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Article

The Crystal Structure and Crystal Chemistry of Mineral-like Cd5(VO4)2(OH)4, a Novel Isomorph of Arsenoclasite and Gatehouseite

by
Ljiljana Karanović
1,* and
Tamara Ðorđević
2,*
1
Faculty of Mining and Geology, University of Belgrade, Ðušina 7, 11000 Belgrade, Serbia
2
Institut für Mineralogie und Kristallographie, Universität Wien, Josef-Holaubek-Platz 2, 1090 Wien, Austria
*
Authors to whom correspondence should be addressed.
Minerals 2022, 12(12), 1601; https://doi.org/10.3390/min12121601
Submission received: 22 November 2022 / Revised: 9 December 2022 / Accepted: 9 December 2022 / Published: 12 December 2022
(This article belongs to the Special Issue Mineral-Related Oxo-Salts: Synthesis and Structural Crystallography)
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Abstract

:
The pentacadmium bis(vanadate(V)) tetrahydroxide Cd5(VO4)2(OH)4 was synthesized under hydrothermal conditions, and its crystal structure was determined with single-crystal X-ray diffraction. The investigated compound is the second known compound next to Cd(VO3)2·4H2O synthesized in the CdO–V2O5–H2O system and crystallizes isotypically to the minerals gatehouseite, Mn5(PO4)2(OH)4, and its As analog arsenoclasite, Mn5(AsO4)2(OH)4. Its symmetry is orthorhombic, with a space group of P212121 and unit cell parameters of a = 19.011(4), b = 6.0133(12), c = 9.5411(19) Å, V = 1090.7(4) Å3, and Z = 4. The structure consists of double ribbons of M(O,OH)6-octahedra (M = Cd2, Cd3, Cd4) extending along [010] interconnected by edge- and corner-shared M(O,OH)6-octahedra (M = Cd1, Cd5) and discrete, slightly distorted VO4 tetrahedra, which form double chains of coupled polyhedra [V1O4–Cd5O4(OH)2–Cd1O5(OH)–V2O4]n running along the same direction. The interesting feature is the existence of V–Cd distances (3.0934(7) and 3.1081(7) Å for V1–Cd5 and V2–Cd1, respectively), which are shorter than the sum of the van der Waals radii of 3.71 Å. The V1–V2 distances of 4.1214(9) Å are also shorter than the sum of the van der Waals radii of 4.26 Å. The O–H···O hydrogen bonds additionally link the two subunits, ribbons, and chains into a three-dimensional structure. Raman spectra confirmed the presence of the hydrogen bonds and mutually isolated VO4 groups.

1. Introduction

The natural and synthetic metal vanadates phosphates and arsenates often form tetrahedral–octahedral framework structures [1,2] with potentially interesting properties, e.g., ion conductivity, ion exchange, magnetic properties, and catalytic activities [3]. In the last two decades, metal vanadates have attracted considerable attention because of their widespread technological significance in an extensive range of applications [4,5] and references therein. The 3d orbital of vanadium in the energy spectrum is usually located below the analogous d orbitals of other transition metals, i.e., Zr, Ti, Nb, or Tl, and therefore the bottom conduction band is lowered to a more positive position [6]. Consequently, vanadium oxides are important candidates for visible light photocatalysis. For instance, Zn-vanadates, such as Zn3(VO4)2 [7,8] and Zn3V2O7(OH)2(H2O)2 [8], as well as Cd-vanadates, such as CdV2O6 and Cd2V2O7 [5], have been extensively synthesized and studied for their photocatalytic performances. However, the majority of these compounds were synthesized by applying high-temperature solid-state reactions [9,10] and references therein. In the scope of our previous research, we have proved that the hydrothermal method is effective for the synthesis of new vanadium compounds [11,12,13,14,15]. All these vanadates(V) were characterized structurally and, in part, by spectroscopic techniques. The title compound was obtained hydrothermally, and it represents the second known synthetic compound next to Cd(VO3)2·4H2O [16] in the CdO‒V2O5‒H2O system. Its crystal structure was refined and compared to those of other analogous M5(XO4)2(OH)4 compounds where M are divalent Cd, Co, Cu, Mn, or Ni cations, and X are pentavalent As, P, or V cations.

2. Materials and Methods

2.1. Synthesis

In the course of the experiments aimed at the preparation of Cd-Co vanadates, a starting mixture of Cd(OH)2 (Alfa Products 89,297, >99%), Co powder (Merck 112,211, ≥99%), and V2O5 (Fluka Chemika 94,710, ≥98%) with the approximate volume ratio of 1:1:1 (the weight ratio was not recorded) was employed.
The mixture was transferred into a Teflon vessel and filled to approximately one-third of the vessel’s volume with distilled water (initial pH was 6). The vessel was then enclosed in a stainless steel autoclave and heated under autogenous pressure from 293.15 to 473.15 K (4 h), held at that temperature (192 h), and slowly cooled (175 h) to room temperature. After the experiment, the final pH of the solution was 6. The reaction products were filtered, washed thoroughly with distilled water, and dried in air at room temperature. Cd5(VO4)2(OH)4 formed yellow-brownish, transparent, prismatic crystals (yield ca. 20%) together with very small (<0.1 mm), light orange, needle-like crystals of CdV3O7 (yield ca. 10%), V2O5 (yield ca. 10%), and Cd-vanadate with apatite type-structure (yield ca. 5%). Single crystals of Cd apatite were too small for single-crystal X-ray analysis but were characterized using Raman spectroscopy.

2.2. Raman Spectrometry

To obtain further information on the vanadate groups and hydrogen bonds, single crystal Raman spectra were acquired. Raman spectra of Cd5(VO4)2(OH)4 were measured with a Horiba LabRam-HR system equipped with Olympus BX41 optical microscope in the range between 100 and 4000 cm–1. The 632.8 nm excitation line of a He–Ne laser was focused with a 50× objective (N.A. = 0.90) on the randomly oriented single crystal. The nominal exposure time was between 60–70 s (confocal mode, Olympus 1800 lines/mm, 1.5 µm lateral resolutions, and approximately 3 µm depth resolution). The density of the laser power was well below the threshold (25% filter was used) for possible sample changes due to intense laser-light absorption and resulting temperature increase.

2.3. X-ray Diffractometry and Crystal Structure Solution

The crystal quality of several single crystals was checked with a Nonius Kappa CCD single-crystal four-circle diffractometer (Mo tube, graphite monochromator, CCD detector frame size: 621 × 576 pixels, binned mode) equipped with a 300 µm diameter capillary-optics collimator. The crystal, which exhibited sharp reflection spots, was chosen for data collection. A complete sphere of reciprocal space (φ and ω scans) was measured at room temperature. The intensity data were processed with the Nonius program suite DENZO-SMN [17] and corrected for Lorentz, polarization, and background effects and, by the multiscan method [18,19], for absorption.
The crystal structure was solved with the SHELXT structure solution program and refined on F2 by full-matrix least-squares using SHELXL-2018/3 [20,21] and WinGX [22]. Starting from the atomic coordinates and the labeling used for gatehouseite [23], Cd and V atoms were located. Other atomic positions were found using difference Fourier syntheses. Anisotropic displacement parameters were refined for all nonhydrogen atoms. H atoms from hydroxyl groups were located in a difference Fourier map and then refined with the distance restraint O–H = 0.82(1) Å and constrained to ride on the corresponding O atom with Uiso(H) = 1.5Ueq(O). Crystal data, information on the data collection, and results of the final structure refinement are compiled in Table 1. Fractional atomic coordinates and equivalent isotropic displacement parameters for Cd5(VO4)2(OH)4 are given in Table 2, the selected bond lengths in Table 3, bond valences in Table 4, and hydrogen bonds in Table 5. All drawings of structure were produced with ATOMS [24].

3. Results

3.1. Crystal Structure

The asymmetric unit of Cd5(VO4)2(OH)4 exhibits two crystallographically unique vanadates(V) tetrahedra and five fully occupied Cd sites, each octahedrally coordinated [Cd1O5(OH), Cd2O3(OH)3, Cd3O4(OH)2, Cd4O2(OH)4, Cd5O4(OH)2] (Figure 1). The Cd1 site is coordinated by one OH group and five O atoms, with the <Cd1–OH,O> average distance of 2.351 Å, which is consistent with the bond length statistics and mean Cd–O distance of 2.302 Å [25]. The mean octahedral distances of <2.326>, <2.309>, <2.283>, and <2.359> Å for Cd2O3(OH)3, Cd3O4(OH)2, Cd4O2(OH)4 and Cd5O4(OH)2 octahedra, respectively, are also very close to 2.302 Å. They are also close to the value of 2.33 Å (0.95 + 1.38) calculated from the effective ionic radii for divalent cadmium octahedrally coordinated with the six nearest oxygen atoms [26].
The bond valence sum calculations [27] for octahedral positions display minor deviations, i.e., all six coordinated Cd atoms have bond valence sums Σνij close to two (Table 4).
Both V sites are tetrahedrally coordinated with four O atoms. The average <V1,2–O> distances of <1.718> and <1.721> Å, respectively, are in very good agreement with the mean V–O distance of 1.717 Å [25] as well as with the value of 1.735 Å (0.355 + 1.38) calculated from effective ionic radii for tetrahedrally coordinated pentavalent vanadium [26]. The O–V–O angles range from 105.39(19) to 112.87(17)°.
The core of the structure is made of infinite ribbons (Figure 2a), buildup from edge-sharing distorted M(O,OH)6-octahedra (M = Cd2, Cd3, Cd4). Each ribbon, interchangeably one and two octahedra wide, is extending along [010]. Two adjacent ribbons are further interconnected to infinite double ribbons by sharing O3 vertices, as shown in Figure 2a.
The V1O4 tetrahedra and Cd5O4(OH)2 octahedra share a common edge as well as the V2O4 tetrahedra and Cd1O5(OH) octahedra. Thus, they form two polyhedral pairs. Each pair VO4‒CdO5(OH) of coupled polyhedra is bonded to adjacent similar pairs sharing common vertices and forming [V1O4‒Cd5O4(OH)2]n and [V2O4‒Cd1O5(OH)]n chains in the [010] direction (Figure 2b). These two adjacent chains are further interconnected by edge-shared M(O,OH)6 (M = Cd1, Cd5) octahedra forming double chains of coupled polyhedra [V1O4-Cd5O4(OH)2-Cd1O5(OH)-V2O4]n and running along the same [010] direction.
Two neighboring double chains are additionally connected via O8 vertices (Figure 2b). The double ribbons of M(O,OH)6 octahedra (M = Cd2, Cd3, Cd4) are connected by pairs of coupled VO4 tetrahedra and M(O,OH)6 octahedra (M = Cd1, Cd5) sharing vertices (Figure 2c). The O–H···O hydrogen bonds additionally link the two subunits, the ribbons, and chains into a three-dimensional structure (Figure 2d).
The V cations in double chains are separated from each other by 4.1214(9) Å, which is slightly less than the sum of the van der Waals radii [28,29] of 4.26 Å [2 × 2.13]. Several V‒Cd distances are also less than the sum of the van der Waals radii of 3.71 Å [rCd + rV = 1.58 + 2.13]. The distances between the V1 and Cd neighbors are ranging from 3.0934(7) to 3.5678(8) Å, which is similar to the distances of V2 and Cd neighbors that are in the range from 3.1081(7) to 3.4731(7) Å. The shortest V1–Cd5 and V2–Cd1 contacts are found in coupled polyhedra where they are 3.0934(7) and 3.1081(7) Å, respectively. All Cd–Cd distances are longer than the sum of the van der Waals radii of 3.16 Å [2 × 1.58] [28], and they are in the interval from 3.4575(7) to 3.5961(8) Å.
Hydrogen bonding (Table 5) plays a significant role in linking the double ribbons with the double chains of coupled polyhedra. This interaction contributes to the stability of the structure. Bond valence analysis shows that considering the contribution of non-hydrogen atoms only, the O1, O2, O3, and O4 atoms are all undersaturated (Σνij are 1.125, 1.079, 1.116, and 1.237 v.u.) as well as O5, O7, and O12 (Σνij are 1.834, 1.805 and 1.800 v.u.). Considering that the O1, O2, O3, and O4 atoms are hydrogen bond donors, O5 and O7 are single acceptors and O12 is a double acceptor of middle strong and weak hydrogen bonds; the bond valences are well balanced. The total amount of the bond strengths, including the contribution of the hydrogen bonds, are in excellent agreement with the expectations.

3.2. Raman Spectrometry

The Raman spectrum is shown in Figure 3. It reflects the complexity of the crystal structure. Bands in the high-energy range (3100–3600 cm–1) are due to the stretching of O–H bonds of hydroxyl groups. Bands in the 100–1100 cm–1 range are caused by internal vibrations either of VO4 tetrahedra or due to external vibrational modes.
According to the d–ν correlation for hydrogen bonds [30], the Raman-shift values observed in the O–H stretching region (Figure 3) are in very good agreement with the refined O–H∙∙∙O bond lengths between 2.869(5) and 3.017(5) Å (Raman bands obtained at 3374 and 3421 cm–1).
In the 600–900 cm–1 spectral range, the Raman bands could be assigned to symmetric and antisymmetric stretching modes of the (VO4)3– groups whereas internal bending vibrations of these tetrahedra are observed below 550 cm–1, here, partially overlaid by various external modes (Figure 3). Precisely, the Raman spectrum of Cd5(VO4)2(OH)4 is characterized by three intense bands at 870 (m), 838 (vs), and 804 (s) cm−1 assigned to ν1 (VO4)3− symmetric stretching modes and two weak bands around 685 and 783 cm–1 assigned to the ν3 (VO4)3− antisymmetric stretching modes. The symmetric stretches of Cd5(VO4)2(OH)4 compare well with the symmetric stretches of the synthetic SrCu(OH)(VO4) [15], which has stretching modes that lie around 883 (w), 840 (vs), 810 (s), 786 (w), and 750 (w) cm–1.

4. Discussion and Relationships to Similar Structures

The synthetic compound Cd5(VO4)2(OH)4 is isostructural with the minerals arsenoclasite, Mn(II)5(AsO4)2(OH)4 [31], and its phosphate analog gatehouseite, Mn(II)5(PO4)2(OH)4 [23]. Pring and Birch [32] refined the structure of gatehouseite in the same space group P212121 but in a c b ¯ a setting. It is also isostructural with two synthetic compounds, Mn5(PO4)2(OH)4 and Co5(PO4)2(OH)4, [33] refined with cyclically permuted a b c axes in a c a b setting (Table 6). This small family of compounds belongs to a Co5(PO4)2(OH)4 structure type, exhibits the same symmetry and topology (Figure 4a,b), and has the general formula M5(XO4)2(OH)4 where M is a divalent Cd, Mn, or Co cation, and X is a pentavalent P, As, or V cation. Topologically, the edge-shared Cd triangle patterns can be described as the corrugated layer parallel to (001) and approximately half c-axis wide (Figure 4b). Each layer consists of ribbons, which are parallel to [010] and connected by an array of Cd1 atoms (Figure 4a).
In spite of their identical stoichiometry, other M5(XO4)2(OH)4 compounds have lower symmetry and adopt different structure types (Table 6). One structural group that includes mineral reppiaite, Mn5(PO4)2(OH)4 [2,34], isostructural synthetic compound Ni5(AsO4)2(OH)4 [35] as well as minerals cornubite, Cu5(AsO4)2(OH)4 [36,37,38] and turanite, Cu5(VO4)2(OH)4, [3,39] corresponds to the layer structures. These are built from alternating octahedral and tetrahedral more or less distorted, basically flat layers which form a 3D framework. While octahedral layers of reppiaite and turanite have the same topology, those of cornubite have different topologies resulting from different patterns of octahedral distortions and vacancy distributions (Figure 4c–e).
The patterns of Mn triangles in reppiaite and Cu triangles in turanite can be described as consisting of two types of chains parallel to [001] in reppiaite and to [100] in turanite. One chain is a buildup of alternating edge- and corner-sharing triangles and one with centered hexagons. In cornubite, one type of chain contains only edge-sharing Cu triangles parallel to the a-axis, and the other contains empty hexagons.
The chemical features of Cd5(VO4)2(OH)4 are also related to the three polymorphs of Cu5(PO4)2(OH)4 minerals [40,41,42]: pseudomalachite [43], reichenbachite [44,45,46], ludjibaite [40,47], and the As analog of pseudomalachite, mineral cornwallite, Cu5(AsO4)2(OH)4 [48]. The structures of these three polymorphs are also characterized by layers of edge-sharing copper coordination octahedra joined in the third dimension by phosphate (arsenate) tetrahedra. Topologically, they are similar mutually but quite different from the other M5(XO4)2(OH)4 compounds (Figure 4h). In pseudomalachite and ludjibaite, which are topologically identical, two different types of chains parallel to [010] are also found. In both structures, chains of type I are formed by triangles sharing edges and vertices, and the chains of type II are created by sharing vertices only. In this way, the Cu patterns contain three- and five-membered rings. The pattern in pseudomalachite is a distorted version of the pattern in ludjibaite. The very distorted Cu lattice of reichenbachite is also formed from three- and five-membered rings that share common edges and vertices, but it is principally different from those in pseudomalachite and ludjibaite.

5. Conclusions

The hydrothermally obtained title compound Cd5(VO4)2(OH)4 is the second known compound next to Cd(VO3)2·4H2O [16] synthesized in the CdO–V2O5–H2O system. It belongs to a small family of compounds adopting the Co5(PO4)2(OH)4 structure type. These compounds exhibit P212121 symmetry and have the general formula M5(XO4)2(OH)4, where M is a divalent Cd, Mn, or Co cation, and X is a pentavalent P, As, or V cation. Other M5(XO4)2(OH)4 compounds have lower symmetry, different structure types, and topologies.
Numerous metal vanadates have been widely studied during the last decades due to their promising properties. Special interest in transition metal vanadates is due to their interesting optical, electric, and magnetic properties and thus can be used in (photo)catalysis, lithium-ion batteries, solar cells, gas sensors, water-splitting technologies, and optoelectronics [50] and references therein.
Detailed study of the selected metal–vanadate systems would lead to a detailed understanding of which topologies and affinities are likely to form under which conditions (e.g., pH, ratios of ionic radii, temperature, etc.). This information could also be useful not only to vanadates but also to phosphates, arsenates, and maybe silicates, whose technological usage is built on the special physical and chemical performance that is basically dependent on their crystal structure.

Author Contributions

Conceptualization, L.K. and T.Đ.; methodology, T.Đ.; formal analysis, L.K. and T.Đ.; investigation, L.K. and T.Đ.; resources, T.Đ.; data curation, L.K. and T.Đ.; writing—original draft preparation L.K.; writing—review and editing, L.K. and T.Đ.; visualization, L.K. and T.Đ.; project administration, T.Đ.; funding acquisition, T.Đ. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the Austrian Science Foundation (FWF) (grant No. V203-N19) and is gratefully acknowledged.

Data Availability Statement

The supplementary crystallographic data for this paper (deposition number 2221388) are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures service www.ccdc.cam.ac.uk/structures (accessed on 21 November 2022).

Acknowledgments

Two anonymous reviewers are thanked for their careful corrections and comments, which helped to improve the manuscript.

Conflicts of Interest

The authors declare no conflict of interest.

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Minerals 12 01601 g001 550
Figure 1. The structural fragment showing ellipsoids of ADP (90% probability), hydrogen bonds, and atomic labeling scheme. Symmetry codes: (i) −x + 1/2, −y, z + 1/2; (ii) −x, y + 1/2, −z + 1/2; (iii) x + 1/2, −y + 1/2, −z.
Figure 1. The structural fragment showing ellipsoids of ADP (90% probability), hydrogen bonds, and atomic labeling scheme. Symmetry codes: (i) −x + 1/2, −y, z + 1/2; (ii) −x, y + 1/2, −z + 1/2; (iii) x + 1/2, −y + 1/2, −z.
Minerals 12 01601 g001
Minerals 12 01601 g002a 550Minerals 12 01601 g002b 550
Figure 2. The linkage of two octahedral ribbons of M(O,OH)6 octahedra (M = Cd2, Cd3, Cd4) via O3 in the projection approximately along the [101] (b-axis is horizontal). Small grey spheres represent H atoms (a). The linkage of neighboring double chains of coupled VO4 tetrahedra and M(O,OH)6 octahedra (M = Cd1, Cd5) via O8 in the projection along the [104] (b-axis is horizontal) (b). The double ribbons of M(O,OH)6 octahedra (M = Cd2, Cd3, Cd4) connected by pairs of coupled VO4 tetrahedra and M(O,OH)6 octahedra (M = Cd1, Cd5) (c). The projection of the structure along the [010] direction (d).
Figure 2. The linkage of two octahedral ribbons of M(O,OH)6 octahedra (M = Cd2, Cd3, Cd4) via O3 in the projection approximately along the [101] (b-axis is horizontal). Small grey spheres represent H atoms (a). The linkage of neighboring double chains of coupled VO4 tetrahedra and M(O,OH)6 octahedra (M = Cd1, Cd5) via O8 in the projection along the [104] (b-axis is horizontal) (b). The double ribbons of M(O,OH)6 octahedra (M = Cd2, Cd3, Cd4) connected by pairs of coupled VO4 tetrahedra and M(O,OH)6 octahedra (M = Cd1, Cd5) (c). The projection of the structure along the [010] direction (d).
Minerals 12 01601 g002aMinerals 12 01601 g002b
Minerals 12 01601 g003 550
Figure 3. The Raman spectrum of Cd5(VO4)2(OH)4 between 100 and 1100 cm–1 and the section between 3100 and 3600 cm–1 showing the OH stretching region.
Figure 3. The Raman spectrum of Cd5(VO4)2(OH)4 between 100 and 1100 cm–1 and the section between 3100 and 3600 cm–1 showing the OH stretching region.
Minerals 12 01601 g003
Minerals 12 01601 g004 550
Figure 4. The nodal representation (nodes symbolize MO6 octahedra) of different topologies observed in M5(XO4)2(OH)4 compounds. The solid lines represent M···M interatomic distances shorter than 4 Å. A trace of the unit cell is drawn for reference (red). The projection (a) along the c-axis direction in synthetic Cd5(VO4)2(OH)4 (Cd1O6 octahedra are grey); (b) along the b-axis direction in synthetic Cd5(VO4)2(OH)4 (The similar metal wavy layers were found in arsenoclasite, Mn5(AsO4)2(OH)4, gatehouseite, Mn5(PO4)2(OH)4, as well as in synthetic Co5(PO4)2(OH)4); (c) along a-axis in reppiaite, Mn5(OH)4(VO4)2; (d) along [0 1 ¯ 1 ¯ ] in turanite, Cu5(OH)4(VO4)2; (e) along [01 1 ¯ ] in cornubite, Cu5(AsO4)2(OH)4; (f) along a-axis in pseudomalachite, Cu5(PO4)2(OH)4 and cornwallite, Cu5(AsO4)2(OH)4; (g) along a-axis in ludjibaite, Cu5(PO4)2(OH)4; (h) along c-axis in reichenbachite, Cu5(PO4)2(OH)4.
Figure 4. The nodal representation (nodes symbolize MO6 octahedra) of different topologies observed in M5(XO4)2(OH)4 compounds. The solid lines represent M···M interatomic distances shorter than 4 Å. A trace of the unit cell is drawn for reference (red). The projection (a) along the c-axis direction in synthetic Cd5(VO4)2(OH)4 (Cd1O6 octahedra are grey); (b) along the b-axis direction in synthetic Cd5(VO4)2(OH)4 (The similar metal wavy layers were found in arsenoclasite, Mn5(AsO4)2(OH)4, gatehouseite, Mn5(PO4)2(OH)4, as well as in synthetic Co5(PO4)2(OH)4); (c) along a-axis in reppiaite, Mn5(OH)4(VO4)2; (d) along [0 1 ¯ 1 ¯ ] in turanite, Cu5(OH)4(VO4)2; (e) along [01 1 ¯ ] in cornubite, Cu5(AsO4)2(OH)4; (f) along a-axis in pseudomalachite, Cu5(PO4)2(OH)4 and cornwallite, Cu5(AsO4)2(OH)4; (g) along a-axis in ludjibaite, Cu5(PO4)2(OH)4; (h) along c-axis in reichenbachite, Cu5(PO4)2(OH)4.
Minerals 12 01601 g004
Table
Table 1. Crystal data, data collection, and refinement details for Cd5(VO4)2(OH)4.
Table 1. Crystal data, data collection, and refinement details for Cd5(VO4)2(OH)4.
Chemical FormulaCd5H4O12V2
Temperature293
Formula weight, Mr (g/mol)859.91
Space group (No.), ZOrthorhombic, P212121, 4
a (Å)19.011 (4)
b (Å)6.0133 (12)
c (Å)9.5411 (19)
V (Å3)1090.7 (4)
F (000), ρcalc (g/cm3)1544, 5.237
Absorption coefficient, μ (mm−1)11.26
Tmin/Tmax0.399/0.552
Crystal size (mm3)0.10 × 0.08 × 0.06
Crystal detector distance (mm)40
Frame rotation width (°)1
Total no. of frames1032
Collection time per frame (s)150
h, k, l ranges±26, ±8, ±13
Absorption correctionMulti-scan
Reflections collected/unique12,585/3180
Observed reflections [I > 2 σ(I)]3079
Rint0.026
2θmax (°)30
Extinction coefficient, k [a]0.00064 (8)
Refined parameters185
R indices [I > 4 σ(I)]R1 = 0.015
wR2 = 0.036
R indices (all data)R1 = 0.016
wR2 = 0.036
Goodness of fit, S1.08
(Δ/σ)max0.001
(Δρ)max, (Δρ)min (e−Å−3)0.74; −1.00
a, b[b]0.0159, 1.4781
[a]Fc* = kFc [1 + 0.001’Fc2λ3/sin(2θ)]−1/4; [b] w = 1/[σ2(Fo2) + (aP)2 + bP].
Table
Table 2. Fractional atomic coordinates and equivalent isotropic displacement parameters for Cd5(VO4)2(OH)4.
Table 2. Fractional atomic coordinates and equivalent isotropic displacement parameters for Cd5(VO4)2(OH)4.
AtomxyzUiso */Ueq (Å2)
Cd10.43166(2)0.27295(6)0.75333(4)0.01236(8)
Cd20.47036(2)−0.05464(6)0.39132(4)0.01098(7)
Cd30.28220(2)−0.06980(6)0.35388(3)0.01123(8)
Cd40.37741(3)0.44179(6)0.37772(4)0.01280(8)
Cd50.31528(3)0.57571(6)0.99733(4)0.01303(8)
V10.37572(4)0.11180(12)1.06892(6)0.00862(11)
V20.37360(4)−0.19731(12)0.68339(8)0.00850(15)
O10.45222(18)0.2654(6)0.5217(4)0.0137(7)
H10.4911(15)0.321(10)0.523(7)0.021 *
O20.29638(18)0.6100(6)1.2347(4)0.0129(7)
H20.2569(15)0.554(10)1.240(7)0.019 *
O30.45626(17)0.6368(6)0.2526(4)0.0141(7)
H30.427(3)0.683(10)0.196(5)0.021 *
O40.21431(18)0.7472(6)0.9713(3)0.0124(7)
H40.203(3)0.789(10)1.050(3)0.019 *
O50.35026(17)0.5523(6)0.7643(4)0.0132(6)
O60.37237(19)−0.2267(6)0.5019(4)0.0126(6)
O70.3196(2)0.0164(6)0.7275(4)0.0170(8)
O80.45553(18)−0.1139(7)0.7297(4)0.0166(8)
O90.37949(18)0.1117(5)0.2501(4)0.0117(6)
O100.29428(19)0.2058(6)1.0171(4)0.0151(7)
O110.43564(19)0.2935(6)0.9938(4)0.0158(7)
O120.39246(19)0.8495(6)1.0155(4)0.0156(7)
Table
Table 3. Bond distances and average lengths (Å) for Cd5(VO4)2(OH)4.
Table 3. Bond distances and average lengths (Å) for Cd5(VO4)2(OH)4.
Distance <Mean>Bond Lengths (Å)Distance <Mean>Bond Lengths (Å)
Cd1—O12.245(4)Cd2—O3 ii2.271(4)
Cd1—O8 i2.256(4)Cd2—O11 iii2.287(3)
Cd1—O52.287(3)Cd2—O3 iv2.295(4)
Cd1—O112.299(4)Cd2—O12.317(4)
Cd1—O82.381(4)Cd2—O62.378(4)
Cd1—O72.642(4)Cd2—O92.408(3)
<Cd1—O>2.352<Cd2—O>2.326
Cd3—O4 v2.241(4)Cd4—O12.244(4)
Cd3—O2 vi2.252(3)Cd4—O32.246(4)
Cd3—O10 vii2.282(3)Cd4—O4 v2.265(4)
Cd3—O7 vii2.302(4)Cd4—O2 viii2.293(4)
Cd3—O92.365(3)Cd4—O6 ix2.321(3)
Cd3—O62.413(4)Cd4—O92.329(3)
<Cd3—O>2.309<Cd4—O>2.283
Cd5—O42.193(3)
Cd5—O122.212(3)
Cd5—O102.268(4)
Cd5—O22.302(4)
Cd5—O52.325(3)
Cd5—O112.849(4)
<Cd5—O>2.358
V1—O12 iv1.688(3)V2—O81.695(4)
V1—O101.721(4)V2—O71.698(3)
V1—O9 x1.731(4)V2—O61.741(4)
V1—O111.733(4)V2—O5 iv1.749(3)
<V1—O>1.718<V2—O>1.721
Symmetry codes: (i) −x + 1, y + 1/2, −z + 3/2; (ii) −x + 1, y − 1/2, −z + 1/2; (iii) −x + 1, y − 1/2, −z + 3/2; (iv) x, y − 1, z;(v) −x + 1/2, −y + 1, z − 1/2; (vi) x, y − 1, z − 1; (vii) −x + 1/2, −y, zv1/2; (viii) x, y, zv1; (ix) x, y + 1, z; (x) x, y, z + 1.
Table
Table 4. Bond valences and bond valence sum Σνij (v.u.) for Cd5(VO4)2(OH)4*.
Table 4. Bond valences and bond valence sum Σνij (v.u.) for Cd5(VO4)2(OH)4*.
SiteCd1Cd2Cd3Cd4Cd5V1V2Σνij **
O10.3980.328 0.399 1.125
O2 0.3890.3490.341 1.079
O3 0.3710.348 0.397 1.116
O4 0.4020.3770.458 1.237
O50.355 0.321 1.1571.834
O6 0.2780.2530.324 1.1822.037
O70.136 0.341 1.3281.805
O80.3860.275 1.3392.001
O9 0.2560.2880.317 1.215 2.076
O10 0.360 0.3741.248 1.982
O110.3440.355 0.0781.208 1.985
O12 0.4351.365 1.800
Σνij1.8941.9362.0332.1632.0075.0365.006
* The values of the bond valence parameters Ro of 1.904 for Cd(II)–O and 1.803 for V(V)–O were used assuming that b = 0.37 Å. ** Neglecting H-atom contributions.
Table
Table 5. Hydrogen-bond geometry (Å, °) for Cd5(VO4)2(OH)4.
Table 5. Hydrogen-bond geometry (Å, °) for Cd5(VO4)2(OH)4.
D–H···AD–HH···AD···AD–H···A
O1—H1···O12 iii0.81(1)2.25(3)3.017(5)157(6)
O2—H2···O5 xiii0.82(1)2.15(2)2.967(5)173(6)
O3—H3···O12 viii0.82(1)2.10(3)2.869(5)156(6)
O4—H4···O7 xiii0.82(1)2.10(2)2.900(5)164(6)
Symmetry codes: (iii) −x + 1, y − 1/2, −z + 3/2; (viii) x, y, z − 1; (xiii) −x + 1/2, −y + 1, z + 1/2.
Table
Table 6. Comparison of the unit cell parameters of analogous structures of M5(XO4)2(OH)4 compounds.
Table 6. Comparison of the unit cell parameters of analogous structures of M5(XO4)2(OH)4 compounds.
Compound
Mineral Name		a(Å), b(Å), c(Å)α(o), β(o), γ(o)V(Å3)Space GroupReference
Mn5(AsO4)2(OH)4
arsenoclasite		18.290(20)
5.75(1)
9.31(2)		90, 90, 90979.11P212121[31]
Mn5(P0.88Si0.09As0.03O4)2(OH)4
gatehouseite		17.9733(18)
5.6916(11)
9.130(4)		90, 90, 90933.9 (3)P212121[23]
Mn5.09Fe0.01Al0.01(OH)4
(P0.90As0.09V0.01O4)2(OH)4
gatehouseite		9.097(2)
5.693(2)
18.002(10)		90, 90, 90932.4 (8)P212121[32]
Mn5(PO4)2(OH)4
gatehouseite synthetic		9.110(1)
18.032(4)
5.6923(6)		90, 90, 90935.08P212121[33]
Co5(PO4)2(OH)4
gatehouseite type synthetic		8.903(2)
17.397(2)
5.5154(4)		90, 90, 90854.26P212121[33]
Cd5(VO4)2(OH)4
gatehouseite type synthetic		19.011(4)
6.0133(12)
9.5411(19)		90, 90, 901090.7 (4)P212121This work
Mn5(V0.89As0.11O4)2(OH)4
reppiaite		9.604(2)
9.558(2)
5.393(1)		90, 98.45(1), 90489.68C2/m[34]
Ni5(AsO4)2(OH)4
reppiaite type synthetic		9.291(2)
9.008(2)
5.149(1)		90, 98.70(3), 90425.98C2/m[35]
Cu5(VO4)2(OH)4
turanite		5.3834(2)
6.2736(3)
6.8454(3)		86.169(1), 91.681(1),92.425(1)230.38 (2)P 1 ¯ [39]
Cu5(AsO4)2(OH)4
cornubite		6.121(1)
6.251(1)
6.790(1)		92.93(1), 111.30(1),107.47(1)227.11P 1 ¯ [36]
Cu5(PO4)2(OH)4
pseudomalachite		4.4728(4)
5.7469(5)
17.032(3)		90, 91.043(7), 90437.73P21/c[43]
Cu5(AsO4)2(OH)4
cornwallite		4.600(2)
5.757(3)
17.380(6)		90, 91.87 (3), 90460.02P21/c[48]
Cu5(PO4)2(OH)4
reichenbachite synthetic		9.186(2)
10.684(2)
4.461(1)		90, 92.31(1), 90437.46P21/a[44]
Cu5(PO4)2(OH)4
ludjibaite		4.445(1)
5.873(1)
8.668(3)		103.62(2), 90.35(2), 93.02(1)219.57P 1 ¯ [49]
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Karanović, L.; Ðorđević, T. The Crystal Structure and Crystal Chemistry of Mineral-like Cd5(VO4)2(OH)4, a Novel Isomorph of Arsenoclasite and Gatehouseite. Minerals 2022, 12, 1601. https://doi.org/10.3390/min12121601

AMA Style

Karanović L, Ðorđević T. The Crystal Structure and Crystal Chemistry of Mineral-like Cd5(VO4)2(OH)4, a Novel Isomorph of Arsenoclasite and Gatehouseite. Minerals. 2022; 12(12):1601. https://doi.org/10.3390/min12121601

Chicago/Turabian Style

Karanović, Ljiljana, and Tamara Ðorđević. 2022. "The Crystal Structure and Crystal Chemistry of Mineral-like Cd5(VO4)2(OH)4, a Novel Isomorph of Arsenoclasite and Gatehouseite" Minerals 12, no. 12: 1601. https://doi.org/10.3390/min12121601

APA Style

Karanović, L., & Ðorđević, T. (2022). The Crystal Structure and Crystal Chemistry of Mineral-like Cd5(VO4)2(OH)4, a Novel Isomorph of Arsenoclasite and Gatehouseite. Minerals, 12(12), 1601. https://doi.org/10.3390/min12121601

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