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The structure of the title compound, ammineaquadi-μ
5-phosphato-trizinc(II), [Zn
3(PO
4)
2(H
2O)
0.8(NH
3)
1.2], consists of two parts: (i) PO
4 and ZnO
4 vertex-sharing tetrahedra arranged in layers parallel to (100) and (ii) ZnO
2(N/O)
2 tetrahedra located between the layers. Elemental analysis establishes the ammine-to-water ratio as 3:2. ZnO
2(N/O)
2 tetrahedra are located at special position 4
e (site symmetry 2) in
C2/
c. The two O atoms of ZnO
2(N/O)
2 are bonded to neighbouring P atoms, forming two Zn—O—P linkages and connecting ZnO
2(N/O)
2 tetrahedra with two adjacent
bc plane layers. A noteworthy feature of the structure is the presence of NH
3 and H
2O 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.
Supporting information
[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.
The terminal ligand at Zn1 was refined as a mixed (N1/O5) site, constrained to
full occupancy and using identical fractional coordinates and displacement
parameters for both atoms. Because the site occupancies for N1 and O5 could
not be refined independently, they were fixed according to the elemental
analysis N1 0.6 and O5 0.4. Fixed site occupancies of 0.87 were assigned to
all three H atoms in order to have their sum fixed at 2.6 H atoms per
(NH3)0.6(H2O)0.4 group.
All three H atoms were found in a difference Fourier map and refined with
restraints [0.88 (2) Å] on the N1/O5—H distances. Uiso(H) values
were fixed at 1.2Ueq(N1/O5).
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).
ammineaquadi-µ
5-phosphato-trizinc(II)
top
Crystal data top
[Zn3(PO4)2(H2O)0.8(NH3)1.2] | F(000) = 816.1 |
Mr = 420.90 | Dx = 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 | Rint = 0.011 |
ϕ + ω scans | θmax = 26.4°, θmin = 3.9° |
Absorption correction: multi-scan (Otwinowski & Minor, 1997) | h = −20→20 |
Tmin = 0.298, Tmax = 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^(Fo^2^) + (0.0138P)^2^ + 1.9417P] where P = (Fo^2^ + 2Fc^2^)/3 |
S = 1.13 | (Δ/σ)max = 0.001 |
913 reflections | Δρmax = 0.34 e Å−3 |
79 parameters | Δρmin = −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 |
Mr = 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) |
Tmin = 0.298, Tmax = 0.513 | Rint = 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 | Δρmax = 0.34 e Å−3 |
913 reflections | Δρmin = −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 | Uiso*/Ueq | 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—N1viii | 3.299 (3) |
Zn2—O3i | 1.9091 (15) | O2—N1vi | 3.321 (3) |
Zn2—O4ii | 1.9839 (14) | O2—O3i | 3.331 (2) |
Zn2—O4iii | 1.9883 (15) | O2—Zn2v | 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—Zn2iv | 2.9487 (16) |
Zn2—P1 | 3.1654 (7) | O3—N1ix | 2.977 (3) |
Zn2—P1ii | 3.1785 (10) | O3—O2iv | 3.163 (2) |
Zn2—O2ii | 3.3709 (16) | O3—O4x | 3.197 (2) |
Zn2—O4 | 3.4056 (16) | O3—O4xi | 3.210 (2) |
Zn2—O2i | 3.4892 (17) | O3—O2i | 3.331 (2) |
P1—O1 | 1.5178 (15) | O3—O3xi | 3.397 (3) |
P1—O2 | 1.5213 (15) | O4—Zn2v | 1.9839 (14) |
P1—O3 | 1.5294 (14) | O4—Zn2iv | 1.9883 (15) |
P1—O4 | 1.5738 (15) | O4—O2v | 3.066 (2) |
P1—Zn2iv | 3.0375 (7) | O4—O4ii | 3.1005 (17) |
P1—Zn2i | 3.1071 (10) | O4—O2iv | 3.102 (2) |
P1—Zn2v | 3.1785 (10) | O4—O3xii | 3.197 (2) |
O1—O2 | 2.492 (2) | O4—O3xi | 3.210 (2) |
O1—O3 | 2.495 (2) | N1—O3ix | 2.977 (3) |
O1—O4 | 2.523 (2) | N1—O5vi | 3.041 (4) |
O1—O1vi | 2.952 (3) | N1—O1iii | 3.165 (3) |
O1—N1iv | 3.165 (3) | N1—O1xiii | 3.232 (3) |
O1—N1vii | 3.232 (3) | N1—O2viii | 3.299 (3) |
O1—N1 | 3.338 (3) | N1—O2vi | 3.321 (3) |
O1—N1vi | 3.403 (3) | N1—O1vi | 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) |
| | | |
O1vi—Zn1—O1 | 98.05 (9) | P1—O2—Zn1 | 71.91 (6) |
O1vi—Zn1—N1 | 117.44 (8) | Zn2—O2—Zn1 | 131.76 (7) |
O1—Zn1—N1 | 113.95 (8) | O4—O2—Zn1 | 86.51 (6) |
O1vi—Zn1—O5vi | 113.95 (8) | O3—O2—Zn1 | 95.99 (6) |
O1—Zn1—O5vi | 117.44 (8) | O4ii—O2—Zn1 | 107.82 (5) |
N1—Zn1—O5vi | 97.26 (13) | O4iii—O2—Zn1 | 101.28 (5) |
O1vi—Zn1—N1vi | 113.95 (8) | O3iii—O2—Zn1 | 108.90 (5) |
O1—Zn1—N1vi | 117.44 (8) | P1—O2—O5viii | 99.34 (8) |
N1—Zn1—N1vi | 97.26 (13) | Zn2—O2—O5viii | 117.93 (7) |
O5vi—Zn1—N1vi | 0.00 (9) | O1—O2—O5viii | 87.97 (7) |
O1vi—Zn1—P1vi | 24.10 (4) | O4—O2—O5viii | 134.63 (7) |
O1—Zn1—P1vi | 118.71 (5) | O3—O2—O5viii | 77.64 (6) |
N1—Zn1—P1vi | 95.83 (6) | O4ii—O2—O5viii | 156.49 (7) |
O5vi—Zn1—P1vi | 109.53 (6) | O4iii—O2—O5viii | 99.02 (6) |
N1vi—Zn1—P1vi | 109.53 (6) | O3iii—O2—O5viii | 54.81 (5) |
O1vi—Zn1—P1 | 118.71 (5) | Zn1—O2—O5viii | 86.13 (5) |
O1—Zn1—P1 | 24.10 (4) | P1—O2—N1viii | 99.34 (8) |
N1—Zn1—P1 | 109.53 (6) | Zn2—O2—N1viii | 117.93 (7) |
O5vi—Zn1—P1 | 95.83 (6) | O1—O2—N1viii | 87.97 (7) |
N1vi—Zn1—P1 | 95.83 (6) | O4—O2—N1viii | 134.63 (7) |
P1vi—Zn1—P1 | 141.50 (3) | O3—O2—N1viii | 77.64 (6) |
O1vi—Zn1—O2 | 145.29 (5) | O4ii—O2—N1viii | 156.49 (7) |
O1—Zn1—O2 | 51.44 (5) | O4iii—O2—N1viii | 99.02 (6) |
N1—Zn1—O2 | 92.86 (7) | O3iii—O2—N1viii | 54.81 (5) |
O5vi—Zn1—O2 | 75.51 (7) | Zn1—O2—N1viii | 86.13 (5) |
N1vi—Zn1—O2 | 75.51 (7) | P1—O2—O5vi | 98.46 (8) |
P1vi—Zn1—O2 | 169.24 (3) | Zn2—O2—O5vi | 95.55 (7) |
P1—Zn1—O2 | 28.05 (3) | O1—O2—O5vi | 70.00 (6) |
O1vi—Zn1—O2vi | 51.44 (5) | O4—O2—O5vi | 93.64 (7) |
O1—Zn1—O2vi | 145.29 (5) | O3—O2—O5vi | 129.28 (7) |
N1—Zn1—O2vi | 75.51 (7) | O4ii—O2—O5vi | 78.30 (6) |
O5vi—Zn1—O2vi | 92.86 (7) | O4iii—O2—O5vi | 68.55 (6) |
N1vi—Zn1—O2vi | 92.86 (7) | O3iii—O2—O5vi | 95.68 (6) |
P1vi—Zn1—O2vi | 28.05 (3) | O5viii—O2—O5vi | 105.86 (7) |
P1—Zn1—O2vi | 169.24 (3) | N1viii—O2—O5vi | 105.86 (7) |
O2—Zn1—O2vi | 162.58 (6) | P1—O2—N1vi | 98.46 (8) |
O1vi—Zn1—O3ix | 78.93 (5) | Zn2—O2—N1vi | 95.55 (7) |
O1—Zn1—O3ix | 87.28 (5) | O1—O2—N1vi | 70.00 (6) |
N1—Zn1—O3ix | 52.46 (7) | O4—O2—N1vi | 93.64 (7) |
O5vi—Zn1—O3ix | 148.29 (7) | O3—O2—N1vi | 129.28 (7) |
N1vi—Zn1—O3ix | 148.29 (7) | O4ii—O2—N1vi | 78.30 (6) |
P1vi—Zn1—O3ix | 69.87 (3) | O4iii—O2—N1vi | 68.55 (6) |
P1—Zn1—O3ix | 102.93 (3) | O3iii—O2—N1vi | 95.68 (6) |
O2—Zn1—O3ix | 111.13 (4) | O5viii—O2—N1vi | 105.86 (7) |
O2vi—Zn1—O3ix | 72.23 (4) | N1viii—O2—N1vi | 105.86 (7) |
O1vi—Zn1—O3xii | 87.28 (5) | P1—O2—O3i | 123.89 (8) |
O1—Zn1—O3xii | 78.93 (5) | O1—O2—O3i | 158.67 (7) |
N1—Zn1—O3xii | 148.29 (7) | O4—O2—O3i | 100.54 (6) |
O5vi—Zn1—O3xii | 52.46 (7) | O3—O2—O3i | 103.37 (6) |
N1vi—Zn1—O3xii | 52.46 (7) | O4ii—O2—O3i | 59.79 (5) |
P1vi—Zn1—O3xii | 102.93 (3) | O4iii—O2—O3i | 59.75 (5) |
P1—Zn1—O3xii | 69.87 (3) | O3iii—O2—O3i | 63.02 (5) |
O2—Zn1—O3xii | 72.23 (4) | Zn1—O2—O3i | 160.34 (6) |
O2vi—Zn1—O3xii | 111.13 (4) | O5viii—O2—O3i | 101.18 (6) |
O3ix—Zn1—O3xii | 158.96 (5) | N1viii—O2—O3i | 101.18 (6) |
O1vi—Zn1—O4vi | 32.69 (5) | O5vi—O2—O3i | 124.38 (6) |
O1—Zn1—O4vi | 106.04 (5) | N1vi—O2—O3i | 124.38 (6) |
N1—Zn1—O4vi | 85.71 (7) | P1—O2—Zn2v | 69.60 (6) |
O5vi—Zn1—O4vi | 130.14 (7) | Zn2—O2—Zn2v | 74.15 (5) |
N1vi—Zn1—O4vi | 130.14 (7) | O1—O2—Zn2v | 80.10 (6) |
P1vi—Zn1—O4vi | 21.82 (2) | O3—O2—Zn2v | 94.37 (6) |
P1—Zn1—O4vi | 130.10 (3) | O4iii—O2—Zn2v | 91.31 (5) |
O2—Zn1—O4vi | 154.31 (4) | O3iii—O2—Zn2v | 136.73 (5) |
O2vi—Zn1—O4vi | 39.59 (4) | Zn1—O2—Zn2v | 85.68 (4) |
O3ix—Zn1—O4vi | 49.13 (3) | O5viii—O2—Zn2v | 167.89 (6) |
O3xii—Zn1—O4vi | 119.79 (3) | N1viii—O2—Zn2v | 167.89 (6) |
O1vi—Zn1—O4 | 106.04 (5) | O5vi—O2—Zn2v | 72.03 (5) |
O1—Zn1—O4 | 32.69 (5) | N1vi—O2—Zn2v | 72.03 (5) |
N1—Zn1—O4 | 130.14 (7) | O3i—O2—Zn2v | 89.44 (5) |
O5vi—Zn1—O4 | 85.71 (7) | P1—O3—Zn2i | 128.94 (9) |
N1vi—Zn1—O4 | 85.71 (7) | Zn2i—O3—O4 | 111.75 (7) |
P1vi—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) |
O2vi—Zn1—O4 | 154.31 (4) | O4—O3—O2 | 60.11 (6) |
O3ix—Zn1—O4 | 119.79 (3) | O1—O3—O2 | 59.34 (6) |
O3xii—Zn1—O4 | 49.13 (3) | P1—O3—Zn2iv | 78.44 (6) |
O4vi—Zn1—O4 | 128.93 (5) | Zn2i—O3—Zn2iv | 94.06 (6) |
O1vi—Zn1—O5iv | 53.70 (6) | O1—O3—Zn2iv | 89.79 (6) |
O1—Zn1—O5iv | 51.69 (6) | O2—O3—Zn2iv | 100.48 (6) |
N1—Zn1—O5iv | 108.91 (8) | P1—O3—O5ix | 125.87 (9) |
O5vi—Zn1—O5iv | 153.83 (6) | Zn2i—O3—O5ix | 105.19 (7) |
N1vi—Zn1—O5iv | 153.83 (6) | O4—O3—O5ix | 126.14 (8) |
P1vi—Zn1—O5iv | 68.66 (3) | O1—O3—O5ix | 91.71 (7) |
P1—Zn1—O5iv | 75.79 (3) | O2—O3—O5ix | 144.50 (8) |
O2—Zn1—O5iv | 102.50 (4) | Zn2iv—O3—O5ix | 99.37 (6) |
O2vi—Zn1—O5iv | 93.64 (4) | P1—O3—N1ix | 125.87 (9) |
O3ix—Zn1—O5iv | 57.29 (4) | Zn2i—O3—N1ix | 105.19 (7) |
O3xii—Zn1—O5iv | 101.71 (4) | O4—O3—N1ix | 126.14 (8) |
O4vi—Zn1—O5iv | 54.44 (4) | O1—O3—N1ix | 91.71 (7) |
O4—Zn1—O5iv | 77.57 (4) | O2—O3—N1ix | 144.50 (8) |
O2—Zn2—O3i | 121.60 (6) | Zn2iv—O3—N1ix | 99.37 (6) |
O2—Zn2—O4ii | 103.99 (7) | P1—O3—O2iv | 90.72 (7) |
O3i—Zn2—O4ii | 110.39 (6) | Zn2i—O3—O2iv | 112.45 (7) |
O2—Zn2—O4iii | 105.52 (6) | O4—O3—O2iv | 65.39 (5) |
O3i—Zn2—O4iii | 110.91 (6) | O1—O3—O2iv | 80.67 (6) |
O4ii—Zn2—O4iii | 102.62 (4) | O2—O3—O2iv | 122.88 (7) |
O2—Zn2—O3iii | 78.07 (6) | O5ix—O3—O2iv | 64.91 (6) |
O3i—Zn2—O3iii | 85.94 (6) | N1ix—O3—O2iv | 64.91 (6) |
O4ii—Zn2—O3iii | 157.81 (5) | P1—O3—O4x | 135.79 (9) |
O4iii—Zn2—O3iii | 56.32 (5) | O4—O3—O4x | 142.75 (7) |
O2—Zn2—P1iii | 88.04 (5) | O1—O3—O4x | 141.64 (8) |
O3i—Zn2—P1iii | 104.34 (5) | O2—O3—O4x | 102.25 (7) |
O4ii—Zn2—P1iii | 128.45 (5) | Zn2iv—O3—O4x | 128.09 (6) |
O4iii—Zn2—P1iii | 27.61 (4) | O5ix—O3—O4x | 87.96 (6) |
O3iii—Zn2—P1iii | 29.56 (3) | N1ix—O3—O4x | 87.96 (6) |
O2—Zn2—P1i | 99.16 (5) | O2iv—O3—O4x | 132.32 (6) |
O3i—Zn2—P1i | 22.51 (4) | P1—O3—O4xi | 143.27 (8) |
O4ii—Zn2—P1i | 119.01 (5) | O4—O3—O4xi | 107.97 (6) |
O4iii—Zn2—P1i | 124.00 (4) | O1—O3—O4xi | 159.46 (8) |
O3iii—Zn2—P1i | 81.83 (3) | O2—O3—O4xi | 132.83 (7) |
P1iii—Zn2—P1i | 107.715 (18) | Zn2iv—O3—O4xi | 72.46 (4) |
O2—Zn2—P1 | 20.04 (4) | O5ix—O3—O4xi | 81.37 (6) |
O3i—Zn2—P1 | 116.54 (5) | N1ix—O3—O4xi | 81.37 (6) |
O4ii—Zn2—P1 | 89.31 (5) | O2iv—O3—O4xi | 78.88 (5) |
O4iii—Zn2—P1 | 122.83 (5) | O4x—O3—O4xi | 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) | Zn2iv—O3—O2i | 85.54 (5) |
O4ii—Zn2—P1ii | 23.54 (4) | O5ix—O3—O2i | 134.18 (7) |
O4iii—Zn2—P1ii | 88.87 (4) | N1ix—O3—O2i | 134.18 (7) |
O3iii—Zn2—P1ii | 143.52 (3) | O2iv—O3—O2i | 116.98 (5) |
P1iii—Zn2—P1ii | 116.48 (2) | O4x—O3—O2i | 55.99 (5) |
P1i—Zn2—P1ii | 114.69 (2) | O4xi—O3—O2i | 56.57 (5) |
P1—Zn2—P1ii | 112.86 (2) | P1—O3—O3xi | 100.33 (8) |
O2—Zn2—O2ii | 138.96 (4) | Zn2i—O3—O3xi | 59.97 (5) |
O3i—Zn2—O2ii | 98.33 (5) | O4—O3—O3xi | 64.01 (6) |
O4ii—Zn2—O2ii | 47.82 (5) | O1—O3—O3xi | 122.05 (8) |
O4iii—Zn2—O2ii | 63.83 (5) | O2—O3—O3xi | 106.19 (7) |
O3iii—Zn2—O2ii | 116.89 (4) | O5ix—O3—O3xi | 106.77 (8) |
P1iii—Zn2—O2ii | 91.08 (3) | N1ix—O3—O3xi | 106.77 (8) |
P1i—Zn2—O2ii | 119.98 (3) | O2iv—O3—O3xi | 60.91 (5) |
P1—Zn2—O2ii | 133.21 (3) | O4x—O3—O3xi | 94.49 (6) |
P1ii—Zn2—O2ii | 26.66 (3) | O2i—O3—O3xi | 56.08 (5) |
O2—Zn2—Zn2v | 73.08 (5) | P1—O3—O5viii | 83.65 (7) |
O3i—Zn2—Zn2v | 123.32 (5) | Zn2i—O3—O5viii | 91.83 (6) |
O4ii—Zn2—Zn2v | 31.47 (4) | O4—O3—O5viii | 119.20 (7) |
O4iii—Zn2—Zn2v | 116.53 (5) | O1—O3—O5viii | 79.23 (6) |
O3iii—Zn2—Zn2v | 146.75 (3) | O2—O3—O5viii | 60.38 (6) |
P1iii—Zn2—Zn2v | 131.95 (2) | Zn2iv—O3—O5viii | 160.80 (6) |
P1i—Zn2—Zn2v | 118.528 (16) | O5ix—O3—O5viii | 96.68 (7) |
P1—Zn2—Zn2v | 57.89 (2) | N1ix—O3—O5viii | 96.68 (7) |
P1ii—Zn2—Zn2v | 54.980 (14) | O2iv—O3—O5viii | 152.20 (6) |
O2ii—Zn2—Zn2v | 77.39 (3) | O4x—O3—O5viii | 62.76 (5) |
O2—Zn2—Zn2ii | 123.75 (5) | O4xi—O3—O5viii | 120.64 (6) |
O3i—Zn2—Zn2ii | 110.73 (5) | O2i—O3—O5viii | 90.81 (6) |
O4ii—Zn2—Zn2ii | 73.47 (5) | O3xi—O3—O5viii | 146.89 (8) |
O4iii—Zn2—Zn2ii | 31.39 (4) | P1—O3—N1viii | 83.65 (7) |
O3iii—Zn2—Zn2ii | 86.93 (3) | Zn2i—O3—N1viii | 91.83 (6) |
P1iii—Zn2—Zn2ii | 58.98 (2) | O4—O3—N1viii | 119.20 (7) |
P1i—Zn2—Zn2ii | 132.106 (14) | O1—O3—N1viii | 79.23 (6) |
P1—Zn2—Zn2ii | 132.72 (2) | O2—O3—N1viii | 60.38 (6) |
P1ii—Zn2—Zn2ii | 57.518 (14) | Zn2iv—O3—N1viii | 160.80 (6) |
O2ii—Zn2—Zn2ii | 32.77 (3) | O5ix—O3—N1viii | 96.68 (7) |
Zn2v—Zn2—Zn2ii | 95.480 (19) | N1ix—O3—N1viii | 96.68 (7) |
O2—Zn2—O4 | 46.65 (5) | O2iv—O3—N1viii | 152.20 (6) |
O3i—Zn2—O4 | 113.75 (5) | O4x—O3—N1viii | 62.76 (5) |
O4ii—Zn2—O4 | 64.01 (5) | O4xi—O3—N1viii | 120.64 (6) |
O4iii—Zn2—O4 | 135.26 (7) | O2i—O3—N1viii | 90.81 (6) |
O3iii—Zn2—O4 | 124.19 (4) | O3xi—O3—N1viii | 146.89 (8) |
P1iii—Zn2—O4 | 131.37 (3) | P1—O4—Zn2v | 126.22 (9) |
P1i—Zn2—O4 | 97.73 (3) | P1—O4—Zn2iv | 116.54 (8) |
P1—Zn2—O4 | 27.40 (3) | Zn2v—O4—Zn2iv | 117.14 (7) |
P1ii—Zn2—O4 | 87.24 (3) | Zn2v—O4—O3 | 156.65 (8) |
O2ii—Zn2—O4 | 111.22 (4) | Zn2iv—O4—O3 | 81.81 (6) |
Zn2v—Zn2—O4 | 33.95 (2) | Zn2v—O4—O2 | 96.38 (7) |
Zn2ii—Zn2—O4 | 126.29 (3) | Zn2iv—O4—O2 | 139.41 (8) |
O2—Zn2—O2i | 80.57 (6) | O3—O4—O2 | 61.12 (6) |
O3i—Zn2—O2i | 45.28 (5) | Zn2v—O4—O1 | 115.97 (7) |
O4ii—Zn2—O2i | 106.79 (5) | Zn2iv—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—O2v | 160.44 (9) |
P1i—Zn2—O2i | 25.84 (3) | Zn2iv—O4—O2v | 80.59 (5) |
P1—Zn2—O2i | 71.48 (3) | O3—O4—O2v | 152.60 (7) |
P1ii—Zn2—O2i | 113.46 (3) | O2—O4—O2v | 125.62 (7) |
O2ii—Zn2—O2i | 130.83 (5) | O1—O4—O2v | 147.54 (7) |
Zn2v—Zn2—O2i | 95.87 (3) | P1—O4—O4ii | 100.13 (6) |
Zn2ii—Zn2—O2i | 155.35 (3) | Zn2iv—O4—O4ii | 129.82 (9) |
O4—Zn2—O2i | 71.92 (4) | O3—O4—O4ii | 118.97 (7) |
O2—Zn2—Zn2xiv | 96.19 (5) | O2—O4—O4ii | 65.24 (4) |
O3i—Zn2—Zn2xiv | 54.24 (5) | O1—O4—O4ii | 112.69 (6) |
O4ii—Zn2—Zn2xiv | 159.53 (4) | O2v—O4—O4ii | 60.39 (6) |
O4iii—Zn2—Zn2xiv | 74.74 (4) | P1—O4—O4v | 151.39 (8) |
O3iii—Zn2—Zn2xiv | 31.70 (3) | Zn2v—O4—O4v | 80.87 (7) |
P1iii—Zn2—Zn2xiv | 54.75 (2) | O3—O4—O4v | 120.08 (7) |
P1i—Zn2—Zn2xiv | 52.970 (15) | O2—O4—O4v | 169.82 (9) |
P1—Zn2—Zn2xiv | 109.36 (2) | O1—O4—O4v | 130.69 (7) |
P1ii—Zn2—Zn2xiv | 137.033 (16) | O2v—O4—O4v | 48.10 (5) |
O2ii—Zn2—Zn2xiv | 116.37 (3) | O4ii—O4—O4v | 108.01 (8) |
Zn2v—Zn2—Zn2xiv | 165.853 (11) | P1—O4—O2iv | 92.18 (7) |
Zn2ii—Zn2—Zn2xiv | 98.213 (17) | Zn2v—O4—O2iv | 135.34 (7) |
O4—Zn2—Zn2xiv | 132.01 (3) | O3—O4—O2iv | 68.01 (6) |
O2i—Zn2—Zn2xiv | 72.87 (3) | O2—O4—O2iv | 126.31 (7) |
O1—P1—O2 | 110.16 (8) | O1—O4—O2iv | 81.51 (6) |
O1—P1—O3 | 109.94 (9) | O2v—O4—O2iv | 107.36 (6) |
O2—P1—O3 | 112.63 (9) | O4ii—O4—O2iv | 165.77 (7) |
O1—P1—O4 | 109.36 (9) | O4v—O4—O2iv | 59.26 (4) |
O2—P1—O4 | 108.59 (8) | P1—O4—O3xii | 106.39 (7) |
O3—P1—O4 | 106.03 (8) | Zn2iv—O4—O3xii | 129.39 (7) |
O1—P1—Zn2iv | 111.22 (6) | O3—O4—O3xii | 142.12 (7) |
O2—P1—Zn2iv | 133.15 (6) | O2—O4—O3xii | 91.19 (6) |
O2—P1—Zn1 | 80.04 (6) | O1—O4—O3xii | 84.39 (6) |
O3—P1—Zn1 | 133.63 (6) | O2v—O4—O3xii | 64.23 (5) |
Zn2iv—P1—Zn1 | 132.342 (19) | O4ii—O4—O3xii | 61.28 (5) |
O1—P1—Zn2i | 137.57 (7) | O4v—O4—O3xii | 91.87 (7) |
O2—P1—Zn2i | 91.25 (6) | O2iv—O4—O3xii | 121.99 (6) |
O4—P1—Zn2i | 96.85 (6) | P1—O4—O3xi | 107.03 (7) |
Zn2iv—P1—Zn2i | 72.285 (18) | Zn2v—O4—O3xi | 115.43 (6) |
Zn1—P1—Zn2i | 151.56 (2) | O3—O4—O3xi | 72.03 (6) |
O1—P1—Zn2 | 128.84 (6) | O2—O4—O3xi | 112.47 (7) |
O3—P1—Zn2 | 112.59 (6) | O1—O4—O3xi | 128.54 (7) |
O4—P1—Zn2 | 84.83 (6) | O2v—O4—O3xi | 81.71 (5) |
Zn2iv—P1—Zn2 | 107.95 (2) | O4ii—O4—O3xi | 105.44 (8) |
Zn1—P1—Zn2 | 97.108 (19) | O4v—O4—O3xi | 60.84 (5) |
Zn2i—P1—Zn2 | 85.099 (19) | O2iv—O4—O3xi | 63.68 (5) |
O1—P1—Zn2v | 103.65 (7) | O3xii—O4—O3xi | 145.79 (5) |
O2—P1—Zn2v | 83.74 (6) | P1—O4—Zn2 | 67.77 (5) |
O3—P1—Zn2v | 133.32 (6) | Zn2v—O4—Zn2 | 72.58 (4) |
Zn2iv—P1—Zn2v | 66.043 (17) | Zn2iv—O4—Zn2 | 135.26 (6) |
Zn1—P1—Zn2v | 90.99 (2) | O3—O4—Zn2 | 84.34 (5) |
Zn2i—P1—Zn2v | 115.10 (2) | O1—O4—Zn2 | 91.29 (5) |
Zn2—P1—Zn2v | 64.591 (16) | O2v—O4—Zn2 | 93.59 (5) |
O1—P1—O2iv | 84.13 (6) | O4v—O4—Zn2 | 137.38 (7) |
O2—P1—O2iv | 165.23 (8) | O2iv—O4—Zn2 | 151.34 (5) |
O3—P1—O2iv | 63.62 (7) | O3xii—O4—Zn2 | 84.46 (4) |
O4—P1—O2iv | 61.37 (6) | O3xi—O4—Zn2 | 101.56 (5) |
Zn1—P1—O2iv | 113.20 (3) | P1—O4—O5vii | 94.01 (7) |
Zn2i—P1—O2iv | 79.88 (3) | Zn2v—O4—O5vii | 93.14 (6) |
Zn2—P1—O2iv | 140.58 (3) | Zn2iv—O4—O5vii | 85.32 (6) |
Zn2v—P1—O2iv | 89.33 (3) | O3—O4—O5vii | 102.40 (7) |
O1—P1—O4ii | 121.56 (7) | O2—O4—O5vii | 116.68 (7) |
O2—P1—O4ii | 53.55 (6) | O1—O4—O5vii | 60.38 (6) |
O3—P1—O4ii | 128.39 (6) | O2v—O4—O5vii | 96.91 (6) |
O4—P1—O4ii | 55.23 (4) | O4ii—O4—O5vii | 126.81 (8) |
Zn2iv—P1—O4ii | 86.01 (3) | O4v—O4—O5vii | 73.37 (6) |
Zn1—P1—O4ii | 95.71 (3) | O2iv—O4—O5vii | 58.60 (5) |
Zn2i—P1—O4ii | 100.73 (3) | O3xii—O4—O5vii | 65.53 (5) |
O2iv—P1—O4ii | 116.24 (4) | O3xi—O4—O5vii | 118.80 (6) |
O1—P1—O5viii | 86.96 (7) | Zn2—O4—O5vii | 139.31 (6) |
O2—P1—O5viii | 57.72 (7) | P1—O4—N1vii | 94.01 (7) |
O3—P1—O5viii | 73.10 (7) | Zn2v—O4—N1vii | 93.14 (6) |
O4—P1—O5viii | 162.37 (7) | Zn2iv—O4—N1vii | 85.32 (6) |
Zn2iv—P1—O5viii | 144.44 (4) | O3—O4—N1vii | 102.40 (7) |
Zn1—P1—O5viii | 78.64 (4) | O2—O4—N1vii | 116.68 (7) |
Zn2i—P1—O5viii | 73.88 (4) | O1—O4—N1vii | 60.38 (6) |
Zn2—P1—O5viii | 79.53 (4) | O2v—O4—N1vii | 96.91 (6) |
Zn2v—P1—O5viii | 141.15 (4) | O4ii—O4—N1vii | 126.81 (8) |
O2iv—P1—O5viii | 129.24 (4) | O4v—O4—N1vii | 73.37 (6) |
O4ii—P1—O5viii | 110.90 (5) | O2iv—O4—N1vii | 58.60 (5) |
O1—P1—N1viii | 86.96 (7) | O3xii—O4—N1vii | 65.53 (5) |
O2—P1—N1viii | 57.72 (7) | O3xi—O4—N1vii | 118.80 (6) |
O3—P1—N1viii | 73.10 (7) | Zn2—O4—N1vii | 139.31 (6) |
O4—P1—N1viii | 162.37 (7) | Zn1—N1—O3ix | 94.88 (9) |
Zn2iv—P1—N1viii | 144.44 (4) | O3ix—N1—O5vi | 135.36 (6) |
Zn1—P1—N1viii | 78.64 (4) | O3ix—N1—N1vi | 135.36 (6) |
Zn2i—P1—N1viii | 73.88 (4) | Zn1—N1—O1iii | 99.01 (8) |
Zn2—P1—N1viii | 79.53 (4) | O3ix—N1—O1iii | 157.50 (9) |
Zn2v—P1—N1viii | 141.15 (4) | O5vi—N1—O1iii | 62.74 (6) |
O2iv—P1—N1viii | 129.24 (4) | N1vi—N1—O1iii | 62.74 (6) |
O4ii—P1—N1viii | 110.90 (5) | Zn1—N1—O1xiii | 96.91 (8) |
O1—P1—O5vi | 61.62 (7) | O3ix—N1—O1xiii | 140.54 (8) |
O2—P1—O5vi | 58.54 (7) | O5vi—N1—O1xiii | 60.49 (6) |
O3—P1—O5vi | 158.76 (7) | N1vi—N1—O1xiii | 60.49 (6) |
O4—P1—O5vi | 95.21 (6) | O1iii—N1—O1xiii | 54.95 (6) |
Zn2iv—P1—O5vi | 128.79 (4) | Zn1—N1—O2viii | 153.01 (10) |
Zn2i—P1—O5vi | 149.71 (4) | O3ix—N1—O2viii | 60.28 (5) |
Zn2—P1—O5vi | 68.44 (4) | O5vi—N1—O2viii | 164.32 (6) |
Zn2v—P1—O5vi | 67.30 (3) | N1vi—N1—O2viii | 164.32 (6) |
O2iv—P1—O5vi | 130.05 (5) | O1iii—N1—O2viii | 101.90 (7) |
O4ii—P1—O5vi | 64.47 (4) | O1xiii—N1—O2viii | 109.02 (7) |
O5viii—P1—O5vi | 86.61 (3) | Zn1—N1—O2vi | 68.28 (6) |
N1viii—P1—O5vi | 86.61 (3) | O3ix—N1—O2vi | 81.21 (7) |
O1—P1—N1vi | 61.62 (7) | O5vi—N1—O2vi | 74.57 (8) |
O2—P1—N1vi | 58.54 (7) | N1vi—N1—O2vi | 74.57 (8) |
O3—P1—N1vi | 158.76 (7) | O1iii—N1—O2vi | 120.41 (8) |
O4—P1—N1vi | 95.21 (6) | O1xiii—N1—O2vi | 68.69 (6) |
Zn2iv—P1—N1vi | 128.79 (4) | O2viii—N1—O2vi | 113.88 (8) |
Zn2i—P1—N1vi | 149.71 (4) | O3ix—N1—O1 | 81.66 (7) |
Zn2—P1—N1vi | 68.44 (4) | O5vi—N1—O1 | 64.27 (5) |
Zn2v—P1—N1vi | 67.30 (3) | N1vi—N1—O1 | 64.27 (5) |
O2iv—P1—N1vi | 130.05 (5) | O1iii—N1—O1 | 100.95 (7) |
O4ii—P1—N1vi | 64.47 (4) | O1xiii—N1—O1 | 124.72 (6) |
O5viii—P1—N1vi | 86.61 (3) | O2viii—N1—O1 | 125.37 (8) |
N1viii—P1—N1vi | 86.61 (3) | O2vi—N1—O1 | 95.29 (7) |
P1—O1—Zn1 | 124.17 (9) | O3ix—N1—O1vi | 74.45 (7) |
Zn1—O1—O2 | 90.73 (7) | O5vi—N1—O1vi | 62.10 (5) |
Zn1—O1—O3 | 147.64 (9) | N1vi—N1—O1vi | 62.10 (5) |
O2—O1—O3 | 61.20 (6) | O1iii—N1—O1vi | 124.80 (6) |
Zn1—O1—O4 | 122.57 (8) | O1xiii—N1—O1vi | 98.22 (7) |
O2—O1—O4 | 60.16 (6) | O2viii—N1—O1vi | 133.28 (8) |
O3—O1—O4 | 59.21 (6) | O1—N1—O1vi | 51.93 (6) |
P1—O1—O1vi | 153.79 (11) | Zn1—N1—O5viii | 102.34 (10) |
O2—O1—O1vi | 129.18 (6) | O3ix—N1—O5viii | 87.92 (8) |
O3—O1—O1vi | 169.55 (7) | O5vi—N1—O5viii | 106.77 (12) |
O4—O1—O1vi | 124.77 (9) | N1vi—N1—O5viii | 106.77 (12) |
P1—O1—O5iv | 136.51 (9) | O1iii—N1—O5viii | 71.91 (8) |
Zn1—O1—O5iv | 99.32 (7) | O1xiii—N1—O5viii | 125.59 (10) |
O2—O1—O5iv | 165.34 (8) | O2viii—N1—O5viii | 68.76 (7) |
O3—O1—O5iv | 105.86 (7) | O2vi—N1—O5viii | 164.79 (12) |
O4—O1—O5iv | 120.96 (7) | O1—N1—O5viii | 72.49 (8) |
O1vi—O1—O5iv | 63.70 (6) | O1vi—N1—O5viii | 123.13 (10) |
P1—O1—N1iv | 136.51 (9) | Zn1—N1—N1viii | 102.34 (10) |
Zn1—O1—N1iv | 99.32 (7) | O3ix—N1—N1viii | 87.92 (8) |
O2—O1—N1iv | 165.34 (8) | O5vi—N1—N1viii | 106.77 (12) |
O3—O1—N1iv | 105.86 (7) | N1vi—N1—N1viii | 106.77 (12) |
O4—O1—N1iv | 120.96 (7) | O1iii—N1—N1viii | 71.91 (8) |
O1vi—O1—N1iv | 63.70 (6) | O1xiii—N1—N1viii | 125.59 (10) |
P1—O1—O5vii | 111.75 (9) | O2viii—N1—N1viii | 68.76 (7) |
Zn1—O1—O5vii | 97.13 (7) | O2vi—N1—N1viii | 164.79 (12) |
O2—O1—O5vii | 132.81 (8) | O1—N1—N1viii | 72.49 (8) |
O3—O1—O5vii | 113.54 (7) | O1vi—N1—N1viii | 123.13 (10) |
O4—O1—O5vii | 76.89 (7) | Zn1—N1—O4xiii | 115.94 (8) |
O1vi—O1—O5vii | 61.36 (5) | O3ix—N1—O4xiii | 98.65 (7) |
O5iv—O1—O5vii | 56.76 (7) | O5vi—N1—O4xiii | 95.81 (8) |
N1iv—O1—O5vii | 56.76 (7) | N1vi—N1—O4xiii | 95.81 (8) |
P1—O1—N1vii | 111.75 (9) | O1iii—N1—O4xiii | 91.10 (7) |
Zn1—O1—N1vii | 97.13 (7) | O2viii—N1—O4xiii | 80.63 (6) |
O2—O1—N1vii | 132.81 (8) | O2vi—N1—O4xiii | 52.86 (5) |
O3—O1—N1vii | 113.54 (7) | O1—N1—O4xiii | 147.18 (7) |
O4—O1—N1vii | 76.89 (7) | O1vi—N1—O4xiii | 96.24 (6) |
O1vi—O1—N1vii | 61.36 (5) | O5viii—N1—O4xiii | 140.24 (10) |
O5iv—O1—N1vii | 56.76 (7) | N1viii—N1—O4xiii | 140.24 (10) |
N1iv—O1—N1vii | 56.76 (7) | Zn1—N1—O3viii | 164.32 (10) |
P1—O1—N1 | 114.99 (8) | O3ix—N1—O3viii | 96.68 (7) |
O2—O1—N1 | 81.54 (7) | O5vi—N1—O3viii | 124.85 (4) |
O3—O1—N1 | 119.56 (8) | N1vi—N1—O3viii | 124.85 (4) |
O4—O1—N1 | 137.30 (7) | O1iii—N1—O3viii | 73.58 (6) |
O1vi—O1—N1 | 65.16 (5) | O1xiii—N1—O3viii | 67.47 (6) |
O5iv—O1—N1 | 100.95 (7) | O2vi—N1—O3viii | 103.09 (7) |
N1iv—O1—N1 | 100.95 (7) | O1—N1—O3viii | 161.11 (8) |
O5vii—O1—N1 | 126.47 (5) | O1vi—N1—O3viii | 145.81 (7) |
N1vii—O1—N1 | 126.47 (5) | O5viii—N1—O3viii | 88.66 (8) |
P1—O1—O5vi | 95.27 (8) | N1viii—N1—O3viii | 88.66 (8) |
O2—O1—O5vi | 66.51 (6) | O4xiii—N1—O3viii | 51.71 (4) |
O3—O1—O5vi | 127.53 (7) | Zn1—N1—P1viii | 171.52 (9) |
O4—O1—O5vi | 91.55 (7) | O3ix—N1—P1viii | 83.06 (6) |
O1vi—O1—O5vi | 62.91 (5) | O5vi—N1—P1viii | 141.56 (4) |
O5iv—O1—O5vi | 126.56 (5) | N1vi—N1—P1viii | 141.56 (4) |
N1iv—O1—O5vi | 126.56 (5) | O1iii—N1—P1viii | 80.60 (6) |
O5vii—O1—O5vi | 98.22 (7) | O1xiii—N1—P1viii | 89.81 (6) |
N1vii—O1—O5vi | 98.22 (7) | O2vi—N1—P1viii | 119.29 (7) |
N1—O1—O5vi | 53.63 (7) | O1—N1—P1viii | 139.26 (7) |
P1—O1—N1vi | 95.27 (8) | O1vi—N1—P1viii | 153.14 (7) |
O2—O1—N1vi | 66.51 (6) | O5viii—N1—P1viii | 69.42 (6) |
O3—O1—N1vi | 127.53 (7) | N1viii—N1—P1viii | 69.42 (6) |
O4—O1—N1vi | 91.55 (7) | O4xiii—N1—P1viii | 72.53 (5) |
O1vi—O1—N1vi | 62.91 (5) | Zn1—N1—H1 | 113 (2) |
O5iv—O1—N1vi | 126.56 (5) | O5vi—N1—H1 | 154 (2) |
N1iv—O1—N1vi | 126.56 (5) | N1vi—N1—H1 | 154 (2) |
O5vii—O1—N1vi | 98.22 (7) | O1iii—N1—H1 | 138 (2) |
N1vii—O1—N1vi | 98.22 (7) | O1xiii—N1—H1 | 140 (2) |
N1—O1—N1vi | 53.63 (7) | O2vi—N1—H1 | 97 (2) |
P1—O1—O2iv | 71.78 (6) | O1—N1—H1 | 93 (2) |
Zn1—O1—O2iv | 153.92 (7) | O1vi—N1—H1 | 95 (2) |
O2—O1—O2iv | 106.67 (7) | O5viii—N1—H1 | 75 (2) |
O3—O1—O2iv | 57.58 (5) | N1viii—N1—H1 | 75 (2) |
O4—O1—O2iv | 56.05 (5) | O4xiii—N1—H1 | 98 (2) |
O1vi—O1—O2iv | 115.20 (4) | O3viii—N1—H1 | 81 (2) |
O5iv—O1—O2iv | 67.96 (5) | P1viii—N1—H1 | 64 (2) |
N1iv—O1—O2iv | 67.96 (5) | Zn1—N1—H2 | 110 (2) |
O5vii—O1—O2iv | 56.79 (5) | O3ix—N1—H2 | 129 (2) |
N1vii—O1—O2iv | 56.79 (5) | O5vi—N1—H2 | 85 (2) |
N1—O1—O2iv | 165.04 (7) | N1vi—N1—H2 | 85 (2) |
O5vi—O1—O2iv | 140.95 (7) | O1xiii—N1—H2 | 81 (2) |
N1vi—O1—O2iv | 140.95 (7) | O2viii—N1—H2 | 82 (2) |
P1—O2—Zn2 | 134.51 (9) | O2vi—N1—H2 | 149 (2) |
Zn2—O2—O1 | 153.44 (9) | O1—N1—H2 | 96 (2) |
Zn2—O2—O4 | 99.86 (7) | O1vi—N1—H2 | 140 (2) |
O1—O2—O4 | 60.53 (6) | O4xiii—N1—H2 | 109 (2) |
Zn2—O2—O3 | 128.26 (8) | O3viii—N1—H2 | 71 (2) |
O1—O2—O3 | 59.47 (6) | P1viii—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) | O3ix—N1—H3 | 103 (2) |
O4—O2—O4ii | 66.66 (4) | O5vi—N1—H3 | 87 (2) |
O3—O2—O4ii | 118.20 (7) | N1vi—N1—H3 | 87 (2) |
P1—O2—O4iii | 159.89 (9) | O1iii—N1—H3 | 90 (2) |
O1—O2—O4iii | 138.31 (7) | O2viii—N1—H3 | 90 (2) |
O4—O2—O4iii | 126.31 (7) | O2vi—N1—H3 | 47 (2) |
O3—O2—O4iii | 162.17 (7) | O1—N1—H3 | 139 (2) |
O4ii—O2—O4iii | 60.35 (4) | O1vi—N1—H3 | 89 (2) |
P1—O2—O3iii | 153.29 (9) | O5viii—N1—H3 | 148 (2) |
Zn2—O2—O3iii | 65.78 (5) | N1viii—N1—H3 | 148 (2) |
O1—O2—O3iii | 135.67 (7) | O3viii—N1—H3 | 60 (2) |
O4—O2—O3iii | 163.55 (7) | P1viii—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] |
Mr | 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) |
Tmin, Tmax | 0.298, 0.513 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1715, 913, 884 |
Rint | 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 |
Δρmax, Δρmin (e Å−3) | 0.34, −0.31 |
Selected bond lengths (Å) topZn1—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, °). topD—H···A | D—H | H···A | D···A | D—H···A |
N1/O5—H1···O3xii | 0.88 (1) | 2.17 (2) | 2.977 (3) | 151 (3) |
N1/O5—H2···O1iv | 0.93 (2) | 2.39 (3) | 3.165 (3) | 140 (3) |
N1/O5—H3···O1xiii | 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. topSample | Be3(PO4)2.2H2Oa | Be3(AsO4)2.2H2Ob | [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. |
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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 P1O4 and two symmetry-related Zn2O4 tetrahedra are connected at shared corners to form each six-membered Zn2—O2—P1—O4—Zn2v—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 Zn2v—O4—Zn2viii and P1—O4—Zn2v (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 Σνij(Zn1) = 2.02, Σνij(Pl) = 4.97 and Σνij(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)2 tetrahedra. 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.