Synthesis and X-ray structures of [H3O+·18-crown-6] n [MCl 4 n− ]; (M=Fe,n=1;M=Co,n=2); compounds which form liquid clathrates with aromatic solutions

The title compounds, [H₃O⁺·18-crown-6][FeCl ₄ ^– ] (1), and [H₃O⁺·18-crown-6]₂[CoCl ₄ ^2– ] (2), were prepared by air oxidation of Fe(CO)₅ for1, and Co₂(CO)₈ for2, in the presence of 18-crown-6, H₂O and HCl(g) in toluene. Liquid clathrates formed immediately for both species:1·4.3 C₇H₈ and2·3.7 C₇H₈.1 crystallizes in the orthorhombic space group P2₁ma witha=10.357(1),b=11.824(1),c=8.961(1) Å, andD _c=1.46 g cm^–3 forZ=2. Refinement based on 935 observed reflections led to a finalR value of 0.089.2 crystallizes in the monoclinic space group C2/c witha=16.225(1),b=11.522(1),c=20.136(1)Å, =97.75(2)^o, andD _c=1.37 g cm^–3 forZ=4. Refinement based on 1322 observed reflections led to a finalR value of 0.11.     

Influence of the spectator cation on the structure of anionic pyridine-2,6-dicarboxylato complexes of cobalt(II), nickel(II), and copper(II)

The structures of anionic pyridine-2,6-dicarboxylato (pdc^2–) complexes of cobalt, nickel, and copper have been studied. The stoichiometries and structures are very much dependent on whether KOH, Et₄NOH, or NaOH is used in the synthesis to deprotonate the H₂pdc ligand. Crystallographic results are: (1) K₂[Co(pdc)₂] · 7H₂O, orthorhombic, Pnna, Z = 4, a = 20.637(2)Å, b = 13.480(1)Å, c = 8.200(1)Å (2) K₂[Ni(pdc)₂] · 7H₂O, orthorhombic, Pnna, Z = 4, a = 20.648(1)Å, b = 13.375(1)Å, c = 8.2393(8)Å (3) [Co₂(H₂O)₅(pdc)₂] · 2H₂O, monoclinic, P2₁/c, Z = 4, a = 8.3880(6)Å, b = 27.384(2)Å, c = 9.6110(8)Å, = 98.271(6)° (4) [Ni(Hpdc)₂] · 3H₂O, monoclinic, P2₁/c, Z = 4, a = 13.679(1)Å, b = 10.0450(9)Å, c = 13.767(2)Å, = 115.184(7)° (5) Na₆[Co(H₂O)₆][Co(pdc)₂]₄ · 28H₂O, monoclinic, P2₁/n, Z = 2, a = 13.363(1)Å, b = 8.437(1)Å, c = 40.689(3)Å, = 91.288(5)° (6) Na[Ni(Hpdc)(pdc)] · 11.5H₂O, monoclinic, C2/m, Z = 4, a = 15.200(2)Å, b = 22.299(2)Å, c = 8.3596(7)Å, = 118.894(7)° (7) Na[Cu(Hpdc)(pdc)] · 3H₂O, monoclinic, P2₁/n, Z = 4, a = 9.516(4)Å, b = 14.917(6)Å, c = 12.247(5)Å, = 92.00(5)°. The potassium and sodium complexes have extensive K⁺—H₂O and Na⁺—H₂O networks. The fact the Et₄N⁺ ion does not appear in any of the complexes is likely due to the fact that it is incapable of forming the intricate cation—water and hydrogen-bonding networks observed in all of the other structures.     

Crystal structure, thermal analysis, and IR spectrometric investigation of 1,2-diammonium-2-methyl propane sulfate monohydrate

Chemical preparation, X-ray single crystal, thermal analysis, and IR spectrometric investigation of C₄H₁₄N₂SO₄·H₂O (denoted DAMPS) are described. DAMPS crystallizes in the orthorhombic system with P2₁2₁2₁ space group, a = 9.2726(4) Å, b = 9.5227(2) Å, c = 10.3807(4) Å, V = 916.62(6) ų, and Z = 4. The DAMPS structure is built up from inorganic chains parallel to the b axis and linked via Ow–H···O hydrogen bonds. These chains are interconnected by organic groups so as to build a three-dimensional arrangement.     

Structure and IR,UV spectroscopic behavior of azabicyclo[2.2.2]octane pentachlorophenolate

The structure of C₆Cl₅O^–·C₇H₁₃NH⁺ has been determined by X-ray diffraction. The crystals are orthorhombic:Pcab,a=10.706(1),b=11.966(2),c=24.913(5)Å,Z=8. The structure was solved by direct methods, and refined to R=0.042 for 1523 nonzero reflections. The N⁺-HO^– hydrogen bond is shortened (2.553(5)Å) and deformed (相似文献   

Heptacoordination in MnII,NiII, and CuII complexes of 2,6-diacetylpyridine bis (acetylhydrazone)

Manganese(II), nickel(II), and copper(II) complexes of 2,6-diacetylpyridine bis (acetylhydrazone) (H₂dapac) have been synthesized and structurally characterized by X-ray diffraction methods. [Mn(H₂dapac) (OH₂)₂](NO₃)₂ crystallizes in the monoclinic space groupP2₁/c witha=11.145(3),b=10.723(4),c=17.189(2) Å, =92.81(2)° andZ=4; [Ni(H₂dapac)(OH₂)₂] (NO₃)₂·H₂O crystallizes in the monoclinic space groupP2₁ witha=9.994(3),b=14.423(4),c=7.697(2)Å, =100.37(2)°, andZ=2; [Cu(H₂dapac)(OH₂)₂](NO₃)₂·H₂O crystallizes in the orthorhombic space groupPbcn witha=20.986(5),b=14.552(3),c=6.905(1)Å andZ=4. In each case the metal atom has a slightly distorted pentagonal bipyramidal environment, the equatorial positions being occupied by three nitrogen and two oxygen atoms from the hydrazone ligand and the apices by two water molecules. The crystalline cohesion in ensured by a three-dimensional network of hydrogen bonds involving the complex cations, the nitrate anions, and, where present, the uncoordinate water molecules.     

Crystal structures of thetrans-cyclooctene complexes of copper(I) chloride and silver nitrate

The crystal and molecular structures of the title compounds CuCl·C₈H₁₄ and AgNO₃·C₈H₁₄, have been determined by single-crystal X-ray diffraction techniques, and refined by full-matrix least squares. Both compounds crystallize in the orthorhombic space groupPbca witha=6.191(7),b=12.456(2),c=23.272(4) Å for CuCl·C₈H₁₄, anda=7.383(2),b=9.825(2),c=26.980(5) Å for AgNO₃·C₈H₁₄;Z=8 in both cases. FinalR factors are 0.047 and 0.029 respectively. The cyclooctene ring has the twist chair-chair (TCC) conformation, with approximateD ₂ symmetry, in both compounds, and the torsion angles around the double bonds are –134.2(4) and –137.0(4)° respectively. Slight lengthening of the metal-complexed double bond is attributed to enhanced olefin metal -donation of thetrans bond.     

Hydrogen bonding in 2-hydroxy((di)thio)benzoates. II. X-ray structures of tetraethylammonium salts

X-ray structural data are reported for tetraethylammonium-2-hydroxythiobenzoate (C₁₅H₂₅NO₂S; orthorhombic,Pna2₁(33);a=14.155(2)Å,b=7.651(1)Å,c=14.855(2)Å;Z=4;R=0.038, at 295 K) and for tetraethylammonium-2-hydroxydithiobenzoate (C₁₅H₂₅NOS₂; orthorhombic,Pna2₁(33);a=15.668(4)Å,b=8.729(2)Å,c=12.350(3)Å;Z=4;R=0.031, at 295 K). In both compounds the OH groups are engaged in intramolecular O-HS hydrogen bonds (OS=2.88 and 2.89 Å, respectively).     

Molecular structure of thiocyanatotris (2,2′-iminodiethanoldithiocarbamato) tellurium(IV) monohydrate

The synthesis, properties, and structural characterization of the title compound, C₁₆H₃₀N₄O₄S₇Te(IV)·H₂O, are reported. The crystals are monoclinic, space groupP2₁/n, withZ=4 in a unit cell of dimensionsa=13.291(5),b=21.306(6),c=10.450(1) Å, 0=104.25(2)° and,V _c=2868 ų. The structure was solved by the heavy atom method and refined by full-matrix least squares toR=0.025 andR _w =0.027 for 2894 reflections. The dithiocarbamate groups are linked in an unequal bidentate manner with Te-S average distance 2.695(1) Å. The thiocyanate group is bonded through the sulfur atom with much larger Te-S length [2.964(2) Å].     

Crystal structure of Zn[Cl2Ti(C5H5)2]2·2C6H6

The structure of crystals of the composition Zn[Cl₂Ti(C₅H₅)₂]₂·2C₆H₆ has been determined from Patterson and Fourier syntheses of two projections, and refined toR = 0·117 by full-matrix three-dimensional least-squares methods. The crystals are orthorhombic:Pbcn,a = 18·45(5),b = 15·40(6),c = 11·35(3) Å,Z= 4. The complex consists of a central distorted ZnCl ₄ ^2– tetrahedron linked along the Cl—Cl edges to two distorted TiCl₂(C₅H₅)₂ ⁺ tetrahedra in such a way that their centres are nearly collinear The two C₆H₆ molecules in the formulae unit may be regarded as benzene of crystallization.     

Molecular structure of 3-phenyl-5-methyl-4-isoxazolyl-penicillin sulfone (oxacillin sulfone): C19H19N3O8S

The crystal structure of oxacillin sulfone has been determined by single-crystal X-ray diffraction techniques and refined by full-matrix least squares. The penicillin molecule cocrystallizes with H₂O in an orthorhombic space groupP2₁2₁2₁ witha=10.303(7) Å,b=26.735(17) Å, andc=7.384(4) Å. The calculated density is 1.526 g cm^–3, with aZ value of 4. FinalR-factor is 0.035. The oxidation of the sulfur atom is discussed in terms ofS1 conformation of the penam moiety and in terms of hydrogen-bond formation between one oxygen of the sulfur atom and the amidic hydrogen of the C₆ side-chain. A comparison with oxacillin and cloxacillin sulfoxide is also made.     

Molecular structure and hydrogen bonding of 4-dimethylaminopyridinioacetate in its crystalline dihydrate and hydrochloride trihydrate,L·2H2O and [L2H]Cl·3H2O (L=p-Me2NC5H4N+CH2CO2 −)

The crystalline dihydrate and hydrochloride trihydrate of a new betaine, namely, L·2H₂O (1) and [L₂H]Cl·3H₂O(2) (L=p-Me₂NC₅H₄N⁺CH₂CO₂), have been synthesized and characterized by X-ray crystallography. Molecule L in compound1 [space groupPbcn, witha=15.732(3),b=7.894(2),c=18.304(4) Å, andZ=8] possesses approximateC _s symmetry. The formation of hydrogen bonds by water molecules bridging neighboring carboxy oxygen atoms leads to an infinite two-dimensional network composed of a packing of two different kinds of 12-membered rings. In compound2 [space group PT witha=7.341(2),b=9.543(2),c=17.010(4) Å, =82.43(2)°, =80.34(2)°, =74.05(2)°, andZ=2], the carboxylate groups of a pair of betaine molecules are bridged by a proton to form a dimeric cation L₂H⁺ with a very strong asymmetric hydrogen bond of length 2.464(7) Å. The crystal structure features a hydrogen-bonded corrugated ribbon comprising an alternate arrangement of edge-sharing centrosymmetric (H₂O)₄(Cl^–)₂ and (H₂O)₄ rings running parallel to thea axis.     

Preparation and X-ray structure of [H3O+·18-crown-6]-[(H5O 2 + )(Cl−)2], a compound containing both H3O+ and H5O 2 + crystallized from aromatic solution

The title compound was synthesized by the reaction of [H₃O⁺·18-crown-6][Cl-H-Cl^–]·3.8 C₆H₅Me with two equivalents of H₂O. Colorless crystals, which slowly deposited from the corresponding liquid clathrate, belong to the monoclinic space group P2₁/n witha=10.648(6),b=9.571(2),c=20.801(6) Å,=98.67(5)°, andD _c=1.24 g cm^–3 forZ=4. Refinement based on 1609 observed reflections led to a finalR value of 0.072. In the crystal structure the [H₃O⁺·18-crown-6]⁺ cations are packed in layers separated by puckered sheets of [(H₅O ₂ ⁺ )(Cl^–)₂]^–.     

Crystal Structures of 6-methyl-3-phenylsulfonylchroman-4-one and trans -6-methyl-3-phenylsulfonylchroman-4-ol

The crystal structures of (i) CH₃(C₉H₆O₂)SO₂C₆H₅ and (ii) CH₃(C₈H₈O₂)SO₂−C₆H₅ have been determined by X-ray diffraction. (i) crystallizes in the monoclinic space groupP2₁/c with unit cell parametersa=8.814(1)?,b=10.310(1)?,c=15.841(4)?, β=98.17(1)^o, andZ=4, and (ii) crystallizes in the orthorhombic space groupP2₁2₁2₁ with unit cell parametersa=6.206(1)?,b=11.752(5)?,c=19.865(3)?, andZ=4. The pyran ring in both of them is in the distorted half-chair conformation with differeing degrees of distortion from the ideal.     

Solid state structure of oxalato-(bis(dicyclohexylphosphino)-ethane) platinum(II)-acetonitrile solvate

C₃₀H₅₁NO₄P₂Pt-[C₂H₃N], orthorhombic,Pbca, a=16.132(1),b=16.610(2),c=24.001(2) Å.Z=8,D _c=1.54 g cm^–3,R=0.042,R _w=0.048, GOF=1.33. The platinaoxalate (PtC₂O₂) ring fragment is essentially planar with Pt–O bond lengths of 2.067(8) and 2.058(7) Å.     

Crystal structure of two lipophilic antifolates: 2,4-diamino-5-(n-hexyl)-6-methylpyrimidine and 2,4-diamino-5-(n-heptyl)-6-methylpyrimidine ethanesulfonate

The 5-hexyl (I) and the 5-heptyl (II) analogs of 2,4-diamino-6-methylpyrimidine both crystallize in the space groupP2₁/c withZ=4. Unit cell parameters of I are C₁₁H₂₀N₄·H₂O,a=17.204(3),b=4.609(9),c=16.765(2)Å,= 91.53(2)°; those of II are C₁₂H₂₃N₄ ⁺·C₂H₅SO₃ ^–,a=12.489(1),b=16.702(2),c=8.9558(7)Å,=99.208(8)°. The molecular packing of I contains one water, while II forms a salt with ethanesulfonic acid. The alkyl chain of I adopts an alltrans conformation; in contrast, II has onegauche orientation between carbons 2 and 3 of heptyl. These are the first structural data on two alkyl lipophilic antifolates with antineoplastic activity.     

Crystal structure of bis(potassium hydrogenl-malate)·malic acid, 2[K+(C4H5O5)]·C4H6O5

The crystal structure of bis(potassium hydrogenl-malate)·malic acid, 2[K⁺(C₄H₅O₅)^–]·C₄H₆O₅, has been determined: C₁₂H₁₆K₂O₁₅, M _r =1913.9, orthorhombic, space groupP2₁2₁2₁ a=7.719(5),b=7.916(5),c=29.863(20) Å,V _c=1824.7 ų,Z=4. The structure was determined by a new application of theDirdif procedure using MoK automatic diffractometer X-ray data, and refined by full-matrix least squares toR=0.059 for 962 reflections. A question on space-group assignment and composition was resolved only after the structure had been determined. The conformation of the central carbon skeleton of all three crystallographic independent malate moieties isanti. The potassium ions are coordinated by eight oxygen atoms, forming face-sharing distorted square antiprisms.     

Synthesis and X-ray structure of 11-N-benzylamido-9,10-dihydro-9,10-ethenoanthracene

As a part of studies on MDR reversing agents, the structure of a benzylamido-9,10-dihydro-9,10-ethenoanthracene is reported: C₂₄ H₁₉ N O; orthorhombic; space group: Pca2₁; a = 9.214(2), b = 18.624(4), c = 10.170(2) Å; 1745.2(6) ų; Z = 4. The three nonplanar rings from the 9,10-dihydro-9,10-ethenoanthracene skeleton of the molecule adopt a boat conformation. The benzamide side-chain is extended (conformation, trans-trans-gauche). The molecules in the crystal are joined by infinite chains of H-bonds N14–H14···O13.     

X-ray diffraction and vibrational spectra of the guanidine:maleic acid (1:1) complex—two crystal forms

From an equimolar mixture of guanidine and maleic acid, two different crystal modifications of guanidinium hydrogen maleate, CH₆N ₃ ⁺ ·C₄H₃O ₄ ^– , were isolated and their crystal structures determined using three-dimensional diffractometer data. Crystals of both forms are orthorhombic:Pca2₁,a=19.012(8)b=3.758(1),c=11.119(5) Å,Z=4 for form I;Fdd2,a=18.505(2),b=20.007(3),c=8.406(2) Å,Z=16 for form II. The structures were solved by direct methods and refined by full-matrix least squares to conventionalR values of 0.064 for form I and 0.043 for form II, with 488 and 605 reflections respectively. The structures consist of planar guanidinium cations C(NH₂) ₃ ⁺ and hydrogen-maleate residues C₄H₃O ₄ ^– . There are no significant differences in distances and angles within the guanidinium and hydrogen-maleate units. However, a substantial difference appears in the length and geometry of the intramolecular hydrogen bond OHO. The packing of cations and anions is also completely different in the two forms. Infrared and Raman spectra of the title compound are presented, and salient differences between them and the spectrum of the symmetrically bonded potassium hydrogen maleate are discussed briefly.     

Crystal structure of 2-{(R)-1-hydroxy-1-[(2S)-1-tritylaziridin-2-yl] methyl}acrylate and spectroscopic properties of the (R,S) and (S,S) stereoisomers

The crystal and molecular structure of 2-{(R)-1-Hydroxy-1-[(2S)-1-tritylaziridin-2-y1] methy1}acrylate is described. Crystal data: C₂₆H₂₅NO₃, orthorhombic, space group P2₁2₁2₁, a = 9.6954(5), b = 13.1458(5), c = 16.7885(7) Å, V = 2139.8(2) ų, Z = 4. The (R,S) diastereomer shows an intramolecular hydrogen bonding N···H—O under formation of a five-membered ring with N···O distance of 2.664 Å. IR, ¹H NMR and ¹³C NMR data are discussed. The ¹H NMR of the (R,S) diastereomer shows a singlet- whereas the (S,S) diastereomer exhibits a doublet-pattern for the hydroxyl proton.     

Rubidium hydrogen glutarate and ammonium hydrogen glutarate: X-ray studies of quasi-isostructural crystals involving very short hydrogen bonds

Rubidium and ammonium hydrogen glutarates (M ^{+ –}CO₂.C₃H₆.CO₂H) each crystallize with four molecules in orthorhombic unit cells of almost identical dimensions: (M = Rb)a = 18·55,b = 7·57,c = 5·29 Å; (M = NH₄)a= 18·59,b= 7·56,c= 5· 27 Å. They have very similar structures, but they are not isomorphous: space groupsCmma (Rb) andPmaa (NH₄).The crystal structures have been determined by three-dimensional X-ray analysis and refined with moderate precision. Both have infinite chains of glutarate residues, linked end-to-end by very short, symmetrical hydrogen bonds, with O···H···O = 2·40(2) (Rb) and O···H···O = 2·460(6) Å (NH₄).In the Rb salt, the glutarate residue has strict, crystallographicm symmetry. The difference in the NH₄ salt arises from small movements of the carbon and (especially) the oxygen atoms out of this symmetry plane. These are due to N-H···O bonding: two equivalent cations in the Rb salt, each making contact with eight oxygen atoms, become differentiated in the NH₄ salt by linkage to different sets of four oxygens.We wish to acknowledge financial support from the Science Research Council, and our indebtedness to Drs. J. G. Sime, K. W. Muir and others for help with KDF9 programs.