双膦配合物Ru（OAc）_2（Ph_3P）（dppe）和Ru（OAc）_2（dppe）_2的设计合成、表征和氢化性能

Ｒｕ（ＯＡｃ）_２（Ｐｈ_３Ｐ）_２和１或２摩尔的双－（二苯基膦）乙烷（ｄｐｐｅ）在回流的甲苯中反应，分别生成双膦配位的Ｒｕ（ＯＡｃ）_２（Ｐｈ_３Ｐ）（ｄｐｐｅ）和Ｒｕ（ＯＡｃ）_２（ｄｐｐｅ）_２。并进行了元素分析、ＩＲ、ＮＭＲ等谱学表征。在温度－５０至４０℃的范围内，测定了Ｒｕ（ＯＡｃ）_２（Ｐｈ_３Ｐ）（ｄｐｐｅ）的￣（３１）Ｐ｛￣１Ｈ｝ＮＭＲ谱，讨论了配合物中膦配体的配位状态。在反应温度３０至９０℃、氢压１．０至５．０ＭＰａ的条件下，考察了两个配合物均相催化丙烯酸和苯乙烯的氢化性能。结果表明，题示的两个配合物是催化丙烯酸和苯乙烯氢化的有效催化剂。     

双（二苯基膦）丁烷的双核银配合物晶体结构

报导了双（二苯基膦）丁烷的双核银配合物－［Ａｇ（Ｐｈ_２ＰＣＨ_２ＣＨ_２ＣＨ_２ＣＨ_２ＰＰｈ_２）－（ＮＯ_３）］_２的合成及晶体结构分析。晶体属于单斜晶系，空间群为Ｐ２_１／ｎ，晶胞参数为：ａ＝１２．８２１（３），ｂ＝１１．２４４（９），ｃ＝１９．３８６（９），β＝１０５．９４（３）°，Ｖ＝２６８７．２~３，Ｚ＝２，Ｄ_ｃ＝１．４７４ｇ／ｃｍ~３，Ｍ_ｒ＝１１９２．７，Ｆ（０００）＝１２１６，μ＝８．８７３ｃｍ~（－１）。晶体结构由直接法和Ｆｏｕｒｉｅｒ合成解出，使用对角块矩阵和全矩阵最小二乘法对原子参数进行修正，最后偏离因子Ｒ＝０．０５６，Ｒ_ｗ＝０．０６８，其中２６３４个Ｉ＞３σ（Ⅰ）的可观察点参加了结构修正，单晶结构分析结果表明，在该配合物中，配体双（二苯基膦）丁烷（ｄｐｐｂ）中的磷原子直接与银离子配位，硝酸根也以双齿配位形式存在，中心银离子的配位采用畸变的四面体构型，整个分子是一个二聚物。     

双膦配合物Ru（OAc）2（Ph3P）（dppe）和Ru（OAc）2（dppe）2的设计合成,表…

Ｒｕ（ＯＡｃ）２（Ｐｈ３Ｐ）２和１或２摩尔的双－（二苯基膦）乙烷（ｄｐｐｅ）在回流的甲苯中反应，分别生成双膦配位的Ｒｕ（ＯＡｃ）２（Ｐｈ３Ｐ）（ｄｐｐｅ）和Ｒｕ（ＯＡｃ）２（ｄｐｐｅ）２。并进行了元素分析、ＩＲ、ＮＭＲ等谱学表征。在温度－５０至４０℃的范围内，测定了Ｒｕ（ＯＡｃ）２（Ｐｈ３Ｐ）（ｄｐｐｅ）的＾３１Ｐ｛＾１Ｈ｝ＮＭＲ谱，讨论了配合物中膦配体的配位状态。在反应温度３０至９０℃、氢压１．     

双核钯配合物［Ph_2P（o－C_6H_4CO）PdCl］_2·2CH_2Cl_

合成了双氯桥双核钯配合物［Ｐｈ_２Ｐ（ｏ－Ｃ_６Ｈ_４ＣＯ）ＰｄＣｌ］_２·２ＣＨ_２Ｃｌ_２进行了元素分析、红外光谱表征和晶体结构测定，研究了其催化氢化性能。在３０～８０℃、氢分压１．０～５．０ＭＰａ的范围内。发现该配合物是催化氢化丙烯酸为丙酸的有效催化剂．晶体［Ｐｄ_２Ｃｌ_２（Ｃ_（１９）Ｈ_（１４）ＯＰ）_２］·２ＣＨ_２Ｃｌ_２属Ｐ１空间群，ａ＝０．９３０４（３）ｎｍ，ｂ＝１．０３９２（２）ｎｍ，ｃ＝１．１０６２（３）ｎｍ；ａ＝１０２．７８（２），Ｂ＝９７．３５（３），γ＝９５．２５（２），Ｖ＝１．０２６４ｎｍ~３，Ｍ＝１０３２．１７，２＝１，Ｄｃ＝１．６７０ｇ／ｃｍ~３，ｕ＝１３．６９５ｃｍ~（－１），Ｆ（０００）＝５１２，用１９４５个独立衍射精修结构，最终Ｒ＝０．０３６。     

二苯并18－冠－6铵与硫氰酸银配合物的晶体结构

标题化合物［（ＮＨ_４）（ＤＢ１８Ｃ６）］_２［Ａｇ（ＳＣＮ）_２］_２其晶体属三斜晶系，空间群为Ｐ１。晶胞参数：ａ＝１４．００３（２），ｂ＝１４．４６１（３），ｃ＝１４．８８７（２），ａ＝６６．５１（２），β＝６６．７０（１），γ＝７６．０９（２）°，Ｖ＝２５２７．１３　３，Ｍ_ｒ＝１２０５．０，Ｚ＝２，Ｄ_ｘ＝１．５８ｇ／ｃｍ~３，μ＝９．８８ｃｍ~（－１）。偏差因子Ｒ_ｗ＝０．０８１，独立可观测点数［Ｉ＞３σ（Ｉ）］为３３５１个，在配合物分子中，二苯并１８－冠－６与ＮＨ４~＋形成配阳离子，Ａｇ~＋与硫氰酸根形成配阴离子，二者以静电力形成配合物。银原子被两个ＳＣＮ~－的Ｓ原子桥联和硫氰酸根上的硫，氮杂配，使整个分子形成一条高分子长链。     

邻香兰素与邻氨基苯甲酸Schiff碱铜（Ⅱ）配合物的合成、晶体结构和热分解动力学

合成了邻香兰素（２－羟基－３－甲氧基苯甲醛）与邻氨基苯甲酸Ｓｃｈｉｆｆ碱铜（Ⅱ）配合物，测定了其晶体结构并研究了其热稳定性。晶体Ｃ_（３０）Ｈ_（２８）Ｃｕ_２Ｎ_２Ｏ_（１１）属正交晶系，空间群Ｐｃａｎ，晶胞参数：ａ＝１．０３４７（４）ｎｍ，ｂ＝１．５４９３（７）ｎｍ，ｃ＝１．７４４１（３）ｎｍ，Ｖ＝２．７９５９ｎｍ~３，Ｍ＝７１９．６４，Ｚ＝４。结构解析最终的一致性因子Ｒ＝０．０４７，Ｒｗ＝０．０４９，热分解反应动力学方程式为：ｄα／ｄｔ＝Ａ·ｅ~（－Ｅ／ＲＴ）·３（１－α）~（２／３）；其补偿效应数学表达式为：１ｎＡ＝０．２８５８Ｅ＋０．４０４５。     

三核钼－硫簇合物的低热固相合成及其晶体结构

三核钼－硫配合物Ｍｏ_３Ｓ_７（ｄｔｃ）_３Ｉ·Ｓ_８·２ＣＨ_２Ｃｌ_２（ｄｔｃ＝Ｃ_４Ｈ_８ＮＣＳ_２~－）是由低热固相合成得到的。晶体属单斜晶系，Ｍ_ｒ＝１５００．１９，空间群Ｐ２_１／ｎ，ａ＝１１．８８１（３），ｂ＝１５．５５９（４），ｃ＝２６．１９７（７），β＝９８．５３（２）°，Ｖ＝４７８９Ａ~３，Ｚ＝４，Ｄ_ｃ＝２．０８ｇ／ｃｍ~３，Ｆ（０００）＝２９２０，μ（ＭｏＫα）＝２５．２４ｃｍ~（－１），对于２３９７个Ｉ≥３σ（Ｉ）的独立衍射点，最终偏离因子Ｒ＝０．０６０，Ｒ＝０．０６６。该配合物的基本骨架是［Ｍｏ_３Ｓ_７（ｄｔｃ）_３］~＋，其簇芯为［Ｍｏ_３Ｓ_７］~（４＋）单元，３中Ｍｏ原子组成正三角形平面，Ｍｏ－Ｍｏ的平均键长力２．７２３，Ｍｏ原子平面上的硫原子形成盖帽的μ_３－Ｓ，其Ｍｏ－Ｓ平均键长为２．３８３Ａ，３个Ｓ_２基团分别位于三角形３个棱的外侧，并分别与邻近的两个Ｍｏ原子结合形成１２中Ｍｏ－Ｓ键。与μ_３－Ｓ相对而位于平面另一侧的Ⅰ原子与３个μ_２－Ｓ连结，平均距离为３．２５７Ａ，成键作用较弱。     

CS_2在Cu－S键中插入产物（Ph_3P）_2Cu（S_2CSR）与溶剂反应的

ＣＳ_２在Ｃｕ－Ｓ键中插入产物（Ｐｈ_３Ｐ）_２Ｃｕ（Ｓ_２ＣＳＰｈ）与ＣＨ_２Ｃｌ_２－Ｃ_２Ｈ_５ＯＨ混合溶剂反应，获得单核铜配合物（Ｐｈ_３Ｐ）_２Ｃｕ（Ｓ_２ＣＯＯＣ_２Ｈ_５）和双核铜配合物（Ｐｈ_３Ｐ）_３Ｃｕ_２Ｃｌ_２等化合物晶体，用Ｘ－射线单晶衍射法测定前者的晶体结构。晶体的化学式为Ｃ_（３９）Ｈ_（３５）ＣｕＯＰ_２Ｓ_２，分子量为７０９．３，空间群Ｐ２１／ｎ，ａ＝９．３２９（６），ｂ＝１８．６６４（１１），ｃ＝２０，３４１（１３），β＝９５．５９（５）°，Ｖ＝３５２５（４）~３，Ｄ_ｃ＝１．３３７ｇ／ｃｍ~３，Ｚ＝４，Ｆ（０００）＝１４９２，μ＝０．８５２ｍｍ~（－１），Ｒ＝０．０４５。     

［Cu_2（C_6H_5COO）_4（C_3H_4N_2S）_2］的合成、晶体结

在２－氨基噻唑存在下，利用铜粉和过氧化苯甲酰的氧比加成反应，在丙酮中合成了双核铜（Ⅱ）配合物［Ｃｕ_２（Ｃ_６Ｈ_５ＣＯＯ）_４（Ｃ_３Ｈ_４Ｎ_２Ｓ）２］．晶体属单斜晶系，Ｐ２１／ｎ空间群，晶胞参数：ａ＝１．０６８５（１）ｎｍ，ｂ＝１．９０２８（６）ｎｍ，ｃ＝１．７０４６（９）ｎｍ；α＝γ＝９０°，β＝９６．４９（３）°，Ｖ＝３．４４３（４）ｎｍ~３，Ｚ＝４．Ｆ（０００）＝８２４，Ｄｃ＝１．５５５８ｇ／ｃｍ~３，μ＝１４．０７８ｃｍ~（－１），最终偏离因子Ｒ＝０．０４８２１，Ｒｗ＝０．０５３１４．通过元素分析、ＩＲ、ＴＧ、Ｘ射线粉末衍射表征了配合物的结构．     

二苯并18－冠－6铵与硫氰酸银配合物的晶体结构

标题化合物［（ＮＨ_４）（ＤＢ１８Ｃ６）］_２［Ａｇ（ＳＣＮ）_２］_２其晶体属三斜晶系，空间群为Ｐ１。晶胞参数：ａ＝１４．００３（２），ｂ＝１４．４６１（３），ｃ＝１４．８８７（２），ａ＝６６．５１（２），β＝６６．７０（１），γ＝７６．０９（２）°，Ｖ＝２５２７．１３　３，Ｍ_ｒ＝１２０５．０，Ｚ＝２，Ｄ_ｘ＝１．５８ｇ／ｃｍ~３，μ＝９．８８ｃｍ~（－１）。偏差因子Ｒ_ｗ＝０．０８１，独立可观测点数［Ｉ＞３σ（Ｉ）］为３３５１个，在配合物分子中，二苯并１８－冠－６与ＮＨ４~＋形成配阳离子，Ａｇ~＋与硫氰酸根形成配阴离子，二者以静电力形成配合物。银原子被两个ＳＣＮ~－的Ｓ原子桥联和硫氰酸根上的硫，氮杂配，使整个分子形成一条高分子长链。     

Synthesis and Structure of Di［bis（diphenylphosphino）ethane］ Copper（Ⅱ） Dinitrate

ＳｙｎｔｈｅｓｉｓａｎｄＳｔｒｕｃｔｕｒｅｏｆＤｉ［ｂｉｓ（ｄｉｐｈｅｎｙｌｐｈｏｓｐｈｉｎｏ）ｅｔｈａｎｅ］Ｃｏｐｐｅｒ（Ⅱ）ＤｉｎｉｔｒａｔｅＬＩＮＫｕｎ－Ｈｕａ；ＹＡＮＧＲｕｉ－Ｎａ；ＣＡＩＤｏｎｇ－Ｍｅｉ；ＪＩＮＤｏｕ－Ｍａｎ（ＨｅｎａｎＩｎ...     

Infrared and laser Raman studies of [Ni(II)(dppe)Cl2] and [Co(III)(dppe)2Cl2]PF6 (dppe = 1,2-bis(diphenylphosphino)ethane)

Infrared and laser Raman spectral investigations of [Ni(II)(dppe)Cl2] and [Co(III)(dppe)2Cl2]PF6 have been made to determine the conformation and nature of bonding in Ni(II) and Co(III) dppe complexes. The stereochemistry of the two forms of these complexes has been confirmed. The role of steric interferences in cis-Planar [Ni(II)(dppe)Cl2] complex is interpreted in terms of reduction in symmetry upon coordination. The strong trans influence of the chelating dppe ligand is observed in the [Co(III)(dppe)2Cl2]PF6 complex. Both complexes exhibit the effect of crystalline field on molecular vibrations. The Fermi resonance overtone is also observed in these complexes.     

New ruthenium(II) complexes with enantiomerically pure bis- and tris(pinene)-fused tridentate ligands. Synthesis, characterization and stereoisomeric analysis

A new set of Ru-Cl complexes containing either the pinene[5,6]bpea ligand (L1) or the C3 symmetric pinene[4,5]tpmOMe (L2) tridentate ligand in combination with the bidentate (B) 2,2'-bipyridine (bpy) or 1,2-diphenylphosphinoethane (dppe) with general formula [RuCl(L1 or L2)(B)](+) have been prepared and thoroughly characterized. In the solid state, X-ray diffraction analysis techniques have been used. In solution, cyclic voltammetry (CV) and 1D and 2D NMR spectroscopy have been employed. DFT calculations have been also performed on these complexes and their achiral analogues previously reported in our group, to interpret and complement experimental results. Whereas isomerically pure complexes ([Ru(II)Cl(L2)(bpy)](BF4), 5 and [Ru(II)Cl(L2)(dppe)](BF4), 6) are obtained when starting from the highly symmetric [Ru(III)Cl3(L2)], 2, isomeric mixtures of cis, fac-[Ru(II)Cl(L1)(bpy)](BF4) (3b/3b'), trans,fac- (3a) and up/down,mer- (3c, 3d) isomers are formed when bpy is added to the less symmetric [Ru(III)Cl3(L1)], 1, in contrast to the case of the bulky dppe ligand that, upon coordination to 1, leads to the trans,fac-[Ru(II)Cl(L1)(dppe)](BF4) (4a) complex as a sole isomer due to steric factors.     

Synthesis, characterization, and spontaneous resolution of chiral nickel(II) complexes with the tripod ligand tris[2-(((2-phenylimidazol-4-yl)methylidene)amino)ethyl]amine

The chiral nickel(II) complexes of a tripod-type ligand with the chemical formulas [Ni(H3L)](NO3)2.MeOH (1), [Ni(H3L)](ClO4)2.MeOH (2), and [Ni(H3L)](C6H5COO)2.6H2O (3) were synthesized and characterized (H3L = tris[2-(((2-phenylimidazol-4-yl)methylidene)amino)ethyl]amine). The crystal structures of 1-3 were determined by their single-crystal X-ray analyses. 1, C37H40N12O7Ni: orthorhombic, P2(1)2(1)2(1); a = 14.198(2) A, b = 22.422(2) A, c = 12.019(2) A, Z = 4. 2, C37H40N10O9Cl2Ni: orthorhombic, P2(1)2(1)2(1); a = 14.206(2) A, b = 22.735(3) A, c = 12.696(3) A, Z = 4. 3, C50H58N10O10Ni: triclinic, P1; a = 14.191(5) A, b = 16.048(4) A, c = 13.692(4) A, alpha = 115.25(2) degrees, beta = 111.07(3) degrees, gamma = 64.75(2) degrees, Z = 2. Each complex has an octahedral coordination environment for the nickel(II) ion, formed by the six nitrogen donor atoms, and is either a delta (clockwise) or a lambda (anticlockwise) enantiomorph, depending on the screw arrangement of the tripod-type ligand around the nickel(II) ion. The circular dichroism (CD) spectrum of a powdered sample of a crystal of 1 showed a positive and a negative peak at 915 and 630 nm, respectively, and that of another crystal showed an enantiomeric pattern. The observation of the Cotton effect and the crystal structure provided evidence for spontaneous resolution of the chiral complex molecule.     

Nickel(II) complexes of bidentate N-heterocyclic carbene/phosphine ligands: efficient catalysts for Suzuki coupling of aryl chlorides

Nickel(II) complexes of bidentate N-heterocyclic carbene (NHC)/phosphane ligand L were prepared and structurally characterized. Unlike palladium, which forms [PdCl(2)(L)], the stable nickel product isolated is the ionic [Ni(L)(2)]Cl(2). These Ni(II) complexes are highly robust in air. Among different N-substituents on the ligand framework, the nickel complex of ligand L bearing N-1-naphthylmethyl groups (2 a) is a highly effective catalyst for Suzuki cross-coupling between phenylboronic acid and a range of aryl halides, including unreactive aryl chlorides. The activities of 2 a are largely superior to those of other reported nickel NHC complexes and their palladium counterparts. Unlike the previously reported [NiCl(2)(dppe)] (dppe=1,2-bis(diphenylphosphino)ethane), 2 a can effectively catalyze the cross-coupling reaction without the need for a catalytic amount of PPh(3), and this suggests that the PPh(2) functionality of hybrid NHC ligand L can partially take on the role of free PPh(3). However, for unreactive aryl chlorides at low catalyst loading, the presence of PPh(3) accelerates the reaction.     

含类立方烷银(Ⅰ)簇的光致蓝光配位聚合物的原位溶剂热合成

A blue photoluminescent coordination polymer [Ag₄Cl₄(dppe)₂]_n has been prepared solvothermally and characterized structurally. The crystal structure was determined by single-crystal X-ray diffraction. The crystal is of tetragonal, space group I4₁/a, a=b=1.936 03(6) nm, c=1.465 63(8) nm, V=5.493 5(4) nm³, Z=4, D_calcd=1.657 Mg·m^-3, μ=1.749 mm^-1. Reflections collected: 17 147, independent reflections: 3 247, R_int=0.021 1. Final R indices [I> 2σ(I)]: R₁=0.044 8, wR₂=0.111 0. The structure of [Ag₄Cl₄(dppe)₂]_n is a 3D-diamond highly symmetrical polymeric network containing Ag₄Cl₄ cubane-like clusters connected by 1,2-bis(diphenylphosphino)ethane (dppe). Each Ag₄Cl₄ cluster is composed of four silver and four chlorine atoms situated at alternate vertexes of a highly distorted cube with each silver atom being further coordinated to one phosphorus atom from a dppe ligand. The stripping of chloride ions from CHCl₃ provides the source for chlorine in the formation of Ag(Ⅰ) clusters. In addition, the emission spectrum of the complex 1 in solid state has been studied. CCDC: 288080.     

Syntheses, Crystal Structures and Magnetism of Two New Coordination Polymers [Ni（bix）2Cl2]n and [Co（bix）Cl2]n

The self-assembly reactions of MIICl2 (M = Ni, Co) with the flexible bix ligand [bix = 1,4-bis(imidazole-1-ylmethyl)benzene] yielded a 2D network [NiII(bix)2Cl2]n 1 and a 1D chain [CoII(bix)Cl2]n 2. Their crystal structures have been determined by X-ray single-crystal diffraction analysis. Complex 1 characters a two-dimensional grid-type structure and crystallizes in monoclinic, space group P21/c with a = 7.7231(7), b = 12.7787(9), c = 13.9374(13) , β = 105.419(4)o, C28H28Cl2N8Ni, Mr = 606.19, Ζ = 2, V = 1326.0(2) 3, Dc = 1.518 g/cm3, μ = 0.969 mm-1, F(000) = 628, R = 0.0429 and wR = 0.0783 for 2503 observed reflections (I > 2σ(I)). Compound 2 is a one-dimensional chain and crystallizes in orthorhombic, space group Pbca with a = 11.3696(6), b = 10.2128(6), c = 14.4943(9) , C14H14Cl2CoN4, Mr = 368.12, Z = 4, V = 1683.01(17) 3, Dc = 1.453 g/cm3, μ = 1.334 mm-1, F(000) = 748, R = 0.0317 and wR = 0.0800 for 1778 observed reflections (I > 2σ(I)). Magnetic properties of the title complexes were also investigated.     

Synthesis and properties of one-dimensional Ni(Ⅱ) and Ni(Ⅱ)Cu(Ⅱ) complexes linked by hydrogen bond

Four dithiooxalato (Dto) bridged one-dimensional Ni(ll) and Ni(ll)Cu(ll) complexes (Me6[14]dieneN4)Ni2(Dto)2) (1), (Me6[14]dieneN4)CuNi(Dto)2 (2), (Me6[14]aneN4)Ni2(Dto)2 (3), and (Me6[14]aneN4)CuNi(Dto)2(4), were synthesized. These complexes have been characterized by elemental analysis, IR, UV and ESR spectra. The crystal structure of complex 3 was determined. It crystallizes in the monoclinic system, space group C2/c with a = 2.2425(4) nm, b = 1.0088(2) nm, c=1.4665(3) nm, β= 125.32(3)° ;Z=4; R = 0.076, Rw = 0.079. In the complex, Ni(1) coordinates four sulphur atoms of two Dto ligands in plane square environment. Ni(2) lies in the center of mac-rocyclic ligand. For Dto ligand, two sulphur atoms coordinate Ni(1), and O(1) coordinates Ni(2) and forms weak coordination bond. O(2) is linked to N(2) of macrocyclic ligand through hydrogen bond.     

Synthesis and Crystal Structure of an Indenylnickel(Ⅱ) NHC Complex (Ind)NiBr(1,3-bisbenzylimidazol-2-ylidene)

The complex (Ind)NiBr(1,3-bisbenzylimidazol-2-ylidene) (Ind = indenyl) 1 has been prepared in ca. 65% yield via the reaction of (Ind)2Ni with an equivalent of 1,3-bis-benzylimidazolium bromide in THF/CH2Cl2 at 45 °C, supported by elemental analysis, NMR spectroscopy and X-ray crystal determination. The crystal belongs to the triclinic system, space group P1 with a = 7.072(1), b = 11.264(2), c = 14.541(3) (A), a = 102.21(3),β = 93.44(3), γ = 90.81(3)°, V= 1129.7(4)(A)3, Z = 2, Mr = 502.08, Dc. = 1.476 g/cm3, F(000) = 512,μ = 2.642 mm-1, R = 0.0490and wR = 0.1137 for 3913 observed reflections (I ＞ 2σ(I)). The center nickel atom is coordinated by a bromide ligand, a carbene carbon and three carbon atoms of the five-membered indenyl group to form either a highly distorted square pyramid or a highly distorted square plane.     

Intrinsic carrier doping in antiferromagnetically interacted supramolecular copper complexes with (pyrazino)tetrathiafulvalene (pyra-TTF) as the ligand, [CuIICl2(pyra-TTF)] and (pyra-TTF)2[CuI3Cl4(pyra-TTF)

New supramolecular copper complexes with pyrazinotetrathiafulvalene (pyra-TTF) as the ligand, [Cu(II)Cl2(pyra-TTF)] (1) and (pyra-TTF) 2[Cu(I)3Cl4(pyra-TTF)] (2), have been synthesized by the diffusion method. Complex 1 is a black block crystal with a three-dimensional (3-D) supramolecular network; the linear chain [-Cu(II)Cl2-(pyra-TTF)-] n extends along the b axis, where the coordinated pyra-TTF donors are stacked in a head-to-tail and ring-over-bond configuration to construct two-dimensional (2-D) sheets, and between the sheets, there are C...Cl(-) or H...Cl(-) contacts. Even though the electron spin resonance (ESR) measurement reveals the nearly Cu(II) state, complex 1 is a semiconductor with sigmaRT=1.0 x 10(-4) S cm(-1) and Ea=0.33 eV. The high-frequency conductivity measurement also confirmed the intrinsic slight carrier doping from Cu(II) to the pyra-TTF donor. This slight doping enhances not only the real and imaginary dielectric constants but also the antiferromagnetic interaction between Cu(II) spins following the 2-D Heisenberg model with 2J=-20 K. In contrast, complex 2 is a very thin black needle. This needle crystal has two crystallographically independent pyra-TTF molecules, which are coordinated and noncoordinated donors. The coordinated donors composed a supramolecular chain [Cu(I)3Cl4(pyra-TTF)(0)]n , whereas the noncoordinated donors formed conducting alpha'-type pyra-TTF(+0.5) sheets. This complex is semiconducting with sigmaRT=0.1 S cm(-1) and Ea=0.15 eV. Both complexes 1 and 2 demonstrate that the pyra-TTF molecule works not only as an oxidized donor by Cu(II) to construct conducting sheets but also as a ligand coordinated to a Cu cation to form supramolecuar chains.