The crystal chemistry of two hausmannite samples from the Kalahari manganese field (KMF), South Africa, was studied using electron-probe microanalysis (EPMA), single-crystal X-ray diffraction (SCXRD) for sample-a, and high-resolution powder X-ray diffraction (HRPXRD) for sample-b, and a synthetic Mn 3 O 4 (97% purity) sample-c as a reference point. Hausmannite samples from the KMF were reported to be either magnetic or non-magnetic with a general formula AB 2 O 4 . The EPMA composition for sample-a is [Mn 2+ 0.88 Mg 2+ 0.11 Fe 2+ 0.01 ] Σ1.00 Mn 3+ 2.00 O 4 compared to Mn 2+ Mn 3+ 2 O 4 obtained by refinement. The single-crystal structure refinement in the tetragonal space groupI4 1 /amd gave R1 = 0.0215 for 669 independently observed reflections. The unit-cell parameters are a = b = 5.7556(6), c = 9.443(1) Å, and V = 312.80(7) Å 3 . The Jahn-Teller elongated Mn 3+ O 6 octahedron of the M site consists of M-O × 4 = 1.9272(5), M-O × 2 = 2.2843(7), and an average [6] = 2.0462(2) Å, whereas the Mn 2+ O 4 tetrahedron of the T site has T-O × 4 = 2.0367(8) Å. The site occupancy factors (sof ) are M(sof ) = 1.0 Mn (fixed, thereafter) and T(sof ) = 1.0008(2) Mn. The EPMA composition for sample-b is [Mn 0.99 Mg 0.01 ](Mn 1.52 Fe 0.48 )O 4 . The Rietveld refinement gave R (F 2 ) = 0.0368. The unit-cell parameters are a = b = 5.78144(1), c = 9.38346(3) Å, and V = 313.642(1) Å 3 . The octahedron has M-O × 4 = 1.9364(3), M-O × 2 = 2.2595(6), and average [6] = 2.0441(2) Å, whereas T-O × 4 = 2.0438(5) Å. The refinement gave T(sof ) = 0.820(9) Mn 2+ + 0.180(9) Fe 2+ and M(sof ) = 0.940(5) Mn 3+ + 0.060(5) Fe 3+ . Samples-a and -b are normal spinels with different amounts of substitutions at the M and T sites. The Jahn-Teller elongation, ∆(M-O), is smaller in sample-b because atom substitutions relieve strain compared to pure Mn 3 O 4 . Minerals 2019, 9, 343 2 of 16and in inverse spinels x = 1. A value of x = 2/3 corresponds to a random distribution of A and B atoms. Alternatively, an order parameter, Q, is used to express the degree of order [5]. The order parameter, Q, varies from Q = 1 for a completely ordered normal spinel to Q = 0 (where x = 2/3) for a random arrangement of cations to Q = −0.5 in inverse spinel. The relationship between Q and x is: Q = 1 -(3/2)x. Magnesioferrite, MgFe 2 O 4 , is partly inverse and partly normal, so it is one of the most interesting ferrite spinels [6][7][8].The structure of cubic spinels consists of T cations at 8a (1/8, 1/8, 1/8), M cations at 16d ( 1 /2 , 1 /2 , 1 /2 ), and O atoms on the body diagonals of a cube at 32e (u, u, u), where u is approximately 1 /4 in space group Fd3m. In a cubic spinel structure, there are only two structural variables (except displacement parameters): the a unit-cell parameter and the O atom positional parameter, u.Hausmannite, ideally Mn 3 O 4, is a normal spinel with a distorted tetragonal structure (Figure 1). End-member hausmannite structural formula is [4] [Mn 2+ ] [6] (Mn 2 3+ )O 4 . The T site may be occupied by divalent cations (e.g., Mn 2+ ...