Synthesis, characterization and magnetic properties of four new organically templated metal sulfates [C5H14N2][M(II)(H2O)6](SO4)2, (M(II) = Mn, Fe, Co, Ni).

International audienceA series of novel organically templated metal sulfates, [C(5)H(14)N(2)][M(II)(H(2)O)(6)](SO(4))(2) with (M(II) = Mn (1), Fe (2), Co (3) and Ni (4)), have been successfully synthesized by slow evaporation and characterized by single-crystal X-ray diffraction as well as with infrared spectroscopy, thermogravimetric analysis and magnetic measurements. All compounds were prepared using a racemic source of the 2-methylpiperazine and they crystallized in the monoclinic systems, P2(1)/n for (1, 3) and P2(1)/c for (2,4). Crystal data are as follows: [C(5)H(14)N(2)][Mn(H(2)O)(6)](SO(4))(2), a = 6.6385(10) Å, b = 11.0448(2) Å, c = 12.6418(2) Å, β = 101.903(10)°, V = 906.98(3) Å(3), Z = 2; [C(5)H(14)N(2)][Fe(H(2)O)(6)](SO(4))(2), a = 10.9273(2) Å, b = 7.8620(10) Å, c = 11.7845(3) Å, β = 116.733(10)°, V = 904.20(3) Å(3), Z = 2; [C(5)H(14)N(2)][Co(H(2)O)(6)](SO(4))(2), a = 6.5710(2) Å, b = 10.9078(3) Å, c = 12.5518(3) Å, β = 101.547(2)°, V = 881.44(4) Å(3), Z = 2; [C(5)H(14)N(2)][Ni(H(2)O)(6)](SO(4))(2), a = 10.8328(2) Å, b = 7.8443(10) Å, c = 11.6790(2) Å, β = 116.826(10)°, V = 885.63(2) Å(3), Z = 2. The three-dimensional structure networks for these compounds consist of isolated [M(II)(H(2)O)(6)](2+) and [C(5)H(14)N(2)](2+) cations and (SO(4))(2-) anions linked by hydrogen-bonds only. The use of racemic 2-methylpiperazine results in crystallographic disorder of the amines and creation of inversion centers. The magnetic measurements indicate that the Mn complex (1) is paramagnetic, while compounds 2, 3 and 4, (M(II) = Fe, Co, Ni respectively) exhibit single ion anisotropy

Synthesis, crystal structures and thermal behaviour of organic-inorganic hybrids incorporating a chiral diamine

This manuscript represents part of collaborative work with a Tunisian solid state chemistry lab. --author-supplied descriptio

Crystal structure and semiconductor properties of copper(II) complex incorporating chiral (R)-(+)-alpha-Ethylbenzylammonium cations:[(R)-C9H14N](3)[CuBr4]center dot Br.

International audienceThe molecular organic-inorganic hybrid halogenometallate [(R)-C9H14N](3)[CuBr4]center dot Br has been synthesized by a slow evaporation method. The single-crystal X-ray diffraction experiment evidences that [(R)-C9H14N](3)[CuBr4]center dot Br crystallizes in the monoclinic system with the non-centrosymmetric space group P2(1) at T = 150K. The compound displays a zero-dimensional (0D) structure which consists in three chiral [(R)-C9H14N](+) cations, one anionic [CuBr4](2-) and free Br- ion. The structure analysis reveals that the Cu(II) has an intermediate geometry between regular tetrahedron (T-d) and square planar (D-4h). In the crystal structure, the cations and anions are arranged in alternating stacks which are interconnected via hydrogen bonding contacts N-H center dot center dot center dot Br. This hybrid compound presents good thermal stability up to 370 K. The DSC and electric measurements show that no phase transition occurs in the compound over the temperature range 223-423 K. Optical absorption measurements suggest that [(R)-C9H14N](3)[CuBr4]center dot Br has a narrow direct optical band gap (E-g) of similar to 2.15 eV which makes it a promising material in optoelectronic devices

Crystal structure, phase transition and thermal decomposition of a copper (II) sulfate dihydrate containing a chiral organic ammonium cation

International audienceThe directed synthesis of a new organically templated copper sulfate has been achieved through the use of chiral organic amine. Reaction containing S-2-methylpiperazine, CuSO(4)center dot 5H(2)O, H(2)SO4 and H(2)O were subjected to the slow evaporation conditions, resulting in the growth of single crystals of [(S)-C(5)H(14)N(2)][ Cu(SO(4))(2)(H(2)O)(4)]center dot(H(2)O)(2). At room temperature, it crystallises in the non-centrosymmetric space group P2(1), Z = 2, a = 7.5583(5), b = 10.1721(6), c = 10.7974(7) angstrom, beta = 94.425(4)degrees and V = 827.67(9) angstrom(3). The structure consists of trimeric units [Cu(SO(4))(2)(H(2)O)(4)](2) , [(S)-C(5)H(14)N(2)](2+) cations and free water molecules, donating hydrogen bonds that stabilize the three-dimensional structure and filling space. The title compound undergoes a reversible phase transition of first-order, which is detected by differential-scanning calorimetry at 347.2 K in the heating cycle and at 318.9 K in the cooling cycle. The evolution of the dielectric constant as a function of frequency and temperature revealed this transition to be ferro-paraelectric. Thermogravimetric analyses indicate that its decomposition proceeds through three stages giving rise to the copper oxide

Crystal structures of two enantiomorphous 2-ethylpiperazinediium hexaaquacopper sulfates (R or S)-C5H14N2 Cu(H2O)(6) (SO4)(2)

International audienceTwo new non-centrosymmetric copper sulfates are synthesized under slow evaporation conditions through the use of enantiomorphically pure sources of either (R)-2-methylpiperazine or (S)-2-methylpiperazine. Both crystallize in the non-centrosymmetric P2(1) space group, crystal data for [(R)-C5H14N2][Cu(H2O)(6)](SO4)(2) (I), a = 6.5276(2) , b = 11.1955(3) , c = 12.4559(4) , beta = 101.196(2)A degrees, Z = 2, V = 892.95(5) (3) and [(S)-C5H14N2][Cu(H2O)(6)](SO4)(2) (II), a = 6.5188(2) , b = 11.1786(2) , c = 12.4365(3) , beta = 101.205(1)A degrees, Z = 2, V = 888.99(4) (3). The three-dimensional structure networks for these compounds consist of isolated [Cu(H2O)(6)](2+) and [(R)-C5H14N2](2+) or [(S)-C5H14N2](2+) cations and SO (4) (2-) anions linked only by hydrogen bonds. The Cu atom is in a slightly distorted octahedral coordination environment. The crystal packings are influenced by cation-to-anion N-HaEuro broken vertical bar O and OW-HaEuro broken vertical bar O hydrogen bonds leading to an open framework structures

Synthesis, crystal structures, high-temperatures phase transition, optic and electric properties of hybrid halogenometallates: [(CH3)(3)N(CH2)(2)Br](2)[(MBr4)-Br-II] (M = Cu, Zn)

International audienceTwo organic-inorganic hybrid compounds [(CH3)(3)N(CH2)(2)Br](2) [(MBr4)-Br-II] (M = Cu, Zn); ((2-bromoethyl) trimethylammonium cations [Br(CH2)(2)N(CH3)(3)](+)) were successfully synthesized with slow evaporation conditions. The structures of the two compounds were determined using single-crystal X-ray diffraction. These materials crystallize in the monoclinic system, space group P2(1)/c. In the molecular arrangement, the [(MBr4)-Br-II](2-) anions are linked to the organic cations through C-H center dot center dot center dot Br hydrogen bonds to form cationanion-cation molecular units, giving a three-dimensional network. The phase transitions, electric and optical properties of [(CH3)(3)N(CH2)(2)Br](2) [CuBr4] (1) and [(CH3)(3)N(CH2)(2)Br](2) [ZnBr4] (2) were carefully characterized. Based on these results, both compounds underwent phase transitions at T-1 = 368 K and T-2 = 385K for (1) and at T-1 = 283K, T-2 = 330K, T-3 = 368K and T-4 = 402K for (2). The optical and electrical properties allow to determinate the gap energy and to characterize the phase transitions. These studies pave the pathway to explore new types of high-phase transition materials with targeted properties for electric and semiconductor applications

1,4,8,11-Tetraazoniacyclotetradecane tetrakis(hydrogensulfate)

In the title salt, C10H28N44+·4HSO4−, the cation lies about an inversion center. In the crystal, O—H...O and N—H...O hydrogen bonds connect the anions and cations, forming a three-dimensional network

Synthesis, crystal structures and thermal behaviour of organic-inorganic hybrids incorporating a chiral diamine

International audienceA series of noncentrosymmetric metal sulfates [R-C5H14N2][MII(H2O)6](SO4)2 and [S-C5H14N2][MII(H2O)6](SO4)2 (MII = Mn (1, 2), Fe (3, 4), Co (5, 6) and Ni (7, 8)) have been synthesized by slow evaporation conditions through the use of enantiomorphically pure sources of either R-2-methylpiperazine (R)-C5H12N2 or S-2-methylpiperazine (S)-C5H12N2. These materials crystallize in the polar, noncentrosymmetric space group P21 (No. 4), crystal class 2 (C2). Isolated [MII(H2O)6]2+, [(R)-C5H14N2]2+ or [(S)-C5H14N2]2+ cations and (SO4)2− anions linked together via two types of hydrogen bonds, Ow-Hw⋯O and N-H⋯O, from which supramolecular structures are formed. The use of single enantiomer of either R-2-methylpiperazine or S-2-methylpiperazine precludes inversion symmetry within the crystal lattices and forces crystallization in noncentrosymmetric structures. Compounds 1-8 were characterized using single crystal X-ray diffraction, infrared spectroscopy and thermal analyses. The structural arrangements and the intermolecular interactions such as hydrogen-bonding are discussed