An open-framework borophosphate, LiCu2BP2O8(OH)2

Zheng, J.; Zhang, A.

doi:10.1107/S1600536809015554

inorganic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page i40

doi:10.1107/S1600536809015554

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An open-framework borophosphate, LiCu₂BP₂O₈(OH)₂

Juan Zheng ^a and Aiyun Zhang ^a ^*

^aDepartment of Physics and Chemistry, Henan Polytechnic University, Jiaozuo 454000, People's Republic of China
^*Correspondence e-mail: zay@hpu.edu.cn

(Received 15 April 2009; accepted 26 April 2009; online 30 April 2009)

The open-framework alkaline-earth metal borophosphate, lithium dicopper(II) borophosphate dihydroxide, LiCu₂BP₂O₈(OH)₂, was synthesized hydrothermally. Its structure may be regarded as a layer formed via BO₄ and PO₄ tetrahedra bonding together with distorted CuO₆ and LiO₆ octahedral units. Each P atom is connected to B, Li and Cu atoms through a bridging O atom. The B atom lies on a crystallographic twofold axis and the Li atom lies on a center of symmetry. The two metal centers are connected to each other by Cu—O—Li bonds.

Related literature

For chiral structures and potential applications in catalysis of borophosphates with the general formula AM(H₂O)₂[BP₂O₈].yH₂O (A = Li, Na, K, NH₄⁺; M = Mg, Mn, Fe, Co, Ni, Cu, Zn, Cd) (y = 0.5–1), see: Ewald et al. (2007 ); Kniep et al. (1997 ). For related structures, see: Boy & Kniep (2001 ); Yang et al. (2008 ).

Experimental

Crystal data

LiCu₂BP₂O₈(OH)₂
M_r = 368.79
Monoclinic, C 2/c
a = 15.0974 (19) Å
b = 4.7617 (6) Å
c = 9.6585 (12) Å
β = 91.0190 (10)°
V = 694.23 (15) Å³
Z = 4
Mo Kα radiation
μ = 6.64 mm⁻¹
T = 296 K
0.20 × 0.18 × 0.17 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.350, T_max = 0.398 (expected range = 0.285–0.324)
4076 measured reflections
925 independent reflections
897 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.019
wR(F²) = 0.054
S = 1.18
925 reflections
79 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.53 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O2ⁱ	0.848 (10)	2.37 (3)	2.9535 (19)	126 (3)
O4—H4⋯O5ⁱⁱ	0.848 (10)	2.32 (2)	3.036 (2)	143 (3)
Symmetry codes: (i) $[x, -y+2, z+{\script{1\over 2}}]$ ; (ii) $[x, -y+1, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809015554/br2104sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809015554/br2104Isup2.hkl

checkCIF report

Comment top

In the last decade, much attention has been paid to the large family of borophosphates with the general formula AM(H₂O)₂[BP₂O₈].yH₂O (A=Li, Na, K, NH4⁺; M=Mg, Mn, Fe, Co, Ni, Cu, Zn, Cd) (y = 0.5–1) due to their chiral structure property and potential applications for catalysts (Kniep et al., 1997; Ewald et al., 2007).

The crystal structure of LiCu₂BP₂O₈(OH)₂contains one unique Li atom, two Cu atoms, one boron atom, two phosphor atoms, and eight oxygen atoms and two –OH groups in the asymmetric unit of the framework. The borophosphate units are isolated anions linked by the bonds them form to Cu, Li and H. (Fig.1) Each BO₄ tetrahedron belongs to the adjacent CuO₆ octahedra. The phosphorous atoms are allocated in regular tetrahedral environments with four types of oxygen atoms. Bond lengths and angles within the anionic partial structure are consistent with related borophosphates (Boy et al., 2001; Yang et al. 2008),. Li⁺ is coordinated by the oxygen functions groups of PO₄groups. Cu²⁺ is adjacent to six oxygen atoms, five from PO₄groups and one BO₄ groups, but one of the five PO₄ links (O3) is also bonded to BO₄ (Fig.2)

Related literature top

For the chiral structure and potential applications in catalysis of borophosphates with the general formula AM(H₂O)₂[BP₂O₈].yH₂O (A = Li, Na, K, NH4⁺; M = Mg, Mn, Fe, Co, Ni, Cu, Zn, Cd) (y = 0.5–1), see: Ewald et al. (2007); Kniep et al. (1997). For related structures, see: Boy & Kniep (2001); Yang et al. (2008).

Experimental top

Blue block crystals were synthesized hydrothermally from a mixture of Cu(NO₃)₂, Li₂B₄O₇,water and H₃PO₄. In a typical synthesis, 0.725 g Cu(NO₃)₂ were dissolved in a mixture of 5 mL water, 1.691 g Li₂B₄O₇ and 2 ml (85%) H₃PO₄with constant stirring. Finally,the mixture was kept in a 30 ml Teflon–lined steel autoclave at 443 K for 6days.The autoclave was slowly cooled to room temperature. Blue block crystals of thetitle compound were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of LiCu₂BP₂O₈(OH)₂. Displacement ellipsoids are drawn at 50% the probability level.
	Fig. 2. Packing diagram of LiCu₂BP₂O₈(OH)₂,viewed along b axis.

lithium dicopper borophosphate dihydroxide top

Crystal data top

LiCu₂BP₂O₈(OH)₂	F(000) = 712
M_r = 368.79	D_x = 3.528 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3236 reflections
a = 15.0974 (19) Å	θ = 2.7–29.3°
b = 4.7617 (6) Å	µ = 6.64 mm⁻¹
c = 9.6585 (12) Å	T = 296 K
β = 91.019 (1)°	Block, blue
V = 694.23 (15) Å³	0.20 × 0.18 × 0.17 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	925 independent reflections
Radiation source: fine-focus sealed tube	897 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ϕ and ω scans	θ_max = 29.3°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −20→20
T_min = 0.350, T_max = 0.398	k = −6→6
4076 measured 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)] = 0.019	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.054	w = 1/[σ²(F_o²) + (0.0258P)² + 1.3109P] where P = (F_o² + 2F_c²)/3
S = 1.18	(Δ/σ)_max = 0.001
925 reflections	Δρ_max = 0.63 e Å⁻³
79 parameters	Δρ_min = −0.53 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0350 (13)

Crystal data top

LiCu₂BP₂O₈(OH)₂	V = 694.23 (15) Å³
M_r = 368.79	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 15.0974 (19) Å	µ = 6.64 mm⁻¹
b = 4.7617 (6) Å	T = 296 K
c = 9.6585 (12) Å	0.20 × 0.18 × 0.17 mm
β = 91.019 (1)°

Data collection top

Bruker APEXII CCD diffractometer	925 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	897 reflections with I > 2σ(I)
T_min = 0.350, T_max = 0.398	R_int = 0.032
4076 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.019	1 restraint
wR(F²) = 0.054	H atoms treated by a mixture of independent and constrained refinement
S = 1.18	Δρ_max = 0.63 e Å⁻³
925 reflections	Δρ_min = −0.53 e Å⁻³
79 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 > 2sigma(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	0.350210 (15)	1.20604 (5)	0.77155 (2)	0.00731 (13)
P2	0.35630 (3)	0.67849 (9)	0.58833 (5)	0.00503 (14)
O3	0.44649 (9)	0.5916 (3)	0.65917 (14)	0.0085 (3)
O2	0.34451 (9)	0.9972 (3)	0.59584 (13)	0.0080 (3)
O1	0.28531 (9)	0.5146 (3)	0.66790 (13)	0.0074 (3)
O5	0.35401 (9)	0.5717 (3)	0.44007 (13)	0.0085 (3)
O4	0.44543 (9)	0.9550 (3)	0.83773 (13)	0.0101 (3)
B	0.5000	0.7756 (6)	0.7500	0.0069 (5)
Li	0.2500	1.2500	0.5000	0.0201 (11)
H4	0.425 (2)	0.852 (6)	0.901 (2)	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01075 (17)	0.00604 (17)	0.00510 (16)	0.00214 (8)	−0.00107 (9)	−0.00075 (7)
P2	0.0066 (2)	0.0042 (2)	0.0042 (2)	−0.00019 (15)	−0.00068 (16)	0.00003 (15)
O3	0.0084 (6)	0.0069 (6)	0.0100 (6)	0.0005 (5)	−0.0034 (5)	−0.0008 (5)
O2	0.0118 (6)	0.0048 (6)	0.0072 (6)	0.0011 (5)	−0.0018 (5)	−0.0006 (5)
O1	0.0082 (6)	0.0068 (6)	0.0073 (6)	0.0005 (5)	0.0014 (4)	0.0022 (5)
O5	0.0130 (7)	0.0076 (6)	0.0049 (6)	0.0003 (5)	−0.0001 (5)	−0.0001 (5)
O4	0.0119 (6)	0.0116 (7)	0.0067 (6)	0.0041 (5)	0.0004 (5)	0.0000 (5)
B	0.0079 (13)	0.0056 (12)	0.0073 (13)	0.000	−0.0006 (10)	0.000
Li	0.021 (3)	0.017 (2)	0.022 (3)	0.006 (2)	−0.012 (2)	−0.006 (2)

Geometric parameters (Å, º) top

Cu1—O5ⁱ	1.9415 (13)	P2—O1	1.5420 (14)
Cu1—O2	1.9674 (14)	P2—O3	1.5686 (14)
Cu1—O4	1.9676 (14)	B—O4^iv	1.467 (2)
Cu1—O1ⁱⁱ	2.0213 (13)	B—O3^iv	1.471 (2)
Cu1—O1ⁱⁱⁱ	2.3242 (13)	Li—O2^v	2.0723 (14)
P2—O5	1.5195 (13)	Li—O1ⁱⁱ	2.1143 (13)
P2—O2	1.5300 (15)	Li—O5ⁱⁱ	2.2758 (14)

O5ⁱ—Cu1—O2	177.21 (6)	P2—O5—Cu1^viii	127.40 (8)
O5ⁱ—Cu1—O4	92.77 (6)	P2—O5—Li^vi	89.42 (6)
O2—Cu1—O4	89.64 (6)	Cu1^viii—O5—Li^vi	124.75 (6)
O5ⁱ—Cu1—O1ⁱⁱ	91.48 (6)	B—O4—Cu1	125.51 (9)
O2—Cu1—O1ⁱⁱ	85.80 (6)	O4^iv—B—O4	108.8 (2)
O4—Cu1—O1ⁱⁱ	161.34 (6)	O4^iv—B—O3	108.09 (7)
O5ⁱ—Cu1—O1ⁱⁱⁱ	90.91 (5)	O4—B—O3	112.53 (8)
O2—Cu1—O1ⁱⁱⁱ	89.63 (5)	O4^iv—B—O3^iv	112.53 (8)
O4—Cu1—O1ⁱⁱⁱ	108.74 (6)	O4—B—O3^iv	108.09 (7)
O1ⁱⁱ—Cu1—O1ⁱⁱⁱ	89.35 (3)	O3—B—O3^iv	106.9 (2)
O5—P2—O2	112.09 (8)	O2—Li—O2^v	180.0
O5—P2—O1	107.21 (8)	O2—Li—O1ⁱⁱ	80.86 (5)
O2—P2—O1	113.33 (8)	O2^v—Li—O1ⁱⁱ	99.14 (5)
O5—P2—O3	109.13 (8)	O2—Li—O1^ix	99.14 (5)
O2—P2—O3	109.99 (8)	O2^v—Li—O1^ix	80.86 (5)
O1—P2—O3	104.75 (7)	O1ⁱⁱ—Li—O1^ix	180.0
B—O3—P2	124.48 (13)	O2—Li—O5ⁱⁱ	91.82 (5)
P2—O2—Cu1	122.61 (8)	O2^v—Li—O5ⁱⁱ	88.18 (5)
P2—O2—Li	129.39 (8)	O1ⁱⁱ—Li—O5ⁱⁱ	68.18 (5)
Cu1—O2—Li	96.37 (6)	O1^ix—Li—O5ⁱⁱ	111.82 (5)
P2—O1—Cu1^vi	106.24 (7)	O2—Li—O5^ix	88.18 (5)
P2—O1—Li^vi	95.01 (6)	O2^v—Li—O5^ix	91.82 (5)
Cu1^vi—O1—Li^vi	93.45 (6)	O1ⁱⁱ—Li—O5^ix	111.82 (5)
P2—O1—Cu1^vii	123.34 (8)	O1^ix—Li—O5^ix	68.18 (5)
Cu1^vi—O1—Cu1^vii	125.56 (6)	O5ⁱⁱ—Li—O5^ix	180.0
Li^vi—O1—Cu1^vii	102.45 (5)

Symmetry codes: (i) x, −y+2, z+1/2; (ii) x, y+1, z; (iii) −x+1/2, y+1/2, −z+3/2; (iv) −x+1, y, −z+3/2; (v) −x+1/2, −y+5/2, −z+1; (vi) x, y−1, z; (vii) −x+1/2, y−1/2, −z+3/2; (viii) x, −y+2, z−1/2; (ix) −x+1/2, −y+3/2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O2ⁱ	0.85 (1)	2.37 (3)	2.9535 (19)	126 (3)
O4—H4···O5^x	0.85 (1)	2.32 (2)	3.036 (2)	143 (3)

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

Experimental details

Crystal data
Chemical formula	LiCu₂BP₂O₈(OH)₂
M_r	368.79
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	15.0974 (19), 4.7617 (6), 9.6585 (12)
β (°)	91.019 (1)
V (Å³)	694.23 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	6.64
Crystal size (mm)	0.20 × 0.18 × 0.17

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.350, 0.398
No. of measured, independent and observed [I > 2σ(I)] reflections	4076, 925, 897
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.689

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.019, 0.054, 1.18
No. of reflections	925
No. of parameters	79
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.53

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O2ⁱ	0.848 (10)	2.37 (3)	2.9535 (19)	126 (3)
O4—H4···O5ⁱⁱ	0.848 (10)	2.32 (2)	3.036 (2)	143 (3)

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

Acknowledgements

This work was supported by the Main Teacher Project of Henan Province (Reference 649082) and the Foundation of Graduate Produce (Reference 2008-M-17).

References

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