Several silicate-minerals, such as ardennite – Mn2+4MgAl5[Si5(As5+,V5+)O22](OH)6, Z = 2, tiragalloite – Mn2+4[Si3As5+O12(OH)], Z = 4 and medaite – Mn2+6[Si5(V5+,As5+)O18(OH)], Z = 4 possess (V5+,As5+,P5+)O4 tetrahedra. Using electron-microprobe analysis (EMPA) and single-crystal X-ray diffraction methods, the crystal chemistry of ardennite from Salam-Château, Belgium and the Vernetto mine, Italy, tiragalloite from the Gambatesa mine, Italy, and medaite from the Molinello mine, Italy and the Fianel mine, Switzerland, were studied. Structure refinements converged to R1 values of 2.10–5.67%. According to chemical analysis, the Σ(As+V+P) content increases with decreasing Si content. Thus, Si replaces pentavalent cations in tetrahedral coordination. The (As5+,V5+,P5+,Si4+)O4 tetrahedra are categorized by their connections to SiO4 tetrahedra. The (As5+,V5+,P5+,Si4+)O4 tetrahedron of ardennite is isolated, and those of tiragalloite and medaite terminate a tetrahedral chain. The <T–O> of the isolated (As5+,V5+,P5+,Si4+)O4 tetrahedron shows a positive correlation with the mean ionic radius. For (As5+,V5+,P5+,Si4+)O4 tetrahedra with one T–O–T link, <T–O> and mean ionic radius are also correlated. In addition, the longest bridging T–O bond occurs between (As,V,P,Si)O4 and the adjacent SiO4 tetrahedron. The bridging O atom is over-bonded to satisfy the charge requirement of Σ(As+V+Si).

The new mineral species braccoite, ideally NaMn2+5[Si5AsO17(OH)](OH), has been discovered in the Valletta mine dumps, in Maira Valley, Cuneo province, Piedmont, Italy. Its origin is probably related to the reaction between ore minerals and hydrothermal fluids. It occurs as subhedral crystals in brown-red coloured thin masses, with a pale-yellow streak and vitreous to resinous lustre. Braccoite is associated with tiragalloite, for which new data are provided, as well as gamagarite, hematite, manganberzeliite, palenzonaite, quartz, saneroite, tokyoite, unidentified Mn oxides, organic compounds, and Mn arsenates and silicates under study.

Braccoite is biaxial positive with refractive indices α = 1.749(1), β = 1.750(1), γ = 1.760(1). It is triclinic, space group P1̄, with a = 9.7354(4), b = 9.9572(3), c = 9.0657(3) Å, α = 92.691(2), β = 117.057(4), γ = 105.323(3)°, V = 740.37(4) Å3 and Z = 2. Its calculated density is 3.56 g/cm3. The ten strongest diffraction lines of the observed powder X-ray diffraction (XRD) pattern are [d in Å, (I), (hkl)]: 3.055 (69)(22̄1), 3.042 (43)(102), 3.012 (65)(32̄1̄), 2.985 (55)(23̄1̄), 2.825 (100)(213̄), 2.708 (92)(220), 2.627 (43)(23̄2̄), 2.381 (58)(41̄1̄), 2.226 (25)(214̄) and 1.680 (433̄)(36). Chemical analyses by wavelength-dispersive spectroscopy electron microprobe gave (wt.%): Na2O 4.06, CaO 0.05, MnO 41.76, MgO 0.96, Al2O3 0.04, CuO 0.02, SiO239.73, As2O5 6.87, V2O5 1.43, SO3 0.01 and F 0.04. H2O 2.20 was calculated on the basis of 2OH groups p.f.u. Raman spectroscopy confirmed the presence of (SiO4)4–, (AsO4)3– and OH groups. The empirical formula, calculated on the basis of Σ cations-(Na,K) = 11 p.f.u., in agreement with the results of the crystal structure, is Na1.06(Mn2+4.46Mn3+0.32Mg0.19V3+0.01Al0.01Ca0.01)[Si5(As0.48Si0.37V5+0.15)O17(OH)](OH0.98F0.02); the simplified formula is Na(Mn,Mg,Al,Ca)5[Si5(As,V,Si)O17(OH)](OH,F).

Single-crystal XRD allowed the structure to be solved by direct methods and revealed that braccoite is the As-dominant analogue of saneroite. The structure model was refined on the basis of 4389 observed reflections to R1 = 3.47%. Braccoite is named in honour of Dr Roberto Bracco (b. 1959), a systematic minerals collector with a special interest in manganese minerals. The new mineral was approved by the International Mineralogical Association Commission on New Minerals, Nomenclature and Classification (IMA 2013-093).