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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 6| June 2012| Page i49
doi:10.1107/S1600536812022775

MnBa2(HPO4)2(H2PO4)2

Wei Sun,a Li-Zhi Sun,a Teng-Teng Zhu,a Biao-Chun Zhaoa and Jin-Xiao Mia*

aFujian Provincial Key Laboratory of Advanced Materials, Department 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 11 May 2012; accepted 18 May 2012; online 26 May 2012)

Crystals of manganese(II) dibarium bis­(hydrogenphosphate) bis­(dihydrogenphosphate), MnBa2(HPO4)2(H2PO4)2, were obtained by hydro­thermal synthesis. The title compound is isotypic with its CdII and CaII analogues. The structure is built up of an infinite {[Mn(HPO4)2(H2PO4)2]4−}n chain running along [100], which consists of alternate MnO6 octa­hedra and [PO4] tetra­hedra, in which the centrosymmetric MnO6 octa­hedra share their four equatorial O-atom corners with tetra­hedral [PO3(OH)] groups and their two axial apices with tetra­hedral [PO2(OH)2] groups. These chains are held together by BaO9 coordination polyhedra, developing into a three-dimensional structure. The O—H⋯O hydrogen bonds additionally stabilize the structural set-up. Due to the ionic radius of Mn2+ being much smaller than those of Ca2+ and Cd2+, this may imply that their adopted structure type has a great tolerance for incorporating various ions and the exploitation of more diverse compounds in the future is encouraged.

Related literature

For background to transition metal phosphates, see: Cheet­ham et al. (1999[Cheetham, A. K., Ferey, G. & Loiseau, T. (1999). Angew. Chem. Int. Ed. 38, 3268-3292.]); Mao et al. (2000[Mao, S.-Y., Huang, Y.-X., Wei, Z.-B., Mi, J.-X., Huang, Z.-L. & Zhao, J.-T. (2000). J. Solid State Chem. 149, 292-297.]); Mi et al. (2000[Mi, J.-X., Zhao, J.-T., Mao, S.-Y., Huang, Y.-X., Engelhardt, H. & Kniep, R. Z. (2000). Z. Kristallogr. New Cryst. Struct. 215, 201-202.]); Sun et al. (2012[Sun, W., Huang, Y.-X., Pan, Y. M. & Mi, J.-X. (2012). J. Solid State Chem. 187, 89-96.]); Escobal et al. (1999[Escobal, J., Mesa, J. L., Pizarro, J. L., Lezama, L., Olazcuaga, R. & Rojo, T. (1999). J. Mater. Chem. 9, 2691-2695.]). For isotypic structures, see: Ben Taher et al. (2001[Ben Taher, L., Smiri, L. & Bulou, A. (2001). J. Solid State Chem. 161, 97-105.]) for CdBa2(HPO4)2(H2PO4)2; Ben Tahar et al. (1999[Ben Tahar, L., Smiri, L. & Driss, A. (1999). Acta Cryst. C55, 1757-1759.]) and Toumi et al. (1997[Toumi, M., Chabchoub, S., Smiri-Dogguy, L. & Laligant, Y. (1997). Eur. J. Solid State Inorg. Chem. 34, 1249-1257.]) for CaBa2(HPO4)2(H2PO4)2. For the bond-valence method, see: Brown (2002[Brown, I. D. (2002). In The Chemical Bond in Inorganic Chemistry: The Bond Valence Model. Oxford University Press.]). For ionic radii, see: Shannon (1976[Shannon, R. D. (1976). Acta Cryst. A32, 751-767.]).

Experimental

Crystal data

  • MnBa2(HPO4)2(H2PO4)2

  • Mr = 715.55

  • Monoclinic, P 21 /c

  • a = 5.4168 (10) Å

  • b = 10.1048 (19) Å

  • c = 12.183 (2) Å

  • β = 100.199 (3)°

  • V = 656.3 (2) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 7.46 mm−1

  • T = 173 K

  • 0.25 × 0.22 × 0.08 mm
Data collection

  • Bruker SMART CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2001[Bruker (2001). SAINT, SMART and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.257, Tmax = 0.587

  • 3807 measured reflections

  • 1515 independent reflections

  • 1491 reflections with I > 2σ(I)

  • Rint = 0.021
Refinement

  • R[F2 > 2σ(F2)] = 0.025

  • wR(F2) = 0.075

  • S = 1.04

  • 1515 reflections

  • 116 parameters

  • 1 restraint

  • All H-atom parameters refined

  • Δρmax = 0.88 e Å−3

  • Δρmin = −1.03 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O6—H1⋯O4i 0.79 (8) 1.82 (8) 2.600 (4) 172 (7)
O7—H2⋯O5ii 0.95 (7) 1.65 (7) 2.504 (4) 149 (6)
O8—H3⋯O2iii 0.80 (2) 1.82 (2) 2.623 (4) 178 (8)
Symmetry codes: (i) [x+1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]; (ii) [-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (iii) x-1, y, z.

Data collection: SMART (Bruker, 2001[Bruker (2001). SAINT, SMART and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2001[Bruker (2001). SAINT, SMART and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; 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, 2011[Brandenburg, K. (2011). DIAMOND. Crystal Impact GbR, Bonn, Germany.]) and ATOMS (Dowty, 2004[Dowty, E. (2004). ATOMS. Shape Software, Kingsport, Tennessee, USA.]); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812022775/br2203sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812022775/br2203Isup2.hkl

checkCIF report


Comment top

Microporous phosphate materials based on transition metal elements have been extensively studied due to their potential optical, electrical, magnetic, and catalytic properties, as well as some interesting properties which are inaccessible to zeolites and other frameworks based on main-group elements only (Cheetham et al., 1999). As a part of our systematical investigation concerning the synthesis and spectroscopic studies of phosphates with transition metal ions, e.g. V3+, Cr3+, Fe3+ and Co2+ etc. (Mao et al., 2000; Mi et al., 2000; Sun et al., 2012), herein we report the crystal structure of MnBa2(HPO4)2(H2PO4)2, which has been prepared under hydrothermal conditions. To the best of our knowledge, there is very scant information on manganese barium hydroxy-hydrated phosphates. This is the second hydroxy-hydrated phosphate after the compound of Ba(MnPO4)2.H2O (Escobal et al., 1999).

The title compound, MnBa2(HPO4)2(H2PO4)2, is isotypic to its Cd and Ca analogues (Ben Taher et al., 2001; Ben Tahar et al., 1999 & Toumi et al., 1997). In the structure, the asymmetric unit contains one Mn atom, two crystallographically distinct P atoms and one Ba atom (Figs 1–3). Mn1 lies on the inversion center (1/2,0,1/2) (i.e. 2d) and adopts slightly distorted octahedral coordination with an average bond distance of Mn–O = 2.206 Å. The [MnO6] octahedron has six O-corners each fused by corner-sharing to an phosphate tetrahedron, four equatorial O-corners to tetrahedral [PO3(OH)] groups and two axial apices to tetrahedral [PO2(OH)2] groups. P1 is surrounded by three O atoms and one OH group forming a tetrahedral hydrogenphosphate group with an average bond length of P–O = 1.541 Å, while P2 is coordinated to two O atoms and two OH groups forming a tetrahedral dihydrogenphosphate group with d(P–O)av = 1.543 Å. Two hydrogenphosphate [PO3(OH)] groups bridge pairs of vertices from each octahedron via their common O-corners, and vice versa, subsequently to develop into a chain running along the direction of [100], and each side of which is decorated by flanking dihydrogenphosphate [PO2(OH)2] groups (Fig. 2). The infinite {[Mn(HPO4)2(H2PO4)2]4-}n anionic chains are held together by BaO9 coordination spheres, which are composed of barium ions (Ba2+) surrounded by nine adjacent oxygen atoms with an average bond distance of Ba–O = 2.868 Å, developing into a three-dimensional structure (Figs 1,3) The structural set-up is additionally stabilized by O–H···O hydrogen bonds, which occur between [PO3(OH)] and [PO2(OH)2], and form a two-dimensional hydrogen bonding network parallel to the plane of (100). With regard to the [PO3(OH)] groups, one of O-corners bridged to [MnO6] octahedra (i.e. O2) and one non-bridged O-corner (i.e. O5) as well as the OH terminal link individually to their adjacent [PO2(OH)2] groups via hydrogen bonds (i.e. 1 OH donor + 2 acceptors). For [PO2(OH)2] groups, except for O3 connected to a [MnO6] octahedron, O4 and two OH terminals link to three [PO3(OH)] groups via hydrogen bonds (i.e. 2 OH donors + 1 acceptor) (Fig. 1). The connectivity of hydrogen bonds is further confirmed by a bond-valence-sum calculation. The bond-valence-sum calculation shows that the bond valence sums of Ba1, Mn1, P1 and P2 are 1.99, 1.96, 4.76 and 4.73 valence units (v.u.), respectively, while those of oxygen atoms O1, O2, O3, O4, O5, O6, O7 and O8 are -1.79, -1.63, -1.81, -1.65, -1.65, -1.36, -1.31 and -1.27 v.u., respectively (Brown, 2002). Oxygen atoms O6, O7 and O8 with the bond valence sums in the ranges of -1.36 to -1.27 v.u. are protonated for compensating the negative charge (i.e. of hydroxy oxygen atoms). Oxygen atoms O2, O4 and O5 with the bond valence sums of -1.63 to -1.65 u.v. require a hydrogen bond to compensate the negative charge. This is why among three oxygen atoms (O1, O2, O3) which link to [MnO6] octahedra, only O2 is involved in a hydrogen bond. Due to the 6-coordinate effective ionic radius of Mn2+ (0.830 Å, HS) is much smaller than those of Ca2+(1.00 Å) and Cd2+(0.95 Å)(Shannon, 1976), this implies that their adopted structure type has a great tolerance for incorporating various ions and the exploitation on more diverse compounds in the future are encouraged.

Related literature top

For background to transition metal phosphates, see: Cheetham et al. (1999); Mao et al. (2000); Mi et al. (2000); Sun et al. (2012); Escobal et al. (1999). For isotypic structures, see: Ben Taher et al. (2001) for CdBa2(HPO4)2(H2PO4)2; Ben Tahar et al. (1999) and Toumi et al. (1997) for CaBa2(HPO4)2(H2PO4)2. For the bond-valence method, see: Brown (2002). For ionic radii, see: Shannon (1976).

Experimental top

The title compound, MnBa2(HPO4)2(H2PO4)2 was synthesized by using a hydrothermal method. Typically a mixture of Ba(NO3)2 (1.04 g), Mn(CH3COO)2.4H2O (0.98 g), KBF4 (0.60 g) and H3PO4 (2 ml) with the molar ratio of Ba:Mn:P=2:2:15 was prepared, and transferred into a Teflon-lined stainless-steel autoclave (30 ml in volume), then heated to and held at 463 K for 3 days. Transparent, light pink 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. Scanning electron microscopy was used to document the crystal morphologies (Fig. 4). Chemical compositions of selected crystals were examined by use of an Oxford Instruments Energy Dispersive X-ray Spectrometer (EDX), which confirmed the ratio of Mn:Ba:P=1:2:4 from single-crystal data.

Refinement top

All hydrogen positions were located from the difference Fourier map and tentatively refined without any restraint. Then a common variable was applied for the refinement of isotropic atomic displacement parameters (Uiso) of all hydrogen atoms. After refinement the bond distance of O8–H3 became improper, so soft restraints on both Uiso and the bond length (d(O–H) = 0.82 (2) Å) were used for H3 during running the refinement.

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
[Figure 1] Fig. 1. Crystal structure of MnBa2(HPO4)2(H2PO4)2. Upper: viewing down approximately along the direction of [100]. Down: the representation of hydrogen bonds occurring between [PO3(OH)] groups and [PO2(OH)2] groups. ([MnO6] are drawn as pink octahedra; [PO3(OH)] as blue tetrahedra; [PO2(OH)2] as green tetrahedra; Ba as black spheres; Mn as pink spheres; H as small black balls).
[Figure 2] Fig. 2. Crystal structure of MnBa2(HPO4)2(H2PO4)2. Upper: the infinite {[Mn(HPO4)2(H2PO4)2]4-}n chain running along the direction of [100]; Down: coordination environment of barium.
[Figure 3] Fig. 3. Coordination environment of barium, manganese, and phosphorus atoms, with displacement ellipsoids drawn at the 50% probability level (symmetry codes: (i) x, –y + 1/2, z - 1/2; (ii) –x + 1, –y + 1, –z + 1; (iii) –x + 2, y + 1/2, –z + 1/2; (iv) –x + 1, y + 1/2, –z + 1/2; (v) x + 1, y, z; (vi) –x + 1, –y, –z + 1; (vii) –x + 2, –y, –z + 1)
[Figure 4] Fig. 4. The crystal morphology and chemical composition. Upper: image of scanning electron microscopy for the crystal morphology. Down: the chemical composition of the selected crystal measured by the EDX.
manganese(II) dibarium bis(hydrogenphosphate) bis(dihydrogenphosphate) top
Crystal data top
MnBa2(HPO4)2(H2PO4)2F(000) = 662
Mr = 715.55Dx = 3.621 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3807 reflections
a = 5.4168 (10) Åθ = 2.6–28.2°
b = 10.1048 (19) ŵ = 7.46 mm−1
c = 12.183 (2) ÅT = 173 K
β = 100.199 (3)°Prism, light pink
V = 656.3 (2) Å30.25 × 0.22 × 0.08 mm
Z = 2
Data collection top
Bruker SMART CCD area-detector
diffractometer		1515 independent reflections
Radiation source: fine-focus sealed tube1491 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.021
1265 images,ϕ=0, 90, 180 degree, and Δω=0.3 degree, χ= 54.74 degree scansθmax = 28.2°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −7→7
Tmin = 0.257, Tmax = 0.587k = −13→8
3807 measured reflectionsl = −15→13
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025Hydrogen site location: difference Fourier map
wR(F2) = 0.075All H-atom parameters refined
S = 1.04 w = 1/[σ2(Fo2) + (0.053P)2 + 1.2855P]
where P = (Fo2 + 2Fc2)/3
1515 reflections(Δ/σ)max < 0.001
116 parametersΔρmax = 0.88 e Å−3
1 restraintΔρmin = −1.03 e Å−3
Crystal data top
MnBa2(HPO4)2(H2PO4)2V = 656.3 (2) Å3
Mr = 715.55Z = 2
Monoclinic, P21/cMo Kα radiation
a = 5.4168 (10) ŵ = 7.46 mm−1
b = 10.1048 (19) ÅT = 173 K
c = 12.183 (2) Å0.25 × 0.22 × 0.08 mm
β = 100.199 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		1515 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		1491 reflections with I > 2σ(I)
Tmin = 0.257, Tmax = 0.587Rint = 0.021
3807 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0251 restraint
wR(F2) = 0.075All H-atom parameters refined
S = 1.04Δρmax = 0.88 e Å−3
1515 reflectionsΔρmin = −1.03 e Å−3
116 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
xyzUiso*/Ueq
Ba10.63461 (4)0.35046 (2)0.322960 (18)0.00907 (12)
Mn10.50000.00000.50000.00694 (18)
P10.91926 (18)0.01271 (9)0.30714 (8)0.0065 (2)
P20.26314 (18)0.30069 (10)0.55243 (8)0.0072 (2)
O10.6833 (5)0.0118 (3)0.3582 (2)0.0111 (6)
O20.8498 (5)0.0497 (3)0.6203 (2)0.0104 (5)
O30.4241 (5)0.2178 (3)0.4898 (2)0.0098 (5)
O40.3420 (5)0.3043 (3)0.6778 (2)0.0121 (6)
O50.8762 (5)−0.0571 (3)0.1943 (2)0.0104 (6)
O60.9749 (6)0.1640 (3)0.2869 (3)0.0113 (6)
O70.2616 (5)0.4494 (3)0.5130 (2)0.0103 (5)
O8−0.0222 (5)0.2624 (3)0.5203 (2)0.0104 (5)
H11.093 (15)0.168 (6)0.258 (7)0.038 (11)*
H20.211 (13)0.479 (7)0.439 (6)0.038 (11)*
H3−0.065 (13)0.197 (5)0.550 (5)0.038 (11)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ba10.00826 (17)0.01023 (17)0.00887 (16)−0.00059 (7)0.00195 (10)−0.00110 (7)
Mn10.0076 (4)0.0059 (4)0.0078 (4)−0.0006 (3)0.0029 (3)−0.0002 (3)
P10.0079 (5)0.0046 (4)0.0074 (4)0.0003 (3)0.0026 (3)−0.0002 (3)
P20.0083 (5)0.0058 (4)0.0080 (4)0.0005 (3)0.0027 (3)0.0001 (3)
O10.0105 (14)0.0141 (14)0.0099 (13)0.0013 (11)0.0047 (11)0.0026 (11)
O20.0078 (13)0.0084 (13)0.0140 (13)0.0005 (10)−0.0007 (10)−0.0007 (10)
O30.0120 (14)0.0076 (13)0.0107 (13)0.0008 (10)0.0043 (10)−0.0006 (10)
O40.0113 (14)0.0143 (16)0.0103 (14)0.0010 (11)0.0007 (11)0.0005 (10)
O50.0144 (15)0.0082 (13)0.0087 (12)0.0008 (10)0.0025 (10)−0.0018 (10)
O60.0145 (16)0.0090 (13)0.0120 (14)−0.0006 (10)0.0064 (12)−0.0016 (10)
O70.0139 (14)0.0050 (12)0.0119 (13)−0.0005 (10)0.0016 (11)−0.0008 (10)
O80.0110 (14)0.0102 (13)0.0104 (13)−0.0022 (11)0.0029 (10)0.0036 (10)
Geometric parameters (Å, º) top
Ba1—O4i2.663 (3)Mn1—O2vi2.238 (3)
Ba1—O62.726 (3)Mn1—O32.238 (3)
Ba1—O7ii2.829 (3)Mn1—O3vi2.238 (3)
Ba1—O32.837 (3)P1—O11.518 (3)
Ba1—O5iii2.852 (3)P1—O51.526 (3)
Ba1—O5iv2.892 (3)P1—O2vii1.534 (3)
Ba1—O8v2.906 (3)P1—O61.586 (3)
Ba1—O1iv3.025 (3)P2—O31.510 (3)
Ba1—O2i3.081 (3)P2—O41.512 (3)
Mn1—O1vi2.142 (3)P2—O81.574 (3)
Mn1—O12.142 (3)P2—O71.577 (3)
Mn1—O22.238 (3)
O4i—Ba1—O680.03 (9)O1—Mn1—O390.42 (10)
O4i—Ba1—O7ii155.43 (9)O2—Mn1—O386.66 (10)
O6—Ba1—O7ii123.55 (9)O2vi—Mn1—O393.34 (10)
O4i—Ba1—O386.04 (8)O1vi—Mn1—O3vi90.42 (10)
O6—Ba1—O399.08 (9)O1—Mn1—O3vi89.58 (10)
O7ii—Ba1—O383.49 (8)O2—Mn1—O3vi93.34 (10)
O4i—Ba1—O5iii126.50 (8)O2vi—Mn1—O3vi86.66 (10)
O6—Ba1—O5iii63.30 (9)O3—Mn1—O3vi180.0
O7ii—Ba1—O5iii75.33 (8)O1—P1—O5111.18 (17)
O3—Ba1—O5iii134.74 (8)O1—P1—O2vii114.92 (17)
O4i—Ba1—O5iv72.07 (9)O5—P1—O2vii107.95 (16)
O6—Ba1—O5iv151.29 (9)O1—P1—O6105.48 (17)
O7ii—Ba1—O5iv83.60 (8)O5—P1—O6107.96 (17)
O3—Ba1—O5iv72.78 (8)O2vii—P1—O6109.14 (17)
O5iii—Ba1—O5iv141.11 (11)O3—P2—O4116.01 (17)
O4i—Ba1—O8v126.01 (9)O3—P2—O8111.55 (16)
O6—Ba1—O8v64.53 (9)O4—P2—O8110.27 (16)
O7ii—Ba1—O8v67.45 (8)O3—P2—O7110.33 (16)
O3—Ba1—O8v62.73 (8)O4—P2—O7105.67 (18)
O5iii—Ba1—O8v72.22 (8)O8—P2—O7101.92 (15)
O5iv—Ba1—O8v128.50 (8)P1—O1—Mn1151.07 (19)
O4i—Ba1—O1iv68.71 (9)P1—O1—Ba1viii96.65 (14)
O6—Ba1—O1iv124.66 (9)Mn1—O1—Ba1viii105.85 (11)
O7ii—Ba1—O1iv98.43 (8)P1vii—O2—Mn1142.65 (17)
O3—Ba1—O1iv121.91 (8)P1vii—O2—Ba1ix93.35 (13)
O5iii—Ba1—O1iv100.73 (8)Mn1—O2—Ba1ix101.64 (10)
O5iv—Ba1—O1iv50.17 (8)P2—O3—Mn1129.37 (16)
O8v—Ba1—O1iv165.22 (8)P2—O3—Ba1116.17 (14)
O4i—Ba1—O2i85.71 (8)Mn1—O3—Ba1114.29 (11)
O6—Ba1—O2i74.60 (8)P2—O4—Ba1ix133.27 (18)
O7ii—Ba1—O2i106.01 (8)P1—O5—Ba1x102.82 (13)
O3—Ba1—O2i170.38 (8)P1—O5—Ba1viii101.91 (13)
O5iii—Ba1—O2i49.12 (8)Ba1x—O5—Ba1viii141.10 (11)
O5iv—Ba1—O2i109.20 (8)P1—O6—Ba1119.25 (17)
O8v—Ba1—O2i119.07 (8)P1—O6—H1108 (5)
O1iv—Ba1—O2i59.06 (8)Ba1—O6—H1132 (5)
O1vi—Mn1—O1180.0P2—O7—Ba1ii118.46 (15)
O1vi—Mn1—O286.79 (11)P2—O7—H2125 (4)
O1—Mn1—O293.21 (11)Ba1ii—O7—H2116 (4)
O1vi—Mn1—O2vi93.21 (11)P2—O8—Ba1xi125.90 (14)
O1—Mn1—O2vi86.79 (11)P2—O8—H3116 (5)
O2—Mn1—O2vi180.0Ba1xi—O8—H3116 (5)
O1vi—Mn1—O389.58 (10)
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, −y+1, −z+1; (iii) −x+2, y+1/2, −z+1/2; (iv) −x+1, y+1/2, −z+1/2; (v) x+1, y, z; (vi) −x+1, −y, −z+1; (vii) −x+2, −y, −z+1; (viii) −x+1, y−1/2, −z+1/2; (ix) x, −y+1/2, z+1/2; (x) −x+2, y−1/2, −z+1/2; (xi) x−1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O6—H1···O4xii0.79 (8)1.82 (8)2.600 (4)172 (7)
O7—H2···O5iv0.95 (7)1.65 (7)2.504 (4)149 (6)
O8—H3···O2xi0.80 (2)1.82 (2)2.623 (4)178 (8)
Symmetry codes: (iv) −x+1, y+1/2, −z+1/2; (xi) x−1, y, z; (xii) x+1, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formulaMnBa2(HPO4)2(H2PO4)2
Mr715.55
Crystal system, space groupMonoclinic, P21/c
Temperature (K)173
a, b, c (Å)5.4168 (10), 10.1048 (19), 12.183 (2)
β (°) 100.199 (3)
V (Å3)656.3 (2)
Z2
Radiation typeMo Kα
µ (mm−1)7.46
Crystal size (mm)0.25 × 0.22 × 0.08
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.257, 0.587
No. of measured, independent and
observed [I > 2σ(I)] reflections		3807, 1515, 1491
Rint0.021
(sin θ/λ)max (Å−1)0.665
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.025, 0.075, 1.04
No. of reflections1515
No. of parameters116
No. of restraints1
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å−3)0.88, −1.03

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···AD—HH···AD···AD—H···A
O6—H1···O4i0.79 (8)1.82 (8)2.600 (4)172 (7)
O7—H2···O5ii0.95 (7)1.65 (7)2.504 (4)149 (6)
O8—H3···O2iii0.80 (2)1.82 (2)2.623 (4)178 (8)
Symmetry codes: (i) x+1, −y+1/2, z−1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) x−1, y, z.
 

Acknowledgements

This work was supported by the National Natural Science Foundation of China (No. 40972035) and the Scientific and Technological Innovation Platform of Fujian Province (No. 2006L2003).

References

First citationBen Tahar, L., Smiri, L. & Driss, A. (1999). Acta Cryst. C55, 1757–1759.  Web of Science CrossRef IUCr Journals Google Scholar
 First citationBen Taher, L., Smiri, L. & Bulou, A. (2001). J. Solid State Chem. 161, 97–105.  Google Scholar
 First citationBrandenburg, K. (2011). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
 First citationBrown, I. D. (2002). In The Chemical Bond in Inorganic Chemistry: The Bond Valence Model. Oxford University Press.  Google Scholar
 First citationBruker (2001). SAINT, SMART and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationCheetham, A. K., Ferey, G. & Loiseau, T. (1999). Angew. Chem. Int. Ed. 38, 3268–3292.  Web of Science CrossRef CAS Google Scholar
 First citationDowty, E. (2004). ATOMS. Shape Software, Kingsport, Tennessee, USA.  Google Scholar
 First citationEscobal, J., Mesa, J. L., Pizarro, J. L., Lezama, L., Olazcuaga, R. & Rojo, T. (1999). J. Mater. Chem. 9, 2691–2695.  Web of Science CrossRef CAS Google Scholar
 First citationMao, S.-Y., Huang, Y.-X., Wei, Z.-B., Mi, J.-X., Huang, Z.-L. & Zhao, J.-T. (2000). J. Solid State Chem. 149, 292–297.  Web of Science CrossRef CAS Google Scholar
 First citationMi, J.-X., Zhao, J.-T., Mao, S.-Y., Huang, Y.-X., Engelhardt, H. & Kniep, R. Z. (2000). Z. Kristallogr. New Cryst. Struct. 215, 201–202.  CAS Google Scholar
 First citationShannon, R. D. (1976). Acta Cryst. A32, 751–767.  CrossRef CAS IUCr Journals Web of Science Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationSun, W., Huang, Y.-X., Pan, Y. M. & Mi, J.-X. (2012). J. Solid State Chem. 187, 89–96.  Web of Science CrossRef CAS Google Scholar
 First citationToumi, M., Chabchoub, S., Smiri-Dogguy, L. & Laligant, Y. (1997). Eur. J. Solid State Inorg. Chem. 34, 1249–1257.  CAS Google Scholar

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ISSN: 2056-9890
Volume 68| Part 6| June 2012| Page i49
doi:10.1107/S1600536812022775
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