Reaction of(NH 4) 2MoOS 3 with CuBr and AgBr(molar ratio=1∶4∶1) in α-MePy produced dark red crystals of [MoOS 3Cu 4(α-MePy) 6Br 2]. The product was characterized by elemental analysis, IR and X-ray diffraction. It crystallizes in a triclinic system with space group P1 and unit cell parameters a=0.950 9(3) nm, b=1.066 8(2) nm, c=2.153 6(3) nm, α=94.846(9)°, β=92.054(7)°, γ=99.299(8)°, V=2.145 5(8) nm 3, Z=2, D c=1.828 g·cm -3, F(000)=1 168, μ=42.79 cm -1, R=0.049 and R w=0.051. The compound consists of a nido-shaped MoS 3Cu 3 cluster unit and a four-membered CuBrCuS ring by sharing the same Cu3—S3 bond. The Mo atom and the four Cu atoms adopt a distorted tetrahedral geometry coordination. The Mo…Cu1, Mo…Cu2 and Mo…Cu3 distances are 0.271 1(3), 0 269 8(2), and 0.268 1(1) nm, respectively.
Reaction of a preformed cluster （Et4N）2[MoS4（CuCN）2]·H2O（1） with acetic acid in MeCN gave rise to an interesting 2D polymeric cluster （Et4N）3 {[MoS4Cu2（μ-CN）]2（μ^1-CN）}·2MeCN （2）. Compound 2 was characterized by elemental analysis, IR spectrum, and single crystal X-ray crystallography. In the structure of 2, the cluster core MoS4Cu2 of the cluster precursor 1 is retained and serves as a 3-connecting node to link equivalent nodes via single cyanide bridges, forming an anionic 2D （6,3） （honeycomb-like） network. The acetic acid induced aggregation of supramolecular compound 2 from the cluster precursor 1 suggests that this simple synthetic strategy be likely applicable to many related systems.
A calculation formula for determining the specific heat capacity of solid compound with an improved RD496-Ⅲ microcalorimeter was derived. The calorimetric constant and precision determined by the Joule effect were （63.901±0.030）μV/mW and 0.3% at 298.15 K, respectively, and the total disequilibrium heat has been measured by the Peltier effect. The specific heat capacities of two standard substances （benchmark benzoic acid and α-Al2O3） were obtained with this microcalorimeter, and the differences between their calculated values and literature values were less than 0.4%. Similarly, the specific heat capacities of thirteen solid complexes, RE（Et2dtc）3（phen） （RE=La, Pr, Nd, Sm-Lu, Et2dtc： diethyldithiocarbamate ion, phen： 1,10-phenanthroline） were gained, and their total deviations were within 1.0%. These values were plotted against the atomic numbers of rare-earth, which presents tripartite effect, suggesting a certain amount of covalent character in the bond of RE^3＋and ligands, according to Nephelauxetic effect of 4f electrons of rare earth ions.
GE, Hong-GuangJIAO, Bao-JuanSHUAI, QiLIU, Ming -YanCHEN, San-PingHU, Rong-ZuGAO, Sheng-Li
Reaction of [Et4N]2[Mo2S2(μ-S)2(edt)2] with CoCl2?6H2O and Phen in MeCN followed by recrystallization in DMSO/Et2O gave rise to dark-red block crystals of {[Co(Phen)3]- [Mo2S2(μ-S)2(edt)2]}2?(DMSO)2?(Et2O) 1 (C88H86Co2Mo4N12O3S18). 1 crystallizes in the monoclinic system, space group P21/c with a = 24.631(4), b = 16.117(3), c = 24.791(4) ?, β = 92.835o, V = 9829.3(3) ?3, Z = 4, Mr = 2438.57, Dc = 1.648 g/cm3, F(000) = 4928, μ = 12.61 cm-1, R = 0.0936 and wR = 0.1682 for 12998 observed reflections with I > 2.0σ(I). In the structure of 1, the Co atom of the [Co(Phen)3]2+ dication is octahedrally coordinated by three Phen ligands. The Mo atom of the [Mo2S2(μ-S)2(edt)2]2- dianion is coordinated by two μ-S, one terminal S and two S atoms from edt, forming a distorted square pyramidal geometry. The mean Co–N and Mo…Mo bond distances are 2.139 and 2.872 ?, respectively.
Reactions of CuBr with equimolar PyHBr or γ MePyHBr afforded two novel one dimensional bromocuprate? polymers {(PyH)3}∞ (1) and {(γ MePyH)2}∞ (2), respectively. Both 1 and 2 were characterized by IR, elemental analysis, and X ray crystallography. Crystal data for 1: monoclinic, space group P21/n, a=0.93262(12)nm, b=1.3497(2)nm, c=1.9149(2)nm, β =93.465(7)° , V=2.4060(5)nm3, Z=4. Crystal data for 2: orthorhombic, space group Pbcm, a=0.8659(4)nm, b=1.5669(6)nm, c=1.2849(5)nm, V=1.7432(2)nm3, Z=4. The structure of 1 has a unique helical chain composed of units and μ bromide anions while that of 2 shows a linear chain consisted of [Cu2(μ Br)2] units bridged by pairs of μ Br atoms. CCDC: 1, 208412; 2, 208413.
The reaction of [Et4N]2WS4 with 4 equiv of CuCN in pyridine produced a new polymeric complex [WS4Cu4(Py)4(m-CN)2]∞ 1, whose crystal structure has been characterized by single-crystal X-ray analysis. 1 (C22H20Cu4N6S4W, Mr = 934.71) crystallizes in monoclinic, space group P21/m with a = 8.994(2), b = 16.038(3), c = 12.026(3) ? b = 90.85(1)? V = 1734.6(6) ?, Z = 2, Dc = 1.789 g/cm3, F(000) = 896, m(MoKa) = 59.8 cm-1 and T = 193 K. The structure was refined to R = 0.064 and Rw = 0.080 for 2209 observed reflections (I > 3.0s(I)). The X-ray analysis shows that the tetrahedral WS4 core is coordinated by four Cu atoms, forming a saddle-like WS4Cu4 unit. These repeating units are further interconnected by four Cum-CNCu bridges to generate a one-dimensional ladder-shaped structure. The W…Cu bond distances are 2.726(2) and 2.723(2) ? respectively.
