Mononuclear Complexes of Cr(II) and Fe(II) with Terminal -SH Groups. Synthesis and X-Ray Crystal Structures of trans-M(SH)2(dmpe)2 (M = Cr,Fe; dmpe = 1,2-Bis(Dimethylphosphino)Ethane)

Abstract

The reaction of two equivalents of NaSH with MCl₂(dmpe)₂ (M = Cr, Fe,) at—78°C gives trans-M(SH)₂(dmpe)₂ (M = Cr, (1), 30%; Fe, (2) 98%). The complexes have been characterized spectroscopically, and the trans geometry has been confirmed by single crystal X-ray diffraction studies. Crystal data (1): C₁₂H₃₄CrP₄S₂, M= 418.42, monoclinic, P2₁/n, a = 8.857 (I), b= 12.719 (2), c = 9.648 (I) Å, β = 92.14(1)°, U= 1086.2 (5)Å, D _c = 1.279gcm^?3, Z = 2, λ(MoK_a) = 0.71073 Å, (graphite mono-chromator), μ(MoK_a) = 9.80cm^?1. Methods: MULTAN, difference Fourier, full-matrix least-squares. Refinement of 1149 reflections (I > 3σ(I)) out of 1901 unique observed reflections (3.0° < 29 < 48.0°) gave R and R _w values of 0.092 and 0.096, respectively. Crystal data (2): C₁₂H₃₄FeP₄S₂, M = 422.28, monoclinic, P2₁/n, a = 8.834 (2), b = 12.594 (2), c = 9.532 (2) Å, β = 90.66 (2)°, U = 1060.3 (5) ų, D _c = 1.323 g cm^?3, Z = 2, γ(MoK_a) = 0.71073 Å, (graphite monochromator), μ(MoK_a) = 11.87 cm^?1. Methods: same as for (1). Refinement of 1178 reflections (I > 3σ (I)) out of 2086 unique observed reflections (2.0° < 20 < 50.0°) gave R and R _w values of 0.056 and 0.059, respectively.     

Alkyl Rearrangement of Derivatives of 2-Anilino-4,6-dialkoxy-1,3,5-triazines in the Solid- and Liquid-state

Abstract

2-Anilino-4,6-dimethoxy-1,3,5-triazine (13), 2-anilino-4,6-diethoxy-1,3,5-triazine (14), 2-(2′-nitoanilino) 4,6-dimethoxy-1,3,5-triazine (15) undergo alkyl rearrangement in the liquid-state, while 2-(4′-nito-anilino) 4,6-dimethoxy-1,3,5-triazine (16) undergoes methyl rearrangement in the solid-state. The crystal structure and thermal behavior of these compounds are described. 13 crystallizes in monoclinic P2₁/c space group, a = 11.030(4), b = 6.345(4), c = 16.315(4) Å, β = 90.76(3)°. The calculated density for Z = 4 is 1.351 Mg/m³. The number of unique reflections collected is 2092, and the final R = 0.0643 [I > 2σ(I)]. 14 crystallizes in triclinic P-1 space group, a = 7.700(2), b = 9.723(3), c = 10.154(3) Å, α = 78.78(3), β = 70.32(3), γ = 73.67(3)°. The calculated density for Z = 2 is 1.266 Mg/m³. The number of unique reflections collected is 2401, and the final R = 0.0561 [I > 2σ(I)]. 15 crystallizes in monoclinic P21/m space group, a = 11.020(3), b = 6.600(2), c = 8.409(3) Å, β = 99.72(3)°. The calculated density for Z = 2 is 1.527 Mg/m³. The number of unique reflections collected is 1153, and the final R = 0.0502 [I > 2σ(I)]. 16 crystallizes in monoclinic P21/c space group, a = 7.499(3), b = 21.846(5), c = 7.895(3) Å, β = 115.42(3)°. The calculated density for Z = 4 is 1.576 Mg/m³. The number of unique reflections collected is 2036, and the final R = 0.0757 [I > 2σ(I)].     

Self-assembly by co-ordination and strong hydrogen bonding. X-ray crystal structures of a dimeric trisodium complex of a new acidic complexing ligand and its dihydrate

Abstract

The new acidic complexing ligand triethanolamine-O,O,O-triacetic acid, 3, is synthesized by reaction of triethanolamine with chloroacetic acid in the presence of sodium tert-butoxide. The resulting Na complex, 4, and its dihydrate, 5, contain two ligand molecules, both with one Na⁺ ion interaction and both co-ordinated to a third, central, Na⁺ ion. In addition the acidic ligands are hydrogen bonded to each other, like carboxylic acids, and in 4, by three crystallographically symmetric hydrogen bonds, while in 5, due to the breakdown of symmetry, two normal and one crystallographically symmetrical hydrogen bond. Inside this extraordinary dimeric assembly (a pseudo-cryptate) are the three sodium ions encapsulated, like in cryptates, with a Na⁺…Na⁺ distance of 3.357(3) Å (4) and 3.325(2) Å (5). Crystal data, 4: a = 12.198(1) Å, c = 40.926(5) Å, V = 5274(3) Å, trigonal, space group = R-3c (no. 157), d _calc = 1.346 g cm^?3, Z = 6, obs. refl. [I > σI] = 396, R = 0.045; 5: a = 25.045(5) Å, b = 11.373(2) Å, c = 14.301(2) Å, β = 122.38(1)°, V = 3440(1) ų, monoclinic, space group = C2/c, d _calc = 1.446 g cm^?3, Z = 4, obs. refl. [I > 2σI] = 1362, R = 0.041.     

Dinuclear copper(II) complex and 1-D copper(II) complex with taurine Schiff base: synthesis,crystal structure,and properties

A dinuclear copper(II) compound, [Cu(btssb)(H₂O)]₂ · 4(H₂O) (1), and a 1-D chain copper(II) compound, [Cu(ctssb)(H₂O)] _n (2) [where H₂btssb is 2-[(5-bromo-2-hydroxy-benzylidene)-amino]-ethanesulfonic acid and H₂ctssb is 2-[(3,5-dichloro-2-hydroxy-benzylidene)-amino]-ethanesulfonic acid], were prepared and characterized. Compound 1 crystallizes in the monoclinic space group P2₁/c, with a = 10.109(2) Å, b = 20.473(4) Å, c = 6.803(1) Å, β = 100.32(3)°, V = 1385.1(5) ų, and Z = 2; R ₁ for 1796 observed reflections [I > 2σ(I)] was 0.0357. The geometry around each copper(II) can be described as slightly distorted square pyramidal. The Cu^II ··· Cu^II distance is 5.471(1) Å. Compound 1 formed a 1-D network through O–H ··· O hydrogen bonds and 1-D water chains exist. The 1-D chain complex 2 crystallizes in the triclinic space group P 1, with a = 5.030(2) Å, b = 7.725(2) Å, c = 17.011(5) Å, α = 92.706(4)°, β = 97.131(4)°, γ = 102.452(3)°, V = 638.6(3) ų, and Z = 2; R ₁ for 1897 observed reflections [I > 2σ(I)] was 0.0171. In 2, Cu(II) was also a slightly distorted square pyramid formed by two oxygens and one nitrogen from ctssb, one oxygen from another ctssb, and one water molecule. The complex formed a 1-D chain through O–S–O bridge of ctssb ligand. The 1-D chain further constructed a double chain through O?H ··· O hydrogen bonds.     

THE CRYSTAL STRUCTURES OF 10,10′-BIS(PHENOXARSINE) OXIDE AND SELENIDE

Abstract

The reaction between 10,10′-bis(phenoxarsine) oxide (I) and HI gives 10-iodophenoxarsine. The latter, on treatment with H₂Se give 10,10′-bis(phenoxarsine) selenide (II). The crystal structures of I and II have been determined from single crystal X-ray data. The unit cell for I is monoclinic, P2₁/c (No. 14) with a = 15.976(3) Å, b = 10.582(2) Å, c = 12.581(2) Å, β = 111.70(1)° V = 2018.6 ų; d(calc.) = 1.65Mg/m³ at 23°C for four molecules per unit cell. From 3279 reflections for which I>0.5σ(I), F>σ(F), R = 0.041 with anisotropic thermal parameters for all non-hydrogen atoms and with fixed positions and thermal parameters for hydrogens. One of the phenoxarsina rings deviates from planarity by approximately 5° while the other deviates by more than 24°. The (As[sbnd]O) distances are 1.810(3) and 1.821(3) Å for the flat and bent ring and the (As[sbnd]O[sbnd]As) angle is 122.3(1)°. The bond distances to As and O from C are nearly the same for both rings, but the bond angles with As and the ring O as the apex are systematically larger for the flat ring. For II the unit cell is triclinic, P1 (No. 2) with a = 9.368(1) Å, b = 14.089 Å, c = 9.269(2) Å, α = 111.37(2), β = 113.11(2), γ = 74.76(1); V = 1037.5 ų, d(calc) = 1.81 Mg/m³ for two molecules per unit cell at 23°C. From 2945 reflections for which I > 0.5σ(I), F > σ(F), R = 0.055 with anisotropic thermal parameters for all non-hydrogen atoms and with fixed positions and thermal parameters for hydrogen. One of the phenoxarsina rings deviates by 3° from planarity and the other by 8°. The (As[sbnd]Se) bond distances are 2.416(1) and 2.406(1) Å. The (As[sbnd]Se[sbnd]As) bond angle is 96.66(4)° and the corresponding (As[sbnd]C) and (C[sbnd]C) distances in the two rings are nearly the same. In comparison with I, the angles with As or O as the central atoms are about the same in both rings of II.     

SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF TRIS(DIMETHYLDITHIOCARBAMATE) INDIUM(III), In[S2CN(CH3)2]3

Abstract

The synthesis and structure of the indium dithiocarbamate, In[S₂CN(CH₃)₂]₃·(1/2) 4-mepy (4-mepy=4-methylpyridine), is described. Indium metal was oxidized by tetramethylthiuram disulfide in 4-methylpyridine at 25°C to form a new, homoleptic indium(III) dithiocarbamate in yields exceeding 60%. In[S₂CN(CH₃)₂]₃ exists as a discrete molecule with a distorted-octahedral geometry. The compound crystallizes in the P 1 (No. 2) space group with a=9.282(1)Å, b=10.081(1)Å, c=12.502Å, α=73.91(1)°, β=70.21(1)°, γ=85.84(1)°, Z=2, V(Å)=1057.3(3), R=0.046 and R_w =0.061.     

Synthesis and Characterization of the Cobalt Complexes of New BF2 + Bridged,Anthracene Substituted Bis(a-Dioxime) Macrocycles

Abstract

The synthesis, characterization and structure are described for new cobalt complexes, with a BF₂ ⁺ bridged, bis(a-dioxime) ligand, based upon a sterically demanding framework derived from an anthracene Diels-Alder adduct. The ligand provides a deep cleft within which axial ligands and/or O₂ can bind. The crystal structures of the bis- and mono(BF₂ ⁺) bridged complexes have space groups P2₁/c and P I, respectively, with unit cell dimensions a = 12.662(2) Å, b = 16.430(3) Å, c = 10.438(3) Å, β = 103.51(2)°, a = 12.046(1)Å, b = I7.596(3)Å, c = 9.939(I)Å, a = 105.15(1)°, β = 102.87(1)°, and γ = 78.13(1), respectively. For both complexes Z = 2 and the residuals R and R _w were 0.070, 0.104, and 0.059, 0.075, respectively. ESR studies show that the cobalt(II) complexes have a strong tendency to bind two axial nitrogen bases, adopting a coordination number of six. The dioxygen affinity of the new cobalt(II) dioxygen carrier is limited by the competition between axial base binding and O₂ binding. This extends the understanding of correlations between electrode potentials and O₂ affinities and possible sources of apparent contradictions.     

Transition Metal Halide Salts of 2-Amino-5-Substituted-Pyridines: Synthesis,Crystal Structure and Magnetic Properties of Two Polymorphs of (5-IAP)2CuCl4[5-IAP = 2-Amino-5-Iodopyridinium]

The reaction of anhydrous CuCl₂ with HCl and 2-amino-5-iodopyridine in 1-propanol resulted in two polymorphs of (5-IAP)₂[CuCl₄] [5-IAP = 2-amino-5-iodopyridinium], one as red rods (1) and one as orange prisms (2). The two polymorphs have been characterized by single crystal x-ray diffraction and variable temperature magnetic susceptibility. Crystal data: triclinic, P-1, F(000) = 606, MoK _α (λ = 0.71073 Å): for (1): a = 9.248(6), b = 10.202(7), c = 10.368(7) Å, α = 102.451(9), β = 96.662(8), γ = 96.725(8)°, V = 938.4(11) &Aringsup3;, Z = 2, D_calc = 2.291 Mg/m³, μ = 5.020 mm^?1, R = 0.0392 for [|I|≥2σ(I)]. For (2): a = 8.966(2), b = 10.755(2), c = 11.359(2) Å, α = 89.63(3), β = 68.04(3), γ = 69.07(3)°, V = 938.6(3) &Aringsup3;, Z = 2, D _calc = 2.291 Mg/m³ , μ = 5.019 mm^?1 , R = 0.0217 for [|I|≥2σ(I)]. The crystal packing for both polymorphs suggests that their magnetic behavior should be that of weakly interacting alternating linear chains. Temperature dependent susceptibility measurements yield: for 1 , C = 0.43, g = 2.14, θ = m 1.98; for 2, C = 0.45, g = 2.19, θ = ?4.15.     

Synthesis and Structural Characterization of a Novel Indium Mercapto Derivative [ClIn(SCH2(CO)O)2]2-[(4-MepyH)2]2+

The synthesis and structural characterization of a novel In(III) complex is described. The reaction between InCl₃ with sodium mercapto-acetic acid (NaSCH₂(CO)OH) in 4-methylpyridine (CH₃(C₅H₅N), (4-Mepy)) at 25°C affords [ClIn(SCH₂(CO)O)₂]^2-[(4-MepyH)₂]²⁺ (1). X-ray diffraction studies of (1) show it to have a distorted square-pyramidal geometry with the [(^-SCH₂(CO)CO^-)] ligands in a trans conformation. The compound crystallizes in the P1(No. 2) space group with a = 7.8624(6) Å, b = 9.950(1) Å, c = 13.793(2) Å, α = 107.60(1)°, β = 90.336(8)°, γ = 98.983(9)°, V = 1014.3(4) ų, R(F°) = 0.037 and R_w = 0.048.     

Influence of the Counterions on the Structures of Ternary Zn/Sn/Se Anions: Synthesis and Properties of [Rb10(H2O)14.5][Zn4(μ4‐Se)2(SnSe4)4] and [Ba5(H2O)32][Zn5Sn(μ3‐Se)4(SnSe4)4]

Reactions of rubidium or barium salts of the ortho‐selenostannate anion, [Rb₄(H₂O)₄][SnSe₄] ( 1 ) or [Ba₂(H₂O)₅][SnSe₄] ( 2 ) with Zn(OAc)₂ or ZnCl₂ in aqueous solution yielded two novel compounds with different ternary Zn/Sn/Se anions, [Rb₁₀(H₂O)_14.5][Zn₄(μ₄‐Se)₂(SnSe₄)₄] ( 3 ) and [Ba₅(H₂O)₃₂][Zn₅Sn(μ₃‐Se)₄(SnSe₄)₄] ( 4 ). 1 – 4 have been determined by means of single crystal X‐ray diffraction: 1 : triclinic space group lattice dimensions at 203 K: a = 8.2582(17) Å, b = 10.634(2) Å, c = 10.922(2) Å, α = 110.16(3)°, β = 91.74(3)°, γ = 97.86(3)°, V = 888.8(3) ų; R₁ [I > 2σ(I)] = 0.0669; wR₂ = 0.1619; 2 : orthorhombic space group Pnma; lattice dimensions at 203 K: a = 17.828(4) Å, b = 11.101(2) Å, c = 6.7784(14) Å, V = 1341.5(5) ų; R₁ [I > 2σ(I)] = 0.0561; wR₂ = 0.1523; 3 : triclinic space group ; lattice dimension at 203 K: a = 17.431(4) Å, b = 17.459(4) Å, c = 22.730(5) Å, α = 105.82(3)°, β = 99.17(3)°, γ = 90.06(3)°, V = 6563.1(2) ų; R₁ [I > 2σ(I)] = 0.0822; wR₂ = 0.1782; 4 : monoclinic space group P2₁/c; lattice dimensions at 203 K: a = 25.231(5) Å, b = 24.776(5) Å, c = 25.396(5) Å, β = 106.59(3)°, V = 15215.0(5) ų; R₁ [I > 2σ(I)] = 0.0767; wR₂ = 0.1734. The results serve to underline the crucial role of the counterion for the type of ternary anion to be observed in the crystal. Whereas Rb⁺(aq) stabilizes a P1‐type Zn/Sn/Se supertetrahedron in 3 like K⁺, the Ba²⁺(aq) ions better fit to an anionic T3‐type Zn/Sn/Se cluster arrangement as do Na⁺ ions. It is possible to estimate a radius:charge ratio for the stabilization of the two structural motifs.     

Bis(2-Amino-5-bromopyrimidinium) Tetrahalometallates: Crystal structures of (2-amino-5-bromopyrimidinium)2 MCl4 (M = Co,Zn)

The reactions of metal(II) chlorides and bromides with 2-amino-5-bromopyrimidine (2-abpm) in neutral and acidic solution were investigated. The reaction with ZnCl₂, ZnBr₂, CoCl₂, CoBr₂ and MnCl₂ in acidic nitromethane solution gave complexes of the formula (2-abpmH)₂MX₄ (1, M?=?Zn, X?=?Cl; 2, M?=?Zn, X?=?Br; 3, M?=?Co, X?=?Cl; 4, M?=?Co, X?=?Br; 5, M?=?Mn, X?=?Cl). Crystals of 1 and 3 suitable for single crystal X-ray diffraction were obtained. Crystal data: For (1): triclinic, P-1, a?=?6.2485(13), b?=?9.0520(14), c?=?15.334(4)?Å, α?=?94.81(2), β?=?95.224(17), γ?=?98.027(17)°, V?=?851.1(3)?ų, Z?=?2, R?=?0.0596 for [|I|?≥?2σ(I)]. For (3): triclinic, P-1, a?=?6.2438(13), b?=?9.0597(15), c?=?15.318(3)?Å, α?=?94.749(18), β?=?95.343(15), γ?=?98.021(17)°, V?=?850.2(3)?ų, Z?=?2, R?=?0.0452 for [|I|?≥?2σ(I) ]. Variable temperature magnetic susceptibility data indicates weak antiferromagnetic interactions in the cobalt and manganese complexes.     

Ground state conformation of diphenylvinylphosphine sulfide and selenide

Single-crystal X-ray diffraction experiments have been performed on diphenylvinylphosphine sulfide ( 1 ): C₁₄H₁₃PS, space group P 2₁/c, a = 10.186(1) Ǎ, b = 11.918(1) Å, c = 11.426 Å, β = 112.22(2)°, V = 1284.1(2) ų, Z = 4, and diphenylvinylphosphine selenide ( 2 ): C₁₄H₁₃PSe, space group Pbca, a = 9.141 (3) Å, b = 16.458 (1) Å, c = 17.451 (1) Å, V = 2625.4 (9) ų, Z = 8. The structures were solved by direct methods and were refined by full matrix least-squares calculations to R = 0.046 and R_w = 0.058 using 2554 unique reflections with I > 3σ(I) in the case of 1 , and to R = 0.052 and R_w = 0.065 using 1953 unique reflections with I > 3σ(I) in the case of 2 . In close analogy to the previously studied vinyl phosphine oxides both 1 and 2 were found to exist in the s-cis conformation with the pertinent CC PX dihedral angles equal to 12.5° and 2.9° for 1 and 2 , respectively.     

NEW THREE DIMENSIONAL [Cd(CN)2]n FRAMEWORK FORMED WITH CADMIUM CYANIDE AND Cd(CN)2·(18-CROWN-6): CRYSTAL STRUCTURE OF [Cd(CN)2]·1/2[Cd(CN)2 (18-CROWN-6)]·3/2EtOH+

Abstract

The cadmium complex Cd(CN)₂·(18-crown-6) (1) was synthesized and its structure was determined by X-ray crystallography. The cadmium ion in 1 has a hexagonal bipyramidal geometry containing six equatorial oxygen atoms from the crown ether and two axial CN ligands. The NC-Cd-CN ‘rod’ is perfectly linear with an end-to-end distance of 6.509 (12) Å. When 1 was allowed to diffuse into a cadmium cyanide solution, the infinite coordination complex [Cd(CN)₂]·1/2[(Cd(CN)₂·(18-crown-6)]·3/2EtOH (2) was obtained in which the cadmium macrocycle 1 was trapped in a 10-faced-cage formed by the [Cd(CN)₂]n framework. The terminal nitrogen atoms of 1 bind two Cd centers across the cage. The trapped Cd(CN)₂·(18-crown-6) has a significantly bent NC-Cd-CN unit and the crown ether ligand disordered over two orientations. The [Cd(CN)₂]_n framework viewed down the c axis shows two types of channels, one octagonal and one tetragonal, which are filled with Cd(CN)₂·(18-crown-6) and ethanol molecules, respectively. Crystallographic data of 1: trigonal, space group R·3 (hexagonal axis), a = 11.757 (1), c = 12.105 (1) Å, V = 1449.1 (2) ų, Z = 3, R = 0.0566, R_w = 0.0674 for 827 unique reflections (I>3σ(I)). Crystallographic data of 2: orthorhombic, Pbcn, a = 16.632 (1), b = 17.391 (3), c = 15.685 (2) Å, V = 4536.8 (9) ų, Z = 8. R = 0.0486, R_w = 0.0492 for 929 unique reflections (I>3σ(I)).     

Alkoxo‐Verbindungen des dreiwertigen Eisen: Synthese und Charakterisierung von [Fe2(OtBu)6], [Fe2Cl2(OtBu)4], [Fe2Cl4(OtBu)2] und [N(nBu)4]2[Fe6OCl6(OMe)12]

Alkoxo Compounds of Iron(III): Syntheses and Characterization of [Fe₂(OtBu)₆], [Fe₂Cl₂(OtBu)₄], [Fe₂Cl₄(OtBu)₂] and [N(nBu)₄]₂[Fe₆OCl₆(OMe)₁₂] The reaction of iron(III)chloride in diethylether with sodium tert‐butylat yielded the homoleptic dimeric tert‐‐butoxide Fe₂(OtBu)₆ ( 1 ). The chloro‐derivatives [Fe₂Cl₂(OtBu)₄] ( 2 ), and [Fe₂Cl₄(OtBu)₂] ( 3 ) could be synthesized by ligand exchange between 1 and iron(III)chloride. Each of the molecules 1 , 2 , and 3 consists of two edge‐sharing tetrahedrons, with two tert‐butoxo‐groups as μ₂‐bridging ligands. For the synthesis of the alkoxides 1 , 2 , and 3 diethylether plays an important role. In the first step the dietherate of iron(III)chloride FeCl₃(OEt₂)₂ ( 4 ) is formed. The reaction of iron(III)chloride with tetrabutylammonium methoxide in methanol results in the formation of a tetrabutylammonium methoxo‐chloro‐oxo‐hexairon cluster [N(nBu)₄]₂[Fe₆OCl₆(OMe)₁₂] ( 5 ). Crystal structure data: 1 , triclinic, P1¯, a = 9.882(2) Å, b = 10.523(2) Å, c = 15.972(3) Å, α = 73.986(4)°, β = 88.713(4)°, γ = 87.145(4)°, V = 1594.4(5) ų, Z = 2, d_c = 1.146 gcm^—1, R₁ = 0.044; 2 , monoclinic, P2₁/n, a = 11.134(2) Å, b = 10.141(2) Å, c = 12.152(2) Å und β = 114.157(3)°, V = 1251.8(4) ų, Z = 2, d_c = 1.377 gcm^—1, R₁ = 0.0581; 3 , monoclinic, P2₁/n, a = 6.527(2) Å, b = 11.744(2) Å, c = 10.623(2), β = 96.644(3)°, V = 808.8(2) ų, Z = 2, d_c = 1.641 gcm^—1, R₁ = 0.0174; 4 , orthorhombic, Iba2, a = 23.266(5) Å, b = 9.541(2) Å, c = 12.867(3) Å, V = 2856(2) ų, Z = 8, d_c = 1.444 gcm^—1, R₁ = 0.0208; 5 , trigonal, P3₁, a = 13.945(2) Å, c = 30.011(6) Å, V = 5054(2) ų, Z = 6, d_c = 1.401 gcm^—1; R_c = 0.0494.     

THE PHENOMENON OF CONGLOMERATE CRYSTALLIZATION. PART 50. THE CRYSTALLIZATION BEHAVIOR OF [trans-Co(en)2(NO2)2]ClO4 (I), MESO-[Co-trans-Me-(N-Me-ETHYLENEDIAMINE)2-trans-(NO2)2]ClO4 (II), K[trans-Co(β-ALANINATO)2(NO2)2] (III) AND THE ISOLATION AND PARTIAL STRUCTURAL DESCRIPTION OF (H5O2)[trans-Co(β-ALANINATO)2(NO2)2] (IV)

Abstract

[trans-Co(en)₂(NO₂)₂]ClO₄ (I) crystallizes, at 22°C, from a deionized water solution, as a racemate, in space group P$1 (No. 2), with lattice constants: a = 6.581(2)Å, b = 8.274(1) Å, c = 12.660(3)Å, α = 77.28(2)Å, β = 76.58(2)°, γ = 75.20(2)° V = 638.71;ų and d(calc; MW = 370.59,z = 2) = 1.927gcm^?3. A total of 2233 data were collected over the range of 4° ≤ 2θ ≤ 50° of these, 1961 (independent and with I ≤ 3σ(I)) were used in the structural analysis. Data were corrected for absorption (μ = 15.989 cm^?1) and the relative transmission coefficients ranged from 0.6792 to 0.9874. The final R(F) and R≤(F) residuals were, respectively, 0.0738 and 0.0763. Two half cations are located at inversion centers; the anions are in general positions.

meso-[Co-trans-Me-(N-Me-ethylenediamine)₂-trans(NO₂)₂]ClO₄ (II) [(N-Meen) = N-methyl-ethylenediamine] crystallizes at 22°C, from a deionized water solution in space group Pbca (No. 61) with lattice constants: a = 16.882(5) Å, b = 11.990(3) Å, c = 15.017(5) Å; V = 3039.72 ų and d (calc;MW = 398.64, z = 8) = 1.742g cm^?3. A total of 5281 data were collected over the range of 4° ≤ 2θ ≤ 50° of these, 1779 (independent and with I ≤ 2.5σ(I) were used in the structural analysis. Data were corrected for absorption (μ = 13.501 cm^?1 and the transmission coefficients ranged from 0.7956 to 0.9947. The final refinement of the structure (anisotropic thermal parameters for the heavy atoms; idealized hydrogens for the cation) are R(F) = 0.045 and R_w (F) = 0.052). The -NO₂ ligands are trans to one another in the axial direction while the N-methyl groups are trans to one another across the basal plane. The cations are located in general positions and the torsional angles of the en rings are δ(N1-C1-C2-N2 = 52.0°) and δ(N3-C3-C4-C4 = 51.0°), in contrast with those of (I) which are of opposite helical chirality. This compound is one of two trans-Co(III)X₂ cations of which we are aware that, while sitting at a general position of the space group, has two ethytenediamine rings of the same helical chirality.

K[trans-Co(β-alaninato)₂(NO₂)₂] (III) obtained after several batches of crystals of (TV) had separated from the mother liquor (see Syntheses). (III) crystallizes at 22°C, in space group Cc (No. 9) with lattice constants: a = 12.385(6)Å, b=13.109(5)Å, c = 8.290(5)Å, β=115.19° V = 1217.97 ų and d(calc; MW = 366.22, z = 4) = 1.997 g cm^?3. A total of 1238 data were collected over the range of 4° ≤ 2θ 50° of these, 1016 (independent and with I ≤ 2.5σ(I) were used in the structural analysis. Data were corrected for absorption (μ 17.90cm^?1) and the transmission coefficients ranged from 0.5322 to 0.6627. The final R(F) and R_w (F) residuals were, respectively 0.020 and 0.022. Solution of the structure, using the first batch of crystals, proved that the compound isolated was the (H₅O₂)⁺ derivative (see below and Discussion). A later batch of crystals contained (III). We have previously observed the precipitation of hydronium salts, trapped by amine carboxylato salts of cobalt (see Discussion). The anions consist of two six-membered rings formed by the metal and two (O,N)-bound β-alaninato ligands; and, both have chair conformations.

(H₅O₂) [trans-Co(β-alaninato)₂(NO₂)₂] (IV) is the substance that first crystalized from an aqueous solution of (III) (see Experimental). It crystallizes, at 22°C, in space group Cc (No. 9) or C2/c (No. 15) with lattice constants: a=12.389(39)Å, b=13.120(11)Å, c=8.299(9) Å, β=115.09(19)° V=1221.72 ų and d(calc; MW=364.15, z=4) = 1.980 g cm^?3. An incomplete data set of 1592 reflections was collected over the range 4° ≤ 2θ ≤ 50° because the crystal decomposes in air due to rapid loss of water of crystallization, as shown by differential scanning calorimetry. 956 data were independent with I ≤ 2.5°(I) and were used in the structural analysis. Data were not corrected for absorption because of decomposition of the crystal. The final R(F) and R_w (F) residuals were, respectively, 0.14 and 0.16. To the precision of such a data set, the anions are identical with those found in (III); however the cation, which sits at an inversion center, consists of a proton sandwiched between the oxygens of two waters thus forming (H₅O₂)⁺ cations similar to those we have described in the past (see Refs. [15–18]).     

Destruction of the propylenediamine ring upon the chlorination of the platinum(IV) tetramine complex [PtpnPy2Cl2]Cl2

The chlorination of an aqueous solution of [PtpnPy₂Cl₂]Cl₂ affords the platinum(IV) dichloroamine complex [PtPy₂(NCl₂)₂Cl₂](I), as the major reaction product formed due to the complete destruction of the five-membered chelate ring. Complex I is obtained in the pure state from acetonitrile. In addition, the [PtPy(NH₂-CH(CH₃)-CH(CH₃)-NH₂)Cl₃]Cl · 1/2 H₂O complex (II) is isolated from the mother liquor upon chlorination. Complex I reacts rapidly with concentrated HCl to form the tetramine complex [PtPy₂(NH₃)₂Cl₂](CF₃SO₃)₂ · 1/2 H₂O(III). The X-ray diffraction study is carried out for complexes I, II, and III. Complex I crystallizes in the monoclinic crystal system: space group C2/c, a = 7.4529(4), b = 15.2143(9), c = 14.9965(8) Å, β = 99.866(1)°, V = 1675.3(2) ų, Z = 4; R _hkl = 0.040. The crystals of complex II are triclinic: space group P $ \bar 1 The chlorination of an aqueous solution of [PtpnPy₂Cl₂]Cl₂ affords the platinum(IV) dichloroamine complex [PtPy₂(NCl₂)₂Cl₂](I), as the major reaction product formed due to the complete destruction of the five-membered chelate ring. Complex I is obtained in the pure state from acetonitrile. In addition, the [PtPy(NH₂-CH(CH₃)-CH(CH₃)-NH₂)Cl₃]Cl · 1/2 H₂O complex (II) is isolated from the mother liquor upon chlorination. Complex I reacts rapidly with concentrated HCl to form the tetramine complex [PtPy₂(NH₃)₂Cl₂](CF₃SO₃)₂ · 1/2 H₂O(III). The X-ray diffraction study is carried out for complexes I, II, and III. Complex I crystallizes in the monoclinic crystal system: space group C2/c, a = 7.4529(4), b = 15.2143(9), c = 14.9965(8) ?, β = 99.866(1)°, V = 1675.3(2) ?³, Z = 4; R _hkl = 0.040. The crystals of complex II are triclinic: space group P , a = 8.163(2), b = 8.656(2), c = 10.638(2) ?, α = 78.30(3)°, β = 83.95(3)°, γ = 84.68(3)°, V = 730.0(3) ?³, Z = 2; R _hkl = 0.026. The crystals of complex III are monoclinic: space group C2/c, a = 11.946(2), b = 19.624(4), c = 10.034(2) ?, β = 95.96(3)°, V = 2339.5(8) ?³, Z = 4; R _hkl = 0.043. The IR spectra of all the compounds synthesized are studied. Original Russian Text ? I.B. Baranovskii, M.D. Surazhskaya, M.A. Golubnichaya, G.G. Aleksandrov, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 12, pp. 2000–2007.     

Tetranuclear cobalt(II) complex and trinuclear copper(II) complex with the ligand 2-hydroxy-3-[(2-sulfoethylimino)-methyl]-benzoic acid: synthesis,structure and properties

A cobalt(II) compound, [Co₄(L)₂(OH)₂(phen)₂(H₂O)₄] · 6H₂O (1), and a copper(II) compound, [Cu₂(L)₂(H₂O)₂][Cu(H₂O)₆] · 6H₂O (2) [where H₃L is 2-hydroxy-3-[(2-sulfoethylimino)-methyl]-benzoic acid and phen is O-phenanthroline], were prepared and characterized. The tetranuclear cobalt complex 1, C₄₄H₆₂N₆O₂₈S₂Co₄, crystallizes in the monoclinic space group P2₁/c, with a = 11.847(10) Å, b = 19.061(15) Å, c = 12.635(10) Å, β = 105.483(9)°, and Z = 2; R ₁ for 4821 observed reflections [I > 2σ(I)] was 0.0679. Complex 1 is a centrosymmetric tetranuclear cobalt complex with all cobalts having distorted octahedral geometry. The molecule can be viewed as two planar [Co₂(OH)(L)(Phen)H₂O] units tied together by two terminal water molecules. The framework of 1 has the appearance of two connected face-sharing cubes, each with one vertex missing. The trinuclear copper complex 2, C₂₀H₄₄Cu₃N₂O₂₆S₂, crystallizes in the triclinic space group P1, with a = 7.524(1) Å, b = 7.902(2) Å, c = 16.885(4) Å, α = 88.993(6)°, β = 80.725(7)°, γ = 66.725(4)° and Z = 1; R ₁ for 4298 observed reflections [I > 2σ (I)] was 0.0360. Complex 2 is an ionic compound, in which the three Cu(II) centers have two coordination modes. The molecule has a centrosymmetric dinuclear copper coordinated anion and a hexa-aqua-copper cation. The sulfonic acid group has less coordination ability than carboxylate oxygen.     

Effects on Coordination of Thioether Sites. 4. Structural Analysis of η3-Tripodal Ligand Manganese(I) Complexes

Crystal structures of a series of manganese(I) complexes containing tripodal ligands were determined. For [η³-{CH₃C(CH₂PPh₂)₂(CH₂SPh)-P,P′,S}Mn(CO)₃]PF₆ ( 1 ): a = 10.856(3) Å, b = 19.698(3) Å, c = 17.596(5) Å, β = 96.17(2)°, monoclinic, Z = 4, P2₁/c, R(F_o) = 0.068, R_w(F_o) = 0.055 for 3617 reflections with I_o > 2σ(I_o). For [η³-{CH₃C(CH₂PPh₂)(CH₂SPh)₂-P,P′,S}Mn(CO)₃]PF₆ ( 2 ): a = 9.890(2) Å, b = 20.403(4) Å, c = 10.269(3) Å, β = 117.44(2)°, monoclinic, Z = 2, P2_l, R(F_o) = 0.050, R_w(F_o) = 0.037 for 1760 reflections with I_o > 2σ(I_o). For [η³-{CH₃C(CH₂PPh₂)₂(CH₂S)-P,P′,S}Mn(CO)₃] ( 4 ): a = 8.191(7) Å, b = 10.495(3) Å, c = 19.858(6) Å, α = 99.61(2)°, β = 96.17(2)°, γ = 92.70(4)°, triclinic, Z = 2, P-I, R(F_o) = 0.048, R_w(F_o) = 0.039 for 2973 reflections with I_o > 2σ(I_o). There is no significant difference in the bond lengths of Mn-S bonds among three species in their crystal structures [2.325(2) Å in 1; 2.358(4) in 2; 2.380(2) in 4], but the better donating ability of thiolate in complex 4 appears on the lower frequencies of its carbonyl stretching absorptions.     

Copper(II) Halide Complexes of 2-Aminopyrimidines: Crystal Structures of [(2-aminopyrimidine) n CuCl2] (n=1,2) and (2-amino-5-bromopyrimidine)2CuBr2

The reaction of CuX₂(X=Cl, Br) with 2-aminopyrimidine in aqueous solution, or 2-amino-5-bromopyrimidine in aqueous acid yields compounds of the forms [LCuCl₂] _n (1), [L₂CuCl₂] (2) and [L'₂CuBr₂] (3) [L=2-aminopyrimidine; L'=2-amino-5-bromo-pyrimidine]. The three compounds all form layered structures in which each copper ion is coordinated to two 2-aminopyrimidine molecules and two halide ions. Common structural threads involve bridging ligation [either by monomeric (1) or hydrogen bonded ligand dimers (2 and 3)], N-H···X and N-H···N hydrogen bonding and π-π stacking interactions as well as semi-coordinate Cu···X bond formation (1 and 2) or Br···Br interactions (3). Compounds 1 and 2 crystallize as two-dimensional coordination polymers with asymmetrically bihalide bridged (CuX₂) _n chains cross-linked into sheets by the 2-aminopyrimidine molecules (1) or by hydrogen bonded L₂ dimers (2). The halide bibridged chains expand their primary copper coordination spheres to give 4 + 2 coordination spheres in 1 and 2. In 3, the layer structure involves coordination of the hydrogen bonded L'₂ dimers and C-Br···Br- interactions. Crystal data: (1): monoclinic, P2₁/m, a=3.929(1), b=12.373(2), c=7.050(1)å, β=91.206(4)°, V=342.7(1)&Aringsup3;, Z=2, D _calc= 2.225Mg/m³, μ=3.878 mm^-1, R=0.0269 for [|I|≥3σ(I)]. For (2): triclinic, P-1, a=4.095(4), b=7.309(5), c=10.123(6) å, α=86.28(6), β=78.44(6), γ=74.55(8)°, V=286.1(4) ų, Z=1, D _calc=1.884 Mg/m³, μ=2.360 mm^-1, R=0.0506 for [|I|≥2σ(I)]. For (3): triclinic, P-1, a=6.074(4), b=7.673(3), c=8.887(3) å, α=108.43(3) β=100.86(5), γ=106.96(4)°, V=357.0(3) ų, Z=1, D _calc=2.657 Mg/m³, μ=12.714mm^-1, R=0.0409 for [|I|≥2σ(I)].     

SYNTHESIS,CHARACTERIZATION AND CRYSTAL STRUCTURE OF A COMPLEX OF EUROPIUM PERCHLORATE WITH METHYLENE BIS(DIPHENYLPHOSPHINE OXIDE)

Abstract

A complex of europium perchlorate with methylene bis(diphenylphosphine oxide) (HMPPO), [Eu(HMPPO)₄](ClO₄)₃·2H₂O has been synthesized and characterized by X-ray crystallography, infrared spectroscopy and thermal analysis. The X-ray structure of the complex shows Eu(III) is coordinated by eight oxygen atoms from four HMPPO ligands, forming a distorted square antiprism coordination geometry. The complex crystallizes in space group P-1 with cell parameters a = 15.807(3), b = 17.868(4), c = 20.656(4) Å, α = 86.85(3)°, β = 82.33(3)°, γ = 66.75(3)°. The final R_l and R_w are 0.0803 and 0.1994, respectively, for 9540 observed reflections [I > 2[sgrave](I)]. Its luminescent properties have also been studied.