Exploring nonlinear optical properties in a hybrid dihydrogen phosphate system: an experimental and theoretical approach.

CONTEXT: The controlled slow evaporation process conducted at room temperature has produced a novel hybrid material denoted as (2-hydroxyethyl) trimethylammonium dihydrogen phosphate [2-HDETDHP] (C5H14NO+, H2PO4-), synthesized through the solution growth method. X-ray crystallography analysis reveals a triclinic structure with a filling rate of P and a Z value of 2. This hybrid material displays noteworthy absorption characteristics in the middle and far ultraviolet regions. UV-visible spectroscopy further establishes its transparency in the visible and near-visible ultraviolet domains. FT-IR spectroscopy examines various vibration modes, elucidating their relationships with the functional groups within the structure. Two- and three-dimensional fingerprint maps, coupled with three-dimensional crystal structures through Hirshfeld Surface Analysis, unveil the dominance of O•••H and H•••H interactions in the structure, comprising 49.40% and 50.40%, respectively. Fingerprint plots derived from the Hirshfeld surface assess the percentages of hydrogen bonding interactions, with 80.6% attributed to a fragment patch. The experiment of antimicrobial efficacy of a synthesized product, conducted in triplicate, demonstrated the synthesized product's potential antimicrobial activity. METHODS: Hirshfeld surfaces are employed to investigate intermolecular hydrogen bonding, specifically within single phosphate groups. The molecular structure of 2-HDETDHP was refined using single-crystal X-ray analysis, while its optical characteristics were examined through UV-visible spectroscopy. FT-IR spectroscopy is employed for the assignment of molecular vibrations of functional groups in the affined structure. Quantum calculations were executed with the GAUSSIAN 09 software package at B3LYP/6-311G level of theory, to optimize the molecular geometries. The antimicrobial efficacy of a synthesized product was evaluated using the disc diffusion method against antibiotic-resistant Candida albicans, Candida tropicalis, Aspergillus niger, Staphylococcus aureus, and Escherichia coli. Microorganisms were cultured on nutrient agar, and inhibition zones were measured after incubation, with streptomycin and amphotericin as positive controls.

A Simple Chiral Cu(II) Complex as an Effective Phase-Transfer Catalyst for the Enantioselective Alkylation of Dissymmetric Glycinate Ketimines.

Catalytic asymmetric benzylation of a dissymmetric tert-butylglycinate ketimine, incorporating 1-naphthyl and phenyl groups as the Schiff base substituents, under phase-transfer conditions was investigated. It was interesting to note that the sense of asymmetric induction of the alkylation of Z-imine stereoisomer is opposite to that of the corresponding E stereoisomer with a similar degree of enantioselectivity. More interestingly, the chiral Cu(II) complex of the Schiff base derived from (R)-2-phenylglycinol and 2-hydroxy-1-naphthaldehyde was found to catalyze the same reaction under solid-liquid conditions with comparable enantioselectivity (up to 60% ee) with respect to known cinchona alkaloid catalysts. The solvent/base-system parameter was shown to control the optimal catalytic activity.

Crystal structure of 1,5-diethyl-1H-1,5-benzodiazepine-2,4(3H,5H)-di-thione.

In the title compound, C13H16N2S2, the seven-membered ring adopts a boat conformation, with the two phenyl-ene C atoms representing the stern and the methyl-ene C atom as the prow. The thione S atoms and N-bound ethyl groups lie on the opposite side of the mol-ecule to the phenyl-ene ring so that the mol-ecule approximates mirror symmetry. In the crystal, supra-molecular layers in the bc plane are sustained by a pair of C-H⋯S inter-actions to the same S atom acceptor.

(3R,4S)-3,4,8-Trihy-droxy-1,2,3,4-tetra-hydro-naphthalen-1-one monohydrate from Embellisia eureka.

In the title hydrate, C(10)H(10)O(4)·H(2)O, the six-membered aliphatic ring that is fused to the benzene ring has a sofa shape, with the hy-droxy group in the 3-position (that represents the sofa back) of the aliphatic ring occupying a quasi-axial position. The hy-droxy group of the aromatic ring is hydrogen-bond donor to the carbonyl O atom; other O-H⋯O hydrogen bonds link the organic mol-ecules and the water mol-ecules into a three-dimensional network.

Ethyl 3-[7-eth-oxy-6-(4-meth-oxy-benzene-sulfonamido)-2H-indazol-2-yl]propano-ate.

In the title compound, C(21)H(25)N(3)O(6)S, the dihedral angle between the meth-oxy-benzene and indazole rings is 74.96 (5)°. The crystal packing is stabilized by an N-H⋯O hydrogen bond into a two-dimensional network. In addition, C-H⋯π inter-actions and a π-π contact, with a centroid-centroid distance of 3.5333 (6) Å, are observed. The crystal packing is stabilized by N-H⋯O and C-H⋯O hydrogen bonds.

5-Nitro-1-(prop-2-yn-1-yl)-2,3-dihydro-1H-1,3-benzodiazol-2-one.

In the two independent mol-ecules of the title compound, C(10)H(7)N(3)O(3), the nitro substitutent is twisted slightly with respect to the benzodiazol fused-ring system [dihedral angles = 4.9 (3) and 8.5 (1)°]. The two independent mol-ecules are disposed about a pseudo inversion center and are held together by N-H⋯O hydrogen bonds. The supramolecular dimer is essentially planar [dihedral angle between the fused rings = 2.0 (1)°]. Adjacent dimers are linked by acetyl-ene-nitro C-H⋯O inter-actions, generating a ribbon motif along (110).

Redetermination of catena-poly[[chlorido-(thio-urea-κS)copper(I)]-µ-thio-urea-κS:S] at 100†K.

The structure of the polymeric title compound, [CuCl(CH(4)N(2)S)(2)](n), has been redetermined to modern standards of precision with anisotropic refinement and location of the H atoms. The previous structure report [Spofford & Amma (1970 ▶). Acta Cryst. B26, 1474-1483] is generally confirmed to higher precision [typical Cu-S bond length s.u. values = 0.005 (old) and 0.001 Š(new)]. The asymmetric unit contains two formula units, with both Cu(I) atoms coordinated by one terminal S atom and two bridging S atoms of thio-urea ligands. This connectivity leads to polymeric [100] chains in the crystal. If very long contacts to nearby chloride ions [2.8687 (9) and 3.1394 (12) Å] are considered to be bonding, then very distorted CuS(3)Cl tetra-hedral coordination polyhedra arise. The crystal structure is consolidated by weak intra- and inter-chain N-H⋯S and N-H⋯Cl hydrogen bonds.

Dichloridobis(thio-urea-κS)nickel(II).

The title complex, [NiCl(2)(CH(4)N(2)S)(2)], has been synthesized from the previously reported (diamino-methyl-idene)sulfonium chloride-thio-urea (3/2) salt [Zouihri (2012b ▶). Acta Cryst. E68, o257]. The Ni(II) ion is coordinated in a distorted tetra-hedral geometry by two mol-ecules of thio-urea [Ni-S = 2.3079 (7) and 2.3177 (6) Å] and two chloride anions [Ni-Cl = 2.2516 (7) and 2.2726 (7) Å]. The bond angles at the Ni atom lie between 96.69 (2) and 115.40 (3)°, while the dihedral angle between the mean planes of the two thio-urea ligands is 6.36 (15)°. The crystal structure is characterized by intra- and inter-molecular N-H⋯Cl hydrogen bonds, which lead to the formation of two-dimensional networks lying parallel to the ab plane. The networks are linked via classical N-H⋯Cl and N-H⋯S hydrogen bonds, forming a three-dimensional arrangement.

(Diamino-methyl-idene)sulfonium chloride-thio-urea (3/2).

The asymetric unit of the title salt, 3CH(5)N(2)S(+)·3Cl(-)·2CH(4)N(2)S, contains two mol-ecules of thio-urea, three (diamino-methyl-idene)sulfonium cations and three chloride anions. The crystal packing is stabilized by N-H⋯Cl, N-H⋯S, S-H⋯Cl and S-H⋯S hydrogen bonds, forming a three-dimensional network.

2-Phenyl-thieno[2,3-b]quinoxaline.

The title compound, C(16)H(10)N(2)S, is almost planar (r.m.s. deviation for all non-H atoms = 0.080 Å). The dihedral angle between the three fused-ring system and the phenyl ring is 9.26 (3)°. The S atom and the opposite C atom of the thio-phene ring are mutually disordered with an occupancy ratio of 0.7706 (19):0.2294 (19).

Silver diaquacobalt(II) catena-borodiphosphate(V) hydrate, (Ag(0.79)Co(0.11))Co(H(2)O)(2)[BP(2)O(8)]·0.67H(2)O.

The structure of the title compound, (Ag(0.79)Co(0.11))Co(H(2)O)(2)[BP(2)O(8)]·0.67H(2)O is isotypic to that of its recently published counterparts AgMg(H(2)O)(2)[BP(2)O(8)]·H(2)O and (Ag(0.57)Ni(0.22))Ni(H(2)O)(2)[BP(2)O(8)]·0.67H(2)O. It consists of infinite borophos-phate helical ribbons [BP(2)O(8)](3-), built up from alternate BO(4) and PO(4) tetra-hedra arranged around the 6(5) screw axes. The vertex-sharing BO(4) and PO(4) tetra-hedra form a spiral ribbon of four-membred rings in which BO(4) and PO(4) groups alternate. The ribbons are connected through slightly distorted CoO(4)(H(2)O)(2) octa-hedra whose four O atoms belong to the phosphate groups. The resulting three-dimensional framework is characterized by hexa-gonal channels running along [001] in which the remaining water mol-ecules are located. The main difference between the Mg-containing and the title structure lies in the filling ratio of Wyckoff positions 6a and 6b in the tunnels. The refinement of the occupancy rate of the site 6a shows that it is occupied by water at 67%, while the refinement of that of the site 6b shows that this site is partially occupied by 78.4% Ag and 10.8% Co, for a total of 82.2%. The structure is stabilized by O-H⋯O hydrogen bonds between water mol-ecules and O atoms that are part of the helices.

3-{2-[(3-{(E)-2-[4-(Dimethyl-amino)-phen-yl]ethen-yl}quinoxalin-2-yl)-oxy]eth-yl}-1,3-oxazolidin-2-one monohydrate.

In the title compound, C(23)H(24)N(4)O(3)·H(2)O, the 1,3-oxazoline ring is nearly planar [maximum deviation = 0.059 (2) Å] and its mean plane is twisted by 30.12 (8)° with respect to the quinoxaline fused-ring system; the benzene ring is nearly coplanar with the quinoxaline fused-ring system [dihedral angle = 2.52 (2)°]. The water mol-ecule of crystallization is hydrogen-bond donor to an N atom of the quinoxaline ring system as well as an O atom of the oxazolinone unit, the two hydrogen bonds generating a chain running along the c axis.

5-Bromo-1-(prop-2-en-1-yl)-2,3-dihydro-1H-indole-2,3-dione.

In the title compound, C(11)H(8)BrNO(2), the nine-membered fused-ring is nearly planar [maximum deviation = 0.022 (2) Å] and the allyl group is arched over the nine-membered fused-ring at a dihedral angle of 89.2 (1)°. Weak inter-molecular C-H⋯O hydrogen bonding is present in the crystal structure.

N-[7-Eth-oxy-2-(prop-2-en-1-yl)-2H-indazol-6-yl]-4-methyl-benzene-sulfonamide.

In the title compound, C(19)H(21)N(3)O(3)S, the C-SO(2)-NH-C torsion angle is 66.20 (9)°. The dihedral angle between the benzene ring and the essentially planar indazole ring system [r.m.s. deviation = 0.0361 (1) Å] is 72.97 (6)°. The S atom has a distorted tetra-hedral geometry [maximum deviation = O-S-O = 119.30 (6)°]. The crystal structure features inversion-related dimers linked by pairs of N-H⋯O hydrogen bonds. In addition, weak C-H⋯O inter-actions may stabilize the crystal packing.

N-(2-Formyl-phen-yl)-4-meth-oxy-N-(4-meth-oxy-phenyl-sulfon-yl)benzene-sulfonamide.

In the title compound, C(21)H(19)NO(7)S(2), the dihedral angles between the formyl-phenyl ring and the two meth-oxy-phenyl rings are 33.87 (9) and 41.00 (10)°. The S atoms have a distorted tetra-hedral geometry and the N atom shows a trigonally planar [r.m.s. deviation = 0.0437 (13) Å] coordination. The crystal structure is stabilized by inter-molecular C-H⋯O hydrogen bonds.

5-Acetyl-3-hy-droxy-4-phenyl-4,5-dihydro-1H-1,5-benzodiazepin-2(3H)-one.

In the title compound, C(17)H(16)N(2)O(3), the seven-membered diazepine ring adopts a boat conformation with the hy-droxy-substituted C atom at the prow and fused benzene ring C atoms at the stern. The phenyl substituent occupies an equatorial position. The amino group of the ring system is a hydrogen-bond donor to the oxo O atom of an inversion-related mol-ecule, and the hy-droxy group is a hydrogen-bond donor to the acetyl O atom of another inversion-related mol-ecule. The two hydrogen bonds generate a ribbon motif parallel to [10[Formula: see text]] in the crystal structure.

(2RS,4'RS)-3'-(3-Chloro-4-meth-oxy-phen-yl)-4'-phenyl-4'H-spiro-[indene-2,5'-isoxazol]-1(3H)-one ethanol monosolvate.

The title compound, C(23)H(17)ClN(2)O(3)·C(2)H(6)O, is the stoichiometric 1:1 ethanol solvate of a racemic reaction product, which forms a conglomerate. The refined Flack parameter of 0.36 (3) indicates racemic twinning. In the structure, mol-ecules are linked into zigzag chains by a series of inter-molecular N-H⋯O and O-H⋯O hydrogen bonds.

Silver(I) diaqua-nickel(II) catena-borodiphosphate(V) hydrate, (Ag(0.57)Ni(0.22))Ni(H(2)O)(2)[BP(2)O(8)]·0.67H(2)O.

The structure framework of the title compound, (Ag(0.57)Ni(0.22))Ni(H(2)O)(2)[BP(2)O(8)]·0.67H(2)O, is the same as that of its recently published counterpart AgMg(H(2)O)(2)[BP(2)O(8)]·H(2)O. In the title structure, the Ag, Ni, B and one O atom are located on special positions (sites symmetry 2). The structure consists of infinite borophosphate helical [BP(2)O(8)](3-) ribbons, built up from alternate BO(4) and PO(4) tetra-hedra arranged around the 6(5) screw axes. The vertex-sharing BO(4) and PO(4) tetra-hedra form a spiral ribbon of four-membered rings in which BO(4) and PO(4) groups alternate. The ribbons are connected through slightly distorted NiO(4)(H(2)O)(2) octa-hedra, four O atoms of which belong to the phosphate groups. The resulting three-dimensional framework is characterized by hexa-gonal channels running along [001]. However, the main difference between the structures of these two compounds lies in the filling ratio of Wyckoff positions 6a and 6b in the tunnels. Indeed, in this work, the refinement of the occupancy rate of sites 6a and 6b shows that the first is occupied by water at 67% and the second is partially occupied by 56.6% of Ag and 21.6% of Ni. In the AgMg(H(2)O)(2)[BP(2)O(8)]·H(2)O structure, these two sites are completely occupied by H(2)O and Ag(+), respectively. The title structure is stabilized by O-H⋯O hydrogen bonds between water mol-ecules and O atoms that are part of the helices.

2-Hy-droxy-2,3,5,10,11,11a-hexa-hydro-1H-pyrrolo-[2,1-c][1,4]benzodiazepine-5,11-dione.

The seven-membered ring of the title compound, C(12)H(12)N(2)O(3), which is fused with the phenyl-ene ring, adopts a boat-shaped conformation (with the methine C atom as the prow and the phenyl-ene C atoms as the stern); the H atom on the methine linkage exists in an axial position. The five-membered ring that is fused with the seven-membered ring adopts an envelope conformation (with the C atom bearing the hy-droxy substituent representing the flap) [the deviation from the plane defined by the other four atoms is 0.200 (7) Šin one mol-ecule and 0.627 (5) Šin the other]. The two independent mol-ecules are disposed about a pseudo center of inversion and are connected by a pair of N-H⋯O hydrogen bonds. Adjacent dimers are linked by a pair of O-H⋯O hydrogen bonds, generating a chain running along the b axis.

5-(Pyridin-4-ylmeth-yl)-1H-pyrazolo-[3,4-d]pyrimidin-4(5H)-one.

In the title compound, C(11)H(9)N(5)O, the pyrazolo-pyrimidin-4-one ring system is almost planar, with a maximum deviation of 0.0546 (13) Šfor the O atom. The crystal packing is stabilized by inter-molecular N-H⋯N, C-H⋯O and C-H⋯N hydrogen bonds. In addition, π-π stacking is found between the pyridine ring and the pyrazolo-pyrimidin-4-one ring systems, with centroid-centroid distances in the range 3.9627 (12)-4.6781 (12) Å.