Transition-metal complexes with bidentate ligands spanning trans-positions. V. Crystal and molecular structures of complexes [RhCl(CO) (1)] and [PdCl2(1)]; 1 = 2,11-bis (diphenylphosphinomethyl)benzo [c]phenanthrene

The structures of [RhCl(CO) ( 1 )] and [PdCl₂ ( 1 )], where 1 is the bidentate ligand (C₆H₅)₂P·CH₂·C₁₈H₁₀· CH₂·P(C₆H₅)₂, have been determined from threedimensional X-ray counter data collected on single crystals of the C₆H₅·CN solvates. The two compounds are isomorphous and crystallize in the triclinic system, space group P 1 , Z = 2: a = 14.580 (8), b = 13.029 (10), c = 11.909 (6) Å, α = 106.33 (5), β = 100.47 (4), γ = 95.73 (5)° for the rhodium complex; a = 14.361 (5), b = 13.044 (7), c = 11.897 (4) Å, α = 105.97 (4), β = 100.27 (3), γ = 94.76 (4)°, for the palladium complex. In both complexes the metal atom is four-coordinate with slightly distorted square-planar configuration. In both cases the ligand 1 spans trans positions with M-P bond lengths in the ranges of the literature data. Also the other bond distances fall in regular ranges. Ligand 1 has almost the same conformation in both complexes and is characterized by a strong out-of-plane deformation of the benzophenanthrene system as a consequence of severe overcrowding.     

Two Heteroleptic Zinc(II) Complexes: [Zn(phen)(C9H15O6)2] and [Zn2(phen)2(H2O)2(C10H16O4)2] · 3H2O

Reactions of a freshly prepared Zn(OH)_2‐2x(CO₃)x · yH₂O precipitate, phenanthroline with azelaic and sebacic acid in CH₃OH/H₂O afforded [Zn(phen)(C₉H₁₅O₄)₂] ( 1 ) and [Zn₂(phen)₂(H₂O)₂(C₁₀H₁₆O₄)₂] · 3H₂O ( 2 ), respectively. They were structurally characterized by X‐ray diffraction methods. Compound 1 consists of complex molecules [Zn(phen)(C₉H₁₅O₄)₂] in which the Zn atoms are tetrahedrally coordinated by two N atoms of one phen ligand and two O atoms of different monodentate hydrogen azelaato groups. Intermolecular C(alkyl)‐H···π interactions and the intermolecular C(aryl)‐H···O and O‐H···O hydrogen bonds are responsible for the supramolecular assembly of the [Zn(phen)(C₉H₁₅O₄)₂] complexes. Compound 2 is built up from crystal H₂O molecules and the centrosymmetric binuclear [Zn₂(phen)₂(H₂O)₂(C₁₀H₁₆O₄)₂] complex, in which two [Zn(phen)(H₂O)]²⁺ moieties are bridged by two sebacato ligands. Through the intermolecular C(alkyl)‐H···O hydrogen bonds and π‐π stacking interactions, the binuclear complex molecules are assembled into layers, between which the lattice H₂O molecules are sandwiched. Crystal data: ( 1 ) C2/c (no. 15), a = 13.887(2), b = 9.790(2), c = 22.887(3)Å, β = 107.05(1)°, U = 2974.8(8)ų, Z = 4; ( 2 ) P1¯ (no. 2), a = 8.414(1), b = 10.679(1), c = 14.076(2)Å, α = 106.52(1)°, β = 91.56(1)°, γ = 99.09(1)°, U = 1193.9(2)ų, Z = 1.     

Darstellung und Kristallstrukturen von [P(C6H5)4][1-(NH3)B10H9] und Cs[(NH3)B12H11] · 2CH3OH

Synthesis and Crystal Structures of [P(C₆H₅)₄][1-(NH₃)B₁₀H₉] and Cs[(NH₃)B₁₂H₁₁] · 2CH₃OH The reduction of [1-(NO₂)B₁₀H₉]^2? with aluminum in alkaline solution yields [1-(NH₃)B₁₀H₉]^? and by treatment of [B₁₂H₁₂]^2? with hydroxylamine-O-sulfonic acid [(NH₃)B₁₂H₁₁]^? is formed. The crystal structures of [P(C₆H₅)₄][1-(NH₃)B₁₀H₉] (triclinic, space group P1 , a = 7.491(2), b = 13.341(2), c = 14.235(1) Å, α = 68.127(9), β = 81.85(2), γ = 86.860(3)°, Z = 2) and Cs[(NH₃)B₁₂H₁₁] · 2CH₃OH (monoclinic, space group P2₁/n, a = 14.570(2), b = 7.796(1), c = 15.076(2) Å, β = 111.801(8)°, Z = 4) reveal for both compounds the bonding of an ammine substituent to the cluster anion.     

Hybrid Inorganic‐Organic Frameworks: Synthesis and Crystal Structures of RbFe(SO4)(C2O4)0.5·H2O and CsM(SO4)(C2O4)0.5·H2O (M = Mn,Fe)

Three new alkali metal transition metal sulfate‐oxalates, RbFe(SO₄)(C₂O₄)_0.5 · H₂O and CsM(SO₄)(C₂O₄)_0.5 · H₂O (M = Mn, Fe) were prepared through hydrothermal reactions and characterized by single‐crystal X‐ray diffraction, solid state UV/Vis/NIR diffuse reflectance spectroscopy, infrared spectra, thermogravimetric analysis, and powder X‐ray diffraction. The title compounds all crystallize in the monoclinic space group P2₁/c (no. 14) with lattice parameters: a = 7.9193(5), b = 9.4907(6), c = 8.8090(6) Å, β = 95.180(2)°, Z = 4 for RbFe(SO₄)(C₂O₄)_0.5 · H₂O; a = 8.0654(11), b = 9.6103(13), c = 9.2189(13) Å, β = 94.564(4)°, Z = 4 for CsMn(SO₄)(C₂O₄)_0.5 · H₂O; and a = 7.9377(3), b = 9.5757(4), c = 9.1474(4) Å, β = 96.1040(10)°, Z = 4 for CsFe(SO₄)(C₂O₄)_0.5 · H₂O. All compounds exhibit three‐dimensional frameworks composed of [MO₆] octahedra, [SO₄]^2– tetrahedra, and [C₂O₄]^2– anions. The alkali cations are located in one‐dimensional tunnels.     

Syntheses of(C_8H_8)Ln(C_9H_7)·(THF)_2(Ln=Pr,Nd)and crystal structure of(C_8H_8)Pr(C_9H_7)·(THF)_2

This paper reports two lanthanide complexes of formula (C_9H_7)Ln(C_8H_8)·(THF)_2 whereLn is Pr or Nd,C_9H_7 is indenyl,and C_8H_8 is cyclooctatetraene (COT).The complexes were preparedby the reaction of LnCl_3 with K(C_9H_7) and K_2(C_8H_8) in THF.(C_9H_7)Pr(C_8H_8)·(THF)_2 crystallizes inTHF at - 15℃ in the monoclinic space group P2_1:with unit cell dimensions a=8.446(0),b=10.083(2),c=13.407(3),β=105.48(1)°,V=1100.43(35)~3,Dc=1.52g/cm~3 and Z=2.The final R valueis 0.033,R_w value is 0.030,respectively.In (C_9H_7)Pr(C_8H_8)·(THF)_2 a five-membered ring centroid ofC_9H_7,the C_8H_8 ring centroid and the two oxygen atoms from the two THF molecules form a distortedtetrahedral geometry around the metal.     

Two Dieneplatinum Synthetic Reagents,Pt(C6H2F3‐2,4,6)2(cod) and Pt(C6HF4‐2,3,4,5)2(cod)

Reactions of PtCl₂(cod) (cod = cycloocta‐1,5‐diene) with 2,4,6‐trifluoro‐ and 2,3,4,5‐tetrafluoro‐phenyllithium in diethyl ether gives Pt(C₆H₂F₃‐2,4,6)₂(cod) ( 1 ) (monoclinic, P2₁/n, Z = 4, a = 7.141(1), b = 15.002(2), c = 17.071(3) Å, β = 91.37(2)°) and Pt(C₆HF₄‐2,3,4,5)₂(cod) ( 2 ) (triclinic, P 1, Z = 2, a = 10.150(2), b = 10.762(2), c = 10.812(2) Å, α = 63.606(3), β = 63.327(3), γ = 76.496(3)°) respectively, which have two ipso carbon atoms and two double bond midpoint centres in a square planar arrangement, and aromatic rings angled near perpendicular to the coordination plane.     

Bildung oktaedrischer Komplexe durch cis-Addition an planar-quadratisches Bis(oxamidoximato)nickel(II): drei Strukturbeispiele

Formation of Octahedral Complexes via cis-Addition to Square Planar Bis (oxamideoximato)nickel(II): Three Structure Examples In the reaction of orange square planar bis(oxamide oximato)nickel(II) with acids, blue to blue-green octahedral complexes are formed with neutral oxamide oximide ligands and two acid anions in cis-positions. Three compounds are described: cis-dichlorobis(oxamide oxime)nickel(II) ( 1 ), NiCl₂(C₂H₆N₄O₂)₂, M_r = 365.81, monoclinic P2₁/n, a = 6.641(2), b = 14.086(4), c = 13.473(3) Å, β = 96.26(2)°, V = 1 252.8 ų, Z = 4, d_c = 1.94 gcm^?3, final R_w = 0.031 for 4090 reflections. In cis-di(sulfanilato)bis(oxamide oxime)nickel(II) dihydrate ( 2 ) one sulfanilic anion coordinates via the sulfonic acid group, the other one via the amino group; Ni(C₆H₆NO₃S)₂(C₂H₆N₄O₂)₂ · 2 H₂O, M_r = 675.30, monoclinic P2₁, a = 6.879(3), b = 14.305(5), c = 13.930(5) Å, β = 103.62(4)°, V = 1332 Å, Z = 2, d_c = 1.68 gcm^?3, R = 0.067 for 2693 reflections. In catena-μ-(phthalato)bis(oxamide oxime)nickel(II) tetrahydrate ( 3 ) bidentate bridging phthalate anions lead to chain formation; Ni(C₈H₄O₄)(C₂H₆N₄O₂)₂ · 4H₂O, M_r = 531.09, monoclinic P2₁/c, a = 10.633(8), b = 11.324(5), c = 17.680(14) Å, β = 98.25(7)°, V = 2107 ų, Z = 4, d_c = 1.67 gcm^?3. Final R = 0.110 for 3290 reflections.     

Structural Studies on Dimethyltin(IV) Carboxylates

In order to correlate ¹¹⁹Sn Mössbauer parameters and structural data for dimethyltin(IV) derivatives, the molecular structures of bis(acetato)dimethyltin(IV) and bis(trifluoroacetato)dimethyltin(IV) were determined by single crystal X-ray diffration. Crystals of Me₂Sn(OOCCH₃)₂ are monoclinic, a = 26.282(4), b = 5.282(1), c = 14.434(3) Å, β = 101.17(2)°, Z = 8, space group C2/c, and those of [Me₂Sn(OOCCF₃)₂]_n are monoclinic, a = 8.444(1), b = 17.689(1), c = 15.368(1) Å, β = 93.013(9)°, Z = 8, space group Cc. The structures were solved by the Patterson method and were refined by full-matrix least-squares procedures to R = 0.025 and 0.027 (R_w = 0.023 and 0.030) for 2 298 and 4 182 reflections with I ≥ 3σ(F²), respectively.     

Ambidentate coordination of the tripyridyl ligands 2,2′:6′,2″-terpyridyl,tris(2-pyridyl)-amine,tris(2-pyridyl)methane and tris(2-pyridyl)phosphine to carbonylrhenium centres: Structural and spectroscopic studies

The reactions of [Re(CO)₅Cl] with the ligands tpy (2,2′:6′,2″-terpyridine), py₃N {tris(2-pyridyl)-amine}, py₃CH {tris(2-pyridyl)methane}, and py₃P {tris(2-pyridyl)phosphine} in toluene solution realize compounds with the general formulation [Re(ligand)(CO)₃Cl] in which the tripyridyl ligands are bidentate. X-ray structural determinations of fac-[Re(typ)(CO)₃Cl].H₂O and fac-[Re(py₃N)(CO)₃Cl] confirm these assignments. [Re(tpy)(CO)₃Cl].H₂O (C₁₈H₁₃ClN₃O₄Re) is monoclinic, space group P2₁/n, with cell dimensions a = 7.432(2) Å, b = 17.016(4) Å, c = 14.466(2) Å, β = 93.51(2)°, and Z = 4; full-matrix least-squares refinement on 2435 reflections with I ? 2.5σ(I) converged to a final R = 0.028 and R_w = 0.029. [Re(py₃N)(CO)₃Cl] (C₁₈H₁₂ClN₄O₃Re) is triclinic, space group P1 with cell dimensions a = 13.761(2) Å, b = 14.636(6)Å, c = 11.110(2) Å, α = 110.70(2)°, β = 102.45(2)°, γ = 107.48(2)°, and Z = 4; full-matrix least-squares refinement on 3459 reflections with I ? 2.5σ(I) converged to a final R = 0.038 and R_w = 0.039. If the synthetic procedure is undertaken under irradiation by visible light, for the ligand py₃N a species [Re(py₃N)(CO)₂Cl] (characterized by infrared spectroscopy and conductance measurements) is also formed, in which the ligand py₃N is tridentate. No analogous tridentate species is formed with the ligands tpy or py₃P, although there is evidence that it also forms for py₃CH.     

Nickel(II) 1,10-Phenanthroline complexes: cis-[Aqua(Bromo) bis (1,10-Phenanthroline)Nickel(II)] Bromide Trihydrate and ( tris (1,10-Phenanthroline)Nickel(II)] Bromide Octahydrate

[Ni(phen)₂(H₂O)Br]Br·3H₂O where phen is 1,10-phenanthroline, is a light-blue material which crystallizes in the monoclinic space group P2₁/c with Z = 4, a = 10.4300(4), b = 25.310(2), c = 9.7790(9)?Å and β = 102.932(6)°. The structure was determined at ambient temperature from 5161 reflections with R = 0.0643 and R _w = 0.1306. The structure consists of a complex cation, a bromide anion and three waters of hydration. The Ni atom is pseudo-octahedral with a cis arrangement of Br and H₂O. This cis geometry persists in solution, as evidenced by ¹H NMR spectroscopy, although the Br may be replaced by another H₂O. [Ni(phen)₃]Br₂·8H₂O is a light-red material which crystallizes in the monoclinic space group C2/m with Z = 8, a = 23.6320(11), b = 21.4880(13), c = 15.5470(9)?Å and β = 107.927(3)°. The structure was determined at 120?K from 6820 reflections with R = 0.0733 and R _w = 0.1022. The structure consists of a complex cation, two bromide anions and eight waters of hydration. The anions and waters are extensively disordered. The Ni atom is pseudo-octahedral.     

From Isolated Polyanions to 1‐D Structure: Synthesis and Crystal Structure of Hybrid Fluorides {[(C2H4NH3)3NH]4+}2 · (H3O)+ · [Al7F30]9– and {[(C2H4NH3)3NH]4+}2 · [Al7F29]8– · (H2O)2

Two new hybrid fluorides, {[(C₂H₄NH₃)₃NH]⁴⁺}₂ · (H₃O)⁺ · [Al₇F₃₀]^9– ( I ) and {[(C₂H₄NH₃)₃NH]⁴⁺}₂ · [Al₇F₂₉]^8– · (H₂O)₂ ( II ), are synthesized by solvothermal method. The structure determinations are performed by single crystal technique. The symmetry of both crystals is triclinic, sp. gr. P 1, I : a = 9.1111(6) Å, b = 10.2652(8) Å, c = 11.3302(8) Å, α = 110.746(7)°, β = 102.02(1)°, γ = 103.035(4)°, V = 915.9(3) ų, Z = 1, R = 0.0489, R_w = 0.0654 for 2659 reflections, II : a = 8.438(2) Å, b = 10.125(2) Å, c = 10.853(4) Å, α = 106.56(2)°, β = 96.48(4)°, γ = 94.02(2)°, V = 877.9(9) ų, Z = 1, R = 0.0327, R_w = 0.0411 for 3185 reflections. In I , seven corner‐sharing AlF₆ octahedra form a [Al₇F₃₀]^9– anion with pseudo 3 symmetry; such units are found in the pyrochlore structure. The aluminum atoms lie at the corners of two tetrahedra, linked by a common vertex. In II , similar heptamers are linked in order to build infinite (Al₇F₂₉)_n^8– chains oriented along a axis. In both compounds, organic moieties are tetra protonated and establish a system of hydrogen bonds N–H…F with four Al₇F₃₀^9– heptamers in I and with three inorganic chains in II .     

Complexation with diol host compounds. 13. Crystal structures and thermal analyses of inclusion compounds of 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol with cyclohexane,O-xylene,m-xylene and p-xylene

Abstract

It has been shown that host compound 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol is able to include polar guests and now we report on its ability to form clathrate compounds with apolar guests. The structures of this host with cyclohexane (1) and the ortho (2), meta (3) and para (4) xylenes have been determined and are discussed. Crystal data: (1) 2C₃₀H₂₂O₂C₆H₁₂, M _r = 913.20 g mol^?1, mono-clinic, C2/c, a = 22.851(6), b = 14.010(2), c = 17.076(6) Å, β = 108.71(3)°, V = 5178(2) ų, Z = 4, D _c = 1.17g cm^?3, N = 3326, R = 0.092. (2) 2C₃₀H₂₂O₂1 ½C₈H₁₀, M _r = 1976.5 g mol^?1, triclinic, P 1, a = 13.185(3), b = 15.466(3), c = 16.573(2) Å, α = 96.39(13)°, β = 106.96(15)°, γ = 114.94(18)°, V = 2822(2) ų, Z = 2, D _c = 1.16 g cm^?3, N = 6152, R = 0.075. (3) 2C₃₀H₂₂O₂1 ½C₈H₁₀, M _r = 1976.5 g mol^?1, triclinic, P 1, a = 13.267(5), b = 15.453(3), c = 16.654(5) Å, α = 97.12(2)°, β = 107.09(3)°, γ = 114.68(3)°, V = 2843(2) ų, Z = 2, D _c = 1.15 g cm^?3, N = 6505, R = 0.083. (4) 2C₃₀H₂₂O₂1 ½C₈H₁₀, M _r = 1976.5 g mol^?1, triclinic, P 1, α = 13.070(2), b = 15.348(3), c = 16.776(3) Å, α = 67.88<2)°, β = 74.27(1)°, γ = 65.29(1)°, V = 2817(1) ų, Z = 2, D _c = 1.15 g cm^?3, N = 6711, R = 0.050. Thermal analysis studies were also performed in order to examine their stability and the strength with which the guest species are held in the crystal lattice.     

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.     

Two New Modifications of [P(C6H5)4]2[Cu2I4]

Single crystals of two new modifications of [P(C₆H₅)₄]₂[Cu₂I₄] were obtained by reaction of granulated copper with iodine and [P(C₆H₅)₄]I in dry acetone under nitrogen atmosphere. They crystallise monoclinically, space group P2₁/n (No. 14), a = 11.550(6), b = 7.236(2), c = 27.232(13) Å, β = 98.13(3)°, V = 2253(2) ų, and Z = 2 ([P(C₆H₅)₄]₂[Cu₂I₄]-C), and space group Cc (No. 9), a = 17.133(5), b = 15.941(5), c = 18.762 (6) Å, β = 114.02(1)°, V = 4681(3) ų, and Z = 4 ([P(C₆H₅)₄]₂[Cu₂I₄]-D), respectively. In these compounds the [CuI₂]^? anions form dimers di-μ-iodo-diiodocuprate(I), which are either planar ( C ) or folded ( D ).     

Structural effects on the solid‐state photodimerization of 2‐pyridone derivatives in inclusion compounds

The structures of six crystalline inclusion compounds between various host molecules and three guest molecules based on the 2‐pyridone skeleton are described. The six compounds are 1,1′‐biphenyl‐2,2′‐dicarboxylic acid–2‐pyridone (1/2), C₁₄H₁₀O₄·2C₅H₅NO, (I–a), 1,1′‐biphenyl‐2,2′‐dicarboxylic acid–4‐methyl‐2‐pyridone (1/2), C₁₄H₁₀O₄·2C₆H₇NO, (I–c), 1,1′‐biphenyl‐2,2′‐dicarboxylic acid–6‐methyl‐2‐pyridone (1/2), C₁₄H₁₀O₄·2C₆H₇NO, (I–d), 1,1,6,6‐tetraphenyl‐2,4‐hexadiyne‐1,6‐diol–1‐methyl‐2‐pyridone (1/2), C₃₀H₂₂O₂·2C₆H₇NO, (II–b), 1,1,6,6‐tetraphenyl‐2,4‐hexadiyne‐1,6‐diol–4‐methy‐2‐pyridone (1/2), C₃₀H₂₂O₂·2C₆H₇NO, (II–c), and 4,4′,4′′‐(ethane‐1,1,1‐triyl)triphenol–6‐methyl‐2‐pyridone–water (1/3/1), C₂₀H₁₈O₃·3C₆H₇NO·H₂O, (III–d). In two of the compounds, (I–a) and (I–d), the host molecules lie about crystallographic twofold axes. In two other compounds, (II–b) and (II–c), the host molecules lie across inversion centers. In all cases, the guest molecules are hydrogen bonded to the host molecules through O—H...O=C hydrogen bonds [the range of O...O distances is 2.543 (2)–2.843 (2) Å. The pyridone moieties form dimers through N—H...O=C hydrogen bonds in five of the compounds [the range of N...O distances is 2.763 (2)–2.968 (2) Å]. In four compounds, (I–a), (I–c), (I–d) and (II–c), the molecules are arranged in extended zigzag chains formed via host–guest hydrogen bonding. In five of the compounds, the guest molecules are arranged in parallel pairs on top of each other, related by inversion centers. However, none of these compounds underwent photodimerization in the solid state upon irradiation. In one of the crystalline compounds, (III–d), the guest molecules are arranged in stacks with one disordered molecule. The unsuccessful dimerization is attributed to the large interatomic distances between the potentially reactive atoms [the range of distances is 4.027 (4)–4.865 (4) Å] and to the bad overlap, expressed by the lateral shift between the orbitals of these atoms [the range of the shifts from perfect overlap is 1.727 (4)–3.324 (4) Å]. The bad overlap and large distances between potentially photoreactive atoms are attributed to the hydrogen‐bonding schemes, because the interactions involved in hydrogen bonding are stronger than those in π–π interactions.     

Syntheses and structures of nine-coordinate K3[DyIII(nta)2(H2O)]·5H2O and eight-coordinate (NH4)3[DyIII(nta)2] complexes

K₃[Dy^III(nta)₂(H₂O)]·5H₂O and (NH₄)₃[Dy^III(nta)₂] have been synthesized in aqueous solution and characterized by IR, elemental analysis and single-crystal X-ray diffraction techniques. In K₃[Dy^III(nta)₂(H₂O)]·5H₂O the Dy^III ion is nine coordinated yielding a tricapped trigonal prismatic conformation, and its crystal belongs to monoclinic system and C2/c space group. The crystal data are as follows: a = 15.373(5) Å, b = 12.896(4) Å, c = 26.202(9) Å; β = 96.122(5)°, V = 5165(3) ų, Z = 8, D _c = 1.965 g·cm^?3, μ = 3.458 mm^?1, F(000) = 3016, R ₁ = 0.0452 and wR ₂ = 0.1025 for 4550 observed reflections with I ≥ 2σ(I). In (NH₄)₃[Dy^III(nta)₂] the Dy^III ion is eight coordinated yielding a usual dicapped trigonal anti-prismatic conformation, and its crystal belongs to monoclinic system and C2/c space group. The crystal data are as follows: a = 13.736(3) Å, b = 7.9389(16) Å, c = 18.781(4) Å; β = 104.099(3)°, V = 1986.3(7) ų, Z = 2, D _c = 1.983 g·cm^?3, μ = 3.834 mm^?1, F(000) = 1172, R ₁ = 0.0208 and wR ₂ = 0.0500 for 2022 observed reflections with I ≥ 2σ(I). The results indicate that the difference in counter ion also influences coordination numbers and structures of rare earth metal complexes with aminopolycarboxylic acid ligands.     

An Azelaato‐bridged Dinuclear Copper(II) Complex, [Cu2(phen)2(C9H14O4)2] · 6 H2O (phen = 1,10‐phenanthroline)

The title compound [Cu₂(phen)₂(C₉H₁₄O₄)₂] · 6 H₂O was prepared by the reaction of CuCl₂ · 2 H₂O, 1,10‐phenanthroline (phen), azelaic acid and Na₂CO₃ in a CH₃OH/H₂O solution. The crystal structure (monoclinic, C2/c (no. 15), a = 22.346(3), b = 11.862(1), c = 17.989(3) Å, β = 91.71(1)°, Z = 4, R = 0.0473, wR² = 0.1344 for 4279 observed reflections) consists of centrosymmetric dinuclear [Cu₂(phen)₂(C₉H₁₄O₄)₂] complexes and hydrogen bonded H₂O molecules. The Cu atom is square‐planar coordinated by the two N atoms of the chelating phen ligand and two O atoms of different bidentate bridging azelaate groups with d(Cu–N) = 2.053, 2.122(2) Å and d(Cu–O) = 1.948(2), 2.031(2) Å. Two azelaate anions bridge two common Cu atoms via the terminal O atoms (d(C–O) = 1.29(2) Å; d(C–C) = 1.550(4)–1.583(4) Å). Phen ligands of adjacent complexes cover each other at distances of about 3.62 Å, indicating π‐π stacking interaction, by which the complexes are linked to 1 D bands.     

Hydrothermal Synthesis and Structure of a New 3D Lanthanide—Carboxylate Framework,[La（btec）1／2（H2btec）1／2（H2O）]n（H4btec=1,2,4,5—Benzeneteracarboxylic acid）

The title complex, [La(btec)_1/2(H₂btec)_1/2 (H₂O)]_n (H₄btec= 1, 2,4,5‐benzenetetracarboxylic acid) (1) was synthesized by the hydrothermal reaction of 1,2,4,5‐benzenetetracarboxylic dianhydride with La(NO₃)₃·6H₂O in H₂O, and crystallizes in the triclinic system, space group P‐1 with a = 0.64403(3) nm, b = 0.94500(4) nm, c = 0.96380(5) nm, a = 88.535(2)°, β = 100.314(2)°, γ = 76.6470(10)°, V = 1.60968(10) nm³, Z = 2, and final R = 0.0274, R_w = 0.0735. In 1, each La(m) ion is coordinated by eight oxygen atoms from six carboxylate groups and one coordinated water molecule. Two different coordination modes of H₄btec were present in the structure, one of which contains two protonated carboxylate groups to balance the charge.     

Crystal Structures of [Mn2(H2O)4(phen)2(C4H4O4)2] · 2 H2O and [Mn(phen)2(H2O)2][Mn(phen)2(C4H4O4)](C4H4O4) · 7 H2O

Reactions of 1,10‐phenanthroline monohydrate, Na₂C₄H₄O₄ · 6 H₂O and MnSO₄ · H₂O in CH₃OH/H₂O yielded a mixture of [Mn₂(H₂O)₄(phen)₂(C₄H₄O₄)₂] · 2 H₂O ( 1 ) and [Mn(phen)₂(H₂O)₂][Mn(phen)₂(C₄H₄O₄)](C₄H₄O₄) · 7 H₂O ( 2 ). The crystal structure of 1 (P1 (no. 2), a = 8.257(1) Å, b = 8.395(1) Å, c = 12.879(2) Å, α = 95.33(1)°, β = 104.56(1)°, γ = 106.76(1)°, V = 814.1(2) ų, Z = 1) consists of the dinuclear [Mn₂(H₂O)₄(phen)₂(C₄H₄O₄)₂] molecules and hydrogen bonded H₂O molecules. The centrosymmetric dinuclear molecules, in which the Mn atoms are octahedrally coordinated by two N atoms of one phen ligand and four O atoms from two H₂O molecules and two bis‐monodentate succinato ligands, are assembled via π‐π stacking interactions into 2 D supramolecular layers parallel to (101) (d(Mn–O) = 2.123–2.265 Å, d(Mn–N) = 2.307 Å). The crystal structure of 2 (P1 (no. 2), a = 14.289(2) Å, b = 15.182(2) Å, c = 15.913(2) Å, α = 67.108(7)°, β = 87.27(1)°, γ = 68.216(8)°, V = 2934.2(7) ų, Z = 2) is composed of the [Mn(phen)₂(H₂O)₂]²⁺ cations, [Mn(phen)₂(C₄H₄O₄)] complex molecules, (C₄H₄O₄)^2– anions, and H₂O molecules. The (C₄H₄O₄)^2– anions and H₂O molecules form 3 D hydrogen bonded network and the cations and complex molecules in the tunnels along [001] and [011], respectively, are assembled via the π‐π stacking interactions into 1 D supramolecular chains. The Mn atoms are octahedrally coordinated by four N atoms of two bidentate chelating phen ligands and two water O atoms or two carboxyl O atoms (d(Mn–O) = 2.088–2.129 Å, d(Mn–N) = 2.277–2.355 Å). Interestingly, the succinato ligands in the complex molecules assume gauche conformation bidentately to chelate the Mn atoms into seven‐membered rings.     

SYNTHESIS AND CRYSTAL STRUCTURE OF TETRAIMIDAZOLE(DIAQUA)-MANGANESE(II) TEREPHTHALATE

Abstract

The title complex, [Mn(C₃H₄N₂)₄(H₂O)₂]·(C₈H₄O₄), was prepared by reaction of terephthalato (diaqua)manganese (II) with imidazole in ethanol/water solution. The complex crystallizes in space group C2/c with cell parameters a = 22.494(5), b = 7.741(2), c = 16.287(3)Å, β = 120.94(3)°, Z = 4. The complex consists of complex Mn(II) cations and uncoordinated terephthalate anions; the latter link cations through an H-bonding network. Thermal analyses and IR spectra are discussed in terms of the formation of the complex.