Acta Cryst. (2009). E65, i85 [ doi:10.1107/S1600536809045632 ]
The title compound, CuHPO4, has been synthesized from a mixture of phosphoric acid and copper oxide. It has the same composition as MHPO4 (M = Ca, Ba, Pb, Sr or Sn), but adopts a rhombohedral structure with all atoms on general positions. The structure features distorted PO4 tetrahedra linked by copper, forming 12-membered rings. The CuII atom is coordinated by five O atoms in a distorted square-pyramidal manner. O-H
O hydrogen bonding leads to an additional stabilization of the structure.
Phosphoric acid (65%) and copper oxide were mixed in a mortar for several hours. Afterwards the mixture was tempered at 373 K for a week. CuHPO4 was obtained in the form of emerald-green needles, which decompose by further tempering.
The hydrogen atom of the hydroxyd-group was located by difference Fourier synthesis and refined isotropically.
Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor 1997); data reduction: DENZO (Otwinowski & Minor 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./fi2089fig1thm.gif)
| Fig. 1. The molecular structure of 1, showing 50% probability displacement ellipsoides and the numbering scheme for the complete coordination polyhedron about Cu1 (Symmetry codes: (A) z,x-1,y-1; (B) -z+2,-x+2,-y+1; (C) -x+2,-y+1,-z+1 and (D) y,z,x-1.) |
![[Figure 2]](./fi2089fig2thm.gif)
| Fig. 2. The intra and inter molecular O2—H2···O1 bonding about Cu1 (Symmetry codes: (A) z,x-1,y; (B) y+1,z,x-1 and (C) -y+1,-z+1,-x+1.) |
![[Figure 3]](./fi2089fig3thm.gif)
| Fig. 3. The intra and inter molecular O2—H2···O1 bonding about Cu1 (Symmetry codes: (A) z,x-1,y; (B) y+1,z,x-1 and (C) -y+1,-z+1,-x+1.) |
![[Figure 4]](./fi2089fig4thm.gif)
| Fig. 4. View of the unit cell of CuHPO~4~ along the z axis. |
![[Figure 5]](./fi2089fig5thm.gif)
| Fig. 5. Projection of the CuHPO4 structure along the z axis, with applied polyhedrale. |
| CuHPO4 | Dx = 3.205 Mg m−3 |
| Mr = 159.52 | Mo Kα radiation, λ = 0.71073 Å |
| Rhombohedral, R3 | Cell parameters from 3338 reflections |
| Hall symbol: -P 3* | θ = 3.4–27.5° |
| a = 9.5145 (4) Å | µ = 6.92 mm−1 |
| α = 114.678 (2)° | T = 183 K |
| V = 495.88 (6) Å3 | Needles, green |
| Z = 6 | 0.05 × 0.03 × 0.03 mm |
| F(000) = 462 |
| Bruker–Nonius KappaCCD diffractometer | 654 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.045 |
| graphite | θmax = 27.5°, θmin = 3.4° |
| φ and ω scans | h = −11→12 |
| 3338 measured reflections | k = −12→12 |
| 755 independent reflections | l = −12→12 |
| 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)] = 0.026 | All H-atom parameters refined |
| wR(F2) = 0.066 | w = 1/[σ2(Fo2) + (0.0403P)2 + 0.166P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.02 | (Δ/σ)max < 0.001 |
| 755 reflections | Δρmax = 0.62 e Å−3 |
| 60 parameters | Δρmin = −0.66 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.014 (2) |
| CuHPO4 | Z = 6 |
| Mr = 159.52 | Mo Kα radiation |
| Rhombohedral, R3 | µ = 6.92 mm−1 |
| a = 9.5145 (4) Å | T = 183 K |
| α = 114.678 (2)° | 0.05 × 0.03 × 0.03 mm |
| V = 495.88 (6) Å3 |
| Bruker–Nonius KappaCCD diffractometer | 654 reflections with I > 2σ(I) |
| 3338 measured reflections | Rint = 0.045 |
| 755 independent reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
| wR(F2) = 0.066 | All H-atom parameters refined |
| S = 1.02 | Δρmax = 0.62 e Å−3 |
| 755 reflections | Δρmin = −0.66 e Å−3 |
| 60 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
| x | y | z | Uiso*/Ueq | ||
| Cu1 | 0.91592 (6) | 0.43161 (6) | 0.19005 (6) | 0.00678 (18) | |
| P1 | 1.31526 (12) | 0.74973 (12) | 0.68353 (13) | 0.0059 (2) | |
| O1 | 1.1314 (4) | 0.5149 (4) | 0.4494 (3) | 0.0083 (5) | |
| O2 | 1.5471 (4) | 0.8561 (4) | 0.7726 (4) | 0.0106 (5) | |
| O3 | 1.3326 (3) | 0.7437 (3) | 0.8490 (3) | 0.0077 (5) | |
| O4 | 1.2753 (4) | 0.8882 (3) | 0.6838 (3) | 0.0087 (5) | |
| H2 | 1.555 (8) | 0.866 (8) | 0.689 (8) | 0.040 (14)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu1 | 0.0063 (2) | 0.0080 (3) | 0.0069 (2) | 0.0048 (2) | 0.0048 (2) | 0.0059 (2) |
| P1 | 0.0063 (4) | 0.0066 (4) | 0.0068 (4) | 0.0049 (3) | 0.0050 (3) | 0.0054 (3) |
| O1 | 0.0084 (11) | 0.0069 (11) | 0.0079 (11) | 0.0053 (10) | 0.0055 (10) | 0.0050 (10) |
| O2 | 0.0096 (11) | 0.0151 (12) | 0.0120 (11) | 0.0095 (10) | 0.0086 (10) | 0.0106 (10) |
| O3 | 0.0079 (10) | 0.0090 (11) | 0.0074 (10) | 0.0056 (9) | 0.0060 (9) | 0.0063 (9) |
| O4 | 0.0109 (11) | 0.0085 (10) | 0.0070 (10) | 0.0076 (9) | 0.0059 (9) | 0.0058 (9) |
| Cu1—O1 | 1.925 (2) | P1—O3 | 1.541 (2) |
| Cu1—O4i | 1.932 (2) | P1—O2 | 1.571 (2) |
| Cu1—O3ii | 1.971 (2) | O2—H2 | 0.87 (5) |
| Cu1—O3iii | 1.992 (2) | O3—Cu1v | 1.971 (2) |
| Cu1—O4iv | 2.360 (2) | O3—Cu1iii | 1.992 (2) |
| P1—O4 | 1.515 (2) | O4—Cu1vi | 1.932 (2) |
| P1—O1 | 1.530 (2) | O4—Cu1vii | 2.360 (2) |
| O1—Cu1—O4i | 163.91 (9) | O1—P1—O3 | 110.78 (12) |
| O1—Cu1—O3ii | 91.59 (9) | O4—P1—O2 | 111.98 (13) |
| O4i—Cu1—O3ii | 94.28 (9) | O1—P1—O2 | 109.68 (13) |
| O1—Cu1—O3iii | 94.20 (9) | O3—P1—O2 | 102.64 (12) |
| O4i—Cu1—O3iii | 84.72 (9) | P1—O1—Cu1 | 123.24 (13) |
| O3ii—Cu1—O3iii | 162.12 (8) | P1—O2—H2 | 110 (3) |
| O1—Cu1—O4iv | 112.90 (9) | P1—O3—Cu1v | 128.15 (13) |
| O4i—Cu1—O4iv | 83.13 (4) | P1—O3—Cu1iii | 126.96 (13) |
| O3ii—Cu1—O4iv | 74.64 (8) | Cu1v—O3—Cu1iii | 101.63 (10) |
| O3iii—Cu1—O4iv | 87.53 (8) | P1—O4—Cu1vi | 132.92 (13) |
| O4—P1—O1 | 110.21 (12) | P1—O4—Cu1vii | 125.51 (12) |
| O4—P1—O3 | 111.35 (12) | Cu1vi—O4—Cu1vii | 90.84 (8) |
| Symmetry codes: (i) z, x−1, y−1; (ii) −z+2, −x+2, −y+1; (iii) −x+2, −y+1, −z+1; (iv) y, z, x−1; (v) −y+2, −z+1, −x+2; (vi) y+1, z+1, x; (vii) z+1, x, y. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2···O1ii | 0.87 (5) | 1.93 (5) | 2.800 (3) | 176 (5) |
| Symmetry codes: (ii) −z+2, −x+2, −y+1. |
| Cu1—O1 | 1.925 (2) | P1—O4 | 1.515 (2) |
| Cu1—O4i | 1.932 (2) | P1—O1 | 1.530 (2) |
| Cu1—O3ii | 1.971 (2) | P1—O3 | 1.541 (2) |
| Cu1—O3iii | 1.992 (2) | P1—O2 | 1.571 (2) |
| Cu1—O4iv | 2.360 (2) |
| Symmetry codes: (i) z, x−1, y−1; (ii) −z+2, −x+2, −y+1; (iii) −x+2, −y+1, −z+1; (iv) y, z, x−1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2···O1ii | 0.87 (5) | 1.93 (5) | 2.800 (3) | 176 (5) |
| Symmetry codes: (ii) −z+2, −x+2, −y+1. |
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The hydrogen phosphate of copper(II) adopts the formula MHPO4 like other divalent cations. However, the monetites CaHPO4 (triclinic, P1; Smith et al., 1955), BaHPO4 (orthorhombic, Pccn; Bengtsson, 1941) and PbHPO4 (monoclinic, P2/c or Pc; Bengtsson, 1941) or SrHPO4 (triclinic, P1; Boudjada et al., 1978) and SnHPO4 (monoclinic, P21/c; Berndt & Lamberg, 1971) have very different structures, which could be due to the much bigger ionic radii of the metals in comparison to copper. CuHPO4 has a rhombohedral (R3) structure. The coordination of Cu can be described as a square pyramid, with the apical C–O bond being significantly longer than the other four bonds. The coordination in the base plane could even be described as a strongly squeezed, almost planar tetrahedron (Fig 1). The Cu ions are linked by distorted PO4 tetrahedra yielding twelve-membered rings (see Fig. 4, and Fig. 5). The distortion of the phosphate tetrahedra is caused by the OH-groups, which point towards the centre of the rings. There is only one hydrogen bond present in the asymmetric unit (see hydrogen bond geometry). But in the whole crystal structure, this leads to two intramolecular and three intermolecular hydrogen bonds (see Fig. 2 and Fig. 3). In other copper phosphates, the copper atoms are coordinated by four, five and/or six oxygen atoms, respectively (Boudjada, 1980; Sierra et al., 2003; Lukaszewicz, 1966; Robertson & Calvo, 1968; Laügt et al., 1972). CuHPO4 formed only trigonal bipyramids of CuO5.