Synthesis, Characterization and Crystal Structure of [Co2Mo2(μ4-C2HPh)(μ-CO)4(CO)4(η5-C5H4C(O)Me)2]

The reaction of μ-alkyne-bridged dimolybdenum compound [Mo2(μ-C2HPh)(CO)4(η5-C5H4C(O)Me)2] 1 with Co2(CO)8 in refluxing toluene gave a new butterfly compound [Co2Mo2(μ4-C2HPh)(μ-CO)4(CO)4(η5-C5H4C(O)Me)2] 2 which was fully characterized by elemental analysis, IR, 1H NMR and X-ray single crystal diffraction techniques. 2 crystallized in monoclinic system, C30H20Co2Mo2O10, Mr=850.23, space group P21/a(#14), a=14.165(5), b=12.498(2), c=16.204(2)(A), β = 96.50(2)°, V = 2850(1)(A)3, Z = 4, Dc = 1.981 g cm-3, F(000)=1672, μ(MoKα)=20.41 cm-1, final R=0.030, Rw=0.039 for 4831 observable reflections with I>2σ(I). The structure contains a Co2Mo2 butterfly core, and each Mo-Co bond is spanned by an asymmetric semi-bridging carbonyl ligand.     

微波辅助新型含1,2,3-三唑基的α-氨基膦酸酯类化合物的合成及其晶体结构（英文）

在微波辐射、无溶剂、无催化条件下,合成了两个新型含1,2,3-三唑基的α-氨基膦酸酯类化合物,结构经IR、NMR、X-射线晶体衍射进行了确证。O,O'-二异丙基-α-苯氨基-α-(2-苯基-1,2,3-三唑-4-基)-甲基膦酸酯(4a)晶体属三斜系,P-1空间群,晶胞参数为a=0. 94630(5) nm,b=1. 16572(6) nm,c=1. 17733(8) nm,α=109. 902(5)°,β=105. 410(5)°,γ=96. 748(5)°,V=1. 14586(12) nm~3,Z=2,C_(21)H_(27)N_4O_3P,Mr=414. 43,Dc=1. 201g·cm~3,F(000)=440,μ(Cu Kα)=1. 54184 mm~(-1)。O,O'-二异丙基-α-(4-氯苯基)氨基-α-(2-苯基-1,2,3-三唑-4-基)-甲基膦酸酯(4b)晶体属单斜系,P21/n空间群,晶胞参数为a=1. 11854(17) nm,b=2. 22135(3)nm,c=1. 90049(3) nm,β=91. 7350(15)°,V=4. 71995(12) nm~3,Z=8,C_(21)H_(26)ClN_4O_3P,Mr=448. 88,Dc=1. 263g·cm~3,F(000)=1888. 0,μ(Cu Kα)=1. 54184 mm~(-1)。     

A New Sandwich Type Transition Metal Substituted Polyoxotungstate under Hydrothermal Conditions:[NH3(CH2)4NH3]6[Co4(HzO)2(B-α-GeW9034)2]}·7H2O

A new sandwich transition metal substituted polyoxotungstate,[NH3(CH2)4NH3]6 [Co4(H2O)2(B-α-GeW9O34)2]·7H2O 1,was hydrothermally synthesized and characterized by IR spectra and single-crystal X-ray diffraction.The single-crystal X-ray analysis reveals that the crystal crystallizes in monoclinic system,space group P21/c with a=16.6073(6),b=15.3333(5),C=19.9869(7)(A),β=103.41(1)°,Mr=5481.38,V=4950.8(3)(A)3,Z=2,Dc=3.677 g/cm3,F(000)=4900,μ(MoKα)=22.165 mm-1,GOOF=1.005,the final R=0.0228 and wR=0.0527.The crystal structure indicates that the[Co4(H2O)2(B-α-GeW9O34)2]12-polyoxoanion contains two trivacant Keggin[B-α-GeW9O34]10-fragments in a staggered fashion linked via a rhomb-like Co4O16 group in a centrosymmetric arrangement(C2h symmetry)leading to a sandwich-type structure.     

1,10-邻菲咯啉衍生物的合成及其晶体结构

以1,10-邻菲咯啉为原料,经氧化反应合成了1,10-邻菲咯啉-5,6-二酮(1);1与对氟苯甲醛反应合成了2-苯基(4-氟)-咪唑[4,5]-1,10-邻啡咯啉(2).1和2的结构经1H NMR,MS和X-射线单晶衍射表征.1为正交晶系,Pna21空间群,晶胞参数为:a=14.329 0(4)(A),b=12.370 0(3)(A),c=6.395 6(16)(A),α=90°,β=90°,γ=90°,V=1 133.5(5)(A)~3,Z=14,Dc=2.521 g·cm~(-3),μ=12.430 mm~(-1),F(000)=789,最终偏离因子R=0.039 8,wR=0.114 7.2为单斜晶系,P21/n,空间群晶胞参数为:a=9.810 0(4)(A),b=10.951 0(4)(A),c=17.3670(7)(A),α=90.000°,β=99.042(5)°,γ=90.000°,V=1 842.5(12)(A)~3,Z=4,Dc=1.292 g·cm~(-3),μ=0.095mm~(-1),F(000)=732,最终偏离因子R=0.091 2,wR=0.334 9.     

Synthesis and Characterization of Tetrametal Cluster [Co2(CO)6][μ-HC2CH2OCH2C2H-μ][Co2(CO)6]

The treatment of dipropargyl ether HC2CH2OCH2C2H with Co2(CO)8 resulted in the formation of a novel cluster [Co2(CO)6][μ-HC2CH2OCH2C2H-μ][Co2(CO)6]. The cluster was characterized by C/H analyses, IR and 1H NMR spectroscopy and X-ray crystal structure determination. It belongs to monoclinic system, space group P21/c with the following crystallographic parameters: a=18.149(2), b=7.0111(7), c=20.897(2)(A), β=115.318(7)°, V=2403.7(5)(A)3, Z=4, Mr=665.97, Dc=1.840 g·cm-3, F(000)=1304.00, μ(Mo-Kα)=27.76 cm-1 and R=0.030 for 2372 observed reflections.     

CRYSTAL AND MOLECULAR STRUCTURE OF(μ-PhCH_2S)(μ-CH_3C(0)CH_2S)Fe_2(CO)_6

<正> The crystal and molecular structures of (μ-PhCH2S)(μ-CH3C(O)CH2S)-Fe2(CO)6 have been determined by X-ray diffraction technique. The complex has chemical formula of C16H12O7S2Fe2 and Mr=492.08. The crystals are tri-clinic, space group P1,with a=8.461(5), b=10.937(5), c=ll.419(4)A,α=81.61 (3), β=78.21(4),γ=71.04(4)°,V=974.5A3, Dc=1.68 gcm-3,μ(MoKα)=17.3cm-1, Z=2,F(000)=495.93. The final R was 0.038 for 2874 independent reflections.     

cis-2,12-二取代环十二酮的合成及晶体结构

以环十二酮为原料合成了cis-2-苯磺酰基-12-苄基环十二酮、2-苯磺酰基-12-溴代环十二酮和2,12-二苄基环十二酮,它们的结构通过1H NMR,13C NMR和元素分析表征.化合物4的晶体结构参数:C25H32O3S,Mr=412.57,三斜晶系,空间群P1,a=0.96531(4)nm,b=1.12703(5)nm,c=1.17486(5)nm,α=89.278(2)°,β=75.582(2)°,γ=65.385(2)°,V=1.11938(8)nm3,Dc=1.224 g/cm3,Z=2,F(000)=444,μ(Mo Kα)=0.167 mm-1,S=1.038.化合物6的晶体结构参数:C18H25BrO3S,Mr=401.35,三斜晶系,空间群P1,a=0.77771(16)nm,b=1.0143(2)nm,c=1.2040(2)nm,α=89.46(3)°,β=80.13(3)°,γ=75.27(3)°,V=0.9044(3)nm3,Dc=1.474 g/cm3,Z=2,F(000)=416和μ(Mo Kα)=2.400 mm-1,S=1.042.cis-2-苯磺酰基-12-苄基环十二酮和cis-2-苯磺酰基-12-溴代环十二酮的X射线衍射结果表明,环十二酮母体骨架采取[3333]-2-酮构象,较小的取代基位于角顺位,较大的取代基位于边外向位.     

Synthesis and Crystal Structure of N-[(3aR,4R,4aR,5aS,6S,6aS)-1,3-Dioxooctahydro-4,6-ethenocyclopropa[f]isoindol-2(1H)yl]-4-(trifiuoromethyl)phenylmethanimine Monohydrate

The crystal structure of the title compound (C19H17F3N2O4,Mr=394.35) was determined by single-crystal X-ray diffraction.The crystal belongs to monoclinic,space group C2/c with a=28.383(6),b=10.355(2),c=12.799(3)(A),β=111.74(3)°,V=3493.8(12)(A)3,Z=8,De=1.499 g/cm3,λ(MoKα)=0.71073,F(000)=1632,μ= 0.127 mm-1,R=0.0412 and wR=0.1019.In the title compound,there exist three intennolecular hydrogen interactions (O(4)...O(1),O(4)...O(3) and O(4)...N(1)) between water.The neighboring molecules are linked to each other generating a two-dimensional network structure via the three intermolecular hydrogen bonds and π-π interactions shaped by phen-phen with centroid distance of 4.049 (A).     

Synthesis and Crystal Structure of Cluster [C6H4-1,2-(CO2CH2C2H-μ)2][Co2(CO)6]2

The reaction of dipropargyl phthalate C6H4-1,2-(CO2CH2C2H-μ)2 1 with octacarbonyldicobalt 2 resulted in the formation of red complex [C6H4-1,2-(CO2CH2C2H-μ)2][Co2(CO)6]2 3, in which each Co2(CO)6 group coordinates to one of the two C≡C bonds of 1. Molecular structure of complex 3 was determined by single crystal X-ray analyses. The crystal belongs to the monoclinic system, space group P21/a with the following crystallographic parameters: a=8.521(2), b=29.143(6), c=12.918(7)(A), β= 100.12(3)°, V=3158(2)(A)3, Z=4, Mr=814.09, Dc=1.712 g.cm-3, F(000)=1608, μ(Mo-Kα)=21.37 cm-1 and final R=0.044 for 3151 observations.     

新型咔唑衍生物的合成及其晶体结构

通过9-乙基咔唑-3-甲醛与4-氨基-3,5-二甲基-1,2,4-三氮唑反应,合成了一种新型咔唑衍生物-- 9-乙基咔唑-3-甲醛缩4-氨基-3,5-二乙基-1,2,4-三氮唑(1),其结构经1H NMR, IR和X-射线单晶衍射表征.1属单斜晶系,P2(1)/n空间群,晶胞参数为:a=8.829(8)(A), b=9.863(10)(A), c=19.530(15)(A), β=101.65(5)°, V=1 666(3)(A)3, Dc=1.266 g·cm-3, Z=4, F(000)=672, μ=0.079 mm-1.最终偏离因子R1=0.075 6.     

Two versatile N,N'-bipyridine-type ligands for preparing organic-inorganic coordination polymers: new cobalt- and nickel-containing framework materials

The Schiff base ligands 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene (L1, monoclinic, P2(1)/c, a = 3.856(1) A, b = 11.032(2) A, c = 12.738(3) A, beta = 92.21(3) degrees, Z = 2) and 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene (L2, monoclinic, P2(1)/c, a = 10.885(2) A, b = 4.613(1) A, c = 14.978(3) A, beta = 92.827(4) degrees, Z = 2) were used in the synthesis of four new organic-inorganic coordination polymers, each of them adopting a different structural motif. Synthesis, X-ray structural determinations, and spectroscopic and thermogravimetric analyses are presented. The reaction between Co(NO(3))(2).6H(2)O and L1 afforded a two-dimensional noninterpenetrating brick-wall structure, [Co(C(12)N(4)H(10))(1.5)(NO(3))(2)(H(2)O)(CH(2)Cl(2))(2)](n)() (1, triclinic, P1; a = 10.242(7) A, b = 10.802(7) A, c = 15.100(1) A, alpha = 70.031(1), beta = 75.168(11), gamma = 76.155(11), Z = 2), while Ni(NO(3))(2).6H(2)O combined with L1 yielded an interpenetrating three-dimensional rhombus-grid polymer, [Ni(C(12)N(4)H(10))(2)(NO(3))(2)(OC(4)H(8))(1.66)(H(2)O)(0.33)](n) (2, monoclinic, C2/c; a = 20.815(8) A, b = 23.427(8) A, c = 17.291(6) A, beta = 116.148(6), Z = 8). The reaction of Co(NO(3))(2).6H(2)O and L2 was found to be solvent-sensitive and resulted in the formation of two different noninterpenetrating compounds: [Co(C(14)N(4)H(14))(2)(NO(3))(2)(C(6)H(6))(1.5)](n)() (3, monoclinic, C2/c; a = 22.760(2) A, b = 21.010(3) A, c = 25.521(2) A, beta = 97.151(2), Z = 8), which adopts a two-dimensional square-grid motif formed by propeller-type modules, and [Co(C(14)N(4)H(14))(1.5)(NO(3))(2)(CH(2)Cl(2))(2)](n)() (4, monoclinic, P2(1)/n; a = 14.432(2) A, b = 14.543(8) A, c = 15.448(4) A, beta = 96.968(0), Z = 4), consisting of T-shaped building blocks assembled into a one-dimensional ladder-type structure. These four coordination polymers all exhibit impressive thermal stability. Thermogravimetric studies showed that after complete removal of the solvents, the frameworks are stable to temperatures between 234 degrees C and 260 degrees C.     

Synthesis and characterization of uranyl compounds with iminodiacetate and oxydiacetate displaying variable denticity

Eight uranyl compounds containing the dicarboxylate ligands iminodiacetate (IDA) or oxydiacetate (ODA) have been characterized in the solid state. The published polymeric structures for [UO(2)(C(4)H(6)NO(4))(2)] and [UO(2)(C(4)H(4)O(5))](n) have been confirmed, while Ba[UO(2)(C(4)H(5)NO(4))(2)] x 3H(2)O, [(CH(3))(2)NH(CH(2))(2)NH(CH(3))(2)][UO(2)(C(4)H(4)O(5))(2)] [orthorhombic space group Pnma, a = 10.996(5) A, b = 21.42(1) A, c = 8.700(3) A, Z = 4], and [C(2)H(5)NH(2)(CH(2))(2)NH(2)C(2)H(5)][UO(2)(C(4)H(4)O(5))(2)] [monoclinic space group P2(1)/n, a = 6.857(3) A, b = 9.209(5) A, c = 16.410(7) A, beta = 91.69(3), Z = 2] contain monomeric anions. The distance from the uranium atom to the central heteroatom (O or N) in the ligand varies. Crystallographic study shows that U-heteroatom (O/N) distances fall into two groups, one 2.6-2.7 A in length and one 3.1-3.2 A, the latter implying no bonding interaction. By contrast, EXAFS analysis of bulk samples suggests that either a long U-heteroatom (O/N) distance (2.9 A) or a range of distances may be present. Three possible structural types, two symmetric and one asymmetric, are identified on the basis of these results and on solid-state (13)C NMR spectroscopy. The two ligands in the complex can be 1,4,7-tridentate, giving five-membered rings, or 1,7-bidentate, to form an eight-membered ring. (C(4)H(12)N(2))[(UO(2))(2)(C(4)H(5)NO(4))(2)(OH)(2)] x 8H(2)O [monoclinic space group P2(1)/a, a = 7.955(9) A, b = 24.050(8) A, c = 8.223(6) A, beta = 112.24(6), Z = 2], (C(2)H(10)N(2))[(UO(2))(2)(C(4)H(5)NO(4))(2)(OH)(2)] x 4H(2)O, and (C(6)H(13)N(4))(2)[(UO(2))(2)(C(4)H(4)O(5))(2)(OH)(2)] x 2H(2)O [monoclinic space group C2/m, a = 19.024(9) A, b = 7.462(4) A, c = 2.467(6) A, beta = 107.75(4), Z = 4] have a dimeric structure with two capping tridentate ligands and two mu(2)-hydroxo bridges, giving edge-sharing pentagonal bipyramids.     

Vanadogermanate cluster anions

Three novel vanadogermanate cluster anions have been synthesized by hydrothermal reactions. The cluster anions are derived from the (V(18)O(42)) Keggin cluster shell by substitution of V=O(2+) "caps" by Ge(2)O(OH)(2)(4+) species. In Cs(8)[Ge(4)V(16)O(42)(OH)(4)].4.7H(2)O, 1, (monoclinic, space group C2/c (No. 15), Z = 8, a = 44.513(2) A, b = 12.7632(7) A, c = 22.923(1) A, beta = 101.376(1) degrees ) and (pipH(2))(4)(pipH)(4)[Ge(8)V(14)O(50).(H(2)O)] (pip = C(4)N(2)H(10)), 2 (tetragonal, space group P4(2)/nnm (No. 134), Z = 2, a = 14.9950(7) A, c = 18.408(1) A), two and four VO(2+) caps are replaced, respectively, and each cluster anion encapsulates a water molecule. In K(5)H(8)Ge(8)V(12)SO(52).10H(2)O, 3, (tetragonal, space group I4/m (No. 87), Z = 2, a = 15.573(1) A, c = 10.963(1) A), four VO(2+) caps are replaced by Ge(2)O(OH)(2)(4+) species, and an additional two are omitted. The cluster ion in 3 contains a sulfate anion disordered over two positions. The cluster anions are analogous to the vanadoarsenate anions [V(18)(-)(n)()As(2)(n)()O(42)(X)](m)(-) (X = SO(3), SO(4), Cl; n = 3, 4) previously reported.     

The Diammoniates of dipotassiumtetraethinylozincate and -cadmate: K2M(C2H)4.2NH3 (M = Zn, Cd)

By reaction of KC(2)H and K(2)Zn(CN)(4) in liquid ammonia, the diammoniate K(2)Zn(C(2)H)(4).2NH(3) was obtained. K(2)Cd(C(2)H)(4).2NH(3) was synthesized by reacting KC(2)H, Cd(NH(2))(2), and acetylene in liquid ammonia. The crystal structures of the air and temperature sensitive compounds were determined by X-ray single crystal diffraction at low temperatures (T = 170 K). Both compounds crystallize in the monoclinic space group I2/a (No. 15) with Z = 4. K(2)Zn(C(2)H)(4).2NH(3): a = 7.289(1) A, b = 12.765(2) A, c = 14.066(2) A, beta = 98.11(2) degrees. K(2)Cd(C(2)H)(4).2NH(3): a = 7.444(1) A, b = 12.619(3) A, c = 14.304(2) A, beta = 98.94(1) degrees. Characteristic structural motifs are tetrahedral [M(C(2)H)(4)](2-) fragments (M = Zn, Cd) and zigzag chains of edge sharing distorted (C(2)H)(6) octahedra centered by potassium ions. These zigzag chains are connected by a second type of crystallographically distinct potassium ions that also bind to two ammonia molecules.     

The effect of pH on the dimensionality of coordination polymers

Hydrothermal reactions of simple alkaline salts or their hydroxides with 3,5-pyrazoledicarboxylic acid (H(3)pdc) yielded seven new compounds. At a lower pH level three one-dimensional structures [Ca(Hpdc)(H(2)O)(4)].2H(2)O (1), [Ca(Hpdc)(H(2)O)(4)].H(2)O (2), and [Ba(H(2)pdc)(2)(H(2)O)(4)].2H(2)O (6) were obtained by evaporation of the solutions resulting from hydro(solvo)thermal reactions of MCl(2) (M = Ca, Ba) with H(3)pdc in water (1, 6) or in water/Et(3)N (2) at 150 degrees C for 3 days. Crystal structures of 1 and 2 contain zigzag chains of metal centers bridged by a single Hpdc(2-) ligand, whereas structure 6 consists of linear chains of metal centers bridged by two H(2)pdc(-) ligands. A dimer molecule [Sr(H(3)pdc)(H(2)pdc)(2)(H(2)O)(3)](2).2(H(3)pdc).4H(2)O (4) was obtained from a similar hydrothermal reaction using Sr(ClO(4))(2).6H(2)O instead of MCl(2). This compound contains [2+2] metallomacrocycles. At higher pH levels (pH = 4-6), the three-dimensional polymers [M(Hpdc)(H(2)O)] (Ca 3, Sr 5, Ba 7 ) were isolated by reactions of MCl(2) (M = Ca, Sr, Ba) with H(3)pdc in water/Et(3)N or in M(OH)(2) (M = Ca, Sr, Ba) with H(3)pdc in water under hydro(solvo)thermal conditions (150 degrees C, 3 days). Calcium and strontium are seven- and nine-coordinated in 3 and 5, respectively; barium is nine- and ten-coordinated in 7. It was observed that the increase in pH resulted in a higher connectivity level of ligands, which in turn leads to a higher dimensionality of the crystal structures. The correlation between the structures and pH values will be discussed. Crystal data: for 1, monoclinic, space group P2(1)/n (No. 14), with a = 8.382(2), b = 12.621(3), c = 11.767(2) A, beta = 98.91(3) degrees, Z = 4; for 2, 3, and 5, monoclinic, space group P2(1)/c (No. 14), Z = 4, a = 7.711(2), b = 15.574(3), c = 9.341(2) A, beta = 96.73(3) degrees, Z = 4 (2), a = 6.616(1), b = 12.654(3), c = 8.782(2) A, beta = 103.65(3) degrees, Z = 4 (3), a = 9.213(2), b = 12.088(3), c = 6.196(2) A, beta = 98.96(3) degrees (5); for 4 and 7, triclinic, space group P1 (No. 2), with a = 11.263(2), b = 11.460(3), c = 12.904(2) A, alpha = 71.54(3), beta = 98.96(3), gamma = 89.03(3) degrees, Z = 1 (4), a = 7.107(1), b = 9.780(2), c = 11.431(2) A, alpha = 74.69(3), beta = 73.39(3), gamma = 85.29(3) degrees, Z = 2 (7); for 6, monoclinic, space group C2/c (No. 15), with a = 20.493(4), b = 6.708(1), c = 15.939(3) A, beta = 123.56(3) degrees, Z = 4.     

New Cd(II)-, Co(II)-, and Cu(II)-containing coordination polymers synthesized by using the rigid ligand 1,2-bis(3-pyridyl)ethyne (3,3'-DPA)

Four new organic/inorganic coordination polymers, [Cd(C(10)H(8)N(2))(2)(H(2)O)(2)(NO(3))(2)](n)(1), [Co(C(10)H(8)N(2))(H(2)O)NO(3)CH(3)OH](n)(2), [Cu(C(10)H(8)N(2))(CH(3)OH)(NO(3))(2)](n) (3), and [Cu(C(10)H(8)N(2))(hfac)(2)](n)(4), were synthesized by using the rigid ligand 1,2-bis(3-pyridyl)ethyne (3,3'-DPA). Complex 1 crystallizes in space group P2/n: a = 12.462(2) A, b = 9.485(1) A, c = 13.383(2) A, beta = 96.629(2) degrees, V = 1559.6(3) A(3), Z = 4. Complex 2 crystallizes in space group Fddd: a = 9.248(4) A, b = 19.982(7) A, c = 35.093(16) A, V = 6485.0(4) A(3), Z = 8. Complex 3 crystallizes in space group I2/a: a = 18.315(2) A, b = 8.517(1) A, c = 20.494(3) A, beta = 104.042(2) degrees, V = 3101.2(7) A(3), Z = 8. Complex 4 crystallizes in space group P21/c: a = 6.576(1) A, b = 16.189(1) A, c = 11.653(1) A, beta = 91.337(1) degrees, V = 1240.3(2) A(3), Z = 2. The coordination polymers display a variety of structural architectures, ranging from sinusoidal and zigzag chains (1, 3, 4) to two-dimensional channel-type architectures (2). The effects of the orientation of the nitrogen atom in the pyridine rings on the resultant structures are discussed.     

Syntheses and Crystal Structures of Two One-dimensional Coordination Polymers Constructed from a Flexible Hinge-like Ligand

By using the flexible hinge-like ligand 2,2＇-bis（3-hydroxy-l,4-naphthoquinone） （H2bhnq）, two isomorphous one-dimensional zigzag chain coordination polymers have been obtained. Single-crystal X-ray analyses revealed that the metal centers in these two complexes are distorted octahedra involving four oxygen atoms of two bhnq2 anions, and two oxygen atoms of two DMF molecules situated in trans positions to one another. Crystal data for [Mn（bhnq）（DMF）2]n 1： C26H22MnN2O8, Mr = 545.40, monoclinic, space group C2/c, a = 14.936（3）, b = 10.362（2）, c = 15.901（3）A., β = 99.86（3）°, V = 2424.7（8）A3, Z = 4, Dc = 1.494 g/cm^3, F（000） = 1124,μ = 0.599 mm^-1, final GOOF = 1.025, R = 0.0654 and wR = 0.1537. Crystal data for [Cd（bhnq）（DMF）2]n 2： C26H22CdN2O8, Mr = 602.86, monoclinic, space group C2/c, a = 14.839（3）, b = 10.493（2）, c = 16.034（3）A, β = 99.40（3）°, V = 2463.1（9）A^3, Z = 4, Dc = 1.626 g/cm^3, F（000） = 1216,μ = 0.941 mm^-1, final GOOF = 1.069, R = 0.0358 and wR = 0.0944.     

Novel metal-organic frameworks with specific topology from new tripodal ligands: 1,3,5-tris(1-imidazolyl)benzene and 1,3-bis(1-imidazolyl)-5-(imidazol-1-ylmethyl)benzene

Reactions of two new tripodal ligands 1,3,5-tris(1-imidazolyl)benzene (4) and 1,3-bis(1-imidazolyl)-5-(imidazol-1-ylmethyl)benzene (5) with metal [Ag(I), Cu(II), Zn(II), Ni(II)] salts lead to the formation of novel two-dimensional (2D) metal-organic frameworks [Ag(2)(4)(2)][p-C(6)H(4)(COO)(2)].H(2)O (6), [Ag(4)]ClO(4) (7), [Cu(4)(2)(H(2)O)(2)](CH(3)COO)(2).2H(2)O (8), [Zn(4)(2)(H(2)O)(2)](NO(3))(2) (9), [Ni(4)(2)(N(3))(2)].2H(2)O (10), and [Ag(5)]ClO(4) (11). All the structures were established by single-crystal X-ray diffraction analysis. Crystal data for 6: monoclinic, C2/c, a = 23.766(3) A, b = 12.0475(10) A, c = 13.5160(13) A, beta = 117.827(3) degrees, Z = 4. For compound 7: orthorhombic, P2(1)2(1)2(1), a = 7.2495(4) A, b = 12.0763(7) A, c = 19.2196(13) A, Z = 4. For compound 8: monoclinic, P2(1)/n, a = 8.2969(5) A, b = 12.2834(5) A, c = 17.4667(12) A, beta = 96.5740(10) degrees, Z = 2. For compound 9: monoclinic, P2(1)/n, a =10.5699(3) A, b = 11.5037(3) A, c = 13.5194(4) A, beta = 110.2779(10) degrees, Z = 2. For compound 10: monoclinic, P2(1)/n, a = 9.8033(3) A, b = 12.1369(5) A, c = 13.5215(5) A, beta = 107.3280(10) degrees, Z = 2. For compound 11: monoclinic C2/c, a = 18.947(2) A, b = 9.7593(10) A, c = 19.761(2) A, beta = 97.967(2) degrees, Z = 8. Both complexes 6 and 7 are noninterpenetrating frameworks based on the (6, 3) nets, and 8, 9 and 10 are based on the (4, 4) nets while complex 11 has a twofold parallel interpenetrated network with 4.8(2) topology. It is interesting that, in complexes 6,7, and 11 with three-coordinated planar silver(I) atoms, each ligand 4 or 5 connects three metal atoms, while in the case of complexes 8, 9, and 10 with six-coordinated octahedral metal atoms, each ligand 4 only links two metal atoms, and another imidazole nitrogen atom of 4 did not participate in the coordination with the metal atoms in these complexes. The results show that the nature of organic ligand and geometric needs of metal atoms have great influence on the structure of metal-organic frameworks.     

Coordination polymers based on cobridging of rigid and flexible spacer ligands: syntheses, crystal structures, and magnetic properties of [Mn(bpy)(H2O)(C4H4O4)].0.5bpy, Mn(bpy)(C5H6O4), and Mn(bpy)(C6H8O4)

Reactions of 4,4'-bipyridine (bpy) with Mn(C(4)H(4)O(4)).4H(2)O and Mn(C(5)H(6)O(4)).4H(2)O in methanolic aqueous solutions yielded [Mn(bpy)(H(2)O)(C(4)H(4)O(4))].0.5bpy (1) and Mn(bpy)(C(5)H(6)O(4)) (2), respectively, and reactions of freshly prepared Mn(OH)(2)(-)(2)(x)(CO(3))(x).yH(2)O, adipic acid and 4,4'-bipyridine in a methanolic aqueous solution afforded Mn(bpy)(C(6)H(8)O(4)) (3). The six-coordinate Mn atoms in 1 are interlinked by flexible succinato ligands to form layers, which are sustained by rigid bpy ligands into an 3D open framework with the free bpy molecules in tunnels. The ribbonlike chains in 2 result from Mn atoms bridged by glutarato ligands and are connected by bpy ligands into open layers. In 3, the Mn atoms are bridged by both bpy and adipato ligands to form 3D nanoporous frameworks and 2-fold interpenetration of the resulting 3D frameworks completes the crystal structure. In comparison with 1 and 2, compound 3 displays significant antiferromagnetic behavior at low temperature. The antiferromagnetic exchange becomes stronger from 1 through 2 to 3, and the antiferromagnetic ordering of Mn(2+) centers is related to the syn-syn bridging mode of the terminal carboxylate groups of alpha,omega-dicarboxylate anions. Crystal data: C(19)H(18)MnN(3)O(5) (1), monoclinic P2(1)/c, a= 11.686(2) A, b = 17.847(2) A, c = 8.852(1) A, beta = 99.67(1) degrees, V = 1819.9(4) A(3), Z = 4, D(c) = 1.545 g.cm(-3); C(15)H(14)MnN(2)O(4) (2), triclinic P, a = 8.145(2) A, b = 9.574(2) A, c = 10.180(1) A, alpha = 108.01(3) degrees, beta = 93.55(3) degrees, gamma = 105.30(1) degrees, V = 719.2(2) A(3), Z = 2, D(c) = 1.576 g.cm(-3); C(15)H(14)MnN(2)O(4) (3), triclinic P, a = 8.544(1) A, b= 8.881(1) A, c = 10.949(2) A, alpha = 108.81(1) degrees, beta = 95.40(1) degrees, gamma = 101.94(1) degrees, V = 757.7(2) A(3), Z = 2, D(c) = 1.557 g.cm(-3).     

Copper(II) complexes of a series of alkoxy diazine ligands: mononuclear, dinuclear, and tetranuclear examples with structural, magnetic, and DFT studies

Picolyl hydrazide ligands have two potentially bridging functional groups (micro-O, micro-N-N) and consequently can exist in different coordination conformers, both of which form spin-coupled polynuclear coordination complexes, with quite different magnetic properties. The complex [Cu(2)(POAP-H)Br(3)(H(2)O)] (1) involves a micro-N-N bridge (Cu-N-N-Cu 150.6 degrees ) and exhibits quite strong antiferromagnetic coupling (-2J = 246(1) cm(-)(1)). [Cu(2)(PZOAPZ-H)Br(3)(H(2)O)(2)] (2) has two Cu(II) centers bridged by an alkoxide group with a very large Cu-O-Cu angle of 141.7 degrees but unexpectedly exhibits quite weak antiferromagnetic exchange (-2J = 91.5 cm(-)(1)). This is much weaker than anticipated, despite direct overlap of the copper magnetic orbitals. Density functional calculations have been carried out on compound 2, yielding a similar singlet-triplet splitting energy. Structural details are reported for [Cu(2)(POAP-H)Br(3)(H(2)O)] (1), [Cu(2)(PZOAPZ-H)Br(3)(H(2)O)(2)] (2), [Cu(2)(PAOPF-2H)Br(2)(DMSO)(H(2)O)].H(2)O (3), [Cu(4)(POMP-H))(4)](NO(3))(4).2H(2)O (4), and PPOCCO (5) (a picolyl hydrazide ligand with a terminal oxime group) and its mononuclear complexes [Cu(PPOCCO-H)(NO(3))] (6) and [Cu(PPOCCO-H)Cl] (7). Compound 1 (C(12)H(13)Br(3)Cu(2)N(5)O(4)) crystallizes in the monoclinic system, space group P2(1)/c, with a = 15.1465(3) A, b = 18.1848(12) A, c = 6.8557(5) A, beta = 92.751(4) degrees, and Z = 4. Compound 2 (C(10)H(13)Br(3)Cu(2)N(7)O(4)) crystallizes in the triclinic system, space group P, with a = 9.14130(1) A, b = 10.4723(1) A, c = 10.9411(1) A, alpha = 100.769(1), beta = 106.271(1) degrees, gamma = 103.447(1) degrees, and Z = 2. Compound 3 (C(23)H(22)Br(2)Cu(2)N(7)O(5.5)S) crystallizes in the monoclinic system, space group P2(1)/c, with a = 12.406(2) A, b = 22.157(3) A, c = 10.704(2) A, beta = 106.21(1) degrees, and Z = 4. Compound 4(C(52)H(48)Cu(4)N(20)O(18)) crystallizes in the monoclinic system, space group P2(1)/n, with a = 14.4439(6) A, b = 12.8079(5) A, c = 16.4240(7) A, beta = 105.199(1) degrees, and Z = 4. Compound 5 (C(15)H(14)N(4)O(2)) crystallizes in the orthorhombic system, space group Pna2(1), with a = 7.834(3) A, b = 11.797(4) A, c = 15.281(3) A, and Z = 4. Compound 6(C(15)H(13)CuN(5)O(5)) crystallizes in the monoclinic system, space group P2(1)/c, with a = 8.2818(9) A, b = 17.886(2) A, c = 10.828(1) A, beta = 92.734(2) degrees, and Z = 4. Compound 7 (C(15)H(13)CuClN(4)O(2)) crystallizes in the orthorhombic system, space group Pna2(1), with a = 7.9487(6) A, b = 14.3336(10) A, c = 13.0014(9) A, and Z = 4. Density functional calculations on PPOCCO are examined in relation to the anti-eclipsed conformational change that occurs on coordination to copper(II).