Methanol Solvent Mol-ecule Research Articles

Chlorido-bis-(1,10-phenanthroline-κ(2) N,N')copper(II) chlorido-(1,10-phen-anthroline-κ(2) N,N')(pyridine-2,6-di-carboxyl-ato-κ(3) O (2),N,O (6))manganate(II) methanol monosolvate.

The title complex, [CuCl(C12H8N2)2][Mn(C7H3NO4)Cl(C12H8N2)]·CH3OH, consists of discrete [CuCl(phen)2]+ cations (phen is 1,10-phenanthroline), [MnCl(pydc)(phen)]− anions (H2pydc is 2,6-pyridine-2,6-di­carb­oxy­lic acid) and one methanol solvent mol­ecule of crystallization per asymmetric unit. It should be noted, that a solvent-masking procedure as implemented in OLEX2 [Dolomanov et al. (2009). J. Appl. Cryst. 42, 339–341 ▶] was used to remove the electronic contribution from one disordered solvent molecule, presumably methanol. Only the atoms used in the refined model are reported in chemical formula and related values. The CuII ion is five-coordinated by two phenanthroline ligands and one chloride ion in a distorted trigonal–bipyramidal geometry. The dihedral angle between the phen ligands is 65.21 (5)°. The MnII ion is six-coordinated by one Cl atom, two N atoms from a phen ligand, as well one N atom and two O atoms from pydc in a distorted octa­hedral coordination geometry, with cis angles ranging from 72.00 (8) to 122.07 (8)° and trans angles ranging from 143.98 (8) to 163.15 (6)°. In the crystal, C—H⋯O, O—H⋯O and C—H⋯Cl hydrogen bonds, cation–anion π–π inter­actions between the phen ring systems with centroid–centroid distances in the range 3.881 (34)–4.123 (36) Å, as well as cation–cation, anion–anion π–π inter­actions between the phen rings with centroid–centroid distances in the range 3.763 (4)–3.99 (5) Å and pydc rings with centroid–centroid distances 3.52 (5) Å link the various components.

(μ-Acetato-κ(2) O:O')[μ-2,6-bis-({bis-[(pyri-din-2-yl-κN)meth-yl]amino-κN}meth-yl)-4-methyl-phenolato-κ(2) O:O](metha-nol-κO)dizinc bis-(perchlorate).

The binuclear title complex, [Zn2(C33H33N6O)(CH3COO2)(CH3OH)](ClO4)2, was synthesized by the reaction between 2,6-bis­({[bis­(pyridin-2-yl)meth­yl]amino}­meth­yl)-4-methyl­phenol (H-BPMP), Zn(OAc)2 and NaClO4. The two ZnII ions are bridged by the phenolate O atom of the octadentate ligand and the acetate group. An additional methanol ligand is terminally coordinated to one of the ZnII ions, rendering the whole structure unsymmetric. Other symmetric dizinc complexes of BPMP have been reported. However, to the best of our knowledge, the present structure, in which the two ZnII ions are distinguishable by the number of coordinating ligands and the coordination geometries (octahedral and square-pyramidal), is unique. The dizinc complex is a dication, and two perchlorate anions balance the charge. The –OH group of the coordinating methanol solvent mol­ecule forms a hydrogen bond with a perchlorate counter-anion. One of the anions is disordered over two sets of sites with an occupancy ratio of 0.734 (2):0.266 (2).

Bis[tetra-kis-(pyridin-2-yl)methane-κ(3) N,N',N'']cobalt(II) tetra-kis-(thio-cyanato-κN)cobaltate(II) methanol monosolvate.

The title complex, [Co(C21H16N4)2][Co(NCS)4]·CH3OH, consists of one [Co{C(py)4}2]2+ complex cation [C(py)4 = tetra­kis­(pyridin-2-yl)methane], one [Co(NCS)4]2− complex anion and a methanol solvent mol­ecule. In the cation, the CoII atom is coordinated by six N atoms of two C(py)4 ligands in a distorted octa­hedral geometry. In the anion, the CoII atom is coordinated by the N atoms of four NCS− ligands in a distorted tetra­hedral geometry. The methanol mol­ecule is disordered and was modelled over three orientations (occupancies 0.8:0.1:0.1). There are two weak hydrogen-bond-like inter­actions between the methanol solvent mol­ecule and NCS− ligands of the anion [O⋯S = 3.283 (3) and 3.170 (2) Å].

Trans-Chlorido-(4-fluoro-benzene-thiol-ato-κS)bis-(tri-phenyl-phosphane-κP)palladium(II) methanol hemisolvate.

The title compound, [Pd(SC6H4F-p)Cl(PPh3)2]·0.5CH3OH, features a PdII complex with two tri­phenyl­phosphane (PPh3) ligands arranged in a trans conformation, with one chloride and one 4-fluoro­benzene­thiol­ate ligand completing the coordination sphere, giving rise to a slightly distorted square-planar geometry of the PdII ion. The methanol solvent mol­ecule is disordered about an inversion centre with an occupancy of 0.25 for each molecule. In the crystal, weak C—H⋯Cl hydrogen-bonding inter­actions between the complex mol­ecules generate chain frameworks parallel to [010].

Di-μ-tricyanido-tetra-cyanidobis[hydro-tris-(pyrazoylborato)]tetra-methanol-diiron(III)iron(II) di-methanol disolvate.

In the title complex, [FeIIFeIII 2(C9H10BN6)2(CN)6(CH3OH)4]·2CH3OH, two [FeIII(Tp)(CN)3]− anions [Tp is hydro­tris­(pyrazoylborate)] are bridged by an [FeII(MeOH)4]2+ cation, forming a centrosymmetric trinuclear unit. These units are connected via O—H⋯O and O—H⋯N hydrogen bonds involving the uncoordinated methanol solvent mol­ecules, forming a three-dimensional network.

Modeling H-Bonding and Protonation States of Membrane Buried ARG-TYR Pairs

Previous X-ray crystallographic studies have shown that in the activated states of G-protein coupled receptors (GPCRs), or in those of microbial rhodopsins, the side chains in conserved R+Y dyads transiently move within several A of each other. In the M state of bR, substantial side-chain perturbation occurs, as has been shown previously, e.g. by FTIR and solid-state (SS) NMR studies of bR with 15N-labeled R82. No simpler system has been able to model the transient spectral perturbations of R82 in M. Here we report the synthesis of crystalline ω-(4-anisolyl)-dodecylguanidine (ADG) and ω-(4-phenolyl)-dodecylguanidine (PDG), with either natural isotope abundance or 98% 15N-enrichment at the 2 terminal nitrogens. The ADG free base, with a deprotonated guanidine group, is a good spectroscopic model for both IR and 15N-SS-NMR signals that were previously seen from R82 in the M photointermediate, particularly for the unusually large 15N chemical shift splitting. In the crystalline PDG free base, however, this chemical shift splitting is reduced to nearly the same value seen for the HBr salts of ADG, PDG, and arginine itself, all of which have protonated guanidinium groups. The high-resolution X-ray structure of the free-base form of PDG, as well as the IR spectrum of these crystals in KBr disk, show clearly that what crystallizes is actually a zwitterion, with guanidinium and phenolate groups; additionally, 2 H-bonding solvent (methanol) molecules co-crystallize with each PDG. These PDG free-base crystals are surprisingly insoluble in most aprotic solvents. However, they are sufficiently soluble in DMSO to observe IR, UV-vis and 1H NMR spectra. These spectra are all consistent with a ∼50/50 mix of rapidly-interchanging zwitterionic and neutral forms. The high proton polarizability of PDG makes this an interesting model system for buried H-bonded uncharged R+Y dyads in proteins.

N1-(Thiophen-2-ylmethyl)-N3,N3-bis[3-(thiophen-2-ylmethylammonio)propyl]propane-1,3-diammonium hexafluoridosilicate methanol trisolvate

In the title compound, C24H40N4S3 4+·2SiF6 2−·3CH3OH, the central tertiary amine function is protonated and is connected to three thio­phen-2-yl­methyl­amino-n-propyl groups, forming the arms of a T-shaped cation that has two pockets. Each arm contains one protonated secondary amine function, and each pocket is occupied by one SiF6 2− anion bonded via two N—H⋯F inter­actions with the protonated amine group on the middle arm, while two methanol solvent mol­ecules are N—H⋯O hydrogen-bonded with the other secondary protonated amine groups on the side arms. Weak O—H⋯O and O—H⋯F hydrogen bonds between the solvent mol­ecules and between the solvent mol­ecules and the anions, respectively, are also observed. All three thio­phene groups in the arms are disordered over two sets of sites, with occupancy ratios of 0.828 (3):0.172 (3), 0.910 (2):0.090 (2) and 0.890 (3):0.110 (3).

Bis[1-methoxy-2,2,2-tris(pyrazol-1-yl-κN2)ethane]nickel(II) bis(trifluoromethanesulfonate) methanol disolvate

In the title salt, [Ni(C12H14N6O)2](CF3SO3)2·2CH3OH, the NiII ion is coordinated by six N atoms from two tridentate 1-meth­oxy-2,2,2-tris­(pyrazol-1-yl)ethane ligands in a distorted octa­hedral geometry. The NiII ion is situated on an inversion centre. The Ni—N distances range from 2.0589 (19) to 2.0757 (19) Å, intra-ligand N—Ni—N angles range from 84.50 (8) to 85.15 (8)°, and adjacent inter-ligand N—Ni—N angles range between 94.85 (8) and 95.50 (8)°. In the crystal, O—H⋯O hydrogen bonds between methanol solvent mol­ecules and tri­fluoro­methane­sulfonate anions are observed.

(Hexafluorosilicato-κ2F,F′)bis(1,10-phenanthroline-κ2N,N′)zinc(II) methanol monosolvate

The title compound, [Zn(SiF6)(C12H8N2)2]·CH3OH, contains a neutral heteroleptic tris-chelate Zn(II) complex, viz. [Zn(SiF6)(phen)2] (phen is 1,10-phenanthroline), exhibiting approximate molecular C2 point-group symmetry. The Zn(II) cation adopts a severely distorted octahedral coordination. As far as can be ascertained, the title complex represents the first structurally characterized example of a Zn(II) complex bearing a bidentate-bound hexafluorosilicate ligand. A density functional theory study of the isolated [Zn(SiF6)(phen)2] complex was undertaken to reveal the influence of crystal packing on the molecular structure of the complex. In the crystal structure, the methanol solvent molecule forms a hydrogen bond to one F atom of the hexafluorosilicate ligand. The hydrogen-bonded assemblies so formed are tightly packed in the crystal, as indicated by a high packing coefficient (74.1%).

4,7-Diphenyl-1,10-phenanthroline methanol hemisolvate

The asymmetric unit of the title compound, C24H16N2·0.5CH3OH, is comprised of two independent bathophenanthroline mol­ecules (systematic name: 4,7-diphenyl-1,10-phenanthroline) and one methanol mol­ecule. The bathophenanthroline mol­ecules are not planar as there is a considerable rotation of all terminal phenyl rings with respect to the central phenanthroline units [dihedral angles in the range 52.21 (12)–62.14 (10)°]. In addition, a non-negligible torsion is apparent in one of the phenanthroline units: the angle between the mean planes of the two pyridine rings is 14.84 (13)°. The methanol solvent mol­ecule is linked to both N atoms of a bathophenanthroline mol­ecule through a bifurcated O—H⋯(N,N) hydrogen bond.

Bis(4,4''-difluoro-1,1':3',1''-terphenyl-2'-carboxyl-ato-κO)tetra-kis-(methanol-κO)calcium methanol tetra-solvate.

In the title compound, [Ca(C19H11F2O2)2(CH3OH)4]·4CH3OH, the Ca2+ ion is located on an inversion centre and is hexa­coordinated by two O atoms of two 4,4′′-difluoro-1,1′:3′,1′′-terphenyl-2′-carboxyl­ate ligands and four O atoms of four methanol ligands, forming a CaO6 polyhedron with a slightly distorted octa­hedral coordination geometry. The Ca—O—C angle between the carboxyl­ate group and the calcium ion is 171.8 (2)°. Two types of inter­molecular hydrogen-bond inter­actions (C=O⋯H and O—H⋯O) between the carboxyl­ate ligand, the methanol solvent mol­ecules and the coordinating methanol ligands generate a two-dimensional network parallel to (001).

A luminescent metal–organic framework for sensing methanol in ethanol solution

A new luminescent Zn-MOF has been synthesized under hydrothermal condition using a semi-rigid ligand H3pcoip (4-(2-carboxyphenoxy)isophthalic acid) is reported. The luminescence properties of 1 in methanol, ethanol, and water have been investigated. Interestingly, compound 1 has a unique response to methanol compared to ethanol and water. Moreover, 1 displays a turn-on switching property triggered by methanol solvent molecules and a high sensitivity towards methanol concentration as low as 2 × 10(-7) (V(MeOH)/V(total)) in ethanol solution. The results indicate that the Zn-MOF has potential application as a sensor for detecting methanol in ethanol solution with excellent selectivity and high sensitivity.

Bis({1-[(1-iminoethyl)imino]ethyl}azanido-κ2N1,N5)nickel(II) methanol monosolvate

The title compound, [Ni(C4H8N3)2]·CH3OH, contains two independent NiII atoms, each located on an inversion center and coordinated by four N atoms from two 1-[(1-imino­eth­yl)imino]­eth­yl}aza­nide ligands in a square-planar geometry. N—H⋯N, N—H⋯O and O—H⋯N hydrogen bonds link the complex mol­ecules and methanol solvent mol­ecules into a corrugated layer parallel to (001).

Trans-Bis(1,3-diphenylpropane-1,3-dionato)(methanol)oxidovanadium(IV) methanol disolvate

In the title compound, [V(C15H11O2)2O(CH3OH)]·2CH3OH, the VIV atom is coordinated by two 1,3-diphenyl­propane-1,3-dionate ligands and an oxide ligand in an axial position. The sixth position is occupied by the O atom of a methanol group bonded trans to the oxide atom. The octa­hedral geometry is significantly distorted, with the VIV atom lying 0.330 (3) Å above the equatorial plane formed by the O atoms of the two β-diketonate ligands. In the crystal, O—H⋯O hydrogen bonds between the coordinating methanol group in the complex and the two methanol solvent mol­ecules lead to the formation of polymeric chains along the c-axis direction. Weak C—H⋯O contacts are also observed.

4-Dimethylamino-N′-(2-hydroxy-4-methoxybenzylidene)benzohydrazide methanol monosolvate

The asymmetric unit of the title compound, C17H19N3O3·CH4O, comprises two Schiff base mol­ecules and two methanol solvent mol­ecules. The Schiff base mol­ecules are approximately planar, with r.m.s. deviations from the planes defined by the non-H atoms of 0.107 and 0.154 Å, and with dihedral angles between the benzene rings of 4.49 (15) and 8.39 (15)°, respectively. This near-planarity is assisted by the formation of intra­molecular O—H⋯N hydrogen bonds in each mol­ecule. In the crystal, the components are linked by N—H⋯O and O—H⋯O hydrogen bonds to form chains along [010].

Iodido[5-methyl-1H-benzimidazole-2(3H)-thione-κS]bis(triphenylphosphane-κP)copper(I) methanol monosolvate

In the title compound, [CuI(C8H8N2S)(C18H15P)2]·CH3OH, the coordination environment around the CuI atom is distorted tetra­hedral, defined by two P atoms of two triphenyl­phosphane ligands, one S atom of a 5-methyl-1H-benzimidazole-2(3H)-thione ligand and one I atom. The complex mol­ecules and the methanol solvent mol­ecules are connected via N—H⋯O and O—H⋯I hydrogen bonds, forming a chain along [010]. An intra­molecular N—H⋯I hydrogen bond is also observed.

7-[(7S)-7-Azaniumyl-5-azaspiro[2.4]hept-5-yl]-8-chloro-6-fluoro-1-[(1S,2R)-2-fluorocyclopropyl]-4-oxo-1,4-dihydroquinoline-3-carboxylate methanol monosolvate

Sitafloxacin is a newly developed fluoro­quinolone anti­bacterial drug. The crystal studied, C19H18ClF2N3O3·CH3OH, consists of one mol­ecule of sitafloxacin and one methanol solvent mol­ecule. The mol­ecule of sitafloxacin is a zwitterion with a protonated primary amine group and a deprotonated carboxylate group. The cyclopropane ring and the CO2 group make dihedral angles of 79.5 (3) and 35.4 (4)°, respectively, with the fused ring system. The supra­molecular structure is defined by N—H⋯O and O—H⋯O hydrogen bonds.

Trichlorido(4,4′-dimethyl-2,2′-bipyridine-κ2N,N′)(methanol-κO)indium(III) methanol monosolvate

In the title compound, [InCl3(C12H12N2)(CH3OH)]·CH3OH, the InIII atom is six-coordinated in a distorted octa­hedral geometry by two N atoms from a chelating 4,4′-dimethyl-2,2′-bipyridine ligand, one O atom from a methanol mol­ecule and three Cl atoms. In the crystal, inter­molecular O—H⋯O and O—H⋯Cl hydrogen bonds link the complex and solvent methanol mol­ecules. Intra­molecular C—H⋯Cl hydrogen bonds are also present in the complex.

(1S,3R)-3-Isobutyl-2,3-dihydrospiro[benzo[f]isoindole-1,3′-indoline]-2′,4,9-trione methanol monosolvate

In the title compound, C23H20N2O3·CH3OH, the hexa­hydro-1H-benzo[f]isoindole and indoline rings are planar, with maximum deviations of 0.092 (1) and −0.095 (1) Å, respectively. The dihedral angle between these two rings is 88.03 (4)°. An O—H⋯N inter­action links the main mol­ecule and the methanol solvent mol­ecule. An intra­molecular C—H⋯O inter­action forms an S(6) ring motif. In the crystal, the mol­ecules form two-dimensional layers parallel to the bc plane through N—H⋯O and C—H⋯O inter­actions.

Bis[2,6-bis(1-methyl-1H-benzimidazol-2-yl-κN3)pyridine-κN]zinc dipicrate methanol disolvate

In the title compound, [Zn(C21H17N5)2](C6H2N3O7)2·2CH3OH, the ZnII atom is coordinated by six N atoms from two tridentate 2,6-bis­(1-methyl-1H-benzimidazol-2-yl)pyridine ligands in a distorted octa­hedral environment. In the crystal, the picrate anions and methanol solvent mol­ecules are connected by O—H⋯O hydrogen bonds. Weak inter­molecular C—H⋯O hydrogen bonds are also observed.