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Magnetic susceptibilities, specific heat, and crystal structure of four S = 3/2, three-dimensional antiferromagnets
The zero-field, ac magnetic susceptibilities of single crystals of four S=3/2 trigonal salts containing the tris(1,2-diaminoethane)chromium(III) cation, [Cr(en)3]3+, and heat-capacity measurements on one of them, [Na(OH2)6][Cr(en)3]2Cl7, are reported. The crystal structures of two of them, [Na(OH2)6][Cr(en3]2Cl7 and [Na(OH)2)6][Cr(en)3]2Br6Cl, have been determined. They both belong to the trigonal P3¯cl space group, with a=11.513(2), c=15.566(6) Å; Z=2; and a=11.740(5), c=16.008(9) Å; Z=2, respectively, and contain discrete octahedral hexaquasodium (i) cations. The salt [K(OH2)6][Cr(en)3]2Cl7 appears to be isomorphous with its sodium analog, and [Cr(en)3]Cl3·3H2O belongs to the same space group. The magnetic measurements on the four salts extend over the temperature interval 60 mK to 4.2 K, and antiferromagnetic ordering is found in all of them. The zero-field-splitting energy is of the same order of magnitude as the magnetic exchange energy. The susceptibility data have been fitted with the parameters 2D/kB=-0.091(8) K, g?=1.994, g¿=1.988, and zJ/kB=-0.061(2) K for [Cr(en)3]Cl3·3H2O; 2D/kB=-0.058(8) K, g?=2.01, g¿=2.00, and zJ/kB=-0.068(4) K for [Na(OH2)6][Cr(en)3]2Cl7; 2D/kB =-0.060(8) K, g?=1.993, g¿=1.951, and zJ/kB=-0.046(4) K for [K(OH2)6][Cr(en)3]2Cl7; and 2D/kB=+0.064(8) K, g?=2.001, g¿=1.991, and zJ/kB=-0.066(4) K for [Na(OH2)6][Cr(en)3]2Br6Cl, where longitudinal (¿) and transverse (¿) refer to the unique threefold crystallographic axis. The ordering temperatures are 0.124(5), 0.116(5), 0.093(5), and 0.112(5) K, respectively. The easy axis for the chloride compounds lies parallel to the longitudinal axis, whereas the easy axis for the bromide lies in the transverse plane. Heat-capacity measurements on [Na(OH2)6][Cr(en)3]2Cl7 confirm that magnetic ordering takes place at 0.112(5) K. The heat-capacity curve and magnetic entropy calculations agree with the three-dimensional character of the ordering of an S=3/2, effective bcc magnetic lattice