Metal-phosphine chalcogenide interactions. Crystal and molecular structures of [di-μ-iodo-bis{(methyl cyanide-N)(triphenylthiophosphorane-S)copper(I)}] and [di-μ-chloro-bis{μ-1,2-ethylenebis(diphenylphosphine selenide-Se,Se)} dicopper(I)]

Complexes of Cu^I with tertiary phosphine chalcogenides are described. CuI reacts with Ph₃PS in MeCN/CH₂Cl₂ to form {CuI(Ph₃PS)(MeCN)} and CuCl reacts with 1,2-ethylene-bis(tertiary phosphine selenide) {dpeSe₂} in MeCN to yield {CuCl(dpeSe₂)}. Both compounds exist as halogen-bridged centrosymmetric dimers: [Cu₂(-I)₂-(Ph₃PS)₂(MeCN)₂] (1) and [Cu₂(-Cl)₂(dpeSe₂)₂] (2) respectively. Compound (1) has almost symmetric Cu—I bonds, d(Cu—I) = 2.6503(8) Å and d(Cu—I) = 2.7196(9) Å, and each Cu is further bonded to a S atom [d(Cu—S) = 2.3444(13) Å] from Ph₃PS and to a N atom [d(Cu—N) = 2.030(5) Å] from MeCN. Compound (2) has unequal Cu—Cl bonds, 2.6390(19) and 2.2806(18) Å and nearly equal Cu—Se bonds [2.4042(11) and 2.4060(11) Å]. The geometry about each Cu center in both cases is distorted tetrahedral. The Cu—Cu bond distance in (2) is 3.249(2) Å as compared with 3.4141(16) Å in (1). MeCN is bonded strongly to Cu^I as the excess of Ph₃PS failed to remove it from the coordination sphere. Compound (2) represents the first structurally characterised example of copper(I) with a bis(tertiary phosphine selenide) (dpeSe₂) acting as a bridging ligand.     

Metal–thiosemicarbazone interactions. Synthesis of an iodo-bridged dinuclear [diiodobis(pyrrole-2-carbaldehydethiosemicarbazone)dicopper(I)] complex

Reaction of copper(I) iodide with pyrrole-2-carbaldehydethiosemicarbazone (Hptsc) in a 1:1 mole ratio in MeCN, followed by addition of one mole of Ph₃P, yielded a complex of empirical formula, CuI(Hptsc)(Ph₃P), whose X-ray structure determination has shown that it exists as an iodo-bridged dinuclear copper(I) complex, [Cu₂(-I)₂( ¹-S-Hptsc)₂(PPh₃)₂](1). The central kernel, Cu(-I)₂Cu forms a parallelogram with unequal Cu—I distances {Cu—I, 2.644(2), 2.707(2)Å} and bond angles {Cu—I—Cu, 70.72(7), I—Cu—I, 109.28(7)°}. Each Cu atom is further bonded to one S atom of Hptsc and one P atom of Ph₃P, thus completing tetracoordination. The Cu...Cu separation of 3.097(4)Å is close to the sum of the van der Waals radius of the Cu atom, 2.80 Å. Compound (1) involves relatively strong inter-dimer hydrogen bonding via hydrazinic and pyrrole ring hydrogens with sulfur and iodine atoms respectively of the adjacent dimer {N(1)H...S^#2, 2.50 Å; N(4)H...I^#3, 2.91 Å}. The complex represents the first report of a copper(I) dimer with a thiosemicarbazone.     

Synthesis and crystal structures of polynuclear complexes of Cu with 1-methyl-1,3-imidazoline-2-thione

Reactions of equimolar solutions of copper(I) halides with 1-methyl-1,3-imidazoline-2-thione (SC₄H₆N₂) in acetonitrile have yielded a trinuclear complex, {Cu₃(η¹-Br)₃(μ-SC₄H₆N₂)₃} · CH₃CN 1, and 1D polymer, {Cu₂(μ-I)₂(μ-SC₄H₆N₂)₂}_n2. The thio-ligands/halogens adopt μ-S, η¹-X or μ-X modes. There is weak interaction between trinuclear units {Cu···Br, 3.025 Å} and Cu···Cu contacts lie in the range, 2.974(2)–3.650(2) Å. Polymer 2 has alternating Cu₂I₂ and Cu₂S₂ cores involving sulfur/iodine bridging in a twisted ribbon type arrangement with short Cu···Cu distances {2.6912(9) and 2.785(9) Å}, respectively. The polynuclear complexes in dimethyl sulfoxide exhibit intense fluorescent bands {λ_em = 319 (1) and 322 (2)}.     

Mixed Complex Salt [Cu4(SCN2H4)7(NO3)](NO3)(SO4) · 3.3H2O: Synthesis and X-Ray Diffraction Analysis

The complex salt [Cu₄(SCN₂H₄)₇(NO₃)](NO₃)(SO₄) · 3.3H₂O was synthesized via reaction of aqueous solutions of thiourea with copper nitrate at 80°C and studied using X-ray diffraction analysis. The conditions and reasons for the partial oxidation of thiourea to sulfate ions were established. The crystals are monoclinic: a = 12.6072(7) Å, b = 15.4265(8) Å, c = 22.108(1) Å, = 120.133(6)°, space group P2₁/c, Z = 4. The crystal structure consists of [Cu₄(SCN₂H₄)₇(NO₃)]³⁺ complex cations, SO₄ ^2–, and NO₃ ^– anions, and molecules of the water of crystallization. Three types of coordination of the Cu atom were distinguished in the structure: trigonal (Cu–S 2.213–2.279 Å), tetrahedral (Cu–S 2.315–2.459 Å), and trigonal–pyramidal (3+1) (Cu–S 2.26–2.288, Cu–O 2.68 Å). The NO₃ ligand was found to be orientationally disordered.     

Further Aspects of the Chemistry of the Dirhenium Complexes [(triphos)Re(μ-X)3Re(triphos)]n+ (n=1 or 0), Where triphos=CH3C(CH2PPh2)3 and X=Cl or Br

The dirhenium(II) complexes [Re₂(-X)₃(triphos)₂]O₃SCF₃ (X=Cl or Br) have been prepared by anion exchange reactions. These salts show well defined simple electron-transfer redox chemistry (two reversible one-electron oxidations and two one-electron reductions) but the [Re(-X)₃Re] unit is remarkably stable to reactions with donor molecules such as monodentate tertiary phosphines which can often induce cleavage of M-X-M bridges. The crystallographic characterization of these two salts show that Re–Re bonds are not present, the Re...Re distances being 3.274(1) Å for X=Cl and 3.277(1) Å for X=Br.     

Synthesis and x-ray crystal structure of a dinuclear copper(I) thiobenzoate triphenylphosphine complex

Summary In 9,10-phenanthrenesemiquinonatobis(triphenylphosphine)copper(I) (1) the semiquione ligand is oxidized by dibenzoyl disulphide to 9,10-phenanthrenequinone and the complex [(PPh₃)Cu(-PhCOS)₂ Cu(PPh₃)₂] (3) is formed. Crystals of the complex are triclinic, space group , with cell parametersa=10.712(1),b=12.887(1).c=22.064 Å, =78.29(1), =81.88(1), =80.83(1), and Z=2. The copper atoms are bridged by the sulphur atoms of the two thiobenzoate groups to form binuclear molecules. The Cu₂S₂ rhombus is strictly co-planar (Cu–S distances from 2.309 to 2.424 Å). The trigonal planar co-ordination around the one and the tetrahedral coordination around the other copper atom are completed by the phosphorus atoms of the triphenylphosphine molecules (Cu–P distances from 2.238 to 2.287 Å). The copper-copper distance (Cu–Cu=2.620 Å) is 0.6 Å longer than that in metallic copper.     

(N,N, N′, N′-tetramethylethylenediammonium)Cu2X6 (X=Cl,Br): crystal structure and magnetic interactions

Summary The crystal structures of (Me₄enH₂)Cu₂Cl₆ and (Me₄enH₂)Cu₂Br₆ have been determined. The triclinic crystals contain chains of symmetrically bibridged [Cu₂X₆]^2– dimers. Within the dimers the Cu–X distances average 2.299 Å (Cl) and 2.408 Å (Br) and the Cu–X–Cu angles are 96.4(1)^o (Cl) and 95.7(1)^o (Br). Longer Cu–X bonds, 2.679(1)Å (Cl) and 2.761(3)Å (Br), link dimers together into infinite chains via asymmetrical bridges. The bridging angles for the asymmetric bridge are 92.2(1)^o (Cl) and 89.4(1)^o (Br). Magnetic susceptibility data for both compounds are indicative of antiferromagnetic coupling. Analyses of the data yields J/k=–23(1)K (Cl) and –82(2)K (Br) for the interdimer coupling and J/k=–5(1)K (Cl) and –4(1)K (Br). The intradimer coupling for the chloride is in accord with magneto-structure relations deduced for similar salts. Similarly, the increased antiferromagnetic contribution upon substitution of Cl by Br follows trends previously observed.     

Diaqua[N,N-di(2-carboxyethyl)-o-anisidinato]copper(II) Dihydrate [Cu(o-Andp)(H2O)2] · 2H2O: Synthesis and Crystal Structure

Crystals of [Cu(o-Andp)(H₂O)₂] · 2H₂O (where o-Andp^2–is -anisidine-N,N-di-3-propionate) were synthesized and studied using X-ray diffraction analysis. The crystals are triclinic: a= 12.063(1) Å, b= 12.483(3) Å, c= 13.586(2) Å, = 91.29(1)°, = 111.67(1)°, = 104.00(1)°, V= 1830.5(5) ų, space group P , Z= 2, and R= 0.0528 for 5965 reflections with I2(I). The two crystallographically independent complexes are isostructural. The tetragonal–bipyramidal coordination of copper(III) involves three O atoms, the N atom of the tetradentate ligand o-Andp^2–, and two O atoms from water. The aminodipropionate group of the ligand (average Cu–O 1.939 Å and Cu–N 2.051 Å) and one of the coordinated water molecules (Cu–O(w) 1.991 Å) lie in the equatorial plane. The second water molecule (Cu–O(w) 2.32 Å) and the methoxy O atom of o-Andp^2–(Cu–O 2.37 Å) are in the apical positions of the bipyramid.     

Copper(II) Cyanoacetate Polymer: Synthesis and Structure

A new copper carboxylate polymer with cyanoacetate anion as a ligand was synthesized and studied using X-ray diffraction, IR, and EPR spectroscopy. The crystal is tetragonal: a= 14.702(2) Å, c= 13.470(3) Å, Z= 8, space group I4₁/a, and R= 0.0634. The copper atoms in the centrosymmetric dimeric fragment have a square-pyramidal surrounding with the CuO₄N coordination core and are joined through four bidentate bridging anions of cyanoacetic acid Cu(1)"–O(1A) 1.931(4) Å, Cu(1)"–O(1B) 1.926(4) Å, Cu(1)–O(2B) 2.018(3) Å, Cu(1)–O(2A) 2.036(4) Å, and Cu(1)–N(1A)" 2.206(5) Å). The Cu···Cu" distance in the dimer is 2.709 Å. The copper atom is extended from the mean equatorial plane toward the axial nitrogen atom by 0.23 Å. EPR data confirm strong antiferromagnetic interaction (2J –275 cm^–1) between the copper(II) ions of the dimeric fragment, whereas the interaction between the dimers is significantly weaker (J< 0.3 cm^–1).     

Cu2O(SO4), dolerophanite: Refinement of the crystal structure,with a comparison of [O Cu(II)4] tetrahedra in inorganic compounds

The refinement of the crystal structure of Cu₂O(SO₄), dolerophanite, [a=9.370 (1) Å,b=6.319 (1) Å,c=7.639 (1) Å, =122.34 (1)°; space group C 2/m;Z=4;R=0.035] confirmed the trigonal dipyramidal coordination of one Cu(II) atom (mean distance Cu-O=2.025 Å). One O atom is tetrahedrally surrounded by four Cu(II) atoms; the mean Cu(II)-O distance of 1.918 Å compares well to [O Cu(II)₄] tetrahedra found in inorganic crystal structures.de|Die Verfeinerung der Kristallstruktur von Cu₂O(SO₄), Dolerophanit, [a=9.370 (1) Å,b=6.319 (1) Å,c=7.639 (1) Å, =122.34 (1)°; Raumgruppe C 2/m;Z=4;R=0.035] bestätigte die trigonal dipyramidale Koordination des einen Cu(II)-Atoms (mittlerer Cu-O-Abstand=2.025 Å). Ein O-Atom ist tetraedrisch von vier Cu(II)-Atomen umgeben; der mittlere Cu(II)-O-Abstand von 1.918 Å entspricht den in ähnlichen [O Cu(II)₄]-Tetraedern von anorganischen Kristallstrukturen gefundenen Werten.

---

Cu₂O(SO₄), Dolerophanit: Verfeinerung der Kristallstruktur mit einem Vergleich von [O Cu(II)₄]-Tetraedern in anorganischen Verbindungen

     

Structure of Complexes Formed in the CuX2–Cu–N-Allylisoquinolinium Chloride System (X = Cl,Br)

The crystals of N-allylisoquinolinium chlorides of the compositions [C₉H₇N(C₃H₅)]₂Cu^IICl₄ (I), [C₉H₇N(C₃H₅)]Cu^ICl₂ · H₂O (II), and [C₉H₇N(C₃H₅)]Cu^ICl_1.43Br_0.57 · H₂O (III) were prepared by alternating-current electrosynthesis. X-ray diffraction analysis (using diffractometer models DARCH1 for I, STOE for II, and KUMA/CCD for III, MoK radiation) showed that the crystals of I are monoclinic, space group P2₁/n, a = 14.91(1) Å, b = 10.41(1) Å, c = 16.90(1) Å, = 109.73(8)°, V = 2470(8) ų, Z = 4. The crystals of isostructural compounds II and III are triclinic, space group P, Z = 2; crystals II: a = 7.2446(6) Å, b = 7.4379(6) Å, c = 12.110(1) Å, = 80.95(1)°, = 85.55(1)°, = 86.60(1)°, V = 641.8(2) ų; crystals III: a = 7.253(2) Å, b = 7.459(4) Å, c = 12.151(5) Å, = 80.82(4)°, = 83.73(3)°, = 86.81(4)°, V = 644.6(9) ų. The structure of I is composed of Cu^IICl₄ ^2– tetrahedra and N-allylisoquinolinium cations united by C–H···Cl hydrogen bonds in corrugated layers. The crystal structures of -complexesII and III are built of [C₉H₇(C₃H₅)]₂Cu₂ ^IX₄ dimers, which form layers along the c axis due to the C–H···X hydrogen bonds. An important role in the structure formation is played by water molecules, which crosslink the organometallic layers to form a three-dimensional framework through the O–H···X contacts.     

Copper(I) Acetylenide π-Complexes. Synthesis and Structure of Cluster Compound HAmp[Cu9Cl8(C≡CCH2OH)2] (HAmp is 4-Aminopyridinium Cation)

Crystals of the HAmp[Cu₉Cl₈(CCCH₂OH)₂] cluster compound (HAmp is the 4-aminopyridinium cation (NH₂–C₅H₄NH)⁺) were obtained through ac electrochemical synthesis and their structure was determined using X-ray diffraction analysis (DARCh autodiffractometer, /2 scan mode, 3435 independent reflections with F 4(F), R = 0.047). The crystals are triclinic: space group P , a = 12.547(5) Å, b = 12.502(4) Å, c = 8.201(2) Å, = 75.93(2)°, = 82.21(3)°, = 76.05(3)°, V = 1207(2) ų, Z = 2. Two crystallographically independent moieties ^–(CCCH₂OH) were detected in the complex structure. Each moiety acts as a double bridging ,-ligand and binds four or five Cu(I) atoms, thus forming the [Cu₄(CCCH₂OH)] and [Cu₈(CCCH₂OH)₂] clusters. The shortest Cu···Cu distance is equal to 2.337(4) Å.     

An approach to the structure and spectra of copper barbiturate trihydrate

In the neutral title complex [Cu(C₄N₂H₃)₂(H₂O)₃] or [Cu(BBR)₂(H₂O)₃] (BBR^– = Barbiturate), the Cu^II ion, in the slightly distorted square-pyramidal geometry, is coordinated by two O atoms of the two monodentate barbiturates and three O atoms of three water ligands. The average bond length of Cu—O (BBR^–) is 1.981(5) Å and the average bond length of Cu—O (H₂O) at the basal sites is 1.94(5) Å, i.e. much shorter than that of Cu—O (H₂O) [2.175(11) Å]. The crystal structure is characterized by an extensive network of hydrogen bonds in which each [Cu(BBR)₂(H₂O)₃] entity links to six adjacent [Cu(BBR)₂(H₂O)₃] by O(C=O) ··· H—O(H₂O) bonds. Tautomerism in the coordination process for BBR^– was found from the crystal structure and i.r. spectral analysis. The interaction of Cu^II and BBR^– in aqueous solution was also investigated by electronic spectra and electrochemical method. It was observed that the copper ion could not only form the [Cu(BBR)₂(H₂O)₃] complex in aqueous but also catalyze the decomposition of BBR^– at pH 1.1.     

On the crystal chemistry of three copper(II)-arsenates: Cu3(AsO4)2-III,Na4Cu(AsO4)2, and KCu4(AsO4)3

The three copper(II)-arsenates were synthesized under hydrothermal conditions; their crystal structures were determined by single-crystal X-ray diffraction methods:Cu₃(AsO₄)₂-III:a=5.046(2) Å,b=5.417(2) Å,c=6.354(2) Å, =70.61(2)°, =86.52(2)°, =68.43(2)°,Z=1, space group ,R=0.035 for 1674 reflections with sin / 0.90 Å^–1.Na₄Cu(AsO₄)₂:a=4.882(2) Å,b=5.870(2) Å,c=6.958(3) Å, =98.51(2)°, =90.76(2)°, =105.97(2)°,Z=1, space group ,R=0.028 for 2157 reflections with sin / 0.90 Å^–1.KCu₄(AsO₄)₃:a=12.234(5) Å,b=12.438(5) Å,c=7.307(3) Å, =118.17(2)°,Z=4, space group C2/c,R=0.029 for 1896 reflections with sin / 0.80 Å^–1.Within these three compounds the Cu atoms are square planar [4], tetragonal pyramidal [4+1], and tetragonal bipyramidal [4+2] coordinated by O atoms; an exception is the Cu(2)^[4+1] atom in Cu₃(AsO₄)₂-III: the coordination polyhedron is a representative for the transition from a tetragonal pyramid towards a trigonal bipyramid. In KCu₄(AsO₄)₃ the Cu(1)^[4]O₄ square and the As(1)O₄ tetrahedron share a common O—O edge of 2.428(5) Å, resulting in distortions of both the CuO₄ square and the AsO₄ tetrahedron. The two Na atoms in Na₄Cu(AsO₄)₂ are [6] coordinated, the K atom in KCu₄(AsO₄)₃ is [8] coordinated by O atoms.Die drei Kupfer(II)-Arsenate wurden unter Hydrothermalbedingungen gezüchtet und ihre Kristallstrukturen mittels Einkristall-Röntgenbeugungsmethoden ermittelt:Cu₃(AsO₄)₂-III:a = 5.046(2) Å,b = 5.417(2) Å,c = 6.354(2) Å, = 70.61 (2)°, = 86.52(2)°, = 68.43(2)°,Z = 1, Raumgruppe ,R = 0.035 für 1674 Reflexe mit sin / 0.90 Å^–1.Na₄Cu(AsO₄)₂:a = 4.882(2) Å,b = 5.870(2) Å,c = 6.958(3) Å, = 98.51(2)°, = 90.76(2)°, = 105.97(2)°,Z = 1, Raumgruppe ,R = 0.028 für 2157 Reflexe mit sin / 0.90 Å^–1.KCu₄(AsO₄)₃:a = 12.234(5) Å,b = 12.438(5) Å,c = 7.307(3) Å, = 118.17(2)°,Z = 4, Raumgruppe C2/c,R = 0.029 für 1896 Reflexe mit sin / 0.80 Å^–1.Die Cu-Atome in diesen drei Verbindungen sind durch O-Atome quadratisch planar [4], tetragonal pyramidal [4 + 1] und tetragonal dipyramidal [4 + 2]-koordiniert; eine Ausnahme ist das Cu(2)^{[4 + 1]}-Atom in Cu₃(AsO₄)₂-III: Das Koordinationspolyeder stellt einen Vertreter des Übergangs von einer tetragonalen Pyramide zu einer trigonalen Dipyramide dar. In KCu₄(AsO₄)₃ haben das Cu(1)^[4]O₄-Quadrat und das As(1)O₄-Tetraeder eine gemeinsame O—O-Kante von 2.428(5) Å, was eine Verzerrung der beiden Koordinationsfiguren CuO₄-Quadrat und AsO₄-Tetraeder bedingt. Die zwei Na-Atome in Na₄Cu(AsO₄)₃ sind durch O-Atome [6]-koordiniert, das K-Atom in KCu₄(AsO₄)₃ ist [8]-koordiniert.

---

Zur Kristallchemie dreier Kupfer (II)-Arsenate: Cu₃(AsO₄)₂-III, Na₄Cu(AsO₄)₂ und KCu₄(AsO₄)₃

     

A novel discrete dinuclear copper(II)–gadolinium(III) complex derived from a Schiff base ligand [Cu(salbn)Gd(NO3)3·H2O] (salbn): N,N′-butylenebis(salicylideaminato)

The synthesis, X-ray and e.p.r. spectral studies of a 3d–4f couple are described here. The crystal structure of [Cu(salbn)Gd(NO₃)₃·H₂O], (2), salbn = N,N-butylenebis(salicylideaminato), has been determined by X-ray crystallography. Compound (2) crystallizes in the monoclinic system, space group p21/n, with a = 9.025(1), b = 22.912(1), c = 12.790(1) Å, = 99.36(1), Z = 4. The deviations of the four coordinating atoms (O(1)O(2)N(1) and N(2) of salbn and the copper atom is displaced from the plane in spite of the lack of any apical ligand. The gadolinium(III) ion is nine-coordinated by the two oxygen atoms of the salbn moiety, three bidentate nitrate ions and one water molecule. The geometry of Gd^III can be described as a square antiprism, in which compound Cu^II and Gd^III are bridged by the two phenolic oxygens of salbn. The Cu^II–Gd^III distance is 3.269(1) Å. The bridging core CuO2Gd is a butterfly shape. Significant distortion was observed for the complex having the larger diamino string. The title compound exhibits seven e.s.r. transitions with |D| = 0.0467 cm^–1, which demonstrates the existence of zero field splitting. This outcome indicates that compound (2) consists of a perfectly isolated dinuclear Cu–Gd core and steric bulk alters the dihedral angle in the Cu–O–Gd bridge.     

Two clathrates of bis(isothiocyanato)tetrakis(4-methylpyridine)magnesium(II) as a host with 4-methylpyridine as a guest

Two clathrate modifications of the title host with 4-methylpyridine (4-CH₃C₅H₄N) as a guest have been determined at –50°C. [Mg(4-CH₃C₅H₄N)₄(NCS)₂] · 2/3(4-CH₃C₅H₄N) · 1/3H₂O is trigonal, space group , witha=27.630(7),c=11.219(3) ÅV=7417(4) ų,Z=9,D _calc=1.171 g cm^–3,(CuK )=18.506 cm^–1, finalR=0.064. [Mg(4-CH₃C₅H₄N)₄(NCS)₂] · (4-CH₃C₅H₄N) is tetragonal, space group I4_l/a, witha=16.944(7),c=23.552(9)Å,V=6762(5) Å,Z=8,D _calc=1.191 g cm^–3, (CuK )=18.200 cm^–1, finalR=0.071.The structures consist of molecular packings of the same host complex units and the guest species. The Mg(II) cation is octahedrally coordinated to theN-atoms of four 4-methylpyridine and twotrans-coordinated isothiocyanato ligands in the host molecule. The conformations of the molecule are considerably different both in symmetry and in geometry in these two structures. The guest 4-methylpyridine molecules are disordered into channels which have different topology in these two clathrates resulting in different thermal stability.     

Di- and trinuclear olato-bridged copper(II) compounds of 3,7-bis(3-olatopropyl)-1,3,5,7-tetraazabicyclo[3,3,1]nonane (protan); the structures of [{Cu(μ-protan)}2Cu](ClO4)2·H2O and [{Cu(μ-protan)}Cu(OH)2](ClO4)2·0.5(EtOH)

A compound with a linear trinuclear copper(II) cation, [Cu₃(μ-protan)₂](ClO₄)₂·H₂O (protanH₂ = 3,7-bis(3-hydroxypropyl)-1,3,5,7-tetraazabicyclo[3,3,1]-nonane) is formed by reaction of copper(II) perchlorate, 3-aminopropanol, ammonia and methanal. The cation is approximately centrosymmetrical with Cu?Cu = 2.9870(5) and 2.9485(5) Å. The terminal copper(II) ions are coordinated by nitrogen atoms 3 and 7 of the tetraazabicycle (Cu–N_mean = 2.021(5) Å) and the two oxygen atoms of the 3,7-bis(3-olatopropyl) substituents (Cu–O_mean = 1.911(3) Å), which also act as bridging groups to the central copper(II) ion (Cu–O_mean = 1.926(4) Å). The cation is both helically twisted (dihedral angle N3?N7?N3′?N7′ = 20(1)°) and bent (angle Cu?Cu?Cu = 171(1)°). The copper(II) ions have tetrahedrally twisted square planar primary coordination, with perchlorate ion oxygen atoms weakly coordinated axially to the two terminal copper(II) ions, on opposite sides of the “plane” of the molecule, while the central copper(II) ion is weakly coordinated axially by a water molecule, with all axial Cu–O distances ca. 2.9 Å. One N·CH₂·CH₂·CH₂·O chelate ring for each protan²⁻ ligand shows conformational disorder and the perchlorate ions show rotational disorder. Partial hydrolysis of the protan²⁻ compound gave a compound [{Cu(μ-protan)}Cu(OH)₂](ClO₄)₂·0.5(EtOH) which has a dinuclear cation, with one copper(II) ion in square-planar coordination by tetradentate protan²⁻ and the other in square-planar coordination by the two bridging oxygen atoms of the protan²⁻ ligand and by two hydroxide ions, with Cu?Cu = 3.045(1) Å. With differing mole ratios of the same reactants compounds of the dinuclear cation [{Cu(μ-pta)}₂]²⁺ (ptaH = 3(3-hydroxypropyl)-1,3,5,7-tetraazabicyclo[3,3,1]nonane) are formed.     

The Synthesis,Infra-Red Spectrum,Room Temperature Crystal Structure and Hydrogen Bonding Network of Bis(2,2′-Bipyridyl)Monobenzoatocopper(II) Nitrate Hydrate. Investigation into the Role of Benzoato Coordination in the Vibronic Coupling Interpretation of Static Copper(II) Complexes

The crystal structure of bis(2,2-bipyridyl)monobenzoatocopper(II) nitrate hydrate, [Cu(bipy)₂(O₂CPh)][NO₃]· H₂O, (1) has been determined. The [Cu(bipy)₂(O₂CPh)]⁺ cation chromophore is basically five-coordinate, but with O(1), the second oxygen atom of the benzoato ligand, occupying the sixth coordinate position at a distance 2.696(2)Å, from the copper. This suggests a (4 + 1 + 1^*) coordination, involving a distorted stereochemistry, with a CuN₄OO chromophore. O(2) is located at a distance 2.009(2)Å from the copper. The two oxygens, O(1) and O(2), therefore occupy cis positions of the distorted octahedral coordination sphere and the coordinated benzoate is a highly asymmetric, bidentate ligand with O = 0.687(2)Å and Cu—O_MEAN= 2.353(2)Å. The two nitrogens, N(1) and N(3), located in positions trans to the oxygen sites, at distances Cu—N(1)= 2.148(2)Å and Cu—N(3)= 2.058(2)Å[Cu—N_mean/in= 2.103(2)Å, N_1,3= 0.090(2)Å] are slightly longer than the bonds to the two mutually trans related 'axial' nitrogens, Cu—N(2)= 1.987(2)Å and Cu—N(4)= 1.977(2)Å. The 'equatorial' angles ₁, ₂ and ₃ have values 147.34(8), 93.29(9) and 105.39(9) respectively. The back-angle, ₃, of 105.39(9)° is unique for a bipy complex, containing a carbonyl-containing oxoanion in such series. The asymmetric nature of the benzoato ligand is further evidence of the static nature of such complexes. The complex also involves a hydrogen bonding network, linking the O(6) of the nitrate to H(2)W of the water molecule at a distance 2.052(6)Å and H(1)W to the long-bonded O(1) of the benzoato ligand, at a distance of 1.804(12)Å.     

Copper(I) π-Complexes with Alkyne Ligands: Synthesis and Crystal Structure of M[CuCl2(HOCH2C≡CCH2OH)] (M = K+, NH+ 4)

Crystals of anionic complexes of the composition M[CuCl₂(HOCH₂CCCH₂OH)], where M = NH₄ ⁺ (I), K⁺ (II), were isolated from concentrated aqueous solutions of CuCl and MCl (M = NH₄ ⁺, K⁺) in the presence of 2-butyne-1,4-diol. Their structures were studied by X-ray diffraction analysis. Isostructural crystals I and II are orthorhombic; Z = 8, space group Ibam; a = 6.735(1) and 6.666(2) Å, b = 17.206(3) and 16.874(6) Å, c = 15.172(3) and 15.032(4) Å, V = 1758(1) and 1691(1) ų, respectively. The compounds are built of individual [CuCl₂(HOCH₂CCCH₂OH)] anions; the NH₄ ⁺ (I) or K⁺ (II) cations are arranged in the voids between the anions. The -coordinated Cu(I) atoms have trigonal-planar environment of two chlorine atoms and CC bond of the 2-butyne-1,4-diol molecule. The Cu–(CC) distances in the -core are 1.892(4) and 1.887(6) Å, CC are 1.233(5) and 1.228(5) Å in I and II, respectively. In complex I, additional hydrogen bonds Cl···H–NH₃ (Cl···H 2.43(4) Å) and O···H–NH₃ (O···H 1.97(3) Å) stabilize the structure.     

μ-Oxo-Bis[(arenesulfonato)triphenylantimony]: Synthesis and Structure

-Oxo-bis[(4-methylbenzenesulfonato)triphenylantimony] (I) and -oxo-bis[(2,5-dimethylbenzenesulfonato)triphenylantimony] (II) were synthesized by reacting triphenylstibine Ph₃Sb with tri-p-tolylbismuth bis(4-methylbenzenesulfonate) and tri-p-tolylbismuth bis(2,5-dimethylbenzenesulfonate), respectively, in toluene in the presence of air moisture. According yo X-ray diffraction data, the antimony atoms in the compounds synthesized have a distorted trigonal bipyramidal configuration. The SbOSb angles are equal to 138.5(2)° and 180°, respectively. A bent molecule I contains the Sb(1)···Sb(2) (3.690(1) Å) and Sb···S(1,2) (3.521(2), 3.559(2) Å) intramolecular contacts. In a linear molecule II, the Sb···S distances are equal to 3.438(1) Å.