Synthesis, Structure and Spectroscopy of Clathrate Inclusion Compounds of Cobalt(II), Cadmium(II) and Zinc(II) trans-4-styrylpyridine nitrates as Host with trans-4-styrylpyridine as Guest (2 : 1)

New clathrate inclusion compounds with the general formula,MA₃X₂ 1/2G (M = Co(II)(1),Cd(II)(2), and Zn(II)(3), X = NO₃ ^- andA and G = trans-4-styrylpyridine), differing from the usualWerner clathrates, MA₄X₂ 2G, have been prepared and characterized by elemental and thermal analyses,IR and electronic spectroscopy and X-ray crystallography. Tworepresentative compounds [Co(stpy)₃(NO₃)₂] 1/2stpy (1) and [Cd(stpy)₃(NO₃)₂] 1/2 stpy (2)are investigated by single crystal X-ray diffraction. Compound (1)crystallizes in the triclinic space group P¯1 with a = 10.966(2),b = 12.802(4), c = 16.063(5) Å = 83.38(3), = 71.30(2), = 76.88(3) °,Z = 2. The structure is made up of discretemolecules of [Co(stpy)₃(NO₃)₂]. The central Co(II) issurrounded by three stpy nitrogen atoms and four oxygen atoms of twoasymmetrically coordinated bidentate nitrate ligands. One of the oxygensis semicoordinated leading to a distorted octahedral geometry for Co(II).Compound (2) crystallizes in the monoclinic space group P2₁/nwith a = 15.597(3), b = 18.313(5), c = 16.188(3) Å = 115.998(14)° and Z = 4. The structure consists of neutralmolecules of [Cd(stpy)₃(NO₃)₂]. The geometry aroundCd(II) is best described as pentagonal bipyramid with four oxygen atomsfrom symmetrical bidentate nitrate groups and one stpy nitrogen atom inthe equatorial positions. Two other nitrogen atoms from stpy ligands occupythe axial positions. The guest stpy molecules are trapped in the centrosymmetricalcavities in lattices of both 1 and 2. Compound 3is found to beisomorphous with 2. A large splitting of the symmetric and asymmetricNO₂ stretching vibrations reveals the presence of bidentate nitrate ligands.Thermogravimetric and DTA studies on the Cd(II) compound, show it to be athermally stable inclusion compound.     

Crystal structure of the dinitratotetrakis(pyridine)nickel(II) clathrate with pyridine as guest, [NiPy4(NO3)2]·2Py

The structure of the [NiPy₄(NO₃)₂]·2Py clathrate was determined by single crystal X-ray diffraction analysis (KM-4 diffractometer, λMoK_a radiation, graphite monochromator, ω/2θ scan mode, θ_max=30°, 640 reflections, R=0.065). Orthorthombic base-centered unit cell, space group Ccca, a=12.148(5), b=15.019(4), c=16.96(1) Å, Z=4C₃₀H₃₀N₈NiO₆, d_calc=1.411 g/cm³. The structure is of island type and consists of distorted octahedral trans-[NiPy₄(NO₃)₂] (host) and pyridine (guest) molecules. The Ni(II) cation coordinated by four nitrogens of the pyridine ligands and two oxygens of the nitrato groups lies in the special position 222; the twofold axes coincide with the directions of the metal-ligand bonds. The guest pyridine molecules lie on the twofold axes that are parallel to the c axes and are oriented in such a way that the total dipole moment of the guest subsystem is zero.     

The crystal structures of α,ω-diaminoalkanecadmium(II) tetracyanonickelate(II)-aromatic molecule inclusion compounds. I. 1,4-diaminobutanecadmium(II) tetracyanonickelate(II)-2,5-xylidine (1/1): Cd(NH2(CH2)4NH2)Ni(CN)4. (CH3)2C6H3NH2

The title compound crystallizes in monoclinic space group P2₁/m with a=9.795(2), b=15.010(2), c=7.125(1) Å, =105.56(1)^o, and Z=2. The structure has been refined to the weighted Rw=0.042 for 2742 reflections collected by counter method. Two-dimensionally extended but wavy cyanometal complex layers are bridged by 1,4-diaminobutane (dabn) to give a three-dimensional host structure which provides a channel-like cavity with the guest 2,5-xylidine molecule. The skeleton of the bridging dabn takes a trans-cis conformation to make the packing efficient between the cavity and the guest molecule. The series of Hofmann-dabn-type Cd(NH₂ (CH₂)₄NH₂) Ni (CN)₄. nG inclusion compounds are described for several aromatic guest molecules G with various stoichiometric coefficients n. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82020 (22 pages).     

Monodentate and Bridging Bidentate Functions of Pyrazine in the Crystal Structures of [Ni(Pz)2{(i-C4H9)2PS2}2] and [Ni(Pz){(i-C4H9)2PS2}2]n

The structures of mixed-ligand complexes [Ni(Pz)₂{(i-C₄H₉)₂PS₂}₂] (I) and [Ni(Pz){(i-C₄H₉)₂PS₂}₂] _n (II) were determined from single-crystal X-ray diffraction data (CAD-4 diffractometer, MoK radiation, 1527 and 2387 F_hkl, R = 0.0360 and R = 0.0491). The crystals of both complexes are monoclinic with cell dimensions a = 9.180(2), b = 16.002(3), c = 11.547(2) , = 104.92(3)°, V = 1639.0(6) ³, Z = 2, space group P2₁/n and a = 30.718(6), b = 11.036(2), c = 19.606(4) , = 118.90(3)°, V = 5819(2) ³, Z = 8, space group C2/c. The crystal structure of I consists of monomer molecules, in which the NiN₂S₄ unit is a compressed octahedron, and the monodentate Pz molecules are in the trans position. The structure of complex II consists of infinite zigzag chains along the c axis. The Ni atom has a distorted octahedral environment (2N+4S). The bridging bidentate Pz molecules are in the cis position. The packing modes and their interactions in the structures are discussed.     

An x-ray diffraction structural investigation of glyoxime derivatives. 4. The molecular and crystal structure of dicyano-and dimesitylglyoximes

An x-ray diffraction structural study was carried out on dicyanoglyoxime trihydrate (DCG) and dimesitylglyoxime (DMG) on an automatic diffractometer using MoK radiation using 851 reflections, R=0.031 (DCG) and 862 reflections, R=0.030 (DMG). The unit cell parameters of the monoclinic crystals of DCG, C₄H₂N₄O₂·3H₂O at –155°C are as follows: a=17.34(1), b=8.395(6), c=6.280(5) Å, =97.23(6)°, Z=4, space group C2/c. The unit cell parameters of the monoclinic crystals of DMG, C₂₀H₂₄N₂O₂ at 23°C are as follows: a=12.734(2), b=8.885(2), c=16.087(2) Å, =101.31(1)°, Z=4, space group I2/a. DCG and DMG molecules in the crystal have anti form with anti-peri-planar orientation of the oxime groups. The planar dioxime fragments features -conjugation of the oxime groups. The molecules in the crystal are connected by hydrogen bonds, which form a three-dimensional framework in the structure of DCG and chains along the a-axis in the structure of DMG.Institute of Heteroorganic Compounds, Academy of Sciences of the USSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 30, No. 6, pp. 117–121, November–December, 1989.     

The crystal structure of caesium tetracyanodioxoosmate(VI) Cs2[OsO2(CN)4]

Summary The crystal structure of the caesium salt of [OsO₂(CN)₄]^2– has been determined from three-dimensional x-ray diffraction data. The orange crystals are monoclinic, space group C2/m with a=12.125(2), b=8.284(1), c=5.457(1) Å, =102.01(1)° with two molecules per unit cell. The final R value using 778 observed reflections and anisotropic thermal parameters for all atoms was 0.028. The [OsO₂(CN)₄]^2– ion has an octahedral geometry. Bond distances: Os=O=1.750(8)Å and Os–C=2.093(9)Å.     

Synthesis and structure of dimeric bis(isothiocyanato)tris (4-methylpyridine)nickel (II)

Summary The Ni₂(NCS)₄(4-Methylpyridine)6 complex has been prepared crystalline from methanolic solutions of Ni(NCS)2(4-Methylpyridine)4. Three dimensional x-ray diffraction data were collected by means of an automated single crystal diffractometer. The structure was solved by Patterson methods and refined to a final R value of 0.075, based on 2422 observed_ reflections. The compound crystallizes in space group P1 with one dimeric molecule in a unit cell of dimensions a = 10.57(1), 6 = 14.06(1), c = 8.66(1) Å, = 105.2(1), = 114.8(1), y = 95.6(1)°. The Ni atoms have distorted octahedral coordination with one sulfur and five nitrogen atoms - two of the four thiocyanate groups form a double bridge between the neighbouring Ni atoms.4-MePy = 4-Methylpyridine     

X-ray diffraction study of a clathrate with the quinoline-containing werner complex ([NiQ 4(NCS)2]·2Q)

The structure of a clathrate with the quinoline-containing Werner complex as a host was determined by single-crystal X-ray diffraction analysis. The crystals of [NiQ ₄(NCS)₂] ·2Q, C₅₆H₄₂N₈S₂Ni are orthorhombic, space group Pca2₁,a = 15.194(9),b = 12.840(7),c = 24.74(1) å, Z = 4, d_calc = 1.307 g/cm³. The final R = 0.063 for 1505 reflections with I > 2Σ(I) and 228 refined parameters; the parameter of the absolute structure is 0.17(7). The structure consists of complex and quinoline guest molecules; the interactions between the molecules are van der Waals interactions. In the host molecule, Ni(II) is surrounded by a distorted octahedron of six nitrogen atoms of two isothiocyanate groups in the trans-position and four quinoline ligands. The molecule has a propeller conformation; the phenylene rings of the quinoline ligands lie on the same side of the equatorial plane. The host molecule is chiral, as the structure on the whole. The quinoline guest molecules lie in the layers that are perpendicular to the z axis. In its general features, the compound is similar to clathrates of [MA₄X₂] type complexes, where A is pyridine and its derivatives.     

Zur Kristallchemie der Kupfer-Lanthanoid-Oxowolframate: (I) triklin-α-CuTbW2O8, (II) monoklin-CuInW2O8 und (III) monoklin-CuYW2O8

The Crystal Chemistry of Copper Rare-Earth Oxotungstates: (I): triclinic-α-CuTbW₂O₈, (II): monoclinic-CuInW₂O₈ and (III): monoclinic-CuYW₂O₈ Single crystals of (I), (II) and (III) were prepared by recrystallisation in closed systems and examined by X-ray technique. (I): space group C? P1 , a = 7.3080, b = 7.8945, c = 7.1476 Å, α = 115.23, β = 116.21, γ = 56.98°, Z = 2; (II): space group C? C2/c, a = 9.6576, b = 11.6496, c = 4.9863 Å, β = 91.17°, Z = 4; (III): space group C? P2/n, a = 10.0504, b = 5.8214, c = 5.0224 Å, β = 94.23°, Z = 2. The crystal structures are discussed with respect to calculations of the coulombterms of lattice energy and possible valence states of Cu²⁺ and Mo⁵⁺.     

Structure–Properties Relations in Werner β-[Ni(NCS)2(4-MePy)4] Clathrates. Part 2. Host–Host Interactions as a Function of the Guest Molecular Size and Shape and the Amount of Absorbed Guest Compound

Careful analysis of changes in the geometry of the host lattice structure on inclusion of different guest molecules was performed for 11 -[Ni(NCS)₂(4-methylpyridine)₄] clathrates reported in the literature, and specific features were established for the geometry of the host crystal lattice structure, which are characteristic for different modes of location of the guest molecules. A new method is suggested for the analysis of the volume and shape of the empty space in clathrates. Experimental data are reported on the dependence of the a and c parameters of the unit cell of clathrate phases (with furan and dichloromethane as guest components) from the guest uptake. Consideration of these data permit us to construct a model of the changes of host–host interactions in the -[Ni(NCS)₂(4-methylpyridine)₄] clathrates with change of guest uptakes. Modeling of the process of diffusion of the guest molecule through the channel of the -[Ni(NCS)₂(4-methylpyridine)₄] clathrate allowed the nature of the rate-determining step of diffusion to be established. Part 1 of this series has been published as [3].     

An infrared and raman spectroscopic study of metal(II) Di(2-methylpyridine) tetracyanonickelate complexes: Ni(C6H7N)2Ni(CN)4 and Cd(C6H7N)2Ni(CN)4

The results of an infrared and Raman spectroscopic study are reported for two new metal 2-methylpyridine tetracyanonickelate complexes, M(C₆H₇N)₂Ni(CN)₄, M=Ni or Cd. Their structure consists of corrugated polymeric layers of {M-Ni(CN)₄} with 2-methylpyridine molecules bound directly to the metal (M). These complexes can act as host lattices in the formation of inclusion compounds with dioxane guest molecules.     

X-ray diffraction study of 1,2-bis(methylidene-2,2-dimethyl-hydrazino)ethylene — product of the oxidation of 1,1,2-trisubstituted hydrazines [1,1-dimethyl-2-(2-cyanoethyl)hydrazine]

It was established by x-ray diffraction analysis of crystals with the composition C₁₀H₁₄N₆ [a=14.869(2), b=11.405(2), c=7.585(1) Å, =107.53(1), d_calc=1.18 g·cm^–3, Z=4, and space group P2₁/c] that the molecule has a linear rather than a cyclic structure and is 1,2-bis(methylidene-2,2-dimethylhydrazino)ethylene rather than 1,4-bis(dimethylamino)-2,5-dicyano-1,4-dihydropyrazine as previously assumed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 541–544, April, 1978.     

Crystal and molecular structure of muurolene and cadinene dihydrochlorides

An x-ray structural investigation ( Mo K2/ scanning for 2<50°, MLS in the anisotropic approximation) has been performed of cadinene dihydrochloride (I) (1213 reflections, R=0.053) and muurolene dihydrochloride (II) 1643 reflections, R=0.087). The crystals of (I) belong to the rhombic system with a=6.053(2), b=14.622(5), c=17.926(7) A, Z=4, sp. gr. P2₁2₁2₁, mp 117°C. The crystals of (II) belong to the monoclinic system, with a=9.842(4), b=11.627(6), c=13.677(9) Å, =95.10(4)°, Z=4, sp. gr. P2₁, mp 86°C. The six-membered rings of the molecules (I) and (II) have the chair conformation with equatorial alkyl groups. The chlorine atoms have the axial arrangement. The molecule of (I) has the 3,9-dichlorocadinane structure, and that of (II) the 3,9-dichlormuurolane structure. The increased mean length of the C-Cl bonds of 1.844 Å in the molecule of (I) and 1.879 Å in the molecule of (II) must be mentioned.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 52–57, January–February, 1981.     

The crystal structures of α,ω-diaminoalkanecadmium(II) tetracyanonickelate(II)-aromatic molecule inclusion compounds. II. 1,6-diaminohexanecadmium(II) tetracyanonickelate(II)-o-toluidine (1/1): Cd(NH2(CH2)6NH2)Ni(CN)4.o-CH3C6H4NH2

The title inclusion compound crystallizes in monoclinic space group P2/m, with a=9.541(2), b=7.569(2), and c=7.199(1) Å, =100.3(1)^o, and Z=1. The structure has been refined to a conventional R=0.036 for 1973 independent reflections collected by counter method. The host metal complex has the structure similar to that of 1,4-diaminobutanecadmium(II) tetracyanonickelate(II)-2,5-xylidine (1/1) with respect to the two-dimensionally extended wavy cyanometal complex sheets bridged by the ,-diaminoalkane ligands at the respective Cd atoms in adjacent sheets providing a channel-like cavity with the guest aromatic molecule. The guesto-toluidine molecule is surrounded by four 1,6-diaminohexane bridges taking an all-trans conformation of the aliphatic chain and show disorder in the orientation in the cavity. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82021 (21 pages).     

The Structure of the Pyridine Complex of p-tetrakis(phenylazo)-tetra-hydroxythiacalix[4]arene

p-Tetrakis(phenylazo)-tetra-hydroxythiacalix[4]arene shows complexing properties with neutral molecules. A complex with pyridine was crystallized and the crystal structure determined. The crystals are monoclinic, space group C2/c, a = 49.953(10), b = 21.566(4), c = 23.448(5) Å, = 105.12(3)°, V = 24386(8) Å ³, Z = 16. Two macrocycles are positioned in such a way that they form a cavity where two pyridine molecules are encapsulated giving a 2:2 endocomplex. 5.5 other pyridine molecules are trapped between the macrocycles, two of them giving H-bonds with the calixarenes.     

An x-ray diffraction structural investigation of organic complexone ligands. XVI. Crystal and molecular structure of the dihydro-chloride salts of ethylene-diamine-N,N′-Di-3-propionic and ethylenediamine-N,N,N′,N′-tetra-3-propionic acids and the monohydrobromide salt of ethylenediamine-N,N,N′,N′-tetraacetic acid monohydrate

An x-ray diffraction structural analysis was carried out on the cationic forms of three complexones: the dihydrochloride salts C₈H₁₈N₂O₄Cl₂ (I) and C₁₄H₂₆N₂O₈Cl₂ (II) and monohydrobromide salt C₁₀H₁₉N₂O₉Br (III). The data were collected on a diffractometer using Mo radiation. The structure was solved by the direct method and refined anisotropically for the nonhydrogen atoms and isotropically for the hydrogen atoms by the method of least squares, R=0.026 (I), 0.040 (II), and 0.044 (III). The crystals of I and II are monoclinic, while the crystals of III are triclinic. I: a=8.047(2), b=10.542(2), c=7.377 Å, =95.10(2)°, Z=2, space group P2₁/c. II: a=6.894(2), b=19.901(5), c=7.738(3) Å, =111.32(2)°, Z=2, space group P2₁/c. III: a=5.458(2), b=6.889(1), c=10.631(2) Å, =107.72(1), =107.02(3), =77.93(2)°, Z=1, space group P1. Differences were found in the structures of the cationic forms and neutral molecules of these complexones in the crystalline state. Bis-zwitter-ionic structure is lacking in centrosymmetric doubly-charged cations I and II. A strong intermolecular hydrogen bond O(1)–O(1) (2.455(5) Å) was found in noncentrosymmetric singly-charged cation III with participation of the proton of dissociated HBr. The cations in the structures of I and II participate only in intermolecular hydrogen bonds, while intramolecular hydrogen bonding is also found in III with the formation of five-membered rings. The structure of these cations depends on the acid properties of the corresponding complexone and composition of the crystals.Communication XV, see ref. [1].All-Union Research Institute for Chemical Reagents and High-Purity Chemicals. Translated from Zhurnal Strukturnoi Khimii, Vol. 30, No. 6, pp. 92–104, November–December, 1989.     

Crystal and molecular structure of dimethyl 4-phenyl-S-methylisothiosemicarbazide diacetate and its complex with copper(II) bromide

The structure of dimethyl 4-phenyl-S-methylisothiosemicarbazide diacetate NH(C₆H₅)C(SCH₃)NN × (CH₂COOCH₃)₂ (Z) hydroiodide (I) (crystals I are triclinic, space group $P\bar 1$ , a=11.671(3), b=10.889(2), c=8.237(2) Å,α=78.59(2),β=77.63(2),γ=106.47(2)°, Z=2, final R=0.088) and a complex of Z with copper(II) bromide, CuBr₂Z (II) (crystals II are orthorhombic, space group Pbca, a=14.487(4), b=18.827(8), c=14.565(5) Å, Z=8, R=0.062) was determined by X-ray diffraction analysis. It is established that methylation of the sulfur atom changes the type of ligand attachment to the metal, namely, the ligand is transformed from the tripod S,N,O,O, into the N,N,O,O type (the sulfur atom is not involved in coordination). When coordinated, the ligand does not change conformation, and the thiosemicarbazide fragment retains the E-configuration. During complexation, Z topologically behaves as a classical complexon of the monoamine series.     

Drei Heterocubanartige (MII4O4)‐Typ Verbindungen (M = FeII,CoII, NiII)

By reaction of M^IICl₂·x H₂O (M = Fe (x = 4), Co, Ni (x = 6)) and LiOH·H₂O in diethylene glycol (DEG) rod‐like crystals of the composition M^II₄Cl₄(OCH₂CH₂OCH₂CH₂OH)₄ are formed. According to X‐ray diffraction data obtained by both, single crystals and powders, the Co^II and Ni^II compounds crystallize monoclinic with C2/c (Co^II₄Cl₄(OCH₂CH₂OCH₂CH₂OH)₄ ( 1 ): a = 2084.1(4), b = 919.0(2), c = 1754.0(4) pm, β = 124.3(1)°, Z = 4; Ni^II₄Cl₄(OCH₂CH₂OCH₂CH₂OH)₄ ( 2 ): a = 2055.2(4), b = 932.1(2), c = 1727.4(4) pm, β = 125.2(1)°, Z = 4), whereas Fe^II₄Cl₄(OCH₂CH₂OCH₂CH₂OH)₄ ( 3 ) crystallizes tetragonal with (a = 1251.4(2), c = 915.3(2) pm, Z = 2). All compounds exhibit analogous molecular structures which are built of a heterocubane‐type core consisting of four metal ions and four deprotonated oxygen atoms of four coordinated diethylene glycol molecules. Neutrality of charge is realized by additional coordination of four chloride anions. In addition to the structural characterization, the thermal and magnetical properties of the title compounds are investigated in detail.     

Li2I(OH): Eine Verbindung mit eindimensional unendlich kantenverknüpften [Li4/2(OH)]+-Pyramiden

Li₂I(OH): A Compound with Onedimensional Infinite Edge Sharing [Li_4/2(OH)⁺] Pyramids The pseudobinary system LiOH/LiI was investigated by X-ray methods. Two compounds, Li₂I(OH) and Li₅I(OH)₄ exist. The structure of Li₂I(OH) was solved by single-crystal data. For Li₅I(OH)₄ lattice constants and space group symmetry are given: Li₂I(OH): Pnma, Z = 4, a = 10.339(4) Å, b = 5.567(1) Å, c = 6.643(2) Å, Z(F_o) mit (F_o)² ≧ 3σ(F_o)² = 439, Z (parameter) = 23, R/R_w = 0.030/0.040 Li₅I(OH)₄: Pmmn or P2₁mn(= Pmn2₁), Z = 2, a = 10.42 Å, b = 5.30 Å, c = 5.81 Å Li₂I(OH) crystallizes in a new type of structure. The motif of a distorted hexagonal close-packed arrangement of iodide ions is penetrated by chains of [Li_4/2(OH)⁺].     

Inclusion of Nonopiate Analgesic Drugs in Cyclodextrins. II. X-ray Structure of a 1 : 1 β-Cyclodextrin – Acetaminophen Complex

Single crystals of a 1 : 1 complex between-cyclodextrin (-CD) and the analgesicacetaminophen (paracetamol) have been prepared and themode of inclusion of the drug has been determined fromX-ray data collected at 293 K. Complexcharacterization by UV and thermogravimetric analysesyielded the composition-(CDacetaminophen13.3H₂O. The complex crystallizes in the space group C2 with a =19.207(7), b = 24.48(1), c =15.700(4)Å, = 109.52(2)° and Z = 4complex units in the crystal unit cell. The hostmolecules form dimeric motifs withC₂ crystallographic symmetry which pack in thechannel mode. Guest molecules residing in the hostdimer are disordered, each acetaminophen moleculebeing statistically distributed over two sites withequal occupancy. In each case, the guest hydroxylgroup is located at the host primary face while theacetamide residue lies at the dimer interface. TwoC₂-related water molecules are trapped inside thehost cavity, being hydrogen bonded to theC₂-related carbonyl groups of one of thedisordered guest conformers. Structural features ofthe complex are discussed with reference to recentspectroscopic and other studies aimed at elucidatingthe nature of the interaction between acetaminophenand -CD.