Triazolite, NaCu₂(N₃C₂H₂)₂(NH₃)₂Cl₃·4H₂O, a new mineral species containing 1,2,4-triazolate anion, from a guano deposit at Pabellón de Pica, Iquique Province, Chile

Abstract

The new mineral triazolite is found in a guano deposit located on the Pabellón de Pica Mountain, Iquique Province, Tarapacá Region, Chile. Associated minerals are salammoniac, halite, dittmarite, joanneumite, chanabayaite, nitratine, natroxalate and möhnite. Triazolite occurs as deep blue prismatic crystals up to 0.1 mm × 0.15 mm × 0.75 mm and their radial aggregates up to 1.5 mm across. The mineral is brittle. Its Mohs hardness is 2.Dcalc= 2.028 g cm–3. The infrared spectrum shows the presence of 1,2,4-triazolate anion and ammonia and water molecules. Triazolite is optically biaxial (–), α = 1.582(4), β = 1.625(3), γ = 1.625(3) and 2Vmeas= 5(3)°. The chemical composition (electron-microprobe data for Cl, Na, Fe and Cu; H, C, N and S contents were measured by gas chromatography of products of ignition at 1200°C; wt.%) is: Na 4.91, Fe 1.51, Cu 22.06, Cl 19.80, S 1.4, C 7.7, H 4.4, N 24.2, O (calc.) 12.83, total 98.81. The empirical formula is Na1.14(Cu1.86Fe0.14)(Cl2.99S0.23)N9.23C3.43H23.34O4.29. The idealized formula is NaCu2(N3C2H2)2(NH3)2Cl3·4H2O. Triazolite is a metalorganic ammine complex in which 1,2,4-triazolate anion and ammonia molecule are ligands coordinating Cu2+. The crystal structure was solved by direct methods and refined toR= 0.0242 based on 4210 unique reflections withI> 2σ(I). Triazolite is orthorhombic, space groupP212121,a= 19.3575(5),b= 7.15718(19),c= 12.5020(4) Å,V= 1732.09(8) Å3andZ= 4. The eight strongest reflections of the powder X-ray diffraction pattern [d, Å (I,%) (hkl)] are: 10.22 (97) (101), 6.135 (40) (011), 5.696 (17) (301), 5.182 (59) (202), 5.119 (100) (211), 4.854 (19) (400), 3.752 (16) (312, 501), 3.294 (18) (221). Triazolite is named for the presence of 1,2,4-triazolate anion.

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

“…The assignment of absorption bands made in accordance with Grinshtein et al (1970), Nakamoto (2008, 2009), Chukanov et al (2015a, 2018) and Chukanov and Chervonnyi (2016) is given in Table 1. Infrared bands of chanabayaite are given in Table 1 for comparison.…”

“…Bojarite is a member of the transformation series triazolite NaCu 2 (N 3 C 2 H 2 ) 2 (NH 3 ) 2 Cl 3 ⋅4H 2 O → chanabayaite Cu 2 (N 3 C 2 H 2 ) 2 Cl(NH 3 ,Cl,H 2 O,□) 4 → bojarite Cu 3 (N 3 C 2 H 2 ) 3 (OH)Cl 2 ⋅6H 2 O. On the first stage of this transformation (pseudomorphisation), partial dehydration, loss of NaCl and evolution of NH 3 took place: chanabayaite replaces triazolite (Chukanov et al , 2018). On the second stage, removal of the rest of NH 3 was accompanied by hydration: a pseudomorph of bojarite after chanabayaite is formed.…”

“…The new mineral species bojarite, Cu 3 (N 3 C 2 H 2 ) 3 (OH)Cl 2 ⋅6H 2 O, described in this paper is the ninth new mineral species discovered in guano deposits at Pabellón de Pica, after ammineite CuCl 2 (NH 3 ) 2 (Bojar et al , 2010), joanneumite Cu(C 3 N 3 O 3 H 2 ) 2 (NH 3 ) 2 (Bojar et al , 2017), chanabayaite Cu 2 (N 3 C 2 H 2 ) 2 Cl(NH 3 ,Cl,H 2 O,□) 4 (Chukanov et al , 2015a), möhnite (NH 4 )K 2 Na(SO 4 ) 2 (Chukanov et al , 2015b), shilovite Cu(NH 3 ) 4 (NO 3 ) 2 (Chukanov et al , 2015c), antipinite KNa 3 Cu 2 (C 2 O 4 ) 4 (Chukanov et al , 2015d), triazolite NaCu 2 (N 3 C 2 H 2 ) 2 (NH 3 ) 2 Cl 3 ⋅4H 2 O (Zubkova et al , 2016; Chukanov et al , 2018) and ammoniotinsleyite (NH 4 ) 2 Al 2 (PO 4 ) 2 (OH)⋅2H 2 O (Chukanov et al , 2020a). All these minerals, except antipinite, contain nitrogen, most of them contain organic groups, and in seven new minerals from this locality Cu 2+ is a species-defining component.…”

Geomimetic approaches in the design and synthesis of metal-organic frameworks

“…An excellent illustration of this possibility is provided by the pair of related minerals chanabayaite [22] and triazolite (figure 2a) [21], discovered in Pabellón de Pica, Chile in 2015 and 2016, respectively, with triazolite also included among the minerals associated with the Carbon Mineral Challenge. In both cases, the naturally occurring crystalline specimens were of sufficiently high quality to allow for structure determination using single crystal X-ray diffraction, which for both minerals revealed 3D metal-organic framework structures unprecedented in the context of geochemistry.…”

Ammoniotinsleyite, (NH4)Al2(PO4)2(OH)⋅2H2O, a new mineral species from the guano deposit at Pabellón de Pica, Iquique Province, Chile

“…The guano deposit situated on Pabellón de Pica Mountain, 1.5 km south of Chanabaya village, Iquique Province, Tarapacá Region, Chile (20°55’S, 70°08’W) belongs to the famous belt of guano occurrences of the Atacama Desert stretching along the northern coast of Chile (Ericksen, 1981; Pankhurst and Herve, 2007; Appelton and Nothold, 2002; Bojar et al ., 2010). Pabellón de Pica is one of the most interesting mineralogical occurrences in this area being the type locality of several nitrogen-bearing and organic minerals: ammineite, CuCl 2 (NH 3 ) 2 (Bojar et al ., 2010), joanneumite, Cu(C 3 N 3 O 3 H 2 ) 2 (NH 3 ) 2 (Bojar et al ., 2017), chanabayaite, Cu 4 (N 3 C 2 H 2 ) 4 (NH 3 ) 4 Cl 2 (Cl,OH) 2 ⋅H 2 O (Chukanov et al ., 2015a), shilovite, Cu(NH 3 ) 4 (NO 3 ) 2 (Chukanov et al ., 2015b), antipinite, KNa 3 Cu 2 (C 2 O 4 ) 4 (Chukanov et al ., 2015c), möhnite, (NH 4 )K 2 Na(SO 4 ) 2 (Chukanov et al ., 2015d) and triazolite, NaCu 2 (N 3 C 2 H 2 ) 2 (NH 3 ) 2 Cl 3 ⋅4H 2 O (Chukanov et al ., 2018).…”