[Zn3(PO4)2(H2O)0.8(NH3)1.2]

Stojanović, J.; Đorđević, T.; Karanović, L.

doi:10.1107/S0108270110014885

Buy article online - an online subscription or single-article purchase is required to access this article.

[Zn₃(PO₄)₂(H₂O)_0.8(NH₃)_1.2]

J. Stojanović, T. Đorđević and L. Karanović

The structure of the title compound, ammineaquadi-μ₅-phosphato-trizinc(II), [Zn₃(PO₄)₂(H₂O)_0.8(NH₃)_1.2], consists of two parts: (i) PO₄ and ZnO₄ vertex-sharing tetrahedra arranged in layers parallel to (100) and (ii) ZnO₂(N/O)₂ tetrahedra located between the layers. Elemental analysis establishes the ammine-to-water ratio as 3:2. ZnO₂(N/O)₂ tetrahedra are located at special position 4e (site symmetry 2) in C2/c. The two O atoms of ZnO₂(N/O)₂ are bonded to neighbouring P atoms, forming two Zn—O—P linkages and connecting ZnO₂(N/O)₂ tetrahedra with two adjacent bc plane layers. A noteworthy feature of the structure is the presence of NH₃ and H₂O at the same crystallographic position and, consequently, qualitative changes in the pattern of hydrogen bonding and weaker N/O—H

O electrostatic interactions, as compared to two closely related structures.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110014885/fa3219sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S0108270110014885/fa3219Isup2.hkl Contains datablock I

Comment top

This work forms part of ongoing research on heteropolyhedral framework structures of divalent metal phosphates and arsenates with potentially interesting structural, physical and chemical properties (Đorđević et al., 2008; Đorđević & Karanović, 2008; Stojanović et al., 2008; Weil et al., 2009). The aim of the current study was the synthesis and characterization of new compounds in the CdO–ZnO–P₂O₅–NH₃–H₂O system. Using the low-temperature hydrothermal method, single crystals of ammineaquadi-µ₅-phosphato-trizinc(II), [Zn₃(PO₄)₂(H₂O)_0.8(NH₃)_1.2], were synthesized.

The crystal structure of [Zn₃(PO₄)₂(H₂O)_0.8(NH₃)_1.2] is constructed from corrugate layers parallel to the bc plane, containing slightly distorted vertex-sharing P1O₄ and Zn2O₄ tetrahedra. The space between these layers is bounded by x ≈ 0.39 and x ≈ 0.61 (Fig. 1).

Considering the network of Zn2—O and P1—O bonds, the layers can be described as being composed of six- and eight-membered rings formed by congeners of Zn2, O and P1, in which O can be O2, O3 or O4 (Figs. 2, 3). Each eight-membered –Zn2/O/P1– ring is formed by alternating corner-sharing pairs of Zn2O₄ and P1O₄ tetrahedra, while one P1O₄and two symmetry-related Zn2O₄ tetrahedra are connected at shared corners to form each six-membered Zn2—O2—P1—O4—Zn2^v—O4ⁱⁱⁱ– ring (symmetry codes from Fig. 3). The eight-membered rings are fused into chains parallel to [010]. These chains are interconnected by chains of six-membered rings, extending in the same direction. Two O atoms (O2, O3ⁱⁱ) from the Zn2O₄ tetrahedron form Zn—O—P bridges, while two symmetry equivalents of three-coordinate O4, which complete the tetrahedron at Zn2, bridge two Zn2 and one P1 congener each. As a result, O4 mediates another set of linkages, namely Zn2^v—O4—Zn2^viii and P1—O4—Zn2^v (symmetry codesf rom Fig. 3). Every Zn—O—Zn bridge in the structure is centred on a three-coordinate O atom. The trigonal coordination of the oxygen bridges is only common in structures with divalent tetrahedral atoms (Bu et al., 1996). The third bond to O in this structure is to P1. In this way every Zn2 is connected through O to six neighbouring tetrahedral cations (four equivalents of P1 and two of Zn2); and every P1 is linked to five Zn (four Zn2 and one Zn1) (Fig. 3).

The Zn2—O distances are, as expected, shorter for O2 and O3 than for the three-coordinate oxygens O4 (Table 1). The average Zn2—O bond length is 1.95 (2) Å. The Zn2O₄ tetrahedron, having O—Zn2—O angles ranging between 102.62 (4) and 121.60 (6)°, is somewhat irregular.

The space between layers is occupied by Zn1O₂(N1/O5)₂ tetrahedra. Each Zn1 atom, located on a twofold axis (position 4e), is tetrahedrally coordinated by two bridging O atoms [two symmetry equivalents O1,O1ⁱ (i): -x, y, -z+3/2] and by two terminal ligands N1/O5 – disordered ammine and water molecules in the ratio 3:2 as established by elemental analysis. O1 and O1ⁱ are bonded to neighbouring P1 atoms forming two Zn1—O1—P1 linkages, thus connecting the Zn1O₂(N1/O5)₂ tetrahedra with the principal bc plane layers. The coordination about Zn1 is considerably distorted tetrahedral, with bond angles varying from 97.3 (1) to 117.4 (1)°. P1 exhibits nearly ideal tetrahedral coordination [mean P1—O 1.54 (1) Å, O—P1—O angles from 106.0 (1) to 112.6 (1)°] with the longest distance P1—O4 involving three-coordinate oxygen (Table 1). The results of bond-valence calculations (Wills, 2009) confirm the presence of divalent zinc and pentavalent phosphorus, [calculated values are Σν_ij(Zn1) = 2.02, Σν_ij(Pl) = 4.97 and Σν_ij(Zn2) = 2.09 v.u.]. In addition to the Zn1—O1—P1 linkages, N1/O5—H···O hydrogen bonds and other electrostatic contacts provide a connection between the ammine/water sites and the main bc plane layers (Table 2).

From the crystallographic and elemental analyses, the ammine and water occupy the same crystallographic site in the ratio 3:2. The NH₃ molecule is pyramidal and the observed H—N—H angles are in the range 105 (3)–111 (3)°. It is evident that water at this site can have any of three orientations, and it is not possible to establish a model distinguishing among the possibilities, which in any event should be equally probable.

The title compound is isostructural with two compounds – one arsenate Be₃(AsO₄)₂.2H₂O (Harrison et al.,1994) and one phosphate Be₃(PO₄)₂.2H₂O (Gier et al., 1999). The incorporation of a larger cation in the structure (As or Zn instead of P or Be, respectively) increases the lengths of the unit-cell axes and decreases β (Table 3). Also, the average M—O—X (M = Be, Zn; X = As, P) bond angle of 126.1° in [Zn(NH₃)_1.2(H₂O)_0.8(ZnPO₄)₂] is 0.9 and 4.7° less than the corresponding M—O—X in Be₃(AsO₄)₂.2H₂O and Be₃(PO₄)₂.2H₂O, respectively. Differences in the structures are presumably related to the polyhedral dimensions and different networks of N/O—H···O hydrogen bonds and electrostatic contacts. In the isostructural Be₃(AsO₄)₂.2H₂O and Be₃(PO₄)₂.2H₂O compounds, there are two water molecules available for hydrogen bonding. It was reported that only one H atom is involved in hydrogen bonding, but from our examination of the structures it appears that in both structures all H atoms participate in hydrogen bonding. Two H atoms in Be₃(AsO₄)₂.2H₂O act similarly to H1 and H2 in [Zn(NH₃)_1.2(H₂O)_0.8(ZnPO₄)₂], while in Be₃(PO₄)₂.2H₂O they are similar to H1 and H3. In all three structures one of the (N/O)—H of each water or water/ammine site is hydrogen bonded to a M—O—X bridge and forms the strongest hydrogen bond between MO₂(N/O)₂(M = Be, Zn) tetrahedra and the bc plane layers. The second O—H or (N/O)—H of each such site form weak hydrogen bonds in the isostructural Be compounds, but in the title compound the interaction distances have expanded to the point that these can be called simply electrostatic contacts, to neighbouring M1O₂(N1/O5)₂tetrahedra. The D—A distances are in the ranges 2.72–3.18, 2.71–3.16 and 2.977 (3)–3.232 (3) Å for Be₃(PO₄)₂.2H₂O, Be₃(AsO₄)₂.2H₂O and [Zn(NH₃)_1.2(H₂O)_0.8(ZnPO₄)₂], respectively. It appears that the influence of As substitution for P on the D···A distances is weak; but the incorporation of Zn instead of the smaller Be causes a significant increase in the D···A distances.

Related literature top

For related literature, see: Bu et al. (1996); Gier et al. (1999); Harrison et al. (1994); Stojanović et al. (2008); Weil et al. (2009); Wills (2009); Đorđević & Karanović (2008); Đorđević, Šutović, Stojanović & Karanović (2008).

Experimental top

[Zn₃(PO₄)₂(H₂O)_0.8(NH₃)_1.2] was synthesized hydrothermally from a mixture of CdO, (NH₄)₂HPO₄(Loba Chemie 10310 >99%) and 5ZnO.2CO₃.4H₂O (Alfa Products, >99%). The solid mixture was transferred into a Teflon vessel which was filled to approximately 70% of its inner volume with distilled water. The pH of the mixture was 7. The vessel was enclosed in a stainless steel autoclave, which was heated under autogenous pressure from room temperature to 473 K (4 h), held at this temperature for 72 h, and finally permitted to cool to room temperature over a period of 96 h. The resulting products were filtered off, washed thoroughly with distilled water and dried in the air at room temperature. The title compound crystallized as regular, colourless, plate-like and lath-like crystals (yield 50%) up to 200 µm in length. Qualitative chemical analyses were performed using a JEOL JSM-6400LV scanning electron microscope connected with a LINK energy-dispersive X-ray analysis (EDX) unit. The presence of Zn and P was confirmed in all samples studied. Elemental analysis (H, N) was performed by the standard micromethods using an ELEMENTAR Vario EL III C.H.N.S=0 analyzer.

Computing details top

Data collection: COLLECT (Nonius, 2002); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski et al., 2003); program(s) used to solve structure: SIR97 (Altomare et al., 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008), WinGX (Farrugia, 1999); molecular graphics: ATOMS (Dowty, 2000); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Side view of the boundaries of layers of P1O₄ and Zn2O₄ vertex-sharing tetrahedra with the volume occupied by Zn1O₂(N1/O5)₂ tetrahedra. The H···A contacts are shown as dashed lines and H atoms as small spheres.
	Fig. 2. Projection of a single polyhedral layer showing Zn2—O—P1 rings generated from the vertex linking of P1O₄ (grey) and Zn2O₄ (black) tetrahedra.
	Fig. 3. Perspective view of neighbouring P1O₄ tetrahedra in the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented by circles of arbitrary radius. Symmetry codes: (i) -x, y, -z+3/2; (ii) -x+1/2, -y+1/2; -z+2; (iii) -x+1/2, y+1/2, -z+3/2; (iv) x, y+1, z; (v) -x+1/2, y-1/2, -z+3/2; (vi) x, -y, z-1/2; (vii) -x+1/2, -y-1/2, -z+2; (viii) x, y-1, z; (ix) x, -y, z+1/2; (x) x, -y+1, z-1/2; (xi) -x+1/2, y+3/2, -z+3/2.

ammineaquadi-µ₅-phosphato-trizinc(II) top

Crystal data top

[Zn₃(PO₄)₂(H₂O)_0.8(NH₃)_1.2]	F(000) = 816.1
M_r = 420.90	D_x = 3.117 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1792 reflections
a = 16.932 (3) Å	θ = 0.4–32.6°
b = 5.0171 (10) Å	µ = 8.34 mm⁻¹
c = 10.564 (2) Å	T = 294 K
β = 91.27 (3)°	Plate-like, colourless
V = 897.2 (3) Å³	0.15 × 0.13 × 0.08 mm
Z = 4

Data collection top

Nonius KappaCCD diffractomer	913 independent reflections
Radiation source: fine-focus sealed X-ray tube	884 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.011
ϕ + ω scans	θ_max = 26.4°, θ_min = 3.9°
Absorption correction: multi-scan (Otwinowski & Minor, 1997)	h = −20→20
T_min = 0.298, T_max = 0.513	k = −6→6
1715 measured reflections	l = −13→13

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.014	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.035	w = 1/[σ^2^(F_o^2^) + (0.0138P)^2^ + 1.9417P] where P = (F_o^2^ + 2F_c^2^)/3
S = 1.13	(Δ/σ)_max = 0.001
913 reflections	Δρ_max = 0.34 e Å⁻³
79 parameters	Δρ_min = −0.31 e Å⁻³
5 restraints	Extinction correction: SHELXL, Fc^*^=kFc[1+0.001xFc^2^λ^3^/sin(2θ)]^-1/4^
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0025 (2)

Crystal data top

[Zn₃(PO₄)₂(H₂O)_0.8(NH₃)_1.2]	V = 897.2 (3) Å³
M_r = 420.90	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 16.932 (3) Å	µ = 8.34 mm⁻¹
b = 5.0171 (10) Å	T = 294 K
c = 10.564 (2) Å	0.15 × 0.13 × 0.08 mm
β = 91.27 (3)°

Data collection top

Nonius KappaCCD diffractomer	913 independent reflections
Absorption correction: multi-scan (Otwinowski & Minor, 1997)	884 reflections with I > 2σ(I)
T_min = 0.298, T_max = 0.513	R_int = 0.011
1715 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.014	5 restraints
wR(F²) = 0.035	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	Δρ_max = 0.34 e Å⁻³
913 reflections	Δρ_min = −0.31 e Å⁻³
79 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.

Refinement. Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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	Occ. (<1)
Zn1	0.0000	0.23458 (7)	0.7500	0.01616 (11)
Zn2	0.252843 (13)	0.54824 (4)	0.85789 (2)	0.01090 (10)
P1	0.14805 (3)	0.03247 (10)	0.89402 (4)	0.00887 (13)
O1	0.06423 (9)	−0.0209 (3)	0.84674 (14)	0.0176 (3)
O2	0.16414 (8)	0.3308 (3)	0.89628 (14)	0.0183 (3)
O3	0.16181 (8)	−0.0984 (3)	1.02338 (13)	0.0159 (3)
O4	0.20795 (9)	−0.1036 (3)	0.80233 (13)	0.0151 (3)
N1	−0.05747 (12)	0.5015 (4)	0.85859 (19)	0.0299 (4)	0.60
O5	−0.05747 (12)	0.5015 (4)	0.85859 (19)	0.0299 (4)	0.40
H1	−0.0874 (17)	0.425 (6)	0.915 (2)	0.036*	0.86667
H2	−0.0210 (17)	0.616 (6)	0.897 (3)	0.036*	0.86667
H3	−0.0906 (17)	0.590 (6)	0.808 (3)	0.036*	0.86667

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.01499 (18)	0.01310 (18)	0.02014 (18)	0.000	−0.00559 (13)	0.000
Zn2	0.01294 (14)	0.00963 (14)	0.01010 (13)	−0.00058 (8)	−0.00076 (8)	0.00024 (8)
P1	0.0090 (2)	0.0082 (2)	0.0094 (2)	−0.00024 (18)	−0.00046 (17)	0.00043 (17)
O1	0.0130 (7)	0.0159 (7)	0.0237 (8)	−0.0027 (6)	−0.0077 (6)	0.0055 (6)
O2	0.0171 (7)	0.0090 (7)	0.0289 (8)	−0.0021 (6)	0.0056 (6)	−0.0015 (6)
O3	0.0153 (7)	0.0221 (8)	0.0101 (6)	−0.0046 (6)	−0.0030 (5)	0.0047 (6)
O4	0.0209 (7)	0.0121 (7)	0.0124 (6)	0.0058 (6)	0.0062 (5)	0.0034 (5)
N1	0.0294 (11)	0.0319 (11)	0.0287 (10)	−0.0002 (9)	0.0055 (8)	−0.0025 (9)
O5	0.0294 (11)	0.0319 (11)	0.0287 (10)	−0.0002 (9)	0.0055 (8)	−0.0025 (9)

Geometric parameters (Å, º) top

Zn1—O1	1.9548 (15)	O2—O4ⁱⁱⁱ	3.102 (2)
Zn1—N1	2.026 (2)	O2—O3ⁱⁱⁱ	3.163 (2)
Zn2—O2	1.9073 (15)	O2—N1^viii	3.299 (3)
Zn2—O3ⁱ	1.9091 (15)	O2—N1^vi	3.321 (3)
Zn2—O4ⁱⁱ	1.9839 (14)	O2—O3ⁱ	3.331 (2)
Zn2—O4ⁱⁱⁱ	1.9883 (15)	O2—Zn2^v	3.3709 (16)
Zn2—O3ⁱⁱⁱ	2.9487 (16)	O3—Zn2ⁱ	1.9091 (15)
Zn2—P1ⁱⁱⁱ	3.0375 (7)	O3—O4	2.479 (2)
Zn2—P1ⁱ	3.1070 (10)	O3—Zn2^iv	2.9487 (16)
Zn2—P1	3.1654 (7)	O3—N1^ix	2.977 (3)
Zn2—P1ⁱⁱ	3.1785 (10)	O3—O2^iv	3.163 (2)
Zn2—O2ⁱⁱ	3.3709 (16)	O3—O4^x	3.197 (2)
Zn2—O4	3.4056 (16)	O3—O4^xi	3.210 (2)
Zn2—O2ⁱ	3.4892 (17)	O3—O2ⁱ	3.331 (2)
P1—O1	1.5178 (15)	O3—O3^xi	3.397 (3)
P1—O2	1.5213 (15)	O4—Zn2^v	1.9839 (14)
P1—O3	1.5294 (14)	O4—Zn2^iv	1.9883 (15)
P1—O4	1.5738 (15)	O4—O2^v	3.066 (2)
P1—Zn2^iv	3.0375 (7)	O4—O4ⁱⁱ	3.1005 (17)
P1—Zn2ⁱ	3.1071 (10)	O4—O2^iv	3.102 (2)
P1—Zn2^v	3.1785 (10)	O4—O3^xii	3.197 (2)
O1—O2	2.492 (2)	O4—O3^xi	3.210 (2)
O1—O3	2.495 (2)	N1—O3^ix	2.977 (3)
O1—O4	2.523 (2)	N1—O5^vi	3.041 (4)
O1—O1^vi	2.952 (3)	N1—O1ⁱⁱⁱ	3.165 (3)
O1—N1^iv	3.165 (3)	N1—O1^xiii	3.232 (3)
O1—N1^vii	3.232 (3)	N1—O2^viii	3.299 (3)
O1—N1	3.338 (3)	N1—O2^vi	3.321 (3)
O1—N1^vi	3.403 (3)	N1—O1^vi	3.403 (3)
O2—O4	2.514 (2)	N1—H1	0.882 (14)
O2—O3	2.539 (2)	N1—H2	0.932 (19)
O2—O4ⁱⁱ	3.066 (2)	N1—H3	0.889 (14)

O1^vi—Zn1—O1	98.05 (9)	P1—O2—Zn1	71.91 (6)
O1^vi—Zn1—N1	117.44 (8)	Zn2—O2—Zn1	131.76 (7)
O1—Zn1—N1	113.95 (8)	O4—O2—Zn1	86.51 (6)
O1^vi—Zn1—O5^vi	113.95 (8)	O3—O2—Zn1	95.99 (6)
O1—Zn1—O5^vi	117.44 (8)	O4ⁱⁱ—O2—Zn1	107.82 (5)
N1—Zn1—O5^vi	97.26 (13)	O4ⁱⁱⁱ—O2—Zn1	101.28 (5)
O1^vi—Zn1—N1^vi	113.95 (8)	O3ⁱⁱⁱ—O2—Zn1	108.90 (5)
O1—Zn1—N1^vi	117.44 (8)	P1—O2—O5^viii	99.34 (8)
N1—Zn1—N1^vi	97.26 (13)	Zn2—O2—O5^viii	117.93 (7)
O5^vi—Zn1—N1^vi	0.00 (9)	O1—O2—O5^viii	87.97 (7)
O1^vi—Zn1—P1^vi	24.10 (4)	O4—O2—O5^viii	134.63 (7)
O1—Zn1—P1^vi	118.71 (5)	O3—O2—O5^viii	77.64 (6)
N1—Zn1—P1^vi	95.83 (6)	O4ⁱⁱ—O2—O5^viii	156.49 (7)
O5^vi—Zn1—P1^vi	109.53 (6)	O4ⁱⁱⁱ—O2—O5^viii	99.02 (6)
N1^vi—Zn1—P1^vi	109.53 (6)	O3ⁱⁱⁱ—O2—O5^viii	54.81 (5)
O1^vi—Zn1—P1	118.71 (5)	Zn1—O2—O5^viii	86.13 (5)
O1—Zn1—P1	24.10 (4)	P1—O2—N1^viii	99.34 (8)
N1—Zn1—P1	109.53 (6)	Zn2—O2—N1^viii	117.93 (7)
O5^vi—Zn1—P1	95.83 (6)	O1—O2—N1^viii	87.97 (7)
N1^vi—Zn1—P1	95.83 (6)	O4—O2—N1^viii	134.63 (7)
P1^vi—Zn1—P1	141.50 (3)	O3—O2—N1^viii	77.64 (6)
O1^vi—Zn1—O2	145.29 (5)	O4ⁱⁱ—O2—N1^viii	156.49 (7)
O1—Zn1—O2	51.44 (5)	O4ⁱⁱⁱ—O2—N1^viii	99.02 (6)
N1—Zn1—O2	92.86 (7)	O3ⁱⁱⁱ—O2—N1^viii	54.81 (5)
O5^vi—Zn1—O2	75.51 (7)	Zn1—O2—N1^viii	86.13 (5)
N1^vi—Zn1—O2	75.51 (7)	P1—O2—O5^vi	98.46 (8)
P1^vi—Zn1—O2	169.24 (3)	Zn2—O2—O5^vi	95.55 (7)
P1—Zn1—O2	28.05 (3)	O1—O2—O5^vi	70.00 (6)
O1^vi—Zn1—O2^vi	51.44 (5)	O4—O2—O5^vi	93.64 (7)
O1—Zn1—O2^vi	145.29 (5)	O3—O2—O5^vi	129.28 (7)
N1—Zn1—O2^vi	75.51 (7)	O4ⁱⁱ—O2—O5^vi	78.30 (6)
O5^vi—Zn1—O2^vi	92.86 (7)	O4ⁱⁱⁱ—O2—O5^vi	68.55 (6)
N1^vi—Zn1—O2^vi	92.86 (7)	O3ⁱⁱⁱ—O2—O5^vi	95.68 (6)
P1^vi—Zn1—O2^vi	28.05 (3)	O5^viii—O2—O5^vi	105.86 (7)
P1—Zn1—O2^vi	169.24 (3)	N1^viii—O2—O5^vi	105.86 (7)
O2—Zn1—O2^vi	162.58 (6)	P1—O2—N1^vi	98.46 (8)
O1^vi—Zn1—O3^ix	78.93 (5)	Zn2—O2—N1^vi	95.55 (7)
O1—Zn1—O3^ix	87.28 (5)	O1—O2—N1^vi	70.00 (6)
N1—Zn1—O3^ix	52.46 (7)	O4—O2—N1^vi	93.64 (7)
O5^vi—Zn1—O3^ix	148.29 (7)	O3—O2—N1^vi	129.28 (7)
N1^vi—Zn1—O3^ix	148.29 (7)	O4ⁱⁱ—O2—N1^vi	78.30 (6)
P1^vi—Zn1—O3^ix	69.87 (3)	O4ⁱⁱⁱ—O2—N1^vi	68.55 (6)
P1—Zn1—O3^ix	102.93 (3)	O3ⁱⁱⁱ—O2—N1^vi	95.68 (6)
O2—Zn1—O3^ix	111.13 (4)	O5^viii—O2—N1^vi	105.86 (7)
O2^vi—Zn1—O3^ix	72.23 (4)	N1^viii—O2—N1^vi	105.86 (7)
O1^vi—Zn1—O3^xii	87.28 (5)	P1—O2—O3ⁱ	123.89 (8)
O1—Zn1—O3^xii	78.93 (5)	O1—O2—O3ⁱ	158.67 (7)
N1—Zn1—O3^xii	148.29 (7)	O4—O2—O3ⁱ	100.54 (6)
O5^vi—Zn1—O3^xii	52.46 (7)	O3—O2—O3ⁱ	103.37 (6)
N1^vi—Zn1—O3^xii	52.46 (7)	O4ⁱⁱ—O2—O3ⁱ	59.79 (5)
P1^vi—Zn1—O3^xii	102.93 (3)	O4ⁱⁱⁱ—O2—O3ⁱ	59.75 (5)
P1—Zn1—O3^xii	69.87 (3)	O3ⁱⁱⁱ—O2—O3ⁱ	63.02 (5)
O2—Zn1—O3^xii	72.23 (4)	Zn1—O2—O3ⁱ	160.34 (6)
O2^vi—Zn1—O3^xii	111.13 (4)	O5^viii—O2—O3ⁱ	101.18 (6)
O3^ix—Zn1—O3^xii	158.96 (5)	N1^viii—O2—O3ⁱ	101.18 (6)
O1^vi—Zn1—O4^vi	32.69 (5)	O5^vi—O2—O3ⁱ	124.38 (6)
O1—Zn1—O4^vi	106.04 (5)	N1^vi—O2—O3ⁱ	124.38 (6)
N1—Zn1—O4^vi	85.71 (7)	P1—O2—Zn2^v	69.60 (6)
O5^vi—Zn1—O4^vi	130.14 (7)	Zn2—O2—Zn2^v	74.15 (5)
N1^vi—Zn1—O4^vi	130.14 (7)	O1—O2—Zn2^v	80.10 (6)
P1^vi—Zn1—O4^vi	21.82 (2)	O3—O2—Zn2^v	94.37 (6)
P1—Zn1—O4^vi	130.10 (3)	O4ⁱⁱⁱ—O2—Zn2^v	91.31 (5)
O2—Zn1—O4^vi	154.31 (4)	O3ⁱⁱⁱ—O2—Zn2^v	136.73 (5)
O2^vi—Zn1—O4^vi	39.59 (4)	Zn1—O2—Zn2^v	85.68 (4)
O3^ix—Zn1—O4^vi	49.13 (3)	O5^viii—O2—Zn2^v	167.89 (6)
O3^xii—Zn1—O4^vi	119.79 (3)	N1^viii—O2—Zn2^v	167.89 (6)
O1^vi—Zn1—O4	106.04 (5)	O5^vi—O2—Zn2^v	72.03 (5)
O1—Zn1—O4	32.69 (5)	N1^vi—O2—Zn2^v	72.03 (5)
N1—Zn1—O4	130.14 (7)	O3ⁱ—O2—Zn2^v	89.44 (5)
O5^vi—Zn1—O4	85.71 (7)	P1—O3—Zn2ⁱ	128.94 (9)
N1^vi—Zn1—O4	85.71 (7)	Zn2ⁱ—O3—O4	111.75 (7)
P1^vi—Zn1—O4	130.10 (3)	Zn2ⁱ—O3—O1	161.76 (9)
P1—Zn1—O4	21.82 (2)	O4—O3—O1	60.95 (6)
O2—Zn1—O4	39.59 (4)	Zn2ⁱ—O3—O2	102.43 (7)
O2^vi—Zn1—O4	154.31 (4)	O4—O3—O2	60.11 (6)
O3^ix—Zn1—O4	119.79 (3)	O1—O3—O2	59.34 (6)
O3^xii—Zn1—O4	49.13 (3)	P1—O3—Zn2^iv	78.44 (6)
O4^vi—Zn1—O4	128.93 (5)	Zn2ⁱ—O3—Zn2^iv	94.06 (6)
O1^vi—Zn1—O5^iv	53.70 (6)	O1—O3—Zn2^iv	89.79 (6)
O1—Zn1—O5^iv	51.69 (6)	O2—O3—Zn2^iv	100.48 (6)
N1—Zn1—O5^iv	108.91 (8)	P1—O3—O5^ix	125.87 (9)
O5^vi—Zn1—O5^iv	153.83 (6)	Zn2ⁱ—O3—O5^ix	105.19 (7)
N1^vi—Zn1—O5^iv	153.83 (6)	O4—O3—O5^ix	126.14 (8)
P1^vi—Zn1—O5^iv	68.66 (3)	O1—O3—O5^ix	91.71 (7)
P1—Zn1—O5^iv	75.79 (3)	O2—O3—O5^ix	144.50 (8)
O2—Zn1—O5^iv	102.50 (4)	Zn2^iv—O3—O5^ix	99.37 (6)
O2^vi—Zn1—O5^iv	93.64 (4)	P1—O3—N1^ix	125.87 (9)
O3^ix—Zn1—O5^iv	57.29 (4)	Zn2ⁱ—O3—N1^ix	105.19 (7)
O3^xii—Zn1—O5^iv	101.71 (4)	O4—O3—N1^ix	126.14 (8)
O4^vi—Zn1—O5^iv	54.44 (4)	O1—O3—N1^ix	91.71 (7)
O4—Zn1—O5^iv	77.57 (4)	O2—O3—N1^ix	144.50 (8)
O2—Zn2—O3ⁱ	121.60 (6)	Zn2^iv—O3—N1^ix	99.37 (6)
O2—Zn2—O4ⁱⁱ	103.99 (7)	P1—O3—O2^iv	90.72 (7)
O3ⁱ—Zn2—O4ⁱⁱ	110.39 (6)	Zn2ⁱ—O3—O2^iv	112.45 (7)
O2—Zn2—O4ⁱⁱⁱ	105.52 (6)	O4—O3—O2^iv	65.39 (5)
O3ⁱ—Zn2—O4ⁱⁱⁱ	110.91 (6)	O1—O3—O2^iv	80.67 (6)
O4ⁱⁱ—Zn2—O4ⁱⁱⁱ	102.62 (4)	O2—O3—O2^iv	122.88 (7)
O2—Zn2—O3ⁱⁱⁱ	78.07 (6)	O5^ix—O3—O2^iv	64.91 (6)
O3ⁱ—Zn2—O3ⁱⁱⁱ	85.94 (6)	N1^ix—O3—O2^iv	64.91 (6)
O4ⁱⁱ—Zn2—O3ⁱⁱⁱ	157.81 (5)	P1—O3—O4^x	135.79 (9)
O4ⁱⁱⁱ—Zn2—O3ⁱⁱⁱ	56.32 (5)	O4—O3—O4^x	142.75 (7)
O2—Zn2—P1ⁱⁱⁱ	88.04 (5)	O1—O3—O4^x	141.64 (8)
O3ⁱ—Zn2—P1ⁱⁱⁱ	104.34 (5)	O2—O3—O4^x	102.25 (7)
O4ⁱⁱ—Zn2—P1ⁱⁱⁱ	128.45 (5)	Zn2^iv—O3—O4^x	128.09 (6)
O4ⁱⁱⁱ—Zn2—P1ⁱⁱⁱ	27.61 (4)	O5^ix—O3—O4^x	87.96 (6)
O3ⁱⁱⁱ—Zn2—P1ⁱⁱⁱ	29.56 (3)	N1^ix—O3—O4^x	87.96 (6)
O2—Zn2—P1ⁱ	99.16 (5)	O2^iv—O3—O4^x	132.32 (6)
O3ⁱ—Zn2—P1ⁱ	22.51 (4)	P1—O3—O4^xi	143.27 (8)
O4ⁱⁱ—Zn2—P1ⁱ	119.01 (5)	O4—O3—O4^xi	107.97 (6)
O4ⁱⁱⁱ—Zn2—P1ⁱ	124.00 (4)	O1—O3—O4^xi	159.46 (8)
O3ⁱⁱⁱ—Zn2—P1ⁱ	81.83 (3)	O2—O3—O4^xi	132.83 (7)
P1ⁱⁱⁱ—Zn2—P1ⁱ	107.715 (18)	Zn2^iv—O3—O4^xi	72.46 (4)
O2—Zn2—P1	20.04 (4)	O5^ix—O3—O4^xi	81.37 (6)
O3ⁱ—Zn2—P1	116.54 (5)	N1^ix—O3—O4^xi	81.37 (6)
O4ⁱⁱ—Zn2—P1	89.31 (5)	O2^iv—O3—O4^xi	78.88 (5)
O4ⁱⁱⁱ—Zn2—P1	122.83 (5)	O4^x—O3—O4^xi	57.88 (4)
O3ⁱⁱⁱ—Zn2—P1	96.78 (4)	P1—O3—O2ⁱ	99.84 (7)
P1ⁱⁱⁱ—Zn2—P1	107.95 (2)	O4—O3—O2ⁱ	87.06 (6)
P1ⁱ—Zn2—P1	94.901 (19)	O1—O3—O2ⁱ	134.03 (7)
O2—Zn2—P1ⁱⁱ	126.63 (5)	O2—O3—O2ⁱ	76.63 (6)
O3ⁱ—Zn2—P1ⁱⁱ	98.47 (5)	Zn2^iv—O3—O2ⁱ	85.54 (5)
O4ⁱⁱ—Zn2—P1ⁱⁱ	23.54 (4)	O5^ix—O3—O2ⁱ	134.18 (7)
O4ⁱⁱⁱ—Zn2—P1ⁱⁱ	88.87 (4)	N1^ix—O3—O2ⁱ	134.18 (7)
O3ⁱⁱⁱ—Zn2—P1ⁱⁱ	143.52 (3)	O2^iv—O3—O2ⁱ	116.98 (5)
P1ⁱⁱⁱ—Zn2—P1ⁱⁱ	116.48 (2)	O4^x—O3—O2ⁱ	55.99 (5)
P1ⁱ—Zn2—P1ⁱⁱ	114.69 (2)	O4^xi—O3—O2ⁱ	56.57 (5)
P1—Zn2—P1ⁱⁱ	112.86 (2)	P1—O3—O3^xi	100.33 (8)
O2—Zn2—O2ⁱⁱ	138.96 (4)	Zn2ⁱ—O3—O3^xi	59.97 (5)
O3ⁱ—Zn2—O2ⁱⁱ	98.33 (5)	O4—O3—O3^xi	64.01 (6)
O4ⁱⁱ—Zn2—O2ⁱⁱ	47.82 (5)	O1—O3—O3^xi	122.05 (8)
O4ⁱⁱⁱ—Zn2—O2ⁱⁱ	63.83 (5)	O2—O3—O3^xi	106.19 (7)
O3ⁱⁱⁱ—Zn2—O2ⁱⁱ	116.89 (4)	O5^ix—O3—O3^xi	106.77 (8)
P1ⁱⁱⁱ—Zn2—O2ⁱⁱ	91.08 (3)	N1^ix—O3—O3^xi	106.77 (8)
P1ⁱ—Zn2—O2ⁱⁱ	119.98 (3)	O2^iv—O3—O3^xi	60.91 (5)
P1—Zn2—O2ⁱⁱ	133.21 (3)	O4^x—O3—O3^xi	94.49 (6)
P1ⁱⁱ—Zn2—O2ⁱⁱ	26.66 (3)	O2ⁱ—O3—O3^xi	56.08 (5)
O2—Zn2—Zn2^v	73.08 (5)	P1—O3—O5^viii	83.65 (7)
O3ⁱ—Zn2—Zn2^v	123.32 (5)	Zn2ⁱ—O3—O5^viii	91.83 (6)
O4ⁱⁱ—Zn2—Zn2^v	31.47 (4)	O4—O3—O5^viii	119.20 (7)
O4ⁱⁱⁱ—Zn2—Zn2^v	116.53 (5)	O1—O3—O5^viii	79.23 (6)
O3ⁱⁱⁱ—Zn2—Zn2^v	146.75 (3)	O2—O3—O5^viii	60.38 (6)
P1ⁱⁱⁱ—Zn2—Zn2^v	131.95 (2)	Zn2^iv—O3—O5^viii	160.80 (6)
P1ⁱ—Zn2—Zn2^v	118.528 (16)	O5^ix—O3—O5^viii	96.68 (7)
P1—Zn2—Zn2^v	57.89 (2)	N1^ix—O3—O5^viii	96.68 (7)
P1ⁱⁱ—Zn2—Zn2^v	54.980 (14)	O2^iv—O3—O5^viii	152.20 (6)
O2ⁱⁱ—Zn2—Zn2^v	77.39 (3)	O4^x—O3—O5^viii	62.76 (5)
O2—Zn2—Zn2ⁱⁱ	123.75 (5)	O4^xi—O3—O5^viii	120.64 (6)
O3ⁱ—Zn2—Zn2ⁱⁱ	110.73 (5)	O2ⁱ—O3—O5^viii	90.81 (6)
O4ⁱⁱ—Zn2—Zn2ⁱⁱ	73.47 (5)	O3^xi—O3—O5^viii	146.89 (8)
O4ⁱⁱⁱ—Zn2—Zn2ⁱⁱ	31.39 (4)	P1—O3—N1^viii	83.65 (7)
O3ⁱⁱⁱ—Zn2—Zn2ⁱⁱ	86.93 (3)	Zn2ⁱ—O3—N1^viii	91.83 (6)
P1ⁱⁱⁱ—Zn2—Zn2ⁱⁱ	58.98 (2)	O4—O3—N1^viii	119.20 (7)
P1ⁱ—Zn2—Zn2ⁱⁱ	132.106 (14)	O1—O3—N1^viii	79.23 (6)
P1—Zn2—Zn2ⁱⁱ	132.72 (2)	O2—O3—N1^viii	60.38 (6)
P1ⁱⁱ—Zn2—Zn2ⁱⁱ	57.518 (14)	Zn2^iv—O3—N1^viii	160.80 (6)
O2ⁱⁱ—Zn2—Zn2ⁱⁱ	32.77 (3)	O5^ix—O3—N1^viii	96.68 (7)
Zn2^v—Zn2—Zn2ⁱⁱ	95.480 (19)	N1^ix—O3—N1^viii	96.68 (7)
O2—Zn2—O4	46.65 (5)	O2^iv—O3—N1^viii	152.20 (6)
O3ⁱ—Zn2—O4	113.75 (5)	O4^x—O3—N1^viii	62.76 (5)
O4ⁱⁱ—Zn2—O4	64.01 (5)	O4^xi—O3—N1^viii	120.64 (6)
O4ⁱⁱⁱ—Zn2—O4	135.26 (7)	O2ⁱ—O3—N1^viii	90.81 (6)
O3ⁱⁱⁱ—Zn2—O4	124.19 (4)	O3^xi—O3—N1^viii	146.89 (8)
P1ⁱⁱⁱ—Zn2—O4	131.37 (3)	P1—O4—Zn2^v	126.22 (9)
P1ⁱ—Zn2—O4	97.73 (3)	P1—O4—Zn2^iv	116.54 (8)
P1—Zn2—O4	27.40 (3)	Zn2^v—O4—Zn2^iv	117.14 (7)
P1ⁱⁱ—Zn2—O4	87.24 (3)	Zn2^v—O4—O3	156.65 (8)
O2ⁱⁱ—Zn2—O4	111.22 (4)	Zn2^iv—O4—O3	81.81 (6)
Zn2^v—Zn2—O4	33.95 (2)	Zn2^v—O4—O2	96.38 (7)
Zn2ⁱⁱ—Zn2—O4	126.29 (3)	Zn2^iv—O4—O2	139.41 (8)
O2—Zn2—O2ⁱ	80.57 (6)	O3—O4—O2	61.12 (6)
O3ⁱ—Zn2—O2ⁱ	45.28 (5)	Zn2^v—O4—O1	115.97 (7)
O4ⁱⁱ—Zn2—O2ⁱ	106.79 (5)	Zn2^iv—O4—O1	116.97 (7)
O4ⁱⁱⁱ—Zn2—O2ⁱ	147.51 (5)	O3—O4—O1	59.84 (6)
O3ⁱⁱⁱ—Zn2—O2ⁱ	95.37 (4)	O2—O4—O1	59.31 (6)
P1ⁱⁱⁱ—Zn2—O2ⁱ	124.69 (3)	P1—O4—O2^v	160.44 (9)
P1ⁱ—Zn2—O2ⁱ	25.84 (3)	Zn2^iv—O4—O2^v	80.59 (5)
P1—Zn2—O2ⁱ	71.48 (3)	O3—O4—O2^v	152.60 (7)
P1ⁱⁱ—Zn2—O2ⁱ	113.46 (3)	O2—O4—O2^v	125.62 (7)
O2ⁱⁱ—Zn2—O2ⁱ	130.83 (5)	O1—O4—O2^v	147.54 (7)
Zn2^v—Zn2—O2ⁱ	95.87 (3)	P1—O4—O4ⁱⁱ	100.13 (6)
Zn2ⁱⁱ—Zn2—O2ⁱ	155.35 (3)	Zn2^iv—O4—O4ⁱⁱ	129.82 (9)
O4—Zn2—O2ⁱ	71.92 (4)	O3—O4—O4ⁱⁱ	118.97 (7)
O2—Zn2—Zn2^xiv	96.19 (5)	O2—O4—O4ⁱⁱ	65.24 (4)
O3ⁱ—Zn2—Zn2^xiv	54.24 (5)	O1—O4—O4ⁱⁱ	112.69 (6)
O4ⁱⁱ—Zn2—Zn2^xiv	159.53 (4)	O2^v—O4—O4ⁱⁱ	60.39 (6)
O4ⁱⁱⁱ—Zn2—Zn2^xiv	74.74 (4)	P1—O4—O4^v	151.39 (8)
O3ⁱⁱⁱ—Zn2—Zn2^xiv	31.70 (3)	Zn2^v—O4—O4^v	80.87 (7)
P1ⁱⁱⁱ—Zn2—Zn2^xiv	54.75 (2)	O3—O4—O4^v	120.08 (7)
P1ⁱ—Zn2—Zn2^xiv	52.970 (15)	O2—O4—O4^v	169.82 (9)
P1—Zn2—Zn2^xiv	109.36 (2)	O1—O4—O4^v	130.69 (7)
P1ⁱⁱ—Zn2—Zn2^xiv	137.033 (16)	O2^v—O4—O4^v	48.10 (5)
O2ⁱⁱ—Zn2—Zn2^xiv	116.37 (3)	O4ⁱⁱ—O4—O4^v	108.01 (8)
Zn2^v—Zn2—Zn2^xiv	165.853 (11)	P1—O4—O2^iv	92.18 (7)
Zn2ⁱⁱ—Zn2—Zn2^xiv	98.213 (17)	Zn2^v—O4—O2^iv	135.34 (7)
O4—Zn2—Zn2^xiv	132.01 (3)	O3—O4—O2^iv	68.01 (6)
O2ⁱ—Zn2—Zn2^xiv	72.87 (3)	O2—O4—O2^iv	126.31 (7)
O1—P1—O2	110.16 (8)	O1—O4—O2^iv	81.51 (6)
O1—P1—O3	109.94 (9)	O2^v—O4—O2^iv	107.36 (6)
O2—P1—O3	112.63 (9)	O4ⁱⁱ—O4—O2^iv	165.77 (7)
O1—P1—O4	109.36 (9)	O4^v—O4—O2^iv	59.26 (4)
O2—P1—O4	108.59 (8)	P1—O4—O3^xii	106.39 (7)
O3—P1—O4	106.03 (8)	Zn2^iv—O4—O3^xii	129.39 (7)
O1—P1—Zn2^iv	111.22 (6)	O3—O4—O3^xii	142.12 (7)
O2—P1—Zn2^iv	133.15 (6)	O2—O4—O3^xii	91.19 (6)
O2—P1—Zn1	80.04 (6)	O1—O4—O3^xii	84.39 (6)
O3—P1—Zn1	133.63 (6)	O2^v—O4—O3^xii	64.23 (5)
Zn2^iv—P1—Zn1	132.342 (19)	O4ⁱⁱ—O4—O3^xii	61.28 (5)
O1—P1—Zn2ⁱ	137.57 (7)	O4^v—O4—O3^xii	91.87 (7)
O2—P1—Zn2ⁱ	91.25 (6)	O2^iv—O4—O3^xii	121.99 (6)
O4—P1—Zn2ⁱ	96.85 (6)	P1—O4—O3^xi	107.03 (7)
Zn2^iv—P1—Zn2ⁱ	72.285 (18)	Zn2^v—O4—O3^xi	115.43 (6)
Zn1—P1—Zn2ⁱ	151.56 (2)	O3—O4—O3^xi	72.03 (6)
O1—P1—Zn2	128.84 (6)	O2—O4—O3^xi	112.47 (7)
O3—P1—Zn2	112.59 (6)	O1—O4—O3^xi	128.54 (7)
O4—P1—Zn2	84.83 (6)	O2^v—O4—O3^xi	81.71 (5)
Zn2^iv—P1—Zn2	107.95 (2)	O4ⁱⁱ—O4—O3^xi	105.44 (8)
Zn1—P1—Zn2	97.108 (19)	O4^v—O4—O3^xi	60.84 (5)
Zn2ⁱ—P1—Zn2	85.099 (19)	O2^iv—O4—O3^xi	63.68 (5)
O1—P1—Zn2^v	103.65 (7)	O3^xii—O4—O3^xi	145.79 (5)
O2—P1—Zn2^v	83.74 (6)	P1—O4—Zn2	67.77 (5)
O3—P1—Zn2^v	133.32 (6)	Zn2^v—O4—Zn2	72.58 (4)
Zn2^iv—P1—Zn2^v	66.043 (17)	Zn2^iv—O4—Zn2	135.26 (6)
Zn1—P1—Zn2^v	90.99 (2)	O3—O4—Zn2	84.34 (5)
Zn2ⁱ—P1—Zn2^v	115.10 (2)	O1—O4—Zn2	91.29 (5)
Zn2—P1—Zn2^v	64.591 (16)	O2^v—O4—Zn2	93.59 (5)
O1—P1—O2^iv	84.13 (6)	O4^v—O4—Zn2	137.38 (7)
O2—P1—O2^iv	165.23 (8)	O2^iv—O4—Zn2	151.34 (5)
O3—P1—O2^iv	63.62 (7)	O3^xii—O4—Zn2	84.46 (4)
O4—P1—O2^iv	61.37 (6)	O3^xi—O4—Zn2	101.56 (5)
Zn1—P1—O2^iv	113.20 (3)	P1—O4—O5^vii	94.01 (7)
Zn2ⁱ—P1—O2^iv	79.88 (3)	Zn2^v—O4—O5^vii	93.14 (6)
Zn2—P1—O2^iv	140.58 (3)	Zn2^iv—O4—O5^vii	85.32 (6)
Zn2^v—P1—O2^iv	89.33 (3)	O3—O4—O5^vii	102.40 (7)
O1—P1—O4ⁱⁱ	121.56 (7)	O2—O4—O5^vii	116.68 (7)
O2—P1—O4ⁱⁱ	53.55 (6)	O1—O4—O5^vii	60.38 (6)
O3—P1—O4ⁱⁱ	128.39 (6)	O2^v—O4—O5^vii	96.91 (6)
O4—P1—O4ⁱⁱ	55.23 (4)	O4ⁱⁱ—O4—O5^vii	126.81 (8)
Zn2^iv—P1—O4ⁱⁱ	86.01 (3)	O4^v—O4—O5^vii	73.37 (6)
Zn1—P1—O4ⁱⁱ	95.71 (3)	O2^iv—O4—O5^vii	58.60 (5)
Zn2ⁱ—P1—O4ⁱⁱ	100.73 (3)	O3^xii—O4—O5^vii	65.53 (5)
O2^iv—P1—O4ⁱⁱ	116.24 (4)	O3^xi—O4—O5^vii	118.80 (6)
O1—P1—O5^viii	86.96 (7)	Zn2—O4—O5^vii	139.31 (6)
O2—P1—O5^viii	57.72 (7)	P1—O4—N1^vii	94.01 (7)
O3—P1—O5^viii	73.10 (7)	Zn2^v—O4—N1^vii	93.14 (6)
O4—P1—O5^viii	162.37 (7)	Zn2^iv—O4—N1^vii	85.32 (6)
Zn2^iv—P1—O5^viii	144.44 (4)	O3—O4—N1^vii	102.40 (7)
Zn1—P1—O5^viii	78.64 (4)	O2—O4—N1^vii	116.68 (7)
Zn2ⁱ—P1—O5^viii	73.88 (4)	O1—O4—N1^vii	60.38 (6)
Zn2—P1—O5^viii	79.53 (4)	O2^v—O4—N1^vii	96.91 (6)
Zn2^v—P1—O5^viii	141.15 (4)	O4ⁱⁱ—O4—N1^vii	126.81 (8)
O2^iv—P1—O5^viii	129.24 (4)	O4^v—O4—N1^vii	73.37 (6)
O4ⁱⁱ—P1—O5^viii	110.90 (5)	O2^iv—O4—N1^vii	58.60 (5)
O1—P1—N1^viii	86.96 (7)	O3^xii—O4—N1^vii	65.53 (5)
O2—P1—N1^viii	57.72 (7)	O3^xi—O4—N1^vii	118.80 (6)
O3—P1—N1^viii	73.10 (7)	Zn2—O4—N1^vii	139.31 (6)
O4—P1—N1^viii	162.37 (7)	Zn1—N1—O3^ix	94.88 (9)
Zn2^iv—P1—N1^viii	144.44 (4)	O3^ix—N1—O5^vi	135.36 (6)
Zn1—P1—N1^viii	78.64 (4)	O3^ix—N1—N1^vi	135.36 (6)
Zn2ⁱ—P1—N1^viii	73.88 (4)	Zn1—N1—O1ⁱⁱⁱ	99.01 (8)
Zn2—P1—N1^viii	79.53 (4)	O3^ix—N1—O1ⁱⁱⁱ	157.50 (9)
Zn2^v—P1—N1^viii	141.15 (4)	O5^vi—N1—O1ⁱⁱⁱ	62.74 (6)
O2^iv—P1—N1^viii	129.24 (4)	N1^vi—N1—O1ⁱⁱⁱ	62.74 (6)
O4ⁱⁱ—P1—N1^viii	110.90 (5)	Zn1—N1—O1^xiii	96.91 (8)
O1—P1—O5^vi	61.62 (7)	O3^ix—N1—O1^xiii	140.54 (8)
O2—P1—O5^vi	58.54 (7)	O5^vi—N1—O1^xiii	60.49 (6)
O3—P1—O5^vi	158.76 (7)	N1^vi—N1—O1^xiii	60.49 (6)
O4—P1—O5^vi	95.21 (6)	O1ⁱⁱⁱ—N1—O1^xiii	54.95 (6)
Zn2^iv—P1—O5^vi	128.79 (4)	Zn1—N1—O2^viii	153.01 (10)
Zn2ⁱ—P1—O5^vi	149.71 (4)	O3^ix—N1—O2^viii	60.28 (5)
Zn2—P1—O5^vi	68.44 (4)	O5^vi—N1—O2^viii	164.32 (6)
Zn2^v—P1—O5^vi	67.30 (3)	N1^vi—N1—O2^viii	164.32 (6)
O2^iv—P1—O5^vi	130.05 (5)	O1ⁱⁱⁱ—N1—O2^viii	101.90 (7)
O4ⁱⁱ—P1—O5^vi	64.47 (4)	O1^xiii—N1—O2^viii	109.02 (7)
O5^viii—P1—O5^vi	86.61 (3)	Zn1—N1—O2^vi	68.28 (6)
N1^viii—P1—O5^vi	86.61 (3)	O3^ix—N1—O2^vi	81.21 (7)
O1—P1—N1^vi	61.62 (7)	O5^vi—N1—O2^vi	74.57 (8)
O2—P1—N1^vi	58.54 (7)	N1^vi—N1—O2^vi	74.57 (8)
O3—P1—N1^vi	158.76 (7)	O1ⁱⁱⁱ—N1—O2^vi	120.41 (8)
O4—P1—N1^vi	95.21 (6)	O1^xiii—N1—O2^vi	68.69 (6)
Zn2^iv—P1—N1^vi	128.79 (4)	O2^viii—N1—O2^vi	113.88 (8)
Zn2ⁱ—P1—N1^vi	149.71 (4)	O3^ix—N1—O1	81.66 (7)
Zn2—P1—N1^vi	68.44 (4)	O5^vi—N1—O1	64.27 (5)
Zn2^v—P1—N1^vi	67.30 (3)	N1^vi—N1—O1	64.27 (5)
O2^iv—P1—N1^vi	130.05 (5)	O1ⁱⁱⁱ—N1—O1	100.95 (7)
O4ⁱⁱ—P1—N1^vi	64.47 (4)	O1^xiii—N1—O1	124.72 (6)
O5^viii—P1—N1^vi	86.61 (3)	O2^viii—N1—O1	125.37 (8)
N1^viii—P1—N1^vi	86.61 (3)	O2^vi—N1—O1	95.29 (7)
P1—O1—Zn1	124.17 (9)	O3^ix—N1—O1^vi	74.45 (7)
Zn1—O1—O2	90.73 (7)	O5^vi—N1—O1^vi	62.10 (5)
Zn1—O1—O3	147.64 (9)	N1^vi—N1—O1^vi	62.10 (5)
O2—O1—O3	61.20 (6)	O1ⁱⁱⁱ—N1—O1^vi	124.80 (6)
Zn1—O1—O4	122.57 (8)	O1^xiii—N1—O1^vi	98.22 (7)
O2—O1—O4	60.16 (6)	O2^viii—N1—O1^vi	133.28 (8)
O3—O1—O4	59.21 (6)	O1—N1—O1^vi	51.93 (6)
P1—O1—O1^vi	153.79 (11)	Zn1—N1—O5^viii	102.34 (10)
O2—O1—O1^vi	129.18 (6)	O3^ix—N1—O5^viii	87.92 (8)
O3—O1—O1^vi	169.55 (7)	O5^vi—N1—O5^viii	106.77 (12)
O4—O1—O1^vi	124.77 (9)	N1^vi—N1—O5^viii	106.77 (12)
P1—O1—O5^iv	136.51 (9)	O1ⁱⁱⁱ—N1—O5^viii	71.91 (8)
Zn1—O1—O5^iv	99.32 (7)	O1^xiii—N1—O5^viii	125.59 (10)
O2—O1—O5^iv	165.34 (8)	O2^viii—N1—O5^viii	68.76 (7)
O3—O1—O5^iv	105.86 (7)	O2^vi—N1—O5^viii	164.79 (12)
O4—O1—O5^iv	120.96 (7)	O1—N1—O5^viii	72.49 (8)
O1^vi—O1—O5^iv	63.70 (6)	O1^vi—N1—O5^viii	123.13 (10)
P1—O1—N1^iv	136.51 (9)	Zn1—N1—N1^viii	102.34 (10)
Zn1—O1—N1^iv	99.32 (7)	O3^ix—N1—N1^viii	87.92 (8)
O2—O1—N1^iv	165.34 (8)	O5^vi—N1—N1^viii	106.77 (12)
O3—O1—N1^iv	105.86 (7)	N1^vi—N1—N1^viii	106.77 (12)
O4—O1—N1^iv	120.96 (7)	O1ⁱⁱⁱ—N1—N1^viii	71.91 (8)
O1^vi—O1—N1^iv	63.70 (6)	O1^xiii—N1—N1^viii	125.59 (10)
P1—O1—O5^vii	111.75 (9)	O2^viii—N1—N1^viii	68.76 (7)
Zn1—O1—O5^vii	97.13 (7)	O2^vi—N1—N1^viii	164.79 (12)
O2—O1—O5^vii	132.81 (8)	O1—N1—N1^viii	72.49 (8)
O3—O1—O5^vii	113.54 (7)	O1^vi—N1—N1^viii	123.13 (10)
O4—O1—O5^vii	76.89 (7)	Zn1—N1—O4^xiii	115.94 (8)
O1^vi—O1—O5^vii	61.36 (5)	O3^ix—N1—O4^xiii	98.65 (7)
O5^iv—O1—O5^vii	56.76 (7)	O5^vi—N1—O4^xiii	95.81 (8)
N1^iv—O1—O5^vii	56.76 (7)	N1^vi—N1—O4^xiii	95.81 (8)
P1—O1—N1^vii	111.75 (9)	O1ⁱⁱⁱ—N1—O4^xiii	91.10 (7)
Zn1—O1—N1^vii	97.13 (7)	O2^viii—N1—O4^xiii	80.63 (6)
O2—O1—N1^vii	132.81 (8)	O2^vi—N1—O4^xiii	52.86 (5)
O3—O1—N1^vii	113.54 (7)	O1—N1—O4^xiii	147.18 (7)
O4—O1—N1^vii	76.89 (7)	O1^vi—N1—O4^xiii	96.24 (6)
O1^vi—O1—N1^vii	61.36 (5)	O5^viii—N1—O4^xiii	140.24 (10)
O5^iv—O1—N1^vii	56.76 (7)	N1^viii—N1—O4^xiii	140.24 (10)
N1^iv—O1—N1^vii	56.76 (7)	Zn1—N1—O3^viii	164.32 (10)
P1—O1—N1	114.99 (8)	O3^ix—N1—O3^viii	96.68 (7)
O2—O1—N1	81.54 (7)	O5^vi—N1—O3^viii	124.85 (4)
O3—O1—N1	119.56 (8)	N1^vi—N1—O3^viii	124.85 (4)
O4—O1—N1	137.30 (7)	O1ⁱⁱⁱ—N1—O3^viii	73.58 (6)
O1^vi—O1—N1	65.16 (5)	O1^xiii—N1—O3^viii	67.47 (6)
O5^iv—O1—N1	100.95 (7)	O2^vi—N1—O3^viii	103.09 (7)
N1^iv—O1—N1	100.95 (7)	O1—N1—O3^viii	161.11 (8)
O5^vii—O1—N1	126.47 (5)	O1^vi—N1—O3^viii	145.81 (7)
N1^vii—O1—N1	126.47 (5)	O5^viii—N1—O3^viii	88.66 (8)
P1—O1—O5^vi	95.27 (8)	N1^viii—N1—O3^viii	88.66 (8)
O2—O1—O5^vi	66.51 (6)	O4^xiii—N1—O3^viii	51.71 (4)
O3—O1—O5^vi	127.53 (7)	Zn1—N1—P1^viii	171.52 (9)
O4—O1—O5^vi	91.55 (7)	O3^ix—N1—P1^viii	83.06 (6)
O1^vi—O1—O5^vi	62.91 (5)	O5^vi—N1—P1^viii	141.56 (4)
O5^iv—O1—O5^vi	126.56 (5)	N1^vi—N1—P1^viii	141.56 (4)
N1^iv—O1—O5^vi	126.56 (5)	O1ⁱⁱⁱ—N1—P1^viii	80.60 (6)
O5^vii—O1—O5^vi	98.22 (7)	O1^xiii—N1—P1^viii	89.81 (6)
N1^vii—O1—O5^vi	98.22 (7)	O2^vi—N1—P1^viii	119.29 (7)
N1—O1—O5^vi	53.63 (7)	O1—N1—P1^viii	139.26 (7)
P1—O1—N1^vi	95.27 (8)	O1^vi—N1—P1^viii	153.14 (7)
O2—O1—N1^vi	66.51 (6)	O5^viii—N1—P1^viii	69.42 (6)
O3—O1—N1^vi	127.53 (7)	N1^viii—N1—P1^viii	69.42 (6)
O4—O1—N1^vi	91.55 (7)	O4^xiii—N1—P1^viii	72.53 (5)
O1^vi—O1—N1^vi	62.91 (5)	Zn1—N1—H1	113 (2)
O5^iv—O1—N1^vi	126.56 (5)	O5^vi—N1—H1	154 (2)
N1^iv—O1—N1^vi	126.56 (5)	N1^vi—N1—H1	154 (2)
O5^vii—O1—N1^vi	98.22 (7)	O1ⁱⁱⁱ—N1—H1	138 (2)
N1^vii—O1—N1^vi	98.22 (7)	O1^xiii—N1—H1	140 (2)
N1—O1—N1^vi	53.63 (7)	O2^vi—N1—H1	97 (2)
P1—O1—O2^iv	71.78 (6)	O1—N1—H1	93 (2)
Zn1—O1—O2^iv	153.92 (7)	O1^vi—N1—H1	95 (2)
O2—O1—O2^iv	106.67 (7)	O5^viii—N1—H1	75 (2)
O3—O1—O2^iv	57.58 (5)	N1^viii—N1—H1	75 (2)
O4—O1—O2^iv	56.05 (5)	O4^xiii—N1—H1	98 (2)
O1^vi—O1—O2^iv	115.20 (4)	O3^viii—N1—H1	81 (2)
O5^iv—O1—O2^iv	67.96 (5)	P1^viii—N1—H1	64 (2)
N1^iv—O1—O2^iv	67.96 (5)	Zn1—N1—H2	110 (2)
O5^vii—O1—O2^iv	56.79 (5)	O3^ix—N1—H2	129 (2)
N1^vii—O1—O2^iv	56.79 (5)	O5^vi—N1—H2	85 (2)
N1—O1—O2^iv	165.04 (7)	N1^vi—N1—H2	85 (2)
O5^vi—O1—O2^iv	140.95 (7)	O1^xiii—N1—H2	81 (2)
N1^vi—O1—O2^iv	140.95 (7)	O2^viii—N1—H2	82 (2)
P1—O2—Zn2	134.51 (9)	O2^vi—N1—H2	149 (2)
Zn2—O2—O1	153.44 (9)	O1—N1—H2	96 (2)
Zn2—O2—O4	99.86 (7)	O1^vi—N1—H2	140 (2)
O1—O2—O4	60.53 (6)	O4^xiii—N1—H2	109 (2)
Zn2—O2—O3	128.26 (8)	O3^viii—N1—H2	71 (2)
O1—O2—O3	59.47 (6)	P1^viii—N1—H2	66 (2)
O4—O2—O3	58.77 (6)	H1—N1—H2	111 (3)
P1—O2—O4ⁱⁱ	102.93 (7)	Zn1—N1—H3	107 (2)
O1—O2—O4ⁱⁱ	114.76 (7)	O3^ix—N1—H3	103 (2)
O4—O2—O4ⁱⁱ	66.66 (4)	O5^vi—N1—H3	87 (2)
O3—O2—O4ⁱⁱ	118.20 (7)	N1^vi—N1—H3	87 (2)
P1—O2—O4ⁱⁱⁱ	159.89 (9)	O1ⁱⁱⁱ—N1—H3	90 (2)
O1—O2—O4ⁱⁱⁱ	138.31 (7)	O2^viii—N1—H3	90 (2)
O4—O2—O4ⁱⁱⁱ	126.31 (7)	O2^vi—N1—H3	47 (2)
O3—O2—O4ⁱⁱⁱ	162.17 (7)	O1—N1—H3	139 (2)
O4ⁱⁱ—O2—O4ⁱⁱⁱ	60.35 (4)	O1^vi—N1—H3	89 (2)
P1—O2—O3ⁱⁱⁱ	153.29 (9)	O5^viii—N1—H3	148 (2)
Zn2—O2—O3ⁱⁱⁱ	65.78 (5)	N1^viii—N1—H3	148 (2)
O1—O2—O3ⁱⁱⁱ	135.67 (7)	O3^viii—N1—H3	60 (2)
O4—O2—O3ⁱⁱⁱ	163.55 (7)	P1^viii—N1—H3	81 (2)
O3—O2—O3ⁱⁱⁱ	122.88 (7)	H1—N1—H3	105 (3)
O4ⁱⁱ—O2—O3ⁱⁱⁱ	102.06 (6)	H2—N1—H3	111 (3)
O4ⁱⁱⁱ—O2—O3ⁱⁱⁱ	46.60 (4)

Symmetry codes: (i) −x+1/2, −y+1/2, −z+2; (ii) −x+1/2, y+1/2, −z+3/2; (iii) x, y+1, z; (iv) x, y−1, z; (v) −x+1/2, y−1/2, −z+3/2; (vi) −x, y, −z+3/2; (vii) −x, y−1, −z+3/2; (viii) −x, −y+1, −z+2; (ix) −x, −y, −z+2; (x) x, −y, z+1/2; (xi) −x+1/2, −y−1/2, −z+2; (xii) x, −y, z−1/2; (xiii) −x, y+1, −z+3/2; (xiv) −x+1/2, −y+3/2, −z+2.

Experimental details

Crystal data
Chemical formula	[Zn₃(PO₄)₂(H₂O)_0.8(NH₃)_1.2]
M_r	420.90
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	294
a, b, c (Å)	16.932 (3), 5.0171 (10), 10.564 (2)
β (°)	91.27 (3)
V (Å³)	897.2 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	8.34
Crystal size (mm)	0.15 × 0.13 × 0.08

Data collection
Diffractometer	Nonius KappaCCD diffractomer
Absorption correction	Multi-scan (Otwinowski & Minor, 1997)
T_min, T_max	0.298, 0.513
No. of measured, independent and observed [I > 2σ(I)] reflections	1715, 913, 884
R_int	0.011
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.014, 0.035, 1.13
No. of reflections	913
No. of parameters	79
No. of restraints	5
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.31

Computer programs: COLLECT (Nonius, 2002), HKL SCALEPACK (Otwinowski & Minor, 1997), DENZO-SMN (Otwinowski et al., 2003), SIR97 (Altomare et al., 1997), SHELXL97 (Sheldrick, 2008), WinGX (Farrugia, 1999), ATOMS (Dowty, 2000), publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Zn1—O1	1.9548 (15)	Zn2—O4ⁱⁱⁱ	1.9883 (15)
Zn1—N1	2.026 (2)	P1—O1	1.5178 (15)
Zn2—O2	1.9073 (15)	P1—O2	1.5213 (15)
Zn2—O3ⁱ	1.9091 (15)	P1—O3	1.5294 (14)
Zn2—O4ⁱⁱ	1.9839 (14)	P1—O4	1.5738 (15)

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

Table 2. Hydrogen bonds and electrostatic contacts (Å, °). top

D—H···A	D—H	H···A	D···A	D—H···A
N1/O5—H1···O3^xii	0.88 (1)	2.17 (2)	2.977 (3)	151 (3)
N1/O5—H2···O1^iv	0.93 (2)	2.39 (3)	3.165 (3)	140 (3)
N1/O5—H3···O1^xiii	0.89 (1)	2.59 (3)	3.232 (3)	130 (3)

Symmetry codes: (iv) x, y+1, z; (xii) -x, -y, -z+2; (xiii) -x, y+1,-z+3/2

Table 3. Unit-cell parameters for three isostructural compounds. top

Sample	Be₃(PO₄)₂.2H₂O^a	Be₃(AsO₄)₂.2H₂O^b	[Zn(NH₃)_1.2(H₂O)_0.8(ZnPO₄)₂]^c
a (Å)	15.9640 (6)	16.318 (2)	16.932 (3)
b (Å)	4.5842 (2)	4.6664 (3)	5.0171 (10)
c (Å)	9.5320 (4)	9.8755 (7)	10.564 (2)
β (°)	94.366 (2)	93.777 (3)	91.27 (3)
V (A³)	695.5 (2)	750.37 (2)	897.2 (3)

References: (a) Gier et al. (1999); (b) Harrison et al. (1994): (c) this study.

Subscribe to Acta Crystallographica Section C: Structural Chemistry

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.

E-mail address*
Repeat e-mail address* (for error checking)

Format*	PDF (US $40)
	HTML (US $40)
	PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number (non-UK EC countries only)
Country*

Terms and conditions of use
Contact us

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page