Fumaric Acid Molecules Research Articles

Bis(4-acetoxy-N-ethyl-N-n-propyl-tryptammonium) fumarate-fumaric acid (1/1).

The solid-state structure of the title salt/adduct (systemic name: bis-{[2-(4-acet-yloxy-1H-indol-3-yl)eth-yl](eth-yl)propyl-aza-nium} but-2-enedioate-(E)-butenedioic acid (1/1)), 2C17H25N2O2 +·C4H2O4 2-·C4H4O4, was determined by single-crystal X-ray diffraction. The asymmetric unit consists of a singly protonated tryptammonium cation, one half of a fumarate dianion and one half of a fumaric acid mol-ecule. In the crystal, the ions and mol-ecules are linked together in infinite chains propagating along [001] through a series of N-H⋯O and O-H⋯O hydrogen bonds.

Bis(oxotremorine) fumarate bis-(fumaric acid).

The title compound, bis-(oxotremorine) fumarate bis-(fumaric acid) {systematic name: 1-[4-(2-oxopyrrolidin-1-yl)but-2-yn-yl]pyrrolidinium (2E)-but-2-ene-di-o-ate bis-[(2E)-but-2-enedioic acid]}, 2C12H19N2O+·C4H2O4 2-·2C4H4O4, has a single oxotremorine monocation protonated at the pyrrolidine nitro-gen, one fumaric acid mol-ecule and half of a fumarate dianion in the asymmetric unit. The ions and fumaric acid mol-ecules are held together by N-H⋯O and O-H-⋯O hydrogen bonds in 40-membered rings with graph-set notation R 6 6(40). The fumarate ions join these rings into infinite chains along [001].

Psilacetin derivatives: fumarate salts of the meth-yl-ethyl, meth-yl-allyl and diallyl variants of the psilocin prodrug.

The solid-state structures of the salts of three psilacetin derivatives, namely, 4-acet-oxy-N-eth-yl-N-methyl-tryptammonium (4-AcO-MET) hydro-fumarate {sys-tematic name: [2-(4-acet-yloxy-1H-indol-3-yl)eth-yl](meth-yl)ethyl-aza-nium 3-carb-oxy-prop-2-enoate}, C15H21N2O2 +·C4H3O4 -, 4-acet-oxy-N-allyl-N-methyl-tryptammonium (4-AcO-MALT) hydro-fumarate {systematic name: [2-(4-acet-yl-oxy-1H-indol-3-yl)eth-yl](meth-yl)prop-2-enyl-aza-nium 3-carb-oxy-prop-2-eno-ate}, C16H21N2O2 +·C4H3O4 -, and 4-acet-oxy-N,N-di-allyl-tryptammonium (4-AcO-DALT) fumarate-fumaric acid (1/1) (systematic name: bis-{[2-(4-acet-yloxy-1H-indol-3-yl)eth-yl]diprop-2-enyl-aza-nium} but-2-enedioate-(E)-butenedioic acid (1/1)), 2C18H23N2O2 +·C4H2O4 2-·C4H4O4, are reported. All three salts possess a protonated tryptammonium cation. The 4-AcO-MET and 4-AcO-MALT compounds are charge-balanced by 3-carb-oxy-acrylate (hydro-fumarate) anions. The 4-AcO-DALT complex crystallizes as a two-to-one tryptammonium-to-fumarate salt, which co-crystallizes with a fumaric acid mol-ecule. Each structure is consolidated by N-H⋯O and O-H⋯O hydrogen bonds.

Crystal growth, structural, spectral, thermal, linear and nonlinear optical characterization of a new organic nonlinear chiral compound: l-tryptophan-fumaric acid-water (1/1/1) suitable for laser frequency conversion

A new organic active nonlinear optical crystal l-tryptophan fumaric acid water (1/1/1), (C15H17N2 O7. H2O)(LTFAW), consisting of zwitterion tryptophan molecule in conjunction with a fumaric acid molecule and a water molecule was grown by slow solvent evaporation technique from aqueous solution. The organic chromophore crystallizes from water in its zwitterions exhibiting tabular habit in monoclinic system with acentric space group C2 (Z = 4). The sharp peaks observed in Powder X-ray diffractogram depicts the crystalline nature. The presence of functional groups in the grown crystal was analyzed using FT-IR spectrum. The carbon and hydrogen environment in molecular structure was investigated using FT-NMR technique using deuterated DMSO solution. Ultraviolet–visible spectral analysis reveal that the crystal possess lower cut-off wavelength down to 275 nm, is a key factor to exhibit Second Harmonic Generation (SHG) signal. The direct optical band gap is evaluated to be 5.28 eV from the UV absorption profile. The evaluation of optical constants by employing UV–visible absorbance data such as, extinction coefficient, reflectance, refractive index, optical conductivity are supportive towards good performance as NLO devices. Temperature of decomposition was investigated using thermogravimetric analysis/differential thermal analysis techniques (TG/DTA). The luminescence profile exhibited two peaks (362 nm, 683 nm) due to the donation of protons from carboxylic group to amino group. The nonlinear optical behavior from the noncentrosymmetric crystal was observed by the generation of frequency doubled (2ω) optical radiation when subjected to pulsed Nd:YAG laser (1064 nm, 10 ns, 10 Hz) using Kurtz-Perry method. The variation of dielectric constant (εʹ) and dielectric loss (εʹʹ) vs. Log f for the title compound was analysed at a few selected temperatures and frequencies.

Co-crystallization of a benzimidazole derivative with carboxylic acids

The co-crystallization of a benzimidazole derivative (1, C27H26N6O3, 3-[[[2-[[(4-Cyanophenyl) amino]methyl]-1-methyl-1H-benzimidazol-5-yl]carbonyl]pyridin-2-ylamino]propionic acid ethyl ester), with fumaric acid (FA) and maleic acid (MA), has been performed. The FA and MA molecules, both are connected with two molecules of C27H26N6O3, giving birth to a three-components compound (1·0.5FA, C29H28N6O5) and a four-components compound (1·MA, C31H30N6O7). Single-crystal X-ray diffractions show that the three different planar moieties (4-cyanophenyl, benzimidazol, and pyridin-2-yl) in compound C27H26N6O3 display “cis-form” conformation (a) in the crystal of 1, while exhibiting “intermediate-state” conformation (b) and “trans-form” conformation (c) in compounds 1·0.5FA and 1·MA, respectively. Hirshfeld surfaces analysis, DFT calculations, DSC measurements, IR and Raman spectroscopy were performed, which revealed that the thermal stability of the three conformations follows the order c > b > a.

Crystal structure of l-tryptophan-fumaric acid-water (1/1/1).

In the title compound, C11H12N2O2·C4H4O4·H2O, the l-tryp­to­phan mol­ecule crystallized as a zwitterion, together with a neutral fumaric acid mol­ecule and a water solvent mol­ecule. In the crystal, the three components are linked by a series of N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds, forming slabs lying parallel to (001). The slabs are connected by O—H⋯O hydrogen bonds, involving inversion-related fumaric acid groups, leading to the formation of a three-dimensional structure.

Hydrogen-Bonded Displacive-Type Ferroelastic Phase Transition in a New Entangled Supramolecular Compound

The framework entanglements show structural transitions by the removal and incorporation of guest molecules, but rarely generate phase transitions by themselves. In this study, we report a new entangled hydrogen-bonded supramolecular compound, [(n-C4H9)2NH2]2H2C4O4·H4C4O4 (1, H4C4O4 = fumaric acid), which undergoes a reversible ferroelastic phase transition with the Aizu notation of 2/mF1̅. Differential scanning calorimetry and specific heat measurements confirm its typical second-order phase transition at around 228.8 K (Tc), while the results of the deuterated analogue (2) are different with those of 1, indicating that proton dynamic motions in hydrogen bonds contribute to the phase transition. Variable-temperature single-crystal X-ray diffraction analyses reveal that the cooperative displacements of hydrogen bonds induce the structural phase transition, which arise from the twisting motions of the fumaric acid molecules. Simultaneously, two types of independent hydrogen bonding layers in the entanglement are altered in response to the transformation of hydrogen bonds aggregates at the low temperature phase, causing the symmetry breaking. These findings will open up a new avenue for the design of ferroic materials with an entangled framework.

A new polymorph of bis(2-aminopyridinium) fumarate–fumaric acid (1/1) from powder X-ray diffraction

A new polymorph of bis(2-aminopyridinium) fumarate-fumaric acid (1/1), 2C₅H₇N₂⁺∙C₄H₂O₄²⁻-·C₄H₄O₄, was obtained and its crystal structure determined by powder X-ray diffraction. The new polymorph (form II) crystallizes in the triclinic system (space group P-1), while the previous reported polymorph [form I; Ballabh, Trivedi, Dastidar & Suresh (2002). CrystEngComm, 4, 135-142; Büyükgüngör, Odabaşoğlu, Albayrak & Lönnecke (2004). Acta Cryst. C60, o470-o472] is monoclinic (space group P2₁/c). In both forms I and II, the asymmetric unit consists of one 2-aminopyridinium cation, half a fumaric acid molecule and half a fumarate dianion. The fumarate dianion is involved in hydrogen bonding with two neighbouring 2-aminopyridinium cations to form a hydrogen-bonded trimer in both forms. In form II, the hydrogen-bonded trimers are interlinked across centres of inversion via pairs of N-H∙∙∙O hydrogen bonds, whereas such trimers are joined via single N-H∙∙∙O hydrogen bonds in form I, leading to different packing modes for forms I and II. The results demonstrate the relevance and application of the powder diffraction method in the study of polymorphism of organic molecular materials.

Bis(N,N′,N′′-triisopropylguanidinium) fumarate–fumaric acid (1/1)

The asymmetric unit of the title compound, C10H24N3 +·0.5C4H2O4 2−·0.5C4H4O4, comprises a triisopropyl­guanidinium cation, half of a fumarate dianion and half of a fumaric acid mol­ecule; both the fumarate dianion and the fumaric acid mol­ecule are located on inversion centres. In the crystal, inter­molecular O—H⋯O hydrogen bonds between the carboxyl groups of the fumaric acid mol­ecules and the carboxyl­ate groups of the fumarate anions lead to the formation of a hydrogen-bonded supra­molecular twisted chain along the b axis. The triisopropyl­guanidinium cations inter­act with the fumarate–fumaric acid chains via extensive N—H⋯O and C—H⋯O hydrogen bonds, leading to a ladder arrangement, with the cation being the rungs that bridge three curled chains of fumarate–fumaric acid. The crystal packing is stabilized by N—H⋯O and C—H⋯O (cation⋯fumarate/fumaric) and O—H⋯O (fumarate⋯fumaric) hydrogen bonds, consolidating a three-dimensional network.

2-Phenyl-1H-imidazol-3-ium hydrogen fumarate–fumaric acid (2/1)

The asymmetric unit of the title compound, C9H9N2 +·C4H3O4 −·0.5C4H4O4, consists of one 2-phenyl­imidazolium cation, one hydrogen fumarate anion and half a fumaric acid mol­ecule, which lies on an inversion center. N—H⋯O and O—H⋯O hydrogen bonds connect the cations, anions and fumaric acid mol­ecules into sheets parallel to the (102) plane.

Molecular structure and stabilities of fumaric acid conformers: Gas phase electron diffraction (GED) and quantum-chemical studies

The molecular structure of fumaric acid was reinvestigated by the gas phase electron diffraction (GED) method because it was determined several years ago assuming the existence of one conformer only. According to MP2/cc-pVTZ predictions, the molecule has six stable conformations, and three of them, sp,sp,sp,sp (I), ap,sp,sp,sp (II) and ap,ap,sp,sp (III), with relative energies within ca. 3 kJ mol −1 should be present in detectable amounts at the experimental temperature of ca. 480 K. The best fit to the GED intensities was achieved at the approximately equal amounts of the conformers I–III. To take into account vibrational effects, the corrections to the experimental r a bond lengths ( r e − r a ) were calculated using quadratic and cubic force constants from high-level ab initio calculations (MP2/cc-pVTZ). The deduced equilibrium bond lengths of the conformer II with the estimated total errors (in Å) are the following: r e (C C) = 1.331(3), r e (C C) s- trans = 1.473(3), r e (C C) s- cis = 1.479(3), r e (C O) s- trans = 1.345(3), r e (C O) s- cis = 1.344(3), r e (C O) s- trans = 1.205(3), r e (C O) s- cis = 1.204(3). The structural effects arising due to presence of the C C double bond were analysed. In comparison to the experiment, the MP2/cc-pVQZ approximation overestimates some bond lengths in fumaric acid and similar molecules by up to 0.005 Å. The rotational constants of the conformers I–III were derived from the GED equilibrium geometries.

2-Amino-5-chloropyridine–fumaric acid (1/2)

The asymmetric unit of the title compound, C5H5ClN2·0.5C4H4O4, comprises a neutral 2-amino-5-chloro­pyridine mol­ecule and one half of a fumaric acid mol­ecule which lies on an inversion center. The dihedral angle between the pyridine ring and the plane formed by the fumaric acid mol­ecule is 3.22 (8)°. The 2-amino-5-chloro­pyridine mol­ecule is planar, with a maximum deviation of 0.004 (1) Å for the pyridine N atom. In the crystal, the 2-amino-5-chloro­pyridine mol­ecules inter­act with the carboxyl groups of fumaric acid mol­ecules through N—H⋯O and O—H⋯N hydrogen bonds, forming centrosymmetric R 2 2(8) ring motifs and another N—H⋯O hydrogen bond links these motifs into a two-dimensional network parallel to (100).

Multicomponent crystals of erlotinib

Erlotinib [systematic name: N-(3-ethynylphenyl)-6,7-bis(2-methoxyethoxy)quinazolin-4-amine], a small-molecule epidermal growth factor receptor inhibitor, useful for the treatment of non-small-cell lung cancer, has been crystallized as erlotinib monohydrate, C(22)H(23)N(3)O(4).H(2)O, (I), the erlotinib hemioxalate salt [systematic name: 4-amino-N-(3-ethynylphenyl)-6,7-bis(2-methoxyethoxy)quinazolin-1-ium hemioxalate], C(22)H(24)N(3)O(4)(+).0.5C(2)O(4)(2-), (II), and the cocrystal erlotinib fumaric acid hemisolvate dihydrate, C(22)H(23)N(3)O(4).0.5C(4)H(4)O(4).2H(2)O, (III). In (II) and (III), the oxalate anion and the fumaric acid molecule are located across inversion centres. The water molecules in (I) and (III) play an active role in hydrogen-bonding interactions which lead to the formation of tetrameric and hexameric hydrogen-bonded networks, while in (II) the cations and anions form a tetrameric hydrogen-bonded network in the crystal packing. The title multicomponent crystals of erlotinib have been elucidated to study the assembly of molecules through intermolecular interactions, such as hydrogen bonds and aromatic pi-pi stacking.

1,4-Bis(4-pyridylmethyl)piperazin-1-ium perchlorate fumaric acid hemisolvate

In the title salt, C16H21N4 +·ClO4 −·0.5C4H4O4, fumaric acid mol­ecules, situated across crystallographic inversion centres, are O—H⋯N hydrogen bonded to two protonated 1,4-bis­(4-pyridylmeth­yl)piperazine cations, forming trimolecular units. These construct one-dimensional supra­molecular ribbons by N—H⋯N hydrogen bonding, and further aggregate via π–π inter­actions [shortest C⋯C contact = 3.640 (1) Å] and perchlorate-mediated C—H⋯O inter­actions.

Salt or Cocrystal? A New Series of Crystal Structures Formed from Simple Pyridines and Carboxylic Acids

The two-component crystals formed from pyridine or 4-dimethylaminopyridine with maleic, fumaric, phthalic, isophthalic, or terephthalic acids were characterized by X-ray diffraction. The two-component solid forms involving pyridine included both salts and cocrystals, while 4-dimethylaminopyridine crystallized exclusively as a salt, in agreement with the differences in the pKa values. Five previously unknown salt solid forms of 4-dimethylaminopyridine and the crystal structure of a pyridine fumaric acid (2:1) cocrystal are reported. An in-situ base catalyzed isomerization of maleic acid was observed in cocrystallization experiments involving pyridine. The salts formed between 4-dimethylaminopyridine and fumaric acid included one or two fumaric acid molecules within the crystal lattice. Thus, the reported grid of crystal forms demonstrates the limitations of empirical rules for predicting the stoichiometry and covalent bonding of the acidic proton within salts and cocrystals. Many of the crystal structures ...

Synthesis and crystal structure of [Fe(phen)3]L·2H2L·4H2O (H2L = fumaric acid)

Reaction of freshly precipitated Fe m (OH) n (CO3)3 m − n /2·xH2O, fumaric acid (H2L) and 1,10-phenanthroline (phen) in aqueous ethanol solution under ambient conditions yielded a new complex [Fe(phen)3]L·2H2L·4H2O, which crystallizes in space group Pī with a = 12.126(1), b = 12.493(2), c = 17.014(2) Å, α = 77.26(1), β = 89.786(8), γ = 63.260(8)°, Z = 1, D calc = 1.506 g cm−3. The title compound consists of [Fe(phen)3]2+ complex cations, fumaric acid molecules, fumarate anions and hydrogen-bonded water molecules. Fe atoms are octahedrally coordinated by six nitrogen atoms of three phenanthroline ligands. The fumaric acid molecules, fumarate anions and water molecules build up a hydrogen-bonded anionic framework with the [Fe(phen)3]2+ complex cations in channels assembled into columnar chains through π–π stacking interactions. IR spectra and thermal analyses are discussed.

2-Aminopyridinium-fumarate-fumaric acid (2/1/1).

The title complex, 2C5H7N2+.C4H2O42-.C4H4O4, contains cyclic eight-membered hydrogen-bonded rings involving 2-aminopyridinium and fumarate ions. The fumaric acid molecules and fumarate ions lie on inversion centers and are linked into zigzag chains by O-H...O hydrogen bonds. The dihedral angle between the pyridinium ring and the hydrogen-bonded fumarate ion is 7.60 (4) degrees. The fumarate anion is linked to the pyridinium cations by intermolecular N-H...O hydrogen bonds. The heterocycle is fully protonated, thus enabling amine-imine tautomerization.

Self-assembly directed by NH–O hydrogen bonding: new molecular assemblies derived from N, N-tetramethyl-1,2-diaminoethane and malonic or fumaric acid incorporating ‘proton transfered’ hydrogen bonds

Co-crystallisation of N, N-tetramethyl-1,2-diaminoethane (TMEN) and malonic or fumaric acid from water in a 1:1 ratio results in crystalline products whose X-ray structures show that they contain hydrogen-bonded motifs in self-assembled arrays. The stoichiometry of the malonate-containing assembly is 1:2, [TMENH 2(hydrogen malonate) 2], while that of the fumarate-containing assembly is 1:1:1 (TMENH 2, fumarate, fumaric acid). In each structure, protons from individual carboxylic acids have been transferred onto the nitrogens of N, N-tetramethyl-1,2-diaminoethane (TMEN) to yield diammonium cations; the ammonium protons hydrogen bond to carboxylate oxygens of hydrogen malonate in one case or to fumarate anions in the other. The hydrogen malonate-containing structure has layers of aligned diprotonated TMEN separated by layers of hydrogen malonate anions. Successive hydrogen malonate ions are hydrogen bound in an 'alternate’ manner between adjacent protonated TMEN layers. Each [TMENH 2(hydrogen malonate) 2] moiety describes an approximate 'Z’ configuration which are in turn stacked at an oblique angle; adjacent ‘columns of Zs’ are partially interlaced to form the overall array. The fumarate-containing structure consists of parallel ribbons of alternating, hydrogen bonded, fumarate dianions and fumaric acid molecules. These form layers alternating with layers of diammonium ions which lie essentially in the xy plane. The diammonium ions form parallel staggered head-to-tail chains along the y axis and so run at an angle across the fumarate-fumaric acid ribbons.

Crystal structures and magnetic properties of acid–base molecular complexes, (p-pyridyl nitronylnitroxide)2X (X=hydroquinone, fumaric acid and squaric acid)

The reactions of 2-(4-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxyl 3-N-oxide (or p-pyridyl nitronylnitroxide, abbreviated as p-PYNN) with the three dibasic organic acids, X [=fumaric acid (FA), squaric acid (SA) and hydroquinone (HQ)], result in the formation of hydrogen-bonding complexes of ( p-PYNN)2 X composition. In their crystals, the organic acids make selective hydrogen bonds to the two kinds of hydrogen-bond accepting sites in p-PYNN; (a) the oxygen atom in the NO group and (b) the nitrogen atom of the pyridyl ring. p-PYNN2HQ crystallizes in the monoclinic P21 /n space group. The HQ molecule bridges two p-PYNNs, and selects site (a) in p-PYNN as the hydrogen bond acceptor [i.e. ( p-PYNN)NOHO(HQ)OHON( p-PYNN)]. p-PYNN2 FA crystallizes in the monoclinic P21 /n space group. The FA molecule connects two p-PYNN molecules with an intermolecular hydrogen bond to site (b) [( p-PYNN)NHO(FA)OHN( p-PYNN)]. The 2:1 compound of p-PYNN and SA crystallizes with the crystal solvent, 1,4-dioxane (abbreviated as diox), in the formula for p-PYNN2 SAdiox. The crystal belongs to the triclinic P space group. The SA molecule occupies the space between two p-PYNNs, making contact with site (b), as FA does in the p-PYNN2 FA crystal. However the structure of SA indicates that it is a dianion in which the two protons are missing and, thus, the hydrogen bond is ionic [( p-PYNN)NH+ O–(SA)O– H+N( p-PYNN)]. The selectivity and features of the hydrogen bonds can be qualitatively understood in terms of competition between the electrostatic and charge-transfer terms in the hydrogen-bonding energy, which is governed by the acidity of the organic acids and the proton accepting abilities of the two sites in p-PYNN. The three molecular compounds exhibited different antiferromagnetic properties, which depend on the mutual arrangement of p-PYNN in the crystals. The intermolecular interactions were interpreted based on the McConnell’s spin polarization mechanism.

Molecular structures of some tertiary phosphine betaines in their crystalline adducts

Direct reaction of Ph 3P and Ph 2P(CH 2) 2PPh 2 with acrylic acid in AcOEt-acetone yielded the tertiary phosphine betaine triphenylphosphoniopropionate, Ph 3P +(CH 2) 2CO − 2 (L 1), and the novel double betaine ethylenebis(diphenylphosphoniopropionate) −O 2C(CH 2) 2Ph 2P +(CH 2) 2Ph 2P +(CH 2) 2CO − 2(L 2), respectively. Reaction of Ph 3P with fumaric acid in AcOEt/acetone did not afford the corresponding betaine derivative Ph 3P +CH(CO 2H)CH 2CO − 2, but decarboxylates to L 1 in situ. Four adducts of L 1, L 2 and Ph 3P +(CH 2) 3CO − 2 (L 3) have been prepared and characterized by single-crystal X-ray analysis. In L 1·2H 2O, 1, two betaine molecules are joined by donor hydrogen bonds from solvated H 2O molecules to form ten-membered rings which are further linked by hydrogen bonds to form chains extending parallel to [1 0 0]. In (HL 1) 2·(O 2CCHCHCO 2)·HO 2CCHCHCO 2H·2H 2O, 2, the fumaric acid molecules, fumarate anions and water molecules are interlinked by hydrogen bonds to form layers with an interlayer separation of 1 c ∗ = 10.713(4) A ̊ ; the HL 1 cations are sandwiched between adjacent layers and connected to them through hydrogen bonding. In L 2·(CH 3) 2CO·5H 2O, 3, two independent L 2 molecules adopt different orientations and are cross-linked by hydrogen bonds with the water molecules to form layers with an interlayer spacing of 1 a ∗ = 10.341(a) A ̊ ; the (CH 3) 2CO molecules are sandwiched between adjacent layers. In [(HL 3) 2(NO 3)]NO 3, 4, two independent HL 3 cations are joined by one of the NO − 3 group to form a dimeric cation.