondence e-mail: filipe.paz@ua.pt

(Received 20 November 2007; accepted 22 November 2007; online 6 December 2007)

The title compound, [Zn₂V₂(C₅H₆NO₇P)₂O₂(H₂O)₁₀]·2H₂O, contains a [V₂O₂(pmida)₂]⁴⁻ dimeric anionic unit [where H₄pmida is N-(phosphonomethyl)iminodiacetic acid] lying on a centre of symmetry which is exo-coordinated via the two deprotonated phosphonate groups to two Zn²⁺ cations, with the coordination environment of Zn completed by five water molecules. The crystal packing is mediated by an extensive network of strong and highly directional O—H⋯O hydrogen bonds involving the water molecules (coordinated and uncoordinated) and the functional groups of pmida⁴⁻, leading to a three-dimensional supramolecular network.

Related literature

For related literature, see: Cunha-Silva, Mafra et al. (2007 ); Cunha-Silva, Shi et al. (2007 ); Shi et al. (2007 ); Mafra et al. (2006 ); Shi, Paz, Girginova, Amaral et al. (2006 ); Shi, Paz, Girginova, Rocha et al. (2006 ); Shi, Almeida Paz, Trindade & Rocha (2006 ); Paz, Rocha, Klinowski et al. (2005 ); Almeida Paz, Shi, Mafra et al. (2005 ); Almeida Paz, Shi, Trindade et al. (2005 ); Shi et al. (2005 ); Paz et al. (2004 ).

Experimental

Crystal data

[Zn₂V₂(C₅H₆NO₇P)₂O₂(H₂O)₁₀]·2H₂O
M_r = 926.97
Monoclinic, P 2₁ /c
a = 10.0161 (5) Å
b = 14.8811 (7) Å
c = 10.8298 (5) Å
β = 111.147 (2)°
V = 1505.48 (12) Å³
Z = 2
Mo Kα radiation
μ = 2.40 mm⁻¹
T = 293 (2) K
0.22 × 0.14 × 0.10 mm

Data collection

Bruker Kappa APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1998 ) T_min = 0.621, T_max = 0.796
95509 measured reflections
4040 independent reflections
3765 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.077
S = 1.04
4040 reflections
238 parameters
15 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.06 e Å⁻³
Δρ_min = −0.87 e Å⁻³

Table 1
Selected bond lengths (Å)

Zn1—O7	2.0133 (14)
Zn1—O3W	2.0609 (16)
Zn1—O1W	2.0860 (17)
Zn1—O4W	2.0974 (16)
Zn1—O5W	2.1440 (18)
Zn1—O2W	2.1660 (15)
V1—O8	1.6086 (16)
V1—O6ⁱ	1.9890 (14)
V1—O5	1.9932 (14)
V1—O2	2.0312 (15)
V1—O4	2.0321 (14)
V1—N1	2.3590 (16)
Symmetry code: (i) -x+2, -y+1, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W⋯O1ⁱⁱ	0.90 (2)	1.88 (2)	2.770 (2)	169 (3)
O1W—H2W⋯O2Wⁱⁱ	0.90 (2)	1.95 (2)	2.828 (2)	164 (3)
O2W—H3W⋯O3ⁱⁱⁱ	0.88 (2)	1.85 (2)	2.725 (2)	172 (3)
O2W—H4W⋯O5ⁱⁱ	0.87 (2)	1.93 (2)	2.795 (2)	173 (3)
O3W—H6W⋯O2ⁱⁱ	0.88 (2)	1.87 (2)	2.733 (2)	171 (3)
O3W—H5W⋯O4^iv	0.89 (2)	1.86 (2)	2.726 (2)	164 (4)
O4W—H7W⋯O3^iv	0.86 (2)	1.98 (2)	2.837 (2)	174 (3)
O4W—H8W⋯O1^v	0.88 (2)	1.94 (2)	2.799 (2)	167 (3)
O5W—H9W⋯O6	0.90 (2)	1.98 (3)	2.805 (2)	150 (4)
O5W—H10W⋯O6W	0.86 (2)	1.84 (3)	2.656 (6)	159 (4)
Symmetry codes: (ii) -x+1, -y+1, -z+1; (iii) $[x-1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iv) x-1, y, z-1; (v) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2006 ); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 ); program(s) used to solve structure: SHELXTL (Bruker 2001 ); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807062253/bg2149sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807062253/bg2149Isup2.hkl

checkCIF report

Comment top

Research on highly crystalline organic–inorganic hybrids, in particular those belonging to the family of coordination polymers, has received a considerable attention over the last two decades. Such occurs as a direct consequence of the fascinating structural architectures achieved by assembling organic ligands and metal centres which, in many cases, can be allied with interesting potential applications (e.g. gas storage, separation, catalysis, guest exchange, magnetic or optical sensors). Following our ongoing research toward the hydrothermal synthesis and structural characterization of this type of materials, we recently focused our attention on the use of multifunctional ligands such as N-(phosphonomethyl)iminodiacetic acid (H₄pmida) (Cunha-Silva, Shi et al., 2007; Mafra et al., 2006; Shi, Paz, Girginova, Amaral et al., 2006; Shi, Paz, Girginova, Rocha et al., 2006; Shi, Almeida Paz, Trindade & Rocha, 2006; Paz, Rocha, Klinowski et al., 2005; Almeida Paz, Shi, Mafra et al., 2005; Almeida Paz, Shi, Trindade et al., 2005; Shi et al., 2005; Paz et al., 2004), 1-hydroxyethylidene-1,1-diphosphonic acid (H₅hedp) (Shi et al., 2007), and nitrilotris(methylenephosphonic acid) (H₆nmp) (Cunha-Silva, Mafra et al., 2007), we report here the structural details of the title compound, [Zn₂V₂O₂(pmida)₂(H₂O)₁₀].2H₂O (I) [where pmida^4– stands for C₅H₆NO₇P^4-].

The structure of (I) contains two crystallographically unique metal centres, Zn1 and V1, both exhibiting octahedral coordination geometries, {ZnO₆} and {VO₅N} (see table of selected geometric parameters and Fig. 1). Zn1 is coordinated by five O atoms of five crystalographically independent water molecules and one O atom from the µ₃-bridging phosphonate group of pmida^4- (Fig. 1), with the overall coordination geometry resembling a slightly distorted octahedron [Zn—O bond lengths found in the 2.0133 (14)–2.1660 (15) Å range; cis and trans O—Zn—O octahedral angles ranging from 87.09 (8) to 91.64 (6)° and from 177.27 (7) to 178.11 (7)°, respectively; see table of selected geometric parameters].

The two symmetry-related Zn²⁺ cations of the neutral tetranuclear [Zn₂V₂O₂(pmida)₂(H₂O)₁₀] molecule depicted in Fig. 1 are connected through the phosphonate groups belonging to the central centrosymmetric dimeric anionic [V₂O₂(pmida)₂]^4- unit, with intermetallic Zn1···Zn1ⁱ, Zn1···V1 and V1···V1ⁱ distances of 10.0170 (5), 3.2447 (5) and 3.8773 (5) Å, respectively [symmetry code: (i) 2 - x, 1 - y, 1 - z]. It is of considerable importance to emphasize that the geometrical aspects of this dimeric anionic unit are typical and in good agreement with those described in detail in our previous publications (Shi et al., 2007; Shi, Paz, Girginova, Amaral et al., 2006; Shi, Paz, Girginova, Rocha et al., 2006; Shi, Almeida Paz, Trindade & Rocha, 2006; Paz, Rocha, Klinowski et al., 2005; Almeida Paz, Shi, Mafra et al., 2005; Almeida Paz, Shi, Trindade et al., 2005; Shi et al., 2005; Paz et al., 2004). V1 is connected to one oxo group and to two pmida^4- ligands, with the geometry of the first coordination sphere resembling a highly distorted octahedron, which is composed by one short V—O bond [1.6088 (16) Å], four intermediate V—O bonds [1.9890 (12)–2.0321 (14) Å] and a long V—N bond [2.3590 (16) Å]; the cis and trans internal octahedral angles range from 86.67 (6) to 103.84 (8)°, and from 154.45 (6) to 169.79 (8)°, respectively. Noteworthy is the structural evidence of the notable trans effect of the oxo group over the long V—N distance (see Table of selected geometric parameters).

Individual [Zn₂V₂O₂(pmida)₂(H₂O)₁₀] molecular units close pack with the water molecules of crystallization in a typical brick-wall-like fashion in the bc plane of the unit cell (Fig. 2), mediated by an extensive network of strong and highly directional O—H···O hydrogen bonding interactions (see Table summarizing the geometrical aspects of the hydrogen bonds).

Related literature top

For related literature, see: Cunha-Silva, Mafra et al. (2007); Cunha-Silva, Shi et al. (2007); Shi et al. (2007); Mafra et al. (2006); Shi, Paz, Girginova, Amaral et al. (2006); Shi, Paz, Girginova, Rocha et al. (2006); Shi, Almeida Paz, Trindade & Rocha (2006); Paz, Rocha, Klinowski et al. (2005); Almeida Paz, Shi, Mafra et al. (2005); Almeida Paz, Shi, Trindade et al. (2005); Shi et al. (2005); Paz et al. (2004).

Experimental top

Starting materials were purchased from commercial sources and were used as received without further purification: N-(phosphonomethyl)iminodiacetic acid hydrate (H₄pmida, C₅H₁₀NO₇P, 97%, Fluka), potassium metavanadate (KVO₃, 98%, Aldrich), zinc oxide (ZnO, 98%, Panreac), imidazole (C₃H₄N₂, 99.0%, Panreac) and adipic acid (HOOC(CH₂)₄COOH, 99%, Aldrich).

A mixture containing 0.26 g of KVO₃, 0.15 g of ZnO, 0.42 g of H₄pmida, 0.13 g of imidazole and 0.27 g of adipic acid in ca 9 g of distilled water, was stirred thoroughly at ambient temperature for 30 minutes, yielding a suspension with a molar composition of ca 1:1:1:1:1:270, respectively, which was transferred to a PTFE-lined stainless steel reaction vessel (total volume ca 40 ml). The reaction vessel was placed inside a preheated oven at 473 K for one day, after which the temperature was decreased to 373 K allowing the reaction to proceed for another four days. After reacting, under autogeneous pressure and static conditions, the vessel was removed from the oven and left to cool to ambient temperature before opening. Small amounts of green and/or blue mixed powders of unknown phases were readily separated from the mother liquor by vacuum filtering. Large single crystals of the title compound were isolated by slow evaporation (in open air) of the mother liquor over the period of one week. It is of considerable importance to emphasize that similar reactions where imidazole and adipic acid were not included in the starting reactive mixture failed in the isolation of the title material.

Structure description top

For related literature, see: Cunha-Silva, Mafra et al. (2007); Cunha-Silva, Shi et al. (2007); Shi et al. (2007); Mafra et al. (2006); Shi, Paz, Girginova, Amaral et al. (2006); Shi, Paz, Girginova, Rocha et al. (2006); Shi, Almeida Paz, Trindade & Rocha (2006); Paz, Rocha, Klinowski et al. (2005); Almeida Paz, Shi, Mafra et al. (2005); Almeida Paz, Shi, Trindade et al. (2005); Shi et al. (2005); Paz et al. (2004).

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Bruker 2001); program(s) used to refine structure: SHELXTL (Bruker 2001); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXTL (Bruker 2001).

Figures top

Fig. 1. Schematic representation of the tetranuclear centrosymmetric [Zn₂V₂O₂(pmida)₂(H₂O)₁₀] molecular unit, showing the labelling scheme for all non-H atoms. Displacement ellipsoids are drawn at the 50% probability level and H atoms are represented as small spheres with arbitrary radii. The water molecule of crystallization O6W was omitted for clarity. Symmetry transformation used to generate equivalent atoms (in grey): 2 - x, 1 - y, 1 - z.

Fig. 2. Crystal packing of the title compound viewed in perspective along the (a) [001], (b) [100] and (c) [010] directions of the unit cell. Hydrogen bonds are represented as orange dashed lines.

Decaaquadioxidobis[µ₃-N– (phosphonatomethyl)iminodiacetato]dizinc(II)divanadium(IV) dihydrate top

Crystal data top

[Zn₂V₂(C₅H₆NO₇P)₂O₂(H₂O)₁₀]·2H₂O	F(000) = 940
M_r = 926.97	D_x = 2.045 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9009 reflections
a = 10.0161 (5) Å	θ = 2.6–37.6°
b = 14.8811 (7) Å	µ = 2.40 mm⁻¹
c = 10.8298 (5) Å	T = 293 K
β = 111.147 (2)°	Prism, blue
V = 1505.48 (12) Å³	0.22 × 0.14 × 0.10 mm
Z = 2

Data collection top

Bruker X8 APEXII Kappa CCD diffractometer	4040 independent reflections
Radiation source: fine-focus sealed tube	3765 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
Thin–slice ω and φ scans	θ_max = 29.1°, θ_min = 3.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	h = −13→13
T_min = 0.621, T_max = 0.796	k = −20→20
95509 measured reflections	l = −14→14

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.038P)² + 2.056P] where P = (F_o² + 2F_c²)/3
4040 reflections	(Δ/σ)_max = 0.002
238 parameters	Δρ_max = 1.06 e Å⁻³
15 restraints	Δρ_min = −0.87 e Å⁻³

Crystal data top

[Zn₂V₂(C₅H₆NO₇P)₂O₂(H₂O)₁₀]·2H₂O	V = 1505.48 (12) Å³
M_r = 926.97	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.0161 (5) Å	µ = 2.40 mm⁻¹
b = 14.8811 (7) Å	T = 293 K
c = 10.8298 (5) Å	0.22 × 0.14 × 0.10 mm
β = 111.147 (2)°

Data collection top

Bruker X8 APEXII Kappa CCD diffractometer	4040 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	3765 reflections with I > 2σ(I)
T_min = 0.621, T_max = 0.796	R_int = 0.028
95509 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	15 restraints
wR(F²) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 1.06 e Å⁻³
4040 reflections	Δρ_min = −0.87 e Å⁻³
238 parameters

Special details top

Experimental. See dedicated section in the main paper

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	0.47946 (2)	0.566124 (16)	0.26276 (2)	0.02202 (7)
V1	1.01192 (3)	0.52639 (2)	0.74230 (3)	0.01679 (8)
P1	0.81721 (5)	0.55866 (3)	0.44467 (5)	0.01775 (10)
N1	0.98913 (17)	0.66771 (11)	0.63798 (15)	0.0188 (3)
O5	0.85567 (14)	0.49988 (10)	0.57024 (13)	0.0223 (3)
O7	0.66854 (14)	0.59666 (10)	0.40459 (14)	0.0242 (3)
O4	1.16206 (16)	0.60558 (10)	0.87361 (13)	0.0252 (3)
C5	0.9481 (2)	0.65025 (13)	0.49415 (17)	0.0199 (3)
H5A	1.0323	0.6340	0.4747	0.024*
H5B	0.9072	0.7041	0.4446	0.024*
O6	0.83989 (15)	0.50552 (10)	0.33263 (14)	0.0249 (3)
O2	0.86146 (16)	0.59104 (10)	0.79428 (16)	0.0275 (3)
C4	1.1990 (2)	0.68247 (13)	0.84317 (19)	0.0229 (4)
C1	0.8075 (2)	0.66657 (14)	0.7474 (2)	0.0239 (4)
O8	1.0159 (2)	0.43890 (11)	0.83081 (18)	0.0348 (4)
C3	1.1313 (2)	0.71027 (15)	0.69835 (19)	0.0263 (4)
H3A	1.1213	0.7751	0.6922	0.032*
H3B	1.1924	0.6920	0.6509	0.032*
C2	0.8762 (2)	0.71885 (14)	0.6657 (2)	0.0266 (4)
H2A	0.8027	0.7359	0.5824	0.032*
H2B	0.9176	0.7736	0.7125	0.032*
O3	1.28796 (19)	0.73187 (12)	0.92367 (16)	0.0371 (4)
O1	0.70218 (18)	0.69941 (11)	0.76509 (19)	0.0360 (4)
O1W	0.5041 (2)	0.43314 (11)	0.32805 (19)	0.0392 (4)
H1W	0.440 (3)	0.390 (2)	0.288 (3)	0.059*
H2W	0.528 (4)	0.419 (2)	0.414 (2)	0.059*
O2W	0.36824 (16)	0.59655 (11)	0.39610 (15)	0.0266 (3)
H3W	0.348 (3)	0.6535 (14)	0.402 (3)	0.040*
H4W	0.298 (3)	0.5638 (17)	0.401 (3)	0.040*
O3W	0.28954 (18)	0.52927 (14)	0.11685 (17)	0.0409 (4)
H5W	0.238 (4)	0.560 (2)	0.045 (3)	0.061*
H6W	0.234 (4)	0.491 (2)	0.136 (3)	0.061*
O4W	0.45023 (17)	0.69926 (11)	0.19464 (16)	0.0304 (3)
H7W	0.397 (3)	0.706 (2)	0.113 (2)	0.046*
H8W	0.531 (3)	0.727 (2)	0.205 (3)	0.046*
O5W	0.58091 (19)	0.53840 (17)	0.12317 (18)	0.0446 (5)
H9W	0.666 (3)	0.513 (2)	0.170 (3)	0.067*
H10W	0.598 (4)	0.574 (2)	0.068 (3)	0.067*
O6W	0.5884 (6)	0.6734 (4)	−0.0345 (5)	0.1474 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.01727 (12)	0.02490 (13)	0.01985 (12)	−0.00060 (8)	0.00183 (8)	0.00210 (8)
V1	0.01574 (14)	0.01789 (15)	0.01586 (14)	0.00001 (10)	0.00464 (11)	0.00076 (10)
P1	0.01270 (19)	0.0220 (2)	0.0165 (2)	−0.00024 (16)	0.00279 (16)	−0.00184 (16)
N1	0.0182 (7)	0.0201 (7)	0.0165 (7)	−0.0029 (6)	0.0045 (5)	−0.0002 (5)
O5	0.0185 (6)	0.0238 (6)	0.0206 (6)	−0.0037 (5)	0.0023 (5)	0.0009 (5)
O7	0.0142 (6)	0.0304 (7)	0.0239 (6)	0.0025 (5)	0.0018 (5)	−0.0048 (6)
O4	0.0279 (7)	0.0252 (7)	0.0171 (6)	−0.0049 (6)	0.0017 (5)	0.0016 (5)
C5	0.0195 (8)	0.0232 (8)	0.0152 (7)	−0.0024 (7)	0.0041 (6)	0.0014 (6)
O6	0.0177 (6)	0.0331 (7)	0.0233 (6)	−0.0002 (5)	0.0067 (5)	−0.0079 (6)
O2	0.0287 (7)	0.0247 (7)	0.0357 (8)	0.0029 (6)	0.0196 (6)	0.0039 (6)
C4	0.0210 (8)	0.0251 (9)	0.0190 (8)	−0.0035 (7)	0.0026 (7)	0.0003 (7)
C1	0.0227 (9)	0.0225 (9)	0.0270 (9)	−0.0022 (7)	0.0094 (7)	−0.0053 (7)
O8	0.0410 (9)	0.0272 (8)	0.0383 (9)	0.0017 (7)	0.0169 (7)	0.0086 (7)
C3	0.0248 (9)	0.0288 (10)	0.0202 (8)	−0.0110 (8)	0.0021 (7)	0.0036 (7)
C2	0.0337 (10)	0.0189 (8)	0.0299 (10)	0.0036 (8)	0.0148 (8)	0.0009 (7)
O3	0.0405 (9)	0.0334 (8)	0.0242 (7)	−0.0151 (7)	−0.0043 (7)	0.0007 (6)
O1	0.0305 (8)	0.0297 (8)	0.0538 (10)	0.0047 (6)	0.0226 (8)	−0.0033 (7)
O1W	0.0428 (10)	0.0270 (8)	0.0340 (9)	−0.0057 (7)	−0.0029 (7)	0.0044 (7)
O2W	0.0235 (7)	0.0261 (7)	0.0316 (7)	−0.0003 (6)	0.0117 (6)	0.0027 (6)
O3W	0.0269 (8)	0.0578 (12)	0.0266 (8)	−0.0179 (8)	−0.0040 (6)	0.0167 (8)
O4W	0.0274 (7)	0.0287 (8)	0.0303 (8)	−0.0041 (6)	0.0046 (6)	0.0066 (6)
O5W	0.0281 (8)	0.0761 (14)	0.0268 (8)	0.0078 (9)	0.0064 (7)	−0.0058 (9)
O6W	0.163 (4)	0.159 (5)	0.143 (4)	−0.009 (4)	0.083 (4)	0.009 (3)

Geometric parameters (Å, º) top

Zn1—O7	2.0133 (14)	C5—H5B	0.9700
Zn1—O3W	2.0609 (16)	O6—V1ⁱ	1.9890 (14)
Zn1—O1W	2.0860 (17)	O2—C1	1.271 (3)
Zn1—O4W	2.0974 (16)	C4—O3	1.238 (2)
Zn1—O5W	2.1440 (18)	C4—C3	1.524 (3)
Zn1—O2W	2.1660 (15)	C1—O1	1.239 (3)
V1—O8	1.6086 (16)	C1—C2	1.517 (3)
V1—O6ⁱ	1.9890 (14)	C3—H3A	0.9700
V1—O5	1.9932 (14)	C3—H3B	0.9700
V1—O2	2.0312 (15)	C2—H2A	0.9700
V1—O4	2.0321 (14)	C2—H2B	0.9700
V1—N1	2.3590 (16)	O1W—H1W	0.90 (2)
P1—O7	1.5030 (14)	O1W—H2W	0.90 (2)
P1—O6	1.5324 (15)	O2W—H3W	0.88 (2)
P1—O5	1.5443 (14)	O2W—H4W	0.87 (2)
P1—C5	1.8323 (19)	O3W—H5W	0.89 (2)
N1—C3	1.478 (2)	O3W—H6W	0.88 (2)
N1—C2	1.481 (3)	O4W—H7W	0.86 (2)
N1—C5	1.484 (2)	O4W—H8W	0.88 (2)
O4—C4	1.282 (2)	O5W—H9W	0.90 (2)
C5—H5A	0.9700	O5W—H10W	0.86 (2)

O7—Zn1—O3W	177.43 (8)	P1—O7—Zn1	134.17 (9)
O7—Zn1—O1W	89.53 (7)	C4—O4—V1	123.17 (12)
O3W—Zn1—O1W	88.34 (7)	N1—C5—P1	109.58 (12)
O7—Zn1—O4W	91.64 (6)	N1—C5—H5A	109.8
O3W—Zn1—O4W	90.49 (7)	P1—C5—H5A	109.8
O1W—Zn1—O4W	178.81 (7)	N1—C5—H5B	109.8
O7—Zn1—O5W	91.53 (6)	P1—C5—H5B	109.8
O3W—Zn1—O5W	87.09 (8)	H5A—C5—H5B	108.2
O1W—Zn1—O5W	91.61 (9)	P1—O6—V1ⁱ	142.36 (9)
O4W—Zn1—O5W	88.58 (8)	C1—O2—V1	123.99 (13)
O7—Zn1—O2W	90.73 (6)	O3—C4—O4	123.37 (18)
O3W—Zn1—O2W	90.71 (7)	O3—C4—C3	120.23 (18)
O1W—Zn1—O2W	89.93 (7)	O4—C4—C3	116.37 (16)
O4W—Zn1—O2W	89.83 (6)	O1—C1—O2	123.4 (2)
O5W—Zn1—O2W	177.27 (7)	O1—C1—C2	118.61 (19)
O8—V1—O6ⁱ	100.84 (8)	O2—C1—C2	118.02 (17)
O8—V1—O5	103.84 (8)	N1—C3—C4	109.82 (15)
O6ⁱ—V1—O5	91.21 (6)	N1—C3—H3A	109.7
O8—V1—O2	94.57 (8)	C4—C3—H3A	109.7
O6ⁱ—V1—O2	164.50 (7)	N1—C3—H3B	109.7
O5—V1—O2	86.67 (6)	C4—C3—H3B	109.7
O8—V1—O4	101.49 (8)	H3A—C3—H3B	108.2
O6ⁱ—V1—O4	87.20 (6)	N1—C2—C1	113.27 (16)
O5—V1—O4	154.45 (6)	N1—C2—H2A	108.9
O2—V1—O4	88.12 (6)	C1—C2—H2A	108.9
O8—V1—N1	169.79 (8)	N1—C2—H2B	108.9
O6ⁱ—V1—N1	88.57 (6)	C1—C2—H2B	108.9
O5—V1—N1	79.69 (6)	H2A—C2—H2B	107.7
O2—V1—N1	75.95 (6)	Zn1—O1W—H1W	122 (2)
O4—V1—N1	74.78 (6)	Zn1—O1W—H2W	121 (2)
O7—P1—O6	112.33 (8)	H1W—O1W—H2W	103 (3)
O7—P1—O5	111.96 (8)	Zn1—O2W—H3W	115.9 (19)
O6—P1—O5	110.11 (9)	Zn1—O2W—H4W	123 (2)
O7—P1—C5	109.55 (9)	H3W—O2W—H4W	109 (2)
O6—P1—C5	108.69 (8)	Zn1—O3W—H5W	128 (2)
O5—P1—C5	103.82 (8)	Zn1—O3W—H6W	119 (2)
C3—N1—C2	111.98 (16)	H5W—O3W—H6W	109 (3)
C3—N1—C5	113.40 (15)	Zn1—O4W—H7W	115 (2)
C2—N1—C5	111.14 (15)	Zn1—O4W—H8W	113 (2)
C3—N1—V1	105.00 (11)	H7W—O4W—H8W	106 (3)
C2—N1—V1	108.06 (11)	Zn1—O5W—H9W	106 (2)
C5—N1—V1	106.80 (11)	Zn1—O5W—H10W	130 (3)
P1—O5—V1	124.99 (8)	H9W—O5W—H10W	105 (3)

O8—V1—N1—C3	95.2 (5)	O5—V1—O4—C4	−10.3 (3)
O6ⁱ—V1—N1—C3	−62.07 (12)	O2—V1—O4—C4	−88.53 (16)
O5—V1—N1—C3	−153.56 (13)	N1—V1—O4—C4	−12.59 (15)
O2—V1—N1—C3	117.32 (13)	C3—N1—C5—P1	155.80 (14)
O4—V1—N1—C3	25.42 (12)	C2—N1—C5—P1	−77.01 (17)
O8—V1—N1—C2	−24.5 (5)	V1—N1—C5—P1	40.64 (13)
O6ⁱ—V1—N1—C2	178.27 (13)	O7—P1—C5—N1	89.70 (14)
O5—V1—N1—C2	86.78 (13)	O6—P1—C5—N1	−147.23 (12)
O2—V1—N1—C2	−2.35 (12)	O5—P1—C5—N1	−30.04 (15)
O4—V1—N1—C2	−94.24 (13)	O7—P1—O6—V1ⁱ	147.90 (15)
O8—V1—N1—C5	−144.1 (4)	O5—P1—O6—V1ⁱ	−86.60 (17)
O6ⁱ—V1—N1—C5	58.62 (11)	C5—P1—O6—V1ⁱ	26.51 (19)
O5—V1—N1—C5	−32.88 (11)	O8—V1—O2—C1	−176.55 (17)
O2—V1—N1—C5	−122.00 (12)	O6ⁱ—V1—O2—C1	9.6 (4)
O4—V1—N1—C5	146.11 (12)	O5—V1—O2—C1	−72.91 (17)
O7—P1—O5—V1	−116.85 (10)	O4—V1—O2—C1	82.07 (17)
O6—P1—O5—V1	117.44 (10)	N1—V1—O2—C1	7.29 (16)
C5—P1—O5—V1	1.24 (12)	V1—O4—C4—O3	178.20 (17)
O8—V1—O5—P1	−173.68 (11)	V1—O4—C4—C3	−4.0 (3)
O6ⁱ—V1—O5—P1	−72.20 (11)	V1—O2—C1—O1	169.44 (16)
O2—V1—O5—P1	92.43 (11)	V1—O2—C1—C2	−10.6 (3)
O4—V1—O5—P1	13.8 (2)	C2—N1—C3—C4	83.0 (2)
N1—V1—O5—P1	16.12 (10)	C5—N1—C3—C4	−150.29 (17)
O6—P1—O7—Zn1	21.40 (16)	V1—N1—C3—C4	−34.07 (19)
O5—P1—O7—Zn1	−103.09 (13)	O3—C4—C3—N1	−153.7 (2)
C5—P1—O7—Zn1	142.29 (12)	O4—C4—C3—N1	28.5 (3)
O1W—Zn1—O7—P1	52.88 (14)	C3—N1—C2—C1	−116.61 (19)
O4W—Zn1—O7—P1	−127.34 (14)	C5—N1—C2—C1	115.43 (18)
O5W—Zn1—O7—P1	−38.72 (15)	V1—N1—C2—C1	−1.4 (2)
O2W—Zn1—O7—P1	142.81 (13)	O1—C1—C2—N1	−172.84 (19)
O8—V1—O4—C4	177.18 (16)	O2—C1—C2—N1	7.2 (3)
O6ⁱ—V1—O4—C4	76.69 (16)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O1ⁱⁱ	0.90 (2)	1.88 (2)	2.770 (2)	169 (3)
O1W—H2W···O2Wⁱⁱ	0.90 (2)	1.95 (2)	2.828 (2)	164 (3)
O2W—H3W···O3ⁱⁱⁱ	0.88 (2)	1.85 (2)	2.725 (2)	172 (3)
O2W—H4W···O5ⁱⁱ	0.87 (2)	1.93 (2)	2.795 (2)	173 (3)
O3W—H6W···O2ⁱⁱ	0.88 (2)	1.87 (2)	2.733 (2)	171 (3)
O3W—H5W···O4^iv	0.89 (2)	1.86 (2)	2.726 (2)	164 (4)
O4W—H7W···O3^iv	0.86 (2)	1.98 (2)	2.837 (2)	174 (3)
O4W—H8W···O1^v	0.88 (2)	1.94 (2)	2.799 (2)	167 (3)
O5W—H9W···O6	0.90 (2)	1.98 (3)	2.805 (2)	150 (4)
O5W—H10W···O6W	0.86 (2)	1.84 (3)	2.656 (6)	159 (4)

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

Experimental details

Crystal data
Chemical formula	[Zn₂V₂(C₅H₆NO₇P)₂O₂(H₂O)₁₀]·2H₂O
M_r	926.97
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	10.0161 (5), 14.8811 (7), 10.8298 (5)
β (°)	111.147 (2)
V (Å³)	1505.48 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.40
Crystal size (mm)	0.22 × 0.14 × 0.10

Data collection
Diffractometer	Bruker X8 APEXII Kappa CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1998)
T_min, T_max	0.621, 0.796
No. of measured, independent and observed [I > 2σ(I)] reflections	95509, 4040, 3765
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.685

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.077, 1.04
No. of reflections	4040
No. of parameters	238
No. of restraints	15
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.06, −0.87

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2005), SHELXTL (Bruker 2001), DIAMOND (Brandenburg, 2006).

Selected bond lengths (Å) top

Zn1—O7	2.0133 (14)	V1—O8	1.6086 (16)
Zn1—O3W	2.0609 (16)	V1—O6ⁱ	1.9890 (14)
Zn1—O1W	2.0860 (17)	V1—O5	1.9932 (14)
Zn1—O4W	2.0974 (16)	V1—O2	2.0312 (15)
Zn1—O5W	2.1440 (18)	V1—O4	2.0321 (14)
Zn1—O2W	2.1660 (15)	V1—N1	2.3590 (16)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O1ⁱⁱ	0.90 (2)	1.88 (2)	2.770 (2)	169 (3)
O1W—H2W···O2Wⁱⁱ	0.90 (2)	1.95 (2)	2.828 (2)	164 (3)
O2W—H3W···O3ⁱⁱⁱ	0.88 (2)	1.85 (2)	2.725 (2)	172 (3)
O2W—H4W···O5ⁱⁱ	0.87 (2)	1.93 (2)	2.795 (2)	173 (3)
O3W—H6W···O2ⁱⁱ	0.88 (2)	1.87 (2)	2.733 (2)	171 (3)
O3W—H5W···O4^iv	0.89 (2)	1.86 (2)	2.726 (2)	164 (4)
O4W—H7W···O3^iv	0.86 (2)	1.98 (2)	2.837 (2)	174 (3)
O4W—H8W···O1^v	0.88 (2)	1.94 (2)	2.799 (2)	167 (3)
O5W—H9W···O6	0.90 (2)	1.98 (3)	2.805 (2)	150 (4)
O5W—H10W···O6W	0.86 (2)	1.84 (3)	2.656 (6)	159 (4)

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

Acknowledgements

The authors are grateful to the Fundação para a Ciência e a Tecnologia (FCT, Portugal) for their general financial support (grant No. POCI-PPCDT/QUI/58377/2004 supported by FEDER), for specific funding toward the purchase of the single-crystal diffractometer, and also for Postdoctoral Research Grants SFRH/BPD/14410/2003 (to LCS) and SFRH/BPD/9309/2002 (to FNS).

References

Almeida Paz, F. A., Shi, F.-N., Mafra, L., Makal, A., Wozniak, K., Trindade, T., Klinowski, J. & Rocha, J. (2005). Acta Cryst. E61, m1628–m1632. Web of Science CSD CrossRef IUCr Journals Google Scholar
Almeida Paz, F. A., Shi, F.-N., Trindade, T., Klinowski, J. & Rocha, J. (2005). Acta Cryst. E61, m2247–m2250. Web of Science CSD CrossRef IUCr Journals Google Scholar
Brandenburg, K. (2006). DIAMOND. Version 3.1e. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2001). SHELXTL. Version 6.12. Bruker AXS Inc. Madison, Wisconsin, USA. Google Scholar
Bruker (2005). SAINT-Plus. Version 7.23a. Bruker AXS Inc. Madison, Wisconsin, USA. Google Scholar
Bruker (2006). APEX2. Version 2.1-RC13. Bruker AXS, Delft, The Netherlands. Google Scholar
Cunha-Silva, L., Mafra, L., Ananias, D., Carlos, L. D., Rocha, J. & Paz, F. A. A. (2007). Chem. Mater. 19, 3527–3538. Web of Science CSD CrossRef CAS Google Scholar
Cunha-Silva, L., Shi, F.-N., Klinowski, J., Trindade, T., Rocha, J. & Almeida Paz, F. A. (2007). Acta Cryst. E63, m372–m375. Web of Science CSD CrossRef IUCr Journals Google Scholar
Mafra, L., Paz, F. A. A., Shi, F.-N., Rocha, J., Trindade, T., Fernandez, C., Makal, A., Wozniak, K. & Klinowski, J. (2006). Chem. Eur. J. 12, 363–375. Web of Science CSD CrossRef Google Scholar
Paz, F. A. A., Rocha, J., Klinowski, J., Trindade, T., Shi, F.-N. & Mafra, L. (2005). Prog. Solid State Chem. 33, 113–125. Web of Science CrossRef CAS Google Scholar
Paz, F. A. A., Shi, F.-N., Klinowski, J., Rocha, J. & Trindade, T. (2004). Eur. J. Inorg. Chem. pp. 2759–2768. Google Scholar
Sheldrick, G. M. (1998). SADABS. Version 2.01. Bruker AXS Inc. Madison, Wisconsin, USA. Google Scholar
Shi, F.-N., Almeida Paz, F. A., Trindade, T. & Rocha, J. (2006). Acta Cryst. E62, m335–m338. Web of Science CSD CrossRef IUCr Journals Google Scholar
Shi, F.-N., Cunha-Silva, L., Sá Ferreira, R. A., Mafra, L., Trindade, T., Carlos, L. D., Paz, F. A. A. & Rocha, J. (2007). J. Am. Chem. Soc. doi: 10.1021/ja074119k. Google Scholar
Shi, F.-N., Paz, F. A. A., Girginova, P. I., Amaral, V. S., Rocha, J., Klinowski, J. & Trindade, T. (2006). Inorg. Chim. Acta, 359, 1147–1158. Web of Science CSD CrossRef CAS Google Scholar
Shi, F.-N., Paz, F. A. A., Girginova, P. I., Mafra, L., Amaral, V. S., Rocha, J., Makal, A., Wozniak, K., Klinowski, J. & Trindade, T. (2005). J. Mol. Struct. 754, 51–60. Web of Science CSD CrossRef CAS Google Scholar
Shi, F.-N., Paz, F. A. A., Girginova, P. I., Rocha, J., Amaral, V. S., Klinowski, J. & Trindade, T. (2006). J. Mol. Struct. 789, 200–208. Web of Science CSD CrossRef CAS Google Scholar

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