inorganic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

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

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[Liebertz, J. & Stahr, S. (1982). Z. Kristallogr. 160, 135-137.]). For crystal growth of β-Zn3(BO3)(PO4), see: Wang et al. (2000[Wang, G. F., Fu, P. Z. & Wu, Y. C. (2000). J. Synth. Cryst. 29, 130-133.]); Wu & Wang (2001[Wu, Y. C. & Wang, G. F. (2001). J. Cryst. Growth, 229, 205-207.]); Liu et al. (2002[Liu, H. J., Wu, Y. C. & Wang, G. F. (2002). J. Synth. Cryst. 31, 81-84.]). For structure refinement of α-Zn3(BO3)(PO4), see: Bluhm & Park (1997[Bluhm, K. & Park, C. H. (1997). Z. Naturforsch. Teil B, 52, 102-106.]). For structurally related compounds, see: Ma et al. (2004[Ma, H. W., Liang, J. K., Wu, L., Liu, G. Y., Rao, G. H. & Chen, X. L. (2004). J. Solid State Chem. 177, 3454-3459. ]); Yilmaz et al. (2001[Yilmaz, A., Bu, X. H., Kizilyalli, M., Kniep, R. & Stucky, G. D. (2001). J. Solid State Chem. 156, 281-285.]). Reviews on borophosphates were given by Kniep et al. (1998[Kniep, R., Engelhardt, H. & Hauf, C. (1998). Chem. Mater. 10, 2930-2934.]) and Ewald et al. (2007[Ewald, B., Huang, Y. X. & Kniep, R. (2007). Z. Anorg. Allg. Chem. 633, 1517-1540.]).

Experimental

Crystal data
  • Zn3(BO3)(PO4)

  • Mr = 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[Rigaku (2005). CrystalClear and NUMABS. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.133, Tmax = 0.221

  • 10584 measured reflections

  • 1453 independent reflections

  • 1226 reflections with I > 2σ(I)

  • Rint = 0.062

Refinement
  • R[F2 > 2σ(F2)] = 0.019

  • wR(F2) = 0.039

  • S = 0.96

  • 1453 reflections

  • 118 parameters

  • Δρmax = 0.61 e Å−3

  • Δρmin = −0.52 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 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—O8iv 1.9656 (17)
Zn2—O4 2.2019 (18)
Zn2—O2 2.3238 (18)
Zn3—O4v 1.9958 (18)
Zn3—O8 2.035 (2)
Zn3—O5 2.0704 (18)
Zn3—O6vi 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[Rigaku (2005). CrystalClear and NUMABS. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: DIAMOND (Brandenburg, 2006[Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


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.

Refinement top

One B atom (B1) has been refined with an isotropic displacement parameter. Refinement with anisotropic displacement parameters for this atom resulted in physically meaningless values.

Structure description 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.

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
[Figure 1] Fig. 1. The asymmetric unit of β-Zn3(BO3)(PO4) with atom labelling and ellipsoids drawn at the 90% probability level.
[Figure 2] Fig. 2. Crystal structure of β-Zn3(BO3)(PO4) illustrated with isolated BO3 and PO4 groups.
[Figure 3] Fig. 3. The structure of β-Zn3(BO3)(PO4) viewed along [001].
trizinc borate phosphate top
Crystal data top
Zn3(BO3)(PO4)Dx = 4.301 Mg m3
Mr = 349.89Melting point: 1200 K
Hexagonal, P6Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 6Cell parameters from 2470 reflections
a = 8.4624 (3) Åθ = 1.6–28.7°
c = 13.0690 (7) ŵ = 13.49 mm1
V = 810.51 (4) Å3T = 294 K
Z = 6Prism, colorless
F(000) = 9960.25 × 0.22 × 0.16 mm
Data collection top
Rigaku Saturn CCD
diffractometer
1453 independent reflections
Radiation source: fine-focus sealed tube1226 reflections with I > 2σ(I)
Confocal monochromatorRint = 0.062
Detector resolution: 7.31 pixels mm-1θmax = 28.6°, θmin = 1.6°
ω scansh = 1110
Absorption correction: numerical
(NUMABS; Rigaku, 2005)
k = 1111
Tmin = 0.133, Tmax = 0.221l = 1717
10584 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: full w = 1/[σ2(Fo2) + (0.0099P)2]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.019(Δ/σ)max = 0.004
wR(F2) = 0.039Δρmax = 0.61 e Å3
S = 0.96Δρmin = 0.52 e Å3
1453 reflectionsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
118 parametersExtinction coefficient: 0.0328 (7)
0 restraintsAbsolute structure: Flack (1983), 718 Friedel pairs
0 constraintsAbsolute structure parameter: 0.011 (10)
Primary atom site location: structure-invariant direct methods
Crystal data top
Zn3(BO3)(PO4)Z = 6
Mr = 349.89Mo Kα radiation
Hexagonal, P6µ = 13.49 mm1
a = 8.4624 (3) ÅT = 294 K
c = 13.0690 (7) Å0.25 × 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)
Tmin = 0.133, Tmax = 0.221Rint = 0.062
10584 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0190 restraints
wR(F2) = 0.039Δρmax = 0.61 e Å3
S = 0.96Δρmin = 0.52 e Å3
1453 reflectionsAbsolute structure: Flack (1983), 718 Friedel pairs
118 parametersAbsolute 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
xyzUiso*/Ueq
Zn10.67111 (7)0.98916 (9)0.88495 (3)0.01824 (11)
Zn20.66452 (5)0.67089 (5)0.74557 (2)0.01218 (11)
Zn30.99324 (6)0.64008 (5)0.38229 (3)0.00982 (9)
B11.00001.00000.8052 (5)0.0097 (11)*
B20.66670.33330.2820 (5)0.0110 (12)
B31.33330.66670.2751 (4)0.0088 (11)
P10.64705 (15)0.63672 (14)1.00000.0085 (2)
P20.68800 (15)0.70242 (14)0.50000.0083 (2)
O10.6018 (3)0.7921 (4)1.00000.0140 (6)
O20.5676 (3)0.5214 (2)0.90172 (13)0.0137 (4)
O30.8535 (3)0.7058 (4)1.00000.0146 (7)
O40.7144 (2)0.8140 (2)0.59811 (13)0.0116 (4)
O50.8298 (4)0.6407 (4)0.50000.0141 (6)
O60.4931 (4)0.5371 (4)0.50000.0135 (6)
O70.8121 (2)0.9147 (2)0.80352 (13)0.0116 (4)
O80.7773 (3)0.5217 (2)0.28461 (17)0.0123 (5)
O91.1480 (2)0.6008 (2)0.27238 (16)0.0124 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0165 (2)0.0204 (2)0.0210 (2)0.01163 (17)0.00515 (18)0.00218 (19)
Zn20.0110 (2)0.01191 (19)0.0137 (2)0.00580 (16)0.00283 (15)0.00386 (13)
Zn30.0110 (2)0.01235 (19)0.00559 (17)0.00543 (19)0.00002 (14)0.00152 (13)
B20.0095 (18)0.0095 (18)0.014 (3)0.0048 (9)0.0000.000
B30.0120 (17)0.0120 (17)0.002 (3)0.0060 (9)0.0000.000
P10.0091 (5)0.0101 (5)0.0051 (5)0.0039 (5)0.0000.000
P20.0109 (6)0.0114 (5)0.0035 (5)0.0064 (5)0.0000.000
O10.0167 (15)0.0155 (15)0.0142 (17)0.0112 (13)0.0000.000
O20.0136 (10)0.0141 (10)0.0083 (10)0.0029 (9)0.0011 (8)0.0003 (8)
O30.0118 (14)0.0173 (15)0.0125 (17)0.0058 (12)0.0000.000
O40.0175 (11)0.0137 (10)0.0060 (10)0.0096 (9)0.0005 (8)0.0016 (8)
O50.0191 (15)0.0243 (16)0.0047 (16)0.0153 (13)0.0000.000
O60.0146 (15)0.0137 (15)0.0075 (16)0.0036 (12)0.0000.000
O70.0119 (9)0.0123 (10)0.0100 (11)0.0056 (8)0.0005 (8)0.0012 (8)
O80.0122 (10)0.0120 (10)0.0141 (13)0.0072 (8)0.0026 (9)0.0014 (9)
O90.0128 (10)0.0109 (10)0.0137 (11)0.0060 (9)0.0004 (9)0.0010 (9)
Geometric parameters (Å, º) top
Zn1—O71.9248 (17)B1—O7ii1.3792 (18)
Zn1—O2i1.9293 (19)B1—O71.3792 (18)
Zn1—O3ii2.084 (2)B1—O7ix1.3792 (18)
Zn1—O12.100 (2)B2—O8vii1.3880 (18)
Zn1—Zn1iii3.0071 (9)B2—O81.3880 (18)
Zn2—O71.9529 (17)B2—O8x1.3880 (18)
Zn2—O9iv1.9604 (18)B3—O91.3775 (17)
Zn2—O8v1.9656 (17)B3—O9xi1.3775 (17)
Zn2—O42.2019 (18)B3—O9xii1.3775 (17)
Zn2—O22.3238 (18)P1—O31.541 (3)
Zn2—Zn3iv3.1202 (5)P1—O11.542 (3)
Zn3—O4vi1.9958 (18)P1—O21.5484 (18)
Zn3—O82.035 (2)P1—O2iii1.5484 (18)
Zn3—O52.0704 (18)P2—O51.529 (3)
Zn3—O6vii2.0748 (18)P2—O61.540 (3)
Zn3—O92.079 (2)P2—O41.5412 (18)
Zn3—Zn3v3.0766 (7)P2—O4v1.5412 (18)
Zn3—Zn2viii3.1202 (5)
O7—Zn1—O2i152.13 (8)O1—P1—O2108.83 (10)
O7—Zn1—O3ii103.27 (9)O3—P1—O2iii106.96 (10)
O2i—Zn1—O3ii101.65 (9)O1—P1—O2iii108.83 (10)
O7—Zn1—O196.22 (8)O2—P1—O2iii112.09 (15)
O2i—Zn1—O1100.50 (9)O5—P2—O6110.90 (15)
O3ii—Zn1—O179.32 (8)O5—P2—O4108.15 (9)
O7—Zn2—O9iv124.56 (7)O6—P2—O4108.54 (9)
O7—Zn2—O8v119.80 (8)O5—P2—O4v108.15 (9)
O9iv—Zn2—O8v115.29 (7)O6—P2—O4v108.54 (9)
O7—Zn2—O485.00 (7)O4—P2—O4v112.59 (15)
O9iv—Zn2—O492.42 (7)P1—O1—Zn1iii125.99 (8)
O8v—Zn2—O499.02 (8)P1—O1—Zn1125.99 (8)
O7—Zn2—O295.72 (7)Zn1iii—O1—Zn191.46 (11)
O9iv—Zn2—O279.41 (8)P1—O2—Zn1xiii124.98 (11)
O8v—Zn2—O288.80 (8)P1—O2—Zn2117.49 (10)
O4—Zn2—O2170.57 (7)Zn1xiii—O2—Zn2107.41 (8)
O4vi—Zn3—O8131.36 (8)P1—O3—Zn1xiv128.42 (8)
O4vi—Zn3—O594.60 (9)P1—O3—Zn1ix128.42 (8)
O8—Zn3—O591.76 (8)Zn1xiv—O3—Zn1ix92.36 (11)
O4vi—Zn3—O6vii103.14 (9)P2—O4—Zn3xv126.50 (11)
O8—Zn3—O6vii125.21 (9)P2—O4—Zn2117.50 (10)
O5—Zn3—O6vii76.73 (8)Zn3xv—O4—Zn2106.43 (8)
O4vi—Zn3—O991.86 (7)P2—O5—Zn3v129.80 (7)
O8—Zn3—O988.31 (8)P2—O5—Zn3129.80 (7)
O5—Zn3—O9171.33 (10)Zn3v—O5—Zn395.98 (11)
O6vii—Zn3—O996.17 (8)P2—O6—Zn3x127.95 (8)
O7ii—B1—O7119.976 (16)P2—O6—Zn3iv127.95 (8)
O7ii—B1—O7ix119.976 (16)Zn3x—O6—Zn3iv95.71 (11)
O7—B1—O7ix119.976 (16)B1—O7—Zn1124.1 (2)
O8vii—B2—O8119.94 (3)B1—O7—Zn2121.32 (16)
O8vii—B2—O8x119.94 (3)Zn1—O7—Zn2112.75 (9)
O8—B2—O8x119.94 (3)B2—O8—Zn2v117.88 (13)
O9—B3—O9xi119.93 (2)B2—O8—Zn3120.3 (2)
O9—B3—O9xii119.93 (2)Zn2v—O8—Zn3114.50 (9)
O9xi—B3—O9xii119.93 (2)B3—O9—Zn2viii112.75 (11)
O3—P1—O1113.22 (15)B3—O9—Zn3126.7 (2)
O3—P1—O2106.96 (10)Zn2viii—O9—Zn3101.09 (8)
Symmetry codes: (i) y+1, xy+1, z; (ii) x+y+1, x+2, z; (iii) x, y, z+2; (iv) y+1, xy, z+1; (v) x, y, z+1; (vi) y+2, xy+1, z+1; (vii) x+y+1, x+1, z; (viii) x+y+1, x+1, z+1; (ix) y+2, xy+1, z; (x) y+1, xy, z; (xi) x+y+2, x+2, z; (xii) y+2, xy, z; (xiii) x+y, x+1, z; (xiv) y+2, xy+1, z+2; (xv) x+y+1, x+2, z+1.

Experimental details

Crystal data
Chemical formulaZn3(BO3)(PO4)
Mr349.89
Crystal system, space groupHexagonal, P6
Temperature (K)294
a, c (Å)8.4624 (3), 13.0690 (7)
V3)810.51 (4)
Z6
Radiation typeMo Kα
µ (mm1)13.49
Crystal size (mm)0.25 × 0.22 × 0.16
Data collection
DiffractometerRigaku Saturn CCD
Absorption correctionNumerical
(NUMABS; Rigaku, 2005)
Tmin, Tmax0.133, 0.221
No. of measured, independent and
observed [I > 2σ(I)] reflections
10584, 1453, 1226
Rint0.062
(sin θ/λ)max1)0.674
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.019, 0.039, 0.96
No. of reflections1453
No. of parameters118
Δρmax, Δρmin (e Å3)0.61, 0.52
Absolute structureFlack (1983), 718 Friedel pairs
Absolute structure parameter0.011 (10)

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

Selected bond lengths (Å) top
Zn1—O71.9248 (17)Zn3—O6vi2.0748 (18)
Zn1—O2i1.9293 (19)Zn3—O92.079 (2)
Zn1—O3ii2.084 (2)B1—O71.3792 (18)
Zn1—O12.100 (2)B2—O81.3880 (18)
Zn2—O71.9529 (17)B3—O91.3775 (17)
Zn2—O9iii1.9604 (18)P1—O31.541 (3)
Zn2—O8iv1.9656 (17)P1—O11.542 (3)
Zn2—O42.2019 (18)P1—O21.5484 (18)
Zn2—O22.3238 (18)P2—O51.529 (3)
Zn3—O4v1.9958 (18)P2—O61.540 (3)
Zn3—O82.035 (2)P2—O41.5412 (18)
Zn3—O52.0704 (18)
Symmetry codes: (i) y+1, xy+1, z; (ii) x+y+1, x+2, z; (iii) y+1, xy, z+1; (iv) x, y, z+1; (v) y+2, xy+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).

References

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