Lithium manganese(II) diaqua­boro­phosphate monohydrate

Abstract

The title compound, LiMn(H₂O)₂[BP₂O₈]·H₂O, is built up of an open framework of helical borophosphate ribbons inter­connected by MnO₄(H₂O)₂ octa­hedra, forming one-dimensional channels along [001] occupied by Li⁺ cations and disordered H₂O mol­ecules (site occupancy 0.5). The Li cations reside in two partially occupied sites [occupancies = 0.42 (3) and 0.289 (13)] near the helices.

Related literature

For related structures, see: Boy & Kniep (2001a ▶,b ▶) for LiCu(H₂O)₂[BP₂O₈]·(H₂O) and LiZn(H₂O)₂[BP₂O₈]·H₂O; Ge et al. (2003 ▶) for LiCd(H₂O)₂[BP₂O₈]·H₂O; Lin et al. (2008 ▶) for LiMg(H₂O)₂[BP₂O₈]·H₂O. For related literature, see: Ewald et al. (2006 ▶); Kniep et al. (1997 ▶).

Experimental

Crystal data

• LiMn(H₂O)₂[BP₂O₈]·H₂O

• M _r = 316.68

• Hexagonal,

• a = 9.5765 (4) Å

• c = 15.857 (1) Å

• V = 1259.4 (1) ų

• Z = 6

• Mo Kα radiation

• μ = 2.01 mm⁻¹

• T = 295 (2) K

• 0.16 × 0.12 × 0.12 mm

Data collection

• Rigaku AFC-7 CCD diffractometer

• Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.740, T _max = 0.795

• 9731 measured reflections

• 1230 independent reflections

• 1223 reflections with I > 2σ(I)

• R _int = 0.032

Refinement

• R[F ² > 2σ(F ²)] = 0.040

• wR(F ²) = 0.097

• S = 1.19

• 1230 reflections

• 85 parameters

• 1 restraint

• Only H-atom coordinates refined

• Δρ_max = 0.61 e Å⁻³

• Δρ_min = −0.44 e Å⁻³

• Absolute structure: Flack (1983 ▶), 443 Friedel pairs

• Flack parameter: −0.01 (4)

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, 2005 ▶) and ATOMS (Dowty, 2004 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected geometric parameters (Å, °).

Mn1—O4i	2.133 (3)
Mn1—O3	2.139 (3)
Mn1—O5	2.311 (4)
P1—O3	1.504 (3)
P1—O4	1.510 (3)
P1—O1ii	1.553 (3)
P1—O2iii	1.560 (2)
O5—H1	0.82 (7)
O5—H2	0.81 (2)
B1—O1iv	1.463 (4)
B1—O2ii	1.470 (4)
Li1—O5ii	2.111 (4)
Li1—O3ii	2.112 (17)
Li2—O6v	1.95 (3)
Li2—O6vi	1.98 (3)
Li2—O4v	2.11 (3)
Li2—O5vii	2.18 (3)

B1viii—O1—P1ii	129.4 (2)
B1—O2—P1ix	131.1 (2)
P1—O3—Mn1	128.38 (17)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) ; (ix) .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H1⋯O4x	0.83 (7)	2.09 (7)	2.878 (5)	159.80
O5—H2⋯O2i	0.81 (4)	2.09 (5)	2.845 (5)	155.74

Symmetry codes: (i) ; (x) .

supplementary crystallographic information

Comment

A large family of compounds contains helical borophosphate anions _∞¹[BP₂O₈]^3- with various combinations of metal cations (M^IM^II, M_0.5^IM^II, M^III) (Kniep et al., 1997; Ewald et al., 2006). To date, the only Li-containing members are LiM^II(H₂O)₂[BP₂O₈]^.H₂O (M^II = Cu, Zn, Cd, Mg) (Boy & Kniep, 2001a, 2001b; Ge et al., 2003; Lin et al., 2008). The structure of LiMn(H₂O)₂[BP₂O₈]^.H₂O is reported here.

The borophosphate helices, built up of four-membered rings of alternating BO₄ and PO₄ tetrahedra, extend along the 6₅ screw axis (Fig. 1 and 2). These helices are interconnected by Jahn-Teller-distorted Mn²⁺-centred octahedra, with four oxygen atoms (O3, O4) from PO₄ groups and two (O5) from water molecules at the vertices (Fig. 3). Unlike the compounds containing Cu and Zn (Boy & Kniep, 2001a, 2001b) but similar to those containing Cd and Mg (Ge et al., 2003; Lin et al., 2008), there are two distinct Li sites: Li1 is close to the outer wall of the borophosphate helices and Li2 is situated at the free loops (inner wall) of the helices. The sum of occupancies of these Li sites refines to almost unity, as required to maintain charge neutrality in the compound.

Experimental

LiMn(H₂O)₂[BP₂O₈].H₂O was obtained in the presence of boric acid as a flux. A mixture of 0.1149 g MnCO₃, 1.484 g H₃BO₃, and 0.6235 g LiH₂PO₄ was ground to a homogeneous powder, which was transferred to a teflon autoclave with 10 ml inline (degree of filling 10%) where it was heated at 443 K for four days.

Refinement

The hydrogen atoms connected to O5 were located from difference Fourier maps with displacement parameters fixed as 1.2*U(O5), whereas those connected to O6 belonging to the disordered water molecules were not located. The sum of the occupancies of Li sites was restrained to maintain charge neutrality within the entire compound. The occupancy of the O6 site associated with the disordered water molecules was fixed at 0.5.

Figures

Fig. 1.

Linkage of borophosphate helices in LiMn(H2O)2[BP2O8].H2O through MnO4(H2O)2 octahedra (BO4, green tetrahedra; PO4, orange tetrahedra; MnO6, violet octahedra; Li, black spheres; H2O, red spheres).

Fig. 2.

Section of LiMn(H2O)2[BP2O8].H2O viewed along the c axis (colour scheme as in Fig. 1).

Fig. 3.

Coordination environment of Mn, B, and P atoms, with displacement ellipsoids drawn at the 50% probability level (symmetry codes: (i) -x+y, y, 1/2-z; (ii) 1-x, 1-x+y, 1/3-z; (iii) y,1-x+y, 1/6+z; (iv) 1-y,1-x, 1/6-z; (v) x-y, x,-1/6+z; (vi) 1+x-y, 1-y,-z, (vii) x-y, 1-y,-z; (viii) 1+x-y,1+x,-1/6+z).

Crystal data

LiMn(H2O)2[BP2O8]·H2O	Dx = 2.505 Mg m−3
Mr = 316.68	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P6522	Cell parameters from 6263 reflections
Hall symbol: P 65 2 (0 0 1)	θ = 2.5–33.2°
a = 9.5765 (4) Å	µ = 2.01 mm−1
c = 15.857 (1) Å	T = 295 K
V = 1259.4 (1) Å3	Hexagonal bipyramid, pale pink
Z = 6	0.16 × 0.12 × 0.12 mm
F(000) = 942

Data collection

Rigaku AFC-7 CCD diffractometer	1230 independent reflections
Radiation source: fine-focus sealed tube	1223 reflections with I > 2σ(I)
graphite	Rint = 0.032
Detector resolution: 14.6306 pixels mm-1	θmax = 30.0°, θmin = 2.5°
thin–slice Δφ=0.6 & Δω=0.6 scans	h = −13→13
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −13→12
Tmin = 0.740, Tmax = 0.795	l = −19→22
9731 measured reflections

Refinement

Refinement on F2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	Only H-atom coordinates refined
R[F2 > 2σ(F2)] = 0.040	w = 1/[σ2(Fo2) + (0.008P)2 + 5.1269P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.097	(Δ/σ)max < 0.001
S = 1.19	Δρmax = 0.62 e Å−3
1230 reflections	Δρmin = −0.44 e Å−3
85 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraint	Extinction coefficient: 0.0054 (19)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 443 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: −0.01 (4)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mn1	0.44888 (4)	0.89775 (9)	0.2500	0.0163 (2)
P1	0.61636 (10)	0.83327 (10)	0.08453 (6)	0.0134 (2)
O1	0.0204 (3)	0.2129 (3)	0.06593 (16)	0.0181 (5)
O2	0.7681 (3)	0.1804 (3)	0.01267 (14)	0.0158 (5)
O3	0.4860 (3)	0.8589 (4)	0.12112 (17)	0.0227 (6)
O4	0.6237 (4)	0.6903 (3)	0.11938 (17)	0.0228 (6)
O5	0.1884 (4)	0.7081 (4)	0.2127 (2)	0.0340 (8)
O6	0.9000 (19)	0.8166 (12)	0.2717 (7)	0.079 (3)*	0.50
B1	0.8493 (3)	0.1507 (3)	0.0833	0.0140 (9)
Li1	0.2428 (18)	0.7572 (18)	0.0833	0.034 (4)	0.42 (3)
Li2	0.899 (4)	0.763 (3)	0.3479 (16)	0.034 (4)	0.289 (13)
H1	0.133 (8)	0.683 (7)	0.256 (4)	0.041*
H2	0.179 (7)	0.620 (4)	0.218 (4)	0.041*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Mn1	0.0170 (3)	0.0165 (4)	0.0153 (3)	0.00826 (18)	0.0028 (2)	0.000
P1	0.0153 (4)	0.0131 (4)	0.0113 (3)	0.0068 (3)	0.0011 (3)	−0.0005 (3)
O1	0.0139 (11)	0.0196 (12)	0.0200 (12)	0.0077 (10)	−0.0012 (9)	−0.0060 (9)
O2	0.0195 (12)	0.0185 (11)	0.0106 (9)	0.0104 (10)	−0.0029 (9)	−0.0024 (8)
O3	0.0222 (14)	0.0306 (15)	0.0177 (12)	0.0151 (12)	0.0028 (10)	−0.0046 (11)
O4	0.0348 (16)	0.0150 (12)	0.0177 (11)	0.0117 (11)	−0.0008 (12)	0.0022 (10)
O5	0.0280 (17)	0.0233 (15)	0.0393 (17)	0.0041 (13)	0.0118 (14)	−0.0065 (14)
B1	0.0157 (17)	0.0157 (17)	0.011 (2)	0.0083 (19)	0.0013 (16)	0.0013 (16)
Li1	0.036 (7)	0.036 (7)	0.023 (8)	0.012 (8)	0.003 (6)	0.003 (6)
Li2	0.036 (7)	0.036 (7)	0.023 (8)	0.012 (8)	0.003 (6)	0.003 (6)

Geometric parameters (Å, °)

Mn1—O4i	2.133 (3)	O5—H1	0.82 (7)
Mn1—O4ii	2.133 (3)	O5—H2	0.81 (2)
Mn1—O3	2.139 (3)	O6—O6ix	0.71 (2)
Mn1—O3iii	2.139 (3)	O6—Li2	1.31 (3)
Mn1—O5	2.311 (4)	O6—Li2ix	1.95 (3)
Mn1—O5iii	2.311 (3)	O6—Li2xii	1.98 (3)
P1—O3	1.504 (3)	O6—Li2x	2.45 (3)
P1—O4	1.510 (3)	O6—Li1xiii	2.53 (3)
P1—O1iv	1.553 (3)	B1—O1xiv	1.463 (4)
P1—O2v	1.560 (2)	B1—O1xv	1.463 (4)
O1—B1vi	1.463 (4)	B1—O2iv	1.470 (4)
O1—P1iv	1.553 (3)	Li1—O5iv	2.111 (4)
O1—Li2vii	2.65 (3)	Li1—O3iv	2.112 (17)
O2—B1	1.470 (4)	Li2—O6ix	1.95 (3)
O2—P1viii	1.560 (2)	Li2—O6xii	1.98 (3)
O3—Li1	2.112 (17)	Li2—O4ix	2.11 (3)
O4—Li2ix	2.11 (3)	Li2—O5xiii	2.18 (3)
O4—Mn1x	2.133 (3)	Li2—Li2xii	2.30 (6)
O5—Li1	2.111 (4)	Li2—O6i	2.45 (3)
O5—Li2xi	2.18 (3)
O4i—Mn1—O4ii	97.89 (17)	O2—B1—O2iv	102.6 (4)
O4i—Mn1—O3	100.17 (11)	O5iv—Li1—O5	177.6 (17)
O4ii—Mn1—O3	91.22 (11)	O5iv—Li1—O3iv	85.4 (4)
O4i—Mn1—O3iii	91.22 (11)	O5—Li1—O3iv	96.0 (5)
O4ii—Mn1—O3iii	100.17 (11)	O5iv—Li1—O3	96.0 (5)
O3—Mn1—O3iii	162.68 (17)	O5—Li1—O3	85.4 (4)
O4i—Mn1—O5	178.14 (13)	O3iv—Li1—O3	112.6 (14)
O4ii—Mn1—O5	83.95 (13)	O5iv—Li1—O6ii	80.8 (8)
O3—Mn1—O5	80.01 (12)	O5—Li1—O6ii	96.8 (9)
O3iii—Mn1—O5	88.19 (12)	O3iv—Li1—O6ii	122.4 (7)
O4i—Mn1—O5iii	83.95 (13)	O3—Li1—O6ii	124.3 (8)
O4ii—Mn1—O5iii	178.14 (14)	O5iv—Li1—O6xi	96.8 (9)
O3—Mn1—O5iii	88.19 (12)	O5—Li1—O6xi	80.8 (8)
O3iii—Mn1—O5iii	80.01 (12)	O3iv—Li1—O6xi	124.3 (8)
O5—Mn1—O5iii	94.2 (2)	O3—Li1—O6xi	122.4 (7)
O3—P1—O4	115.17 (17)	O6ii—Li1—O6xi	16.0 (5)
O3—P1—O1iv	111.97 (16)	O6—Li2—O6ix	10.8 (10)
O4—P1—O1iv	104.62 (16)	O6—Li2—O6xii	90.8 (17)
O3—P1—O2v	105.62 (15)	O6ix—Li2—O6xii	101.7 (15)
O4—P1—O2v	111.81 (15)	O6—Li2—O4ix	119.9 (19)
O1iv—P1—O2v	107.54 (14)	O6ix—Li2—O4ix	110.3 (14)
B1vi—O1—P1iv	129.4 (2)	O6xii—Li2—O4ix	138.2 (14)
B1—O2—P1viii	131.1 (2)	O6—Li2—O5xiii	117.8 (18)
P1—O3—Mn1	128.38 (17)	O6ix—Li2—O5xiii	114.8 (14)
Li1—O5—H1	157 (4)	O6xii—Li2—O5xiii	102.8 (13)
Li2xi—O5—H1	93 (4)	O4ix—Li2—O5xiii	87.8 (11)
Mn1—O5—H1	107 (4)	O6—Li2—O6i	104.2 (18)
Li1—O5—H2	103 (4)	O6ix—Li2—O6i	115.0 (14)
Li2xi—O5—H2	162 (4)	O6xii—Li2—O6i	13.8 (7)
Mn1—O5—H2	107 (4)	O4ix—Li2—O6i	125.5 (12)
H1—O5—H2	84 (5)	O5xiii—Li2—O6i	99.1 (11)
Li2—O6—Li2ix	146 (2)	O6—Li2—O1xvi	100.4 (16)
O1xiv—B1—O1xv	103.7 (4)	O6ix—Li2—O1xvi	100.1 (12)
O1xiv—B1—O2	113.70 (14)	O6xii—Li2—O1xvi	89.1 (11)
O1xv—B1—O2	111.75 (14)	O4ix—Li2—O1xvi	59.9 (8)
O1xiv—B1—O2iv	111.75 (14)	O5xiii—Li2—O1xvi	139.4 (13)
O1xv—B1—O2iv	113.70 (14)	O6i—Li2—O1xvi	83.4 (9)

Symmetry codes: (i) y, −x+y+1, z+1/6; (ii) −x+1, −x+y+1, −z+1/3; (iii) −x+y, y, −z+1/2; (iv) −y+1, −x+1, −z+1/6; (v) x−y, −y+1, −z; (vi) x−1, y, z; (vii) −y+1, x−y, z−1/3; (viii) x−y+1, −y+1, −z; (ix) −x+y+1, y, −z+1/2; (x) x−y+1, x, z−1/6; (xi) x−y, x, z−1/6; (xii) y, x, −z+2/3; (xiii) y, −x+y, z+1/6; (xiv) −y+1, −x, −z+1/6; (xv) x+1, y, z; (xvi) −x+y+1, −x+1, z+1/3.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H1···O4iii	0.83 (7)	2.09 (7)	2.878 (5)	159.80
O5—H2···O2i	0.81 (4)	2.09 (5)	2.845 (5)	156.

Symmetry codes: (iii) −x+y, y, −z+1/2; (i) y, −x+y+1, z+1/6.