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The title compound, {[Na3(C5H9N2O7P2)2(C5H9.5N2O7P2)2(H2O)4]·2H2O}n, (II), is polymeric and consists of undulating chains parallel to [011] inter­connected by hydrogen-bonding and π–π inter­actions. There are two independent Na+ cations in the asymmetric unit (one lying on an inversion centre), two zoledronate anions and three water mol­ecules, two of which are coordinated and one of which is a free solvate. Each cation is surrounded in an octa­hedral fashion by O atoms from four different zoledronate units and two/one coordinated water mol­ecules. The zoledronate groups present their usual zwitterionic character, with negative charges in the protonated phospho­nates and a positive charge at the protonated imidazole N atom. Two symmetry-related phospho­nate groups share (in the form of a very strong linear hydrogen bond) an H atom lying on a symmetry centre, midway between the O atoms involved. The zoledronate binding modes present in (II) are both unreported for bis­phospho­nate anions. Intra- and inter-chain inter­actions are enhanced by a variety of hydrogen bonds where all the available O—H and N—H donors are involved, in addition to a strong imidazole–phospho­nate C—H...O inter­action, typical in these kinds of structures.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827011001022X/dn3137sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827011001022X/dn3137Isup2.hkl
Contains datablock I

CCDC reference: 774887

Comment top

Initiating a line of research on mono- and divalent alkaline cation complexes with the zoledronate anion (hereafter represented by the generic term Zol, irrespective of their different ionic forms), we have recently reported the first structure of this type, [K(Zol)(H2O).(H2O)]n, (I) (Freire et al., 2010), where all constituents (cation:anion: watercoord.: watersolv.) appeared in a rather simple 1:1:1:1 ratio. A thorough introduction to zoledronate complexes has been included in that report, to which the interested reader is referred.

As a continuation of this line of research we present herein the sodium counterpart, (II), which shows a quite different formulation {viz 3:4:4:2, or explicitly [Na3(Zol)4(H2O)4.2(H2O)]n}, a difference which is readily reflected in important structural differences, to be discussed below.

There are two independent Na cations in the asymmetric unit, one of them lying on an inversion centre (Na1) and the remaining one on a general position (Na2), two zoledronate anions and three water molecules, two of which are coordinated while the remaining one is a free solvate. The centre of symmetry at Na1 transforms the group into a three-nuclear unit (Scheme and Fig. 1) much simpler to describe and which we shall adopt as our `molecular formula' (z = 1, z' = 0.5 ). The metallic centres present rather distorted NaO6 octahedral environments, each independent Na1(Na2) cation being connected to four zoledronate anions, respectively, and completing the coordination polyhedron with two(one) aqua (Table 1). Coordination parameters span the range Na1—O 2.349 (3)-2.488 (3) Å, O—Na1—Oopposite 180° (due to centrosymmetry); O—Na1—Oneighbour 78.93 (12)-101.07 (12)°; Na2—O 2.363 (4)-2.554 (4) Å, O—Na2—Oopposite 158.68 (17)-176.02 (14)°; O—Na2—Oneighbour 77.69 (11)-102.25 (15)°. The two independent zoledronate ligands, in turn, bind in µ3 mode to three metal centres each. Unit 1 binds in a simple threefold (O:O':O") monocoordinated fashion through O21, O1 and O12 to Na1, Na2 and Na2(-x,1-y,1-z), respectively; unit 2 is a little more complex with two oxygens (O32,O41) chelating one metal centre (Na2) with O41 also binding Na2(-x,1-y,1-z). Finally, there is one monocoordinated oxygen (O31) bound to Na1, all of which leads to an overall (O,O':O':O") chelating bridging mode for the anion.

These coordination schemes are very simple compared to the extremely complex connectivity modes usually displayed by bisphosphonates in general; in fact we could not trace any similar arrangement for any reported bisphosphonate in the Cambridge Structural Darabase (CSD, version 5.31; Allen, 2002), for what these binding modes are also new for the zoledronate anion (See Fig. 2 in Freire et al., 2010, for the zoledronate binding modes reported so far). The bridging character of both independent anions results in the formation of a chain structure running along [011] consisting in the juxtaposition of the individual three nuclear motifs shown in Fig. 1, linked in a `slanted' fashion into a rather undulated one-dimensional structure. This is shown in full detail in Fig. 2, and schematically in Fig. 3, where the two different types of loops joining metal centres are clearly seen: a very simple Na2O2 one, in the form of a rhomboid around a symmetry centre joining two symmetry-related Na2 cations through an O41 bridge, and a much more complicated one, joining Na1 and Na2 through both extended zoledronates.

In order to discuss charge balance in (II) we shall first briefly analyse the other related zoledronate complexes in the literature (see Freire et al., 2010 for a detailed survey). The cases reported so far, with the exception of DOGYOO (see Table 2 for details), present one single independent zoledronate group, for what they display a general M+xn(Zol-y)m core (M, the metallic cation; Zol, the zoledronate anion; x, y, positive numbers accounting for the total charge over each group). Charge balance is achieved within each compound through a set of integer values for the (n, x, m, y) `quartet' subject to the condition n × x = m × y (Table 2, upper block). Different values for the charge in the bisphosphonate units (-1, -3) are the result of the different protonation states of the individual phosphonates, where each PO3HnH group carries a formal negative charge of (2-nH) electrons, (circumstantially, all these cases present the same number of hydrogens `nH' in both PO3HnH groups, but this symmetry is obviously not a necessary condition). The protonated imidazol group adds a positive charge to the total sum. As already stated, the structure DOGYOO is the exception to this, in that it presents two independent zoledronate anions, each one with different charges and thus the compound should be formulated as M+xn(Zol-y)m (Zol-z)p , y and z being the individual (not necessarily equal) number of charges for each Zol group. The charge balance equation would read, in this case, n × x = m × y + p × z (Table 2, lower block, first entry)

A similar situation is found in (II), where the corresponding `sextet' would be (3, 1, 2, y, 2, z) and the associated balance equation: 3 × 1 = 2 × y + 2 × z. It is apparent that there is not a possible integer solution for that equation, requiring instead a fractional charge somewhere, which could be achieved, for example, through some half-occupied H site. Instead of that the structure fulfils this condition by placing one proton at a symmetry centre, midway two symmetry-related O atoms (O33, O33iv, (iv): -x,1-y,1-z) in a symmetric O···H···O' bridge, O···H: 1.21Å (See Fig. 1., H33 at 0,1/2,1/2). The alternative possibility of a disordered H atom with 0.50 occupancy at both sides of the symmetry centre was disregarded after a difference map calculated through the symmetry related oxygens, which showed a well defined, spherical single peak at the centre.

In addition to the key role it plays in the charge balance equation, this H33 atom is central to the structure packing, since it serves to join parallel chains along the a direction to form a two-dimensional structure parallel to (0 1 1) (viewed in projection in Fig. 4 as horizontal linear arrays, limited by square brackets). These planes present the imidazole rings protruding outwards (at both sides) so that piling up of planes leads to interdigitation and the concomitant appearance of ππ contacts between neighbouring layers [viz Cg1···Cg2i (i):1+x,y,1+z with an intercentroid distance of 3.791 (3) Å and Cg2···Cg2ii (ii): -x,2-y,1-z, with 3.700 (2) Å], where Cg1 and Cg2 are the imidazole centroids (Fig. 1). Both types of interchain interactions are complemented by a survey of hydrogen bonds to which all the available O—H and N—H (and some C—H, see below) donors take part (Table 2). Many of these interactions are visible in Fig. 4, in particular as bridging agents between layers.

It has been shown (Freire et al., 2010) that zoledronate compounds very often present unusually short (C—H)imid···Ophosphonate interactions, with H···O as short as 2.24 Å, e.g. in VIMXIZ (Cao et al., 2007). The present structure, (II), is not an exception to the rule, as the last entry in Table 2 confirms (H···O 2.31 Å).

At this stage it is worth comparing the structure of (II) with two closely related compounds in the literature, with similarities and differences originating for quite different reasons. The first one, Na(isoZol).4H2O, (III) (isoZol: isoZoledronate; a zoledronate isomer; Gossman et al., 2002) shares with (II) the same Na cation, while the anion has its imidazole unit `rotated' around its plane and bound to the main frame via a C atom instead of N, thus leaving two active N—Hs free for hydrogen bonding, instead of the single one found in zoledronate. In spite of the obvious molecular similarities, this slight change in the way in which the imidazole group is attached to the ligand seems crucial in defining the way both structures build up, the differences including formulation [in the above-mentioned notation, 3:4:4:2 for (II), 1:1:3:1 for (III)], and a direct consequence of the different formulation, charge balance [achieved in a straightforward 1:1 fashion in (III) but in the rather complicated way already discussed, in (II)], dimensionality [while (II) is a chain structure, (III) is dimeric] etc.

The second analogue is the structure reported under CSD code DOGYOO (See Table 2 and the charge-balance discussion); the compound is one of the copper zoledronates reported in Cao et al. (2008), Cu3(Zol)4.4H2O, (IV), which bears a similar 3:4 cation:anion ratio to (II) and many structural similarities, viz in both structures there is one cation on a symmetry centre and the second one in a general position, they are joined by the two independent Zol groups into chains formed by two types of links: those in the form of small centrosymmetric M—O—M—O loops, and another ones larger and more irregular, involving unrelated cations. However, the difference in cation valence (NaI vs CuII) leads to differences in the way charge balance is achieved (we have already discussed the point), as well as different coordination geometries: there are no coordinated water molecules in (IV). The result is reflected in the formulation, (3:4:4:2) for (II), (3:4:0:4) for (IV)

However, all three structures coincide in the existence of a complex and extensive hydrogen-bonding scheme, which is the result of a rich provision of hydrogen-bonding donors and acceptors, and which in all cases results in a tightly bound three-dimensional structure.

Related literature top

For related literature, see: Allen (2002); Cao et al. (2007, 2008); Freire et al. (2010); Gossman et al. (2002).

Experimental top

Crystals of (II) were synthesized by neutralization of a solution of zoledronic acid (from GADOR Argentina S.A.) with a NaOH solution in a 1:1 stoichometric ratio. The unperturbed solution was allowed to concentrate slowly, and after a few days large, colourless blocks were obtained, suitable for X-ray diffraction.

Refinement top

The H atoms attached to O and N were found in a difference Fourier map, further further adjusted along the X—H bond to reach ideal values (O—H = 0.85Å and N—H = 0.88Å) and finally allowed to ride. The exception to this was atom H33, which was constrained to lie on an inversion centre, midway between both donor/acceptor of the hydrogen bond in which it takes part. Those attached to C atoms were placed at calculated positions (CH 0.93 Å, CH2 0.97 Å) and allowed to ride. Displacement factors were taken as U(H)iso = 1.2/1.5Uhost.

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), PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. Ellipsoid plot of (II), showing (heavy outline) the asymmetric unit and (light outline) the symmetry-related part completing the three-nuclear unit. Symmetry codes: (i) 1-x, 1-y, 1-z; (ii) 1-x, 2-y, 2-z; (iii) x,-1+y, -1+z; (iv) -x, 1-y, 1-z.
[Figure 2] Fig. 2. The zoledronate coordination schemes in (II). This should be considered an addenda to Fig. 2 in Freire et al. (2010).
[Figure 3] Fig. 3. Schematic packing diagram of (II) showing the undulated chain formed by the two types of loops. The pendant imidazole and hydroxyl groups, as well as H atoms, are not shown for clarity.
[Figure 4] Fig. 4. Packing diagram of (II) viewed along a and showing the planes in projection. Note the overlap of neighbouring imidazole rings.
catena-Poly[[tetraaquabis[hemihydrogen µ3-1-hydroxy-2-(imidazol-3-ium-1-yl)ethylidene-1,1-diphosphonato- κ3O:O':O'']bis[µ3-1-hydroxy-2-(imidazol-3-ium- 1-yl)ethylidene-1,1-diphosphonato- κ4O,O':O':O'']trisodium] dihydrate] top
Crystal data top
[Na3(C5H9N2O7P2)2(C5H9.5N2O7P2)2(H2O)4]·2H2OZ = 1
Mr = 1262.40F(000) = 650
Triclinic, P1Dx = 1.888 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.0690 (18) ÅCell parameters from 25 reflections
b = 11.309 (2) Åθ = 10–15°
c = 12.594 (3) ŵ = 0.46 mm1
α = 115.58 (3)°T = 295 K
β = 98.86 (3)°Blocks, colourless
γ = 99.76 (3)°0.36 × 0.22 × 0.20 mm
V = 1110.1 (6) Å3
Data collection top
Rigaku AFC6
diffractometer
3797 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.034
Graphite monochromatorθmax = 26.0°, θmin = 1.9°
ω/2θ scansh = 111
Absorption correction: ψ scan
(North et al., 1968)
k = 1313
Tmin = 0.78, Tmax = 0.83l = 1515
5236 measured reflections3 standard reflections every 150 reflections
4366 independent reflections intensity decay: 1%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.056Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.170H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.0756P)2 + 5.2734P]
where P = (Fo2 + 2Fc2)/3
4366 reflections(Δ/σ)max = 0.003
331 parametersΔρmax = 1.05 e Å3
0 restraintsΔρmin = 0.78 e Å3
Crystal data top
[Na3(C5H9N2O7P2)2(C5H9.5N2O7P2)2(H2O)4]·2H2Oγ = 99.76 (3)°
Mr = 1262.40V = 1110.1 (6) Å3
Triclinic, P1Z = 1
a = 9.0690 (18) ÅMo Kα radiation
b = 11.309 (2) ŵ = 0.46 mm1
c = 12.594 (3) ÅT = 295 K
α = 115.58 (3)°0.36 × 0.22 × 0.20 mm
β = 98.86 (3)°
Data collection top
Rigaku AFC6
diffractometer
3797 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.034
Tmin = 0.78, Tmax = 0.833 standard reflections every 150 reflections
5236 measured reflections intensity decay: 1%
4366 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0560 restraints
wR(F2) = 0.170H-atom parameters constrained
S = 1.09Δρmax = 1.05 e Å3
4366 reflectionsΔρmin = 0.78 e Å3
331 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Na10.50000.50000.50000.0275 (6)
Na20.4010 (2)0.86196 (18)0.97693 (16)0.0291 (4)
P10.81134 (12)0.87339 (10)0.85118 (9)0.0161 (2)
P20.78005 (12)0.57570 (11)0.78593 (9)0.0186 (3)
P30.23490 (12)0.65463 (10)0.66490 (9)0.0166 (2)
P40.35479 (12)0.95424 (10)0.72521 (9)0.0172 (2)
O110.9822 (3)0.8855 (3)0.8558 (3)0.0213 (6)
O120.7902 (4)1.0070 (3)0.9547 (3)0.0227 (6)
H120.86711.04351.01670.027*
O130.7104 (3)0.8453 (3)0.7325 (3)0.0217 (6)
O210.7076 (4)0.5386 (3)0.6581 (3)0.0280 (7)
O220.9535 (4)0.5955 (3)0.8246 (3)0.0267 (7)
O230.7029 (4)0.4659 (3)0.8224 (3)0.0286 (7)
H230.62420.40650.76760.034*
O310.3976 (3)0.6450 (3)0.6657 (3)0.0221 (6)
O320.2082 (3)0.6991 (3)0.7958 (3)0.0218 (6)
H320.12090.66820.80400.026*
O330.1133 (3)0.5210 (3)0.5769 (3)0.0240 (7)
H330.00000.50000.50000.029*
O410.3977 (4)0.9744 (3)0.8527 (3)0.0245 (7)
O420.4974 (4)0.9409 (3)0.6668 (3)0.0250 (7)
H420.55960.90510.69250.030*
O430.2953 (4)1.0631 (3)0.7076 (3)0.0244 (7)
O10.5772 (3)0.7160 (3)0.8798 (3)0.0211 (6)
H10.53420.68730.80510.025*
O20.0522 (3)0.8098 (3)0.6390 (3)0.0223 (6)
H20.04730.83330.71200.027*
C110.7409 (5)0.7364 (4)0.8901 (3)0.0167 (8)
C210.8212 (5)0.7916 (4)1.0251 (4)0.0196 (8)
H21A0.93010.83181.03850.024*
H21B0.77780.86341.07350.024*
C310.9220 (6)0.6375 (5)1.0909 (4)0.0291 (10)
H311.02090.65841.08080.035*
N110.8079 (4)0.6906 (4)1.0688 (3)0.0217 (8)
N210.8717 (5)0.5503 (4)1.1296 (4)0.0353 (10)
H210.92630.50261.15020.042*
C410.7206 (7)0.5463 (5)1.1321 (5)0.0357 (12)
H410.65750.49291.15530.043*
C510.6797 (6)0.6351 (5)1.0943 (4)0.0307 (10)
H510.58410.65431.08710.037*
C120.2026 (4)0.7905 (4)0.6274 (3)0.0157 (8)
C220.1953 (5)0.7354 (4)0.4903 (4)0.0204 (8)
H22A0.29810.73150.47890.024*
H22B0.12860.64340.44590.024*
N120.1373 (4)0.8183 (3)0.4388 (3)0.0188 (7)
N220.0210 (5)0.8996 (4)0.3609 (3)0.0256 (8)
H220.10730.91470.33340.031*
C320.2236 (5)0.9067 (5)0.4089 (4)0.0264 (9)
H32A0.33030.92710.41980.032*
C420.1251 (6)0.9578 (5)0.3613 (4)0.0298 (10)
H42A0.15081.02080.33380.036*
C520.0099 (5)0.8170 (4)0.4089 (4)0.0232 (9)
H520.09230.76610.41990.028*
O1W0.6987 (4)0.6772 (3)0.4948 (3)0.0303 (7)
H1WA0.76630.63290.49150.036*
H1WB0.70800.72770.57000.036*
O2W0.3069 (6)0.7597 (5)1.1031 (4)0.0538 (11)
H2WA0.30070.69321.11860.065*
H2WB0.33820.82581.17490.065*
O3W0.4790 (4)0.2543 (4)0.6585 (4)0.0406 (9)
H3WA0.41210.27090.61550.049*
H3WB0.43570.19890.68040.049*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Na10.0281 (13)0.0287 (13)0.0241 (13)0.0039 (10)0.0021 (10)0.0137 (11)
Na20.0332 (10)0.0245 (9)0.0225 (9)0.0010 (8)0.0022 (7)0.0103 (8)
P10.0182 (5)0.0152 (5)0.0138 (5)0.0010 (4)0.0001 (4)0.0083 (4)
P20.0226 (5)0.0164 (5)0.0155 (5)0.0034 (4)0.0011 (4)0.0081 (4)
P30.0174 (5)0.0146 (5)0.0146 (5)0.0003 (4)0.0031 (4)0.0079 (4)
P40.0187 (5)0.0151 (5)0.0155 (5)0.0016 (4)0.0005 (4)0.0078 (4)
O110.0198 (15)0.0240 (15)0.0172 (14)0.0032 (12)0.0017 (11)0.0090 (12)
O120.0265 (16)0.0179 (14)0.0176 (14)0.0045 (12)0.0005 (12)0.0053 (12)
O130.0267 (16)0.0224 (15)0.0158 (14)0.0040 (12)0.0005 (12)0.0117 (12)
O210.0419 (19)0.0244 (16)0.0142 (15)0.0088 (14)0.0007 (13)0.0080 (13)
O220.0251 (16)0.0245 (16)0.0320 (17)0.0063 (13)0.0020 (13)0.0166 (14)
O230.0384 (19)0.0190 (15)0.0232 (16)0.0021 (13)0.0019 (14)0.0108 (13)
O310.0210 (15)0.0220 (15)0.0186 (14)0.0050 (12)0.0007 (12)0.0077 (12)
O320.0230 (15)0.0245 (15)0.0161 (14)0.0012 (12)0.0011 (11)0.0119 (12)
O330.0218 (15)0.0167 (14)0.0238 (16)0.0040 (12)0.0073 (12)0.0085 (13)
O410.0300 (17)0.0229 (15)0.0149 (14)0.0003 (13)0.0005 (12)0.0084 (12)
O420.0224 (16)0.0313 (17)0.0304 (17)0.0080 (13)0.0089 (13)0.0215 (14)
O430.0273 (16)0.0161 (14)0.0272 (16)0.0042 (12)0.0004 (13)0.0108 (13)
O10.0172 (14)0.0266 (16)0.0169 (14)0.0021 (12)0.0003 (11)0.0108 (13)
O20.0189 (15)0.0330 (17)0.0177 (14)0.0089 (12)0.0039 (11)0.0139 (13)
C110.0189 (19)0.0177 (19)0.0134 (18)0.0038 (15)0.0020 (15)0.0083 (16)
C210.028 (2)0.0160 (19)0.0140 (19)0.0006 (16)0.0010 (16)0.0096 (16)
C310.038 (3)0.028 (2)0.020 (2)0.010 (2)0.0020 (19)0.0114 (19)
N110.031 (2)0.0185 (17)0.0148 (16)0.0047 (15)0.0003 (14)0.0101 (14)
N210.048 (3)0.032 (2)0.031 (2)0.0143 (19)0.0036 (19)0.0194 (19)
C410.051 (3)0.025 (2)0.032 (3)0.001 (2)0.009 (2)0.019 (2)
C510.037 (3)0.028 (2)0.029 (2)0.002 (2)0.009 (2)0.017 (2)
C120.0168 (19)0.0174 (19)0.0128 (18)0.0045 (15)0.0019 (14)0.0077 (15)
C220.029 (2)0.0179 (19)0.0145 (19)0.0067 (17)0.0013 (16)0.0088 (16)
N120.0233 (18)0.0171 (16)0.0133 (16)0.0017 (14)0.0003 (13)0.0076 (14)
N220.031 (2)0.0252 (19)0.0200 (18)0.0069 (16)0.0003 (15)0.0120 (16)
C320.026 (2)0.030 (2)0.026 (2)0.0034 (18)0.0076 (18)0.017 (2)
C420.039 (3)0.027 (2)0.027 (2)0.003 (2)0.006 (2)0.019 (2)
C520.025 (2)0.023 (2)0.018 (2)0.0024 (17)0.0006 (16)0.0101 (17)
O1W0.0386 (19)0.0266 (17)0.0232 (16)0.0077 (14)0.0024 (14)0.0115 (14)
O2W0.071 (3)0.045 (2)0.042 (2)0.003 (2)0.009 (2)0.024 (2)
O3W0.034 (2)0.039 (2)0.044 (2)0.0065 (16)0.0043 (16)0.0262 (18)
Geometric parameters (Å, º) top
Na1—O212.349 (3)O2—C121.437 (5)
Na1—O21i2.349 (3)O2—H20.8502
Na1—O31i2.463 (3)C11—C211.536 (5)
Na1—O312.463 (3)C21—N111.462 (5)
Na1—O1W2.488 (3)C21—H21A0.9700
Na1—O1Wi2.488 (3)C21—H21B0.9700
Na2—O41ii2.363 (4)C31—N211.323 (7)
Na2—O322.389 (4)C31—N111.333 (6)
Na2—O412.404 (3)C31—H310.9300
Na2—O12ii2.485 (4)N11—C511.375 (6)
Na2—O2W2.502 (5)N21—C411.369 (7)
Na2—O12.554 (4)N21—H210.8800
P1—O131.498 (3)C41—C511.363 (7)
P1—O111.522 (3)C41—H410.9300
P1—O121.579 (3)C51—H510.9300
P1—C111.862 (4)C12—C221.548 (5)
P2—O211.482 (3)C22—N121.472 (5)
P2—O221.520 (3)C22—H22A0.9700
P2—O231.594 (3)C22—H22B0.9700
P2—C111.858 (4)N12—C521.326 (6)
P3—O311.496 (3)N12—C321.379 (6)
P3—O331.530 (3)N22—C521.322 (6)
P3—O321.574 (3)N22—C421.374 (6)
P3—C121.845 (4)N22—H220.8800
P4—O411.497 (3)C32—C421.342 (7)
P4—O431.509 (3)C32—H32A0.9300
P4—O421.581 (3)C42—H42A0.9300
P4—C121.869 (4)C52—H520.9300
O12—H120.8500O1W—H1WA0.8501
O23—H230.8500O1W—H1WB0.8500
O32—H320.8500O2W—H2WA0.8500
O33—H331.2095O2W—H2WB0.8501
O42—H420.8500O3W—H3WA0.8499
O1—C111.440 (5)O3W—H3WB0.8502
O1—H10.8501
Na2···Na2ii3.085 (4)Na1···Na25.943 (4)
O21—Na1—O21i180.0P2—O21—Na1153.3 (2)
O21—Na1—O31i95.39 (11)P2—O23—H23112.8
O21i—Na1—O31i84.61 (11)P3—O31—Na1129.37 (17)
O21—Na1—O3184.61 (11)P3—O32—Na2122.60 (17)
O21i—Na1—O3195.39 (11)P3—O32—H32120.1
O31i—Na1—O31180.00 (12)Na2—O32—H32117.2
O21—Na1—O1W78.96 (12)P3—O33—H33129.3
O21i—Na1—O1W101.04 (12)P4—O41—Na2ii130.77 (19)
O31i—Na1—O1W80.08 (11)P4—O41—Na2144.83 (19)
O31—Na1—O1W99.92 (11)Na2ii—O41—Na280.66 (12)
O21—Na1—O1Wi101.04 (12)P4—O42—H42114.0
O21i—Na1—O1Wi78.96 (12)C11—O1—Na2136.0 (2)
O31i—Na1—O1Wi99.92 (11)C11—O1—H1106.3
O31—Na1—O1Wi80.08 (11)Na2—O1—H199.5
O1W—Na1—O1Wi180.0C12—O2—H2109.5
O21—Na1—H1WA67.9O1—C11—C21107.2 (3)
O21i—Na1—H1WA112.1O1—C11—P2109.8 (3)
O31i—Na1—H1WA67.5C21—C11—P2114.4 (3)
O31—Na1—H1WA112.5O1—C11—P1109.4 (3)
O1W—Na1—H1WA18.6C21—C11—P1105.7 (3)
O1Wi—Na1—H1WA161.4P2—C11—P1110.2 (2)
O21—Na1—H1WB68.5N11—C21—C11115.0 (3)
O21i—Na1—H1WB111.5N11—C21—H21A108.5
O31i—Na1—H1WB96.9C11—C21—H21A108.5
O31—Na1—H1WB83.1N11—C21—H21B108.5
O1W—Na1—H1WB19.0C11—C21—H21B108.5
O1Wi—Na1—H1WB161.0H21A—C21—H21B107.5
H1WA—Na1—H1WB29.8N21—C31—N11108.9 (5)
O41ii—Na2—O32175.99 (14)N21—C31—H31125.6
O41ii—Na2—O4199.34 (12)N11—C31—H31125.6
O32—Na2—O4177.69 (11)C31—N11—C51108.7 (4)
O41ii—Na2—O12ii92.15 (13)C31—N11—C21124.4 (4)
O32—Na2—O12ii89.96 (12)C51—N11—C21127.0 (4)
O41—Na2—O12ii79.54 (12)C31—N21—C41108.7 (4)
O41ii—Na2—O2W90.25 (14)C31—N21—H21125.7
O32—Na2—O2W93.44 (14)C41—N21—H21125.7
O41—Na2—O2W158.67 (17)C51—C41—N21107.3 (4)
O12ii—Na2—O2W81.12 (15)C51—C41—H41126.3
O41ii—Na2—O194.11 (13)N21—C41—H41126.3
O32—Na2—O183.59 (12)C41—C51—N11106.4 (5)
O41—Na2—O196.08 (12)C41—C51—H51126.8
O12ii—Na2—O1172.88 (12)N11—C51—H51126.8
O2W—Na2—O1102.23 (15)O2—C12—C22105.6 (3)
O41ii—Na2—Na2ii50.26 (9)O2—C12—P3109.6 (3)
O32—Na2—Na2ii126.71 (12)C22—C12—P3106.2 (3)
O41—Na2—Na2ii49.08 (9)O2—C12—P4110.2 (3)
O12ii—Na2—Na2ii83.53 (11)C22—C12—P4112.7 (3)
O2W—Na2—Na2ii136.83 (15)P3—C12—P4112.3 (2)
O1—Na2—Na2ii97.90 (11)N12—C22—C12113.4 (3)
O13—P1—O11115.55 (17)N12—C22—H22A108.9
O13—P1—O12108.14 (17)C12—C22—H22A108.9
O11—P1—O12110.21 (17)N12—C22—H22B108.9
O13—P1—C11109.72 (18)C12—C22—H22B108.9
O11—P1—C11107.52 (18)H22A—C22—H22B107.7
O12—P1—C11105.23 (18)C52—N12—C32107.9 (4)
O21—P2—O22119.0 (2)C52—N12—C22125.3 (4)
O21—P2—O23111.19 (19)C32—N12—C22126.8 (4)
O22—P2—O23105.30 (18)C52—N22—C42108.4 (4)
O21—P2—C11109.49 (18)C52—N22—H22125.8
O22—P2—C11106.11 (19)C42—N22—H22125.8
O23—P2—C11104.77 (18)C42—C32—N12107.3 (4)
O31—P3—O33113.37 (18)C42—C32—H32A126.3
O31—P3—O32110.50 (17)N12—C32—H32A126.3
O33—P3—O32107.73 (18)C32—C42—N22107.1 (4)
O31—P3—C12109.31 (18)C32—C42—H42A126.4
O33—P3—C12110.04 (17)N22—C42—H42A126.4
O32—P3—C12105.60 (17)N22—C52—N12109.2 (4)
O41—P4—O43117.12 (19)N22—C52—H52125.4
O41—P4—O42111.08 (18)N12—C52—H52125.4
O43—P4—O42105.64 (18)Na1—O1W—H1WA92.4
O41—P4—C12109.63 (18)Na1—O1W—H1WB89.1
O43—P4—C12106.83 (18)H1WA—O1W—H1WB106.0
O42—P4—C12105.87 (18)Na2—O2W—H2WA145.9
P1—O12—Na2ii143.72 (18)Na2—O2W—H2WB103.1
P1—O12—H12111.1H2WA—O2W—H2WB100.2
Na2ii—O12—H12104.2H3WA—O3W—H3WB110.8
O13—P1—O12—Na2ii35.8 (3)O23—P2—C11—C2165.3 (3)
O11—P1—O12—Na2ii163.0 (3)O21—P2—C11—P156.4 (3)
C11—P1—O12—Na2ii81.4 (3)O22—P2—C11—P173.2 (2)
O22—P2—O21—Na1171.7 (4)O23—P2—C11—P1175.73 (19)
O23—P2—O21—Na165.8 (5)O13—P1—C11—O150.3 (3)
C11—P2—O21—Na149.5 (5)O11—P1—C11—O1176.7 (2)
O31i—Na1—O21—P2158.3 (4)O12—P1—C11—O165.9 (3)
O31—Na1—O21—P221.7 (4)O13—P1—C11—C21165.4 (3)
O1W—Na1—O21—P2123.0 (5)O11—P1—C11—C2168.2 (3)
O1Wi—Na1—O21—P257.0 (5)O12—P1—C11—C2149.2 (3)
O33—P3—O31—Na130.5 (3)O13—P1—C11—P270.6 (2)
O32—P3—O31—Na1151.53 (19)O11—P1—C11—P255.9 (2)
C12—P3—O31—Na192.7 (2)O12—P1—C11—P2173.33 (18)
O21—Na1—O31—P3158.7 (2)O1—C11—C21—N1175.5 (4)
O21i—Na1—O31—P321.3 (2)P2—C11—C21—N1146.5 (5)
O1W—Na1—O31—P3123.5 (2)P1—C11—C21—N11167.9 (3)
O1Wi—Na1—O31—P356.5 (2)N21—C31—N11—C510.0 (5)
O31—P3—O32—Na237.9 (2)N21—C31—N11—C21179.8 (4)
O33—P3—O32—Na2162.22 (18)C11—C21—N11—C31104.9 (5)
C12—P3—O32—Na280.2 (2)C11—C21—N11—C5175.4 (5)
O41—Na2—O32—P348.6 (2)N11—C31—N21—C410.2 (5)
O12ii—Na2—O32—P3127.9 (2)C31—N21—C41—C510.4 (6)
O2W—Na2—O32—P3151.0 (2)N21—C41—C51—N110.3 (6)
O1—Na2—O32—P349.1 (2)C31—N11—C51—C410.2 (5)
Na2ii—Na2—O32—P346.0 (3)C21—N11—C51—C41180.0 (4)
O43—P4—O41—Na2ii66.8 (3)O31—P3—C12—O2174.0 (2)
O42—P4—O41—Na2ii54.6 (3)O33—P3—C12—O260.9 (3)
C12—P4—O41—Na2ii171.3 (2)O32—P3—C12—O255.1 (3)
O43—P4—O41—Na2144.8 (3)O31—P3—C12—C2272.4 (3)
O42—P4—O41—Na293.8 (4)O33—P3—C12—C2252.8 (3)
C12—P4—O41—Na222.9 (4)O32—P3—C12—C22168.8 (3)
O41ii—Na2—O41—P4156.3 (4)O31—P3—C12—P451.2 (2)
O32—Na2—O41—P421.0 (3)O33—P3—C12—P4176.35 (19)
O12ii—Na2—O41—P4113.2 (4)O32—P3—C12—P467.6 (2)
O2W—Na2—O41—P488.0 (5)O41—P4—C12—O283.8 (3)
O1—Na2—O41—P461.1 (4)O43—P4—C12—O244.0 (3)
Na2ii—Na2—O41—P4156.3 (4)O42—P4—C12—O2156.3 (2)
O41ii—Na2—O41—Na2ii0.0O41—P4—C12—C22158.5 (3)
O32—Na2—O41—Na2ii177.26 (15)O43—P4—C12—C2273.7 (3)
O12ii—Na2—O41—Na2ii90.48 (12)O42—P4—C12—C2238.6 (3)
O2W—Na2—O41—Na2ii115.7 (4)O41—P4—C12—P338.6 (3)
O1—Na2—O41—Na2ii95.19 (12)O43—P4—C12—P3166.4 (2)
O41ii—Na2—O1—C1120.3 (3)O42—P4—C12—P381.3 (2)
O32—Na2—O1—C11156.4 (3)O2—C12—C22—N1251.3 (4)
O41—Na2—O1—C1179.6 (3)P3—C12—C22—N12167.7 (3)
O2W—Na2—O1—C11111.5 (3)P4—C12—C22—N1269.0 (4)
Na2ii—Na2—O1—C1130.1 (3)C12—C22—N12—C5277.4 (5)
Na2—O1—C11—C2155.2 (4)C12—C22—N12—C32105.1 (5)
Na2—O1—C11—P2179.96 (18)C52—N12—C32—C420.2 (5)
Na2—O1—C11—P159.0 (4)C22—N12—C32—C42178.0 (4)
O21—P2—C11—O164.1 (3)N12—C32—C42—N220.6 (5)
O22—P2—C11—O1166.3 (2)C52—N22—C42—C320.9 (5)
O23—P2—C11—O155.2 (3)C42—N22—C52—N120.8 (5)
O21—P2—C11—C21175.4 (3)C32—N12—C52—N220.4 (5)
O22—P2—C11—C2145.8 (3)C22—N12—C52—N22177.5 (4)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y+2, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O12—H12···O11iii0.851.712.561 (4)178
O23—H23···O3W0.851.792.628 (5)167
O32—H32···O22iv0.851.712.559 (4)174
O33—H33···O33v1.211.212.419 (6)180
O42—H42···O130.851.732.565 (4)169
O1—H1···O310.851.802.628 (4)163
O2—H2···O11iv0.851.872.700 (4)165
N21—H21···O22vi0.881.772.644 (5)172
N22—H22···O43vii0.881.802.669 (5)171
O1W—H1WA···O33i0.852.152.961 (5)161
O1W—H1WB···O130.851.892.739 (5)174
O2W—H2WA···O23viii0.852.223.068 (5)174
O2W—H2WB···O42ii0.852.523.305 (6)153
O3W—H3WA···O1Wi0.851.942.771 (5)166
O3W—H3WB···O43ix0.852.012.844 (5)168
C21—H21B···O41ii0.972.603.538 (6)164
C22—H22B···O33v0.972.513.370 (6)147
C31—H31···O2Wx0.932.573.483 (8)167
C52—H52···O1Wiv0.932.493.404 (6)167
C42—H42A···O13xi0.932.313.205 (7)161
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y+2, z+2; (iii) x+2, y+2, z+2; (iv) x1, y, z; (v) x, y+1, z+1; (vi) x+2, y+1, z+2; (vii) x, y+2, z+1; (viii) x+1, y+1, z+2; (ix) x, y1, z; (x) x+1, y, z; (xi) x+1, y+2, z+1.

Experimental details

Crystal data
Chemical formula[Na3(C5H9N2O7P2)2(C5H9.5N2O7P2)2(H2O)4]·2H2O
Mr1262.40
Crystal system, space groupTriclinic, P1
Temperature (K)295
a, b, c (Å)9.0690 (18), 11.309 (2), 12.594 (3)
α, β, γ (°)115.58 (3), 98.86 (3), 99.76 (3)
V3)1110.1 (6)
Z1
Radiation typeMo Kα
µ (mm1)0.46
Crystal size (mm)0.36 × 0.22 × 0.20
Data collection
DiffractometerRigaku AFC6
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.78, 0.83
No. of measured, independent and
observed [I > 2σ(I)] reflections
5236, 4366, 3797
Rint0.034
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.056, 0.170, 1.09
No. of reflections4366
No. of parameters331
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.05, 0.78

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

Selected interatomic distances (Å) top
Na1—O212.349 (3)Na2—O412.404 (3)
Na1—O312.463 (3)Na2—O12i2.485 (4)
Na1—O1W2.488 (3)Na2—O2W2.502 (5)
Na2—O41i2.363 (4)Na2—O12.554 (4)
Na2—O322.389 (4)
Na2···Na2i3.085 (4)Na1···Na25.943 (4)
Symmetry code: (i) x+1, y+2, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O12—H12···O11ii0.851.712.561 (4)178
O23—H23···O3W0.851.792.628 (5)167
O32—H32···O22iii0.851.712.559 (4)174
O33—H33···O33iv1.211.212.419 (6)180
O42—H42···O130.851.732.565 (4)169
O1—H1···O310.851.802.628 (4)163
O2—H2···O11iii0.851.872.700 (4)165
N21—H21···O22v0.881.772.644 (5)172
N22—H22···O43vi0.881.802.669 (5)171
O1W—H1WA···O33vii0.852.152.961 (5)161
O1W—H1WB···O130.851.892.739 (5)174
O2W—H2WA···O23viii0.852.223.068 (5)174
O2W—H2WB···O42i0.852.523.305 (6)153
O3W—H3WA···O1Wvii0.851.942.771 (5)166
O3W—H3WB···O43ix0.852.012.844 (5)168
C21—H21B···O41i0.972.603.538 (6)164
C22—H22B···O33iv0.972.513.370 (6)147
C31—H31···O2Wx0.932.573.483 (8)167
C52—H52···O1Wiii0.932.493.404 (6)167
C42—H42A···O13xi0.932.313.205 (7)161
Symmetry codes: (i) x+1, y+2, z+2; (ii) x+2, y+2, z+2; (iii) x1, y, z; (iv) x, y+1, z+1; (v) x+2, y+1, z+2; (vi) x, y+2, z+1; (vii) x+1, y+1, z+1; (viii) x+1, y+1, z+2; (ix) x, y1, z; (x) x+1, y, z; (xi) x+1, y+2, z+1.
Table 2. Charge-balance summary in zoledronate complexes. top
CSD REFCODEReferenceMnxmypz
VIMXEV(a)Co3223
VIMXIZ(a)Ni3223
VIMXOF(a)Co1221
VIMXUL(a)Ni1221
DOGYEE(b)Cu1221
DOGYII(b)Cu1221
DOGYUU(b)Cu3223
——(c)Zn1221
——(d)Zn1221
(I)(e)K1111
DOGYOO(b)Cu322221
(II)(f)Na312120.5
(a): Cao et al. (2007) (b): Cao et al. (2008) (c): Freire & Vega (2009a) (d): Freire & Vega (2009b), (e): Freire et al. (2010); (f): this work.
 

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