rac-{[2-(Diphenyl­thio­phosphor­yl)ferrocen­yl]meth­yl}dimethyl­ammonium diphenyl­dithio­phosphinate

2-(Diphenyl­thio­phosphino)dimethyl­amino­methyl­ferrocene is a key inter­mediate in the synthesis of various ferrocenyl ligands. During one such synthesis, the title compound, [Fe(C₅H₅)(C₂₀H₂₂NPS)](C₁₂H₁₀PS₂), was isolated as a by-product. It is built up by association of (2-(diphenyl­phosphino)ferrocen­yl)meth­yl)dimethyl­ammonium cations and diphenyl­phosphino dithio­ate anions. N—H...S, C—H...S and C—H...π inter­actions link the anions and cations. Each anion–cation pair is linked two by two through C—H...π inter­actions, forming pseudo dimers.

9α-Hy­droxy-12-{[4-(4-meth­oxy­phen­yl)piperazin-1-yl]meth­yl}-4,8-dimethyl-3,14-dioxatricyclo­[9.3.0.0^2,4]tetra­dec-7-en-13-one

The title compound, C₂₆H₃₆N₂O₅, was synthesized from 9α-hy­droxy­parthenolide (9α-hy­droxy-4,8-dimethyl-12-methyl­ene-3,14-dioxatricyclo­[9.3.0.0^2,4]tetra­dec-7-en-13-one), wich was isolated from the chloro­form extract of the aerial parts of Anvillea radiata. The mol­ecule is built up from fused five- and ten-membered rings with the meth­oxy­phenyl­piperazine group as a substituent. The ten-membered ring adopts an approximate chair–chair conformation, while the piperazine ring displays a chair conformation and the five-membered ring a flattened envelope conformation; the C(H)—C—C(H) atoms representing the flap lie out of the mean plane through the remaining four atoms by 0.343 (3) Å. The dihedral angle between the mean planes of the ten-membered ring and the lactone ring is 18.12 (14)°. An intra­molecular O—H...N hydrogen bond occurs. The crystal structure features weak C—H...O inter­actions.

(R)-2-[(Dimethyl­amino)­meth­yl]-1,1′-bis­(diphenyl­phosphinothio­yl)ferrocene dichloromethane monsolvate

In the title compound, [Fe(C₂₀H₂₁NPS)(C₁₇H₁₄PS)]·CH₂Cl₂, both cyclo­penta­dienyl (Cp) rings constituting the ferrocene unit are substituted by a sulfur-protected diphenyl­phosphine. One of the Cp ligands is additionally substituted by a dimethyl­amino­methyl group causing the chirality of the mol­ecule. Surprisingly, although the synthetic procedure yielded the title compound as a racemic mixture, the reported crystal is enanti­omerically pure with the R absolute configuration. The dimethyl­amino group is exo with respect to the Cp ring. Both diphenyl­thio­phosphine groups are trans with respect to the centroid–Fe–centroid direction. Weak intra­molecular C—H...S and C—H...π inter­actions between symmetry-related mol­ecules are observed. The contribution of the disordered solvent was removed from the refinement using SQUEEZE in PLATON [Spek (2009). Acta Cryst. D65, 148–155].

catena-Poly[[(5,5,7,12,12,14-hexa­methyl-1,4,8,11-tetra­aza­cyclo­tetra­deca-1,7-diene)copper(II)]-μ-chlorido-[dichloro­cuprate(II)]-μ-chlorido]

In the title compound, [Cu₂Cl₄(C₁₆H₃₂N₄)]_n, the central Cu^II anion of the macrocyclic complex cation is weakly linked to two Cl atoms of the tetrachloridocuprate anion with Cu—Cl distances of 3.008 (3) and 3.220 (3) Å, respectively, forming a chain parallel to [10-1]. The geometry of the Cu–macrocyclic complex is distorted octa­hedral with the bridging Cl atoms occupying the axial position at an angle of 173.44 (7)° about the central Cu^II atom. The tetrachloridocuprate anion adopts a distorted tetra­hedral geometry. In the crystal, the chain is stabilized by intra- and inter­molecular N—H...Cl hydrogen bonds.

Chlorido(pyridine-κN)(5,10,15,20-tetra­phenyl­porphyrinato-κ⁴N)cobalt(III) chloro­form hemisolvate

In the title complex, [CoCl(C₄₄H₂₈N₄)(C₅H₅N)]·0.5CHCl₃ or [Co^III(TPP)Cl(py)]·0.5CHCl₃ (where TPP is the dianion of tetra­phenyl­porphyrin and py is pyridine), the average equatorial cobalt–pyrrole N atom bond length (Co—N_p) is 1.958 (7) Å and the axial Co—Cl and Co—N_py distances are 2.2339 (6) and 1.9898 (17) Å, respectively. The tetra­phenyl­porphyrinate dianion exhibits an important nonplanar conformation with major ruffling and saddling distortions. In the crystal, mol­ecules are linked via weak C—H...π inter­actions. In the difference Fourier map, a region of highly disordered electron density was estimated using the SQUEEZE routine [PLATON; Spek (2009), Acta Cryst. D65, 148–155] to be equivalent to one half-mol­ecule of CHCl₃ per mol­ecule of the complex.

(2,3,7,8,12,13,17,18-Octa­ethyl­porphyrinato-κ⁴N)cobalt(II)–2-nitro­benzaldehyde (1/2)

The asymmetric unit of the title compound, [Co(C₃₆H₄₄N₄)]·2C₇H₅NO₃, is composed of one half of the complex, arranged about an inversion center, and a complete 2-nitro­benzaldehyde (NBA) mol­ecule. The structure consists of columns that contain inter­leaved mol­ecules of NBA and [Co^II(OEP)] (OEP is 2,3,7,8,12,13,17,18-octa­ethyl­porphyrin), which are stacked along the a axis. The Co^II atom is involved in a π inter­action with the ring of the NBA mol­ecule with a centroid–metal distance of 3.508 (6) Å. There is an intra­molecular C—H...O hydrogen bond in the NBA mol­ecule.

(2.2.2-Cryptand)potassium bis­(cyanato-κN)(5,10,15,20-tetra­phenyl­por­phy­rin­ato-κ⁴N)cobaltate(III) chloro­benzene hemisolvate

In the title compound, [K(C₁₈H₃₆N₂O₆)][Co(NCO)₂(C₄₄H₂₈N₄)]·0.5C₆H₅Cl or [K(2,2,2-crypt)⁺][Co^III(NCO)₂(TPP)⁻]·0.5C₆H₅Cl, the Co^III ion is octa­hedrally coordin­ated by two axial N-bonded NCO⁻ anions and four pyrrole N atoms of the porphyrin. There is a major ruffling distortion of the porphyrin: the dihedral angles between trans pyrrole rings are 34.32 (14) and 34.72 (14)°. The potassium ion is coordinated by the six O atoms and two N atoms of the cryptand-222 mol­ecule and a weak K—O [3.407 (3) Å] bond to one of the cyanate O atoms also occurs. The packing also features weak C—H...O and C—H...π inter­actions. The contribution to the scattering of the disordered chloro­benzene solvent mol­ecules was removed with the SQUEEZE function in PLATON [Spek (2009). Acta Cryst. D65, 148–155].

Bis[4-(dimethyl­amino)­pyridinium] octa­aqua­chloridolanthanum(III) tetra­chloride trihydrate

The title organic–inorganic salt, (C₇H₁₁N₂)₂[LaCl(H₂O)₈]Cl₄·3H₂O, consists of two 4-(dimethyl­amino)­pyridinium and one [La(H₂O)₈Cl]²⁺ cations, four chloride anions and three solvent water mol­ecules. In the crystal, the various units are connected by N—H...Cl, O—H...Cl, O—H...O and N—H...O hydrogen bonds, forming a network of alternating organic and inorganic layers. The 4-(dimethyl­amino)­pyridinium cations stack along the c axis, while the inorganic layers lie parallel to the ac plane. The chloride anions are located between these entities, forming hydrogen bonds with the NH atom of the pyridinium ions and the water mol­ecules. There are also C—H...Cl hydrogen bonds present involving one of the 4-(dimethyl­amino)­pyridinium cations, resulting in the formation of a three-dimensional supra­molecular architecture.

Bis(5-amino-3-carb­oxy-1H-1,2,4-triazol-4-ium) dihydrogenphosphate nitrate 5-amino-1H-1,2,4-triazol-4-ium-3-carboxyl­ate

In the title compound, 2C₃H₅N₄O₂⁺·H₂PO₄^-·NO₃^-·C₃H₄N₄O₂, three independent 5-amino-1H-1,2,4-triazol-3-carb­oxy­lic acid moieties are observed. Two are in the form of cations, while the third is in the zwitterionic form. The triazole rings in the two cations are almost coplanar, making an angle of 4.11 (7)°. Layers parallel to the (20-1) plane, resulting from hydrogen bonding of the organic mol­ecules and the nitrate anions, are linked via H₂PO₄^- infinite zigzag chains running parallel to the c axis. The crystal studied was an inversion twin, with refined components of 0.33 (7) and 0.67 (7).

Tris[4-(dimethyl­amino)­pyridinium][(bis-μ-dichlorido)-deca­aqua­dichlorido­dineodymium(III)] penta­chloride dihydrate

The title compound, (C₇H₁₁N₂)₃[Nd₂Cl₄(H₂O)₁₀]Cl₅·2H₂O, consists of three 4-(dimethyl­amino)­pyridinium cations, one of which is disordered about an inversion center, one [Nd₂Cl₄(H₂O)₁₀]²⁺ dication possessing inversion symmetry, five chloride anions, one of which is disordered over two inversion centers, and two lattice water mol­ecules. The 4-(dimethyl­amino)­pyridinium cations are protonated at the pyridine N atoms and form N—H...Cl hydrogen bonds with Cl⁻ counter-ions. The dimethyl­amino groups (C/N/C) lie close to the plane of the pyridinium rings, making dihedral angles of 1.6 (6)° and 6.5 (3)°. In the crystal, the [Nd₂Cl₄(H₂O)₁₀]²⁺ dications are linked via O—H...O and O—H...Cl hydrogen bonds, forming sheets lying parallel to the bc plane. These sheets are linked via O—H...Cl hydrogen bonds, forming a three-dimensional network. The 4-(dimethyl­amino)­pyridinium cations are located in the cavities and linked to the framework by C—H...Cl interactions.

Bis[μ-(3-acetyl-2-hy­droxy-6-methyl-4H-pyran-4-one-κ³O:O′,O′′)]diaqua­tetra­kis­(pyridine-κN)dicopper(II) diperchlorate

In the centrosymmetric binuclear cation of the title compound, [Cu(C₈H₇O₄)(H₂O)(C₅H₅N)₂]₂(ClO₄)₂, the Cu^II atoms are bridged by a pair of two dehydro­acetate anions in a bis-/monodentate mode. The distorted octa­hedral N₂O₄ coordination sphere of the metal cation is completed by two pyridine N atoms and one O atom of a water mol­ecule. The complex cations and the perchlorate counter anions are arranged in layers parallel to (100). O—H...O hydrogen bonds between the coordinating water mol­ecules and the perchlorate anions constitute ribbons parallel to [10-1]. C—H...O hydrogen bonds are also observed.

4-(Dimethyl­amino)­pyridinium octa­aqua­erbium(III) tetra­chloride monohydrate

In the title compound, (C₇H₁₁N₂)[Er(H₂O)₈]Cl₄·H₂O, the asymmetric unit consists of one 4-(dimethyl­amino)­pyridinium and one octa­aqua­erbium cation balanced by four Cl⁻ anions, and one water mol­ecule. The 4-(dimethyl­amino)­pyridinium cation is protonated at the pyridine N atom. The dimethyl­amino group (C/N/C) lies close to the plane of the pyridinium ring, making a dihedral angle of 4.5 (3)°. In the crystal, the [Er(H₂O)₈]³⁺ cations are linked via O—H...O and O—H...Cl hydrogen bonds, forming two-dimensional networks propagating in the ab plane. These networks are linked via O—H...O and O—H...Cl hydrogen bonds, forming a three-dimensional network. The 4-(dimethyl­amino)­pyridinium cations are located in the cavities and are linked to the framework via N—H...Cl, C—H...O and C—H...Cl hydrogen bonds.

5,5,7,12,14,14-Hexamethyl-1,8-diaza-4,11-diazo­niacyclo­tetra­deca-4,11-diene dichloride trihydrate

In the title compound, C₁₆H₃₄N₄²⁺·2Cl⁻·3H₂O, the two protonated N atoms in the macrocyclic ring of the dication are located at diagonally opposite positions. There are two intramolecular N—H...N hydrogen bonds in the cation. The crystal structure features O—H...Cl, O—H...O, C—H...Cl and N—H...Cl hydrogen bonds.

rac-{[2-(Diphenyl­thio­phosphan­yl)ferrocen­yl]meth­yl}trimethyl­ammonium iodide chloro­form monosolvate

The title compound, [Fe(C₅H₅)(C₂₁H₂₄NPS)]I·CHCl₃, is built up from a (ferrocenylmeth­yl)trimethyl­ammonium cation, a iodine anion and a chloro­form solvent mol­ecule, all residing in general positions. The N atom of the ammonium group is displaced by 1.182 (2) Å from the plane of the substituted cyclo­penta­dienyl (Cp) ring towards the Fe atom, whereas the C atom attached to the same Cp ring is slightly below this plane by -0.128 (2) Å. These deviations might result from weak agostic interactions between the two H atoms of the CH₂ group and the Fe atom.

2-Amino-3-carb­oxy­pyridinium chloride hemihydrate

The asymmetric unit of the title compound, C₆H₇N₂O₂⁺·Cl⁻·0.5H₂O, consists of two protonated 2-amino-3-carb­oxy­pyridine cations, two chloride anions and one mol­ecule of water. The crystal packing can be described as alternating layers of cations and anions parallel to (110), which are linked together by O_w—H...Cl inter­actions. In the crystal, four types of classical hydrogen bonds are observed, viz. cation–anion (O—H...Cl and N—H...Cl), cation–cation (N—H...O), cation–water (N—H...O_w) and water–anion (O_w—H...Cl), resulting in the formation of an infinite three-dimensional network.

Di-μ-azido-bis­(μ-1,4,7,10,13,16-hexa­oxacyclo­octa­deca­ne)bis­(5,10,15,20-tetra­phenyl­porphyrinato)dicadmium­disodium

The asymmetric unit of the title compound, [Cd₂Na₂(N₃)₂(C₄₄H₂₈N₄)₂(C₁₂H₂₄O₆)₂], consists of one half of the dimeric complex; the tetra­nuclear mol­ecule lies about an inversion centre. The Cd^II atom is coordinated by the four pyrrole N atoms of the 5,10,15,20-tetra­phenyl­porphyrinate ligand and one N atom of the axial azide ligand in a square-pyramidal geometry. The azide group is also linked to the Na^I atom, which is surrounded by one 18-crown-6 molecule and additionally bonded to a second 18-crown-6 molecule trans to the azide group. The porphyrin core exhibits a major doming distortion (∼40%) and the crystal structure is stabilized by weak C—H...π inter­actions. The mol­ecular structure features weak intra­molecular hydrogen bonds: two O—H...O inter­actions within the 18-crown-6 mol­ecule and one C—H(18-crown-6)...N(azido) contact.

(±)-Bis(1-carb­oxy-2-phenyl­ethanaminium) hexa­fluoro­silicate(VI)

The asymmetric unit of the title fluoro­silicate salt, 2C₉H₁₂NO₂⁺·SiF₆^2-, consists of a phenylalaninium cation and half of a fluorosilicate anion, the Si atom being located on an inversion center. In the crystal, all of the F atoms act as hydrogen-bond acceptors and link the cations through different graph-set motifs, forming layers developing parallel to (100).

1-Isopropyl-4,7-dimethyl-2,8-dinitro­naphthalene

The title compound, C₁₅H₁₆N₂O₄, was synthesized from a mixture of α-himachalene (2-methyl­ene-6,6,9-trimethyl­bicyclo­[5.4.O^1,7]undec-8-ene) and β-himachalene (2,6,6,9-tetra­methyl­bicyclo­[5.4.0^1,7]undeca-1,8-diene) which were isolated from an oil of the Atlas cedar (Cedrus atlantica). The asymmetric unit contains two independent mol­ecules. In each of the two mol­ecules, two O atoms of one nitro group are disordered over two sets of sites with site-occupancy factors of 0.636 (5):0.364 (5) and 0.832 (5):0.168 (5). The crystal structure features weak C—H...O hydrogen bonds.

Methyl 2-(4a,8-Dimethyl-7-oxodeca­hydro­naphthalen-2-yl)acrylate

The title compound, C₁₆H₂₄O₃, was isolated from the aerial part of Inula Viscosa­ (L) Aiton [or Dittrichia Viscosa­ (L) Greuter]. The mol­ecule contains two fused (trans) six-membered rings which both exibit a chair conformation. In the crystal, mol­ecules are linked into chains along [100] by weak C—H...O hydrogen bonds involving the methyl and carbonyl groups.

1-Chloro­methyl­sulfinyl-2-nitro­benzene

In the title compound, C₇H₆ClNO₃S, the nitro group forms a dihedral angle of 2.7 (4)° with the benzene ring. The bond-angle sum at the S atom is 303.7°. In the crystal, mol­ecules are linked by weak C—H...O hydrogen bonds, forming layers lying parallel to (-101).

(1S,3R,8R)-2,2-Dibromo-10-bromo­methyl-3,7,7-trimethyl­tricyclo­[6.4.0.0^1,3]dodec-9-ene

The title compound, C₁₆H₂₃Br₃, was synthesized from β-himachalene (3,5,5,9-tetra­methyl-2,4a,5,6,7,8-hexa­hydro-1H-benzocyclo­heptene), which was isolated from the essential oil of the Atlas cedar (Cedrus Atlantica). The mol­ecule is built up from fused six- and seven-membered rings and an additional three-membered ring from the reaction of himachalene with dibromo­carbene. The six-membered ring has an envelope conformation (the flap atom being the C atom shared with the three-membered ring, whereas the seven-membered ring displays a screw boat conformation; the dihedral angle between the rings (defined by the near coplanar atoms) is 56.5 (2)°.