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.     

Investigation of the crystal and molecular structure of a novel coordination polymer formed by manganese(II) nitrate and 4,4,10,10-tetramethyl-1,3,7,9-tetraazospiro[5.5]undecan-2,8-dione

A coordination polymer {[Mn(H₂O)₂(C₁₁H₂₀N₄O₂)₂]²⁺·2(NO ₃ ^? )} _n is synthesized and its structure is determined. The crystals are monoclinic: space group P2₁/c, a = 12.3771(3) Å, b = 14.8775(3) Å, c = 18.1388(4) Å, β = 106.611(2)°, V = 3200.70(12) ų, d _x = 1.44 g/cm³, Z = 4. Manganese ions are coordinated with four oxygen atoms of four organic ligands (two unique) and two water molecules. The coordination polyhedron is a distorted octahedron; the O-Mn-O angles between the adjacent oxygen atoms fall within 83.96(5)–98.11(5)°. The nitrate anions are in the outer coordination sphere. The Mn...Mn distances in the polymer are 8.56 Å. In the crystal, polymeric coordination chains are joined in layers perpendicular to the b axis by hydrogen bonds involving the organic ligands, water molecules, and nitrate anions.     

New binuclear complex of bis(2,4,6,8-tetramethyl-2,4,6,8- tetraazabicyclo(3.3.0)octane-3,7-dione-<Emphasis Type="Italic">O,O</Emphasis>')-diaquatetrakis(nitrato-<Emphasis Type="Italic">O,O</Emphasis>')-dimanganese(II) monohydrate: Synthesis and crystal structure

The centrosymmetric binuclear manganese(II) nitrate complex with a bicyclic bis-carbamide, namely, 2,4,6,8-tetramethyl-2,4,6,8-tetraazabicyclo(3.3.0)octane-3,7-dione, or mebicar (Mk) [Mn(C₈H₁₄N₄O₂)(H₂O)(NO₃)₂]₂ · H₂O (I), has been synthesized for the first time. The structure of complex I has been solved (CCDC no. 1435139). Crystals of complex I are monoclinic, space group P2₁/c, a = 12.8108(11) Å, _b = 10.0662(2) Å, c = 18.6367(17) Å, β = 136.512(16)°, V = 1654.0(4) ų, ρcalcd = 1.659 g/cm³, Z = 2. Each manganese atom is coordinated to the two oxygen atoms of two Mk molecules related by the symmetry codes (1–x, 2–y, 1–z) and to two bidentate nitrate anions and one water molecule. The coordination polyhedron of the manganese atom is a strongly distorted pentagonal bipyramid. The Mn···Mn distance in the complex is 8.7261(9) Å.     

Crystal structure of barium (cyclohexane-1,2-diaminetetraacetato)cobaltate(III) nonahydrate Ba[Co(Cdta)]2 · 9H2O

The crystal structure of Ba[Co(Cdta)]₂ · 9H₂O has been determined by X-ray diffraction. The crystals are monoclinic, a = 15.9415(10) Å, b = 7.8449(6) Å, c = 32.230(2) Å, β = 100.387(8)°, Z = 4, space group C2/c)). The cyclohexane-1,2-diaminetetraacetate ion forms the octahedral [Co(Cdta)]^? complex through two donor nitrogen atoms and four oxygen atoms and is also connected to two barium atoms through oxygens. The Ba atoms are on a twofold axis. Its nearest environment comprises five O atoms of water molecules, one also being located on a twofold axis, and four O atoms of the four neighboring complex ions. This gives infinite layers parallel to the ab plane. All water molecules form hydrogen bonds within one layer.     

A novel oxo-bridged Mn4 mixed salt, {[(n-Bu4N)(ClO4)]2[Mn4O6(Tacn)4](ClO4)4} · 2H2O and its analogue Mn4 cluster [Mn4O6(Tacn)4](ClO4)4 · 2H2O (Tacn = 1,4,7-triazacyclononane)

A novel Mn₄ mixed salt, {[(n-Bu4N)(ClO₄)₂]₂[Mn₄O₆(Tacn)₄](ClO₄)} · 2H₂O (I) and its analogue [Mn₄O₆(Tacn)₄](ClO₄)₄ · 2H₂O (II) (Tacn = 1,4,7-triazacyclononane), have been constructed and structurally characterized by X-ray crystallography. The [Mn₄O₆]⁴⁺ core of these two complexes presents an adamantine-like skeleton. Each Mn atom of both complexes is coordinated by three nitrogen atoms of Tacn and connects other Mn atoms through a single-oxo bridge in an octahedral environment. Two complexes crystallize in monoclinic crystal system, space group C2/c with a = 24.296(11) Å, b = 10.986(5) Å, c = 32.746(15) Å, β = 101.975(6)°, Z = 8 for I and space group P2₁/n with a = 21.141(10), b = 11.306(5), c = 21.576(10) Å, β = 111.155(5)°, Z = 4 for II.     

Four- and five-coordinate metal atoms in a supramolecular polymeric assembly of silver(I) with (4-methyl-2-quinolylthio)acetate

The coordination compound [Ag₂L₂(H₂O)₂] · ₂H₂O (I), L = C₁₂H₁₀NO₂S has been synthesized by the reaction of AgNO₃ with 4-methyl-2-quinolylthioacetic acid (HL) preliminarily neutralized with an equimolar amount of NBu₄OH. Its crystal structure has been determined, and luminescence properties have been studied. Crystals of I are monoclinic, space group C2/_c, _a = 31.239(6) Å, _b = 12.056(2) Å, _c = 16.846(3) Å, β = 122.17(3)°, V = 5370.4(2) ų, ρ_calc = 1.861 g/cm³, Z = 16. The structure is formed by two crystallographically nonequivalent silver atoms Ag(1) and Ag(2) and two tridentate bridging ligands L coordinated through the S, N, and O atoms. These atoms, together with water molecules, form the coordination environments of the metal atoms with CN = 5 and 4, respectively. The Ag⁺ ions and the tridentate ligands form infinite [Ag₄L₄]_n bands extended in the [001] direction. The presence of outer-sphere water molecules involved in O–H···O hydrogen bonding is responsible for the formation of a supramolecular framework structure. The photoluminescence spectrum of compound I shows two bands at ~450 and ~485 nm corresponding to the blue spectral range.     

Synthesis,Crystal Structure and Magnetic Properties of a Two-Dimensional Heterometallic Assembly ∣[Mn(salen)]∣2∣[Ni(CN)4∣·1/2H2O

A heterometallic assembly, [Mn(salen)]₂[Ni(CN)₄ ]·1/2H₂O (where salen=N, N'-ethylene-bis(salicylideneiminato)-dianion), has been prepared from the reaction of [Mn(salen)H₂O]ClO₄ ·H₂O with K₂ [Ni(CN)₄ ]·H₂O in methanol/water. The compound crystallizes in the tetragonal space group P 4/ncc with the cell dimensions of a =14.604(2) Å, c =16.949(3) Å, and Z=4. The compound assumes a two-dimensional distorted square network structure, formed from Ni―CN―Mn(salen)―NC―Ni linkages with dimensions of Ni―C = 1.867(7)Å, Mn―N - 2.312(6) Å, Mn―N―C - 163.8(6)° Ni―C―N = 178.4(6)°. The two metal atoms Ni(II) and MN(III) have square and slightly distorted octahedral arrangements, respectively. Magnetic susceptibility measurements indicate the presence of an intramolecular antiferro-magnetic interaction and gives a Mn―Mn exchange integral of ?3.2cm^?1.     

Crystal structure of barium α-(Ethylenediamine-N,N-diacetato)malonatocobaltate(III) perchlorate pentahydrate Ba[Co(Edda)(Mal)(ClO4) · 5H2O

The crystal structure of [Co (Edda)(Mal)](ClO₄) · 5H₂O is determined by X-ray diffraction analysis (the crystals are triclinic: a = 10.1363(12) Å, b = 11.0801(13) Å, c = 11.3173(13) Å, α = 101.129(13)°, β = 108.594(13)°, γ = 112.883(13)°, Z = 2, space group P $\overline 1 $ ). The Co³⁺ ion coordinates two O atoms of the malonate ion, as well as two N atoms and two trans-O atoms of the ethylene-N,N-diacetate ion. The [(H₂O)₄Ba(ClO₄)]⁺ subunits interact with the [Co(Edda)(Mal)]^? complexes to form infinite ribbons, and each complex is bonded with three Ba atoms through the O atoms of the carboxyl groups. The coordination number of the Ba atom is nine (four O atoms of the water molecule, one O atom of the perchlorate ion, and four O atoms of three adjacent complexes).     

Synthesis,Crystal Structure,and Magnetic Properties of {[Cu(phen)]2(C4H2O4)2} · 4.5H2O with C4H4O4 = Maleic Acid

Reaction of CuCl₂ · 2H₂O, phenanthroline, maleic acid and NaOH in CH₃OH/H₂O (1:1 v/v) at pH = 7.0 yielded blue {[Cu(phen)]₂(C₄H₂O₄)₂} · 4.5H₂O, which crystallizes in the monoclinic space group C2/c (no. 15) with cell dimensions: a = 18.127(2)Å, b = 12.482(2)Å, c = 14.602(2)Å, β = 103.43(1)°, U = 3213.5(8)ų, Z = 4. The crystal structure consists of the centrosymmetric dinuclear {[Cu(phen)]₂(C₄H₂O₄)₂} complex molecules and hydrogen bonded H₂O molecules. The Cu atoms are each square‐pyramidally coordinated by two N atoms of one phen ligand and three carboxyl O atoms of two maleato ligands with one carboxyl O atom at the apical position (d(Cu‐N) = 2.008, 2.012Å, equatorial d(Cu‐O) = 1.933, 1.969Å, axial d(Cu‐O) = 2.306Å). Two square‐pyramids are condensed via two apical carboxyl O atoms with a relatively larger Cu···Cu separation of 3.346(1)Å. The dinuclear complex molecules are assembled via the intermolecular π—π stacking interactions into 1D ribbons. Crossover of the resulting ribbons via interribbon π—π stacking interactions forms a 3D network with the tunnels occupied by H₂O molecules. The title complex behaves paramagnetically between 5—300 K, following the Curie‐Weiss law _χm(T—θ) = 0.435 cm³ · mol^—1 · K with θ = 1.59 K.     

Crystal structures of three complexes structurally similar to KTbW(CN)8 · 7H2O

Three complexes that crystallize into structures like KTbW(CN)₈ · 7H₂O (triclinic crystal system, space group P $ \bar 1 $ ) were structurally characterized by X-ray diffraction: KYMo(CN)₈ · 7H₂O, a = 7.6371(5), b = 9.2569(6), c = 14.4976(2) Å, α = 80.782(6)°, β = 87.644(5)°, γ = 77.645(5)°, V = 988.23(11) ų, Z = 2, ρ_calcd = 1.876 g/cm³; KHoW(CN)₈ · 7H₂O, a = 7.5887(4), b = 9.2232(5), c = 14.4479(9) Å, α = 80.709(5)°, β = 87.525(5)°, γ = 77.457(5)°, V = 974.12(10) ų, Z = 2, ρ_calcd = 2.462 g/cm³; KErW(CN)₈ · 7H₂O, a = 7.6180(5), b = 9.2356(6), c = 14.4903(11) Å, α = 80.655(6)°, β = 87.492(6)°, γ = 77.557(6)°, V = 982.29(13) ų, Z = 2, ρ_calcd = 2.449 g/cm³. The coordination polyhedra of the d element atoms [M(CN)₈] (M⁴⁺ = Mo and W) are dodecahedra; the coordination polyhedra of the rare-earth metal atoms [RN₄(OH₂)₄] (R³⁺ = Y, Ho, and Er) are tetragonal antiprisms. Four bridging cyano groups are coordinated to the W/Mo and rare-earth metal atoms through the C and N atoms, respectively, to form a polymeric 3D structure involving potassium atoms. The coordination polymers can be formulated as {[K(H₂O)][R(H₂O)₄][M(CN)₈] · 2H₂O} _n (R³⁺ = Y, M⁴⁺ = Mo; R³⁺ = Ho and Er, M⁴⁺ = W).     

Crystal structure of [Cu2(Edta)(Py)2(H2O)2] · 2H2O and [Cu(Im)6]{;Cu(Im)4[Cu(Edta)(Im)]2} · 6H2O, Products of the interaction of (Ethylenediaminetetraacetato)diaquadicopper(II) with pyridine and imidazole

The crystals of [Cu₂(Edta)(Py)₂(H₂O)₂] · 2H₂O (I) and [Cu(Im)₆]{;Cu(Im)₄[Cu(Edta)(Im)]₂} · 6H₂O (II) were isolated as a result of the reaction of an aqueous solutions of Cu₂(Edta) · 4H₂O with pyridine or imidazole, respectively. The crystals were studied by X-ray diffraction. The crystals of I are monoclinic, a = 12.682 Å, b = 6.788 Å, c = 14.834 Å, β = 91.44°, Z = 2, space group P2₁/n. The crystals of II are triclinic, a = 9.118 Å, b = 14.889 Å, c = 15.130 Å, α = 72.59°, β = 72.94°, γ = 82.54°, Z = 1, space group P{ie241-1}. In the centrosymmetric binuclear complex molecule of I, an N atom and two O atoms of the Edta ligand are coordinated to each Cu atom (Cu-N, 2.046 Å; Cu-O, 1.941 and 1.954 Å). The N atom of the pyridine molecule (Cu-N, 1.993 Å) completes the base of an elongated tetragonal pyramid (4 + 1) with the O atom of the H₂O molecule in the apex (Cu-O(w), 2.244 Å). The crystals of II are built of centrosymmetric complex cations [Cu(Im)₆]²⁺ (Cu(1)-N, 2.469, 2.021, and 2.056 Å), centrosymmetric trinuclear complex anions {;Cu(Im)₄[Cu(Edta)(Im)]₂}^2?, and crystal water molecules. In the anion, the central fragment [Cu(Im)₄]²⁺ (Cu(2)-N, 1.985 and 2.023 Å) is bonded to two peripheral complexes [Cu(Edta)(Im)]^2? through atoms O of the Edta ligand (Cu(2)-O, 2.615 Å). In the [Cu(Edta)(Im)]^2? fragment of the complex anion, the Cu(3) atom is bonded to the Edta ligand through the two N atoms and three O atoms (Cu(3)-N, 1.970 and 2.071 Å; Cu(3)-O, 1.966, 1.969, and 2.238 Å) and with the imidazole molecule, through an N atom (Cu(3)-N, 2.397 Å). The coordination polyhedra of the three copper atoms (Cu(1)-Cu(3)) in the structure of II are elongated tetragonal bipyramids (4 + 2). In the structures studied, Edta^4? is a hexadentate chelating/bridging ligand. However, the coordination mode of the ligand in these structures is different: in the binuclear complex I, the Edta ligand is coordinated to each Cu atom through an N atom and two O atoms with the formation of two chelate rings (symmetric (trans) coordination mode), whereas, in the trinuclear complex II, the Edta ligand is coordinated to the Cu(2) atom through an O atom and to the Cu(3) atom through the two N atoms and three O atoms with the formation of three chelate rings (asymmetric (cis) coordination mode).     

Synthesis and structure of novel Mn(II) complex with in situ synthesized ligand

Based on in situ synthesized Schiff base ligand Dppd (Dppd = N-(di(2-pyridyl)methylene)-p-phenylenediamine), a novel dinuclear Mn(II) complex, [Mn₂(Dppd)₄(OAc)₂](ClO₄)₂(CH₂Cl₂)₂ · 2(H₂O) (I), was synthesized and characterized by IR and single-crystal X-ray diffraction. The crystals belong to monoclinic system, space group C2/c with a = 26.3868(2), b = 20.0379(4), c = 19.16260(10)Å, β = 126.6900(10)°, V = 8124.61(18) ų, Z = 4. The complex exhibits a dinuclear structure in which two symmetric Mn(II) atoms adopt somewhat distorted octahedral geometry. The 2D structure is further constructed through intermolecular benzene-benzene offset π···π interactions.     

Coordination compounds of cobalt(II) and cadmium(II) with 2-amino-4-methylpyrimidine: Synthesis, crystal structure, and luminescent properties

The coordination compounds [CoL₂Cl₂] (I) and [CdL₂(H₂O)₂(NO₃)₂] (II) have been synthesized by the reaction of CoCl₂ · 6H₂O and Cd(NO₃)₂ · 4H₂O with L = 2-amino-4-methylpyrimidine (Ampym, C₅H₇N₃), and their structures have been solved. The crystals of complex I are triclinic, space group $P\bar 1$ , a = 5.627(1) Å, b = 11.191(1) Å, c = 12.445(1) Å, α = 81.00(1)°, β = 77.21(1)°, γ = 76.18(1)°, V = 737.7(2) ų, ρ_calcd = 1.567 g/cm³, Z = 2. The crystals of complex II are monoclinic, space group P2₁/c, a = 10.390(1) Å, b = 11.982(1) Å, c = 7.624(1) Å, β = 102.61(1)°, V = 926.1(2) ų, ρ_calcd = 1.760 g/cm³, Z = 2. Discrete [CoL₂Cl₂] moieties are realized in the structure of complex I. The cobalt atom is tetrahedrally coordinated to the two nitrogen atoms of crystallographically nonequivalent ligands L and two chlorine atoms (Co(1)-N_avg, 2.051(4)Å; Co(1)-Cl(1), 2.241(1) Å; Co(1)-Cl(2), 2.263 Å; bond angles at the cobalt atom lie within a range of 102.1°–118.6°). The complexes are linked into supramolecular zigzag chains by N-H...N(Cl) hydrogen bonds. In the structure of complex II, the Cd²⁺ ion (at the inversion center) is coordinated in pairs to the nitrogen atoms of ligand L and the O(NO₃) and O(H₂O) oxygen atoms. The coordination of the Cd²⁺ ion is distorted octahedral (Cd(1)-N(1), 2.341Å; Cd(1)-O(1), 2.340(4) Å; Cd(1)-O(4), 2.327(3) Å; bond angles at the cadmium atom lie within a range of 79.1°–100.9°). N-H...N hydrogen bonds link the complexes into supramolecular chains. These chains are linked into a supramolecular framework by the O-H...O hydrogen bonds between water molecules and NO₃ groups.     

Copper(I) complexes with 2-butyne-1,4-diol: Synthesis and crystal structure of the anionic π-complex (ImH)[CuCl2(HOCH2C≡CCH2OH)] (ImH[CuCl2(HOCH2C≡CCH2OH)] (ImH+ is imidazolium cation)

The crystalline complex ImH[CuCl₂(HOCH₂C≡CCH₂OH)] has been synthesized by the direct interaction of 2-butyne-1,4-diol with CuCl in concentrated aqueous solution of (ImH)Cl (ImH⁺ is imidazolium cation) and studied by X-ray crystallography. The crystals are triclinic, space group P $\overline 1 $ , a = 7.08(2) Å, b = 7.49(1) Å, c = 10.962(8) Å, α = 101.76(8)°, β = 95.85(8)°, γ = 99.57(8)°, Z = 2. The structure consists of stacks of discrete anions [CuCl₂(HOCH₂C≡CCH₂OH)]^? arranged along the [100] axis and [ImH]⁺ cations occupying the free space. The environment of π-coordinated Cu(I) atoms is trigonal and consists of two chlorine atoms and the C≡C bond of 2-butyne-1,4-diol molecule. The alcohol groups do not participate in the coordination, but they form strong hydrogen bonds N-H···O (H···O, 1.76(6) Å) and O-H···Cl(H···Cl, 2.29(5) Å).     

A New Succinato‐bridged Supramolecular Helix Chain: Crystal Structure of [Mn(H2O)2(bpy)(C4H4O4)] · H2O with bpy = 2,2′‐bipyridine

Yellow crystals of [Mn(H₂O)₂(bpy)(C₄H₄O₄)] · H₂O were obtained by the reaction of 2,2′‐bipyridine, succinic acid, MnSO₄ · H₂O and Na₂CO₃ in an aqueous methanol solution. The crystal structure (monoclinic, P2₁/c (no. 14), a = 8.294(1), b = 11.556(1), c = 17.064(1)Å, β = 95.181(6)°, Z = 4, R = 0.0349, wR² = 0.0887) consists of 1D supramolecular helix chains [Mn(H₂O)₂(bpy)(C₄H₄O₄)_2/2] and hydrogen bonded H₂O molecules. The Mn atoms are octahedrally coordinated by two N atoms of one bidentate chelating bpy ligand and four O atoms of two H₂O molecules and two bis‐monodentate bridging succinato ligands with d(Mn–O) = 2.139–2.237Å and d(Mn–N) = 2.268, 2.281 Å. The helix chains are held together by π‐π stacking interactions and hydrogen bonds.     

Crystal Structure and Thermal Property of a Binuclear Manganese(II) Sulfate Complex with Carbohydrazide

The binuclear manganese(II) complex of formula [Mn₂(CHZ)₂(H₂O)₂(SO₄)₂] (CHZ = carbohydrazide) (1) has synthesized in aqueous solution and characterized by elemental analysis, IR, and single crystal X-ray diffraction. The compound 1 crystallizes in monoclinic system, space group P2(1)/n, a = 7.083(1) Å, b = 7.985(1) Å, c = 14.045(2) Å, β = 90.46(1)^°, V = 794.42(16) ų, Z = 2, R = 0.0308 with 1481 reflections. In the title complex, two Mn(II) cations are bonded via the bridging oxygen atoms into a centrosymmetric dimeric unit. The Mn(II) dimers are further extended into layers by means of the bridging sulfate groups. Each Mn atom in the complex is in bivalent state with a distorted pentagonal bipyramid configuration and has a N₂O₅ donor set which consists of two nitrogen atoms and five oxygen atoms provided by the ligands of two CHZ molecules, one water molecule, and two sulfate ions. The CHZ tridentate ligands are coordinated with adjacent Mn(II) cation via two terminal N atoms and the carbonyl O atom and sulfate anions act as bidentate bridge ligand. Four kinds of Mn(II) CHZ complex structures are compared. The thermal property of title complex was studied by using DSC and TG-DTG techniques. The results exhibit the title complex is highly stable.     

Barium (nitrilotriacetato)oxalatocobaltate(III) trihydrate Ba[Co(Nta)(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)] · 3H<Subscript>2</Subscript>O: Crystal structure

Crystals of Ba[Co(Nta)(C₂O₄)] · 3H₂O were prepared, and their structure was solved by X-ray diffraction (monoclinic space group P2₁/c), a = 10.0111(10) Å, b = 10.2838(6) Å, c = 14.2748(15) Å, ß = 100.350(12)°, Z = 4). The local environment of a Ba²⁺ ion includes two O atoms of water molecules and seven O atoms of the carboxyl groups of Nta^3? and C₂O ₄ ^2? ions of five complex anions. Honeycomb type layers can be distinguished in the crystal lattice; within the layers, each Ba²⁺ atom interacts with three complexes and vice versa. In addition, each Ba atom of the layer is bonded to complexes of the upper and lower layers. Thus, the crystal represents a three-dimensional coordination polymer.     

Crystal and molecular structures of triaquabis(5-nitro-2-acetamidobenzoato)copper(II) dihydrate

A new copper(II) complex [Cu(5-NO₂-2-CH₃CONHC₆H₃COO)₂(H₂O)₃] · 2H₂O was synthesized by the reaction of sodium 5-nitro-5-acetamidobenzoate with CuSO₄ · 5H₂O (2: 1), and its structure was determined by X-ray diffraction. Crystals are monoclinic: a = 11.7146(7) Å, b = 16.8463(10) Å, c = 13.2408(9) Å, β = 113.896(5)°, Z = 4, ρ_calc = 1.668 g/cm³, space group P2₁/c, R = 0.0338. In the monomer complex, the copper atom has an elongated square-pyramidal coordination (4 + 1); the coordination sphere is formed by two oxygen atoms of the carboxylate groups of two monodentate organic ligands and the three oxygen atoms O(w) of the water molecules (the O(3w) atom is in the axial position). In the structure, the complex molecules are linked by hydrogen bonds involving two uncoordinated water molecules.     

Study of the molecular and crystal structure of a new coordination polymer of copper(II) nitrate with 4,4,10,10-tetramethyl-1,3,7,9-tetraazospiro[5.5]undecane-2,8-dione

A coordination polymer {[Cu(C₁₁H₂₀N₄O₂)₂(H₂O)]²⁺·2(NO ₃ ^? )} _n (I) is synthesized and analyzed using single-crystal XRD. The crystals are monoclinic: space group P2/c, a = 12.5237(6) Å, b = 7.3310(3) Å, c = 16.8926(8) Å, β = 92.569(4)°, V = 1549.38(13) ų, ρ_calc = 1.47 g/cm³, and Z = 2. The copper atom is in a special position in the second-order axis. The coordination polyhedron of the metal is a trigonal bipyramid. In the axial direction, it is coordinated by two oxygen atoms O(1) of the organic ligand molecules connected by the symmetry operation [?x, y, 0.5-z]; the angle O(1)Cu(1)O(1) ⁱ is 175.16(15)°. In the equatorial direction, the copper atom is coordinated by oxygen atoms O(2) of two ligand molecules connected with the reference molecule by the symmetry operations [?x, y, 0.5-z] and [x, 1-y, ?0.5+z] and the water molecule O(6) in a special position on the twofold axis. The OCuO angles between the equatorial oxygen atoms are 96.80(16)–131.60(8)°, and those between the axial and equatorial atoms are 87.58(8)-91.60(10)°. It is noteworthy that the length of the Cu-O(1) bond (1.955(2) Å) with the axial carbonyl oxygen atom is somewhat shorter than the bond (2.060(3) Å) with the equatorial atom. Nitrate anions are outside the coordination sphere of the metal. The Cu…Cu distance in the polymer is 8.33 Å. To confirm the purity of the sample of I, the powder X-ray pattern is refined by the Rietveld method; the lattice parameters at room temperature are: a = 12.535(4) Å, b = 7.3161(13) Å, c = 16.841(5) Å, β = 92.11(2)°, and V = 1543.4(7) ų.     

Synthesis and crystal structure of aqua(2.2.2-cryptand)(perchlorato-O)lead(II) diaqua(2.2.2-cryptand)lead(II) tris(perchlorate)

A mixed complex aqua(2.2.2-cryptand)(perchlorato-O)lead(II) diaqua(2.2.2-cryptand)lead(II) tris(perchlorate), [Pb(2.2.2-Crypt)(CIO₄)(H₂O)]⁺ [Pb(2.2.2-Crypt)(H₂O)₂]²⁺ (ClO ₄ ^? )₃, is synthesized and studied by X-ray diffraction analysis. The crystals are orthorhombic: space group Pbca, a = 19.118 Å, b = 15.360 Å, c = 39.020 Å, Z = 8. The structure is solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.089 for 7712 reflections (CAD-4 automated diffractometer, λMoK _α radiation). In each of the two complex cations of the host-guest type in the structure, the Pb²⁺ cation is coordinated by all the eight heteroatoms (6O + 2N) of the cryptand ligand and by two O atoms of the water molecule and ClO ₄ ^? anion or by two O atoms of two water molecules. In the crystal, alternating complex cations and ClO ₄ ^? anions are linked into infinite chains (along the z axis) through interionic hydrogen bonds O-H···O-Cl.