A one‐dimensional zinc(II) coordination polymer incorporating [1,1′‐biphenyl]‐4,4′‐dicarboxylate and N,N′‐bis(pyridin‐3‐ylmethyl)‐[1,1′‐biphenyl]‐4,4′‐dicarboxamide ligands

In the title compound, catena‐poly[[[N,N′‐bis(pyridin‐3‐ylmethyl)‐[1,1′‐biphenyl]‐4,4′‐dicarboxamide]chloridozinc(II)]‐μ‐[1,1′‐biphenyl]‐4,4′‐dicarboxylato‐[[N,N′‐bis(pyridin‐3‐ylmethyl)‐[1,1′‐biphenyl]‐4,4′‐dicarboxamide]chloridozinc(II)]‐μ‐[N,N′‐bis(pyridin‐3‐ylmethyl)‐[1,1′‐biphenyl]‐4,4′‐dicarboxamide]], [Zn₂(C₁₄H₈O₄)Cl₂(C₂₆H₂₂N₄O₂)₃]_n, the Zn^II centre is four‐coordinate and approximately tetrahedral, bonding to one carboxylate O atom from a bidentate bridging dianionic [1,1′‐biphenyl]‐4,4′‐dicarboxylate ligand, to two pyridine N atoms from two N,N′‐bis(pyridin‐3‐ylmethyl)‐[1,1′‐biphenyl]‐4,4′‐dicarboxamide ligands and to one chloride ligand. The pyridyl ligands exhibit bidentate bridging and monodentate terminal coordination modes. The bidentate bridging pyridyl ligand and the bridging [1,1′‐biphenyl]‐4,4′‐dicarboxylate ligand both lie on special positions, with inversion centres at the mid‐points of their central C—C bonds. These bridging groups link the Zn^II centres into a one‐dimensional tape structure that propagates along the crystallographic b direction. The tapes are interlinked into a two‐dimensional layer in the ab plane through N—H...O hydrogen bonds between the monodentate ligands. In addition, the thermal stability and solid‐state photoluminescence properties of the title compound are reported.     

N,N′‐Bis(2‐pyridylmeth­yl)ferrocene‐1,1′‐diyldicarboxamide and N,N′‐bis­(3‐pyridylmeth­yl)ferrocene‐1,1′‐diyldicarboxamide

The mol­ecules of N,N′‐bis­(2‐pyridylmeth­yl)ferrocene‐1,1′‐diyl­dicarboxamide, [Fe(C₁₂H₁₁N₂O)₂], contain intra­molecular N—H⋯N hydrogen bonds and are linked into sheets by three independent C—H⋯O hydrogen bonds. The mol­ecules of the isomeric compound N,N′‐bis­(3‐pyridylmeth­yl)ferrocene‐1,1′‐diyldicarboxamide lie across inversion centres, and the mol­ecules are linked into sheets by a combination of N—H⋯N hydrogen bonds and π–π stacking inter­actions between pyridyl groups.     

Synthesis of New C2‐Symmetric Chiral Bisamides from (1S,2S)‐Cyclohexane‐1,2‐dicarboxylic Acid

A series of new C₂‐symmetric (1S,2S)‐cyclohexane‐1,2‐dicarboxamides was synthesized from (1S,2S)‐cyclohexane‐1,2‐dicarbonyl dichloride and N‐benzyl‐substituted aromatic amines, which were prepared from 2‐aminopyridine, 2‐chloroaniline, and 2‐aminophenol via imine formation with benzaldehyde and subsequent reduction with NaBH₄. (1S,2S)‐N,N′‐Dibenzyl‐N,N′‐bis[2‐(benzyloxy)phenyl]cyclohexane‐1,2‐dicarboxamide was converted to (1S,2S)‐N,N′‐dibenzyl‐N,N′‐bis(2‐hydroxyphenyl)cyclohexane‐1,2‐dicarboxamide via hydrogenolysis in the presence of Pd(OH)₂ on active carbon powder.     

catena‐Poly[[[N,N′‐bis­(salicyl­idene)propane‐1,3‐diaminato]cobalt(III)]‐μ‐azido] and catena‐poly[[[N,N′‐bis(salicyl­idene)propane‐1,3‐diaminato]cobalt(III)]‐μ‐thio­cyanato]

The two title complexes, catena‐poly[[{2,2′‐[1,3‐propane­diylbis(nitrilo­methyl­idyne)]diphenolato}cobalt(III)]‐μ‐azido], [Co(C₁₇H₁₆N₂O₂)(N₃)]_n, (I), and catena‐poly[[{2,2′‐[1,3‐propane­diylbis(nitrilo­methyl­idyne)]diphenolato}cobalt(III)]‐μ‐thio­cyanato], [Co(C₁₇H₁₆N₂O₂)(NCS)]_n, (II), are isomorphous polynuclear cobalt(III) compounds. In both structures, the Co^III atom is six‐coordinated in an octa­hedral configuration by two N atoms and two O atoms of one Schiff base, and two terminal N or S atoms from two bridging ligands. The [N,N′‐bis­(salicyl­idene)propane‐1,3‐diaminato]cobalt(III) moieties are linked by the bridging ligands, viz. azide in (I) and thio­cyanate in (II), giving zigzag polymeric chains with backbones of the type [–Co—N—N—N—Co]_n in (I) or [–Co—N—C—S—Co]_n in (II) running along the c axis.     

Novel hydrazone derivatives of 7‐hydroxy‐3′,3′‐dimethyl‐3′H‐spiro[chromene‐2,1′‐isobenzofuran]‐8‐carbaldehyde

The structures of new oxaindane spiropyrans derived from 7‐hydroxy‐3′,3′‐dimethyl‐3′H‐spiro[chromene‐2,1′‐isobenzofuran]‐8‐carbaldehyde (SP1), namely N‐benzyl‐2‐[(7‐hydroxy‐3′,3′‐dimethyl‐3′H‐spiro[chromene‐2,1′‐isobenzofuran]‐8‐yl)methylidene]hydrazinecarbothioamide, C₂₇H₂₅N₃O₃S, (I), at 120 (2) K, and N′‐[(7‐hydroxy‐3′,3′‐dimethyl‐3′H‐spiro[chromene‐2,1′‐isobenzofuran]‐8‐yl)methylidene]‐4‐methylbenzohydrazide acetone monosolvate, C₂₇H₂₄N₂O₄·C₃H₆O, (II), at 100 (2) K, are reported. The photochromically active C_spiro—O bond length in (I) is close to that in the parent compound (SP1), and in (II) it is shorter. In (I), centrosymmetric pairs of molecules are bound by two equivalent N—H...S hydrogen bonds, forming an eight‐membered ring with two donors and two acceptors.     

New 3,3′[2,2′‐oxy‐bis‐(oxazaborolidine)]‐ethylenes. Structural studies by NMR,X‐ray,and quantum chemistry methods

3,3′‐[2,2′‐Oxy‐bis‐(4S‐methyl, 5R‐phenyl‐1,3,2‐oxazaborolidine)]ethylene ( 4a ) and 3,3′‐[2, 2′‐oxy‐(4S‐methyl‐5R‐phenyl‐1,3,2‐oxazaborolidine)‐ (1,3,2‐benzoxazaborolidine)]ethylene ( 4b ) were synthesized by the reaction of N,N′‐bis‐[(1R,2S)‐norephedrine]oxalyl ( 3a ) or N,N′‐[((1R,2S)‐norephedrine, o‐hydroxyphenylamine]oxalyl ( 3b ) with BH₃‐THF. The molecular structure of these compounds was established by NMR and infrared spectroscopy. The molecular geometry for 4 was studied by means of theoretical methods, resulting in structures that were in total agreement with those obtained by spectroscopy data and X‐ray diffraction. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:513–519, 2005; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20151     

Synthesis,characterization and crystal structures of the bidentate Schiff base N,N′‐bis(2‐nitrocinnamaldehyde)ethylenediamine and its complex with CuNCS and triphenylphosphane

Reaction of copper(I) thiocyanate and triphenylphosphane with the bidentate Schiff base N,N′‐bis(trans‐2‐nitrocinnamaldehyde)ethylenediamine {Nca₂en, (1); systematic name (1E,1′E,2E,2′E)‐N,N′‐(ethane‐1,2‐diyl)bis[3‐(2‐nitrophenyl)prop‐2‐en‐1‐imine]}, C₂₀H₁₈N₄O₄, in a 1:1:1 molar ratio in acetonitrile resulted in the formation of the complex {(1E,1′E,2E,2′E)‐N,N′‐(ethane‐1,2‐diyl)bis[3‐(2‐nitrophenyl)prop‐2‐en‐1‐imine]‐κ²N,N′}(thiocyanato‐κN)(triphenylphosphane‐κP)copper(I)], [Cu(NCS)(C₂₀H₁₈N₄O₄)(C₁₈H₁₅P)] or [Cu(NCS)(Nca₂en)(PPh₃)], (2). The Schiff base and copper(I) complex have been characterized by elemental analyses, IR, electronic and ¹H NMR spectroscopy, and X‐ray crystallography [from synchrotron data for (1)]. The molecule of (1) lies on a crystallographic inversion centre, with a trans conformation for the ethylenediamine unit, and displays significant twists from coplanarity of its nitro group, aromatic ring, conjugated chain and especially ethylenediamine segments. It acts as a bidentate ligand coordinating via the imine N atoms to the Cu^I atom in complex (2), in which the ethylenediamine unit necessarily adopts a somewhat flattened gauche conformation, resulting in a rather bowed shape overall for the ligand. The NCS⁻ ligand is coordinated through its N atom. The geometry around the Cu^I atom is distorted tetrahedral, with a small N—Cu—N bite angle of 81.56 (12)° and an enlarged opposite angle of 117.29 (9)° for SCN—Cu—P. Comparisons are made with the analogous Schiff base having no nitro substituents and with metal complexes of both ligands.     

The reaction of 3,4‐diamino‐1,2,5‐oxadiazoles with formaldehyde

The compounds 5,6‐dihydro‐4H‐imidazo[4,5‐c][1,2,5]oxadiazole ( 3a , R?H), 4,6,10,12‐tetramethyl‐5,6,11,12‐tetrahydro‐4H,10H‐bis(1,2,5)oxadiazolo[3,4‐d:3′,4′‐I][1,3,6,8]tetraazecine ( 4b , R?CH₃), N³,N³′‐methylenebis‐3,4‐diamino‐1,2,5‐oxadiazole ( 5a , R?H) and N³,N³′‐methylenebis(N,N′‐dimethyl‐3,4‐diamino‐1,2,5‐oxadiazolee) ( 5b , R?CH₃) were synthesized from the reaction of formaldehyde with 3,4‐diamino‐1,2,5‐oxadiazole and N,N′‐3,4‐dimethylamino‐1,2,5‐oxadiazole in an acetonitrile.     

Non‐merohedrally twinned crystals of N,N′‐bis(3‐methyl­phenyl)‐N,N′‐di­phenyl‐1,1′‐bi­phenyl‐4,4′‐di­amine: an excellent tri­phenyl­amine‐based hole transporter

N,N′‐Bis(3‐methyl­phenyl)‐N,N′‐di­phenyl‐1,1′‐bi­phenyl‐4,4′‐di­amine (TPD), C₃₈H₃₂N₂, crystallizes in the monoclinic space group P2₁ with a pseudo‐orthogonal lattice, rather than the previously reported orthorhombic space group P2₁2₁2₁ [Kennedy, Smith, Tackley, David, Shankland, Brown & Teat (2002). J. Mater. Chem. 12 , 168–172]. The asymmetric unit consists of two independent mol­ecules, A and B, which are arranged along the [100] direction to form vertical layers of alternately stacked A and B mol­ecules. Molecule A shows a great deal of rotational movement in the four terminal aryl rings, resulting in two disordered tolyl groups split over two sites, while mol­ecule B exhibits an almost cis configuration of the two terminal tolyl groups with respect to these ring planes.     

Synthesis and crystal structure of the dinuclear copper(II) Schiff base complex μ‐hydroxido‐μ‐chlorido‐bis{[bis(trans‐2‐nitrocinnamaldehyde)ethylenediamine]chloridocopper(II)} dichloromethane sesquisolvate

Transition metal complexes of Schiff base ligands have been shown to have particular application in catalysis and magnetism. The chemistry of copper complexes is of interest owing to their importance in biological and industrial processes. The reaction of copper(I) chloride with the bidentate Schiff base N,N′‐bis(trans‐2‐nitrocinnamaldehyde)ethylenediamine {Nca₂en, systematic name: (1E,1′E,2E,2′E)‐N,N′‐(ethane‐1,2‐diyl)bis[3‐(2‐nitrophenyl)prop‐2‐en‐1‐imine]} in a 1:1 molar ratio in dichloromethane without exclusion of air or moisture resulted in the formation of the title complex μ‐chlorido‐μ‐hydroxido‐bis(chlorido{(1E,1′E,2E,2′E)‐N,N′‐(ethane‐1,2‐diyl)bis[3‐(2‐nitrophenyl)prop‐2‐en‐1‐imine]‐κ²N,N′}copper(II)) dichloromethane sesquisolvate, [Cu₂Cl₃(OH)(C₂₀H₁₈N₄O₄)₂]·1.5CH₂Cl₂. The dinuclear complex has a folded four‐membered ring in an unsymmetrical Cu₂OCl₃ core in which the approximate trigonal bipyramidal coordination displays different angular distortions in the equatorial planes of the two Cu^II atoms; the chloride bridge is asymmetric, but the hydroxide bridge is symmetric. The chelate rings of the two Nca₂en ligands have different conformations, leading to a more marked bowing of one of the ligands compared with the other. This is the first reported dinuclear complex, and the first five‐coordinate complex, of the Nca₂en Schiff base ligand. Molecules of the dimer are associated in pairs by ring‐stacking interactions supported by C—H…Cl interactions with solvent molecules; a further ring‐stacking interaction exists between the two Schiff base ligands of each molecule.     

Hydrogen‐bonding network of N,N′‐bis[2‐(tert‐butyldimethylsiloxy)ethyl]ethylenediammonium dichloride

The title salt, C₁₈H₄₆N₂O₂Si₂²⁺·2Cl⁻, has been synthesized by reaction of N,N′‐bis(2‐hydroxyethyl)ethylenediamine with tert‐butyldimethylsilyl chloride. The zigzag backbone dication is located across an inversion centre and the two chloride anions are related by inversion symmetry. The ionic components form a supramolecular two‐dimensional network via N—H...Cl hydrogen bonding, which is responsible for the high melting point compared with the oily compound N,N′‐bis[2‐(tert‐butyldimethylsiloxy)ethyl]ethylenediamine.     

Planarity of heteroaryldithiocarbazic acid derivatives showing tuberculostatic activity. II. Crystal structures of 3‐[amino(pyrazin‐2‐yl)methylidene]‐2‐methylcarbazic acid esters

Four compounds showing moderate antituberculostatic activity have been studied to test the hypothesis that the planarity of the 2‐[amino(pyrazin‐2‐yl)methylidene]dithiocarbazate fragment is crucial for activity. N′‐Anilinopyrazine‐2‐carboximidamide, C₁₁H₁₁N₅, D1, and diethyl 2,2′‐[({[amino(pyrazin‐2‐yl)methylidene]hydrazinylidene}methylidene)bis(sulfanediyl)]diacetate, C₁₄H₁₉N₅O₄S₂, B1, maintain planarity due to conjugation and attractive intramolecular hydrogen‐bond contacts, while methyl 3‐[amino(pyrazin‐2‐yl)methylidene]‐2‐methyldithiocarbazate, C₈H₁₁N₅S₂, C1, and benzyl 3‐[amino(pyrazin‐2‐yl)methylidene]‐2‐methyldithiocarbazate, C₁₄H₁₅N₅S₂, C2, are not planar, due to methylation at one of the N atoms of the central N—N bond. The resulting twists of the two molecular halves (parts) of C1 and C2 are indicated by torsion angles of 116.5 (2) and −135.9 (2)°, respectively, compared with values of about 180° in the crystal structures of nonsubstituted compounds. As the methylated derivatives show similar activity against Mycobacterium tuberculosis to that of the nonsubstituted derivatives, maintaining planarity does not seem to be a prerequisite for activity.     

Controlled helical orientation of carbazole in amino acid derived poly(N‐propargylamide)s

Novel L ‐alanine and L ‐glutamic acid derivatized, carbazole‐containing N‐propargylamides [N‐(9‐carbazolyl)ethyloxycarbonyl‐L ‐alanine N′‐propargylamide and N‐(9‐carbazolyl)ethyloxycarbonyl‐L ‐glutamic acid‐γ‐benzyl ester N′‐propargylamide] were synthesized and polymerized with (nbd)Rh⁺[η⁶‐C₆H₅B^?(C₆H₅)₃] (nbd = norbornadiene) as a catalyst to obtain the corresponding polymers with moderate molecular weights in high yields. Polarimetry, circular dichroism, and ultraviolet–visible spectroscopy studies revealed that both poly[N‐(9‐carbazolyl)ethyloxycarbonyl‐L ‐alanine N′‐propargylamide] and poly[N‐(9‐carbazolyl)ethyloxycarbonyl‐L ‐glutamic acid‐γ‐benzyl ester N′‐propargylamide] took a helical structure with a predominantly one‐handed screw sense in tetrahydrofuran, CHCl₃, and CH₂Cl₂. The helix content of poly[N‐(9‐carbazolyl)ethyloxycarbonyl‐L ‐alanine N′‐propargylamide] could be tuned by heat or the addition of a protic solvent, and the helical sense of poly[N‐(9‐carbazolyl) ethyloxycarbonyl‐L ‐glutamic acid‐γ‐benzyl ester N′‐propargylamide] was inverted by heat in CHCl₃ or in mixtures of tetrahydrofuran and CH₂Cl₂. Poly[N‐(9‐carbazolyl) ethyloxycarbonyl‐L ‐alanine N′‐propargylamide] and poly[N‐(9‐carbazolyl)ethyloxycarbonyl‐L ‐glutamic acid‐γ‐benzyl ester N′‐propargylamide] also took a helical structure in film states. They showed small fluorescence in comparison with the monomers and redox activity based on carbazole. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 253–261, 2007     

1,2‐Bis(N‐fluoro‐p‐toluene­sulfon­amido)­ethane chloroform solvate

The title compound, N,N′‐difluoro‐N,N′‐ethylenedi‐p‐tolu­enesulfonamide, C₁₆H₁₈F₂N₂O₄S₂·CHCl₃, is a novel stable compound of the N—F class of reagents containing two R₂N—F functionalities. The compound, as the chloro­form solvate, is the first such bis(N—F) compound to be structurally characterized. It adopts a solid‐state structure in which the two aromatic rings are antiperiplanar and a combination of weak C—H?F and C—H?O hydrogen bonds [distances and angles range from 3.265 (4) to 3.439 (4) Å and 150 to 170°, respectively] and π‐stacking between the rings of different mol­ecules (separations of 3.717 and 3.926 Å) results in a solid‐state structure containing well defined channels in which CHCl₃ solvent mol­ecules are located. The N—F distances are 1.428 (3) and 1.433 (3) Å.     

Three isomorphous Ln complexes: {[Ln2(bt)6(bno)(H2O)4]·bno}n (bt is but‐2‐enoate and bno is 4,4′‐bipyridyl N,N′‐dioxide), with Ln = Nd,Er and Y

The polymeric title compounds, namely catena‐poly[[[di‐μ‐but‐2‐enoato‐κ³O:O,O′;κ³O,O′:O′‐bis[diaquadibut‐2‐enoato‐κO;κ²O,O′‐neodymium(III)]]‐μ‐4,4′‐bipyridyl N,N′‐dioxide‐κ²O:O′] 4,4′‐bipyridyl N,N′‐dioxide solvate] and the erbium(III) and yttrium(III) analogues, {[Ln₂(C₄H₅O₂)₆(C₁₀H₈N₂O₂)(H₂O)₄]·C₁₀H₈N₂O₂}_n (Ln = Nd, Er and Y), form from [Ln₂(bt)₆(H₂O)₄] dimers (bt is but‐2‐enoate) bridged by 4,4′‐bipyridyl dioxide (bno) spacers into sets of parallel chains; these linear arrays are interconnected by aqua‐mediated hydrogen bonds into broad two‐dimensional structures, which in turn interact with each other though the hydrogen‐bonded bridged bno solvent units. Both independent bno units in the structures are bisected by symmetry centres.     

Nickel and zinc complexes with a monodentate heterocycle and tridentate Schiff base ligands: self‐assembly to one‐ and two‐dimensional supramolecular networks via hydrogen bonding

In the complex (morpholine)[2‐hydroxy‐N′‐(5‐nitro‐2‐oxidobenzylidene)benzohydrazidato]nickel(II), [Ni(C₁₄H₉N₃O₅)(C₄H₉NO)], (I), the Ni^II center is in a square‐planar N₂O₂ coordination geometry. The complex bis[μ‐2‐hydroxy‐N′‐(2‐oxidobenzylidene)benzohydrazidato]bis[(morpholine)zinc(II)], [Zn₂(C₁₄H₁₀N₂O₃)₂(C₄H₉NO)₂], (II), consists of a neutral centrosymmetric dimer with a coplanar Zn₂(μ₂‐O)₂ core. The two Zn^II centers are bridged by phenolate O atoms. Each Zn^II center exhibits a distorted square‐pyramidal stereochemistry, in which the four in‐plane donors come from the O,N,O′‐tridentate 2‐hydroxy‐N′‐(2‐oxidobenzylidene)benzohydrazidate(2−) ligand and a symmetry‐related phenolate O atom, and the axial position is coordinated to the N atom from the morpholine molecule. There are intramolecular phenol–hydrazide O—H...N hydrogen bonds present in both (I) and (II). In (I), square‐planar nickel complexes are linked by intermolecular morpholine–morpholine N—H...O hydrogen bonds, leading to a one‐dimensional chain, while in (II) an infinite two‐dimensional network is formed via intermolecular hydrogen bonds between the coordinated morpholine NH groups and the uncoordinated phenolate O atoms.     

N,N′‐Bis(2‐hydroxybenzylidene)pentane‐1,5‐diamine

In the title potential O,N,N′,O′‐tetradentate Schiff base ligand {systematic name: 2,2′‐[pentane‐1,5‐diylbis(nitrilomethylidyne)]diphenol}, C₁₉H₂₂N₂O₂, the mutual orientation of the three planar fragments determines the conformation of the molecule. The dihedral angles between the planes of the two salicylidene groups and the plane of the central extended pentane chain are 78.4 (2) and 62.0 (3)°, and the angle between the terminal ring planes is 55.4 (1)°. Strong intramolecular O—H...N hydrogen bonds close almost‐planar six‐membered rings, and the O—H bonds are elongated as a result of hydrogen‐bond formation.     

A novel one‐dimensional coordination polymer,catena‐poly[[diaquacobalt(II)]‐μ‐(2,2′‐bipyridyl‐3,3′‐dicarboxylato‐κ4N,N′:O,O′)]

The title compound, [Co(C₁₂H₆N₂O₄)(H₂O)₂]_n, has been hydro­thermally synthesized and structurally characterized. It consists of polymeric chains of [Co{μ‐(2,2′‐bipyridyl‐3,3′‐di­carboxyl­ato‐κ⁴N,N′:O,O′)}(H₂O)₂] units, in which each Co^II cation is octahedrally coordinated by two chelating pyridyl N atoms, two chelating carboxyl O atoms from different carboxylate groups of another bipyridyl ligand, and two water mol­ecules as terminal ligands. A crystallographic twofold axis parallel to the chain axis, passes through the Co atom.     

Hydrogen‐bonded one‐dimensional networks in 1:1 complexes of N,N′‐bis(2‐pyridyl)aryldiamines with anilic acid

The 1:1 complexes N,N′‐bis(2‐pyridyl)­benzene‐1,4‐di­amine–anilic acid (2,5‐di­hydroxy‐1,4‐benzo­quinone) (1/1), C₁₆H₁₄N₄·C₆H₄O₄, (I), and N,N′‐bis(2‐pyridyl)­bi­phenyl‐4,4′‐di­amine–anilic acid (1/1), C₂₂H₁₈N₄·C₆H₄O₄, (II), have been prepared and their solid‐state structures investigated. The component mol­ecules of these complexes are connected via conventional N—H?O and O—H?N hydrogen bonds, leading to the formation of an infinite one‐dimensional network generated by the cyclic motif R(9). The anilic acid molecules in both crystal structures lie around inversion centres and the observed bond lengths are typical for the neutral mol­ecule. Nevertheless, the pyridine C—N—C angles [120.9 (2) and 120.13 (17)° for complexes (I) and (II), respectively] point to a partial H‐atom transfer from anilic aicd to the bispyridyl­amine, and hence to H‐atom disorder in the OHN bridge. The bispyridyl­amine mol­ecules of (I) and (II) also lie around inversion centres and exhibit disorder of their central phenyl rings over two positions.     

Three new [XC(O)NH]P(O)[N(CH2C6H5)2]2 phosphoric triamides (X = CClF2, 3‐F‐C6H4 and 3,5‐F2‐C6H3): a database analysis of tertiary N‐atom geometry in compounds with a C(O)NHP(O)[N]2 core

In the phosphoric triamides N,N,N′,N′‐tetrabenzyl‐N′′‐(2‐chloro‐2,2‐difluoroacetyl)phosphoric triamide, C₃₀H₂₉ClF₂N₃O₂P, (I), N,N,N′,N′‐tetrabenzyl‐N′′‐(3‐fluorobenzoyl)phosphoric triamide, C₃₅H₃₃FN₃O₂P, (II), and N,N,N′,N′‐tetrabenzyl‐N′′‐(3,5‐difluorobenzoyl)phosphoric triamide, C₃₅H₃₂F₂N₃O₂P, (III), the tertiary N atoms of the dibenzylamido groups have sp² character with minimal deviation from planarity. The sums of the three bond angles about the N atoms in (I)–(III) deviate by less than 8° from the planar value of 360°. The geometries of the tertiary N atoms in all phosphoric triamides with C(O)NHP(O)[N]₂ skeletons deposited in the Cambridge Structural Database [CSD; Allen (2002). Acta Cryst. B 58 , 380–388] have been examined and the bond‐angle sums at the two tertiary N atoms (SUM1 and SUM2) and the parameter ΔSUM (= SUM1 − SUM2) considered. It was found that in compounds with a considerable ΔSUM value, the more pyramidal N atoms are usually oriented so that the corresponding lone electron pair is anti with respect to the P=O group. In (I), (II) and (III), the phosphoryl and carbonyl groups, separated by an N atom, are anti with respect to each other. In the C(O)NHP(O) fragment of (I)–(III), the P—N bond is longer and the O—P—N angle is contracted compared with the other two P—N bonds and the O—P—N angles in the molecules. These effects are also seen in analogous compounds deposited in the CSD. Compounds with [C(O)NH]P(O)[N]X (X≠ N), such as compounds with a [C(O)NH]P(O)[N][O] skeleton, have not been considered here. Also, compounds with a [C(O)NH]₂P(O)[N] fragment have not been reported to date. In the crystal structures of all three title compounds, adjacent molecules are linked via pairs of P=O...H—N hydrogen bonds, forming dimers with C_i symmetry.