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Redetermination of junitoite, CaZn2Si2O7·H2O

aDepartment of Geosciences, University of Arizona, 1040 E. 4th Street, Tucson, Arizona 85721-0077, USA, and bSabino High School, 5000 North Bowes Road, Tucson, Arizona 85749, USA
*Correspondence e-mail: hyang@u.arizona.edu

(Received 28 August 2012; accepted 31 August 2012; online 8 September 2012)

The crystal structure of the mineral junitoite, ideally CaZn2Si2O7·H2O (calcium dizinc disilicate monohydrate), was first determined by Hamilton & Finney [Mineral. Mag. (1985), 49, 91–95] based on the space group Ama2, yielding a reliability factor R of 0.10, with isotropic displacement parameters for all non-H atoms. The present study reports a structure redetermination of junitoite using single-crystal X-ray diffraction data from a natural sample, demonstrating that the space group of this mineral is actually Aea2, which can be attained simply by shifting the origin. Topologically, the structure models in the space groups Aea2 and Ama2 are analogous, consisting of chains of corner-sharing ZnO4 tetra­hedra parallel to the b axis, cross-linked by Si2O7 tetra­hedral dimers (the site symmetry of the bridging O atom is ..2) along a and c, forming a three-dimensional framework. The Ca2+ cations (site symmetry ..2) are situated in cavities of the framework and are bonded to five O atoms and one H2O mol­ecule (site symmetry ..2) in a distorted octa­hedral coordination environment. However, some bond lengths, especially for the SiO4 tetra­hedron, are noticeably different between the two structure models. Hydrogen bonding in junitoite is found between the water mol­ecule and a framework O atom.

Related literature

For junitoite, see: Williams (1976[Williams, S. A. (1976). Am. Mineral. 61, 1255-1258.]); Hamilton & Finney (1985[Hamilton, R. D. & Finney, J. J. (1985). Mineral. Mag. 49, 91-95.]). For junitoite-related minerals and compounds, see: Lin et al. (1999[Lin, J. H., Lu, G. X., Du, J., Su, M. Z., Loong, C.-K. & Richardson, J. W. Jr (1999). J. Phys. Chem. Solids, 60, 975-983.]); Fleet & Liu (2001[Fleet, M. E. & Liu, X. (2001). J. Solid State Chem. 161, 166-172.]); Kolitsch et al. (2009[Kolitsch, U., Wierzbicka-Wieczorek, M. & Tillmanns, E. (2009). Can. Mineral. 47, 421-431.]); Yang et al. (2012[Yang, H., Downs, R. T., Evans, S. H. & Pinch, W. W. (2012). Am. Mineral. In the press.]). Parameters for bond-valence calculations were taken from Brese & O'Keeffe (1991[Brese, N. E. & O'Keeffe, M. (1991). Acta Cryst. B47, 192-197.]).

Experimental

Crystal data
  • CaZn2Si2O7·H2O

  • Mr = 357.02

  • Orthorhombic, A e a 2

  • a = 12.530 (4) Å

  • b = 6.3056 (18) Å

  • c = 8.562 (3) Å

  • V = 676.5 (3) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 8.21 mm−1

  • T = 293 K

  • 0.06 × 0.06 × 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 = 0.639, Tmax = 0.684

  • 2719 measured reflections

  • 1257 independent reflections

  • 1189 reflections with I > 2σ(I)

  • Rint = 0.021

Refinement
  • R[F2 > 2σ(F2)] = 0.017

  • wR(F2) = 0.044

  • S = 1.07

  • 1257 reflections

  • 65 parameters

  • 1 restraint

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.52 e Å−3

  • Δρmin = −0.65 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 580 Friedel pairs

  • Flack parameter: 0.023 (12)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
OW5—H⋯O1 0.70 (3) 2.18 (2) 2.875 (2) 170 (3)

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

Junitoite, CaZn2Si2O7.H2O, from the Christmas Mine, Gila County, Arizona was first described by Williams (1976) with orthorhombic symmetry in space group Bbm2 (non-standard setting of space group No. 40) and unit-cell parameters a = 6.309, b = 12.503, c = 8.549 Å. By adopting the standard unit-cell setting of this space group in Ama2 (a = 12.510, b = 6.318, c = 8.561 Å) for this mineral, Hamilton & Finney (1985) noted that while the Weissenberg photographic data pointed to Ama2, the X-ray diffractometer data were also compatible with the space group Aea2. Although the two space groups yielded similar reliability factors R1 ~ 0.10 with isotropic displacement parameters for all atoms (H atoms were not located), Hamilton & Finney (1985) chose Ama2 for their final structure report because it "produces less distortion of the coordination polyhedra and provides a structure in which the site symmetry of the cations is more similar to other zinc silicates". Their attempts at refinement with anisotropic displacement parameters resulted in non-positive definite displacement parameters for a number of atoms. In our efforts to understand the hydrogen bonding environments in minerals and their relationships to Raman spectra, we concluded that the structural model for junitoite needed improvement. This study reports a structure redetermination of junitoite from the type locality by means of single-crystal X-ray diffraction data, demonstrating that the space group of this mineral is actually Aea2, rather than Ama2.

The crystal structure of junitoite consists of chains of corner-sharing ZnO4 tetrahedra parallel to the b axis, cross-linked by Si2O7 tetrahedral dimers along a and c to form a three-dimensional framework. The Ca2+ cations, situated in cavities of the framework, are bonded to five O atoms and one H2O molecule in a distorted octahedral [CaO5(H2O)] coordination environment (Figs. 1, 2). As described below, it may be useful to consider that there is a Ca—H2O bonded pair in the cavity. The structure of junitoite in space group Aea2 resembles that in space group Ama2 (Hamilton & Finney, 1985). In fact, as noted by Hamilton & Finney (1985), the structure model in Aea2 can be attained simply by shifting the origin of the structure model in Ama2 from (x, y, z) to (x - 1/4, y - 1/4, z). Upon this shift, the only major structural change is that the two unique Zn atoms at the 4a sites in the Ama2 structure model are transformed into a single atom at the 8b site in the Aea2 structure model. The numbers and coordination polyhedra of the distinct Ca, Si, and O sites remain unaffected. However, some bond lengths are noticeably different between the two structure models. For example, the Si—O, Zn—O, and Ca—O bond lengths range from 1.55 (5) to 1.69 (5) Å, 1.93 (4) to 1.99 (4) Å, and 2.29 (7) to 2.44 (5) Å in the Ama2 structure model, respectively, but from 1.6130 (14) to 1.6719 (12) Å, 1.9454 (13) to 1.9691 (13) Å, and 2.286 (2) to 2.439 (2) Å in the Aea2 structure model. The Si—O—Si angle within the Si2O7 disiilicate group is 124.8 (1)° in our study, which is slightly greater than that (122.4°) determined by Hamilton & Finney (1985).

The hydrogen bond in junitoite is found between Ow5 and O1, with Ow5 as the donor and O1 as the acceptor. This agrees with the calculated bond-valence sums of 0.42 valence units for Ow5 and 1.77 valence units for O1 by using the parameters given by Brese & O'Keeffe (1991). For numerical details of the hydrogen-bonding geometry, see: Table 1.

Remarkably, junitoite is topologically related to a group of compounds with the general formula BaM2+2Si2O7, where M = Be (barylite and clinobarylite), Fe (andremeyerite), Cu (scottyite), and Mg, Mn, Co, and Zn in synthetic phases. These Ba-silicates are all comprised of corner-sharing MO4 tetrahedral chains that are interlinked by Si2O7 tetrahedral dimers and Ba2+ cations, despite their diverse structural symmetries (Yang et al., 2012). Intriguingly, there is no documentation for any SrM2Si2O7 compounds. It then begs the question whether the BaM2Si2O7 compounds are capable of accommodating a significant amount of cations smaller than Ba2+. Similar to the pair (Ca2+ + H2O) in junitoite, the Ba2+ cations in the BaM2Si2O7 structures are also situated in the cavities of the framework formed by the Si2O7 dimers and the MO4 tetrahedral chains. Conceivably, any substantial replacement of large Ba2+ by smaller divalent cations (such as Sr2+) would require, in addition to the other structural adjustments (such as the tilting or distortion of MO4 and/or SiO4 tetrahedra), a further narrowing of the Si—O—Si angle in the Si2O7 group in order to satisfy the bonding environment for smaller cations. This, however, would not be energetically favorable, because the Si—O—Si angles in the BaM2Si2O7 compounds, ranging from 124 to 135°, are already among the smallest of disilicate materials, e.g. for high-temperature BaZn2Si2O7 (Lin et al., 1999), high-pressure rare earth (RE) disilicates RE2Si2O7 (Fleet & Liu, 2001) or BaKY(Si2O7) (Kolitsch et al., 2009). Accordingly, any sizable substitution of smaller Sr2+ for Ba2+ would worsen the bonding energetics for this site and thus destabilize the structure. For junitoite, Ca2+ by itself, which is even smaller than Sr2+, is apparently too small to occupy the cavities in the framework. Therefore, the presence of the H2O—Ca2+ bonded pair is essential to stabilize its structure. By the same token, one could argue that the pair (Sr2+ + H2O) together may be too large for the cavities in the structures analogous to those for the BaM2Si2O7 materials, since there is no report for any SrM2+2Si2O7.H2O compound up to date. Based on this reasoning, we postulate that more compounds with composition CaM2+2Si2O7.H2O may be found in nature or synthesized in laboratories. Furthermore, it would be interesting if the Sr—H2O pair might be found in digermanates, where this structural unit is even larger.

Related literature top

For junitoite, see: Williams (1976); Hamilton & Finney (1985). For junitoite-related minerals and compounds, see: Lin et al. (1999); Fleet & Liu (2001); Kolitsch et al. (2009); Yang et al. (2012). Parameters for bond-valence calculations were taken from Brese & O'Keeffe (1991).

Experimental top

The junitoite crystal used in this study is from the type locality, the Christmas Mine, Gila County, Arizona and is in the collection of the RRUFF project (http://rruff.info/R120100). Its chemical composition measured by Williams (1976) is Ca0.98Zn1.96Si1.84O6.6.1.13H2O.

Refinement top

The H atom was located near Ow5 from difference Fourier syntheses and its position refined freely with a fixed isotropic displacement (Uiso = 0.03). For simplicity, the ideal chemistry, CaZn2Si2O7.H2O, was assumed during the final refinement. The highest residual peak in the difference Fourier maps was located at (0.6270, 0.1150, 0.9598), 0.69 Å from O1, and the deepest hole at (0.3072, 0.2596, 0.0874), 0.81 Å from Zn.

Structure description top

Junitoite, CaZn2Si2O7.H2O, from the Christmas Mine, Gila County, Arizona was first described by Williams (1976) with orthorhombic symmetry in space group Bbm2 (non-standard setting of space group No. 40) and unit-cell parameters a = 6.309, b = 12.503, c = 8.549 Å. By adopting the standard unit-cell setting of this space group in Ama2 (a = 12.510, b = 6.318, c = 8.561 Å) for this mineral, Hamilton & Finney (1985) noted that while the Weissenberg photographic data pointed to Ama2, the X-ray diffractometer data were also compatible with the space group Aea2. Although the two space groups yielded similar reliability factors R1 ~ 0.10 with isotropic displacement parameters for all atoms (H atoms were not located), Hamilton & Finney (1985) chose Ama2 for their final structure report because it "produces less distortion of the coordination polyhedra and provides a structure in which the site symmetry of the cations is more similar to other zinc silicates". Their attempts at refinement with anisotropic displacement parameters resulted in non-positive definite displacement parameters for a number of atoms. In our efforts to understand the hydrogen bonding environments in minerals and their relationships to Raman spectra, we concluded that the structural model for junitoite needed improvement. This study reports a structure redetermination of junitoite from the type locality by means of single-crystal X-ray diffraction data, demonstrating that the space group of this mineral is actually Aea2, rather than Ama2.

The crystal structure of junitoite consists of chains of corner-sharing ZnO4 tetrahedra parallel to the b axis, cross-linked by Si2O7 tetrahedral dimers along a and c to form a three-dimensional framework. The Ca2+ cations, situated in cavities of the framework, are bonded to five O atoms and one H2O molecule in a distorted octahedral [CaO5(H2O)] coordination environment (Figs. 1, 2). As described below, it may be useful to consider that there is a Ca—H2O bonded pair in the cavity. The structure of junitoite in space group Aea2 resembles that in space group Ama2 (Hamilton & Finney, 1985). In fact, as noted by Hamilton & Finney (1985), the structure model in Aea2 can be attained simply by shifting the origin of the structure model in Ama2 from (x, y, z) to (x - 1/4, y - 1/4, z). Upon this shift, the only major structural change is that the two unique Zn atoms at the 4a sites in the Ama2 structure model are transformed into a single atom at the 8b site in the Aea2 structure model. The numbers and coordination polyhedra of the distinct Ca, Si, and O sites remain unaffected. However, some bond lengths are noticeably different between the two structure models. For example, the Si—O, Zn—O, and Ca—O bond lengths range from 1.55 (5) to 1.69 (5) Å, 1.93 (4) to 1.99 (4) Å, and 2.29 (7) to 2.44 (5) Å in the Ama2 structure model, respectively, but from 1.6130 (14) to 1.6719 (12) Å, 1.9454 (13) to 1.9691 (13) Å, and 2.286 (2) to 2.439 (2) Å in the Aea2 structure model. The Si—O—Si angle within the Si2O7 disiilicate group is 124.8 (1)° in our study, which is slightly greater than that (122.4°) determined by Hamilton & Finney (1985).

The hydrogen bond in junitoite is found between Ow5 and O1, with Ow5 as the donor and O1 as the acceptor. This agrees with the calculated bond-valence sums of 0.42 valence units for Ow5 and 1.77 valence units for O1 by using the parameters given by Brese & O'Keeffe (1991). For numerical details of the hydrogen-bonding geometry, see: Table 1.

Remarkably, junitoite is topologically related to a group of compounds with the general formula BaM2+2Si2O7, where M = Be (barylite and clinobarylite), Fe (andremeyerite), Cu (scottyite), and Mg, Mn, Co, and Zn in synthetic phases. These Ba-silicates are all comprised of corner-sharing MO4 tetrahedral chains that are interlinked by Si2O7 tetrahedral dimers and Ba2+ cations, despite their diverse structural symmetries (Yang et al., 2012). Intriguingly, there is no documentation for any SrM2Si2O7 compounds. It then begs the question whether the BaM2Si2O7 compounds are capable of accommodating a significant amount of cations smaller than Ba2+. Similar to the pair (Ca2+ + H2O) in junitoite, the Ba2+ cations in the BaM2Si2O7 structures are also situated in the cavities of the framework formed by the Si2O7 dimers and the MO4 tetrahedral chains. Conceivably, any substantial replacement of large Ba2+ by smaller divalent cations (such as Sr2+) would require, in addition to the other structural adjustments (such as the tilting or distortion of MO4 and/or SiO4 tetrahedra), a further narrowing of the Si—O—Si angle in the Si2O7 group in order to satisfy the bonding environment for smaller cations. This, however, would not be energetically favorable, because the Si—O—Si angles in the BaM2Si2O7 compounds, ranging from 124 to 135°, are already among the smallest of disilicate materials, e.g. for high-temperature BaZn2Si2O7 (Lin et al., 1999), high-pressure rare earth (RE) disilicates RE2Si2O7 (Fleet & Liu, 2001) or BaKY(Si2O7) (Kolitsch et al., 2009). Accordingly, any sizable substitution of smaller Sr2+ for Ba2+ would worsen the bonding energetics for this site and thus destabilize the structure. For junitoite, Ca2+ by itself, which is even smaller than Sr2+, is apparently too small to occupy the cavities in the framework. Therefore, the presence of the H2O—Ca2+ bonded pair is essential to stabilize its structure. By the same token, one could argue that the pair (Sr2+ + H2O) together may be too large for the cavities in the structures analogous to those for the BaM2Si2O7 materials, since there is no report for any SrM2+2Si2O7.H2O compound up to date. Based on this reasoning, we postulate that more compounds with composition CaM2+2Si2O7.H2O may be found in nature or synthesized in laboratories. Furthermore, it would be interesting if the Sr—H2O pair might be found in digermanates, where this structural unit is even larger.

For junitoite, see: Williams (1976); Hamilton & Finney (1985). For junitoite-related minerals and compounds, see: Lin et al. (1999); Fleet & Liu (2001); Kolitsch et al. (2009); Yang et al. (2012). Parameters for bond-valence calculations were taken from 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 junitoite. The gray, green, and small blue spheres represent Ca, Ow5, and H atoms, respectively. The yellow and red tetrahedra represent ZnO4 and SiO4 groups, respectively.
[Figure 2] Fig. 2. Atoms in junitoite with corresponding ellipsoids at the 99.9% probability level. The gray, yellow, purple, red, and green ellipsoids represent Ca, Zn, Si, O, and Ow5, respectively. The small blue spheres represent H atoms.
calcium dizinc disilicate monohydrate top
Crystal data top
CaZn2Si2O7·H2OF(000) = 696
Mr = 357.02Dx = 3.506 Mg m3
Orthorhombic, Aea2Mo Kα radiation, λ = 0.71073 Å
Hall symbol: A 2 -2acCell parameters from 1387 reflections
a = 12.530 (4) Åθ = 4.3–33.2°
b = 6.3056 (18) ŵ = 8.21 mm1
c = 8.562 (3) ÅT = 293 K
V = 676.5 (3) Å3Cuboid, colorless
Z = 40.06 × 0.06 × 0.05 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
1257 independent reflections
Radiation source: fine-focus sealed tube1189 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.021
φ and ω scanθmax = 33.3°, θmin = 3.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2005)
h = 819
Tmin = 0.639, Tmax = 0.684k = 98
2719 measured reflectionsl = 1213
Refinement top
Refinement on F2Hydrogen site location: difference Fourier map
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.017 w = 1/[σ2(Fo2) + (0.0094P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.044(Δ/σ)max = 0.001
S = 1.07Δρmax = 0.52 e Å3
1257 reflectionsΔρmin = 0.65 e Å3
65 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: 0.0120 (4)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 580 Friedel pairs
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.023 (12)
Crystal data top
CaZn2Si2O7·H2OV = 676.5 (3) Å3
Mr = 357.02Z = 4
Orthorhombic, Aea2Mo Kα radiation
a = 12.530 (4) ŵ = 8.21 mm1
b = 6.3056 (18) ÅT = 293 K
c = 8.562 (3) Å0.06 × 0.06 × 0.05 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
1257 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2005)
1189 reflections with I > 2σ(I)
Tmin = 0.639, Tmax = 0.684Rint = 0.021
2719 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.017H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.044Δρmax = 0.52 e Å3
S = 1.07Δρmin = 0.65 e Å3
1257 reflectionsAbsolute structure: Flack (1983), 580 Friedel pairs
65 parametersAbsolute structure parameter: 0.023 (12)
1 restraint
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
Ca0.00000.50000.51882 (6)0.00899 (12)
Zn0.252164 (9)0.244531 (17)0.13494 (6)0.00808 (7)
Si0.11827 (4)0.00274 (4)0.39406 (7)0.00615 (9)
O10.12311 (9)0.2992 (2)0.01003 (15)0.0107 (3)
O20.12739 (10)0.21991 (19)0.49272 (17)0.0099 (3)
O30.20596 (13)0.00482 (13)0.25347 (15)0.0101 (3)
O40.00000.00000.3037 (2)0.0082 (3)
OW50.00000.50000.2518 (3)0.0209 (7)
H0.035 (3)0.448 (4)0.200 (3)0.030*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ca0.0106 (2)0.0078 (2)0.0085 (2)0.00019 (13)0.0000.000
Zn0.00755 (10)0.00739 (10)0.00931 (11)0.00067 (7)0.00070 (15)0.00072 (18)
Si0.00563 (18)0.00687 (18)0.00596 (19)0.00022 (11)0.00019 (16)0.00035 (16)
O10.0084 (5)0.0112 (5)0.0126 (8)0.0010 (4)0.0020 (4)0.0046 (5)
O20.0086 (5)0.0109 (5)0.0102 (8)0.0019 (4)0.0026 (4)0.0035 (5)
O30.0124 (7)0.0080 (6)0.0099 (6)0.0001 (3)0.0045 (4)0.0003 (4)
O40.0063 (8)0.0112 (8)0.0071 (9)0.0000 (4)0.0000.000
OW50.0272 (15)0.0278 (18)0.0076 (11)0.0100 (7)0.0000.000
Geometric parameters (Å, º) top
Ca—OW52.286 (2)Zn—O3v1.9501 (11)
Ca—O2i2.3910 (12)Zn—O31.9589 (11)
Ca—O22.3910 (12)Zn—O11.9691 (13)
Ca—O1ii2.4381 (13)Si—O21.6130 (14)
Ca—O1iii2.4381 (13)Si—O1vi1.6239 (14)
Ca—O4ii2.439 (2)Si—O31.6305 (16)
Zn—O2iv1.9454 (13)Si—O41.6719 (12)
OW5—Ca—O2i84.64 (4)O1iii—Ca—O4ii91.77 (4)
OW5—Ca—O284.64 (4)O2iv—Zn—O3v100.47 (6)
O2i—Ca—O2169.28 (8)O2iv—Zn—O3119.31 (6)
OW5—Ca—O1ii88.23 (4)O3v—Zn—O3117.42 (7)
O2i—Ca—O1ii81.25 (6)O2iv—Zn—O1108.13 (8)
O2—Ca—O1ii98.41 (6)O3v—Zn—O1111.21 (6)
OW5—Ca—O1iii88.23 (4)O3—Zn—O1100.32 (6)
O2i—Ca—O1iii98.41 (6)O2—Si—O1vi110.37 (11)
O2—Ca—O1iii81.25 (6)O2—Si—O3111.33 (7)
O1ii—Ca—O1iii176.46 (7)O1vi—Si—O3113.77 (7)
OW5—Ca—O4ii180.0O2—Si—O4108.30 (6)
O2i—Ca—O4ii95.36 (4)O1vi—Si—O4107.94 (6)
O2—Ca—O4ii95.36 (4)O3—Si—O4104.79 (10)
O1ii—Ca—O4ii91.77 (4)
Symmetry codes: (i) x, y+1, z; (ii) x, y+1/2, z+1/2; (iii) x, y+1/2, z+1/2; (iv) x+1/2, y, z1/2; (v) x+1/2, y+1/2, z; (vi) x, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
OW5—H···O10.70 (3)2.18 (2)2.875 (2)170 (3)

Experimental details

Crystal data
Chemical formulaCaZn2Si2O7·H2O
Mr357.02
Crystal system, space groupOrthorhombic, Aea2
Temperature (K)293
a, b, c (Å)12.530 (4), 6.3056 (18), 8.562 (3)
V3)676.5 (3)
Z4
Radiation typeMo Kα
µ (mm1)8.21
Crystal size (mm)0.06 × 0.06 × 0.05
Data collection
DiffractometerBruker APEXII CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2005)
Tmin, Tmax0.639, 0.684
No. of measured, independent and
observed [I > 2σ(I)] reflections
2719, 1257, 1189
Rint0.021
(sin θ/λ)max1)0.771
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.017, 0.044, 1.07
No. of reflections1257
No. of parameters65
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.52, 0.65
Absolute structureFlack (1983), 580 Friedel pairs
Absolute structure parameter0.023 (12)

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
OW5—H···O10.70 (3)2.18 (2)2.875 (2)170 (3)
 

Acknowledgements

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

References

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