Mineralogical Magazine (2020), 84, 921–927 doi:10.1180/mgm.2020.85

Article

Bojarite, Cu3(N3C2H2)3(OH)Cl2⋅6H2O, a new species with a microporous metal–organic framework from the guano deposit at Pabellón de Pica, ,

Nikita V. Chukanov1,2*, Gerhard Möhn3, Natalia V. Zubkova2, Dmitry A. Ksenofontov2, Igor V. Pekov2, Atali A. Agakhanov4, Sergey N. Britvin5 and Joy Desor6 1Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow region, 142432 Russia; 2Faculty of Geology, Moscow State University, Vorobievy Gory, Moscow, 119991 Russia; 3Dr.-J.-Wittemannstrasse 5, 65527 Niedernhausen, Germany; 4Fersman Mineralogical Museum of the Russian Academy of Sciences, Leninsky Prospekt 8–2, Moscow, 119071 Russia; 5Department of Crystallography, St Petersburg State University, Universitetskaya Nab. 7/9, 199034 St Petersburg, Russia; and 6Im Langenfeld 4, 61350 Bad Homburg, Germany

Abstract ⋅ The new triazolate mineral bojarite (IMA2020-037), Cu3(N3C2H2)3(OH)Cl2 6H2O, is found in a guano deposit located at the Pabellón de Pica Mountain, Iquique Province, Tarapacá Region, Chile. Associated are salammoniac, halite, nitratine and belloite. Bojarite occurs as blue fine-grained porous aggregates up to 1 mm × 3 mm × 5 mm combined typically in interrupted earthy crusts. The mineral –3 is brittle. The Mohs hardness is 2. Dcalc = 2.057 g cm . The IR and Raman spectra show the presence of the 1,2,4-triazolate anion and λ H2O molecules. Bojarite is optically isotropic and n = 1.635(2) ( = 589 nm). The chemical composition (electron-microprobe data for Na, Mg, Fe, Cu and Cl; H, C and N contents measured by gas chromatography on products of ignition at 1200°C; wt.%) is: Na 0.22, Mg 0.74, Fe 0.99, Cu 29.73, Cl 13.62, N 20.4, C 11.6, H 3.3, O (calculated by stoichiometry) 19.93, total 100.53. ⋅ The empirical formula is (Cu2.68Mg0.17Fe0.10Na0.05)Σ3(N3C2H2)2.755[(OH)][Cl2.19(H2O)3.77(OH)0.04]Σ6 2.3H2O. The idealised formula is Cu (N C H ) (OH)Cl ⋅6H O. The of bojarite was refined based on powder X-ray diffraction data, using the Rietveld 3 3 2 2 3 2 2  method. The final agreement factors are: Rp = 0.0225, Rwp = 0.0310 and Robs = 0.0417. The new mineral is cubic, space group Fd3c; a = 24.8047(5) Å, V = 15,261.6(5) Å3 and Z = 32. The strongest reflections of the powder X-ray diffraction pattern [d,Å(I,%)(hkl)] are: 8.83 (31)(220), 7.19 (100)(222), 6.23 (35)(400), 5.077 (28)(422), 4.194 (28)(531), 3.584 (23)(444), 2.865 (28)(660, 751) and 2.723 (22)(753, 842).

Keywords: bojarite, new mineral, 1,2,4-triazolate anion, crystal structure, metal–organic microporous framework, guano deposit, Pabellón de Pica, Chile (Received 2 September 2020; accepted 26 October 2020; Accepted Manuscript published online: 30 October 2020; Associate Editor: Peter Leverett)

Introduction Cu(C3N3O3H2)2(NH3)2 (Bojar et al., 2017), chanabayaite Cu (N C H ) Cl(NH ,Cl,H O,□) (Chukanov et al., 2015a), The guano deposit situated at the Pabellón de Pica Mountain, 2 3 2 2 2 3 2 4 möhnite (NH )K Na(SO ) (Chukanov et al., 2015b), shilovite 1.5 km south of the Chanabaya village, Iquique Province, 4 2 4 2 ′ ′ Cu(NH ) (NO ) (Chukanov et al., 2015c), antipinite KNa Cu Tarapacá Region, Chile (20°55 S, 70°08 W) is a unique locality 3 4 3 2 3 2 (C O ) (Chukanov et al., 2015d), triazolite NaCu (N C H ) among those belonging to the belt of guano occurrences of the 2 4 4 2 3 2 2 2 (NH ) Cl ⋅4H O(Zubkovaet al., 2016;Chukanovet al., 2018) Atacama Desert (Ericksen, 1981; Pankhurst and Herve, 2007; 3 2 3 2 and ammoniotinsleyite (NH ) Al (PO ) (OH)⋅2H O(Chukanov Appelton and Nothold, 2002; Bojar et al., 2010). The specific geo- 4 2 2 4 2 2 et al., 2020a). All these minerals, except antipinite, contain chemical feature of this deposit is the high content of copper , most of them contain organic groups, and in seven extracted from chalcopyrite, which is an accessory but rather newmineralsfromthislocalityCu2+ is a species-defining abundant component of the host rock, amphibole gabbro. component. The new mineral species bojarite, Cu (N C H ) (OH) 3 3 2 2 3 Specimens in which bojarite was discovered were collected at Cl ⋅6H O, described in this paper is the ninth new mineral 2 2 Pabellón de Pica in 2019 by one of the authors (G.M.). species discovered in guano deposits at Pabellón de Pica, after Bojarite is named in honour of the well-known Austrian mineral- ammineite CuCl (NH ) (Bojar et al., 2010), joanneumite 2 3 2 ogist Dr Hans-Peter Bojar (b. 1967) who works in the Department of Mineralogy, Universalmuseum Joanneum, Graz, Austria. Dr. Bojar is *Author for correspondence: Nikita V. Chukanov, Email: [email protected] a geoscientist who has contributed in many areas of Earth Science Cite this article: Chukanov N.V., Möhn G., Zubkova N.V., Ksenofontov D.A., Pekov I.V., (e.g. Bojar et al., 2009, 2013). In particular, he is the Senior author ⋅ Agakhanov A.A., Britvin S.N. and Desor J. (2020) Bojarite, Cu3(N3C2H2)3(OH)Cl2 6H2O, of the discoveries of several new mineral species, including two N- a new mineral species with a microporous metal–organic framework from the guano deposit at Pabellón de Pica, Iquique Province, Chile. Mineralogical Magazine 84, and Cu-bearing minerals from Pabellón de Pica Mountain, ammi- 921–927. https://doi.org/10.1180/mgm.2020.85 neite and joanneumite (Bojar et al., 2010, 2017).

© The Author(s), 2020. Published by Cambridge University Press on behalf of The Mineralogical Society of Great Britain and Ireland 922 Nikita V. Chukanov et al.

The new mineral and its name have been approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association (IMA2020-037, Chukanov et al., 2020b). The holotype specimen is deposited in the collection of the Fersman Mineralogical Museum of the Russian Academy of Sciences, Moscow, Russia with the registra- tion number 5574/1.

Occurrence, general appearance and physical properties Bojarite occurs in a guano deposit on the lower part of the steep southern slope of the Pabellón de Pica Mountain. It forms fine- grained porous aggregates up to 1 mm × 3 mm × 5 mm typically combined in interrupted earthy crusts (Fig. 1), which are composed of pseudomorphs after chanabayaite aggregates (Fig. 2) and overgrow the host amphibole gabbro or granular aggregates consisting of sal- ammoniac, halite and minor nitratine and an unidentified Mn oxide. Aggregates of bojarite are opaque and dull due to the fine- grained character. The colour and are blue. The Mohs hard- Fig. 2. Pseudomorphs of bojarite after radiated aggregates of chanabayaite crystals. ness is 2 (for aggregates). Bojarite is brittle. Density could not be Field of view: 1.7 mm wide, fragment of a sample collected by G.M. measured due to the porosity of the fine-grained bojarite aggregates. –3 Density calculated using the empirical formula is 2.057 g cm . Raman spectroscopy Bojarite is optically isotropic and n = 1.635(2) (λ = 589 nm). Under the polarising microscope, the mineral is pale blue and The Raman spectrum of a randomly oriented bojarite sample non-pleochroic. (Fig. 4) was obtained using a spectrometer based on a Horiba XploRA Raman microscope with a 532 nm 3B DPSS Nd:YAG laser. The spectrum was recorded in the range from 100 to Infrared spectroscopy – – 4000 cm 1 with a diffraction grating of 1800 gr mm 1. Laser radi- In order to obtain the infrared (IR) absorption spectrum (Fig. 3), ation with the output power of 20–25 mW was attenuated to 1%. a powdered sample of bojarite was mixed with dried KBr, pelle- The diameter of the focal spot on the sample was <5 μm. The tised, and analysed using an ALPHA FTIR spectrometer back-scattered Raman signal was collected with a 100× objective; – (Bruker Optics) in the range 360–4000 cm 1 with a resolution signal acquisition time for a single scan of the spectral range was – of 4 cm 1. A total of 16 scans were collected. The IR spectrum 66 s, and the signal was averaged over 4 scans. No sample damage of an analogous pellet of pure KBr was used as a reference. was observed under these conditions. The assignment of absorption bands made in accordance with The assignment of the Raman bands is nearly the same as the – Grinshtein et al. (1970), Nakamoto (2008, 2009), Chukanov et al. assignment of the IR bands. The bands at 3300–3500 cm 1 are – (2015a, 2018) and Chukanov and Chervonnyi (2016) is given in attributed to O–H stretching vibrations; 3148 cm 1 to C–H – Table 1. Infrared bands of chanabayaite are given in Table 1 for stretching vibrations; and 1600–1700 cm 1 to bending vibrations comparison. of H2O molecules (the splitting of this band corresponding to a – The broad bands at 1751 and 2096 cm 1 may correspond to nondegenerate mode indicates the presence of two kinds of acid groups, which could arise for example, as a result of partial H2O molecules, in accordance with structural data). The bands – protonation of triazolate anions in accordance with the dynamic at 990–1520 cm 1 are attributed to in-plane stretching and – – – equilibrium C N H +H O ↔ C N H +OH . mixed vibrations of the 1,2,4-triazole ring; 899 cm 1 to in-plane 2 3 2 2 2 3 3 – The IR spectrum of bojarite is distinct and can be used as a bending vibrations of the 1,2,4-triazole ring; and 677 cm 1 to very reliable diagnostic feature of this mineral. out-of-plane bending vibrations of the 1,2,4-triazole ring. The – bands at 463, 254 and 152 cm 1 are tentatively assigned to lattice modes with significant contribution of Cu–O, Cu–N and Cu–Cl stretching vibrations, respectively.

Chemical data Chemical data (mean of three electron microprobe analyses for Na, Mg, Fe, Cu and Cl) were obtained using an electron micro- probe (energy dispersive spectroscopy mode, 20 kV, 600 pA, beam rastered on an area 10 μm×10 μm in order to minimise unstable sample damage). Attempts to use wavelength dispersive spectroscopy, with higher beam current, were unsuccessful because of the instability of the mineral. Hydrogen, N and C were analysed by gas chromatography of products of ignition at 1200°C. Structural data and chemical tests show the absence of 2– Fig. 1. Blue interrupted crusts of bojarite on an aggregate of salammoniac–halite. Dark the CO3 anion. All carbon belongs to the triazolate anion, – areas are very thin films of an unidentified Mn oxide. Field of view: 7 cm wide, holotype. (N3C2H2) . Analytical data are given in Table 2. Mineralogical Magazine 923

Fig. 3. Powder infrared absorption spectrum of bojarite.

The empirical formula calculated based on the formula Bojarite is insoluble in and dissolves in dilute hydrochloric ⋅ Cu3(N3C2H2)3[Cl2(H2O)4](OH) 2H2O obtained from the structure acid without gas evolution. Reactions of bojarite solution in 20% refinement data (see below) and three Cu+Mg+Fe+Na atoms per HCl with potassium hexacyanoferrate(II) and potassium hexacyano- formula unit is (Cu2.68Mg0.17Fe0.10Na0.05)Σ3(N3C2H2)2.755[(OH)] ferrate(III) show that all copper in the mineral is bivalent. ⋅ [Cl2.19(H2O)3.77(OH)0.04]Σ6 2.3H2O. Excessive Na, N, Cl and H2O as well as some deficiency of triazolate anions may be due to analytical errors. The simplified X-ray diffraction and crystal structure ⋅ formula is (Cu,Mg,Fe)3(N3C2H2)3(OH)[(H2O),Cl]6 2H2O. The Single-crystal X-ray diffraction studies of bojarite could not be ⋅ idealised formula is Cu3(N3C2H2)3(OH)[Cl2(H2O)4] 2H2O carried-out due to the absence of suitable single crystals: aggre- which requires Cu 32.26, Cl 12.00, N 21.34, C 12.20, H 3.24, O gates of bojarite (Figs 1, 2) are polycrystalline and consist of 18.96, total 100 wt.%. very small imperfect individuals. For this reason, the crystal

– Table 1. Wavenumbers (cm 1) of absorption bands in the IR spectra of bojarite and chanabayaite and their assignment.

Bojarite Chanabayaite Assignment

3445sh, 3355s, 3230sh, 2950sh 3430s, 3369s O–H stretching vibrations 3310s, 3253s, 3233s N–H stretching vibrations 3147, 3138 3173, 3150sh C–H stretching vibrations of the 1,2,4–triazolate anion 1700 to 2900 (multiple weak bands) 1700 to 2900 (multiple weak bands) Overtones and combination modes 1646, 1646, 1400, 1269 NH3 bending vibrations 1627 1622 Bending vibrations of H2O molecules 1514s, 1392, 1349w, 1296s, 1206, 1172s, 1101s, 1512s, 1395, 1299s, 1198, 1173s, 1095s, In-plane stretching and mixed vibrations of the 1,2,4-triazole ring 1040w, 1001 1035w, 1004 885 887 In-plane bending vibrations of 1,2,4-triazole ring 667 667 Out-of-plane bending vibrations of 1,2,4-triazole ring Below 630 Below 630 Cu–O and Cu–N stretching vibrations and librational vibrations of H2O molecules

Note: w – weak band, s – strong band, sh – shoulder. 924 Nikita V. Chukanov et al.

Fig. 4. Raman spectrum of bojarite.

– structure of bojarite was refined based on powder X-ray diffrac- [Cu3(trz)3(OH)]Cl2·6H2O(trz = 1,2,4-triazole anion N3C2H2) tion data, using the Rietveld method. (Yamada et al., 2011) as the starting point. Hydrogen atoms Powder X-ray diffraction data of bojarite (Table 3, Fig. 5) were were not located. Data treatment and the Rietveld structure ana- collected with a Rigaku R-AXIS Rapid II single-crystal diffracto- lysis were carried using the JANA2006 program package meter equipped with cylindrical image plate detector (radius (Petříček et al., 2006). The profiles were modelled using a 127.4 mm) using Debye-Scherrer geometry, CoKα radiation pseudo-Voigt function. The structure was refined in isotropic (rotating anode with VariMAX microfocus optics), at the acceler- approximation of atomic displacements. Only Cu and Cl sites ating voltage of 40 kV, current of 15 mA and exposure of 15 min. were allowed to move whereas Uiso was refined for all atomic Angular resolution of the detector is 0.045° (for 2θ) and pixel size sites. The structural analysis was complemented by addition of is 0.1 mm. The data were integrated using the software package halite, NaCl, (Abrahams and Bernstein, 1965) and belloite, Cu Osc2Tab (Britvin et al., 2017). (OH)Cl, (Effenberger, 1984) as impurities, to account for a few Refinement of the crystal structure of bojarite was performed low-intensity diffraction peaks in the powder pattern. The relative by the Rietveld method using the model for synthetic contents of the three minerals in the powder mixture are: 92% of bojarite, 6% of belloite and 2% of halite. The final agreement fac- tors are: Rp = 0.0225, Rwp = 0.0310 and Robs = 0.0417. The refined Table 2. Chemical composition of bojarite. parameters of the cubic unit cell are a = 24.8047(5) Å and V = 15,261.6(5) Å3; space group Fd3c and Z = 32. The observed and Constituent Wt.% Range S.D. Probe standard calculated powder XRD diagrams demonstrate a good agreement Na 0.22 0–0.37 0.16 Albite (Fig. 5). Coordinates and thermal displacement parameters of Mg 0.74 0.70–0.79 0.12 Diopside atoms are given in Table 4 and selected interatomic distances in Fe 0.99 0.81–1.19 0.16 Fe Table 5. The crystallographic information file has been deposited Cu 29.73 28.84–30.65 0.89 Cu with the Principal Editor of Mineralogical Magazine and is avail- Cl 13.62 13.02–14.13 0.46 NaCl N 20.4 ± 0.5 able as Supplementary material (see below). C 11.6 ± 0.5 H 3.3 ± 0.2 O 19.93* Total 100.53 Discussion

Note: Contents of other elements with atomic numbers > 6 are below detection limits. Bojarite is a natural analogue of the synthetic compound – ⋅ *Calculated by stoichiometry; S.D. standard deviation. [Cu3(trz)3(OH)]Cl2 6H2O and is isostructural with Mineralogical Magazine 925

Table 3. Powder X-ray diffraction data of bojarite.

Iobs dobs (Å) Icalc* dcalc (Å) hkl Iobs dobs (Å) Icalc* dcalc (Å) hkl

31 8.83 22 8.769 220 6 1.936 2 1.936 886 100 7.19 100 7.160 222 8 1.895 5, 4 1.896, 1.891 11.7.1, 10.6.6 35 6.23 24 6.201 400 6 1.854 4 1.853 13.3.1 28 5.077 17 5.063 422 4 1.829 1 1.828 12.6.2 14 4.394 2 4.384 440 4 1.790 2 1.790 888 28 4.194 15 4.192 531 6 1.774 3, 2 1.776, 1.771 11.7.5, 12.6.4 40 4.143 32 4.134 442 4 1.754 1 1.753 10.10.0 15 3.744 6 3.739 622 5 1.740 2, 2 1.740, 1.736 11.9.1, 14.2.2 23 3.584 15 3.580 444 3 1.719 1 1.719 12.8.0 11 3.317 4 3.314 642 3 1.687 1 1.687 10.10.4 10 3.225 1 3.229 731 3 1.645 1, 1 1.646, 1.642 13.7.3, 10.8.8 9 3.103 1 3.100 800 3 1.628 1 1.628 14.6.0 17 3.010 11 3.008 644 4 1.616 1, 2 1.618, 1.614 15.3.1, 10.10.6 28 2.865 1, 24 2.923, 2.864 660, 751 2 1.566 1 1.565 15.5.1 14 2.824 2 2.845 662 3 1.550 1 1.550 16.0.0 14 2.774 7 2.773 840 3 1.539 1, 1 1.541, 1.538 13.9.3, 12.10.4 22 2.723 16, 2 2.722, 2.706 753, 842 3 1.527 1 1.526 10.10.8 13 2.644 8 2.644 664 3 1.504 2 1.504 16.4.0 10 2.602 3 2.600 931 2 1.475 1 1.474 15.7.3 7 2.533 1 2.531 844 3 1.454 2, 1 1.454, 1.451 13.11.1, 12.12.2 7 2.431 1 2.432 10.2.0 4 1.434 2, 1 1.434, 1.432 13.9.7, 14.10.2 16 2.396 12, 5 2.397, 2.386 951, 10.2.0 2 1.415 1 1.415 15.9.1 6 2.304 2 2.303 864 2 1.398 1 1.397 15.9.3 5 2.193 1 2.192 880 2 1.380 1 1.380 17.5.3 12 2.167 9, 1 2.167, 2.158 11.3.1, 882 2 1.370 1 1.369 18.2.0 8 2.127 5 2.126 10.6.0 2 1.361 2 1.361 14.10.6 5 2.102 1, 1 2.103, 2.096 973, 10.6.2 2 1.347 1 1.347 17.7.1 5 2.068 1 2.067 12.0.0 2 1.336 1 1.337 14.12.2 4 2.047 1 2.045 11.5.1 2 1.330 1 1.331 15.11.1 7 2.012 4 2.011 10.6.4 2 1.316 1, 1 1.316, 1.314 15.11.3, 18.4.4 10 1.994 5 1.992 11.5.3 2 1.302 1 1.301 17.7.5 4 1.964 1 1.960 12.4.0 2 1.288 1 1.287 17.9.1

*For the calculated pattern only reflections with intensities ≥1 are given. The strongest lines are given in bold.

Fig. 5. Observed and calculated powder X-ray diffraction patterns of bojarite with admixed belloite (B) and halite (H). The solid line corresponds to calculated data. The crosses correspond to the observed pattern. The vertical bars mark all possible Bragg reflections. The difference between the observed and calculated patterns is shown by the curve at the bottom. 926 Nikita V. Chukanov et al.

2 Table 4. Сoordinates and isotropic parameters (Uiso in Å ) of atoms and site occupancy factors (s.o.f.) in the structure of bojarite.

Site xyZUiso s.o.f.

Cu 0.80639(2) ½ 0.05639(2) 0.0438(4) 1 Cl 0.87429(15) 0.42900(15) –0.01232(14) 0.123(2) 0.333 O1 = OH ¾ ½ 0 0.105(4) 1 O2 = H2O 0.8583 0.438 –0.0009 0.073(3) 0.667 O3 = H2O 0.9726 0.4726 –0.0274 0.133(3) 1 N1 0.8636 ½ 0.1136 0.0294(15) 1 N2 0.8394 0.5634 0.0207 0.0502(14) 1 C 0.883 0.5922 0.0317 0.0219(14) 1

Table 5. Selected interatomic distances (Å) in the structure of bojarite.

Cu–O1 1.9781(5) Triazole ring Cu–N2 1.9817(3) ×2 C–N1 1.352 ×2 Cu–N1 2.0069(5) C–N2 1.325 ×2 Cu–Cl / O2 2.974(3) / 2.4581(4) ×2 N1–N2 1.373

[Cu (trz) (OH)]Br ·6H O where trz denotes 1,2,4-triazolate 3 3 2 2 Fig. 6. A fragment of the crystal structure of bojarite. Cu atoms are light blue, O red, anion (Yamada et al., 2011). The crystal structure of bojarite is Cl green, N dark blue and C black. built by equilateral triangular units involving Cu2+ cations: three Cu2+ cations of the unit are linked by an oxygen atom (O1 = OH – – – with the bond-valence sum of 1.32) at the centre of the ligand, and halogen anions F ,Cl and Br are known to stabilise equilateral triangle and connected to two nitrogen atoms of crystal structures of triazolate complexes. the triazole ring (Fig. 6), leading to the formation of the Bojarite is a member of the transformation series triazolite 2+ ⋅ → [Cu3(trz)3(OH)] building block reported for the synthetic com- NaCu2(N3C2H2)2(NH3)2Cl3 4H2O chanabayaite Cu2(N3C2H2)2 □ → ⋅ pound by Yamada et al. (2011). The third nitrogen atom of each Cl(NH3,Cl,H2O, )4 bojarite Cu3(N3C2H2)3(OH)Cl2 6H2O. trz group of the triangular unit coordinates to an adjacent triangu- On the first stage of this transformation (pseudomorphisation), lar unit, leading to the formation of a three-dimensional network. partial dehydration, loss of NaCl and evolution of NH3 took The Cu2+ cation is coordinated by three N atoms, one O atom (of place: chanabayaite replaces triazolite (Chukanov et al., 2018). On – the OH group) and, in a statistically mixed arrangement (see the second stage, removal of the rest of NH3 was accompanied – Table 4), either two Cl anions (site occupancy factor = 0.333) or, by hydration: a pseudomorph of bojarite after chanabayaite is in the adjacent O2 site, two H2O molecules (s.o.f. = 0.667), with formed. Thus, the 1,2,4-triazolate anion is the most stable and elongate Cu–(Cl,H2O) distances (Table 5). The fragment of the immobile unit in these minerals. 2+ crystal structure containing the [Cu3(trz)3(OH)] building block with additional Cl anions and three additional trz ligands is Acknowledgements. The authors are grateful to the referees Peter Leverett and shown in Fig. 6. Two additional H O molecules per formula unit Sándor Szakáll for useful comments. This work was supported by the Russian 2 Foundation for Basic Research, grant no. 18-29-12007-mk in part of the crystal are located at the O3 site, in cavities of the positively charged three- 2+ structure study. A part of this work (IR spectroscopy and chemical analyses) dimensional network formed by the [Cu3(trz)3(OH)] building was carried-out in accordance with the state task, state registration number blocks. These extra-framework H2O molecules can be deleted ААAА-А19-119092390076-7. The authors thank the X-ray Diffraction Centre of from the structure on heating to 150°C without destruction of Saint-Petersburg State University for instrumental and computational resources. the framework (Yamada et al., 2011). 2+ Supplementary material. To view supplementary material for this article, Note that the [Cu3(trz)3(OH)] building block has been found in a number of synthetic compounds (Ouellette et al., 2011 and please visit https://doi.org/10.1180/mgm.2020.85 references therein). Thus, for example, the same building block, a topologically similar three-dimensional framework, the same space group and close unit cell parameters were reported for the References II ⋅ compounds [Cu3 (trz)3(OH)3(H2O)4] 4.5H2O (cubic, space group Abrahams S.C. and Bernstein J.L. (1965) Accuracy of an automatic diffractom-  3 Fd3c, a = 24.7233(4) Å, V = 15,111.9(4) Å and Z = 32) and eter. Measurement of the sodium chloride structure factors. Acta II I  18 – [Cu3 (trz)3OH][Cu2Br4](cubic,spacegroupFd3c, a = 24.5326(6) Å, Crystallographica, , 926 932. V = 14,764.9(6) Å3 and Z = 32) which are structurally close to Appleton J.D. and Nothold A.J.G. (2002) Local phosphate resources for sus- bojarite and are characterised by the same cationic framework tainable development of Central and South America. Economic Minerals 2n+ and Geochemical Baseline Programme Report CR/02/122/N. British substructure {Cu3(OH)(trz)3}n (Ouellette et al., 2011). A review of metal coordination compounds with 1,2,4-triazole Geological Survey, 95 pp. Bojar H.-P., Ottner F., Bojar A.V., Grigorescu D. and Perşoiu P. (2009) Stable derivatives as ligands is given by Haasnoot (2000). In the 5-mem- – – isotope and mineralogical investigations on clays from the Late Cretaceous bered 1,2,4-triazole ring all C N and N N bonds are conjugated sequences, Haţeg Basin, Romania. Applied Clay Science, 45, 155–163. – and have fractional bond orders between 1 and 2. As a result, C N Bojar H.-P., Walter F., Baumgartner J. and Färber G. (2010) Ammineite, – and N N bond lengths are rather short (typically, between 1.30 CuCl2(NH3)2, a new species containing an ammine complex: mineral and 1.38 Å). Copper and zinc show high affinity for the tetrazolate data and crystal structure. The Canadian Mineralogist, 48, 1359–1371. Mineralogical Magazine 927

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