Di­propyl 3,6‐di­phenyl‐1,2‐di­hydro‐1,2,4,5‐tetrazine‐1,2‐di­carboxyl­ate

The title compound, C₂₂H₂₄N₄O₄, was prepared from propyl chloro­formate and 3,6‐di­phenyl‐1,2‐di­hydro‐s‐tetrazine. This reaction yields the title compound rather than di­propyl 3,6‐di­phenyl‐1,4‐di­hydro‐s‐tetrazine‐1,4‐di­carboxyl­ate. The 2,3‐di­aza­buta­diene group in the central six‐membered ring is not planar; the C=N double‐bond length is 1.285 (2) Å, and the average N—N single‐bond length is 1.401 (3) Å, indicating a lack of conjugation. The ring has a twist conformation, in which adjacent N atoms lie 0.3268 (17) Å from the plane of the ring. The mol­ecule has twofold crystallographic symmetry.     

2,4‐Di­nitro­phenyl­hydrazones of 2,4‐di­hydroxy­benz­aldehyde, 2,4‐di­hydroxy­aceto­phenone and 2,4‐di­hydroxy­benzo­phenone

In 2,4‐di­hydroxy­benz­aldehyde 2,4‐di­nitro­phenyl­hydrazone N,N‐di­methyl­form­amide solvate {or 4‐[(2,4‐di­nitro­phenyl)­hydrazono­methyl]­benzene‐1,3‐diol N,N‐di­methyl­form­amide solvate}, C₁₃H₁₀N₄O₆·C₃H₇NO, (X), 2,4‐di­hydroxy­aceto­phenone 2,4‐di­nitro­phenyl­hydrazone N,N‐di­methyl­form­am­ide solvate (or 4‐{1‐[(2,4‐di­nitro­phenyl)hydrazono]ethyl}benzene‐1,3‐diol N,N‐di­methyl­form­amide solvate), C₁₄H₁₂N₄O₆·C₃H₇NO, (XI), and 2,4‐di­hydroxy­benzo­phenone 2,4‐di­nitro­phenyl­hydrazone N,N‐di­methyl­acet­amide solvate (or 4‐­{[(2,4‐di­nitro­phenyl)hydrazono]phenyl­methyl}benzene‐1,3‐diol N,N‐di­methyl­acet­amide solvate), C₁₉H₁₄N₄O₆·C₄H₉NO, (XII), the molecules all lack a center of symmetry, crystallize in centrosymmetric space groups and have been observed to exhibit non‐linear optical activity. In each case, the hydrazone skeleton is fairly planar, facilitated by the presence of two intramolecular hydrogen bonds and some partial N—N double‐bond character. Each molecule is hydrogen bonded to one solvent mol­ecule.     

NiII and ZnII complexes of the hexadentate macrocyclic ligand cis‐6,13‐di­methyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane‐6,13‐di­amine

The title pendent‐arm macrocyclic hexa­amine ligand binds stereospecifically in a hexadentate manner, and we report here its isomorphous Ni^II and Zn^II complexes (both as perchlorate salts), namely (cis‐6,13‐di­methyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane‐6,13‐di­amine‐κ⁶N)­nickel(II) di­per­chlorate, [Ni(C₁₂H₃₀N₆)]­­(ClO₄)₂, and (cis‐6,13‐di­methyl‐1,4,8,11‐tetraaza‐cyclo­tetra­decane‐6,13‐di­amine‐κ⁶N)­zinc(II) di­per­chlorate, [Zn(C₁₂H₃₀N₆)]­(ClO₄)₂. Distortion of the N—M—N valence angles from their ideal octahedral values becomes more pronounced with increasing metal‐ion size and the present results are compared with other structures of this ligand.     

1‐Chloro‐3,6‐di­methoxy‐2,5‐di­methyl­benzene and 1‐chloro‐3,6‐di­methoxy‐2,4‐di­methyl­benzene

The title compounds, 1‐chloro‐3,6‐di­methoxy‐2,5‐di­methyl­benzene, (IIIa), and 1‐­chloro‐3,6‐di­methoxy‐2,4‐di­methyl­benzene, (IIIb), both C₁₀H₁₃ClO₂, were obtained from 2,5‐ and 2,6‐di­methyl‐1,4‐benzo­quinone, respectively, and are intermediates in the synthesis of ammonium quinone derivatives. The isomers have different substituents around the methoxy groups and crystallize in different space groups. In both mol­ecules, the methoxy groups each have different orientations with respect to the benzene ring. In both cases, one methoxy group lies in the plane of the ring and can participate in conjugation with the aromatic system, while the second is almost perpendicular to the plane of the aromatic ring. The C—O—C bond angles around these substituents are also different: 117.5 (4) and 118.2 (3)° in (IIIa) and (IIIb), respectively, when the methoxy groups lie in the plane of the ring, and 114.7 (3) and 113.6 (3)° in (IIIa) and (IIIb), respectively, when they are out of the plane of the ring.     

Three methoxy‐substituted diethyl 4‐­phenyl‐2,6‐di­methyl‐1,4‐di­hydro­pyridine‐3,5‐di­carboxyl­ate compounds

Diethyl 4‐(2,5‐di­methoxy­phenyl)‐2,6‐di­methyl‐1,4‐di­hydro­pyridine‐3,5‐di­carboxyl­ate, C₂₁H₂₇NO₆, (I), diethyl 4‐(3,4‐di­methoxy­phenyl)‐2,6‐di­methyl‐1,4‐di­hydro­pyridine‐3,5‐di­carboxyl­ate, C₂₁H₂₇NO₆, (II), and diethyl 2,6‐di­methyl‐4‐(3,4,5‐tri­methoxy­phenyl)‐1,4‐di­hydro­pyridine‐3,5‐di­carboxyl­ate, C₂₂H₂₉NO₇, (III), crystallize with hydrogen‐bonding networks involving the H atom bonded to the N atom of the 1,4‐di­hydro­pyridine ring and carbonyl O atoms in (I) and (II). Unusually, (III) shows O atoms of methoxy groups serving as hydrogen‐bond acceptors.     

Diphenyl(2‐thioxo‐1,3‐dithiole‐4,5‐di­thiolato‐S,S′)plumbane at 295 K and diphenyl(2‐thioxo‐1,3‐dithiole‐4,5‐di­thiolato‐S,S′)stannane at 150 K

Molecules of di­phenyl(2‐thio­xo‐1,3‐di­thiole‐4,5‐di­thiol­ato‐S,S′)­plumbane, [Pb(C₃S₅)(C₆H₅)₂], are linked into sheets via two intermolecular Pb?S_thione interactions of 3.322 (4) and 3.827 (4) Å; the Pb centre has a distorted octahedral geometry. In contrast, mol­ecules of ­di­phenyl(2‐thio­xo‐1,3‐di­thiole‐4,5‐di­thiol­ato‐S,S′)­stannane, [Sn(C₃S₅)(C₆H₅)₂], are linked into chains via a single intermolecular Sn—S_thione interaction of 2.8174 (9) Å; the Sn centre has a distorted trigonal‐bipy­ramidal geometry.     

Charge‐transfer complexes of 4‐(di­methyl­amino)­pyridine with 2,4‐, 3,4‐ and 3,5‐di­nitro­benzoic acid

In the three title crystal structures 4‐(di­methyl­amino)­pyridinium 2,4‐di­nitro­benzoate, (I), 4‐(di­methyl­amino)­pyri­dinium 3,4‐di­nitro­benzo­ate, (II), and 4‐(di­methyl­amino)pyri­din­ium 3,5‐di­nitro­benzo­ate, (III), all C₇H₁₁N₂⁺·C₇H₃N₂O₆^?, the ions are connected by an N—H?O hydrogen bond. Dihedral angles between the pyridine and phenyl rings are 69.9 (1), 26.7 (1) and 56.2 (1)° in (I), (II) and (III), respectively. Donor–acceptor π–π stacking is observed in (II) and (III), but not in (I).     

Hydro­gen‐bonded adducts of ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol): monomeric and polymeric adducts with 1,2‐bis(4‐pyridyl)­ethene and 1,6‐di­amino­hexane

In the adduct ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol)–1,2‐bis(4‐pyridyl)­ethene (1/1), [Fe(C₁₈H₁₅O)₂]·C₁₂H₁₀N₂, there is an intramolecular O—H?O hydrogen bond in the ferro­cene­diol component and a single O—H?N hydrogen bond linking the diol to the di­amine, which is disordered over two sets of sites, so forming a finite monomeric adduct. In the adduct ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol)–1,6‐di­amino­hexane (2/1), 2[Fe(C₁₈H₁₅O)₂]·C₆H₁₆N₂, the amine lies across a centre of inversion in space group P. There is an intramolecular O—H?O hydrogen bond in the ferrocenediol, and the molecular components are linked by O—H?N and N—H?O hydrogen bonds, one of each type, into a C(13)[R(12)] chain of rings.     

2,3,6,7‐Tetra­hydroxy‐9,10‐di­methyl‐9,10‐di­hydro‐9,10‐ethano­anthracene bis(1,4‐dioxane) solvate

2,3,6,7‐Tetra­hydroxy‐9,10‐di­methyl‐9,10‐di­hydro‐9,10‐ethano­anthracene crystallizes with 1,4‐dioxane to give a bis‐solvate, C₁₈H₁₈O₄·2C₄H₈O₂. The bis­(catechol) mol­ecule is located on a twofold axis and the two aromatic rings form a dihedral angle of 130.61 (4)°. Hydro­gen bonds are formed between the hydroxyl groups and either a neighbouring bis­(catechol) mol­ecule or the ether‐O atom of a dioxane mol­ecule.     

N,N′‐Bis(2‐methoxy­benzyl­idene) adducts of ethane‐1,2‐di­amine,propane‐1,3‐di­amine and butane‐1,4‐di­amine

We have isolated and crystallographically characterized the three homologous compounds N,N′‐bis(2‐methoxy­benzyl­idene)­ethane‐1,2‐di­amine (MeSalen), C₁₈H₂₀N₂O₂, N,N′‐bis(2‐methoxy­benzyl­idene)­propane‐1,3‐di­amine (MeSalpr), C₁₉H₂₂N₂O₂, and N,N′‐bis(2‐methoxy­benzyl­idene)­butane‐1,4‐di­amine (MeSalbu), C₂₀H₂₄N₂O₂. In contrast with MeSalpr, the mol­ecules of MeSalen and MeSalbu, which have an even number of methyl­ene units, have crystallographic symmetry. Comparing these methoxy‐substituted species with their hydroxy equivalents shows that the aryl rings rotate upon removal of the O—H⋯N hydrogen bonds. The packing of MeSalen and MeSalpr is controlled by C—H⋯π interactions, whereas that of MeSalbu has only van der Waals contacts.     

(±)‐6‐Benzyl‐3,3‐di­methyl­morpholine‐2,5‐dione and its 5‐mono­thio and 2,5‐di­thio derivatives

The morpholine ring of the title dione, C₁₃H₁₅NO₃, shows a boat conformation that is distorted towards a twist‐boat, with the boat ends being the two Csp³ atoms of the ring. The benzyl substituent is in the favoured `exo' position. In the mono­thione derivative, (±)‐6‐benzyl‐3,3‐di­methyl‐5‐thioxo­morpholin‐2‐one, C<sub>13</sub>H<sub>15</sub>NO<sub>2</sub>S, this ring has a much flatter conformation that is midway between a boat and an envelope, with the di­methyl end being almost planar. The orientation of the benzyl group is `endo'. The di­thione derivative, (±)‐6‐benzyl‐3,3‐di­methyl­morpholine‐2,5‐di­thione, C₁₃H₁₅N­OS₂, has two symmetry‐independent mol­ecules, which show different puckering of the morpholine ring. One mol­ecule has a flattened envelope conformation distorted towards a screw‐boat, while the conformation in the other mol­ecule is similar to that in the mono­thione derivative. Intermolecular hydrogen bonds link the mol­ecules in the three compounds, respectively, into centrosymmetric dimers, infinite chains, and dimers made up of one of each of the symmetry‐independent mol­ecules.     

4,4′‐(Azino­di­methyl­ene)­dipyridinium chloranilate di­chloro­methane disolvate

The di­chloro­methane disolvate of 4,4′‐(azino­di­methyl­ene)­dipyridinium chloranilate, C₁₂H₁₂N₄²⁺·C₆Cl₂O₄²⁻·2CH₂Cl₂, con­sists of one‐dimensional hydrogen‐bonded molecular tapes that propagate along the [10] direction. Both cations and anions lie across centres of inversion. The molecular tapes are planar but do not stack in the expected segregated manner, instead having chloranilate anions sandwiched between azine groups.     

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).     

[Bis­(di­phenyl­phosphino)­alkane](pentane‐2,4‐di­thionato) complexes of nickel(II)

The structures of a series of four‐coordinate nickel(II) complexes of the form [Ni(sacsac)L] PF₆ (sacsac = pentane‐2,4‐di­thione anion; L = (Ph₂P)₂(CH₂)_n, n = 1,2,3) have beendetermined. These are [bis­(di­phenyl­phosphino)­methane](pentane‐2,4‐di­thionato‐S,S′)­nickel(II) hexa­fluoro­phosphate, [Ni(C₂₅H₂₂P₂)(C₅H₇S₂)]PF₆, [1,2‐bis­(di­phenylphosphino)­ethane](pentane‐2,4‐di­thionato–S,S′)­nickel(II) hexa­fluoro­phosphate, [Ni(C₂₆H₂₄P₂)(C₅H₇S₂)]PF₆, and [1,3‐bis­(di­phenyl­phosphino)­propane](pentane‐2,4‐di­thionato‐S,S′)­nickel(II) hexa­fluoro­phosphate, [Ni(C₂₇H₂₆P₂)(C₅H₇S₂)]PF₆. All have a distorted square‐planar arrangement about Ni with angles around Ni varying with the length of the hydro­carbon chain.     

Linear chains in polymeric di­cyclo­hexyl­ammonium tri­butyl­(4‐oxo‐4H‐pyran‐2,6‐di­carboxyl­ato)­stannate and methyl­phenyl­ammonium tri­butyl(pyridine‐2,6‐di­carboxyl­ato)­stannate containing trigonal bipyramidal tin

catena‐Poly­[di­cyclo­hexyl­ammonium [tri­butyl­tin‐μ‐(4‐oxo‐4H‐pyran‐2,6‐di­carboxyl­ato‐O²:O⁶)]], (C₁₂­H₂₄N)­[Sn(C₇­H₂­O₆)(C₄H₉)₃], consists of 4‐oxo‐4H‐pyran‐2,6‐di­carboxyl­ato groups that axially link adjacent tri­butyl­tin units into a linear polyanionic chain. The ammonium counter‐ions surround the chain, and each cation forms a pair of hydrogen bonds to the double‐bond carbonyl O atoms of the same dianionic group. The chain propagates in a zigzag manner along the c axis of the monoclinic cell. In catena‐poly­[methyl­(phenyl)­ammonium [tri­butyl­tin‐μ‐(pyridine‐2,6‐di­carboxyl­ato‐O²:O⁶)]], (C₇H₁₀N)­[Sn(C₇H₃NO₄)­(C₄H₉)₃], the pyridine‐2,6‐di­carboxyl­ato groups also link the tri­butyl­tin groups into a chain, but the hydrogen‐bonded chain propagates linearly on the ac face of the monoclinic cell.     

catena‐Poly­[[trans‐bis­(ethane‐1,2‐di­amine‐κ2N,N′)copper(II)]‐μ‐di­thion­ato‐κ2O:O′] and trans‐di­aqua­bis­(propane‐1,3‐di­amine‐κ2N,N′)copper(II) di­thionate

In title an­hydro­us catena‐poly­[[trans‐bis­(ethane‐1,2‐di­amine‐κ²N,N′)copper(II)]‐μ‐di­thionato‐κ²O:O′], [Cu(S₂O₆)(C₂H₈N₂)₂]_n or [{H₂N(CH₂)₂NH₂}₂Cu(O·O₂SSO₂·O)]_∞, successive Cu atoms are bridged by a single doubly charged di­thionate group, forming a one‐dimensional polymer with inversion centres at the metal atoms and the mid‐point of the S—S bond [Cu—O = 2.5744 (15) Å]. In title (hydrated) trans‐di­aqua­bis­(propane‐1,3‐di­amine‐κ²N,N′)copper(II) di­thionate, [Cu(C₃H₁₀N₂)₂(H₂O)₂](S₂O₆) or [{H₂N(CH₂)₃NH₂}₂Cu(OH₂)₂](S₂O₆), both ions have imposed 2/m symmetry. The `axial' anion components are displaced by a pair of water ligands [Cu—O = 2.439 (3) Å], the shorter Cu—O distance being compensated by the lengthened Cu—N distance [2.0443 (18), cf. 2.0100 (13) and 2.0122 (16) Å].     

Bis(1,3‐di­phenyl­propane‐1,3‐dionato‐O,O′)(di­phenyl sulfoxide‐O)dioxouranium(VI)

In the title complex, [UO₂(dbm)₂(PhSOPh)] or [UO₂(C₁₅H₁₁O₂)(C₁₂H₁₀OS)], where dbm is 1,3‐di­phenyl­propane‐1,3‐dionate, the U atom is surrounded by seven O atoms to give a distorted pentagonal bipyramidal geometry. The U—O_uranyl and U—O_dbm distances (dbm is 1,3‐di­phenyl­propane‐1,3‐dionate) are in the ranges 1.760 (6)–1.776 (5) and 2.308 (4)–2.417 (4) Å, respectively, while the U—O_sulfoxide distance is 2.427 (4) Å.     

4,5‐Bis­(ferrocenyl­methyl­thio)‐1,3‐di­thiol‐2‐one

In the compound 4,5‐bis­(ferrocenyl­methyl­thio)‐1,3‐di­thiol‐2‐one, [Fe₂(C₅H₅)₂(C₁₅H₁₂OS₄)], the values of the geometric parameters of the ferrocene and 1,3‐di­thiol‐2‐one (dmio) moieties are within normal ranges. The dmio group is essentially planar. There are no short S?S contacts.     

cis‐[1,4‐Bis(di­phenyl­phosphino)­butane](μ‐tetra­thio­tungstato)­palladium(II) N,N′‐di­methyl­form­amide hemisolvate hemihydrate

In the title compound, [1,4‐bis(di­phenyl­phosphino)­butane‐2κ²P,P′]­di‐μ‐thio‐1:2κ⁴S‐di­thio‐1κ²S‐palladium(II)­tung­sten(VI) N,N′‐di­methyl­form­amide hemisolvate hemihydrate, [PdWS₄­(C₂₈H₂₈P₂)]·0.5C₃H₇NO·0.5H₂O, the Pd atom is coordinated by two S atoms from the distorted‐tetrahedral [WS₄]²⁻ anion and two P atoms from the dppb mol­ecule [dppb is 1,4‐bis(di­phenyl­phos­phino)­butane] in an approximately square‐planar configuration. A puckered seven‐membered ring is formed by the Pd atom and the dppb ligand.     

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.