The β-modification of trizinc borate phosphate, Zn3(BO3)(PO4)

Zhang, E.; Zhao, S.; Zhang, J.; Fu, P.; Yao, J.

doi:10.1107/S1600536810051871

inorganic compounds

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Volume 67| Part 1| January 2011| Page i3

https://doi.org/10.1107/S1600536810051871

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The β-modification of trizinc borate phosphate, Zn₃(BO₃)(PO₄)

Erpan Zhang,^a,^b Sangen Zhao,^a,^b Jianxiu Zhang,^a Peizhen Fu ^a and Jiyong Yao ^a ^*

^aKey Laboratory of Functional Crystal and Laser Technology, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, People's Republic of China, and ^bGraduate University of Chinese Academy of Sciences, Beijing 100049, People's Republic of China
^*Correspondence e-mail: jyao@mail.ipc.ac.cn

(Received 20 October 2010; accepted 10 December 2010; online 24 December 2010)

Crystals of β-Zn₃(BO₃)(PO₄) have been grown by the Kyropoulos method. The asymmetric unit contains three Zn sites, three B-atom sites (all with symmetry 3), two P sites (both with m symmetry) and nine O-atom sites (four with m symmetry). The fundamental building units of the title structure are isolated BO₃ triangles and PO₄ tetrahedra, which are bridged by ZnO₄ tetrahedra or ZnO₅ trigonal bipyramids through common O atoms, leading to a three-dimensional framework structure. Some significant structural differences between the β-polymorph and the α-polymorph are discussed.

Related literature

For general backround to Zn₃(BO₃)(PO₄), see: Liebertz & Stahr (1982 ). For crystal growth of β-Zn₃(BO₃)(PO₄), see: Wang et al. (2000 ); Wu & Wang (2001 ); Liu et al. (2002 ). For structure refinement of α-Zn₃(BO₃)(PO₄), see: Bluhm & Park (1997 ). For structurally related compounds, see: Ma et al. (2004 ); Yilmaz et al. (2001 ). Reviews on borophosphates were given by Kniep et al. (1998 ) and Ewald et al. (2007 ).

Experimental

Crystal data

Zn₃(BO₃)(PO₄)
M_r = 349.89
Hexagonal, $[P \overline 6]$
a = 8.4624 (3) Å
c = 13.0690 (7) Å
V = 810.51 (4) Å³
Z = 6
Mo Kα radiation
μ = 13.49 mm⁻¹
T = 294 K
0.25 × 0.22 × 0.16 mm

Data collection

Rigaku Saturn CCD diffractometer
Absorption correction: numerical (NUMABS; Rigaku, 2005 ) T_min = 0.133, T_max = 0.221
10584 measured reflections
1453 independent reflections
1226 reflections with I > 2σ(I)
R_int = 0.062

Refinement

R[F² > 2σ(F²)] = 0.019
wR(F²) = 0.039
S = 0.96
1453 reflections
118 parameters
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.52 e Å⁻³
Absolute structure: Flack (1983 ), 718 Friedel pairs
Flack parameter: 0.011 (10)

Table 1
Selected bond lengths (Å)

Zn1—O7	1.9248 (17)
Zn1—O2ⁱ	1.9293 (19)
Zn1—O3ⁱⁱ	2.084 (2)
Zn1—O1	2.100 (2)
Zn2—O7	1.9529 (17)
Zn2—O9ⁱⁱⁱ	1.9604 (18)
Zn2—O8^iv	1.9656 (17)
Zn2—O4	2.2019 (18)
Zn2—O2	2.3238 (18)
Zn3—O4^v	1.9958 (18)
Zn3—O8	2.035 (2)
Zn3—O5	2.0704 (18)
Zn3—O6^vi	2.0748 (18)
Zn3—O9	2.079 (2)
B1—O7	1.3792 (18)
B2—O8	1.3880 (18)
B3—O9	1.3775 (17)
P1—O3	1.541 (3)
P1—O1	1.542 (3)
P1—O2	1.5484 (18)
P2—O5	1.529 (3)
P2—O6	1.540 (3)
P2—O4	1.5412 (18)
Symmetry codes: (i) -y+1, x-y+1, z; (ii) -x+y+1, -x+2, z; (iii) -y+1, x-y, -z+1; (iv) x, y, -z+1; (v) -y+2, x-y+1, -z+1; (vi) -x+y+1, -x+1, z.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810051871/wm2419sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810051871/wm2419Isup2.hkl

checkCIF report

Comment top

Liebertz & Stahr reported the existence of Zn₃(BO₃)(PO₄) in 1982 (Liebertz & Stahr, 1982). Zn₃(BO₃)(PO₄) (ZBP) can exist in two modifications, one low-temperature phase denoted α and one high-temperature phase denoted β. The phase transition point is 875 K. Some significant features of β-Zn₃(BO₃)(PO₄) make it attractive as a promising NLO material. However, β-Zn₃(BO₃)(PO₄) crystals grown from the melt frequently have a poor quality when cooling to room temperature. Hence considerable effort has been made to obtain high-quality β-Zn₃(BO₃)(PO₄) crystals (Wang et al., 2000; Wu & Wang, 2001; Liu et al., 2002). In this paper, β-Zn₃(BO₃)(PO₄) crystals were obtained through a rapid cooling method. The structural differences between α-Zn₃(BO₃)(PO₄) and β-Zn₃(BO₃)(PO₄) are described, and we also briefly discuss the structural differences between β-Zn₃(BO₃)(PO₄) and the structures of other borate-phosphates and borophosphates.

The asymmetric unit of the title structure contains three Zn sites, three B sites (all with site symmetry 3), two P sites (both with m symmetry) and nine O sites (four of which with m symmetry) (Fig. 1). The fundamental structural building units are isolated BO₃ triangles and PO₄ tetrahedra. These units are alternately oriented parallel to (001) and stacked layer upon layer along [001] (Figs. 2 and 3). The isolated character of the anionic units classifies this compound as a borate-phosphate in contrast to borophosphates, where at least one BO₃ (or BO₄) group and one PO₄ tetrahedron share a common O atom. Reviews on the crystal chemistry of the latter class of compounds were given by Kniep et al. (1998) and Ewald et al. (2007).

The BO₃ triangles show an equilateral trigonal-planar configuration. The P—O distances range between 1.529 (3) Å and 1.5484 (18) Å, indicating a slight distortion of the two PO₄ tetrahedra in this structure. The Zn atoms selectively occupy the space between the anionic layers and are bonded to the terminal O atoms of the anions. The coordination environments of the three independent Zn are different from another. Zn1 is tetrahedrally surrounded by atoms O7, O2, O3 and O1, with Zn—O distances in the range 1.9248 (17) Å – 2.100 (2) Å. Zn2 and Zn3 are five-coordinate by oxygen within a trigonal bipyramid and Zn—O distances range from 1.9529 (17) Å to 2.3238 (18) Å for Zn2 and from 1.9958 (17) Å to 2.079 (2) Å for Zn3. The isolated BO₃ and PO₄ groups are linked to ZnO₅ or ZnO₄ polyhedra by sharing one corner O atom. In addition, ZnO₅ and ZnO₄ polyhedra are linked together by sharing one corner O atom. Individual ZnO₄ tetrahedra and ZnO₅ polyhedra, respectively, also share a common edge.

To the best of our knowledge, besides β-Zn₃(BO₃)(PO₄), α-Zn₃(BO₃)(PO₄) (Bluhm & Park, 1997), Co₃(BO₃)(PO₄) (Yilmaz et al., 2001) and Ba₃(BO₃)(PO₄) (Ma et al.., 2004) are the only three other borate-phosphates. In comparison with β-Zn₃(BO₃)(PO₄), in the structure of α-Zn₃(BO₃)(PO₄) the BO₃ and PO₄ groups are also linked to ZnO₅ trigonal bipyramids and ZnO₄ tetrahedra by sharing O atoms. However, the symmetry of the two structures is different. During the α → β phase transformation, the positions of the isolated BO₃ and PO₄ groups are rearranged, accompanied with a change from space group Cm (α-phase) to P6 (β-phase). The density of low-temperature α-Zn₃(BO₃)(PO₄) is 4.44 g/cm³ (Bluhm & Park, 1997), while the density of high-temperature β-Zn₃(BO₃)(PO₄) is 4.30 g/cm³, pointing to α-Zn₃(BO₃)(PO₄) as the thermodynamically stable phase. It should be noted that the β-Zn₃(BO₃)(PO₄) structure type is different from Ba₃(BO₃)(PO₄) (space group P6₃mc) whereas Co₃(BO₃)(PO₄) is isotypic with α-Zn₃(BO₃)(PO₄). The differences between the Ba-containing structure and the structures containing the first row-transition metals is caused by the different ionic radii of the metal cations and consequently by a different coordination environment.

Related literature top

For general backround to Zn₃(BO₃)(PO₄), see: Liebertz & Stahr (1982). For crystal growth of β-Zn₃(BO₃)(PO₄), see: Wang et al. (2000); Wu & Wang (2001); Liu et al. (2002). For structure refinement of α-Zn₃(BO₃)(PO₄), see: Bluhm & Park (1997). For structurally related compounds, see: Ma et al. (2004); Yilmaz et al. (2001). Reviews on borophosphates were given by Kniep et al. (1998) and Ewald et al. (2007).

Experimental top

Zn₃(BO₃)(PO₄) was synthesized by a standard solid-state reaction of the starting components, using chemically pure ZnO, H₃BO₃ and NH₄H₂PO₄ in the molar ratio of 3:1:1. A platinum crucible filled with Zn₃(BO₃)(PO₄) was heated to 1273 K, kept at that temperature for 12 h, and then was cooled to the saturation temperature. A seed crystal of β-Zn₃(BO₃)(PO₄) attached to a platinum rod was inserted into the solution, and then the temperature was cooled at a rate of 0.3 K^.d^-1 until the end of the growth. The obtained crystal was pulled out of the surface of the solution, cooled to 700 K at a rate of 20 K/h, and then cooled rapidly to 620 K in 1.5 h. Finally, the crystal was removed out of the furnace and cooled to room temperature.

Structure description top

For general backround to Zn₃(BO₃)(PO₄), see: Liebertz & Stahr (1982). For crystal growth of β-Zn₃(BO₃)(PO₄), see: Wang et al. (2000); Wu & Wang (2001); Liu et al. (2002). For structure refinement of α-Zn₃(BO₃)(PO₄), see: Bluhm & Park (1997). For structurally related compounds, see: Ma et al. (2004); Yilmaz et al. (2001). Reviews on borophosphates were given by Kniep et al. (1998) and Ewald et al. (2007).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The asymmetric unit of β-Zn₃(BO₃)(PO₄) with atom labelling and ellipsoids drawn at the 90% probability level.
	Fig. 2. Crystal structure of β-Zn₃(BO₃)(PO₄) illustrated with isolated BO₃ and PO₄ groups.
	Fig. 3. The structure of β-Zn₃(BO₃)(PO₄) viewed along [001].

trizinc borate phosphate top

Crystal data top

Zn₃(BO₃)(PO₄)	D_x = 4.301 Mg m⁻³
M_r = 349.89	Melting point: 1200 K
Hexagonal, P6	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 6	Cell parameters from 2470 reflections
a = 8.4624 (3) Å	θ = 1.6–28.7°
c = 13.0690 (7) Å	µ = 13.49 mm⁻¹
V = 810.51 (4) Å³	T = 294 K
Z = 6	Prism, colorless
F(000) = 996	0.25 × 0.22 × 0.16 mm

Data collection top

Rigaku Saturn CCD diffractometer	1453 independent reflections
Radiation source: fine-focus sealed tube	1226 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.062
Detector resolution: 7.31 pixels mm^-1	θ_max = 28.6°, θ_min = 1.6°
ω scans	h = −11→10
Absorption correction: numerical (NUMABS; Rigaku, 2005)	k = −11→11
T_min = 0.133, T_max = 0.221	l = −17→17
10584 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0099P)²] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.019	(Δ/σ)_max = 0.004
wR(F²) = 0.039	Δρ_max = 0.61 e Å⁻³
S = 0.96	Δρ_min = −0.52 e Å⁻³
1453 reflections	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
118 parameters	Extinction coefficient: 0.0328 (7)
0 restraints	Absolute structure: Flack (1983), 718 Friedel pairs
0 constraints	Absolute structure parameter: 0.011 (10)
Primary atom site location: structure-invariant direct methods

Crystal data top

Zn₃(BO₃)(PO₄)	Z = 6
M_r = 349.89	Mo Kα radiation
Hexagonal, P6	µ = 13.49 mm⁻¹
a = 8.4624 (3) Å	T = 294 K
c = 13.0690 (7) Å	0.25 × 0.22 × 0.16 mm
V = 810.51 (4) Å³

Data collection top

Rigaku Saturn CCD diffractometer	1453 independent reflections
Absorption correction: numerical (NUMABS; Rigaku, 2005)	1226 reflections with I > 2σ(I)
T_min = 0.133, T_max = 0.221	R_int = 0.062
10584 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.019	0 restraints
wR(F²) = 0.039	Δρ_max = 0.61 e Å⁻³
S = 0.96	Δρ_min = −0.52 e Å⁻³
1453 reflections	Absolute structure: Flack (1983), 718 Friedel pairs
118 parameters	Absolute structure parameter: 0.011 (10)

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
Zn1	0.67111 (7)	0.98916 (9)	0.88495 (3)	0.01824 (11)
Zn2	0.66452 (5)	0.67089 (5)	0.74557 (2)	0.01218 (11)
Zn3	0.99324 (6)	0.64008 (5)	0.38229 (3)	0.00982 (9)
B1	1.0000	1.0000	0.8052 (5)	0.0097 (11)*
B2	0.6667	0.3333	0.2820 (5)	0.0110 (12)
B3	1.3333	0.6667	0.2751 (4)	0.0088 (11)
P1	0.64705 (15)	0.63672 (14)	1.0000	0.0085 (2)
P2	0.68800 (15)	0.70242 (14)	0.5000	0.0083 (2)
O1	0.6018 (3)	0.7921 (4)	1.0000	0.0140 (6)
O2	0.5676 (3)	0.5214 (2)	0.90172 (13)	0.0137 (4)
O3	0.8535 (3)	0.7058 (4)	1.0000	0.0146 (7)
O4	0.7144 (2)	0.8140 (2)	0.59811 (13)	0.0116 (4)
O5	0.8298 (4)	0.6407 (4)	0.5000	0.0141 (6)
O6	0.4931 (4)	0.5371 (4)	0.5000	0.0135 (6)
O7	0.8121 (2)	0.9147 (2)	0.80352 (13)	0.0116 (4)
O8	0.7773 (3)	0.5217 (2)	0.28461 (17)	0.0123 (5)
O9	1.1480 (2)	0.6008 (2)	0.27238 (16)	0.0124 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0165 (2)	0.0204 (2)	0.0210 (2)	0.01163 (17)	0.00515 (18)	−0.00218 (19)
Zn2	0.0110 (2)	0.01191 (19)	0.0137 (2)	0.00580 (16)	−0.00283 (15)	−0.00386 (13)
Zn3	0.0110 (2)	0.01235 (19)	0.00559 (17)	0.00543 (19)	−0.00002 (14)	−0.00152 (13)
B2	0.0095 (18)	0.0095 (18)	0.014 (3)	0.0048 (9)	0.000	0.000
B3	0.0120 (17)	0.0120 (17)	0.002 (3)	0.0060 (9)	0.000	0.000
P1	0.0091 (5)	0.0101 (5)	0.0051 (5)	0.0039 (5)	0.000	0.000
P2	0.0109 (6)	0.0114 (5)	0.0035 (5)	0.0064 (5)	0.000	0.000
O1	0.0167 (15)	0.0155 (15)	0.0142 (17)	0.0112 (13)	0.000	0.000
O2	0.0136 (10)	0.0141 (10)	0.0083 (10)	0.0029 (9)	0.0011 (8)	−0.0003 (8)
O3	0.0118 (14)	0.0173 (15)	0.0125 (17)	0.0058 (12)	0.000	0.000
O4	0.0175 (11)	0.0137 (10)	0.0060 (10)	0.0096 (9)	−0.0005 (8)	−0.0016 (8)
O5	0.0191 (15)	0.0243 (16)	0.0047 (16)	0.0153 (13)	0.000	0.000
O6	0.0146 (15)	0.0137 (15)	0.0075 (16)	0.0036 (12)	0.000	0.000
O7	0.0119 (9)	0.0123 (10)	0.0100 (11)	0.0056 (8)	−0.0005 (8)	−0.0012 (8)
O8	0.0122 (10)	0.0120 (10)	0.0141 (13)	0.0072 (8)	−0.0026 (9)	−0.0014 (9)
O9	0.0128 (10)	0.0109 (10)	0.0137 (11)	0.0060 (9)	0.0004 (9)	−0.0010 (9)

Geometric parameters (Å, º) top

Zn1—O7	1.9248 (17)	B1—O7ⁱⁱ	1.3792 (18)
Zn1—O2ⁱ	1.9293 (19)	B1—O7	1.3792 (18)
Zn1—O3ⁱⁱ	2.084 (2)	B1—O7^ix	1.3792 (18)
Zn1—O1	2.100 (2)	B2—O8^vii	1.3880 (18)
Zn1—Zn1ⁱⁱⁱ	3.0071 (9)	B2—O8	1.3880 (18)
Zn2—O7	1.9529 (17)	B2—O8^x	1.3880 (18)
Zn2—O9^iv	1.9604 (18)	B3—O9	1.3775 (17)
Zn2—O8^v	1.9656 (17)	B3—O9^xi	1.3775 (17)
Zn2—O4	2.2019 (18)	B3—O9^xii	1.3775 (17)
Zn2—O2	2.3238 (18)	P1—O3	1.541 (3)
Zn2—Zn3^iv	3.1202 (5)	P1—O1	1.542 (3)
Zn3—O4^vi	1.9958 (18)	P1—O2	1.5484 (18)
Zn3—O8	2.035 (2)	P1—O2ⁱⁱⁱ	1.5484 (18)
Zn3—O5	2.0704 (18)	P2—O5	1.529 (3)
Zn3—O6^vii	2.0748 (18)	P2—O6	1.540 (3)
Zn3—O9	2.079 (2)	P2—O4	1.5412 (18)
Zn3—Zn3^v	3.0766 (7)	P2—O4^v	1.5412 (18)
Zn3—Zn2^viii	3.1202 (5)

O7—Zn1—O2ⁱ	152.13 (8)	O1—P1—O2	108.83 (10)
O7—Zn1—O3ⁱⁱ	103.27 (9)	O3—P1—O2ⁱⁱⁱ	106.96 (10)
O2ⁱ—Zn1—O3ⁱⁱ	101.65 (9)	O1—P1—O2ⁱⁱⁱ	108.83 (10)
O7—Zn1—O1	96.22 (8)	O2—P1—O2ⁱⁱⁱ	112.09 (15)
O2ⁱ—Zn1—O1	100.50 (9)	O5—P2—O6	110.90 (15)
O3ⁱⁱ—Zn1—O1	79.32 (8)	O5—P2—O4	108.15 (9)
O7—Zn2—O9^iv	124.56 (7)	O6—P2—O4	108.54 (9)
O7—Zn2—O8^v	119.80 (8)	O5—P2—O4^v	108.15 (9)
O9^iv—Zn2—O8^v	115.29 (7)	O6—P2—O4^v	108.54 (9)
O7—Zn2—O4	85.00 (7)	O4—P2—O4^v	112.59 (15)
O9^iv—Zn2—O4	92.42 (7)	P1—O1—Zn1ⁱⁱⁱ	125.99 (8)
O8^v—Zn2—O4	99.02 (8)	P1—O1—Zn1	125.99 (8)
O7—Zn2—O2	95.72 (7)	Zn1ⁱⁱⁱ—O1—Zn1	91.46 (11)
O9^iv—Zn2—O2	79.41 (8)	P1—O2—Zn1^xiii	124.98 (11)
O8^v—Zn2—O2	88.80 (8)	P1—O2—Zn2	117.49 (10)
O4—Zn2—O2	170.57 (7)	Zn1^xiii—O2—Zn2	107.41 (8)
O4^vi—Zn3—O8	131.36 (8)	P1—O3—Zn1^xiv	128.42 (8)
O4^vi—Zn3—O5	94.60 (9)	P1—O3—Zn1^ix	128.42 (8)
O8—Zn3—O5	91.76 (8)	Zn1^xiv—O3—Zn1^ix	92.36 (11)
O4^vi—Zn3—O6^vii	103.14 (9)	P2—O4—Zn3^xv	126.50 (11)
O8—Zn3—O6^vii	125.21 (9)	P2—O4—Zn2	117.50 (10)
O5—Zn3—O6^vii	76.73 (8)	Zn3^xv—O4—Zn2	106.43 (8)
O4^vi—Zn3—O9	91.86 (7)	P2—O5—Zn3^v	129.80 (7)
O8—Zn3—O9	88.31 (8)	P2—O5—Zn3	129.80 (7)
O5—Zn3—O9	171.33 (10)	Zn3^v—O5—Zn3	95.98 (11)
O6^vii—Zn3—O9	96.17 (8)	P2—O6—Zn3^x	127.95 (8)
O7ⁱⁱ—B1—O7	119.976 (16)	P2—O6—Zn3^iv	127.95 (8)
O7ⁱⁱ—B1—O7^ix	119.976 (16)	Zn3^x—O6—Zn3^iv	95.71 (11)
O7—B1—O7^ix	119.976 (16)	B1—O7—Zn1	124.1 (2)
O8^vii—B2—O8	119.94 (3)	B1—O7—Zn2	121.32 (16)
O8^vii—B2—O8^x	119.94 (3)	Zn1—O7—Zn2	112.75 (9)
O8—B2—O8^x	119.94 (3)	B2—O8—Zn2^v	117.88 (13)
O9—B3—O9^xi	119.93 (2)	B2—O8—Zn3	120.3 (2)
O9—B3—O9^xii	119.93 (2)	Zn2^v—O8—Zn3	114.50 (9)
O9^xi—B3—O9^xii	119.93 (2)	B3—O9—Zn2^viii	112.75 (11)
O3—P1—O1	113.22 (15)	B3—O9—Zn3	126.7 (2)
O3—P1—O2	106.96 (10)	Zn2^viii—O9—Zn3	101.09 (8)

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

Experimental details

Crystal data
Chemical formula	Zn₃(BO₃)(PO₄)
M_r	349.89
Crystal system, space group	Hexagonal, P6
Temperature (K)	294
a, c (Å)	8.4624 (3), 13.0690 (7)
V (Å³)	810.51 (4)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	13.49
Crystal size (mm)	0.25 × 0.22 × 0.16

Data collection
Diffractometer	Rigaku Saturn CCD
Absorption correction	Numerical (NUMABS; Rigaku, 2005)
T_min, T_max	0.133, 0.221
No. of measured, independent and observed [I > 2σ(I)] reflections	10584, 1453, 1226
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.674

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.019, 0.039, 0.96
No. of reflections	1453
No. of parameters	118
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.52
Absolute structure	Flack (1983), 718 Friedel pairs
Absolute structure parameter	0.011 (10)

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Zn1—O7	1.9248 (17)	Zn3—O6^vi	2.0748 (18)
Zn1—O2ⁱ	1.9293 (19)	Zn3—O9	2.079 (2)
Zn1—O3ⁱⁱ	2.084 (2)	B1—O7	1.3792 (18)
Zn1—O1	2.100 (2)	B2—O8	1.3880 (18)
Zn2—O7	1.9529 (17)	B3—O9	1.3775 (17)
Zn2—O9ⁱⁱⁱ	1.9604 (18)	P1—O3	1.541 (3)
Zn2—O8^iv	1.9656 (17)	P1—O1	1.542 (3)
Zn2—O4	2.2019 (18)	P1—O2	1.5484 (18)
Zn2—O2	2.3238 (18)	P2—O5	1.529 (3)
Zn3—O4^v	1.9958 (18)	P2—O6	1.540 (3)
Zn3—O8	2.035 (2)	P2—O4	1.5412 (18)
Zn3—O5	2.0704 (18)

Symmetry codes: (i) −y+1, x−y+1, z; (ii) −x+y+1, −x+2, z; (iii) −y+1, x−y, −z+1; (iv) x, y, −z+1; (v) −y+2, x−y+1, −z+1; (vi) −x+y+1, −x+1, z.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant No. 50932005).

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