Reaction of 5,5-diphenyl-2-thiohydantoin with 1,2-dibromoethane.crystal and molecular structures of 2,3-dihydro-6,6-diphenylimi-dazo-[2,1-b]-thiazol-5(6h)-one and 2,3-dihydro-5,5-diphenylimi-dazo-[2,-1-b]-thiazol-6(5h)-one and their reactivity

The crystal and molecular structures of the title isomeric compounds $\text{1}$ and $\text{2}$, obtained by intramolecular N,S--dialkylation of 5,5-diphenyl-2-thiohydantoin with 1,2-dibro-moethane, have been determined from X-ray diffractometer data. 2,3-Dihydro-6,6-diphenylimidazo-[2,1-b]-thiazol-5(6H)-one $\text{1}$ crystallizes in space group P2₁2₁2₁ with a=11.376(3), b=12,255(5), c=8.434(3) Å and Z=4. Crystals of $\text{2}$, containing one molecule of benzene, are monoclinic,space group P2₁/c with a=11.539(6), b=10.242(3), c=16.353(5) Å, β=95.45(5)° and Z=4. In both cases a planar geometry of the two fused five-membered heterocyclic rings was found. The selected bond lengths in $\text{1}$ and $\text{2}$, as well as those analogous imidazothiazinones $\text{3}$ and $\text{4}$, were used to calculate E_HOSE (Harmonic Oscillation Stabilization Energy). The problem of stability and chemical reactivity of compounds $\text{1}$ to $\text{4}$ is also discussed.     

Determination of structure and 13C chemical shift assignments of the nitration products of 2-chloro-10-methylphenothiazine. X-Ray molecular structure of 2-chloro-7-nitro-10-methylphenothiazine 5-oxide

Nitration of 2-chloro-10-methylphenothiazine, 1 , yields two mono-nitro compounds identified as sulfoxide 2 and sulfone 3 . The nmr analyses of the ¹³C spectra of 2 and 3 establish unequivocally that in both compounds substitution has occurred at the seven position. This is supported by the X-ray crystal structure of one of the compounds 2-chloro-7-nitro-10-methylphenothiazine 5-oxide, 2 , which also shows that the sulfoxide group is in the “pseudo-axial” configuration. Crystals of 2 are monoclinic, space group P2₁/n, a = 11.606(4), b = 13.970(4)Å, c = 9.837(2), β = 127.49(2)° and Z = 4. The structure has been refined by full-matrix least-squares to R = 0.033 and R_w = 0.035, using 1704 observed reflections.     

Variation of 2 D Hydrogen Bond Topology in Diaqua-tetrafluoromanganates(III): 2-picoH[MnF4(H2O)2], TMEDAH2[MnF4(H2O)2]2, and TMBDAH2[MnF4(H2O)2]2

The crystal structures of three new diaqua-tetrafluoro-manganate(III) compounds with different organic N-cations have been determined: 2-picoH[MnF₄(H₂O)₂] 1 (2-pico = 2-methyl-pyridine), space group P2₁/c, a = 9.439, b = 13.662, c = 7.641 Å, β = 91.31°; R = 0.059; TMEDAH₂[MnF₄(H₂O)₂]₂ 2 (TMEDA = N,N,N′,N′-tetramethyl ethane diamine), space group P2₁/c, a = 5.421, b = 15.970, c = 9.677 Å, β = 96.37°, R = 0.031, and TMBDAH₂[MnF₄(H₂O)₂]₂ 3 (TMBDA = N,N,N′,N′-tetramethyl-1,4-butane-diamine), space group P2₁/n, a = 12.631, b = 5.577, c = 12.976 Å, β = 98.10°, R = 0.040. All three compounds show 2 D H-bonding networks of [MnF₄(H₂O)₂]^– anions separated by the organic cations. However, the topology of the anionic H-bonding nets is different for each compound. The anions are strongly elongated by the Jahn-Teller effect and are arranged in a ferrodistortive way in compounds 1 and 2 , whereas in compound 3 the arrangement is described as in a herringbone-like antiferrodistortive variant.     

Synthesis and structure of a 1:1 complex of a chiral methyl 4,6-0-benzylidene-2 , 3-0 (1 ,2-bis (ethoxyethoxy) -benzenediyl) - α,d-glucopyranoside and potassium iodide

The chiral crown ether was prepared according to the method described in the literature and its complex with potassium iodide was obtained. The crystal data are as follows: a = 10.315(4), b = 9.265(4), c = 15.88(2) Å, β = 100.70(7)°. V = 1494 Å,³ Z = 2, D₀ = 1.55 Mg m^?3 space group symmetry P2₁.The structure was determined by the heavy atom method using 2214 independent observed reflections. The conformation of the macrocyclic ring is discussed.     

Molecular-crystal structure of 5-methyl-1,2-dihydro-3H-1,4-benzodiazepin-2-one

5-Methyl-1,2-dihydro-3H-1,4-benzodiazepin-2-one, which is an antagonist of 5-aryl-1,2-dihydro-3H-1,4-benzodiazepin-2-ones, was subjected to a complete x-ray diffraction study. The crystals have monoclinic syngony witha = 11.456(5), b = 8.195(3), c = 9.257(4) Å, = 93.10(3) °, and space group P2₁/b. The nonplanar molecules (with a boat conformation) form cyclic dimers by means of NH...O hydrogen bonds (2.937 Å) in the vicinity of the center of symmetry (0, 0, 1/2). Replacement of the phenyl ring in the 5 position by a less bulky methyl group does not lead to appreciable changes in the geometry and conformation of the heteroring. It is assumed that the substituent in the 5 position plays a role in determining the character of the pharmacological action of 1,4-benzodiazepines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 985–988, July, 1982.     

Monosubstituted Trinuclear and Tetranuclear VIB Metal Carbonyl Complexes: Syntheses of [{M(CO)5}3(Pf-Pf-Pf)] [Pf-Pf-Pf = PhP(CH2CH2PPh2)2] and [{M(CO)5}4(P-Pf3)] [P-Pf3 = P(CH2CH2PPh2)3] (M = Cr,Mo) and Crystal Structures of the Latter Three

The triligate trimetallic complexes, [{M(CO)₅}₃(Pf-Pf-Pf)] and tetraligate tetrametallic complexes, [{M(CO)₅}₄(P-Pf₃)] (M = Cr and Mo), were prepared from [M(CO) ₆] and the corresponding ligands in MeCN/CH₂Cl₂ promoted by Me₃NO at 0 °C. Crystals of trimer lb are monoclinic, space group P 2₁/n, with a = 13.407(3), b = 15.002(5), c = 26.52(1) Å, β = 90.65(2)°, Z = 4, and R = 0.060 for 2760 observed reflections. Crystals of tetramer 2a are monoclinic, space group P 2₁/c, with a – 14.183(8), b = 29.880(4), c = 16.103(2) Å, β = 94.98(3)°, Z = 4, and R = 0.039 for 5014 observed reflections. Crystals of 2b are monoclinic, space group C 2/c, with a = 42.120(8), b = 13.679(1), c = 23.486(2) Å, β = 92.14(1)°, Z = 8, and R = 0.032 for 6897 observed reflections. Each phosphorus atom of the ligands is coordinated to the M(CO)₅ moiety in each title compounds. The geometry of the four metals is a distorted tetrahedron for the tetramers.     

Übergangsmetallphosphidokomplexe. VIII. Strukturuntersuchungen an Übergangsmetallphosphor-Vier- und Sechsringkomplexen. Die Strukturen von [(CO)4MnPH2]2, [(CO)4MnPH2]3 und [cpNiPH2]3

Transition Metal Phosphido Complexes. VIII. X-Ray Diffraction Studies of Transition Metal Phosphorus Four- and Six-Membered Ring Complexes. Structures of [(CO)₄MnPH₂]₂, [(CO)₄MnPH₂]₃, and [cpNiPH₂]₃ [(CO)₄MnPH₂]₂ 1 crystallizes triclinic in the space group P1 with a = 680.4 pm, b = 706.4 pm, c = 919.1 pm, α 110.5°, β = 91.92°, γ 115.65°, and Z = 1 formula unit. The molecule exhibits a centrosymmetrical structure. The bond angles within the planar four-membered (Mn? P)₂-ring are 76.1° at the Mn atoms and 103.9° at the P atoms, respectively. The average Mn? P bond distance is found to be 235.1 pm. [(CO)₄MnPH₂]₃ 2 crystallizes monoclinic in the space group P2/n with a = 905.2 pm, b = 974.8 pm, c = 1264.2 pm, β = 109.1°, and Z = 2 formula units. The framework of the six-membered (Mn? P)₃-ring can be described as having a twist boat conformation. The average endocyclic bond angles are with 89.1° at the Mn atoms and 130.1° at the P atoms, respectively, largely widened compared to 1 . The average Mn? P bond distance, which is found to be 238.5 pm, is also slightly increased compared to 1 . [cpNiPH₂]₃ 3 crystallizes rhombohedral in the space group R3. The cell constants (hexagonal setting) are a = b = 1686.1 pm, c = 561.1 pm and Z = 3 formula units. The six-membered (Ni? P)₃-ring exhibits a chair conformation. The endocyclic bond angles are with 92.3° at the Ni atoms and 124.3° at the P atoms, respectively, comparable with those of the six-membered ring compound 2 . The Ni? P bond distance is found to be 215.2 pm. The eyclopentadienyl ligands are disordered and have been refined as rigid groups.     

Verbindungen im System CsN3?Sr(N3)2?H2O

Compounds in the System CsN₃? Sr(N₃)₂? H₂O Three new compounds between cesium azide and strontium azide have been crystalized from aqueous solutions at room temperature. The lattice parameters wee investigated by means of x-ray single crystal techniques, the indexed powder patterns are listed. CsSr(N₃)₃ crystalizes monoclinic: a = 1 589, b = 1 015, c = 904 pm, β = 90.47°, N = 8, space group P2₁/c. Cs₂Sr(N₃)₄ crystallizes orthorhombic: a = 1 263, b = 1 454, c = 1 183 pm, N = 8, space group Cmca. Cs₂Sr(N₃)₄ · 4 H₂O crystalizes orthorhombic: a = 2 061, b = 1 114, c = 637 pm, N = 4, space group Ccca     

Crystal and molecular structure of caryophyllene α-oxide

An x-ray study (λMo K^α, 2θ/ω scanning for 2θ<30°, MLS in the anisotropic approximation) has been made of caryophyllene α-oxide (I) at ?(98–100)°C (1182 reflections, R=0.051); crystals of the orthorhombic system,a=8.975, b=10.160, c=14.882 Å, z=4, space group P2₁2₁2₁, mp 62–63°C. The crystalline and molecular structures of caryophyllene α-oxide (I) have been studied and the configuration of the oxide ring has been confirmed.     

Crystal structure of the 2-hydroxy-3,3,4-trimethyl-2-oxo-5-cyanimino-1, 4,2-diazaphospholidine diethylammonium salt

Crystal structure of the 2-hydroxy-3,3,4-trimethyl-2-oxo-5-cyanimino-1,4,2-diazaphospholidine diethylammonium salt (I) was studied by X-ray diffraction analysis: space group P2₁/c, a=9.773(1), b=12.7617(8), c=12.064(2) Å, β=95.02(1)°, Z=4; R=0.041 (CAD-4 automatic diffractometer, λCuK_α, 2518 independent reflections with I≥3δ). In anion I, the P atom (forming two Pō sesquibonds) has a considerably distorted tetrahedral coordination. In the extended flattened molecular fragment of anion I involving 7 atoms [P?N?C(?N)=N?C≡N], the π-electron densities of the atoms are conjugated. The five-membered heterocycle of anion I has a distorted P,C₃-half-chair conformation. The crystal structure of compound I has interionic hydrogen bonds linking anions I into centrosymmetric H-dimers and also linking anions I and Et₂NH ₂ ⁺ into centrosymmetric H-tetramers.     

Crystal and molecular structure of Dicyanotetrasulfane S4(CN)2

S₄(CN)₂ crystallizes in the monoclinic space group P2₁/c with a = 885.7 pm, b = 794.2 pm, c = 1032.6 pm, β = 109.0° (at 173 K). The molecules occupy general sites but are of approximate C₂ symmetry. The conformation of the molecules is all-trans with torsional angles CSSS = 74.6° and 81.7° and SSSS = 84.8°. The central SS bond (201.7 pm) is much shorter than the terminal SS bonds (av. 206.8 pm). There are no stronger than van-der-Waals type intermolecular interactions.     

The Crystal and Molecular Structure of 1-Methyl-1-Thionia-Cyclohexane Iodide

Crystals of 1-methyl-1-thionia-cyclohexane iodide are orthorhombic with space group Pna2₁, a = 18.036, b = 6.611, c = 7.420 Å, Z = 4. The crystal structure was solved by the heavy-atom method. Very strong parameter interactions prevented least-squares refinement of atoms other than S and I. The molecule adopts the chair conformation with the methyl group in equatorial position.     

Crystal and molecular structure of cis- and trans-2,4-dihydroxy-2,4-dimethylcyclohexanetrans-1-acetic acid γ-lactone

During the transformation process of limonene to tetrahydrofuran derivatives, the title compounds (±)-( 4 ) have been obtained as crystalline products and subjected to X-ray analysis. The crystals of trans-( 4 ) are orthorhombic, space group P2₁2₁2₁, with the lattice constants a = 7.0445(5) Å, b = 10.0908(4) Å, c = 14.0309(6) Å; the absolute configuration at atoms C1, C2, and C4 is R_c1, S_c2, and R_c4, respectively. The isomeric form cis-( 4 ) crystallizes in the monoclinic system, space group P2₁, with the following unit-cell parameters: a = 10.8275(4) Å, b = 8.6994(5) Å, c = 16.4722(6) Å, β = 106.515(3)°. The asymmetric part of the unit cell of cis-( 4 ) contains three independent molecules. Each of these three molecules has the identical absolute configuration at all centers of chirality: S_c1, S_c2, and R_c4. © John Wiley & Sons, Inc.     

Molecular and crystal structures and chemical properties of 2,6-dim ethyl-4-phenyl-3,5-diethoxycarbonyl-1, 4-dihydropyridine

The molecular and crystal structures of 2,6-dimethyl-4-phenyl-3,5-diethoxycarbonyl-1,4-dihydropyridine were determined by x-ray diffraction analysis. The following crystallographic data were obtained: a=9.754(2), b = 7.401(1), c=24.384(5) Å, =92.61(2)°, Z=4, d_calc= 1.24 g-cm^–3, space group P2₁/c. The structure was decoded from 1531 reflections, the intensities of which were measured with a P2₁ automatic diffractometer and refined by the method of least squares within the total matrix anisotropic approximation to R=0.061. The dihydropyridine ring has a boat conformation. Packing of the molecules in the crystal is realized at the van der Waals distances and is stabilized by an N₁- H ... O₁₅ hydrogen bond (2.98 Å). From the data on the geometry of the molecule, the compound is closer to aminovinylcarbonyl compounds, whereas according to the data on the conformation, it is closer to Meisenheimer compounds than to pyridine derivatives. The C=O bond length corresponds to its length in esters and acid amides, despite the exceptionally low reactivity of this group in 3,5-dicarbonyl-1,4-dihydropyridines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1229–1234, September, 1977.     

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).     

Zur Protonierung und Methylierung des 1, 1-Dicyanoethylen-2, 2-dithiolat Dianions: Präparative und strukturelle Untersuchungen

Protonation and Methylation of 1, 1-Dicyanoethylene-2, 2-dithiolate Dianion. Preparative and Structural Investigations Protonation of alkaline metal salts of [S₂C = C(CN)₂]^2? ( I ) in water yields a product of composition H₂S₂C₄N₂ ( II ). The species has to be formulated as dimere and crystallizes with two moles DMSO from DMSO solution with space group C2/c and a = 20.611(3), b = 4.800(1), c = 20.638(3) Å, β = 103.3(1)°, Z = 4. The X-ray structural analysis shows II to be a centrosymmetric 1, 3-Dithiacyclobutane system. On methylation of I with CH₃I in the molar ratio 1:1, the monomethylated anion III can be isolated as AsPh₄ salt. The compound crystallizes in the monoclinic space group P2₁/c, with a = 23.632(2), b = 14.304(1), c = 7.989(1) Å, β = 100.1(8)° and Z = 4. There are nearly planar anions [MeS(S)C?C(CN)₂]^? with an anti-conformation of the MeS group.     

The First Aqua Pentafluoro Manganates(III) – Syntheses and Structures

For the first time aqua pentafluoro manganate(III) compounds with different organic N-cations have been prepared and their crystal structures have been determined: N,N′-DMenH₂[MnF₅(H₂O)] · H₂O 1 (N,N′-DMen = N,N′-Dimethylethylenediamine), space group P2₁/c, a = 916.0, b = 1004.8, c = 1247.9 pm, β = 106.03°, R = 0.035; NMpipzH₂ · [MnF₅(H₂O)] · H₂O 2 (NMpipz = N-Methylpiperazine), space group P2₁/n, a = 757.7, b = 1261.9, c = 1197.1 pm, β = 105.09°, R = 0.027; N,N′-DMpipzH₂[MnF₅(H₂O)] · 2 HF 3 (N,N′-DMpipz = N,N′-Dimethylpiperazine), space group P1, a = 677.1, b = 863.9, c = 1187.7 pm, α = 79.18°, β = 81.63° γ = 67.62°, R = 0.026; and N,N-DMenH₂[MnF₅(H₂O)] · 1/2 HF 4 (N,N-DMen = N,N-Dimethylethylenediamine), space group P1, a = 859.3, b = 1086.5, c = 1092.0 pm, α = 86.96°, β = 78.52° γ = 89.01°, R = 0.035. In all compounds the [MnF₅(H₂O)]^2– octahedra are connected via H-bonds forming 3 D and 2 D network arrangements. The anions are strongly elongated by the Jahn-Teller effect. The FTIR spectra are presented.     

Synthesis and Crystal Structures of Bis(tetraethylammonium)(2-oxo-1,3-dithiole-4,5-dithiolato)zincate(II) and Bis(tetra-n-butylammonium)(2-oxo-1,3-dithiole-4,5-dithiolato)zincate(II)

The title compounds were prepared from 1,3,4,6-tetrathiapentalene-2,5-dione ( 1 ) in one step via the in situ generated intermediate 2-oxo-1,3-dithiole-4,5-dithiolate (dmid; 2 ). The X-ray single crystal structure of (Et₄N)₂[Zn(dmid)₂] ( 3 a ) gave the tetragonal space group P4₃2₁2 with a = b = 13.810(2) Å, c = 16.480(3) Å, and Z = 4. (n-Bu₄N)₂[Zn(dmid)₂] ( 3 b ) gave the triclinic space group P 1 with a = 11.947(4) Å, b = 14.665(5) Å, c = 16.662(8) Å, α = 100.21(3)°, β = 104.46(3)°, γ = 110.73(3)°, and Z = 2.     

Hydrido-Silyl-Komplexe. V. Strukturelle Änderungen in Hydrido-Silyl-Komplexen infolge Si?H-Wechselwirkung; Strukturvergleich zwischen (π-CH3C5H4)(CO)2Mn(H)SiR3- und analogen (π-C5H5)(CO)2FeSiR3-Komplexen

Hydrido Silyl Complexes. V. Structural Changes in Hydrido Silyl Complexes Due to Si? H Interaction; Comparison between the Structures of (π-CH₃C₅H₄)(CO)₂Mn(H)SiR₃ and Analogous (π-C₅H₅)(CO)₂FeSiR₃ Complexes The structures of the complexes Cp(CO)₂FeSiFPh₂ ( 2a ) and Cp(CO)₂FeSiCl₃ ( 2b ), containing ?normal”? metal-silicon bonds, are compared with the known structures of the complexes MeCp(CO)₂Mn(H)SiFPh₂ ( 1a ) and MeCp(CO)₂Mn(H)SiCl₃ ( 1b ), containing Mn? H? Si three-center bonds. 2a crystallizes in space group P2₁/c, a = 805.8(3), b = 1417.5(6), c = 1498.2(4) pm, β = 90.99(3)°, 2b in space group P2₁/n, a = 817(1), b = 1244(1), c = 1142(1)pm, β = 99.9(1)°. In 2a gauche conformation in respect to the Fe? Si bond is found; in 2b the silylligand is rotated 12° around the Fe? Si axis out of a staggered conformation. Possible reasons for the unsymmetrical conformations are discussed. Lengthening of the Fe? Si distance from 221.6(1)pm in 2b to 227.8(1) pm in 2a corresponds to the expected increase in the bond radius of silicon due to exchange of the substituents at silicon. Additional lengthening of the Mn? Si distance by about 3.5 pm in 1a compared with 1b is attributed to the increased delocalization of the Mn? H? Si bond in 1a .     

Synthesis and crystal structure of two fluorophosphated compounds with different infinite sheets: Sr2Ga(HPO4)(PO4)F2 and Sr2Fe2(HPO4)(PO4)2F2

New compounds, Sr₂Ga(HPO₄)(PO₄)F₂ and Sr₂Fe₂(HPO₄)(PO₄)₂F₂, have been prepared by hydrothermal synthesis (700°C, 180 MPa, 24 h) and characterized by single-crystal X-ray diffraction. Sr₂Ga(HPO₄)(PO₄)F₂ crystallizes in the monoclinic space group P2₁/n with a = 8.257(1) Å, b = 7.205(1) Å, c = 13.596(2) Å, β = 108.02(1)°, V = 769.2(2) ų and Z = 4 and Sr₂Fe₂(HPO₄)(PO₄)₂F₂ in the triclinic space group P2₁/n with a = 8.072(1) Å, b = 8.794(1) Å, c = 8.885(1) Å, α = 102.46(1)°, β = 115.95(1)°, γ = 89.95(1)°, V = 550.6(1) ų and Z = 2. Structures are both based on different sheets involving corner-linkage between octahedra and tetrahedra. The sheets are linked by Sr²⁺ cations. Structural relationships exist between the descloizite mineral and the title compounds.