Mechanochemical synthesis and crystal structure of a 1:2 co-crystal of 1,3,6,8-tetra-aza-tri-cyclo[188.8.131.52,8]undecane (TATU) and 4-chloro-3,5-dimethyl-phenol.
ABSTRACT: Solvent-free treatment of 1,3,6,8-tetra-aza-tri-cyclo-[184.108.40.206,8]undecano (TATU) with 4-chloro-3,5-di-methyl-phenol led to the formation of the title co-crystal, C7H14N4·2C8H9ClO. The asymmetric unit contains one aminal cage mol-ecule and two phenol mol-ecules linked via two O-H?N hydrogen bonds. In the aminal cage, the N-CH2-CH2-N unit is slightly distorted from a syn periplanar geometry. Aromatic ?-? stacking between the benzene rings from two different neighbouring phenol mol-ecules [centroid-centroid distance = 4.0570?(11)?Å] consolidates the crystal packing.
Project description:In the title compound, C7H14N4·2C6H5ClO, which crystallized with two crystallographically independent 4-chloro-phenol mol-ecules and one 1,3,6,8-tetra-aza-tri-cyclo-[220.127.116.11,8]undecane (TATU) mol-ecule in the asymmetric unit, the independent components are linked by two O-H?N hydrogen bonds. The hydrogen-bond acceptor sites are two non-equivalent N atoms from the aminal cage structure, and the tricyclic system distorts by changing the C-N bond lengths. In the crystal, these hydrogen-bonded aggregates are linked into chains along the c axis by C-H?N hydrogen bonds. The crystal structure also features C-H?? contacts.
Project description:In the crystal of the title co-crystalline adduct, C8H16N4·C8H9ClO, (I), prepared by solid-state reaction, the mol-ecules are linked by inter-molecular O-H?N hydrogen bonds, forming a D motif. The aza-adamantane structure in (I) is slightly distorted, with N-CH2-CH2-N torsion angles of 10.4?(3) and -9.0?(3)°. These values differ slightly from the corresponding torsion angles in the free aminal cage (0.0°) and in related co-crystalline adducts, which are not far from a planar geometry and consistent with a D 2d mol-ecular symmetry in the tetra-aza-tri-cyclo structure. The structures also differ in that there is a slight elongation of the N-C bond lengths about the N atom that accepts the hydrogen bond in (I) compared with the other N-C bond lengths. In the crystal, the two mol-ecules are not only linked by a classical O-H?N hydrogen bond but are further connected by weak C-H?? inter-actions, forming a two-dimensional supra-molecular network parallel to the bc plane.
Project description:The structure of the 1:2 co-crystalline adduct C8H16N4·2C6H5BrO, (I), from the solid-state reaction of 1,3,6,8-tetra-aza-tri-cyclo-[18.104.22.168(3,8)]dodecane (TATD) and 4-bromo-phenol, has been determined. The asymmetric unit of the title co-crystalline adduct comprises a half mol-ecule of aminal cage polyamine plus a 4-bromo-phenol mol-ecule. A twofold rotation axis generates the other half of the adduct. The primary inter-species association in the title compound is through two inter-molecular O-H?N hydrogen bonds. In the crystal, the adducts are linked by weak non-conventional C-H?O and C-H?Br hydrogen bonds, giving a two-dimensional supra-molecular structure parallel to the bc plane.
Project description:The asymmetric unit of the title co-crystalline adduct, 1,3,6,8-tetra-aza-tri-cyclo[22.214.171.124,8]dodecane (TATD)-4-iodo-phenol (1/2), C8H16N4·2C6H5IO, comprises a half mol-ecule of the aminal cage polyamine plus a 4-iodo-phenol mol-ecule. A twofold rotation axis generates the other half of the adduct. The components are linked by two inter-molecular O-H?N hydrogen bonds. The adducts are further linked into a three-dimensional framework structure by a combination of N?I halogen bonds and weak non-conventional C-H?O and C-H?I hydrogen bonds.
Project description:In the title ternary co-crystalline adduct, C7H14N4·2C6H5NO3, mol-ecules are linked by two inter-molecular O-H?N hydrogen bonds, forming a tricomponent aggregates in the asymmetric unit. The hydrogen-bond formation to one of the N atoms is enough to induce structural stereoelectronic effects in the normal donor?acceptor direction. In the title adduct, the two independent nitro-phenol mol-ecules are essentially planar, with maximum deviations of 0.0157?(13) and 0.0039?(13)?Å. The dihedral angles between the planes of the nitro group and the attached benzene rings are 4.04?(17) and 5.79?(17)°. In the crystal, aggregates are connected by C-H?O hydrogen bonds, forming a supra-molecular dimer enclosing an R 6 (6)(32) ring motif. Additional C-H?O inter-molecular hydrogen-bonding inter-actions form a second supra-molecular inversion dimer with an R 2 (2)(10) motif. These units are linked via C-H?O and C-H?N hydrogen bonds, forming a three-dimensional network.
Project description:In the title compound, C13H16N2O2S, the pyrrolidine ring has a twisted conformation on the central -CH2-CH2- bond. Its mean plane is inclined to the 4-meth-oxy-benzoyl ring by 72.79?(15)°. In the crystal, mol-ecules are linked by N-H?O and C-H?O hydrogen bonds to the same O-atom acceptor, forming chains along . The chains are linked via slipped parallel ?-? inter-actions [inter-centroid distance = 3.7578?(13)?Å], forming undulating slabs parallel to (100).
Project description:The crystal structure of the title compound, C7H4BrNO, has been determined, revealing a partial mol-ecular packing disorder such that a 180° rotation of the mol-ecule about the phenol C-O bond results in disorder of the bromine and nitrile groups. The disorder has been parameterized as a disorder of only the bromine and nitrile substituents on a unique phenol ring. An intra-molecular O-H?Br contact occurs. In the crystal, O-H?Br/O-H?Nnitrile hydrogen bonding is present between the disordered bromine and nitrile substituents and the phenol group, forming a spiral chain about a twofold screw axis extending parallel to the b-axis direction. Within this spiral chain, the mol-ecules also inter-act, forming offset face-to-face ?-stacking inter-actions with plane-to-centroid distance of 3.487?(1)?Å.
Project description:The asymmetric unit of the title compound, C3H6N6·2C6H5NO3, contains one melamine and two 3-nitro-phenol mol-ecules. The mean planes of the 3-nitro-phenol mol-ecules are almost orthogonal to the plane of melamine, making dihedral angles of 82.77?(4) and 88.36?(5)°. In the crystal, mol-ecules are linked via O-H?N, N-H?N and N-H?O hydrogen bonds, forming a three-dimensional network. The crystal also features weak C-H?? and ?-? inter-actions [centroid-centroid distance = 3.9823?(9)?Å].
Project description:In the title compound, C12H8BrN3O, the 4-bromo-phenol ring is coplanar with the planar imidazo[4,5-b]pyridine moiety (r.m.s deviation = 0.015?Å), making a dihedral angle of 1.8?(2)°. There is an intra-molecular O-H?N hydrogen bond forming an S(6) ring motif. In the crystal, mol-ecules are linked via N-H?N and O-H?Br hydrogen bonds, forming undulating sheets parallel to (10-2). The sheets are linked by ?-? inter-actions [inter-centroid distance = 3.7680?(17)?Å], involving inversion-related mol-ecules, forming a three-dimensional structure.
Project description:The asymmetric unit of the title compound, C12H10N2, which may serve as a model for mitosenes, contains two independent mol-ecules. The conformation of the five-membered rings in both molecules is envelope, with the central CH2-CH2-CH2 C atom at the flap in each case. In the crystal, they inter-act by a combination of weak C-H?N and ?-? inter-actions [centroid-centroid distances = 3.616?(1) and 3.499?(1)?Å] and C-H?? contacts.