The title compound, Ph3(PhCH2)P(+)·Cl(-)·H2O, was obtained unintentionally as the product of an attempted synthesis of a silver di-thio-carbamate complex using benzyl-tri-phenyl-phospho-nium as the counter-ion. The asymmetric unit consists of a phospho-nium cation and a chloride anion, and a water mol-ecule of crystallization. In the crystal, the chloride ion is linked to the water mol-ecule by an O-H⋯Cl hydrogen bond. The three units are further linked via C-H⋯Cl and C-H⋯O hydrogen bonds and C-H⋯ π inter-actions, forming a three-dimensional structure.
The title compound, C14H19NS2, crystallizes in the thione form with the presence of a C=S bond. The piperidine ring adopts a chair conformation. The dihedral angle between the essentially planar di-thio-carbamate and p-tolyl fragments is 74.46 (10)°.
The common feature of the title compounds, [Zn(C5H10NO2S2)2(C10H8N2)]·2H2O, (I), and [Zn(C6H12NOS2)2(C10H8N2)], (II), is the location of the Zn(II) atoms on a twofold rotation axis. Further, each Zn(II) atom is chelated by two symmetry-equivalent and symmetrically coordinating di-thio-carbamate ligands and a 2,2'-bi-pyridine ligand. The resulting N2S4 coordination geometry is based on a highly distorted octa-hedron in each case. In the mol-ecular packing of (I), supra-molecular ladders mediated by O-H⋯O hydrogen bonding are found whereby the uprights are defined by {⋯HO(water)⋯HO(hy-droxy)⋯} n chains parallel to the a axis and with the rungs defined by 'Zn[S2CN(CH2CH2)2]2'. The water mol-ecules connect the ladders into a supra-molecular layer parallel to the ab plane via water-O-H⋯S and pyridyl-C-H⋯O(water) inter-actions, with the connections between layers being of the type pyridyl-C-H⋯S. In (II), supra-molecular layers parallel to the ab plane are sustained by hy-droxy-O-H⋯S hydrogen bonds with connections between layers being of the type pyridyl-C-H⋯S.
The title compound, [Cd(C6H12NOS2)2(C4H10N2)], features a distorted square-pyramidal coordination geometry about the central Cd(II) atom. The di-thio-carbamate ligands are chelating, forming similar Cd-S bond lengths and define the approximate basal plane. One of the N atoms of the piperazine mol-ecule, which adopts a chair conformation, occupies the apical site. In the crystal, supra-molecular layers propagating in the ac plane are formed via hy-droxy-O-H⋯O(hy-droxy), hy-droxy-O-H⋯N(terminal-piperazine) and coordinated-piperazine-N-H⋯O(hy-droxy) hydrogen bonds; the layers also feature methine-C-H⋯S inter-actions and S⋯S [3.3714 (10) Å] short contacts. The layers stack along the b-axis direction with very weak terminal-piperazine-N-H⋯O(hy-droxy) inter-actions between them. An evaluation of the Hirshfeld surfaces confirms the importance of inter-molecular inter-actions involving oxygen and sulfur atoms.
The asymmetric unit of the title 2:1 co-crystal, 2C8H8O2·C14H14N4O2, comprises an acid mol-ecule in a general position and half a di-amide mol-ecule, the latter being located about a centre of inversion. In the acid, the carb-oxy-lic acid group is twisted out of the plane of the benzene ring to which it is attached [dihedral angle = 28.51 (8)°] and the carbonyl O atom and methyl group lie approximately to the same side of the mol-ecule [hy-droxy-O-C-C-C(H) torsion angle = -27.92 (17)°]. In the di-amide, the central C4N2O2 core is almost planar (r.m.s. deviation = 0.031 Å), and the pyridyl rings are perpendicular, lying to either side of the central plane [central residue/pyridyl dihedral angle = 88.60 (5)°]. In the mol-ecular packing, three-mol-ecule aggregates are formed via hy-droxy-O-H⋯N(pyrid-yl) hydrogen bonds. These are connected into a supra-molecular layer parallel to (12[Formula: see text]) via amide-N-H⋯O(carbon-yl) hydrogen bonds, as well as methyl-ene-C-H⋯O(amide) inter-actions. Significant π-π inter-actions occur between benzene/benzene, pyrid-yl/benzene and pyrid-yl/pyridyl rings within and between layers to consolidate the three-dimensional packing.
The title 2:1 co-crystal, 2C7H5NO4·C14H14N4O2, in which the complete di-amide mol-ecule is generated by crystallographic inversion symmetry, features a three-mol-ecule aggregate sustained by hydroxyl-O-H⋯N(pyrid-yl) hydrogen bonds. The p-nitro-benzoic acid mol-ecule is non-planar, exhibiting twists of both the carb-oxy-lic acid and nitro groups, which form dihedral angles of 10.16 (9) and 4.24 (4)°, respectively, with the benzene ring. The di-amide mol-ecule has a conformation approximating to a Z shape, with the pyridyl rings lying to either side of the central, almost planar di-amide residue (r.m.s. deviation of the eight atoms being 0.025 Å), and forming dihedral angles of 77.22 (6)° with it. In the crystal, three-mol-ecule aggregates are linked into a linear supra-molecular ladder sustained by amide-N-H⋯O(nitro) hydrogen bonds and orientated along [10-4]. The ladders are connected into a double layer via pyridyl- and benzene-C-H⋯O(amide) inter-actions, which, in turn, are connected into a three-dimensional architecture via π-π stacking inter-actions between pyridyl and benzene rings [inter-centroid distance = 3.6947 (8) Å]. An evaluation of the Hirshfeld surfaces confirm the importance of inter-molecular inter-actions involving oxygen atoms as well as the π-π inter-actions.
The asymmetric unit of the title salt, C14H16N4O2 (2+)·2C9H5O6 (-), comprises half a dication, being located about a centre of inversion, and one anion, in a general position. The central C4N2O2 group of atoms in the dication are almost planar (r.m.s. deviation = 0.009 Å), and the carbonyl groups lie in an anti disposition to enable the formation of intra-molecular amide-N-H⋯O(carbon-yl) hydrogen bonds. To a first approximation, the pyridinium and amide N atoms lie to the same side of the mol-ecule [Npy-C-C-Namide torsion angle = 34.8 (2)°], and the anti pyridinium rings are approximately perpendicular to the central part of the mol-ecule [dihedral angle = 68.21 (8)°]. In the anion, one carboxyl-ate group is almost coplanar with the ring to which it is connected [Cben-Cben-Cq-O torsion angle = 2.0 (3)°], whereas the other carboxyl-ate and carb-oxy-lic acid groups are twisted out of the plane [torsion angles = 16.4 (3) and 15.3 (3)°, respectively]. In the crystal, anions assemble into layers parallel to (10-4) via hy-droxy-O-H⋯O(carbon-yl) and charge-assisted hy-droxy-O-H⋯O(carboxyl-ate) hydrogen bonds. The dications are linked into supra-molecular tapes by amide-N-H⋯O(amide) hydrogen bonds, and thread through the voids in the anionic layers, being connected by charge-assisted pyridinium-N-O(carboxyl-ate) hydrogen bonds, so that a three-dimensional architecture ensues. An analysis of the Hirshfeld surface points to the importance of O-H⋯O hydrogen bonding in the crystal structure.
The title mol-ecule, C(26)H(30)O(9)S(3), adopts an extended conformation whereby two approximately parallel benzene rings [dihedral angle = 8.32 (10)°] are orientated in opposite directions along the pseudo-threefold axis through the central quaternary C atom, while a third ring occupies a position mid-way and face-on to these rings [dihedral angles = 82.28 (10) and 78.81 (7)°]. The crystal packing is dominated by C-H⋯O contacts and π-π inter-actions [ring centroid distance = 3.6902 (12) Å].
In the title compound, C(10)H(9)N(3)O(3), there is a small twist between the benzene and triazole rings [dihedral angle = 6.32 (7)°]; the carb-oxy-lic acid residue is almost coplanar with the benzene ring to which it is attached [O-C-C-C torsion angle = 1.49 (19)°]. The main deviation from coplanarity of the non-H atoms is found for the hy-droxy group which is almost perpendicular to the remaining atoms [N-C-C-O torsion angle = -75.46 (16)°]. In the crystal, the presence of O-H⋯O (between carboxyl groups) and O-H⋯N (between the hy-droxy group and the triazole ring) hydrogen bonds leads to supra-molecular chains along [03[Formula: see text]]. The chains are connected into sheets via C-H⋯O(hy-droxy) inter-actions.
The complete mol-ecule in the title compound, C(22)H(20)N(2)O(4), is generated by the application of an inversion centre. With the exception of the terminal acetyl-ene groups [C-O-C-C = -78.02 (17)°], the remaining atoms constituting the mol-ecule are essentially coplanar. The configuration around the C=N bond [1.282 (2) Å] is E. The formation of supra-molecular chains mediated by C-H⋯O inter-actions, occurring between methyl-ene H and meth-oxy O atoms, is the most notable feature of the crystal packing.
In the title compound, [Mn(C(13)H(8)N(3)O(3))(2)]·C(3)H(7)NO·H(2)O, the metal atom is O,N,O'-chelated by two deprotonated Schiff bases and exists in a distorted octa-hedral geometry. The N-H groups, the carbonyl group of the DMF mol-ecule and the uncoord-inated water mol-ecule engage in N-H⋯O and O-H⋯O hydrogen-bonding inter-actions, generating a hydrogen-bonded ribbon that propagates along [110].
The metal atom of the title compound, [Zn(C(13)H(8)N(3)O(2)S)(2)]·C(3)H(7)NO·H(2)O, is O,N,O'-chelated by two deprotonated Schiff bases and it exists in a distorted octa-hedral geometry. The N-H groups of the ligands, the carbonyl group of the DMF mol-ecule and uncoordinated water mol-ecule engage in N-H⋯O and O-H⋯O inter-actions, generating a hydrogen-bonded ribbon that propagates along [110]. One thienyl ring is disordered over two positions in a 1:1 ratio.
Evidence for C-H···π(CuCl···HNCS) interactions, i.e. C-H···π(quasi-chelate ring) where a six-membered quasi-chelate ring is closed by an N-H···Cl hydrogen bond, is presented based on crystal structure analyses of (Ph3P)2Cu[ROC(=S)N(H)Ph]Cl. Similar intramolecular interactions are identified in related literature structures. Calculations suggest that the energy of attraction provided by such interactions approximates 3.5 kcal mol(-1).
A novel porous coordination polymer adsorbent (BTCA-P-Cu-CP) based on a piperazine(P) as a ligand and 1,2,4,5-benzenetetracarboxylic acid (BTCA) as a linker was synthesized and magnetized to form magnetic porous coordination polymer (BTCA-P-Cu-MCP). Fourier transform infrared (FTIR), X-ray diffraction (XRD), vibrating sample magnetometer (VSM), field emission scanning electron microscope(FESEM), energy-dispersive X-ray spectroscopy(EDS), CHN, and Brunauer-Emmett-Teller(BET) analysis were used to characterize the synthesized adsorbent. BTCA-P-Cu-MCP was used for removal and preconcentration of Pb(II) ions from environmental water samples prior to flame atomic absorption spectrometry(FAAS) analysis. The maximum adsorption capacity of BTCA-P-Cu-MCP was 582 mg g-1. Adsorption isotherm, kinetic, and thermodynamic parameters were investigated for Pb(II) ions adsorption. Magnetic solid phase extraction (MSPE) method was used for preconcentration of Pb(II) ions and the parameters influencing the preconcentration process have been examined. The linearity range of proposed method was 0.1-100 μg L-1 with a preconcentration factor of 100. The limits of detection and limits of quantification for lead were 0.03 μg L-1 and 0.11 μg L-1, respectively. The intra-day (n = 7) and inter-day (n = 3) relative standard deviations (RSDs) were 1.54 and 3.43% respectively. The recoveries from 94.75 ± 4 to 100.93 ± 1.9% were obtained for rapid extraction of trace levels of Pb(II) ions in different water samples. The results showed that the BTCA-P-Cu-MCP was steady and effective adsorbent for the decontamination and preconcentration of lead ions from the aqueous environment.
The synthesis and characterisation of R3PAu[S2CN((i)Pr)CH2CH2OH], for R = Ph (1), Cy (2) and Et (3)4, is reported. Compounds 1-3 are cytotoxic against the doxorubicin-resistant breast cancer cell line, MCF-7R, with 1 exhibiting greater potency and cytotoxicity than either of doxorubicin and cisplatin. Based on human apoptosis PCR-array analysis, caspase activities, DNA fragmentation, cell apoptotic assays, intracellular reactive oxygen species (ROS) measurements and human topoisomerase I inhibition, induction of apoptosis by 1, and necrosis by 2 and 3, are demonstrated, by both extrinsic and intrinsic pathways. Compound 1 activates the p53 gene, 2 activates only the p73 gene, whereas 3 activates both the p53 and p73 genes. Compounds 1 and 3 activate NF-κB, and each inhibits topoisomerase I.
The phosphanegold(I) carbonimidothioates, Ph3PAu{SC(OR)=NC6H4Me-4} for R = Me (1), Et (2) and iPr (3), feature linear P-Au-S coordination geometries and exhibit potent in vitro cytotoxicity against HT-29 colon cancer cells in both monolayer and multi-cellular spheroid models (e.g., IC50 = 11.9 ± 0.4 and 20.3 ± 0.3 μM for 2, respectively). Both intrinsic and extrinsic pathways of apoptosis are demonstrated by human apoptosis PCR array analysis, caspase activities, DNA fragmentation and cell apoptotic assays. Compounds 1-3 induce an extrinsic pathway that leads to down-regulation of NFκB. Compound 2 also exhibits an extrinsic apoptotic pathway involving the activation of both p53 and p73, whereas 3 activates p53 only. Lys48- and Lys63-linked polyubiquitination are also promoted by 1-3. Each of cytotoxic Ph3PAu{SC(OR)=NC6H4Me-4}, for R = Me (1), Et (2) and iPr (3), induce an intrinsic apoptotic pathway as well as an extrinsic pathway leading to down-regulation of NFκB. Lys48- and Lys63-linked polyubiquitination are promoted by 1-3 and these are able to inhibit cell invasion and to suppress the activity of TrxR.
This article demonstrates the first application of a copper-based porous coordination polymer (BTCA-P-Cu-CP) as a carbon paste electrode (CPE) modifier for the detection of malathion. The electrochemical behavior of BTCA-P-Cu-CP/CPE was explored using cyclic voltammetry (CV) while chrono-amperometry methods were applied for the analytical evaluation of the sensor performance. Under optimized conditions, the developed sensor exhibited high reproducibility, stability, and wide dynamic range (0.6-24 nM) with the limits of detection and sensitivity equal to 0.17 nM and 5.7 µAnMcm-1, respectively, based on inhibition signal measurement. Furthermore, the presence of common coexisting interfering species showed a minor change in signals (<4.4%). The developed sensor has been applied in the determination of malathion in spiked vegetable extracts. It exhibited promising results in term of fast and sensitive determination of malathion in real samples at trace level with recoveries of 91.0 to 104.4%. (RSDs < 5%, n = 3). A comparison of the two studied techniques showed that the HPLC technique is unable to detect malathion when the concentration is lower than 1.8 µM while 0.006 µM is detected with appropriate RSDs 0.2-5.2% (n = 3) by amperometric method. Due to the high sensitivity and selectivity, this new electrochemical sensor will be useful for monitoring trace malathion in real samples.
Four compounds, R3PAu[S2CN(CH2CH2OH)2], R=Ph (1) and cyclohexyl (2), and Et3PAuS2CNRꞌ2, Rꞌ=Rꞌ=Et (3) and Rꞌ2=(CH2)4(4), have been evaluated for antibacterial activity against a panel of 24 Gram positive (8) and Gram negative (16) bacteria. Based on minimum inhibitory concentration (MIC) scores, compounds 1 and 2 were shown to be specifically potent against Gram positive bacteria whereas compounds 3 and, to a lesser extent, 4 exhibited broad range activity. All four compounds were active against methicillin resistant Staphylococcus aureus (MRSA). Time kill assays revealed the compounds to exhibit both time- and concentration-dependent pharmacokinetics against susceptible bacteria. Each compound was bactericidal against one or more bacteria with 3 being especially potent after 8h exposure; compounds 1 and 3 were bactericidal against MRSA. Compound 3 was the most effective bactericide across the series especially toward B. subtilis, S. saprophyticus, A. hydrophila, P. vulgaris, and V. parahaemolyticus. This study demonstrates the potential of this class of compounds as antibacterial agents, either broad range or against specific bacteria.
The compound with R=CH2CH3 in Bi(S2CNR2)3 (1) is highly cytotoxic against a range of human carcinoma, whereas that with R=CH2CH2OH (2) is considerably less so. Both 1 and 2 induce apoptosis in HepG2 cells with some evidence for necrosis induced by 2. Based on DNA fragmentation, caspase activities and human apoptosis PCR-array analysis, both the extrinsic and intrinsic pathways of apoptosis have been shown to occur. While both compounds activate mitochondrial and FAS apoptotic pathways, compound 1 was also found to induce another death receptor-dependent pathway by induction of CD40, CD40L and TNF-R1 (p55). Further, 1 highly expressed DAPK1, a tumour suppressor, with concomitant down-regulation of XIAP and NF-κB. Cell cycle arrest at the S and G2/M phases correlates with the inhibition of the growth of HepG2 cells. The cell invasion rate of 2 is 10-fold higher than that of 1, a finding correlated with the down-regulation of survivin and XIAP expression by 1. Compounds 1 and 2 interact with DNA through different binding motifs with 1 interacting with AT- or TA-specific sites followed by inhibition of restriction enzyme digestion; 2 did not interfere with any of the studied restriction enzymes.
The Ph3PAu[SC(OR)=NPh], R=Me (1), Et (2) and iPr (3), compounds are significantly cytotoxic to the HT-29 cancer cell line with 1 being the most active. Based on human apoptosis PCR-array analysis, caspase activities, DNA fragmentation, cell apoptotic assays, intracellular reactive oxygen species (ROS) measurements and human topoisomerase I inhibition, induction of apoptosis is demonstrated and both the extrinsic and intrinsic pathways of apoptosis have been shown to occur. Compound 1 activates the p73 gene, whereas each of 2 and 3 activates the p53 gene. An additional apoptotic mechanism is exhibited by 2, that is, via the JNK/MAP pathway.