Di­cyclo­hexyl­ammonium 2,4‐di­chloro­phenoxy­acetate and (2,4‐di­chloro­phenoxy­acetato‐O,O′)bis­(tri­phenylphosphine‐P)silver(I)

The monoclinic cell of di­cyclo­hexyl­ammonium 2,4‐di­chloro­phenoxy­acetate contains four C₁₂H₂₄N⁺·C₅H₈Cl₂O₃^? ion pairs. The ammonium N atom is hydrogen bonded to the oxy­gen ends of two carboxyl groups to form a 12‐membered O—C—O?HNH?O—C—O?HNH ring. In (2,4‐di­chloro­phenoxy­lacetato)­bis­(tri­phenyl­phosphine)silver(I), [Ag(C₈H₅Cl₂O₃)(C₁₈H₁₅P)₂], the carboxyl CO₂ unit chelates to the Ag atom in an anisobidentate manner [Ag—O = 2.436 (2) and 2.517 (2) Å]; the Ag atom shows distorted tetrahedral geometry.     

Bis­(tri­chloro­phosphine)­iminium salts, [Cl3P=N=PCl3]+, with transition metal halide counter‐ions

The structures of four bis­(tri­chloro­phosphine)­iminium {[Cl₃P=N=PCl₃]⁺; systematic name: tri­chloro­[(tri­chloro­phos­phor­an­yl­idene)im­in­io]phos­phor­us(V)} salts, namely bis(tri­chloro­phosphine)­iminium hexa­chloro­niobate, (Cl₆NP₂)[NbCl₆], (I), bis­(tri­chloro­phosphine)­iminium hexa­chloro­tantalate, (Cl₆NP₂)[TaCl₆], (II), bis­(tri­chloro­phosphine)­iminium tri‐μ‐chloro‐bis­[tri­chloro­titanium(IV)], (Cl₆NP₂)[Ti₂Cl₉], (III), and bis­[bis­(tri­chloro­phosphine)­iminium] di‐μ‐chloro‐bis­[tetrachloro­zirconium(IV)], (Cl₆NP₂)₂[Zr₂Cl₁₀], (IV), have been determined. The P=N distances in the discrete [Cl₃P=N=PCl₃]⁺ moieties in structures (I), (II) and (IV) range from 1.5460 (14) to 1.5554 (16) Å, and the P=N=P angles range from 136.8 (3) to 143.4 (4)°. The [Cl₃P=N=PCl₃]⁺ cation in (III) is disordered and the calculated geometries for the cation are therefore less reliable. Compounds (I) and (II) are isostructural and the metal anions have slightly distorted octahedral geometries. The anion in compound (III) consists of two distorted octahedral Ti centres linked by three μ₂‐Cl atoms, while in compound (IV), the dianion is derived from two distorted edge‐shared ZrCl₆ octahedra.     

β‐Pyridinium di­chloro­iodide

The β modification of pyridinium di­chloro­iodide, C₅H₆N⁺·Cl₂I^?, was obtained as yellow crystals by the reaction of (C₅NH₅)AuCl₃, C₅H₆N⁺·Cl^? and I₂ in a vacuum‐sealed ampoule. The di­chloro­iodide ion is nearly symmetric and linear with I—Cl bond lengths of 2.544 (3) and 2.550 (3) Å and a Cl—I—Cl angle of 179.68 (12)°.     

Tetrameric di­chloro­(tri­methyl­ammonio‐p‐toluene­sulfonamidate)­mercury(II)

In the title compound, hexa‐μ‐chloro‐di­chloro­tetrakis(N‐tri­methyl­ammonio‐p‐toluene­sulfonamidate‐κ²N,O)­tetramer­cury(II), [Hg{Me₃N(+)N(−)SO₂C₆H₄CH₃‐p}Cl₂]₄ or [Hg₄Cl₈(C₁₀H₁₆N₂O₂S)₄], four nearly linear and parallel Cl—Hg—Cl units associate through pairwise Hg⋯Cl interactions of 3.1–3.2 Å. Each Hg atom is also coordinated through N and O atoms to a yl­ide mol­ecule. The available structural data indicate that coordination of a sulfonyl‐stabilized nitro­gen yl­ide to a metal atom (Hg or Ag) has no detectable effect on its geometry.     

Di­chloro­bis(3,5‐di­methyl­pyrazole‐N2)methyl­phenyl­tin(IV)

The title compound, [SnCl₂(CH₃)(C₆H₅)(C₅H₈N₂)₂], was obtained by reaction of di­chloro­methyl­phenyl­tin(IV) and 3,5‐di­methyl­pyrazole (dmpz) in chloro­form, and was recrystallized from acetone. The structure consists of octahedral all‐trans [SnMePhCl₂(dmpz)₂] mol­ecules, with the Sn atom coordinated to two C [Sn—C 2.127 (5) and 2.135 (4) Å], two Cl [Sn—Cl 2.5753 (8) Å] and two N atoms [Sn—N 2.357 (3) Å]. The dmpz ligands, bound to the metal through their unprotonated N atoms, form weak intra‐ and intermolecular hydrogen bonds with the Cl ligands via their NH groups, giving rise to a polymeric chain along the c axis.     

1:2 Complexes of chloranilic acid with pyrazole and imidazole,and the aceto­nitrile solvate of a 1:1 complex with imidazole

2,5‐Di­chloro‐3,6‐di­hydroxy‐1,4‐benzo­quinone (chloranilic acid) forms X—H?Y (X, Y = N or O) and C—H?Cl hydrogen bonds with pyrazole and imidazole to afford bis­(pyrazolium) di­chloro­anilate and bis­(imidazolium) di­chloro­anilate, (I) and (II), both 2C₃H₅N₂⁺·C₆Cl₂O₄^2?, and imidazolium chloro­anilate aceto­nitrile solvate, C₃H₅N₂⁺·­C₆HCl₂O₄^?·C₂H₃N, (III). Their crystal structures demonstrate three novel supramolecular architectures based on supramolecular synthons to build a ladder, (I), a two‐dimensional network, (II), and a flat ribbon, (III).     

2‐Amino‐5‐chloro‐1,3‐benzoxazol‐3‐ium 2‐(3,4‐di­chloro­phenoxy)­acetate

The 1:1 organic salt of the title compound, C₇H₆ClN₂O⁺·C₈H₅Cl₂O₃^? or [(2‐ABOX)(3,4‐D)], comprises the two constituent mol­ecules associated by an R₂²(8) graph‐set interaction through the carboxyl­ate group of 3,4‐D across the protonated N/N sites of 2‐ABOX [N?O 2.546 (3) and 2.795 (3) Å]. Cation/anion pairs associate across an inversion centre forming discrete tetramers via an additional three‐centre hydrogen‐bonding association from the latter N amino proton to a phenoxy O atom [N?O 3.176 (3) Å] and a carboxyl­ate O atom [N?O 2.841 (3) Å]. This formation differs from the polymeric hydrogen‐bonded chains previously observed for adduct structures of 2‐ABOX with carboxyl­ic acids.     

Three monoalkoxy‐substituted nido‐platinaboranes: [(PPh3)2PtB10H11‐8‐(OCH3)], [(PPh3)2PtB10H11‐8‐{OCH(CH3)2}] and [(PPh3)2PtB10H10‐9‐{OCH(CH3)2}]

Each of the title compounds, 8‐methoxy‐7,7‐bis­(tri­phenyl­phosphine‐P)‐8,9:10,11‐di‐μH‐7‐platina‐nido‐undecaborane di­chloro­methane hemisolvate, [Pt(CH₁₄B₁₀O)(C₁₈H₁₅P)₂]·0.5CH₂Cl₂, (I), 8‐isopropoxy‐7,7‐bis­(tri­phenyl­phosphine‐P)‐8,9:10,11‐di‐μH‐7‐platina‐nido‐undecaborane di­chloro­methane solvate, [Pt(C₃H₁₈B₁₀O)(C₁₈H₁₅P)₂]·CH₂Cl₂, (II), and 9‐isopropoxy‐7,7‐bis­(tri­phenyl­phosphine‐P)‐8,9:10,11‐di‐μH‐7‐platina‐nido‐undecaborane di­chloro­methane solvate, [Pt(C₃H₁₈B₁₀O)(C₁₈H₁₅P)₂]·CH₂Cl₂, (III), has an 11‐vertex nido polyhedral skeleton, with the 7‐platinum centre ligating to two exo‐polyhedral PPh₃ groups and an alkoxy‐substituted polyhedral borane ligand. Compounds (II) and (III) are isomers. The Pt—B distances are in the range 2.214 (7)–2.303 (7) Å for (I), 2.178 (16)–2.326 (16) Å for (II) and 2.205 (6)–2.327 (6) Å for (III).     

A novel bridged asymmetric binuclear manganese(II) complex with DTPB [DTPB is 1,1,4,7,7‐pentakis(1H‐benz­imidazol‐2‐yl­methyl)‐1,4,7‐tri­aza­heptane]

The crystal structure of the title compound, tetra­chloro­[μ‐1,1,4,7,7‐pentakis(1H‐benzimidazol‐2‐yl­methyl)‐1,4,7‐tri­azaheptane]­dimanganese(II) methanol pentasolvate tetrahydrate, [Mn₂Cl₄(C₄₄H₄₃N₁₃)]·5CH₄O·4H₂O, contains an ­asymmetric dinuclear Mn^II–DTPB [DTPB is 1,1,4,7,7‐pentakis(1H‐benzimidazol‐2‐yl­methyl)‐1,4,7‐tri­aza­heptane] complex with an intra‐ligand bridging group (–NCH₂CH₂N–), as well as several solvate mol­ecules (methanol and water). Both Mn^II cations have similar distorted octahedral coordination geometries. One Mn^II cation is coordinated by a Cl⁻ anion and five N atoms from the ligand, and the other is coordinated by three Cl⁻ anions and three N atoms of the same ligand. The Mn⋯Mn distance is 7.94 Å. A Cl⋯H—O⋯H—O⋯H—N hydrogen‐bond chain is also observed, connecting the two parts of the complex.     

The crystal packing of 4,7‐dichloro‐ and 4,7‐dibromobenzo[c]furazan 1‐oxide

The molecular structures of 4,7‐di­chloro­benzo­[c]­fur­azan 1‐­oxide, C₆H₂Cl₂N₂O₂, (I), and 4,7‐di­bromo­benzo­[c]­fur­azan 1‐oxide, C₆H₂Br₂N₂O₂, (II), are normal. Compound (I) occurs in two polymorphic forms. One polymorph contains one mol­ecule in the asymmetric unit, organized into two‐dimensional sheets involving intermolecular N?Cl and O?Cl inter­actions. The second polymorph has three mol­ecules in the asymmetric unit, organized into two crystallographically different two‐dimensional sheets with similar interactions. Compound (II) is isomorphous with the second polymorph of (I). The three two‐dimensional sheets in the two polymorphs comprise a set of three two‐dimensional polymorphic arrangements.     

Hydrogen bonding in two salts of 3‐methylthio‐4‐(propargylthio)quinoline

In 3‐methyl­thio‐4‐(propargyl­thio)­quinolinium chloride monohydrate, C₁₃H₁₂NS₂⁺·Cl^?·H₂O, and 3‐methyl­thio‐4‐(propargyl­thio)­quinolinium tri­chloro­acetate, C₁₃H₁₂­NS₂⁺·­C₂Cl₃O₂^?, the terminal alkyne group forms C[triple‐bond]C—H?O hydrogen bonds of favourable geometry. The conformation of the flexible propargyl­thio group is different in the two structures.     

Racemic and chiral 1‐[N‐(chloro­acetyl)carbamoylamino]‐2,3‐dihydro‐1H‐inden‐2‐yl chloroacetate

In the racemic crystals of (1S,2R)‐ or (1R,2S)‐1‐[N‐(chloro­acetyl)­carbamoyl­amino]‐2,3‐di­hydro‐1H‐inden‐2‐yl chloro­acetate, C₁₄H₁₄Cl₂N₂O₄, (I), the enantiomeric mol­ecules form a dimeric structure via the N—H?O cyclic hydrogen bond of the carbamoyl moieties. In the chiral crystals of (—)‐(1S,2R)‐1‐[N‐(chloro­acetyl)­carbamoyl­amino]‐2,3‐di­hydro‐1H‐inden‐2‐yl chloro­acetate, C₁₄H₁₄Cl₂N₂O₄, (II), the N—­H?O intermolecular hydrogen bond forms a zigzag chain around the twofold screw axis. The melting points and calculated densities of (I) and (II) are 446 and 396 K, and 1.481 and 1.445 Mg m^?3, respectively.     

Two isomorphous complexes: di­chloro­[phthalocyaninato(2–)]­tin(IV) and di­chloro­[phthalocyaninato(2–)]­germanium(IV)

Isomorphous triclinic forms of di­chloro­[phthalocyaninato(2−)]­tin(IV), [Sn(C₃₂H₁₆N₈)Cl₂], and di­chloro­[phthalocyaninato(2−)]­ger­manium(IV), [Sn(C₃₂H₁₆N₈)Cl₂], and a monoclinic form of the latter have been obtained from the reaction of pure tin and germanium powder, respectively, with phthalo­nitrile under a stream of ICl vapour. All three crystal structures consist of centrosymmetric [SnPcCl₂] and [GePcCl₂] [Pc is phthalocyaninate(2−)] mol­ecules, which are separated but interacting. In the triclinic forms (Sn and Ge), the Pc macrocycles are not staggered but slipped, and in the monoclinic form (Ge), the mol­ecules are additionally inclined. In both cases, the central Sn or Ge atom is six‐coordinated by the four iso­indole N atoms of the Pc macrocyclic ligand and by two Cl atoms (located trans) into a tetragonal–bipyramidal structure. The arrangement of [SnPcCl₂] and [GePcCl₂] mol­ecules in the crystal structure is determined mainly by intermolecular C—H⃛Cl, π–π and van der Waals interactions.     

Hydro­gen‐bonding patterns in two structural isomers of 3,6‐bis(2‐chloro­phenyl)‐1,4‐di­hydro‐1,2,4,5‐tetrazine

Two structural isomers, 3,6‐bis(2‐chloro­phenyl)‐1,4‐di­hydro‐1,2,4,5‐tetrazine, (I), and 3,5‐bis(2‐chloro­phenyl)‐4‐amino‐1H‐1,2,4‐triazole, (II), both C₁₄H₁₀Cl₂N₄, form chain‐like structures in the solid state, stabilized by N—H⋯N and N—H⋯Cl hydrogen bonds. A contribution from weak interactions to the strong hydrogen‐bond network is observed in both structures. The secondary graph sets for intermolecular hydrogen bonds [(11) for (I) and (12) for (II)] indicate the similarity between the networks.     

3‐Germyl‐3,3‐di­methyl­propionic acid derivatives

The crystal structures of 3,3‐di­methyl‐3‐(tri­chloro­germyl)­propionic acid, [Ge(C₅H₉O₂)Cl₃], 3,3‐di­methyl‐3‐(tri­phenyl­germyl)­propionic acid, [Ge(C₆H₅)₃(C₅H₉O₂)], and 3,3‐di­methyl‐3‐(tri‐p‐toly­lgermyl)­propionic acid, [Ge(C₇H₇)₃(C₅H₉O₂)], have slightly distorted tetrahedral geometries about the Ge atoms. All the structures form dimers via strong O—H·O hydrogen bonds, resulting in eight‐membered rings that can be best described in terms of graph‐set notation (8).     

Chloro­(3,6,13,16‐tetraethyl‐2,7,12,17‐tetra­methyl­porphycenato‐κ4N)iron(III) chloro­form solvate

The X‐ray crystallographic analysis of the title complex, chloro­[3,10,13,20‐tetraethyl‐4,9,14,19‐tetra­methyl­penta­cyclo[16.2.1.1^2,5.1^8,11.1^12,15]­tetracosa‐2,4,6,8(23),9,12,14,16,18(21),19‐decaene]­iron(III) chloro­form solvate, [Fe(C₃₃H₃₇N₄)Cl]·CHCl₃, reveals a twisted macrocyclic framework with a slightly distorted rectangular pyramidal core, where the deviation of the central Fe^III atom from the least‐squares plane of the C₂₀N₄ core is 0.594 (1) Å. Some important bond distances are as follows: Fe—N 2.019 (3), 2.026 (3), 2.028 (3) and 2.034 (3) Å; Fe—Cl 2.232 (1) Å.     

3‐Chloro­propion­amide

The crystal structure of 3‐chloro­propion­amide, C₃H₆ClNO, (I), was determined in order to obtain coordinates for molecular‐orbital calculations. Intermolecular N—H?O and C—H?O hydrogen bonds link the mol­ecules into continuous two‐dimensional sheets parallel to the (100) plane. The bond distances are C—Cl 1.793 (3), C=O 1.233 (3) and C—N 1.320 (3) Å.     

9‐(Tri­chloro­acetyl­imino)­acridine monohydrate

The title compound, alternatively called N‐acridin‐9(10H)‐yl­idene‐2,2,2‐tri­chloro­acet­amide mono­hydrate, C₁₅H₉Cl₃N₂O·H₂O, crystallizes in space group P2₁/c with Z = 4. The acridine moieties are arranged in layers, tilted at an angle of 15.20 (4)° relative to the ac plane, while adjacent mol­ecules pack in a head‐to‐tail manner. Acridine and water mol­ecules form columns along the b axis held in place by a network of hydrogen bonds, which is the major factor stabilizing the lattice. The acridine mol­ecule exhibits structural features of both the amino and imino forms, which could be due to the presence of the strong electronegative tri­chloro­acetyl substituent at the exocyclic N atom.     

Triphenylphosphine oxide–3‐chlorobenzoic acid (1/1)

In the title compound, C₁₈H₁₅OP·C₇H₅ClO₂, the tri­phenyl­phosphine oxide molecule forms a single directed hydrogen bond with the 3‐chloro­benzoic acid molecule, with an O⃛O=P distance of 2.607 (2) Å. The C—Cl and C=O bonds adopt a cisoid conformation in the 3‐chloro­benzoic acid molecule.     

Dichlorobis(pyridine‐κN)bis(3,3,3‐trifluoropropyl‐κC1)tin(IV)

In the title compound, [Sn(C₃H₄F₃)₂Cl₂(C₅H₅N)₂], the Sn atom lies on an inversion centre and is octahedrally coordinated by two Cl atoms, two tri­fluoro­propyl groups and two N atoms in an all‐trans configuration. The electronegative tri­fluoro­propyl groups increase the electrophilic properties of the Sn atom, and the Sn—Cl and Sn—N bonds are shortened in comparison with those reported for analogous compounds.