Structural Units Of Crystals Research Articles

Synthesis and crystal structure of (NH4)(CN3H6)[UO2(SeO3)2

Single crystals of (NH4)(CN3H6)[UO2(SeO3)2] (I) are synthesized and studied by X-ray diffraction analysis. The compound crystallizes in the triclinic crystal system with the unit cell parameters: a = 7.0051(2) A, b = 9.4234(3) A, c = 9.5408(3) A, α = 88.727(1)°, β = 70.565(1)°, γ= 77.034(1)°, space group P1, Z = 2, R = 0.0224. The main structural units of crystals I are the [UO2(SeO3)2]2− chains of the crystal-chemical group AB2B11 (A = UO22+, B2= SeO32−, B11= SeO32−) of the uranyl complexes. The uranium-containing complexes are joined into a three-dimensional framework by the ammonium and guanidinium ions and a system of hydrogen bonds.

Synthesis and crystal structure of catena-bis(nicotinamide)aqua(μ-phthalato)copper(II) hemihydrate

The copper(II) phthalate complex with nicotinamide [CuL2(μ-Pht)(H2O)] · 0.5H2O(I) (where L is nicotinamide and Pht2− is an anion of phthalic acid) is synthesized and investigated using IR spectroscopy and X-ray diffraction. The crystals of compound I are monoclinic, a = 13.368(2) A, b = 7.891(3) A, c = 20.480(2) A, β = 108.69(2)°, Z = 4, and space group P21/c. The structural units of crystal I are linear chains formed by bridging phthalate anions and crystallization water molecules. The copper atom is coordinated by two pyridine nitrogen atoms of two nicotinamide ligands (Cu-N, 2.001 and 2.045 A), two oxygen atoms of different phthalate anions (Cu-O, 1.964 and 2.235 A), and the oxygen atom of the H2 O molecule (Cu-O, 2.014 A). The coordination polyhedron of the copper atom is completed to an elongated (4 + 1 + 1) tetragonal bipyramid by the second (chelating) oxygen atom of the carboxyl group (Cu-O, 2.587 A), which is one of the anions of phthalic acid. The linear polymer molecules are joined into complex macromolecular dimers with the closest internal contacts of the specific type. The macromolecular dimers are the main supramolecular ensembles of the crystal structure.

Synthesis and structure of Na[UO2(SeO3)(HSeO3)] · 4H2O

Compound Na[UO2(SeO3)(HSeO3)] · 4H2O (I) has been synthesized and studied by single-crystal X-ray diffraction. The crystals of I are monoclinic with the unit cell parameters a = 8.8032(5) A, b = 10.4610(7) A, c = 13.1312(7) A, β = 105.054(2)°, space group P21/n, Z = 4, V = 1167.76(12) A3, R = 0.0394. The main structural units of crystals I are the [UO2(SeO3)(HSeO3)]− layers belonging to the AT3B2 crystal-chemical group (A = UO22+, T3 = SeO32−, B2 =HSeO3−) of the uranyl complexes. The sodium ions are linked with oxygen atoms of two uranyl ions of the same layer and with four water molecules. Electroneutral packets that formed are linked into a three-dimensional framework through a system of hydrogen bonds.

Synthesis and Crystal Structure of 4-Aminoquinolinium Dicitratoborate Monohydrate

4-Aminoquinolinium dicitratoborate monohydrate [(4-NH2)C9H6NH][(C6H6O7)2B] · H2O (I) has been synthesized for the first time. Single crystals have been studied by X-ray crystallography. The structural units of crystal I are large complex dicitratoborate anions with a spirane structure, 4-aminoquinolinium cations and crystal water molecules. The crystal packing of I is three-dimensional. Seventeen independent contacts O(N)-H⋯O and N-H⋯O,O’ form an intricate system of hydrogen bonds.

Diphenylguanidinium (ethylenediaminetetraacetato)hydroxogermanate hydrate (HDphg)[Ge(OH)(Edta)] · H2O: Synthesis, physicochemical characterization, and crystal structure

The onium compound based on the germanium(IV) complex with ethylenediamine-N,N,N1,N1-tetraacetic acid (H4Edta) and diphenylguanidine (Dphg), (HDphg)[Ge(OH)(Edta)] · H2O, has been isolated in the solid state and studied by physicochemical methods. Its crystal structure has been determined by the X-ray diffraction method. The crystals are monoclinic, a = 7.0179(9) A, b = 28.797(8) A, c = 13.477(2) A, β = 104.301(12)°, V = 2639.3(9) A3, Z = 4, space group P21/c, R = 0.045 for 2524 reflections with I > 2σ(I). The onium compound is built of diphenylguanidinium cations HDphg+, [Ge(OH)(Edta)]− anions, and water molecules of crystallization. In the complex anion, the Ge atom is coordinated by two nitrogen atoms and three oxygen atoms of three acetate arms of the pentadentate chelating ligand Edta4− (av. Ge-N, 2.095(4) A; Ge-O, 1.891(3) A). The fourth acetate arm is deprotonated and is not involved in coordination with the metal. The coordination of the metal atom is completed to an octahedral one by the O atom of the hydroxo ligand (Ge-OH 1.759(3) A). The structural units in crystal are linked by a system of hydrogen bonds.

Synthesis and crystal structure of octaaquaerbium(III) 4,7,13,16,21,24-Hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane pentabromide hydrate

A new complex salt [Er(H2O)8]3+·[H2(Crypt-222)]2+·5Br−·1.5H2O(I) is synthesized, and its crystal structure is studied by single-crystal X-ray diffraction analysis (space group P21, a = 8.315 A, b = 32.000 A, c = 8.383 A, β = 120.03°, Z = 2; direct method, anisotropic full-matrix least-squares approximation, R = 0.050 for 3755 independent reflections; CAD4 automated diffractometer, λMoK α radiation). The structural units of crystal I are complex cations [Er(H2O)8]3+, disordered dications of the 2.2.2-cryptand (with two protonated nitrogen atoms), Br− anions, and water molecules. The coordination polyhedron of the Er3+ cation is a tetragonal antiprism with the oxygen atoms of eight water molecules at its vertices. The disordered [H2(Crypt-222)]2+ dication contains trifurcate hydrogen bonds N+-H(⋯O)3.

Five-coordinate Co(II) complexes with nitrilotriacetic acid: Crystal structures of Ca[Co(Nta)X] · nH2O (X − = Cl, Br, or NCS)

The synthesis and X-ray diffraction study of three Ca[Co(Nta)X] · nH2O complexes [X − = Cl, n = 2.3 (I); X − = Br, n = 2 (II); and X − = NCS, n = 2 (III)] are performed. The main structural units of crystals I–III are the [CoX(Nta)]2− anionic complexes and hydrated Ca2+ cations. The anionic complexes have similar structures. The coordination of the Co2+ atom in the shape of a trigonal bipyramid is formed by N + 3O atoms of the Nta 3− ligand and the X − anion in the trans position with respect to N. In structures I–III, the Co-O and Co-N bond lengths lie in the ranges 1.998–2.032 and 2.186–2.201 A, respectively. The Co-X bond lengths are 2.294 (I), 2.436 and 2.445 (II), and 1.982 A (III). The environments of the Ca2+ cations include oxygen atoms of one or two water molecules and six or seven O(Nta) atoms with the coordination number of 9 in I or 8 in II and III. The Ca-O(Nta) bonds form a three-dimensional framework in I or layers in II and III. Water molecules are involved in the hydrogen bonds O(w)-H···O(Nta), O(w)-H···X, and O(w)-H···O(w). Structural data for crystals I–III are deposited with the Cambridge Structural Database (CCDC nos. 287 814–287 816).

Crystal Structure of [UO2SO4{(CH3)HNCONH(CH3)}2

The single crystals of [UO2SO4{(CH3)HNCONH(CH3)}2] (I) were synthesized and studied by X-ray diffraction. The crystals are monoclinic, a = 6.847(1) A, b = 14.259(3) A, c = 14.297(3) A, β = 93.451(4)°, space group P21/n, Z = 4. The main structural units of crystals I are ribbons whose composition coincides with the composition of the compound. The crystal chemical formula of the complex is AT3M 2 1 (A = UO 2 2+ ).

Crystal structure of bis[diethylenetriamine-N′-(3-propionato)-N, N′,N″,O,O′]dicopper(II) Diperchlorate, [Cu2(4-Dtmp)2](ClO4)2

A complex of copper(II) with the diethylenetriaminemonopripionate ligand [Cu2(4-Dtmp)2](ClO4)2 (I) is synthesized and characterized using X-ray diffraction. The crystals of compound I are monoclinic, a = 7.740(2) A, b = 19.199(3) A, c = 8.449(2) A, β = 91.61(2)°, Z = 2, and space group P21/n. The structural units of crystal I are centrosymmetric dimeric cations and statistically disordered ClO 4 − anions. In the cation, the copper atom is coordinated by three N atoms [mean Cu-N, 2.01(1) A] and two O atoms [Cu-O, 2.134(6) A and 1.958(7) A] of the pentadentate bridging-chelate Dtmp ligand, which occupy vertices of the trigonal bipyramid. The binuclear cations are linked via centrosymmetric pairs of hydrogen bonds into ribbons aligned parallel to the a axis of the crystal. The ClO 4 − anions form columns in the same direction. In the crystal, the cationic ribbons and anionic columns alternate in a chessboard fashion.

Crystal structure of zinc(II) hydrated trinuclear complex with monoprotonated ethylenediaminetetraacetate anion(3−), [Zn3(HEdta)2(H2O)6

The crystal structure of the [Zn{sub 3}(HEdta){sub 2}(H{sub 2}O){sub 6}] complex (I) is determined by X-ray diffraction analysis. The crystals are orthorhombic, a = 14.780 A, b = 29.699 A, c = 7.032 A, Z = 4, and space group Pna2{sub 1}. The structural units of crystals I are trinuclear linear molecules, in which the peripheral atoms Zn(1) and Zn(2) each coordinate two N atoms and three O atoms of the HEdta{sup 3-} ligand and the O(w) atom of the H{sub 2}O molecule, whereas the central Zn(3) atom coordinates four O(w) atoms of the H{sub 2}O molecules and two terminal O atoms of the two HEdta{sup 3-} ligands. The HEdta{sup 3-} ligand fulfills a hexadentate chelating-bridging function. The bond lengths are as follows: Zn-O(HEdta), 2.006(4)-2.123(4) A; Zn-N, 2.214(6) and 2.128(5) A; and Zn-O(w), 2.006(6)-2.225(5) A. In structure I, there is a specific contact formed by hydrogen bonds, owing to which the distance between the central atoms of individual molecules appears to be shorter than that in covalently bonded complexes.

Tetrakis(Isothiocyanato)zinc(II) 4,7,13,16,21,24-Hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane: Synthesis and Crystal Structure

The salt tetrakis(isothiocyanato)zinc(II) 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane, [H2(Crypt-222)]2+ · [Zn(NCS)4]2– (I), was synthesized and its structure was determined using X-ray diffraction analysis: space group P21/n, a = 13.734 A, b = 11.627 A, c = 20.816 A, β = 91.51°, Z = 4. The structure was solved by direct methods and anisotropically refined by the full-matrix least-squares method to R =0.093 for 4920 independent reflections (CAD4 autodiffractometer, λCuKα radiation). The structural units of crystal I are 2.2.2-cryptand dications (with two protonated nitrogen atoms) and complex anions [Zn(NCS)4]2–. The coordination polyhedron of the Zn2+ cation is a distorted tetrahedron. The 2.2.2-cryptand dication contains trifurcate N–H(...O)3 hydrogen bonds.

Crystal Structure of Bis(dibenzo-18-crown-6)rubidium Triiodide

Crystalline bis(dibenzo-18-crown-6)rubidium triiodide complex [Rb(DB18C6)2]+ · I3– (I) is synthesized and its structure is studied by X-ray diffraction analysis. The structure of I (space group Pnma, a = 23.854 A, b = 23.612 A, c = 7.863 A, Z = 4) is solved by the direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.079 against 3990 independent reflections (CAD4 automated diffractometer, λMoKα). Structural units of crystal I are the I3– anions and [Rb(DB18C6)2]+ cations. The crystal has the structure intermediate between that of a standard host–guest complex and a sandwich complex. In the structure of complex I, the crystallographic plane with symmetry m passes through the I3– anion (perpendicularly to its axis) and complex cation. The coordination polyhedron of the Rb+ cation is a strongly distorted hexagonal pyramid with the O atom of one crown ligand at the axial vertex and a base of six O atoms of another DB18C6 crown ligand.

Insertion of ethyl isothiocyanate into tungsten hexachloride: Crystal structure of ethyl-(4-ethyl-5-thioxo[1.2.4]dithiazolidin-3-ylidene)ammonium oxopentachlorotungstate(VI)

A product of the insertion of two isothiocyanate molecules into the same W-Cl bond, namely, W-Cl-WCl5{N(Et)C(S)N(Et)C(S)Cl} (I), is synthesized by the reaction of WCl6 with EtNCS in a dichloroethane solution. The hydrolysis of compound I results in the formation of single crystals of the complex . The structure of crystals II is determined using X-ray diffraction. It is demonstrated that structural units of crystals II are the [WVIOCl5]− anionic complexes and the ethyl-(4-ethyl-5-thioxo[1.2.4]dithiazolidin-3-ylidene)ammonium cations.

Interaction of cystamine with palladium(II) monoethanolaminate complex: Crystal structure of [Pd(NH2CH2CH2OH)4][Pd6(NH2CH2CH2S)8]Cl6 · 5H2O

The new compound [Pd(NH2CH2CH2OH)4][Pd6(NH2CH2CH2S)8]Cl6 · 5H2O (I) is synthesized and its crystal structure is determined. The crystals are monoclinic, a = 25.625(6) A, b = 9.633(5) A, c = 24.847(7) A, β = 91.47(2)°, Z = 4, and space group C2/c. The structural units of crystals I are the centrosymmetric hexanuclear [Pd6(NH2CH2CH2S)8]4+ cations, the mononuclear [Pd(NH2CH2CH2OH)4]2+ cations with C2 symmetry, the Cl− anions, and crystallization water molecules. In the hexanuclear cation, the interaction between the Pd atoms occurs through the S atoms of the mercaptoethylaminate ligands. The Pd(2) and Pd(3) atoms and the ligands form two metallochelate fragments in which the N and S atoms are located in cis positions. The average lengths of the Pd-S and Pd-N bonds are equal to 2.274(1) and 2.074(6) A, respectively. The metallochelate fragments are joined to each other and to their centrosymmetric analogues through the Pd(1) atom, which coordinates four S atoms [the average Pd-Sav bond length is 2.332(1) A]. In the mononuclear cation, the Pd(4) atom coordinates four N atoms of the monoethylaminate ligands [the Pd-N bond lengths are 2.045(6) and 2.056(6) A]. The shortest Pd⋯Pd distance is equal to 3.207(1) A. The bonding in the structure is provided by numerous hydrogen bonds with the participation of all the H2O molecules, NH2 groups, and Cl− anions.

Crystal Structure of Rb[UO2(SO4)F

Single crystal of Rb[UO2(SO4)F] (I) was studied by X-ray diffraction [rhombic system, space group Pca21, Z = 12, unit cell parameters: a = 25.393(3), b = 6.735(1), c = 11.496(3) A]. The main structural units of crystals of I are [UO2(SO4)F]- layers belonging to the crystallochemical group AT3M2 (A = UO22+) of uranyl complexes and combined into three-dimensional framework by electrostatic interactions involving interlayer rubidium ions.