Cerium(III) dihydroxidohexa­oxidotetra­borate chloride

Sun, W.; Zhao, B.-C.; Huang, Y.-X.; Mi, J.-X.

doi:10.1107/S1600536812002875

inorganic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page i17

doi:10.1107/S1600536812002875

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Cerium(III) dihydroxidohexaoxidotetraborate chloride

Wei Sun,^a Biao-Chun Zhao,^a Ya-Xi Huang ^a and Jin-Xiao Mi ^a ^*

^aDepartment of Materials Science and Engineering, College of Materials, Xiamen University, Xiamen 361005, Fujian Province, People's Republic of China
^*Correspondence e-mail: jxmi@xmu.edu.cn

(Received 6 December 2011; accepted 23 January 2012; online 31 January 2012)

The crystal structure of the title compound, Ce[B₄O₆(OH)₂]Cl, is built from polyborate sheets parallel to the (001) plane. These sheets stack along the [001] direction and are linked by Ce atoms exhibiting an CeO₈Cl₂ coordination sphere. O—H⋯O and O—H⋯Cl hydrogen bonds additionally stabilize the structural set-up. The polyborate sheet is made up of zigzag borate chains running along the [ $[\overline{1}]$ 10] direction. These zigzag chains are interconnected by shared O-vertices, resulting in a two-dimensional layer with nine-membered rings. All B and O atoms (except for the terminal OH atoms) lie in the nearly planar sheets of polyborates, leading to their isotropic atomic displacement parameters being significantly smaller than usual. This may be attributed to the fact that the atomic displacement parameters correlate not only with their atomic masses but with their coordination environments also.

Related literature

For background to borate compounds and their applications, see: Burns et al. (1995 ); Chen et al. (1985 ); Zhao et al. (1990 ); Sun, Sun et al. (2010 ); Sun, Zhou et al. (2010 ). For isotypic structures, see: Belokoneva et al. (2002 ) for Ln[B₄O₆(OH)₂]Cl (Ln = Pr, Nd).

Experimental

Crystal data

Ce[B₄O₆(OH)₂]Cl
M_r = 348.83
Monoclinic, C c
a = 6.5169 (11) Å
b = 11.245 (2) Å
c = 9.7575 (17) Å
β = 105.284 (3)°
V = 689.8 (2) Å³
Z = 4
Mo Kα radiation
μ = 7.00 mm⁻¹
T = 295 K
0.16 × 0.07 × 0.03 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.401, T_max = 0.818
2825 measured reflections
1532 independent reflections
1523 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.020
wR(F²) = 0.051
S = 1.00
1532 reflections
134 parameters
10 restraints
All H-atom parameters refined
Δρ_max = 0.53 e Å⁻³
Δρ_min = −1.64 e Å⁻³
Absolute structure: Flack (1983 ), 716 Friedel pairs
Flack parameter: 0.034 (19)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O8—H1⋯O1ⁱ	0.82 (2)	2.43 (7)	2.859 (5)	114 (6)
O8—H1⋯Cl1ⁱⁱ	0.82 (2)	2.52 (5)	3.219 (4)	145 (7)
O7—H2⋯O4ⁱⁱ	0.83 (2)	2.13 (6)	2.860 (6)	148 (10)
O7—H2⋯Cl1ⁱⁱ	0.83 (2)	2.81 (11)	3.220 (4)	112 (9)
Symmetry codes: (i) $[x, -y+1, z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2011 ) and ATOMS (Dowty, 2004 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812002875/fj2495sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812002875/fj2495Isup2.hkl

checkCIF report

Comment top

Borate compounds have been extensively studied due to their variety of fundamental building blocks and crystal structure types (Burns et al., 1995), as well as their successful industry applications as nonlinear optical materials, e.g. β-Ba(B₂O₄) (BBO) (Chen et al., 1985) and LiB₃O₅ (LBO) (Zhao et al., 1990). Besides alkali metals and alkaline-earth metals (Sun, Sun et al., 2010), rare-earth elements become highlighted with being introduced into the borate system in order to obtain multifunctional materials with the distinctive luminescence properties of rare-earth elements. Belokoneva et al. (2002) claimed that Ln(B₄O₆(OH)₂)Cl (Ln = Pr, Nd) exhibits excellent nonlinear optical properties. But the atomic coordinates of its cerium analogue have not been reported until now. Herein, we report the crystal structure of Ce(B₄O₆(OH)₂)Cl determined from single-crystal X-ray diffraction data, including the sites of hydrogen atoms.

The crystal structure of Ce(B₄O₆(OH)₂)Cl is characterized as a layered strcuture of polyborate sheets parallel to (001)(Fig. 1 & 2). In the structure boron atoms have two types of polyhedral coordinations. One is 3-coordinated by oxygen atoms, forming a triangular planar [BO₃] group. The other is 4-coordinated to three O-atoms and one hydroxyl group to form a [BO₃(OH)] tetrahedron (Fig. 3). Both [BO₃] group and [BO₃(OH)] polyhedron link to three neighbouring borate groups via their common O-corners except for OH terminals. Two [BO₃(OH)] tetrahedra and two triangular planar [BO₃] groups compose a borate tetramer as a fundamental building block (FBB) (Fig. 2) (Burns et al., 1995). The FBBs share their common oxygen vertices to form a zigzag borate chain running along the [110] direction. The zigzag chains are further interconnected with each other by sharing their common O-corners, resulting in a two-dimensional layer with 9-membered rings within the layer. The 9-membered ring has a nearly equilateral (about 7.00 Å) triangular motif (Fig. 2). The Ce atoms just reside at the center of 9-membered rings and adopt a 10-coordination with the surrounding eight oxygen and two chlorine atoms, forming a 1-6-3 crown-shaped polyhedron (Fig. 2). The two-dimensional layers stack along the [001] direction and are linked by Ce and Cl atoms as well as hydrogen bonds to form the three-dimensional crystal structure (Fig. 1). It is interesting that all boron and oxygen atoms (except for OH terminals) lying in the nearly planar sheets of polyborates lead to their isotropic atomic parameters significantly smaller than as-expected usually. For example, the isotropic atomic parameters of boron atoms are distributed in the range of 0.0062 (10) to 0.0085 (10) Å², significantly smaller than that of chlorine atom (0.0130 (2) Å²). This may give a hint that the atomic displacement parameters correlate not only with their atomic masses but with their coordination environments also. However the standard uncertainties of atomic displacement parameters do have close correlation with their atomic masses of individual elements. As-observed in the title compound, standard uncertainties of atomic displacement parameters of all atoms distribute as-expected in the sequence of Ce, Cl, O, B and H, increasing while their atomic masses decrease.

Related literature top

For background to borate compounds and their applications, see: Burns et al. (1995); Chen et al. (1985); Zhao et al. (1990); Sun, Sun et al. (2010); Sun, Zhou et al. (2010). For related structures, see: Belokoneva et al. (2002) for Ln(B₄O₆(OH)₂)Cl (Ln = Pr, Nd).

Experimental top

The title compound, Ce(B₄O₆(OH)₂)Cl was synthesized by using a hydrothermal method during our systematically exploiting rare earth borates (Sun, Zhou et al., 2010). Typically, a mixture of Ce₂O₃ (0.33 g), CrCl₃.6H₂O (0.80 g), H₃BO₃ (2.00 g) and 2 ml distilled water with molar ratio of Ce: Cl: B = 1: 9: 32 was prepared, and transferred into a Teflon-lined stainless-steel autoclave (30 ml in volume), then heated to and kept at 468 K for three days. Transparent, colorless crystals of the title compound were obtained by filtration, rinsed with distilled water several times, and dried in desiccators. Optical examination and powder X-ray diffraction (PXRD) analyses were used to identify the phases of the solid products.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2011) and ATOMS (Dowty, 2004); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Crystal structure of Ce(B₄O₆(OH)₂)Cl. ([BO₄] drawn in red tetrahedra; [BO₃] in blue triangular groups; Ce in black spheres; Cl in green spheres; H in small black balls).
	Fig. 2. Left: a two-dimensional sheet with 9-membered rings, the fundamental building block (FBB) marked by a dash-line ellipse; Right upper: a 9-membered ring with a nearly equilateral triangular motif; Right down: coordination environment of Ce in a 1-6-3 crown-shaped polyhedron.
	Fig. 3. Coordination environment of metal atoms, with displacement ellipsoids drawn at the 50% probability level (symmetry codes: (vi) x–1/2, y–1/2, z; (vii) x–1, y, z; (viii) x + 1/2, y–1/2, z)

Cerium(III) dihydroxidohexaoxidotetraborate chloride top

Crystal data top

Ce[B₄O₆(OH)₂]Cl	F(000) = 644
M_r = 348.83	D_x = 3.359 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 2825 reflections
a = 6.5169 (11) Å	θ = 3.6–28.0°
b = 11.245 (2) Å	µ = 7.00 mm⁻¹
c = 9.7575 (17) Å	T = 295 K
β = 105.284 (3)°	Prism, colorless
V = 689.8 (2) Å³	0.16 × 0.07 × 0.03 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1532 independent reflections
Radiation source: fine-focus sealed tube	1523 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
1800 images,ϕ = 0, 90, 180°, χ = 54.74°, Δω=0.3°, Exp time: 15 s. scans	θ_max = 28.0°, θ_min = 3.6°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −8→8
T_min = 0.401, T_max = 0.818	k = −14→14
2825 measured reflections	l = −12→12

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.020	All H-atom parameters refined
wR(F²) = 0.051	w = 1/[σ²(F_o²) + (0.0285P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
1532 reflections	Δρ_max = 0.53 e Å⁻³
134 parameters	Δρ_min = −1.64 e Å⁻³
10 restraints	Absolute structure: Flack (1983), 716 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.034 (19)

Crystal data top

Ce[B₄O₆(OH)₂]Cl	V = 689.8 (2) Å³
M_r = 348.83	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 6.5169 (11) Å	µ = 7.00 mm⁻¹
b = 11.245 (2) Å	T = 295 K
c = 9.7575 (17) Å	0.16 × 0.07 × 0.03 mm
β = 105.284 (3)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1532 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1523 reflections with I > 2σ(I)
T_min = 0.401, T_max = 0.818	R_int = 0.022
2825 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.020	All H-atom parameters refined
wR(F²) = 0.051	Δρ_max = 0.53 e Å⁻³
S = 1.00	Δρ_min = −1.64 e Å⁻³
1532 reflections	Absolute structure: Flack (1983), 716 Friedel pairs
134 parameters	Absolute structure parameter: 0.034 (19)
10 restraints

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
Ce1	0.98063 (4)	0.706775 (17)	0.56430 (4)	0.00585 (8)
Cl1	0.6202 (2)	0.82445 (12)	0.37031 (14)	0.0130 (2)
B1	0.1685 (9)	0.4466 (5)	0.6439 (6)	0.0073 (10)
B2	0.8287 (9)	0.4064 (5)	0.6939 (6)	0.0085 (10)
B3	0.5112 (9)	0.5338 (5)	0.6256 (6)	0.0068 (10)
B4	0.5809 (9)	0.7447 (5)	0.7169 (6)	0.0062 (10)
O1	0.9639 (5)	0.4852 (3)	0.6324 (3)	0.0076 (7)
O2	0.7362 (6)	0.8358 (3)	0.6858 (4)	0.0086 (7)
O3	0.6294 (6)	0.6361 (3)	0.6426 (4)	0.0093 (7)
O4	0.3652 (6)	0.7819 (3)	0.6635 (4)	0.0068 (7)
O5	0.2933 (6)	0.5383 (3)	0.6124 (4)	0.0087 (7)
O6	0.6027 (6)	0.4259 (3)	0.6207 (4)	0.0086 (7)
O7	0.6335 (7)	0.7247 (3)	0.8706 (4)	0.0116 (7)
O8	0.8688 (6)	0.4269 (3)	0.8477 (4)	0.0101 (7)
H1	0.894 (13)	0.495 (3)	0.876 (7)	0.04 (2)*
H2	0.731 (13)	0.706 (6)	0.940 (7)	0.04 (2)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ce1	0.00577 (12)	0.00558 (12)	0.00601 (12)	0.00003 (13)	0.00121 (8)	0.00002 (14)
Cl1	0.0132 (6)	0.0155 (6)	0.0094 (6)	0.0047 (5)	0.0012 (5)	−0.0001 (5)
B1	0.004 (2)	0.009 (2)	0.009 (3)	−0.0008 (19)	0.001 (2)	−0.002 (2)
B2	0.009 (3)	0.006 (2)	0.009 (3)	0.001 (2)	0.002 (2)	−0.001 (2)
B3	0.011 (3)	0.005 (2)	0.005 (2)	0.001 (2)	0.0029 (19)	0.0021 (19)
B4	0.009 (3)	0.003 (2)	0.006 (2)	0.003 (2)	0.002 (2)	−0.0001 (19)
O1	0.0040 (16)	0.0072 (16)	0.0124 (17)	0.0020 (13)	0.0036 (14)	0.0006 (13)
O2	0.0079 (18)	0.0045 (16)	0.0131 (19)	0.0007 (14)	0.0025 (14)	−0.0005 (14)
O3	0.0083 (18)	0.0063 (15)	0.0145 (18)	0.0011 (14)	0.0055 (14)	−0.0014 (14)
O4	0.0061 (17)	0.0036 (16)	0.0105 (19)	0.0009 (12)	0.0015 (14)	−0.0010 (12)
O5	0.0046 (16)	0.0042 (15)	0.0180 (18)	−0.0009 (13)	0.0041 (14)	0.0023 (14)
O6	0.0027 (15)	0.0077 (14)	0.0138 (17)	−0.0020 (13)	−0.0004 (13)	−0.0019 (13)
O7	0.0091 (19)	0.0155 (17)	0.0097 (19)	0.0059 (15)	0.0017 (15)	0.0023 (15)
O8	0.0161 (18)	0.0084 (17)	0.0048 (17)	−0.0029 (14)	0.0007 (14)	−0.0010 (13)

Geometric parameters (Å, º) top

Ce1—O7ⁱ	2.480 (4)	B1—O5	1.396 (6)
Ce1—O8ⁱⁱ	2.539 (4)	B2—O4^viii	1.464 (6)
Ce1—O4ⁱⁱⁱ	2.579 (4)	B2—O8	1.472 (6)
Ce1—O1	2.589 (3)	B2—O6	1.474 (6)
Ce1—O6^iv	2.603 (3)	B2—O1	1.483 (7)
Ce1—O2	2.654 (4)	B3—O6	1.359 (6)
Ce1—O3	2.716 (4)	B3—O3	1.370 (6)
Ce1—O5ⁱⁱⁱ	2.731 (3)	B3—O5	1.392 (7)
Ce1—Cl1^v	2.9041 (14)	B4—O4	1.427 (6)
Ce1—Cl1	2.9168 (14)	B4—O7	1.465 (6)
B1—O2^vi	1.349 (6)	B4—O3	1.496 (6)
B1—O1^vii	1.378 (6)	B4—O2	1.526 (7)

O7ⁱ—Ce1—O8ⁱⁱ	68.55 (12)	O8ⁱⁱ—Ce1—Cl1	73.91 (9)
O7ⁱ—Ce1—O4ⁱⁱⁱ	68.81 (13)	O4ⁱⁱⁱ—Ce1—Cl1	129.17 (8)
O8ⁱⁱ—Ce1—O4ⁱⁱⁱ	122.93 (12)	O1—Ce1—Cl1	121.47 (8)
O7ⁱ—Ce1—O1	123.18 (11)	O6^iv—Ce1—Cl1	81.76 (8)
O8ⁱⁱ—Ce1—O1	67.76 (11)	O2—Ce1—Cl1	64.30 (8)
O4ⁱⁱⁱ—Ce1—O1	108.75 (10)	O3—Ce1—Cl1	73.81 (8)
O7ⁱ—Ce1—O6^iv	72.87 (12)	O5ⁱⁱⁱ—Ce1—Cl1	149.66 (8)
O8ⁱⁱ—Ce1—O6^iv	137.83 (11)	Cl1^v—Ce1—Cl1	134.62 (5)
O4ⁱⁱⁱ—Ce1—O6^iv	53.00 (10)	Ce1^ix—Cl1—Ce1	126.35 (5)
O1—Ce1—O6^iv	152.63 (11)	O2^vi—B1—O1^vii	123.2 (5)
O7ⁱ—Ce1—O2	125.41 (12)	O2^vi—B1—O5	125.8 (5)
O8ⁱⁱ—Ce1—O2	128.40 (12)	O1^vii—B1—O5	110.9 (4)
O4ⁱⁱⁱ—Ce1—O2	106.95 (11)	O4^viii—B2—O8	111.2 (4)
O1—Ce1—O2	109.92 (11)	O4^viii—B2—O6	103.8 (4)
O6^iv—Ce1—O2	64.77 (11)	O8—B2—O6	110.9 (4)
O7ⁱ—Ce1—O3	147.45 (13)	O4^viii—B2—O1	110.1 (4)
O8ⁱⁱ—Ce1—O3	89.01 (12)	O8—B2—O1	110.8 (4)
O4ⁱⁱⁱ—Ce1—O3	142.92 (12)	O6—B2—O1	109.9 (4)
O1—Ce1—O3	63.28 (10)	O6—B3—O3	121.1 (5)
O6^iv—Ce1—O3	116.78 (11)	O6—B3—O5	118.4 (5)
O2—Ce1—O3	52.04 (11)	O3—B3—O5	120.6 (4)
O7ⁱ—Ce1—O5ⁱⁱⁱ	85.14 (13)	O4—B4—O7	111.1 (4)
O8ⁱⁱ—Ce1—O5ⁱⁱⁱ	76.69 (11)	O4—B4—O3	112.1 (4)
O4ⁱⁱⁱ—Ce1—O5ⁱⁱⁱ	63.61 (10)	O7—B4—O3	110.4 (4)
O1—Ce1—O5ⁱⁱⁱ	50.80 (10)	O4—B4—O2	111.9 (4)
O6^iv—Ce1—O5ⁱⁱⁱ	116.61 (11)	O7—B4—O2	108.6 (4)
O2—Ce1—O5ⁱⁱⁱ	144.19 (12)	O3—B4—O2	102.5 (4)
O3—Ce1—O5ⁱⁱⁱ	113.23 (11)	B1ⁱⁱⁱ—O1—B2	116.4 (4)
O7ⁱ—Ce1—Cl1^v	137.84 (10)	B1^iv—O2—B4	119.9 (4)
O8ⁱⁱ—Ce1—Cl1^v	136.70 (9)	B3—O3—B4	124.1 (4)
O4ⁱⁱⁱ—Ce1—Cl1^v	69.13 (9)	B4—O4—B2^x	113.8 (4)
O1—Ce1—Cl1^v	69.06 (8)	B3—O5—B1	126.3 (4)
O6^iv—Ce1—Cl1^v	84.35 (8)	B3—O6—B2	120.5 (4)
O2—Ce1—Cl1^v	70.67 (8)	B4—O7—H2	143 (8)
O3—Ce1—Cl1^v	74.57 (8)	Ce1^xi—O7—H2	80 (8)
O5ⁱⁱⁱ—Ce1—Cl1^v	73.87 (8)	B2—O8—H1	117 (5)
O7ⁱ—Ce1—Cl1	77.35 (10)	Ce1^xii—O8—H1	107 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O8—H1···O1^xii	0.82 (2)	2.43 (7)	2.859 (5)	114 (6)
O8—H1···Cl1^v	0.82 (2)	2.52 (5)	3.219 (4)	145 (7)
O7—H2···O4^v	0.83 (2)	2.13 (6)	2.860 (6)	148 (10)
O7—H2···Cl1^v	0.83 (2)	2.81 (11)	3.220 (4)	112 (9)

Symmetry codes: (v) x+1/2, −y+3/2, z+1/2; (xii) x, −y+1, z+1/2.

Experimental details

Crystal data
Chemical formula	Ce[B₄O₆(OH)₂]Cl
M_r	348.83
Crystal system, space group	Monoclinic, Cc
Temperature (K)	295
a, b, c (Å)	6.5169 (11), 11.245 (2), 9.7575 (17)
β (°)	105.284 (3)
V (Å³)	689.8 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	7.00
Crystal size (mm)	0.16 × 0.07 × 0.03

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.401, 0.818
No. of measured, independent and observed [I > 2σ(I)] reflections	2825, 1532, 1523
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.020, 0.051, 1.00
No. of reflections	1532
No. of parameters	134
No. of restraints	10
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.53, −1.64
Absolute structure	Flack (1983), 716 Friedel pairs
Absolute structure parameter	0.034 (19)

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2011) and ATOMS (Dowty, 2004).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O8—H1···O1ⁱ	0.82 (2)	2.43 (7)	2.859 (5)	114 (6)
O8—H1···Cl1ⁱⁱ	0.82 (2)	2.52 (5)	3.219 (4)	145 (7)
O7—H2···O4ⁱⁱ	0.83 (2)	2.13 (6)	2.860 (6)	148 (10)
O7—H2···Cl1ⁱⁱ	0.83 (2)	2.81 (11)	3.220 (4)	112 (9)

Symmetry codes: (i) x, −y+1, z+1/2; (ii) x+1/2, −y+3/2, z+1/2.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant No. 40972035), the Natural Science Foundation of Fujian Province of China (grant No. 2010 J01308) and the Scientific and Technological Innovation Platform of Fujian Province (grant No. 2009 J1009).

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