Band 209, Heft 10

The syntheses, crystal structures and some properties of K 2/3 Li 1/3 Nb 2 PO 8 , K 2/3 Li 1/3 Ta 2 PO 8 and K 2/3 Ag 1/3 Nb 2 PO 8 are reported. They consist of an octahedral (MO 6 : M = Nb, Ta)/tetrahedral (PO 4 ) framework, built up from M–O–P and M–O–M bonds, surrounding cavities and channels occupied by the Ag + /Li + and K + cations. The degree of distortion of the NbO 6 and TaO 6 octahedra are similar for all these phases. The extraframework cations occupy different, distinct sites, depending primarily on their ionic radii, with a concomitant effect on physical properties of the crystals. The degree of “underbonding” of these guest species is similar to that found for the same cations in aluminosilicate zeolite materials. Crystal data: K 2/3 Li 1/3 Nb 2 PO 8 , M r = 373.22, rhombohedral, space group R 32 (No. 155), a = 8.3918(2) Å, α = 104.148(1)°, V = 525.79(3) Å 3 , Z = 3, R p = 4.88%, R wp = 7.61% and χ 2 = 1.19 for 117 parameters and 21505 observations (time-of-flight powder neutron diffraction data; 0.6 < d < 4.0 Å). K 2/3 Li 1/3 Ta 2 PO 8 , M r = 549.24, rhombohedral, R 32 (No. 155), a = 8.3791(2) Å, α = 104.141(1)°, V = 523.46(3) Å 3 , Z = 3, R p = 4.06%, R wp = 6.23%, χ 2 = 1.15, 113 parameters, 21505 observations, 0.6 < d < 4.0 Å. K 2/3 Ag 1/3 Nb 2 PO 8 , M r = 406.80, rhombohedral, R 32 (No. 155), a = 8.5215(2) Å, α = 104.698(1)°, V = 544.42(8) Å 3 , Z = 3, R p = 5.47%, R wp = 6.95%, χ 2 = 1.75 (constant-wavelength powder neutron diffraction data), 51 parameters, 3395 observations.

Lithium hydrogen cis -4-cyclohexene-1,2-dicarboxylate dihydrate, LiHC 8 H 8 O 4 · 2 H 2 O, is monoclinic, C 2/ c , a = 28.276(7) Å, b = 5.3069(15) Å, c = 13.962(3) Å, β = 106.78(2)°; R w = 0.029. The anions are linked to chains by intermolecular hydrogen bonds (O … O 2.658(2) Å). Lithium is tetrahedrally coordinated. The water molecules build hydrogen-bonded chains, which extend in the [001] direction. The protons within this chain are disordered and have two possible positions with site occupation factors of 0.5. The disorder is interpreted as being caused by a random distribution of internally ordered chains of different alignment.

Tetrabutylbis[(2-(benzoylthio)acetato)]-distannoxane C 68 H 100 O 14 S 4 Sn 4 crystallizesas a dimer ( a = 12.2015(7) Å, b = 12.2182(6) Å, c = 14.0068(8) Å, α = 71.737(4)°, β = 79.400(5)°, γ = 83.490(5)°) containing a centrosymmetric tetranuclear unit. The tin atoms occupy cis -trigonal bipyramidal (C–Sn a –C = 132.1(3)°, C–Sn b –C = 132.2(3)°) sites. Tetrabutylbis[2-(2,4-dichloro-5-methylphenylthio)-acetato]distannoxane C 68 H 100 Cl 8 O 10 S 4 Sn 4 ( a = 11.590(2) Å, b = 13.817(2) Å, c = 14.304(2) Å, α = 71.05(1)°, β = 80.62(1)°, γ = 81.39(1)°) has this unit, but the geometries at the tin atoms are more distorted cis -trigonal bipyramids (C–Sn a –C = 145.7(3)°; C–Sn b –C = 140.5(3)°) owing to a different bonding mode of the carboxylato anions.

The title compound was obtained by a copper-assisted ring opening reaction of cyclohexene oxide using 4-methylphenyl-magnesium-bromide. It crystallizes from n-pentane in the triclinic system, space group P [unk], with a = 1122.0(6) pm, b = 1174.5(5) pm, c = 917.2(3) pm, α = 107.11(3)°, β = 90.69(4)°, γ = 76.18(4)°.

The title compound was prepared from the corresponding alcohol, by hydroxy/halogen exchange reaction. It crystallizes from petroleum ether in the orthorhombic system, space group Pbcn , with a = 2830.1(6) pm, b = 821.7(2) pm, c = 1444.2(4) pm.

The crystal structures of the sodium, thallium(I) and Silver(I) salts of hydrogen (+)-tartrate, Na + (HC 4 H 4 O 6 ) − , ( 1 ) Tl + (HC 4 H 4 O 6 ) − , ( 2 ) and Ag + · (HC 4 H 4 O 6 ) − · H 2 O, ( 3 ) have been determined by X-ray diffraction and refined to residuals R = 0.033, 0.028 and 0.019 for 2038, 1009 and 651 observed reflections respectively. All structures are network polymers with metal centres involved in coordination to both carboxylate and hydroxyl oxygens of tartrate residues, and in the case of ( 3 ), to a single water. The anhydrous sodium compound, ( 1 ) differs from the common monohydrate in having distorted octahedral coordination about the metal, linking six different tartrate residues [4 carboxyl, 2 hydroxyl: Na–O range, 2.319(1)–2.460(1) Å]. The thallium(I) salt ( 2 ) is a member of an isomorphous series (which includes the NH 4 + , K + , Rb + and Cs + salts), with square antiprismatic coordination about Tl[5 carboxyl, 3 hydroxyl: Tl–O range 2.805(8)–3.188(8) Å]. The monohydrated silver hydrogen tartrate salt ( 3 ) is similar to but not isomorphous with Na + (HC 4 H 4 O 6 ) − · H 2 O, with the water and five tartrate oxygens coordinated [3 carboxyl, 2 hydroxyl: Ag–O range, 2.353(4)–2.801(3) Å]. The stereochemistry about silver in ( 3 ) is distorted skew trapezoidal bipyramidal.

The crystal structures of three N-glycosides are reported. The N-p-nitrophenyl-N-(2,3,4-tri-O-acetyl- β -D-lyxopyranosyl)amine ( 1 ), N-p-nitrophenyl-N-(2,3,4-tri-O-acetyl- α -L-arabinopyranosyl)amine ( 2 ) and N-acetyl-N-p-nitrophenyl-N-(2,3,4-tri-O-acetyl- α -L-arabinopyranosyl)amine ( 3 ) have the following space groups and unit cell parameters: compound 1 (C 17 H 20 N 2 O 9 ), orthorhombic, P 2 1 2 1 2 1 a = 8.004(2) Å, b = 10.603(2) Å, c = 22.695(5) Å; Z = 4 compound 2 (C 17 H 20 N 2 O 9 )), tetragonal, P 4 3 2 1 2, a = 9.704(2) Å, c = 41.271(9) Å Z = 8 and compound 3 (C 19 H 22 N 2 O 10 ), orthorhombic, P 2 1 2 1 2 1 , a = 8.132(2) Å, b = 12.705(2) Å, c = 21.160(4) Å Z = 4. The structures were solved by using direct methods and refined by full-matrix least-squares techniques to R indices of 0.050, 0.041 and 0.067, respectively. These compounds have normal geometry with the 4 C 1 conformation of the pyranoid ring.

The coordination environment of the tin atom in 2-triphenylstannyl 1,2-benzisothiazol-3(2 H )-one 1,1-dioxide · quinoline N -oxide, C 34 H 26 N 2 O 3 SSn, is a trigonal bipyramid in which the ipso -carbons of the phenyl rings (Sn–C = 2.117(9) Å, 2.122(9) Å, 2.128(9) Å; ΣC–Sn–C = 359.9(9)°) comprise the equatorial, and the imido nitrogen of the 1,2-benzoisothiazol-3(2 H )-onyl 1,1-dioxide anion (Sn–N = 2.266(7) Å) and the oxygen of quinoline N -oxide donor (Sn ← O = 2.319(6) Å) the apical (O–Sn ← O = 175.4(2)°) sites.

The crystal structure of benzoyl-histidine monohydrate (BYLH hereafter), C 13 H 12 N 3 O 3 · H 2 O was determined from three dimensional data of 3012 independent reflections measured on a Enraf-Nonius (CAD4) single crystal diffractometer. The compound crystallizes in the orthorhombic space group P 2 1 2 1 2 1 with cell dimensions α = 7.102(1) Å, β = 13.783(3) Å, c = 14.160(4) Å, V = 1385.92 Å 3 , F.W . = 277.28, F (000) = 584 ϱ calc = 1.32 g cm −3 and Z = 4. The structure was solved with direct methods. All positional and anisotropic thermal parameters were refined by full-matrix least-squares calculations. The final reliability factor was R = 0.040, while the weighted one was Rw = 0.034. The H atoms found in the difference Fourier map were refined isotropically. The compound consists of a histidine molecule bound to a benzoyl group. There is also a cocrystallized water molecule stabilized through a hydrogen bridge. The 5-membered ring of the histidine has its tautomeric form, after the transfer of the H atom from the N δ to the N ε atom of the ring. There is an sp 2 conformation around C6 while the conformation around C3 is that of sp 3 . The histidine ring forms with the benzene ring a dihedral angle of 109.8(1)°. All angle values and bond distances agree very well with the expected values in the literature.

The title compound appeared to be isomorphous and isostructural to one of two polymorphs of the corresponding iron(III) complexes. The crystals of the complex belong to the triclinic system, space group P [unk]. The cell dimensions are: a = 9.851(3) Å, b = 10.647(3) Å, c = 18.008(6) Å, α = 93.44(2)°, β = 94.91(2)°, γ = 107.14(2)°, V = 179(1) Å 3 , Z = 2, μ (Mo K α = 0.52 mm −1 ), D x = 1.351 gcm −3 . Data collection was made with Philips PW1100 (STOE upgraded) automatic diffractometer using Mo K α radiation. The structure was solved by the heavy-atom method and refined by least-squares techniques to a conventional R factor 0.034 for 2997 unique reflections. The structure is built up of discrete molecules separated by normal van der Waals distances. The cobalt atom coordination is distorted octahedrally with an averaged Co–O bond length 1.833(3) Å. The rotational orientation of the terminal phenyl rings with regard to the plane of the chelate ring are dictated by both electronic and dominant steric effect.

C 19 H 21 N 3 O 2 , M r = 323.4, triclinic, P [unk], a = 9.877(2) Å, b = 10.587(2) Å, c = 8.309(2) Å, α = 96.96(1)°, β = 93.21(1)°, γ = 94.13(1)°, V = 858.4 Å 3 , Z = 2, D calc = 1.251 g cm −3 , μ = 6.28 cm −1 , F (000) = 344, T = 293 K, R = 0.059 and wR = 0.058 for 1720 observed reflections. The piperidine ring adopts distorted boat conformation. The phenyl rings (A and B) are oriented at angles of 70.4(2)° and 89.8(1)° to the best plane of the piperidine ring. The nitroso moiety exists in perpendicular orientation while the oximino group is in planar position with respect to the piperidine ring.