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ISSN: 2056-9890

Li­thio­marsturite, LiCa2Mn2Si5O14(OH)

aDepartment of Geosciences, University of Arizona, 1040 E. 4th Street, Tucson, Arizona 85721-0077, USA, and bDepartment of Chemsitry and Biochemistry, University of Arizona, 1306 E. University Blvd, Tucson, Arizona 85721-0041, USA
*Correspondence e-mail: hyang@u.arizona.edu

(Received 19 September 2011; accepted 9 November 2011; online 16 November 2011)

Lithio­marsturite, ideally LiCa2Mn2Si5O14(OH), is a member of the pectolite–pyroxene series of pyroxenoids (hydro­pyroxenoids) and belongs to the rhodonite group. A previous structure determination of this mineral based on triclinic symmetry in space group P[\overline{1}] by Peacor et al. [Am. Mineral. (1990), 75, 409–414] converged with R = 0.18 without reporting any information on atomic coordinates and displacement param­eters. The current study redetermines its structure from a natural specimen from the type locality (Foote mine, North Carolina) based on single-crystal X-ray diffraction data. The crystal structure of lithio­marsturite is characterized by ribbons of edge-sharing CaO6 and two types of MnO6 octa­hedra as well as chains of corner-sharing SiO4 tetra­hedra, both extending along [110]. The octa­hedral ribbons are inter­connected by the rather irregular CaO8 and LiO6 polyhedra through sharing corners and edges, forming layers parallel to ([\overline{1}]1[\overline{1}]), which are linked together by the silicate chains. Whereas the coordination environments of the Mn and Li cations can be compared to those of the corresponding cations in nambulite, the bonding situations of the Ca cations are more similar to those in babingtonite. In contrast to the hydrogen-bonding scheme in babingtonite, which has one O atom as the hydrogen-bond donor and a second O atom as the hydrogen-bond acceptor, our study shows that the situation is reversed in lithio­marsturite for the same two O atoms, as a consequence of the differences in the bonding environments around O atoms in the two minerals.

Related literature

For a previous structural study of lithiomartusite, see: Peacor et al. (1990[Peacor, D. R., Dunn, P. J., White, J. S., Grice, J. D. & Chi, P. H. (1990). Am. Mineral. 75, 409-414.]). For other minerals of the rhodonite group, see: Liebau et al. (1959[Liebau, F., Hilmer, W. & Lindemann, G. (1959). Acta Cryst. 12, 182-187.]); Peacor & Niizeki (1963[Peacor, D. R. & Niizeki, N. (1963). Z. Kristallogr. 119, 98-116.]); Araki & Zoltai (1972[Araki, T. & Zoltai, T. (1972). Z. Kristallogr. 135, 355-373.]); Kosoi (1976[Kosoi, A. (1976). Sov. Phys. Crystallogr. 20, 446-451.]); Narita et al. (1975[Narita, H., Koto, K., Morimoto, N. & Yoshii, M. (1975). Acta Cryst. B31, 2422-2426.]); Tagai et al. (1990[Tagai, T., Joswig, W. & Fuess, H. (1990). Miner. J. 15, 8-18.]); Orlandi et al. (1998[Orlandi, P., Pasero, M. & Vezzalini, G. (1998). Am. Mineral. 83, 1330-1334.]); Armbruster (2000[Armbruster, T. (2000). Schw. Miner. Petro. Mitt. 80, 279-284.]). For the definition of polyhedral distortion, see: Robinson et al. (1971[Robinson, K., Gibbs, G. V. & Ribbe, P. H. (1971). Science, 172, 567-570.]). For bond-valence calculations, see: Brese & O'Keeffe (1991[Brese, N. E. & O'Keeffe, M. (1991). Acta Cryst. B47, 192-197.]).

Experimental

Crystal data
  • LiCa2Mn2Si5O14(OH)

  • Mr = 578.44

  • Triclinic, [P \overline 1]

  • a = 7.6467 (3) Å

  • b = 11.7315 (6) Å

  • c = 6.8100 (3) Å

  • α = 91.874 (4)°

  • β = 94.465 (3)°

  • γ = 105.933 (3)°

  • V = 584.72 (5) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 3.65 mm−1

  • T = 293 K

  • 0.06 × 0.05 × 0.05 mm

Data collection
  • Bruker APEXII CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick 2005[Sheldrick, G. M. (2005). SADABS. University of Göttingen, Germany.]) Tmin = 0.811, Tmax = 0.839

  • 14045 measured reflections

  • 4191 independent reflections

  • 3317 reflections with I > 2σ(I)

  • Rint = 0.035

Refinement
  • R[F2 > 2σ(F2)] = 0.033

  • wR(F2) = 0.078

  • S = 1.03

  • 4191 reflections

  • 230 parameters

  • Only H-atom coordinates refined

  • Δρmax = 1.26 e Å−3

  • Δρmin = −0.56 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O11—H1⋯O1i 1.07 (4) 1.44 (4) 2.462 (3) 157 (3)
Symmetry code: (i) -x+1, -y, -z+1.

Data collection: APEX2 (Bruker, 2004[Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2004[Bruker (2004). APEX2 and SAINT. 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: XtalDraw (Downs & Hall-Wallace, 2003[Downs, R. T. & Hall-Wallace, M. (2003). Am. Mineral. 88, 247-250.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Comment top

Lithiomarsturite, ideally LiCa2Mn2Si5O14(OH), is a member of the pectolite-pyroxene series of pyroxenoids (hydropyroxenoids) and belongs to the rhodonite group, which includes rhodonite MnSiO3, babingtonite Ca2Fe2+Fe3+Si5O14(OH), manganbabingtonite Ca2Mn2+Fe3+Si5O14(OH), scandiobabingtonite (Ca,Na)2(Fe2+,Mn)(Sc,Fe3+)Si5O14(OH), nambulite LiMn4Si5O14(OH), natronambulite NaMn4Si5O14(OH), marsturite NaCa2Mn2Si5O14(OH), and lithiomarsturite. Thus far, only the crystal structures of four minerals in this group have been determined, including rhodonite (Liebau et al. 1959; Peacor & Niizeki, 1963), babingtonite (Araki & Zoltai, 1972; Kosoi, 1976), nambulite (Narita et al., 1975), and scandiobabingtonite (Orlandi et al., 1998).

Lithiomarsturite was first described by Peacor et al. (1990) from the Foote mine in North Carolina, with space group P1, and unit-cell parameters a = 7.652 (3), b = 12.119 (3), c = 6.805 (2) Å, α = 85.41 (2), β = 94.42 (3), γ = 111.51 (2)°. The reported empirical chemical formula, derived from electron and ion microprobe analyses, is Li1.01Ca1.98Mn1.35Fe0.56Mg0.10H1.00Si5.00O15, which can be simplified as LiCa2Mn2Si5O14(OH). Although Peacor et al. (1990) showed that this mineral belongs to the rhodonite group, they did not provide any detailed information on atomic coordinates and displacement parameters, because their structure refinement with 2338 single-crystal X-ray diffraction intensity data converged with R = 18%, due probably to the presence of common chain-periodicity faults. Since then, no further study on lithiomarsturite has been reported. This study presents the first structure refinement of lithiomarsturite based on single-crystal X-ray diffraction data.

Lithiomarsturite is isotypic with nambulite. Its structure is characterized by ribbons of edge-sharing Ca1O6, Mn1O6 and Mn2O6 octahedra and chains of corner-sharing SiO4 tetrahedra, both extending along [110] (Fig. 1). The octahedral ribbons are interconnected by the Ca2O8 and Li1O6 polyhedra through sharing corners and edges to form layers parallel to (1 1 1), which are linked together by the silicate chains. Whereas the Ca1, Mn1, and Mn2 octahedra are fairly regular, the Ca2O8 and Li1O6 polyhedra are rather irregular. The average Mn1—O and Mn2—O bond distances are 2.202 and 2.172 Å, respectively, both of which are slightly shorter than the corresponding Mn—O distances (2.233 and 2.188 Å) in nambulite (Narita et al., 1975). Within 2.9 Å, Li is coordinated to six O atoms in lithiomarsturite (the next nearest O atom is at 3.12 Å), with an average Li—O distance of 2.322 Å, but to eight O atoms in nambulite, with an average Li—O distance of 2.485 Å (Narita et al., 1975). This difference can be ascribed mostly to the replacement of the significant amount of Li (43%) by Na in nambulite examined by Narita et al. (1975).

The two Ca polyhedra in lithiomarsturite are better compared to those in babingtonite (Tagai et al., 1990; Armbruster, 2000). The Ca1O6 octahedra in lithiomarsturite, on the one hand, are much less distorted than those in babingtonite in terms of both the octahedral angle variance (OAV) and quadratic elongation (OQE) (Robinson et al., 1971), which are 146 and 1.040, respectively, for the former, and 311 and 1.092 for the latter. The greater distortion of the Ca1 octahedra in babingtonite is understandable, because they share edges with the Fe1O6 and Fe2O6 octahedra in the octahedral ribbons, which are primarily occupied by cations with different sizes and charges (Fe2+ and Fe3+, respectively). In contrast, both Mn1O6 and Mn2O6 octahedra that share edges with the Ca1O6 octahedra in lithiomarsturite (Fig. 1) are filled with the same kind of cation (Mn2+). On the other hand, the Ca2 cations in lithiomarsturite and babingtonite exhibit similar coordination environments, both of which have seven Ca—O bond lengths shorter than 2.65 Å and one Ca—O bond length greater than 2.84 Å. If we only take the seven shorter Ca—O bond lengths into account, then a calculation of the bond-valence sums using the parameters given by Brese & O'Keeffe (1991) yields 2.03 and 2.09 v.u. for the Ca2 cations in lithiomarsturite and babingtonite, respectively, suggesting that the Ca2 cations may be only bonded to seven, rather eight, O atoms in these two minerals. At least, this should be the case for Ca2 in lithiomarsturite, because the next nearest O atom (except the seven closer O atoms) is 3.059 Å away.

Very intriguingly, both previous neutron and X-ray diffraction studies (Tagai et al., 1990; Armbruster, 2000) have demonstrated that the hydrogen bonding in babingtonite is between O1 and O11, with the former as the H-donor and the latter as the H-acceptor. However, our study shows the opposite case for lithiomarsturite, in which O11 is the H-donor and O1 the H-acceptor. This difference is the direct result of the change in the bonding environments around O1 and O11 in the two minerals. In babingtonite, both O1 and O11 are bonded to two non-hydrogen cations, with O1 to Si1 and Ca1, and O11 to Si4 and Fe2, but in lithiomarsturite, O1 is bonded to three non-hydrogen cations (Si1, Ca1, and Li1), and O11 to two (Si4 and Mn2). Note that Fe2 in babingtonite is chiefly trivalent Fe3+, whereas Mn2 in lithiomarsturite is essentially divalent Mn2+. As a consequence of this coupled effect, the more underbonded O1 (relative to O11) in babingtonite becomes less underbonded in lithiomarsturite. Because the more underbonded O atom will be more tightly bonded to the H atom to better satisfy its bond-valence requirement, we see the change from O1 being the H-donor in babingtonite to O11 in lithiomarsturite. Accordingly, it is most likely that other members of the rhodonite group that contain Li or Na as an essential component, such as nambulite, natronambulite, and marsturite, may all behave as lithiomarsturite in terms of the hydrogen bonding scheme, with O11 being the H-donor and O1 the H-acceptor. For some specific chemical compositions, nevertheless, it may also be possible that the H atom is situated halfway between O1 and O11 or hops between the two positions.

Related literature top

For lithiomarsturite, see: Peacor et al. (1990). For other minerals of the rhodonite group, see: Liebau et al. (1959); Peacor & Niizeki (1963); Araki & Zoltai (1972); Kosoi (1976); Narita et al. (1975); Tagai et al. (1990); Orlandi et al. (1998); Armbruster (2000). For the definition of polyhedral distortion, see: Robinson et al. (1971). For bond-valence calculations, see: Brese & O'Keeffe (1991).

Experimental top

The lithiomarsturite sample used in this study is from the type locality: the Foote mine, Kings Mountains, North Carolina, USA, and is in the collection of the RRUFF project (deposition No. R100094; http://rruff.info). The chemical composition analyzed by Peacor et al. (1990) was adopted for the structure refinement. To keep consistent with the unit-cell settings for other minerals in the rhodonite group, such as rhodonite, babingtonite, and nambulite, we have adopted a unit-cell setting that differs from the one given by Peacor et al. (1990). The matrix for the transformation from the unit-cell setting of Peacor et al. (1990) to ours is [-1 0 0 / 1 1 0 / 0 0 - 1]. The labeling scheme of the atoms in lithiomarsturite is similar to that for numbulite (Narita et al., 1975).

Refinement top

The H atom was located from difference Fourier syntheses and its position refined freely with a fixed isotropic displacement (Uiso = 0.04). During the structure refinements, Fe was treated as Mn, because of their similar X-ray scattering powers. The final refinement assumed an ideal chemistry for lithiomarsturite, as the overall effects of the trace amount of Mg on the final structure results are negligible. The highest residual peak in the difference Fourier maps was located at (0.5254, 0.8418, 0.2798), 1.48 Å from O13, and the deepest hole at (0.1839, 0.5391, 0.3061), 0.49 Å from Ca2.

Structure description top

Lithiomarsturite, ideally LiCa2Mn2Si5O14(OH), is a member of the pectolite-pyroxene series of pyroxenoids (hydropyroxenoids) and belongs to the rhodonite group, which includes rhodonite MnSiO3, babingtonite Ca2Fe2+Fe3+Si5O14(OH), manganbabingtonite Ca2Mn2+Fe3+Si5O14(OH), scandiobabingtonite (Ca,Na)2(Fe2+,Mn)(Sc,Fe3+)Si5O14(OH), nambulite LiMn4Si5O14(OH), natronambulite NaMn4Si5O14(OH), marsturite NaCa2Mn2Si5O14(OH), and lithiomarsturite. Thus far, only the crystal structures of four minerals in this group have been determined, including rhodonite (Liebau et al. 1959; Peacor & Niizeki, 1963), babingtonite (Araki & Zoltai, 1972; Kosoi, 1976), nambulite (Narita et al., 1975), and scandiobabingtonite (Orlandi et al., 1998).

Lithiomarsturite was first described by Peacor et al. (1990) from the Foote mine in North Carolina, with space group P1, and unit-cell parameters a = 7.652 (3), b = 12.119 (3), c = 6.805 (2) Å, α = 85.41 (2), β = 94.42 (3), γ = 111.51 (2)°. The reported empirical chemical formula, derived from electron and ion microprobe analyses, is Li1.01Ca1.98Mn1.35Fe0.56Mg0.10H1.00Si5.00O15, which can be simplified as LiCa2Mn2Si5O14(OH). Although Peacor et al. (1990) showed that this mineral belongs to the rhodonite group, they did not provide any detailed information on atomic coordinates and displacement parameters, because their structure refinement with 2338 single-crystal X-ray diffraction intensity data converged with R = 18%, due probably to the presence of common chain-periodicity faults. Since then, no further study on lithiomarsturite has been reported. This study presents the first structure refinement of lithiomarsturite based on single-crystal X-ray diffraction data.

Lithiomarsturite is isotypic with nambulite. Its structure is characterized by ribbons of edge-sharing Ca1O6, Mn1O6 and Mn2O6 octahedra and chains of corner-sharing SiO4 tetrahedra, both extending along [110] (Fig. 1). The octahedral ribbons are interconnected by the Ca2O8 and Li1O6 polyhedra through sharing corners and edges to form layers parallel to (1 1 1), which are linked together by the silicate chains. Whereas the Ca1, Mn1, and Mn2 octahedra are fairly regular, the Ca2O8 and Li1O6 polyhedra are rather irregular. The average Mn1—O and Mn2—O bond distances are 2.202 and 2.172 Å, respectively, both of which are slightly shorter than the corresponding Mn—O distances (2.233 and 2.188 Å) in nambulite (Narita et al., 1975). Within 2.9 Å, Li is coordinated to six O atoms in lithiomarsturite (the next nearest O atom is at 3.12 Å), with an average Li—O distance of 2.322 Å, but to eight O atoms in nambulite, with an average Li—O distance of 2.485 Å (Narita et al., 1975). This difference can be ascribed mostly to the replacement of the significant amount of Li (43%) by Na in nambulite examined by Narita et al. (1975).

The two Ca polyhedra in lithiomarsturite are better compared to those in babingtonite (Tagai et al., 1990; Armbruster, 2000). The Ca1O6 octahedra in lithiomarsturite, on the one hand, are much less distorted than those in babingtonite in terms of both the octahedral angle variance (OAV) and quadratic elongation (OQE) (Robinson et al., 1971), which are 146 and 1.040, respectively, for the former, and 311 and 1.092 for the latter. The greater distortion of the Ca1 octahedra in babingtonite is understandable, because they share edges with the Fe1O6 and Fe2O6 octahedra in the octahedral ribbons, which are primarily occupied by cations with different sizes and charges (Fe2+ and Fe3+, respectively). In contrast, both Mn1O6 and Mn2O6 octahedra that share edges with the Ca1O6 octahedra in lithiomarsturite (Fig. 1) are filled with the same kind of cation (Mn2+). On the other hand, the Ca2 cations in lithiomarsturite and babingtonite exhibit similar coordination environments, both of which have seven Ca—O bond lengths shorter than 2.65 Å and one Ca—O bond length greater than 2.84 Å. If we only take the seven shorter Ca—O bond lengths into account, then a calculation of the bond-valence sums using the parameters given by Brese & O'Keeffe (1991) yields 2.03 and 2.09 v.u. for the Ca2 cations in lithiomarsturite and babingtonite, respectively, suggesting that the Ca2 cations may be only bonded to seven, rather eight, O atoms in these two minerals. At least, this should be the case for Ca2 in lithiomarsturite, because the next nearest O atom (except the seven closer O atoms) is 3.059 Å away.

Very intriguingly, both previous neutron and X-ray diffraction studies (Tagai et al., 1990; Armbruster, 2000) have demonstrated that the hydrogen bonding in babingtonite is between O1 and O11, with the former as the H-donor and the latter as the H-acceptor. However, our study shows the opposite case for lithiomarsturite, in which O11 is the H-donor and O1 the H-acceptor. This difference is the direct result of the change in the bonding environments around O1 and O11 in the two minerals. In babingtonite, both O1 and O11 are bonded to two non-hydrogen cations, with O1 to Si1 and Ca1, and O11 to Si4 and Fe2, but in lithiomarsturite, O1 is bonded to three non-hydrogen cations (Si1, Ca1, and Li1), and O11 to two (Si4 and Mn2). Note that Fe2 in babingtonite is chiefly trivalent Fe3+, whereas Mn2 in lithiomarsturite is essentially divalent Mn2+. As a consequence of this coupled effect, the more underbonded O1 (relative to O11) in babingtonite becomes less underbonded in lithiomarsturite. Because the more underbonded O atom will be more tightly bonded to the H atom to better satisfy its bond-valence requirement, we see the change from O1 being the H-donor in babingtonite to O11 in lithiomarsturite. Accordingly, it is most likely that other members of the rhodonite group that contain Li or Na as an essential component, such as nambulite, natronambulite, and marsturite, may all behave as lithiomarsturite in terms of the hydrogen bonding scheme, with O11 being the H-donor and O1 the H-acceptor. For some specific chemical compositions, nevertheless, it may also be possible that the H atom is situated halfway between O1 and O11 or hops between the two positions.

For lithiomarsturite, see: Peacor et al. (1990). For other minerals of the rhodonite group, see: Liebau et al. (1959); Peacor & Niizeki (1963); Araki & Zoltai (1972); Kosoi (1976); Narita et al. (1975); Tagai et al. (1990); Orlandi et al. (1998); Armbruster (2000). For the definition of polyhedral distortion, see: Robinson et al. (1971). For bond-valence calculations, see: Brese & O'Keeffe (1991).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XtalDraw (Downs & Hall-Wallace, 2003); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Crystal structure of lithiomarsturite. The green tetrahedra represent SiO4 groups. Large gray, medium yellow, and small bright blue sphares represent Ca2, Li1, H1 atoms, respectively. Both ribbons of edge-sharing octahedra and chains of vertex-sharing tetrahedra run parallel to [110].
Lithiomarsturite top
Crystal data top
LiCa2Mn2Si5O14(OH)Z = 2
Mr = 578.44F(000) = 568
Triclinic, P1Dx = 3.285 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.6467 (3) ÅCell parameters from 2086 reflections
b = 11.7315 (6) Åθ = 3.5–28°
c = 6.8100 (3) ŵ = 3.65 mm1
α = 91.874 (4)°T = 293 K
β = 94.465 (3)°Cube, light gray
γ = 105.933 (3)°0.06 × 0.05 × 0.05 mm
V = 584.72 (5) Å3
Data collection top
Bruker APEXII CCD area-detector
diffractometer
4191 independent reflections
Radiation source: fine-focus sealed tube3317 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.035
φ and ω scanθmax = 32.6°, θmin = 3.0°
Absorption correction: multi-scan
(SADABS; Sheldrick 2005)
h = 1111
Tmin = 0.811, Tmax = 0.839k = 1717
14045 measured reflectionsl = 1010
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033Only H-atom coordinates refined
wR(F2) = 0.078 w = 1/[σ2(Fo2) + (0.0354P)2 + 0.2944P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.006
4191 reflectionsΔρmax = 1.26 e Å3
230 parametersΔρmin = 0.56 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0023 (5)
Crystal data top
LiCa2Mn2Si5O14(OH)γ = 105.933 (3)°
Mr = 578.44V = 584.72 (5) Å3
Triclinic, P1Z = 2
a = 7.6467 (3) ÅMo Kα radiation
b = 11.7315 (6) ŵ = 3.65 mm1
c = 6.8100 (3) ÅT = 293 K
α = 91.874 (4)°0.06 × 0.05 × 0.05 mm
β = 94.465 (3)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
4191 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick 2005)
3317 reflections with I > 2σ(I)
Tmin = 0.811, Tmax = 0.839Rint = 0.035
14045 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.078Only H-atom coordinates refined
S = 1.03Δρmax = 1.26 e Å3
4191 reflectionsΔρmin = 0.56 e Å3
230 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
Li10.6570 (12)0.1276 (10)0.3338 (12)0.067 (3)
Ca10.80601 (7)0.94132 (4)0.13944 (7)0.01028 (10)
Ca20.23393 (7)0.52331 (5)0.28673 (7)0.01254 (10)
Mn10.59386 (5)0.64710 (3)0.06116 (5)0.00721 (8)
Mn20.04394 (5)0.23677 (3)0.18152 (5)0.00722 (8)
Si10.28154 (9)0.05291 (6)0.34656 (9)0.00840 (13)
Si20.46371 (9)0.32017 (6)0.42345 (9)0.00704 (12)
Si30.80739 (9)0.44983 (6)0.21522 (9)0.00627 (12)
Si40.99738 (9)0.71828 (6)0.30096 (9)0.00756 (12)
Si50.33975 (9)0.84444 (6)0.10838 (9)0.00758 (12)
O10.2071 (3)0.00760 (16)0.5439 (3)0.0155 (4)
O20.1231 (2)0.06860 (15)0.1893 (3)0.0116 (3)
O30.4399 (2)0.17592 (14)0.4144 (2)0.0104 (3)
O40.3253 (2)0.34697 (15)0.2519 (2)0.0108 (3)
O50.5434 (2)0.62430 (15)0.3623 (2)0.0113 (3)
O60.6815 (2)0.37564 (15)0.3790 (2)0.0107 (3)
O70.9617 (2)0.39040 (15)0.1616 (3)0.0116 (3)
O80.6769 (2)0.47395 (15)0.0349 (2)0.0098 (3)
O90.9282 (2)0.57625 (14)0.3373 (2)0.0103 (3)
O100.8758 (2)0.75807 (15)0.1281 (3)0.0118 (3)
O110.9976 (3)0.21112 (16)0.4905 (3)0.0170 (4)
O120.2081 (2)0.74122 (15)0.2372 (2)0.0109 (3)
O130.5208 (2)0.80942 (16)0.0672 (3)0.0127 (3)
O140.7740 (2)0.13142 (15)0.0878 (2)0.0121 (3)
O150.3966 (2)0.96997 (15)0.2470 (3)0.0135 (3)
H10.938 (5)0.117 (3)0.480 (5)0.040*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Li10.060 (5)0.126 (8)0.046 (4)0.067 (6)0.036 (4)0.035 (5)
Ca10.0128 (2)0.0071 (2)0.0100 (2)0.00122 (17)0.00179 (16)0.00081 (16)
Ca20.0095 (2)0.0128 (2)0.0139 (2)0.00159 (18)0.00014 (17)0.00341 (17)
Mn10.00686 (16)0.00675 (16)0.00782 (15)0.00160 (12)0.00084 (12)0.00022 (12)
Mn20.00669 (16)0.00570 (15)0.00900 (16)0.00153 (12)0.00000 (12)0.00028 (12)
Si10.0086 (3)0.0066 (3)0.0092 (3)0.0012 (2)0.0004 (2)0.0006 (2)
Si20.0065 (3)0.0060 (3)0.0078 (3)0.0006 (2)0.0005 (2)0.0000 (2)
Si30.0060 (3)0.0054 (3)0.0070 (3)0.0011 (2)0.0002 (2)0.0002 (2)
Si40.0076 (3)0.0058 (3)0.0088 (3)0.0012 (2)0.0005 (2)0.0002 (2)
Si50.0071 (3)0.0072 (3)0.0085 (3)0.0021 (2)0.0009 (2)0.0000 (2)
O10.0164 (9)0.0155 (9)0.0103 (8)0.0036 (7)0.0035 (7)0.0019 (7)
O20.0107 (8)0.0119 (8)0.0118 (8)0.0030 (7)0.0007 (6)0.0001 (6)
O30.0111 (8)0.0059 (7)0.0135 (8)0.0020 (6)0.0011 (6)0.0011 (6)
O40.0096 (8)0.0102 (8)0.0118 (8)0.0025 (6)0.0024 (6)0.0001 (6)
O50.0112 (8)0.0108 (8)0.0109 (8)0.0018 (7)0.0014 (6)0.0026 (6)
O60.0085 (8)0.0119 (8)0.0104 (7)0.0001 (6)0.0017 (6)0.0028 (6)
O70.0100 (8)0.0103 (8)0.0155 (8)0.0044 (6)0.0033 (6)0.0016 (6)
O80.0085 (7)0.0114 (8)0.0093 (7)0.0024 (6)0.0003 (6)0.0014 (6)
O90.0123 (8)0.0052 (7)0.0123 (8)0.0010 (6)0.0007 (6)0.0002 (6)
O100.0107 (8)0.0114 (8)0.0142 (8)0.0043 (7)0.0003 (6)0.0037 (6)
O110.0269 (10)0.0094 (8)0.0118 (8)0.0008 (8)0.0078 (7)0.0032 (6)
O120.0078 (8)0.0118 (8)0.0126 (8)0.0010 (6)0.0019 (6)0.0036 (6)
O130.0109 (8)0.0127 (8)0.0164 (8)0.0053 (7)0.0046 (7)0.0018 (7)
O140.0138 (8)0.0121 (8)0.0100 (8)0.0032 (7)0.0016 (6)0.0029 (6)
O150.0128 (8)0.0099 (8)0.0171 (8)0.0029 (7)0.0006 (7)0.0036 (6)
Geometric parameters (Å, º) top
Li1—O141.956 (7)Mn2—O14vii2.1304 (18)
Li1—O32.004 (7)Mn2—O11vii2.1778 (18)
Li1—O1i2.121 (8)Mn2—O42.1912 (17)
Li1—O15ii2.336 (11)Mn2—O22.2180 (18)
Li1—O112.642 (10)Mn2—O10v2.2396 (18)
Li1—O62.869 (11)Si1—O21.6068 (18)
Ca1—O1iii2.2873 (19)Si1—O11.6105 (19)
Ca1—O132.3074 (19)Si1—O31.6346 (18)
Ca1—O14iv2.3441 (18)Si1—O15ii1.6431 (19)
Ca1—O2v2.3506 (18)Si2—O5iii1.5891 (18)
Ca1—O102.3534 (18)Si2—O41.6119 (17)
Ca1—O2vi2.4648 (18)Si2—O31.6502 (17)
Ca2—O7vii2.3119 (18)Si2—O61.6690 (18)
Ca2—O8v2.3429 (18)Si3—O71.5856 (19)
Ca2—O52.3455 (18)Si3—O81.6035 (17)
Ca2—O42.3688 (18)Si3—O61.6428 (18)
Ca2—O6iii2.4857 (18)Si3—O91.6709 (18)
Ca2—O9vii2.6230 (19)Si4—O101.6033 (18)
Ca2—O122.6477 (18)Si4—O11viii1.6129 (19)
Mn1—O132.1268 (18)Si4—O91.6374 (18)
Mn1—O52.1281 (17)Si4—O12ix1.6542 (19)
Mn1—O102.1952 (18)Si5—O131.5900 (19)
Mn1—O8v2.2010 (17)Si5—O14v1.6125 (17)
Mn1—O4v2.2635 (18)Si5—O151.6560 (18)
Mn1—O82.2941 (18)Si5—O121.6695 (18)
Mn2—O7vii2.0704 (17)
O2—Si1—O1113.72 (10)O7—Si3—O9102.31 (9)
O2—Si1—O3114.40 (9)O8—Si3—O9111.55 (9)
O1—Si1—O3107.47 (9)O6—Si3—O9104.52 (9)
O2—Si1—O15ii110.10 (10)O10—Si4—O11viii112.69 (11)
O1—Si1—O15ii107.53 (10)O10—Si4—O9113.18 (9)
O3—Si1—O15ii102.87 (10)O11viii—Si4—O9107.23 (10)
O5iii—Si2—O4115.99 (10)O10—Si4—O12ix109.06 (9)
O5iii—Si2—O3114.15 (9)O11viii—Si4—O12ix109.23 (10)
O4—Si2—O3108.16 (9)O9—Si4—O12ix105.14 (9)
O5iii—Si2—O6103.34 (9)O13—Si5—O14v113.97 (10)
O4—Si2—O6111.94 (9)O13—Si5—O15108.72 (10)
O3—Si2—O6102.39 (9)O14v—Si5—O15106.07 (9)
O7—Si3—O8116.88 (10)O13—Si5—O12110.06 (10)
O7—Si3—O6111.46 (10)O14v—Si5—O12110.83 (9)
O8—Si3—O6109.28 (9)O15—Si5—O12106.85 (9)
Symmetry codes: (i) x+1, y, z+1; (ii) x, y1, z; (iii) x+1, y+1, z+1; (iv) x, y+1, z; (v) x+1, y+1, z; (vi) x+1, y+1, z; (vii) x1, y, z; (viii) x+2, y+1, z+1; (ix) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O11—H1···O1i1.07 (4)1.44 (4)2.462 (3)157 (3)
Symmetry code: (i) x+1, y, z+1.

Experimental details

Crystal data
Chemical formulaLiCa2Mn2Si5O14(OH)
Mr578.44
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)7.6467 (3), 11.7315 (6), 6.8100 (3)
α, β, γ (°)91.874 (4), 94.465 (3), 105.933 (3)
V3)584.72 (5)
Z2
Radiation typeMo Kα
µ (mm1)3.65
Crystal size (mm)0.06 × 0.05 × 0.05
Data collection
DiffractometerBruker APEXII CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick 2005)
Tmin, Tmax0.811, 0.839
No. of measured, independent and
observed [I > 2σ(I)] reflections
14045, 4191, 3317
Rint0.035
(sin θ/λ)max1)0.759
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.078, 1.03
No. of reflections4191
No. of parameters230
H-atom treatmentOnly H-atom coordinates refined
Δρmax, Δρmin (e Å3)1.26, 0.56

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XtalDraw (Downs & Hall-Wallace, 2003), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O11—H1···O1i1.07 (4)1.44 (4)2.462 (3)157 (3)
Symmetry code: (i) x+1, y, z+1.
 

Acknowledgements

The authors gratefully acknowledge support of this study by the Arizona Science Foundation.

References

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