Copper(II) hydrogenphosphate, CuHPO4

Günther, C.; Görls, H.; Stachel, D.

doi:10.1107/S1600536809045632

inorganic compounds

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Copper(II) hydrogenphosphate, CuHPO₄

Christiane Günther,^a Helmar Görls ^b and Dörte Stachel ^a ^*

^aOtto-Schott-Institut, Friedrich-Schiller-Universität Jena, Frauenhoferstrasse 6, 07745 Jena, Germany, and ^bInstitute of Inorganic and Analytical Chemistry, Friedrich-Schiller-Universität Jena, August-Bebel-Strasse 2, D-07743 Jena, Germany
^*Correspondence e-mail: doerte.stachel@uni-jena.de

(Received 2 September 2009; accepted 30 October 2009; online 7 November 2009)

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 Cu^II 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.

Related literature

For the structure of CaHPO₄, see: Smith et al. (1955 ); MacLennan & Beevers (1955 ). For a report about BaHPO₄ and PbHPO₄, see: Bengtsson (1941 ). For the structure of SnHPO₄, see: Berndt & Lamberg (1971 ). For information about SrHPO₄, see: Boudjada et al. (1978 ). For a report about CuHPO₄·H₂O, see: Boudjada (1980 ). For information about CuHPO₄·0.5 H₂O see: Sierra et al. (2003 ). For the structure of α-Cu₂P₂O₇, see: Lukaszewicz (1966 ). For information about β-Cu₂P₂O₇, see: Robertson & Calvo (1968 ). For a report about Cu₂P₄O₁₂, see: Laügt et al. (1972 ).

Experimental

Crystal data

CuHPO₄
M_r = 159.52
Rhombohedral, $[R \overline 3]$
a = 9.5145 (4) Å
α = 114.678 (2)°
V = 495.88 (6) Å³
Z = 6
Mo Kα radiation
μ = 6.92 mm⁻¹
T = 183 K
0.05 × 0.03 × 0.03 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: none
3338 measured reflections
755 independent reflections
654 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.066
S = 1.02
755 reflections
60 parameters
All H-atom parameters refined
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.66 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—O1	1.925 (2)
Cu1—O4ⁱ	1.932 (2)
Cu1—O3ⁱⁱ	1.971 (2)
Cu1—O3ⁱⁱⁱ	1.992 (2)
Cu1—O4^iv	2.360 (2)
P1—O4	1.515 (2)
P1—O1	1.530 (2)
P1—O3	1.541 (2)
P1—O2	1.571 (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.

Table 2
Hydrogen-bond geometry (Å, °)

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 code: (ii) -z+2, -x+2, -y+1.

Data collection: COLLECT (Nonius, 1998 ); cell refinement: DENZO (Otwinowski & Minor 1997 ); data reduction: DENZO; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809045632/fi2089sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809045632/fi2089Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

For the structure of CaHPO₄, see: Smith et al. (1955); MacLennan & Beevers (1955). For a report about BaHPO₄ and PbHPO₄, see: Bengtsson (1941). For the structure of SnHPO₄, see: Berndt & Lamberg (1971). For information about SrHPO₄, see: Boudjada et al. (1978). For a report about CuHPO₄*H₂O, see: Boudjada (1980). For information about CuHPO₄.0.5 H₂O see: Sierra et al. (2003). For the structure of α-Cu₂P₂O₇, see: Lukaszewicz (1966). For information about β-Cu₂P₂O₇, see: Robertson & Calvo (1968). For a report about Cu₂P₄O₁₂, see: Laügt et al. (1972).

Experimental top

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.

Computing details top

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).

Figures top

	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.)
	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.)
	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.)
	Fig. 4. View of the unit cell of CuHPO~4~ along the z axis.
	Fig. 5. Projection of the CuHPO₄ structure along the z axis, with applied polyhedrale.

Copper(II) hydrogenphosphate top

Crystal data top

CuHPO₄	D_x = 3.205 Mg m⁻³
M_r = 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

Data collection top

Bruker–Nonius KappaCCD diffractometer	654 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.045
Graphite monochromator	θ_max = 27.5°, θ_min = 3.4°
ϕ and ω scans	h = −11→12
3338 measured reflections	k = −12→12
755 independent reflections	l = −12→12

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)] = 0.026	All H-atom parameters refined
wR(F²) = 0.066	w = 1/[σ²(F_o²) + (0.0403P)² + 0.166P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
755 reflections	Δρ_max = 0.62 e Å⁻³
60 parameters	Δρ_min = −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)

Crystal data top

CuHPO₄	Z = 6
M_r = 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

Data collection top

Bruker–Nonius KappaCCD diffractometer	654 reflections with I > 2σ(I)
3338 measured reflections	R_int = 0.045
755 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.066	All H-atom parameters refined
S = 1.02	Δρ_max = 0.62 e Å⁻³
755 reflections	Δρ_min = −0.66 e Å⁻³
60 parameters

Special details top

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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—Cu1^v	1.971 (2)
Cu1—O4^iv	2.360 (2)	O3—Cu1ⁱⁱⁱ	1.992 (2)
P1—O4	1.515 (2)	O4—Cu1^vi	1.932 (2)
P1—O1	1.530 (2)	O4—Cu1^vii	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—O4^iv	112.90 (9)	P1—O3—Cu1^v	128.15 (13)
O4ⁱ—Cu1—O4^iv	83.13 (4)	P1—O3—Cu1ⁱⁱⁱ	126.96 (13)
O3ⁱⁱ—Cu1—O4^iv	74.64 (8)	Cu1^v—O3—Cu1ⁱⁱⁱ	101.63 (10)
O3ⁱⁱⁱ—Cu1—O4^iv	87.53 (8)	P1—O4—Cu1^vi	132.92 (13)
O4—P1—O1	110.21 (12)	P1—O4—Cu1^vii	125.51 (12)
O4—P1—O3	111.35 (12)	Cu1^vi—O4—Cu1^vii	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.

Hydrogen-bond geometry (Å, º) top

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 code: (ii) −z+2, −x+2, −y+1.

Experimental details

Crystal data
Chemical formula	CuHPO₄
M_r	159.52
Crystal system, space group	Rhombohedral, R3
Temperature (K)	183
a, c (Å)	9.5145 (4), 9.5145 (4)
α (°)	114.678 (2)
V (Å³)	495.88 (6)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	6.92
Crystal size (mm)	0.05 × 0.03 × 0.03

Data collection
Diffractometer	Bruker–Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3338, 755, 654
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.066, 1.02
No. of reflections	755
No. of parameters	60
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.62, −0.66

Computer programs: COLLECT (Nonius, 1998), DENZO (Otwinowski & Minor 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006).

Selected bond lengths (Å) top

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—O4^iv	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.

Hydrogen-bond geometry (Å, º) top

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 code: (ii) −z+2, −x+2, −y+1.

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page i85

doi:10.1107/S1600536809045632

Open

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