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1.
K.-F. Tebbe 《无机化学与普通化学杂志》1982,489(1):93-110
Studies on Polyhalides. III. Crystal Structures of [Cu(NH3)4I2 · I2] and [Cu(NH3)4I3]I3 Tetramminecopper(II)tetraiodide [Cu(NH3)4I2 · I2] (I) crystallizes monoclinically in the space group C2/m with a = 1 185.9 pm, b = 892.8 pm, c = 656.8 pm, β = 111.10° and Z = 2 formula units. Tetramminecopper(II)hexaiodide [Cu(NH3)4I3]I3 (II) crystallizes orthorhombically in the space group Pnnm with a = 874.9 pm, b = 1 089.8 pm, c = 885.3 pm, and Z = 2 formula units. A special feature of these structures are coordinated polyiodide ions I42? (I) or I3? (II). In both compounds four coplanar nitrogen atoms and two axial iodine atoms form a quasi-octahedral coordination around copper with the usual (4+2)-tetragonal distortion. The copper ions are connected by linear, centrosymmetric polyiodide ions I42? (I) or I3? (II). Therefore infinite planar zigzag chains of units [Cu(NH3)4I4] (I) or [Cu(NH3)4I3]+(II) are resulting. The counterion I3? (II) is intercalated between these chains. 相似文献
2.
L’ubica Triščíková Ivan Potočňák Jozef Chomič Peter Baran 《Transition Metal Chemistry》2006,31(4):504-515
The new mixed-valence mixed-metal complex Cu(py)6Cu2Ag2(CN)6 (py = pyridine) possesses a three dimensional polymeric crystal structure. The Cu(I) atom is tetrahedrally coordinated by
two nitrogen atoms of pyridine molecules, by one nitrogen atom of the dicyanoargentate anion and by one carbon atom of the
cyano group. Both the dicyanoargentate anion and the cyano group bridge the Cu(I) atom with neighboring Cu(II) atoms. These
are hexacoordinated in the form of an elongated tetragonal bipyramid. The equatorial plane is formed by two nitrogen atoms
from two pyridine molecules and two nitrogen atoms from bridging cyano groups. Axial positions are occupied by nitrogen atoms
of the bridging [Ag(CN2]− anions. Correlation between structures of the title compound and seven other dicyanoargentates with their i.r. spectra has
been studied. The coordination mode of [Ag(CN2]− anions in compounds Cu8-xAgx(tn)3(CN)10 x = 0.25, Cu(3-Mepy)2Ag2(CN)4, Cu(py)2Ag2(CN)4 and Cu(py)4Ag2(CN)4 (tn is 1,3-diaminopropane, 3-Mepy is 3-methylpyridine) is predicted based on this correlation. 相似文献
3.
The title compound, {[Cu(NH3)4][Cu(CN)3]2}n, features a CuI–CuII mixed‐valence CuCN framework based on {[Cu2(CN)3]−}n anionic layers and [Cu(NH3)4]2+ cations. The asymmetric unit contains two different CuI ions and one CuII ion which lies on a centre of inversion. Each CuI ion is coordinated to three cyanide ligands with a distorted trigonal–planar geometry, while the CuII ion is ligated by four ammine ligands, with a distorted square‐planar coordination geometry. The interlinkage between CuI ions and cyanide bridges produces a honeycomb‐like {[Cu2(CN)3]−}n anionic layer containing 18‐membered planar [Cu(CN)]6 metallocycles. A [Cu(NH3)4]2+ cation fills each metallocyclic cavity within pairs of exactly superimposed {[Cu2(CN)3]−}n anionic layers, but there are no cations between the layers of adjacent pairs, which are offset. Pairs of N—H...N hydrogen‐bonding interactions link the N—H groups of the ammine ligands to the N atoms of cyanide ligands. 相似文献
4.
Juraj ernk Jozef Chomi
Werner Massa 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(10):m490-m493
From the 1:1 system of [Cu(dien)2](NO3)2 and K[Ag(CN)2] in water (dien is diethylenetriamine, C4H13N3), the novel compound catena‐poly[bis[[μ‐cyano‐1:2κ2C:N‐diethylenetriamine‐2κ3N‐copper(II)silver(I)]‐μ‐cyano‐1:2′κ2C:N] dicyanosilver(I) tricyanodisilver(I)], [CuAg(CN)2(dien)]2[Ag(CN)2][Ag2(CN)3], has been isolated. The structure is formed from positively charged [–Cu(dien)–NC–Ag–CN–]nn+ chains and two isolated centrosymmetric [Ag(CN)2]? and [Ag2(CN)3]? anions. In the cationic chains, the Cu atoms are linked by bridging dicyanoargentate groups, and the deformed square‐pyramidal coordination polyhedron of the CuII cation is formed from a tridentate chelate‐like bonded dien ligand and two N‐bonded bridging cyano groups. One of the bridging cyano groups occupies the apical (ap) position [mean Cu—Neq = 2.02 (2) Å, and Cu—Nap = 2.170 (3) Å; eq is equatorial]. Short argentophilic interactions in the range 3.16–3.30 Å are present in the crystal structure. 相似文献
5.
Hui‐Bo Zhou Wen Dong Mao Liang Dai‐Zheng Liao Zong‐Hui Jiang Shi‐Ping Yan Peng Cheng 《无机化学与普通化学杂志》2004,630(4):498-500
A three‐dimensional cyano‐bridged copper(II) complex, [Cu(dien)Ag(CN)2]2[Ag2(CN)3][Ag(CN)2] ( 1 ) (dien = diethylenetriamine), has been prepared and characterized by X‐ray crystallography. Complex 1 crystallized in the monoclinic space group P21/n with a = 6.988(2), b = 17.615(6), c = 12.564(4) Å, β = 90.790(5)°. The crystal consists of cis‐[Cu(dien)]2+ units bridged by [Ag(CN)2]— to form a zig‐zag chain. The Ag atoms of the free and bridging [Ag(CN)2]— link together to form additional infinite zig‐zag chains with short Ag···Ag distances. The presence of Ag···Ag interactions effectively increases the dimensionality from a 1‐D chain to a 3‐D coordination polymer. 相似文献
6.
Synthesis and Structure Investigations of Iodocuprates(I). XV Iodocuprate(I) with Solvated Cations: [Li(CH3CN)4] [Cu2I3] and [Mg{(CH3)2CO}6][Cu2I4] [Li(CH3CN)4][Cu2I3] 1 and [Mg((CH3)2CO)6][Cu2I4] 2 were prepared by reactions of CuI with LiI in acetonitrile and of CuI with MgI2 in acetone. 1 crystallizes orthorhombic, Pnma, a = 552.7(2), b = 1258.8(8), c = 2516(1) pm, z = 4. [Li(CH3CN)4]+ cations are located between rod packings of CuI4 tetrahedra double chains [(CuI2/2I2/4)2]? parallel to the axis. Short intermolecular anion/cation contacts were observed. The crystal structure of 2 (monoclinic, P21/n, a = 1840(2), b = 1059.2(2), c = 1879(2)pm, β = 112.94(4)°, z = 4) is built up by [Mg((CH3)2CO)6]2+ cations forming a simple hexagonal sphere packing. The binuclear anions [Cu2I4]2? occupy holes in the trigonal prismatic channels formed by the cations. 相似文献
7.
Attempts to build up polyanionic networks on the basis of thiocyanatometallates of CuI and AgI led to the synthesis of three new tris(thiocyanato)dimetallates(I) A[M2(SCN)3] with M = Cu, Ag and A = Me3NH and A = [Me2CNMe2]. The crystal structures show distorted tetrahedral [M(SCN)3(NCS)] and [M(SCN)2(NCS)2] building groups interlinked by SCN bridges. The resulting 3‐dimensional frame works accommodate the counter cations in spacious voids. Me3NHCu2(SCN)3 ( 1 ) was synthesized by reaction of CuSCN with (CH3)3NHCl in the presence of an excess of KSCN in acetone. 1 crystallizes in the monoclinic space group P21/c with a = 578.4(1), b = 3025.1(5), c = 754.7(3) pm; β = 112.53°; Z = 4. The reaction of CuSCN or AgSCN with (CH3)2NH2Cl and KSCN in acetone resulted in the formation of [Me2CNMe2]Cu2(SCN)3 ( 2 ) and [Me2CNMe2]Ag2(SCN)3 ( 3 ). Compound 2 crystallizes in the orthorhombic space group P212121 with a = 720.6(1), b = 1161.5(1), c = 1655.0(2) pm; Z = 4. The isotypical structure of 3 exhibits somewhat larger unit cell dimensions; a = 743.4(1), b = 1222.5(1), c = 1683.9(2) pm. 相似文献
8.
Structurally Chemical Investigation of Monoammin Copper (I) Complexes : [CuNH3]2[Pt(CN)6], [CuNH3]2[Pt(CN)4] and Cu3[Co(CN)6] · 2NH3 The preparation and the properties of [CuNH3]2[Pt(CN)6], [CuNH3]2[Pt(CN)4] and Cu3[Co(CN)6] · 2NH3 are described. I.R. and Raman spectra have been recorded and assigned. According to X-ray powder diagrams, [CuNH3]2[Pt(CN)6] crystallizes in the trigonal space group D–P3 ml, a = 7.771, c = 5.988 Å, Z = 1. According to the spectroscopic and crystallographic data, it is concluded that the CuI ion is coordinated with one NH3 group and with the N atoms of the cyanometallate anions. The coordination number of the Cu+ is 4 in [CuNH3]2[Pt(CN)6] and 3 in [CuNH3]2[Pt(CN)4]. In the Cu3[Co(CN)6] · 2 NH3 complex two Cu atoms have the coordination number 2, the third Cu atom 4. 相似文献
9.
Crystal Structures of the Terpyridine Complexes [Cd(terpy)Cl2], [Cu(terpy)(CN)Cl], and [Cu(terpy)][Cu(CN)3] · H2O By reaction of cadmium chloride with 2,2′ : 6′,2″-terpyridine (“terpy”) in water/acetone crystals of [Cd(terpy)Cl2] ( 1) were formed. The compound crystallizes monoclinic, space group P21/c, a = 1111.70(10), b = 823.10(7), c = 1643.00(14) pm, β = 93.913(1)°, Z = 4. Starting from mixtures of different molar ratios of copper(II) chloride, terpyridine, and KCN in water/methanole, two complexes of different composition were obtained. At the molar ratio of 1 : 1 : 2 a copper(II) coordination compound with both halide and pseudohalide ligands, [Cu(terpy)(CN)Cl] ( 2 ), was formed which also crystallizes monoclinic, P21/c, a = 1065.6(3), b = 824.6(2), c = 1644.5(7) pm, β = 98.214(3)°, Z = 4. At a molar ratio of 1 : 1 : 10 a partial reduction of copper(II) occured with formation of a mixed valency compound [Cu(terpy)][Cu(CN)3] · H2O ( 3 ) which crystallizes in the hexagonal space group P6522, with a = b = 800.29(1), c = 4771.05(7) pm, Z = 6. Compounds 1 and 2 are structurally similar, the coordination of the metal atoms is square pyramidal. Networks are formed by hydrogen bridges. In 3 the copper(II) ions show a distorted square planar coordination by the three N atoms of the terpy ligand and one N atom of a bridging CN– group, the copper(I) atoms, however, show trigonal planar coordination by three CN– ligands to which the water molecules are bonded by hydrogen bridges. Thus helical chains are formed which stretch in the direction of the screw axes. The EPR spectrum of 3 was measured. 相似文献
10.
Michael Berkei Eduard Bernhardt Markus Schürmann Michael Mehring Helge Willner 《无机化学与普通化学杂志》2002,628(8):1734-1740
Preparation, Spectroscopic Characterization and Crystal Structures of Mercury(II)‐bis(tetracyanoborate) Hg[B(CN)4]2 and Dimercury(I)‐bis(tetracyanoborate) Hg2[B(CN)4]2 Hg[B(CN)4]2 ( 1 ) is synthesised by the reaction between Hg(NO3)2 and K[B(CN)4]2. In a comproportionation reaction of 1 with elemental mercury the corresponding mercury(I) salt Hg2[B(CN)4]2 ( 2 ) is obtained. The compounds were characterised by vibrational‐ and NMR‐spectroscopy, and their crystal structures were determined. Hg[B(CN)4]2 crystallizes in the trigonal system in the space group P3¯m1 with a = 781.75(3) pm, c = 601.68(2) pm, V = 318.44(2)Å3, and one formula unit per unit cell. For Hg2[B(CN)4]2 an orthorhombic unit cell with a = 568.9(1) pm, b = 3280.9(7) pm, c = 601.68(2) pm, V = 1389.6(5)Å, and Z = 4 is observed. 相似文献
11.
New Copper(I, II) Compounds Complexes of the type [CuII(N∩N)2][CuICl1+x]2x (N∩N = en, pn, 2-amino picoline) are prepared from Cu(N∩N)2Cl2 and copper(I) chloride. [CuII(enac)][CuICl2]2 — a complex with a macrocyclic cation — is obtained, by the reaction of Cuen2Cl2 in aqueous acetone. Diacetyl monoxime partially reduces copper(II) of Cu(NSMe)2Cl2 and in this way causes the formation of [Cu(NSMe)2][CuCl3] (NSMe = β-aminoethyl methylsulfide). On the other hand a template reaction of this oxime with Cu(NSMe)2 (ClO4)2 produces CuII(ONNSMe)(ClO4) (HONNSMe?CH3C(NOH)C(NCH2CH2SCH3)CH3), which shows a reduced paramagnetism. Basing on magnetic behaviour, i. r. and vis spectra the structure of the new compounds is discussed. 相似文献
12.
Ryo Sekiya Kazumasa Hosoya Shin‐ichi Nishikiori 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(5):i32-i34
The title compound, poly[diamminehexa‐μ‐cyano‐dicopper(I)copper(II)mercury(II)], [Cu3Hg(CN)6(NH3)2]n, has a novel threefold‐interpenetrating structure of three‐dimensional frameworks. This three‐dimensional framework consists of two‐dimensional network Cu3(CN)4(NH3)2 complexes and rod‐like Hg(CN)2 complexes. The two‐dimensional network complex contains trigonal–planar CuI (site symmetry m) and octahedral CuII (site symmetry 2/m) in a 2:1 ratio. Two types of cyanide group form bridges between three coordination sites of CuI and two equatorial sites of CuII to form a two‐dimensional structure with large hexagonal windows. One type of CN− group is disordered across a center of inversion, while the other resides on the mirror plane. Two NH3 molecules (site symmetry 2) are located in the hexagonal windows and coordinate to the remaining equatorial sites of CuII. Both N atoms of the rod‐like Hg(CN)2 group (Hg site symmetry 2/m and CN− site symmetry m) coordinate to the axial sites of CuII. This linkage completes the three‐dimensional framework and penetrates two hexagonal windows of two two‐dimensional network complexes to form the threefold‐interpenetrating structure. 相似文献
13.
The novel complex [Cu(men)2][Cu2Cd2Cl2(CN)6] (I) was isolated from the aqueous-ethanol system containing CuCl2, men (men = N-methylethane-1,2-diamine) and K2[Cd(CN)4] in the presence of dilute hydrochloric acid and chemically and spectroscopically characterised. The crystal structure of I consists of [Cu 2 I (CN)6] and [Cd2Cl2(CN)6] building units bridged by cyanide ligands and forms a three-dimensional skeleton with cavities. [Cu(men)2]2+ cations in which two men ligands are chelated (mean Cu-N is 2.033(6) Å) are located in the cavities. The coordination polyhedron around the Cu(II) atoms is formed as a tetragonal bipyramidal by two weaker axial Cu-Cl bonds (2.8642(12) Å) with chlorido ligands from the skeleton. The Cu(I) and Cd(II) atoms in the skeleton exhibit tetra-(CuC4 chromophore) and penta-coordination (CdN3Cl2), respectively. The temperature-dependent susceptibility measurements indicate a Curie-Weiss-like behaviour and the presence of weak anti-ferromagnetic interaction. 相似文献
14.
Synthesis, Vibrational Spectra, and Crystal Structures of the Nitrato Argentates (Ph4P)[Ag(NO3)2(CH3CN)]·CH3CN and (Ph4P)[Ag2(NO3)3] Tetraphenylphosphonium bromide reacts in acetonitril suspension with excess silver nitrate to give (Ph4P)[Ag(NO3)2(CH3CN)]·CH3CN ( 1 ), whereas (Ph4P)[Ag2(NO3)3] ( 2 ) is obtained in a long‐time reaction from (Ph4P)Br and excess AgNO3 in dichloromethane suspension. Both complexes were characterized by vibrational spectroscopy (IR, Raman) and by single crystal structure determinations. 1 : Space group P21/c, Z = 4, lattice dimensions at 193 K: a = 1781.5(3), b = 724.8(1), c = 2224.2(3) pm, β = 96.83(1)°, R1 = 0.0348. 1 contains isolated complex units [Ag(NO3)2(CH3CN)]?, in which the silver atom is coordinated by the chelating nitrate groups and by the nitrogen atom of the solvated CH3CN molecule with a short Ag—N distance of 220.7(4) pm. 2 : Space group I2, Z = 4, lattice dimensions at 193 K: a = 1753.4(4), b = 701.7(1), c = 2105.5(4) pm, R1 = 0.072. In the polymeric anions [Ag2(NO3)3]? each silver atom is coordinated in a chelating manner by one nitrate group and by two oxygen atoms of two bridging nitrate ions. In addition, each silver atom forms a weak π‐bonding contact with a phenyl group of the (Ph4P)+ ions with shortest Ag···C separations of 266 and 299 pm, respectively, indicating a (4+1) coordination of silver atoms. 相似文献
15.
Crystal Structures of Octacyanomolybdates(IV). IV Dodecahedral [Mo(CN)8] Coordination of the Cyano‐Bridged Cobalt and Nickel Ammin Complexes MII2(NH3)8[Mo(CN)8] · 1.5 H2O (MII = Co, Ni) and Ni2(NH3)9[Mo(CN)8] · 2 H2O At single crystals of the hydrated cyano complexes Co2(NH3)8[Mo(CN)8] · 1.5 H2O (a = 910.0(4), b = 1671(2), c = 1501(1) pm, β = 93.76(6)°) and Ni2(NH3)8[Mo(CN)8] · 1.5 H2O (a = 899.9(9), b = 1654.7(4), c = 1488(1) pm, β = 94.01°), isostructurally crystallizing in space group P21/c, Z = 4, and of trigonal Ni2(NH3)9[Mo(CN)8] · 2 H2O (a = 955.1(1), c = 2326.7(7) pm, P31, Z = 3), X‐ray structure determinations were performed at 168 resp. 153 K. The [Mo(CN)8]4– groups of the three compounds, prepared at about 275 K and easily decomposing, show but slightly distorted dodecahedral coordination (mean distances Mo–C: 216.3, 215.4 and 216.1 pm). Within the monoclinic complexes the anions twodimensionally form cyano bridges to the ammin cations [M(NH3)4]2+ and are connected with the resulting [MN6] octahedra (Co–N: 215.1 pm, Ni–N: 209.8 pm) into strongly puckered layers. The trigonal complex exhibits a chain structure, as one [Ni(NH3)5]2+ cation is only bound as terminal octahedron (Ni–N: 212.0 pm). Details and the influence of hydrogen bridges are discussed. 相似文献
16.
Melting reactions of Bi2S3, CuX (X = Cl, Br), copper, and sulfur resulted in black needles of qua‐ and quinternary copper bismuth sulfide halogenides. Cu3BiS2Br2 (I) has a melting point of 638(5) K and crystallizes in the orthorhombic space group Pnma with a = 804.50(6) pm, b = 393.27(3) pm, and c = 2253.2(2) pm at T = 293(2) K. Cu4Bi3S5Br3–xClx (x = 1.19(2)) (II) crystallizes in the monoclinic space group I2/m with lattice parameters a = 1573.7(2) pm, b = 397.52(3) pm, c = 2164.9(3) pm, and β = 95.66(1) °. Both compounds exhibit networks of thio‐halogenido‐bismuthate(III) polyhedra that join corners, edges, and faces. The copper(I) cations are spread over numerous contiguous trigonal or tetrahedral voids. In case of (II) a continuous pathway for copper ion transport along [010] is formed. The pseudo‐potential barrier for hopping of copper ions was calculated as 30 meV only. 相似文献
17.
《Journal of Coordination Chemistry》2012,65(16):2648-2655
Single crystals of Ag(I) and Cu(II) complexes with 4-pyridin-4-yl-(1,3) dithiol-2-one (PYDO), [Ag(PYDO)2]ClO4, [Ag(PYDO)2(NO3)], and [Cu(PYDO)2(NO3)2] have been prepared and characterized. PYDO displays excellent coordination to Cu(II) and Ag(I). The 1,3-dithiol five-member ring is an electron donor that enhances the coordination ability of the py group. HOMO-1 σ coordination and d–π electron back-donating from metal to ligand (LUMO) are suggested based on the calculation. Weak interactions and secondary bonds from the anion to cation play an important role in the molecular assembly. 相似文献
18.
Thallium(I), Silver(I), and Mixed Thallium(I)/Copper(I) Clusters with Bridging {Me2Si(N‐C6H4‐2‐SPh)2}2– Ligands
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The S‐functionalized aminosilane Me2Si(NH‐C6H4‐2‐SPh)2 (H2L) ( 1 ) was prepared from dichlorodimethylsilane and lithiated 2‐(phenylthio)aniline. Treatment of compound 1 with two equivalents of n‐butyllithium led to the dilithium derivative Li2L, which was used in subsequent reactions with MCl (M = Tl, Cu, Ag) to prepare the complexes [Tl2L] ( 2 ), [Cu2Tl2L2] · 2THF ( 3a ), [Cu2Tl2L2(THF)2] ( 3b ), and [Ag4L2(THT)2] ( 4 ) (THT = tetrahydrothiophene). Compound 2 consists of two thallium atoms, which are connected by a L2– ligand to give a puckered Tl2N2 ring with Tl–N distances of 255(1)–268(1) pm. Compounds 3a and 3b are heterobimetallic complexes, which are based on [Cu2L2]2– cores featuring a Cu2N4Si2 ring with linearly coordinated copper atoms [Cu–N: 190.7(3)–192.5(3) pm] and two peripherally attached Tl atoms [Tl–N: 272.7(3)–281.9(3) pm]. The molecular structure of the tetranuclear silver(I) complex 4 is closely related to the structure of compounds 3a and 3b by replacement of the Cu and Tl atoms with Ag atoms. The Ag–N distances are 217.5(3)–245.7(3) pm. 相似文献
19.
Studies on Polypseudohalides. 4. Preparation and Crystal Structure of KxRb1?x[I(CN)2] · 1/2 C6H12N2O2 (x = 0.6) The new compound KxRb1?x[I(CN)2] · 1/2 C6H12N2O2 (x = 0.6), C10H12I2K1·2N6O2Rb0·8, may be prepared by the addition of rubidium bromide to a saturated solution of iodine cyanide and potassium cyanide in a mixture of ethanol and water. Potassium bromide and rubidium bromide are formed as by-products. The compound has been investigated by chemical analysis, spectroscopy and structural analysis based on single crystal X-ray data. At room temperature it crystallizes in the monoclinic space group P21/c with a = 436.34 pm, b = 1933.5 pm, c = 1240.5 pm, β = 92.30° and Z = 4. The compound may be described as a solvated salt which is built up by a cation statistically occupied with potassium and rubidium and the trihalide-analogous anion [I(CN)2]?. Additional there is one molecule Diimino-oxalic-acid-di-ethyl-ester per two formula units M[I(CN)2]. The asymmetricanion is nearly linear. The bond lengths d(I? C) = 226.5 pm, 235.1 pm are extended compared with the analogous distance in iodine cyanide. The surrounding of the cation is a distorted octahedron. The structure of the solvating molecule is quite normal. The crystal structure may be interpreted as a sequence of puckered ionic layers paralledl to (001) which are connected through the cations. The organic molecules are intercalated in channels along [100] between these layers. 相似文献
20.
Karl Eberhard Bessler Lincoln Lucílio Romualdo Victor Marcelo Deflon Adelheid Hagenbach 《无机化学与普通化学杂志》2000,626(9):1942-1945
Preparation and Crystal Structures of Ag[N(CN)2](PPh3)2, Cu[N(CN)2](PPh3)2, and Ag[N(CN)2](PPh3)3 The coordination compounds Ag[N(CN)2](PPh3)2 ( 1 ), Cu[N(CN)2](PPh3)2 ( 2 ), and Ag[N(CN)2](PPh3)3 ( 3 ) are obtained by the reaction of AgN(CN)2 or CuN(CN)2 with triphenylphosphane in CH2Cl2. X‐ray structure determinations were performed on single crystals of 1 , 2 , and 3 · C6H5Cl. The three compounds crystallize monoclinic in the space group P21/n with the following unit cell parameters. 1 : a = 1216.07(9), b = 1299.5(2), c = 2148.4(3) pm, β = 99.689(13)°, Z = 4; 2 : a = 1369.22(10), b = 1257.29(5), c = 1888.04(15) pm, β = 94.395(7)°, Z = 4; 3 · C6H5Cl: a = 1276.6(4), b = 1971.7(3), c = 2141.3(5) pm, β = 98.50(3)°, Z = 4. In all structures the metal atoms have a distorted tetrahedral coordination. The crystal structure of 3 · C6H5Cl shows monomeric molecular units with terminal coordinated dicyanamide. The crystal structure of 1 is built up by dinuclear units, which are bridged by dicyanamide ligands. However, the crystal structure of 2 corresponds to a onedimensional coordination polymer, bridged by dicyanamide anions. 相似文献