Band 48, Heft 12

The zwitterionic A 5 -spirosilicates bis[1,2-benzenediolato(2–)][(morpholinio)methyl]silicate (1), bis[2,3-naphthalenediolato(2–)][(morpholinio)methyl]silicate (2; isolated as 2 • CH 3 CN), bis[1,2-benzenediolato(2–)][3-(morpholinio)propyl]silicate (3) and bis[2,3-naphthalenediolato(2 –)][3-(morpholinio)propyl]silicate (4; isolated as 4·1/2CH 3 CN) have been synthesized by various methods including Si – C bond cleavage reactions. The crystal structures of 2 • CH 3 CN and 4 · 1/2 CH 3 CN have been determined. 1,2 • CH 3 CN, 3 and 4 · 1/2 CH 3 CN have also been characterized by solution-state ( 1 H, 13 C, 29 Si) and solid-state NMR spectroscopy ( 29 Si CP/MAS). The pentacoordinate silicon atoms of the zwitterions 1-4 are surrounded by four oxygen atoms and one carbon atom. In the crystal, the coordination polyhedra around the silicon atoms of 2 • CH 3 CN (two crystallographically independent zwitterions and two crystallographically independent acetonitrile molecules) can be described as nearly ideal trigonal bipyramids, with the carbon atoms occupying equatorial sites. The crystal structure of 2 • CH 3 CN is considerably influenced by intermolecular N – H···N hydrogen bonds between the zwitterions and the acetonitrile molecules. The coordination polyhedron observed for the silicon atom in the crystal of 4 · 1/2 CH 3 CN can be described as a distorted square pyramid, with the carbon atom in the apical position. The crystal structure of 4 · 1/2 CH 3 CN is considerably governed by intermolecular N –H···O hydrogen bonds between the zwitterions which form infinite chains in the crystal. The 29 Si chemical shifts (δ = – 75,5 to – 85,8) observed for 1,2 • CH 3 CN, 3 and 4 · 1/2 CH 3 CN in solution ([D 6 ]DMSO) and in the crystal are typical of pentacoordinate silicon of the type SiO 4 C. For all compounds very similar 29 Si chemical shifts have been observed for the solution and solid state [⊿(δ 29 Si) ≤ 0,9] indicating that the zwitterions 1-4 do also exist in solution.

The tripod ligands RCH 2 C(CH 2 PPh 2 ) 3 react with (CH 3 CN) 6 Fe(BF 4 ) 2 to yield the tripod-Fe(II) complexes RCH 2 C(CH 2 PPh 2 ) 3 Fe(CH 3 CN) 3 (BF 4 ) 2 (R = H, la; R = Ph, lb). The octahedral low spin Fe(II) compounds are shown by cyclic voltammetry to undergo reversible one electron oxidation at +1.47 V (vs. SCE) to give the corresponding Fe(III) derivatives. In a similar way (CH 3 CN) 6 Co(BF 4 ) 2 reacts with the same tripod ligands to produce the tripod-Co(II) complexes RCH 2 C(CH 2 PPh 2 ) 3 Co(CH 3 CN) 2 (BF 4 ) 2 (R = H, 2a; R = Ph, 2b). The compounds are paramagnetic (2a, g = 2.123; 2b, g = 2.129). The structure of complex 2b shows that the tripod ligand is facially coordinated with one longer (233.1 pm) and two shorter (about 222 pm) Co—P bonds. Reversible reduction is found for 2a at —0.30 V by cyclic voltammetry. The compounds have been characterized by spectroscopic and analytical techniques including X-ray analyses.

Reaction of [WI(CO)(NCMe)(dppm)(η 2 -MeC 2 Me)][BF 4 ] {dppm = Ph 2 P(CH 2 )PPh 2 } with an equimolar quantity of L {L = RR′CNNHCONH 2 (R = R′ = Me; R = H, R′ = Ph)} or L {L = RR′CNNHCSNH 2 (R = R′ = Me, Et; R = Me, R′ = Et, Pr n , Bu t , Ph; R = H, R′ = Ph)} gives the monodentately coordinated semicarbazone or thiosemicarbazone products [WI(CO)L(dppm)(η 2 -MeC 2 Me)][BF 4 ] (1-9). 13 C NMR spectroscopy suggests that the but-2-yne ligand is donating four electrons to the tungsten in [WI(CO){H(Ph)CNNHCSNH 2 }(dppm)(η 2 -MeC 2 Me)] [BF 4 ].

Tris(oxamide oxime-N 1 ,N 1′ )cobalt(III) triiodide, [Co(H 2 oxao) 3 ]I 3 , has been synthesized, and its structure determined by single crystal X-ray diffraction at room temperature. The trigonal structure (rhombohedral space group R 3̄ c) was refined by full matrix least-squares to a final R (R w ) of 4.1 (3.5)% for 51 parameters and 911 observed independent reflections. The structure consists exclusively of quasi-octahedral chiral cobaloxime cations, [Co(H 2 oxao) 3 ] 3+ , and iodide anions. This structure is isotypic to that of the homologous Ni-based salt analyzed previously in which, as a matter of specific difference, one H 2 O molecule of crystallization per formula unit is present. Moreover, whereas nickel in the latter salt was identified as Ni II on the basis of magnetic data, preliminary voltammetric data clearly reveals Co m in the present salt.

The new chiral ligands (4 R, 5 R)-2,2-dimethyl-a,a,a′,a′-tetra(p-N,N-dimethylaminophenyl)-1,3-dioxolane-4,5-dimethanol and [(4 R, 5 R)-2,2-dimethyl-a,a,a′,a′-tetra(p-triphenylphosphoniumphenyl)-1,3-dioxolane-4,5-dimethanol]X 4 (X = I, BPh 4 ) have been synthesized and characterized. Their catalytic efficiency has been tested in the reaction of benzaldehyde and diethylzinc in the presence of Ti(OPr) 4 . Enantioselectivities up to S/R = 98.7 :1.3 have been observed.

By electrochemical oxidation of [B 6 H 6 ] 2- in the presence of nitrite ions and the base DBU in dichloromethane solution mononitropentahydrohexaborate [B 6 H 5 (NO 2 )] 2- ions are formed and can be isolated by ion exchange chromatography on diethylaminoethyl cellulose. The crystal structures of the K and Cs salt were determined from single crystal X-ray diffraction analyses. K 2 [B 6 H 5 (NO 2 )] is monoclinic, space group P2 1 /m with a = 5.953(1), b = 8.059(4), c = 8.906(1) Å, β = 109.553(9)°; Cs 2 [B 6 H 5 (NO 2 )] is monoclinic, space group P2 1 /a with a = 9.438(6), b = 9.644(7), c = 11.138(9) Å, β = 101.44(9)°. The B 6 octahedron is compressed in the direction of the B—NO 2 bond by about 5%, with bond lengths between 1.67 and 1.77 A.

The reaction of diisobutylamine, H 2 S, and sulfur in a mixture of dimethylformamide, formamide, and ethanol yields orange crystals of bis(diisobutylammonium)-heptasulfide. The compound crystallizes in the centrosymmetric orthorhombic space group Pbca, the lattice constants are a = 11.234(4), b = 17.875(7), c = 27.009(10) Å. The S 7 2- chain does not have the common helical all-trans-conformation, but a mixed conformation trans-cis-trans (sequence of the signs of torsion angles + + - - and - - + +).

A technique to record Raman spectra of deeply coloured solids at low temperature (10 K) is described, using a closed cycle He-cryogenerator and moving the cell by an excentric attachment. The spectroscopic resolution is considerably enhanced as compared to room temperature or 80 K measurements. This is obvious from splittings of Raman lines observed at 10 K on the isotopomers Cs 2 [Pt 35 Cl n 37 Cl 6-n ], n = 1 -5, which have been prepared by stereospecific ligand exchange reactions. As a consequence of lowered symmetry the degenerate valence vibration v 2 (E g , O h ) is split into two lines for the isotopomers belonging to the point groups D 4h , C 4v and C 2v . The isotopic effects calculated by normal coordinate analysis are in good agreement with the observed frequencies.

A variety of triphosphines [(Et 2 N) 2 P] 2 PR 4a–h, [( i Pr 2 N) 2 P] 2 PR 5a–e and [Ph 2 P] 2 PR 9e–g [R = Cy (a), t Bu (b), Mes (c), Me 3 Si (d), t BuMe 2 Si (e), ThexMe 2 Si (f), i Pr 3 Si (g), Ad (h), H (i)] has been obtained by the reaction of the dilithiated primary phosphines RPH 2 la–h with 2 equiv. of the chlorophosphines (Et 2 N) 2 PCl 2, ( i Pr 2 N) 2 PCl 3 or Ph 2 PCl 8. Methanolysis of the trimethylsilyl substituted derivative [( i Pr 2 N) 2 P] 2 P(SiMe 3 ) 5d yields the hydrogen substituted triphosphine [( i Pr 2 N) 2 P] 2 PH 5i. The lithiated diphosphine ( i Pr 2 N) 2 P–P(SiMe 3 )Li 6 reacts with the chlorophosphine 2 to give the unsymmetrically substituted triphosphine ( i Pr 2 N) 2 P–P(SiMe 3 )–P(NEt 2 ) 2 7d. The compounds have been chracterized by their NMR and mass spectra. The structures of 4d and 9g have been determined by X-ray diffraction, representing the first structures of uncomplexed triphosphines.

The reactions of (η 5 -C 5 Me 5 ) 2 Ln(μ-Cl) 2 ML 2 (Ln = Y, La, Lu; M = Li, K; L = Et 2 O, dme) 3a-c with the sodium iminoacetylacetonates 2a-b yield monomeric metallocene chelate complexes , (Ln = Y, La, Lu; R = C 6 H 5 , C 6 H 4 -4-Me) 4a-d which have been characterized by IR, NMR and mass spectrometry. In the case of the lanthanum complex 4c, the chelating structure was confirmed by an X-ray structure analysis. 4c crystallizes monoclinically in space group P2 1 /c with a = 10.232(3), b = 10.216(1), c = 29.047(7)Å, α = γ = 90.0°, β = 97.76(3)°, Ζ = 4, and R = R w = 0.0378 for 4026 observed reflections. The new complexes are sensitive to oxygen and moisture and soluble in all common organic solvents.

Iodomethyltriphenylphosphonium iodide, (C 6 H 5 ) 3 PCH 2 I + I-, has been prepared by the reaction of (C 6 H 5 ) 3 P with CH 2 I 2 in dichloromethane forming colourless needle like crystals. The crystal and molecular structures have been determined by an X-ray structure analysis. The crystals are orthorhombic, space group Pca2 1 , Z = 8; a = 1478,8(3) pm, b = 1249,3(3) pm, c = 2053,2(3) pm. R = 0.050 for 3219 observed reflections with I ≥ 2 σ(Ι). In the solid state the title compound exists as two discrete monomeric units, (C 6 H 5 ) 3 PCH 2 I + I-. In both symmetry independent units the I-I distances are surprisingly short with 346,5(1) pm and 356,3(1) pm. For the title compound the results of AM 1, PM 3, and MNDO calculations are in good agreement with corresponding values determined by the X-ray analysis.

Well-crystallized samples of the rhenium aluminides Re 4 Al 11 and ReAl 6 were obtained by reaction of rhenium with an excess of aluminum. Re 4 Al 11 was found to be isotypic with Mn 4 Al 11 . The MnAl 6 type structure of ReAl 6 was confirmed. The crystal structures of both compounds were refined from single-crystal X-ray data. Re 4 Al 11 :P1̄, Z = 1, a = 516.0(1) pm, b = 896.3(2) pm, c = 516.9(1) pm, a = 90.44(1)°, β = 99.76(1)°, γ = 105.17(1)°, V = 0.2271 nm 3 , R = 0.036 for 2315 structure factors and 74 variable parameters. ReAl 6 : Cmcm, Z = 4, a = 761.0(1) pm, b = 660.5(1) pm, c = 903.4(1) pm, V = 0.4541 nm 3 , R = 0.013 for 711F values and 23 variables. In both structures the rhenium atoms have ten aluminum neighbors at distances from 245 to 277 pm. The Al-Al distances cover the whole range from 251 to 362 pm rather continuously. The previously reported compound Re 2 Al with the tetragonal MoSi 2 -type structure has the lattice constants a = 298.1(1) pm, c = 958.4(4) pm, V = 0.08519 nm 3 . ReAl 6 shows Pauli-paramagnetism.

The title compounds were prepared by reacting powders of the binary transition metal alloys with phosphorus in a tin melt. They crystallize with a monoclinic structure of space group C 2/c, which was determined from single-crystal X-ray data; VNi 4 P 16 : a = 1956.0(3), b = 565.9(1), c = 1106.6(2) pm, β = 100.99(1)°, R = 0.020 for 1904 structure factors and 97 variable parameters; NbNi 4 P 16 : α = 1973.0(3), b = 571.2(3), c = 1117.2(2) pm, β = 100.74(1)°, R = 0.023 for 2431 F-values and 97 variables; WNi 4 P 16 : a = 1964.2(3), b = 568.3(2), c = 1109.3(2) pm, β = 101.04(2)°, R = 0.031 for 371 F-values and 43 variables. The T atoms (T = V, Nb, W) have eight Ρ neighbors, which form a slightly distorted square antiprism, and the Ni atoms have approximately octahedral Ρ coordination. The Ρ atoms form novel P 8 units, which consist of 6-membered rings with a P 2 side chain. Chemical bonding is discussed on the basis of classical twoelectron bonds. A comparison of the interatomic distances suggests that the Fermi level cuts through a band formed by antibonding nickel-phosphorus states. A band structure is proposed, which also rationalizes the metallic conductivity and the Pauli paramagnetism of the compounds.

(Me 3 Sn) 3 PO 3 S has been prepared from the reaction of Me 3 SnCl with Na 3 PO 3 S • 12 H 2 O under cooling in aqueous medium. Its IR and Raman spectra are found to be consistent with a polymeric structure with tetra- and penta-coordinated tin atoms. The 31 P NMR and mass spectra of (Me 3 Sn) 3 PO 3 S are reported and discussed.

The metallo-phosphaalkenes (η 5 -C 5 Me 5 )(CO) 2 M-P=C(NR 2 ) 2 (4a,b, 5) result from the reaction of the corresponding bromo compounds (η 5 -C 5 Me 5 )(CO) 2 MBr with Me 3 Si-P=C(NR 2 ) 2 . The complexes 4a and 5a are cleanly converted into the 1-metallo- l ,2-dihydrophosphetes (10a-c) (M = Fe, Ru; E = CO 2 Me, CN) by treatment with equimolar amounts of dimethyl fumarate or fumarodinitrile, respectively. The products 4a,b, 5 and 10 a-c have been characterized by elemental analysis as well as by spectroscopic data (IR, 1 H, 13 C, 31 P NMR, MS). The molecular structures of 4a and 10a have been determined by single crystal X-ray analysis.

The structures of [Cu(pic)(NCS)(H 2 O) 2 ] · 2H 2 O, complex 1, and [Na 2 Co(pic) 2 (N 3 ) 2 (H 2 O) 6 ][Co(pic) 2 (N 3 ) 2 ] · 2H 2 O, complex 2, were determined by X-ray crystallography. Crystal data: 1, C 7 H 12 CuSN 2 O 6 , orthorhombic, space group Pbca, a = 8.749(4), b = 10.786(5), c = 26.882(9) Å, Z = 8, R w =0.046 for 826 observed diffractometer data; 2, C 24 H 32 Co 2 Na 2 N 16 O 16 , triclinic, space group P1̄, a = 7.297(3), b = 8.806(4), c = 15.820(7) Å, a = 105.31(3), β = 95.09(3), γ = 99.86(3)°, Z = 1, and R w = 0.064 for 1680 observed MoKa data. Complex 1 features six-coordinated copper atoms, N,O-bidentate chelate picolinato anions, and μ(N,S) bridging thiocyanato groups with N at the basal site and S at the apical site of tetragonal bipyramid. The remaining two sites are occupied by aqua molecules, whereas two other water molecules serve as lattice water. The bridging thiocyanato groups link the copper polyhedra to form chains along the b axis of the unit cell. Complex 2 contains two Co(III) atoms located at different inversion centers. Co 1 in the [Na 2 Co(pic) 2 (N 3 ) 2 (H 2 O) 6 ] + cation is six-coordinated by two trans picolinato anions (A) via their N 1 and O 1 atoms and by two terminal azido ligands. Two oxygen atoms (O 2 and O 2a) of two picolinate anions (A) act as μ(Ο,Ο) bridging atoms at basal sites to form a four-membered Na 2 O 2 ring. Each sodium atom is further linked to three aqua ligands giving rise to trigonal-bipyramidal coordination environments. Two additional lattice water molecules are located between the dimeric sodium polyhedra. Co 2, in the [Co(pic) 2 (N 3 ) 2 ]- anion, is also six-coordinated by pairs of trans N,O-picolinate anions (B) and terminal azido groups.

Polystyrene-polyethyleneglycol tentacle polymers (PS–PEG) are a novel class of graft copolymer beads based on a polystyrene matrix grafted with a brush-like layer of polyoxyethylene tentacles [9-12]. Immunogenic materials were obtained by synthesizing on tentacle polymer-bound amino derivatives as a solid support the following haptens: The C-terminal sequence 187—211 KPKAA KPKAA KPKAA KPKAA KPKKA APKKK and the N-terminal sequence 3-31 APAAP AAAPP AEKTP VKKKA AKKPA GA of histone H 1 (calf thymus), as well as the sequences 93-116 of the horse liver alcohol dehydrogenase EE (FTPQC GKCRV CKHPE GNFCL KNDL) and SS (FIPQC GKCSV CKHPE GNLCL KNSL) isozymes (Jörnvall (1970) Eur. J. Biochem. 16, 41-49), respectively. These materials proved to be efficient immunogens both in vivo and in vitro, showing excellent biocompatibility compared to other solid hapten carriers. Tentacle-based immunogens are generally available by standard synthetic procedures either by in situ synthesis of hapten molecules on or by covalent attachment of available antigens or haptens to the beads. Advantageous is the possibility to synthesize the peptide on the tentacle polymer, and to use the solid phase bound peptide directly as hapten. The beads serve as carriers, and no separate splitting off the peptide and binding to another carrier is necessary.

Compounds with two mesogenic groups without terminal alkyl chains or other groups containing thiophene systems have been prepared from α.ω-bis(5-formyl-2-thienyl)alkanes (series 1) and various phosphonium salts by Wittig-reaction. The chemical structures of the new compounds have been characterized by their elemental analyses, IR and 1 H NMR spectra and MS. The liquid crystalline properties of these compounds were characterized by differential scanning calorimetry (DSC) and polarizing microscopy. Mesogenic cores with one thiophene system and two benzene systems give rise to liquid crystalline phases. These compounds with one vinylene group in each core (series 2 and 3) are mostly monotropic, those with two or three vinylene groups are enantiotropic liquid crystalline. Exchanging one vinylene group by a azomethine group in each core reduces the temperature range of the mesophase or destroys the liquid crystallinity completely. In contrast to E,E-1-(5-butyl-2-thienylvinyl)-4-(styryl)benzene (9) with no mesophase the corresponding all-E-α.ω-bis{5-[4-(4-styryl)styryl]-2-thienyl}alkanes (series 5) show over a wide temperature range with increasing inner chain length more and more high ordered mesophases. all-E-α.ω-Bis{5-[4-(4-phenylbuta-1.3-dienyl)styryl]-2-thienyl}alkanes (series 7) decompose in their mesophases.

The first study on the crystal and molecular structures of basic forms of bis(amidinohydrazones) is reported. The structures of the free base and the monohydrochloride salt of the antileukemic agent glyoxal bis(amidinohydrazone) (GBG) were determined by single crystal X-ray diffraction and were refined to R-values of 0.038 and 0.040, respectively. These structures are of special interest because recent results indicate that, in contrast to previous assumptions, the free base may be the actual antileukemic form of bis(amidinohydrazones) and that the monocation form is the predominant species of antileukemic bis(amidinohydrazones) at physiological conditions. In the crystals of the free base as well as in those of the monohydrochloride salt, GBG was found to exist solely in the all-trans configuration of the chain and to consist of one of the three possible geometrical isomers only. In the solid state, GBG free base consists solely of the endiamine tautomer instead of the 'classical’ carboximidamide tautomer, as does also the non-protonated part of GBG monocation in the monohydrochloride salt. Proton NMR measurements indicated that the free base consists of the endiamine tautomer also in dimethyl sulfoxide solution. In the solid state, both of the compounds studied consist of stacks of planes. In the case of the free base, the stacks are crisscross to each other. The distance between the mean planes of the molecules or the monocations is approximately 3.5 Å. The crystals of the monohydrochloride salt contain one molecule of water per each GBG monocation. In both compounds studied, the molecules in the crystals are held together by very extensive hydrogen bond networks and by the interaction of delocalized π-electrons. The crystal of C 4 H 10 N 8 is monoclinic, space group C2/c with a = 15.874(6), b = 6.972(4), c = 7.8l3(5)Å, β = 90.34(4)° and Z = 4. The crystal of C 4 H 13 N 8 OC1 is monoclinic, space group P2 1 /n with α = 7.010(3), b = 22.307(9), c = 7.028(3)Å, β = 66.33(3)° and Ζ = 4.

The new compound Y 7 I 6 C 3 O is prepared by reaction of stoichiometric amounts of Y, YI 3 , Y 2 O 3 and C in closed Ta capsules at 1370 K. Y 7 I 6 C 3 O forms bronze coloured, metallic, air and moisture sensitive crystals. It crystallizes in the space group Pmma (No. 51) with the lattice constants a = 2249.4(4), b = 383.7(1), c = 1079.1(1) pm. Within the crystal structure the C atoms and the O atoms are surrounded by Y atoms octahedrally and tetrahedrally, respectively. The Y 6 C octahedra and Y 4 O tetrahedra are condensed to form ondulated layers, which are separated by double layers of I atoms.

Ca 3 [MnN 3 ] (orthorhomb. Cmcm (Nr. 63); a = 842.6(1), b = 1024.7(2), c= 501.4(1) pm; Z=4) was prepared by reaction of mixtures of Li, Ca and Mn (molar ratio 6:1:1) in tantalum crucibles with nitrogen (1 atm) at 900°C. The crystal structure contains distorted trigonal-planar anions [MnN 3 ] 6- with C 2v -symmetry (Mn—N: 179.4(4) pm and 179.9(5) pm; N—Mn—N: 114.7(1)° and 130.6(2)°). Ca 3 [MnN 3 ] is an isotype of Ca 3 [CrN 3 ] and Ca 3 [VN 3 ].

The crystal structure of KLiTe described earlier as a dark grey powder compound has been determined by X-ray diffraction of single crystals. Very hygroscopic KLiTe crystallizes in the tetragonal space group P4/nmm (Z = 2) with the cell parameters a = 483.0(1) and c = 770.4(2) pm. The structure was determined from 211 independent reflections by Patterson and Fourier methods (R = 0.013; wR = 0.013).

The grey compound CsNaSe has been prepared. The characterization by X-ray powder methods leads to a tetragonal lattice (P 4/nmm) with a = 499.0(1), c = 808.7(2) pm and Z = 2. The structure is related to the PbFCl structure type.

The grey compound CsNaS has been prepared. The characterization by X-ray powder methods leads to a tetragonal lattice (P 4/nmm) with a = 482.1(1), c = 785.6(2) pm and Z = 2. The structure is related to the PbFCl structure type.

The complexes [MoNCl 3 ·DME] and [WNCl 3 ·DME] (DME = 1,2-dimethoxyethane) have been prepared by the reaction of the nitride chlorides MNC1 3 with equimolar amounts of DME in CH 2 Cl 2 suspensions. They form orangered, moisture sensitive crystals, which are soluble in organic solvents. The molybdenum complex has been characterized by a crystal structure determination. Space group Pbca, Z = 8, structure solution with 1781 observed unique reflections, R = 0.031. Lattice dimensions at –60°C: a = 738.6(1), b = 1182.2(1), c = 2314.1(1) pm. [MoNCl 3 ·DME] forms monomeric complexes with chelating DME molecules and Mo–O bond lengths of 215.4(4) and 247.4(4) pm, the longer one being in trans-position of the nitrido ligand. The MoN bond length of 163.3(5) pm suggests a triple bond.

The interaction of VO 2+ with the nucleic bases adenine, guanine, cytosine, thymine and uracil has been investigated spectrophotometrically in a wide pH-range and with metal to base ratios 1:1 and 1:10. Adenine, guanine and uracil interact with the cation at pH-values >5, but whereas adenine apparently coordinates through Natoms, the other two bases seem to be coordinated through oxygen donors.

The dimeric title complex contains a V 2 O 3 4+ unit with a rather small (112.6°) V-O-V angle and exhibits crystallographic C 2 symmetry. Each vanadium center is equatorially coordinated by the tridentate doubly deprotonated hydrazone formed from salicylaldehyde and benzoylhydrazine. The coordination sphere is distorted square pyramidal. Crystal data: orthorhombic, space group Pnc2, a = 758.2(2), b = 1454.4(3), c = 1186.1(2) pm, Z = 4, 1137 reflections, 184 parameters, R (Rw) = 0.032 (0.032).