X-ray crystal structures ofcis-bis(diphenylphosphinamide)tetracarbonylmolybdenum(0) andtrans-bis(N-methyl diphenylphosphinamide)tetracarbonylmolybdenum(0)

The X-ray crystal structures ofcis-Mo(CO)₄(Ph₂PNH₂)₂,I, andtrans-Mo(CO)₄(Ph₂PNHMe)₂,II, are presented. ComplexI crystallizes in the monoclinic space groupP2₁/c(a=13.433(1),b=12.2719(8),c=17.318(2)Å;=109.79(1)°;V=2686.1(8)ų;Z=4). ComplexII crystallizes in the triclinic space groupP¯1 (a=6.9986(8),b=10.328(1),c=11.241(2)Å,=107.58(1)°,=91.76(1)°, =101.28(1)°,V=756.1(4)ų,Z=1). The molybdenum coordination geometry in each complex is a slightly distorted octahedron. The molybdenum-carbon bond lengths for the carbonyls trans to phosphorus in complexI are shorter than those the carbonyls trans to other carbonyls. The average molybdenum-phosphorus distance inI (2.525(5)Å) is similar to those in other diphenylphosphinamide complexes and longer than the molybdenum-phosphorus distance inII in 2.4585(7)Å). The distance between two nitrogen atoms incis Mo(CO)₄(Ph₂PNH₂)₂ (3.74(3)Å) is significantly larger than the sum of their van der Waals radii (3.10 Å) indicating that the two nitrogens are not hydrogen bonded.     

Crystal structure of (E)-5-hydroxypyrrolizidin-3-one and (Z)-5-thioketalpyrrolizidin-3-one

The crystal structures of (E)-5-hydroxypyrrolizidin-3-one (2) and (Z)-5-thioketalpyrrolizidin-3-one (3) have been determined by single-crystal x-ray diffraction techniques and refined by full-matrix least squares. Molecule2 crystallizes in the monoclinic space groupP2₁/a(No. 14) witha=7.887(3) Å,b=9.788(5) Å,c=9.316(4) Å,=100.6(1), andZ=4. Molecule 3 crystallizes in the monoclinic space groupP2₁/c witha=12.947(14) Å,b=10.553(14) Å,c=9.629(14) Å,=101.4(1), andZ=4. The calculated density for both molecules is 1.33 g cm^–1. FinalR-factors were 5.1% for2 and 8.59% for3. The x-ray results showed that a change in configuration occurred in the reaction going from2 to3.     

Crystal and molecular structures of 1-(2-methyloxycarbonylo-propan-2-ylamino)-3-(1-naphthyloxy) propan-2-ol hydrochloride (1) (C18H24NO4Cl) and 1-(2-methylcarbamoylpropan-2-ylamino)-3-(1-naphthyloxy) propan-2-ol (2) (C18H24N2O3)

The crystal structures of two new-adrenergic antagonists, derivatives of propranolol, are reported in this paper. The space groups and unit-cell parameters are: compound1 (C₁₈H₂₄NO₄Cl), monoclinic,P2₁,a=7.215(1),b=8.591(1),c=15.017(1)Å,=95.64(1)°; compound2 (C₁₈H₂₄N₂O₃), monoclinic,P2₁/c,a=10.218(3),b=21.616(5),c=8.124(2)Å,=101.28(2)°. The structures were solved with direct methods and refined by full-matrix least-squares techniques toR indices of 0.036 and 0.066, respectively. The molecule of compound1 has an extended external chain, and thus its structure is linear, whereas the molecule of compound2 is compact, and its external chain is twisted in a characteristic way, as is the case of peptides.     

Crystal structure of 10-oxa-3,4 benzobicyclo [5.3.0] deca-1 (7) ene-8,9 dione,C13H10O3

The crystal and molecular structure of the title compound, C₁₃H₁₀O₃, determined by single crystal X-ray diffraction is reported. Crystals are triclinic, space groupP¯1,a=9.251(1),b=8.837(1),c=7.091(1)Å;=85.6(1)°,=108.2(1)°, =110.1(1)°;V=517(3)ų;Dx=1.38 mg m^–3, (MoK)=0.7107 Å;=0.91 mm^–1;F(000)=224. The structure was solved by direct methods and the finalR value is 0.059 (R=0.078) for 1393 independent observed relfections. In the crystal the cycloheptadienic moiety adopts an approximate twist chair conformation with a pseudo-twofold axis and presents disorder.     

Crystal and molecular structure of 1-(2-isopropylcarbamoylpropan-2-ylamino) 3-(1-naphthyloxy)propan-2-ol (C20H28N2O3)

The crystal structure of the title compound has been determined with three-dimensional MoK X-ray diffraction data. The space group and unit-cell parameters are:P2₁/c,a=8.610(3) Å,b=13.516(5) Å,c=16.818(5) Å,=94.95(3)° andV=1950.0(7) ų. The structure was solved by direct methods, and refined by full-matrix least-squares techniques toR=0.0608 andR _w=0.0648. The compound is a derivative of the popular-adrenolytic propranolol, and in the propanol part of the side chain shows the typicalgauche conformation.     

Preparation,spectral studies,and X-ray crystal structures of (16S, 17R, 20S)-3-oxo-16-hydroxy-25-nor-lanostan-24-oic lactone (II) and (16S, 17R, 20S)-4,16-dihydroxy-25-nor-3,4-seco-lanostan-3,24-dioic acid dilactone (III)

The crystal and molecular structures of the title compounds have been determined by direct methods, and refined to a finalR of 0.059 forII and 0.046 forIII. Both molecules crystallize in space group P2₁2₁2₁. The cell dimensions forII area=10.096(5),b=11.255(3),c=20.300(7) Å;Z=4,D _x=1.188 g cm^–3, (MoK)=0.70 cm^–1, while the cell dimensions forIII area=7.346(1),b=10.470(3),c=30.546(5) Å;Z=4,D _x=1.212 g cm^–3, (MoK)=0.74 cm^–1. The rings of the triterpene skeletons aretrans-cis-trans-cis connected. The conformations of both molecules are discussed. Also the preparation and the spectral data of (17R, 20S)-3,16-dioxo-25-nor-lanostan-24-oic acid (V) and (17R, 20S)-3,16,24-trioxo-25-hydroxy-16,24-seco-lanostan-25-acetate (VI) are given.     

Structural characterization of 2,6-bis(N-methylenepiperidino)-4-nitrophenol (MPN) and 2,6-bis-(N-methylenemorpholino)-4-nitrophenol (MMN)3

MPN: C₁₈H₂₇N₃O₃,M _r=333.43, monoclinic,P2₁/n. a=6.207(2),b=21.893(6),c=13.693(3) Å; =96.12(2)^o,V=1850.1(8) ų.,Z=4,D _cal=1.20 mg/m³,F(000)=720, (CuK)=1.5418 Å, andT=298K.R=0.042 andwR=0.049 for 1675 observed reflections. MMN: C₁₆H₂₃N₃O₅,M _r=337.38, triclinic,P,a=9.642(1) Å,b=10.123(5) Å,c=9.341(2) Å, =93.00(3)^o, =90.96(1)^o, =110.46(1)^o, V=852.5(5) ų,D _cal=1.31 mg m^–3.F(000)=360,Z=2, (CuK)=1.5418 Å,R=0.054 andwR=0.074 for 2804 observed reflections. The piperidine and morpholino rings assumechair conformation and orient each other at an angle of 44.8(1)^o (MPN) and 47.1(1)^o (MMN), respectively.Contribution No. 827 from DCB.     

Crystal and molecular structures of 1-(2-iso butylylcarbamoyl propan-2-ylamino) 3-(1-naphthyloxy)propan-2-ol hydrochloride (1) (C21H31N2O3Cl) and 1-(2-isobutyloxycarbonylo propan-2-ylamino) 3-(1-naphthyloxy)propan-2-ol hydrochloride (2) (C21H30NO4Cl)

This paper shows the crystal structures of two new-adrenergic antagonists, derivatives of propranolol, which were determined with three-dimensional x-ray diffraction data. The space groups and unit-cell parameters are: compound1 (C₂₁H₃₁N₂O₃Cl) monoclinic space groupP2₁/c,a=20.523(4),b=6.909(2),c=15.950(2) Å,=105.03(1)°; compound2 (C₂₁H₃₁NO₄Cl) monoclinic space groupP2₁/c,a=6.364(2),b=36.043(8),c=10.149(1) Å,=104.48(2)°. The structures were solved with direct methods, and refined with full-matrix least-squares techniques toR indices of 0.059 and 0.067, respectively. The-CH(OH)-CH₂-NH-sections of the side chains show the conformation approximate togauche.     

Crystal and molecular structures of 1-(2-carboxypropan-2-ylamino)-3-(1-naphthyloxy) propan-2-ol (1) (C17H21NO4) and 1-(2-carbamoyl propan-2-ylamino)-3-(1-naphthyloxy) propan-2-ol (2) (C17H22N2O3)

The crystal structures of two new-adrenergic antagonists, derivatives of propranolol containing 2-methylalanine fragment are described in this paper. The space groups and unit-cell parameters are: compound1 (C₁₇H₂₁NO₄): monoclinic, space groupP2₁/n,a=5.787(1),b=18.703(4),c=23.526(5)Å,=96.49(2)°; compound2 (C₁₇H₂₂N₂O₃): triclinic, space groupP¯1,a=8.321(1),b=10.121(1),c=10.368(1)Å,=109.49(1)°,=90.49(1)°, =103.48(1)°. The structures were solved by direct methods and refined with full matrix least-squares techniques toR indices of 0.055 and 0.049, respectively. The molecules of compound1 exist in the crystal as dual ions. The molecules of compound2 are compact and their external chain is twisted in a characteristic way (similar to that found in peptides).     

Structural characterization of the edge double-bridged triruthenium cluster complex Ru3(μ-Cl)2(CO)8(PPh3)2

The title compound is Ru₃(-Cl)₂(CO)₈(PPh₃)2. Crystal data: formula C₄₄H₃₀O₈Cl2P2Ru₃;f _w =1122.9; monoclinic,P2₁; cell parameters (at 293 K)a=10.971(2) Å,b=17.066(2) Å,c=11.833(2) Å,=92.91(1)°,V=2213 ų,Z=2, _calcd=1.68, _meas=1.68. Final discrepancy indices areR(F)=0.030,R _W (F)=0.036. The structure consists of an open trinuclear unit involving two metal-metal bonds [Ru(1)-Ru(2)=2.845(1) Å, Ru(2)-Ru(3)=2.860(1) Å]. The open edge of the metal framework [Ru(1)Ru(3)=3.254(1) Å] is supported by two symmetric bridging chloride ligands [Cl(1)-Ru(1)=2.461(2) Å; Cl(1)-Ru(3)=2.464(2) Å; Cl(2)-Ru(1)=2.470(2) Å; Cl(2)-Ru(3)=2.472(2) Å]. Both phosphorus ligands are cis to the Cl atoms and trans to the unique ruthenium atom Ru(2). Geometric features of the edge dibridged complex are discussed.     

Structures of 355-1355-1355-1tricarbonyl: structural evidence for the near-electroneutrality of the dialkylacetal substituent

The structures of the (benzene dialkylacetal)tricarbonyl chromium complexes [⁶-C₆H₅-CH(OR)₂]Cr(CO)₆ (R=Me,1; Et,2), are reported. The compounds were examined as part of a study of the conformations of the tripodal tricarbonylchromium group. For [⁶-C₆H₅-CH(OMe)₂]Cr(CO)₃,1, monoclinic,P2₁/c (# 14),a=15.235(1) Å,b=6.5304(5) Å,c=12.702 Å, =103.197(1)^o,Z=4. For [⁶-C₆H₅-CH(OEt)₂]Cr(CO)₃,2, monoclinic,P2₁/c (# 14),a=9.859(3) Å,b=10.547(3) Å,c=15.138(3) Å, =108.42(2)^o,Z=4. The data show that the molecules adopt the expected three-legged piano stool structure. The carbonyl ligands in1 adopt an eclipsed arrangement with respect to the arene ring and its substituent, while those in2 are staggered. These conformations are consistent with the notion that the acetal substituent behaves largely as an electroneutral group, or at most as a weak electronic acceptor.     

The structures of three trimethylarsine-boron trihalide adducts: (CH3)3AsBCl3, (CH3)3AsBBr3, and (CH3)3AsBI3

An X-ray structure analysis of three trimethylarsine-boron trihalide adducts has been undertaken. Crystals of (CH₃)₃AsBCl₃ and (CH₃)₃AsBBr₃ are monoclinic with space groupP2₁/m (No. 11) withZ=2 while those of (CH₃)₃AsBI₃ are orthorhombic with space groupPnma (No. 62) withZ=4. For (CH₃)₃AsBCl₃,a=6.497(3) Å,b=10.735(3) Å,c=7.070(2) Å,=111.8(3)°,V=458.4(3) ų,R=0.0343. For (CH₃)₃AsBBr₃,a=6.672(4) Å,b=11.135(7) Å,c=7.199(4) Å,=111.5(1)°,V=497.7(5) ų,R=0.0434. For (CH₃)₃ÅsBI₃,a=13.113(7) Å,b=11.733(5) Å,c=7.387(3) Å,V=1136.5(5) ų,R=0.0329. The As-B bond lengths are 2.065(6), 2.04(1), and 2.03(1) Å, respectively, for the chloride, bromide, and iodide. These and other structural parameters are discussed with reference to previous predictions based on vibrational spectra and previous structural studies on the trimethyl-phosphine and trimethylamine adducts.     

The preparation and crystal structures of some tricarbonylmanganese(I) octahedral complexes containing the 1,1-dimethylamino-2,2-diphenylphosphinoethane ligand

Four new complexes of (pn) the titled ligand have been prepared and characterized: (CO)₃Mn(pn)Br, 1; (CO)₃Mn(pn)N₃, 2; the triazalato (tz) complex, (CO)₃Mn(pn)(tz), 3 and [(CO)₄Mn(pn)]BF₄, 4. Crystal structures for the first three of these were determined. Crystal data for 1, monoclinic crystal system, space group = C2, a = 17.8587(6) Å, b = 7.9611(3) Å, c = 14.2349(4) Å, = 90.281(1)°, V = 2023.82(12) ų, Z = 4; for 2, monoclinic crystal system, space group = P2₁/c, a = 8.8933(14) Å, b = 13.844(2) Å, c = 16.361(3) Å, = 95.712(3)°, V = 2004.4(6) ų, Z = 4; for 3, orthorhombic crystal system, space group = Pbca, a = 17.9097(4) Å, b = 13.1308(4) Å, c = 21.2838(6) Å, V = 5005.3(2) ų, Z = 8.     

Crystal and molecular structures of 1-phenyl-4,6-dimethylpyrimidine-2-thionetetraaquacobalt(II) dinitrate complex and of two pyrimidine thiones

The crystal structures of 1-phenyl-4,6-dimethylpyrimidine-2-thionetetraaquacobalt(II) dinitrate (I)a=9.032(2),b=12.458(2),c=18.067(3)Å,=103.25(3)°,Z=4;P2₁/c,R=0.049; 1-phenyl-4,6-dimethylpyrimidine-2-thione (II)a=12.005(3),b=10.090(2),c=9.649(2)Å,=104.4(1)°,Z=4;P2₁/n,R=0.038; and 4,6-dimethylpyrimidine-2-thione (III)a=15.485(3),b=13.255(3),c=7.127(2)Å,=104.3(1)°,Z=8,C2/c,R=0.041 are reported. In (I) the coordination around the cobalt(II) is distorted octahedral involving one ligand moleculevia sulphur and nitrogen atoms and four water molecules. It is relevant that the parameters in the complexed ligand are not different from those found in the uncomplexed one (II), excepting the distances on the nitrogen atom directly involved in the coordination. Bond distances and angles in compound (III) agree with those found in (II).     

Crystal and molecular structure of dibromobis(benzimidazole)copper(II)

The reaction of CuBr₂ with benzimidazole and HBr in aqueous solution leads to the formation of Cu(C₇H₆N₂)₂Br₂ as dark-brown, stable monoclinic crystals. Space groupP2₁/c witha=13.794(5),b=7.875(2),c=14.510(6) Å;=105.82(5)°;V _c =1516(5) ų;D _x =2.010(3) Mg m^–3. The structure was refined by a full-matrix least-squares procedure to giveR=R _w =0.045 for 1932 intensities above 3(I). The copper (II) ions are four coordinates in the form of a distorted flattened tetrahedron CuN₂Br₂, with the bond lengths Cu-Br(1)=2.402(1), Cu-Br(2)=2.446(1), Cu-N(1)=1.976(7), and Cu-N(11)=1.946(7) Å. The flattened angles are Br-Cu-Br=139.0(1) and N-Cu-N=154.6(3)°. The geometry of intermolecular and intramolecular hydrogen bonds is discussed.     

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).     

Crystal and molecular structure of trans-(tricarbonyl)bis(trans-2,2,3,4,4-pentamethyl-1-phenylphosphetane)iron

The title compound crystallizes in the monoclinic space groupP2₁/a witha=13.092(2) Å,b=15.853(2) Å,c=15.406(3) Å,=103.00(1)°,V=3116(1) ų, andD _calc=1.237 g cm^–3 forZ=4. The structure was solved by direct methods, and refined to a finalR value of 0.057. The phosphetane ligands adopt a nonlinear trans relationship. The four-membered rings are non-planar and have different flap angles of 6.1 and 20.3°. Virtual coupling is evident in the¹³C NMR spectrum of the title compound. Comparison of the¹³C NMR spectral data of this molecule with the parent phosphine ligand, the ligand oxide, and the mono-phosphine iron complex is provided.     

X-ray crystal structures of twocis-Mo(CO)4{(Ph2PO)2P(O)R} (R=Me,MeO-p-C6H4) complexes with unusual Mo-PPh2-O-P(O)R-O-PPh2 chelate rings

The X-ray crystal structures of twocis-Mo(CO)₄{(Ph₂PO)₂P(O)R} (I:R=Me; II: R=C₆H₄-p-OMe) complexes are presented. Complex I crystallizes in the monoclinic space groupP2₁/n (a=11.566(1),b=10.045(2),c=25.959(4)Å;=97.64(1)°;V=2989.0 ų;Z=4). Complex II crystallizes in the triclinic space group P¯1 (a=8.868(2),b=11.552(2),c=16.818(3)Å,=78.32(1)°,=93.70(2)°, =86.59(2)°,V=1679.0 ų,Z=2). The coordination geometry of the molybdenum in each of these complexes is a slightly distorted octahedron. The six-membered chelate rings in these complexes have twist boat configurations with both ends flattened. The two rings differ in the degree of twisting in the boat and in the degree to which both ends of the boat are distorted from the ideal configurations. The twisting is greater in II, but the distortion is greater in I. Both appear to be due to the differing sizes of the substituent on the phosphonate phosphorus with larger substituents giving less twisting and flattening.     

Crystal and molecular structures of 5,7-dimethyl-1,8-naphthyridine-2-ol (=LH) and of its mercury (II) complex HgL2 and synthesis of some lanthanide/HgL2 heterometallic complexes

The crystal structures of the title compounds have been determined by single crystal diffraction methods. Crystals of 5,7-dimethyl-1,8-naphthyridine-2-ol (1) are monoclinic, space groupP2₁/n witha=7.336(2),b=8.989(2),c=13.125(3)Å,=95.72(3)°,V=861.2(4)ų,Z=4,D _c =1.34 g cm^–3, finalR=0.052. The molecules are linked in pairs by two N-HO hydrogen bonds, and these dimers are stacked in a discontinuous, stepped fashion. Crystals of HgL₂ (2) are monoclinic space groupP2₁,/c witha=4.044(2),b=12.147(2),c=18.093(5)Å,=93.32(2)°,V=887.3(4)ų,Z=2,D _c =2.05 g cm^–3, finalR=0.051. In2 the mercury binds to N(1) to form a linear N-Hg-N coordination geometry, and the HgL₂ molecules form a continuous stacked structure. The syntheses of the compounds ML₄(NO₃)₃·H₂O (M=Nd, Gd, and Er), PrHg₂L₄(NO₃)₃, andM ₂Hg₃L₆(NO₃)₆ (M=Gd, Er) are also reported.     

Isolation and crystal structures of triethylenediamine-hydroquinone (1/1) and triethylenediamine-phenol (1/2)

Two crystalline adducts of triethylenediamine with hydroquinone [N(CH₂CH₂)₃N·C₆H₄(OH)₂,I] and phenol [N(CH₂CH₂)₃N·2C₆H₅OH,II] have been isolated and characterized by X-ray analysis. ComplexI crystallizes in the monoclinic space groupC2/c, witha=11.944(2),b=9.491(2),c=11.986(2) Å,=121.70(1)°, andZ=4. Both molecular components occupy sites of symmetry 2, and are linked alternately by N H-O hydrogen bonds to form infinite zigzag chains. Crystals ofII are also monoclinic, with space groupP2₁/c,a=12.987(2),b=6.376(1),c=21.350(3) Å,=106.94(1)°, andZ=4. The structure is composed of discrete hydrogen-bonded molecular aggregates corresponding to the stoichiometric formula. The triethylenediamine moieties in both adducts closely approximate to the idealizedD ₃ h conformation. The structures have been refined toR values of 0.097 (I) and 0.092 (II) using, respectively, 479 and 1580 observed MoK data.