Lithium manganese(II) diaqua­boro­phosphate monohydrate

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.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](Mn-O) = 0.004 Å
• H-atom completeness 67%
• Disorder in main residue
• R factor = 0.040
• wR factor = 0.097
• Data-to-parameter ratio = 14.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT301_ALERT_3_C Main Residue  Disorder .........................       1.00 Perc.
PLAT031_ALERT_4_C Refined Extinction Parameter within Range ......       2.84 Sigma
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:H6 B1 Li1 Mn1 O11 P2
            Atom count from the _atom_site data:  H4 B1 Li1.003 Mn1 O11 P2
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
           From the CIF: _cell_formula_units_Z    6
           From the CIF: _chemical_formula_sum  B1 H6 Li1 Mn1 O11 P2
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           B          6.00      6.00    0.00
           H         36.00     24.00   12.00
           Li         6.00      5.99    0.01
           Mn         6.00      6.00    0.00
           O         66.00     66.00    0.00
           P         12.00     12.00    0.00
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           29.99
           From the CIF: _reflns_number_total               1230
           Count of symmetry unique reflns          787
           Completeness (_total/calc)            156.29%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       443
           Fraction of Friedel pairs measured     0.563
           Are heavy atom types Z>Si present        yes
PLAT791_ALERT_4_G Confirm the Absolute Configuration of P1     ...          R

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   5 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. 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.

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).

S2. 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.

S3. 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.

Computing details

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, 2005) and ATOMS (Dowty, 2004); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

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).

Lithium manganese diaquaborophosphate monohydrate

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) Å^3	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 monochromator	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 F^2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	Only H-atom coordinates refined
R[F^2 > 2σ(F^2)] = 0.040	w = 1/[σ^2(Fo^2) + (0.008P)^2 + 5.1269P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 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+0.001xFc^2λ^3/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	Absolute structure 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)

	U^11	U^22	U^33	U^12	U^13	U^23
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, º)

Mn1—O4^i	2.133 (3)	O5—H1	0.82 (7)
Mn1—O4^ii	2.133 (3)	O5—H2	0.81 (2)
Mn1—O3	2.139 (3)	O6—O6^ix	0.71 (2)
Mn1—O3^iii	2.139 (3)	O6—Li2	1.31 (3)
Mn1—O5	2.311 (4)	O6—Li2^ix	1.95 (3)
Mn1—O5^iii	2.311 (3)	O6—Li2^xii	1.98 (3)
P1—O3	1.504 (3)	O6—Li2^x	2.45 (3)
P1—O4	1.510 (3)	O6—Li1^xiii	2.53 (3)
P1—O1^iv	1.553 (3)	B1—O1^xiv	1.463 (4)
P1—O2^v	1.560 (2)	B1—O1^xv	1.463 (4)
O1—B1^vi	1.463 (4)	B1—O2^iv	1.470 (4)
O1—P1^iv	1.553 (3)	Li1—O5^iv	2.111 (4)
O1—Li2^vii	2.65 (3)	Li1—O3^iv	2.112 (17)
O2—B1	1.470 (4)	Li2—O6^ix	1.95 (3)
O2—P1^viii	1.560 (2)	Li2—O6^xii	1.98 (3)
O3—Li1	2.112 (17)	Li2—O4^ix	2.11 (3)
O4—Li2^ix	2.11 (3)	Li2—O5^xiii	2.18 (3)
O4—Mn1^x	2.133 (3)	Li2—Li2^xii	2.30 (6)
O5—Li1	2.111 (4)	Li2—O6^i	2.45 (3)
O5—Li2^xi	2.18 (3)
O4^i—Mn1—O4^ii	97.89 (17)	O2—B1—O2^iv	102.6 (4)
O4^i—Mn1—O3	100.17 (11)	O5^iv—Li1—O5	177.6 (17)
O4^ii—Mn1—O3	91.22 (11)	O5^iv—Li1—O3^iv	85.4 (4)
O4^i—Mn1—O3^iii	91.22 (11)	O5—Li1—O3^iv	96.0 (5)
O4^ii—Mn1—O3^iii	100.17 (11)	O5^iv—Li1—O3	96.0 (5)
O3—Mn1—O3^iii	162.68 (17)	O5—Li1—O3	85.4 (4)
O4^i—Mn1—O5	178.14 (13)	O3^iv—Li1—O3	112.6 (14)
O4^ii—Mn1—O5	83.95 (13)	O5^iv—Li1—O6^ii	80.8 (8)
O3—Mn1—O5	80.01 (12)	O5—Li1—O6^ii	96.8 (9)
O3^iii—Mn1—O5	88.19 (12)	O3^iv—Li1—O6^ii	122.4 (7)
O4^i—Mn1—O5^iii	83.95 (13)	O3—Li1—O6^ii	124.3 (8)
O4^ii—Mn1—O5^iii	178.14 (14)	O5^iv—Li1—O6^xi	96.8 (9)
O3—Mn1—O5^iii	88.19 (12)	O5—Li1—O6^xi	80.8 (8)
O3^iii—Mn1—O5^iii	80.01 (12)	O3^iv—Li1—O6^xi	124.3 (8)
O5—Mn1—O5^iii	94.2 (2)	O3—Li1—O6^xi	122.4 (7)
O3—P1—O4	115.17 (17)	O6^ii—Li1—O6^xi	16.0 (5)
O3—P1—O1^iv	111.97 (16)	O6—Li2—O6^ix	10.8 (10)
O4—P1—O1^iv	104.62 (16)	O6—Li2—O6^xii	90.8 (17)
O3—P1—O2^v	105.62 (15)	O6^ix—Li2—O6^xii	101.7 (15)
O4—P1—O2^v	111.81 (15)	O6—Li2—O4^ix	119.9 (19)
O1^iv—P1—O2^v	107.54 (14)	O6^ix—Li2—O4^ix	110.3 (14)
B1^vi—O1—P1^iv	129.4 (2)	O6^xii—Li2—O4^ix	138.2 (14)
B1—O2—P1^viii	131.1 (2)	O6—Li2—O5^xiii	117.8 (18)
P1—O3—Mn1	128.38 (17)	O6^ix—Li2—O5^xiii	114.8 (14)
Li1—O5—H1	157 (4)	O6^xii—Li2—O5^xiii	102.8 (13)
Li2^xi—O5—H1	93 (4)	O4^ix—Li2—O5^xiii	87.8 (11)
Mn1—O5—H1	107 (4)	O6—Li2—O6^i	104.2 (18)
Li1—O5—H2	103 (4)	O6^ix—Li2—O6^i	115.0 (14)
Li2^xi—O5—H2	162 (4)	O6^xii—Li2—O6^i	13.8 (7)
Mn1—O5—H2	107 (4)	O4^ix—Li2—O6^i	125.5 (12)
H1—O5—H2	84 (5)	O5^xiii—Li2—O6^i	99.1 (11)
Li2—O6—Li2^ix	146 (2)	O6—Li2—O1^xvi	100.4 (16)
O1^xiv—B1—O1^xv	103.7 (4)	O6^ix—Li2—O1^xvi	100.1 (12)
O1^xiv—B1—O2	113.70 (14)	O6^xii—Li2—O1^xvi	89.1 (11)
O1^xv—B1—O2	111.75 (14)	O4^ix—Li2—O1^xvi	59.9 (8)
O1^xiv—B1—O2^iv	111.75 (14)	O5^xiii—Li2—O1^xvi	139.4 (13)
O1^xv—B1—O2^iv	113.70 (14)	O6^i—Li2—O1^xvi	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, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H1···O4^iii	0.83 (7)	2.09 (7)	2.878 (5)	159.80
O5—H2···O2^i	0.81 (4)	2.09 (5)	2.845 (5)	156

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