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Crystals of the title compounds, namely 1-(diaminomethylene)thiouron-1-ium perchlorate, C2H7N4S+.ClO4-, 1-(diaminomethylene)thiouron-1-ium hydrogen sulfate, C2H7N4S+.HSO4-, 1-(diaminomethylene)thiouron-1-ium dihydrogen phosphate, C2H7N4S+.H2PO4-, and its isomorphic relative 1-(diaminomethylene)thiouron-1-ium dihydrogen arsenate, C2H7N4S+.H2AsO4-, are built up from a nonplanar 1-(diaminomethylene)thiouron-1-ium cation and the respective anion linked together via N-H...O hydrogen bonds. Both arms of the cation are planar, but they are twisted with respect to one another around the central N atom. Ionic and extensive hydrogen-bonding interactions join oppositely charged units into layers in the perchlorate, double layers in the hydrogen sulfate, and a three-dimensional network in the dihydrogen phosphate and dihydrogen arsenate salts. This work demonstrates the usefulness of 1-(diaminomethylene)thiourea in crystal engineering for the formation of supramolecular networks with acids.

Four salts, namely, 2,4,6‐triaminopyrimidinium 6‐chloronicotinate dihydrate, C4H8N5+·C6H3ClNO2−·2H2O, (I), 2,4,6‐triaminopyrimidinediium pyridine‐2,6‐dicarboxylate dihydrate, C4H9N52+·C7H3NO42−·2H2O, (II), 2,4,6‐triaminopyrimidinediium sulfate monohydrate, C4H9N52+·SO42−·H2O, (III), and 2,4,6‐triaminopyrimidinium 3,5‐dinitrobenzoate dihydrate, C4H8N5+·C7H3N2O6−·2H2O, (IV), were synthesized and characterized by X‐ray diffraction techniques. Proton transfer from the corresponding acid to the pyrimidine base has occurred in all four crystal structures. Of the four salts, two [(I) and (IV)] exist as monoprotonated bases and two [(II) and (III)] exist as diprotonated bases. In all four crystal structures, the acid interacts with the pyrimidine base through N—H...O hydrogen bonds, generating an R22(8) ring motif. The sulfate group mimics the role of the carboxylate anions. The water molecules present in compounds (I)–(IV) form water‐mediated large ring motifs. The formation of water‐mediated interactions in these crystal structures can be used as a model in the study of the hydration of nucleobases. Water molecules play an important role in building supramolecular structures. In addition to these strong hydrogen‐bonding interactions, some of the crystal structures are further enriched by aromatic π–π stacking interactions [(I) and (II)]. [ABSTRACT FROM AUTHOR]

A simple, readily prepared biphenyl bis‐amidinium compound (1⋅Cl2) is able to selectively precipitate sulfate from water. The precipitant is effective at concentrations as low as 1 mM and shows complete selectivity against monovalent anions, and high selectivity even against CO32− and HPO42−. It is highly effective (>90 % sulfate removed) in both seawater and highly acidic conditions relevant to mining waste‐streams. X‐ray crystallography reveals that 1⋅SO4 forms a tightly packed, anhydrous, structure where each sulfate anion receives eight hydrogen bonds from amidinium N−H hydrogen bond donors. [ABSTRACT FROM AUTHOR]

The formation and crystal structure of a hydrated molecular salt that results in a square network is reported. The crystalline solid is based upon the tetraprotonated photoproduct rtct‐tetrakis(pyridin‐4‐yl)cyclobutane (4H‐rtct‐TPCB)4+ along with two sulfate anions (SO42−) and eight waters of hydration, namely, 4,4′,4′′,4′′′‐(cyclobutane‐1,2,3,4‐tetrayl)tetrapyridinium bis(sulfate) octahydrate, C24H24N44+·2SO42−·8H2O. The fully protonated photoproduct acts as a four‐connecting node within the square network by engaging in four charge‐assisted N+—H...O hydrogen bonds to the sulfate anion. The observed hydrogen‐bonding pattern in this square network is akin to T‐silica, which is a metastable form of SiO2. The included water molecules and sulfate anions engage in numerous O—H...O hydrogen bonds to form various hydrogen‐bonded ring structures. [ABSTRACT FROM AUTHOR]

Luminol is chemically sufficiently stable to be diprotonated at high proton concentrations as provided by concentrated sulfuric acid. The luminol dication (5‐ammonium‐2‐hydro‐1,4‐phthalzinediol) sulfate was isolated as macroscopic single crystals and its structure was determined and refined from single‐crystal X‐ray data collected at 173 K [cell parameters: a = 8.3994(17) Å, b = 6.9985(14) Å, c = 17.486(4) Å, β = 90.85(3)°, V = 1027.8(4) Å3, space group P21/c]. The structure is comprised of layers stacked along the b axis. Intralayer interactions are accomplished by strong hydrogen bonds of three luminol dications to one central [SO4]2– ion. Interlayer interactions are formed by weak hydrogen bonds of one luminol dication to two [SO4]2– ions in the adjacent layers, respectively, and alternating sandwich and parallel‐displaced π‐π‐stacking of the 1‐hydropyridazine‐3,6‐diol moieties of luminol dications in adjacent layers, respectively. [ABSTRACT FROM AUTHOR]

Studies on α‐nickel sulfate hexahydrate (NSH) crystals grown under different conditions are undertaken to investigate how changes in growth conditions affect crystal properties and whether or not there is any modification of the average crystal structure due to changes in crystallization conditions. Thermogravimetric and microhardness studies were carried out on the crystals grown from two different aqueous solutions, one of them containing an excess of sulfuric acid. Raman spectra were recorded and a single‐crystal neutron diffraction investigation was conducted on both crystals. A detailed comparison between the two crystal structures and their Raman spectra showed that, although the two crystal structures are very similar, there are slight differences, such as the change in unit‐cell volume, differences in the ionic structure, particularly of the sulfate ions, and changes in the hydrogen‐bonding network. During solution crystal growth of a salt like NSH, varying the ionic environment around the solute ions influences the interionic interactions between them. Hence it is suggested that the above‐mentioned structural differences result from a fine‐tuning of the interionic interaction between the cations and anions of NSH in the solution phase. This difference is finally carried over to the crystalline phase. The resulting small crystal structure differences are enough to produce measurable changes in the thermal stability and fragility of the crystals. These differences in crystal properties can be explained on the basis of the observed structural differences between the two crystals grown under different conditions. [ABSTRACT FROM AUTHOR]

The chemistry of organically templated metal sulfates has attracted interest from the materials science community and the development of synthetic strategies for the preparation of organic-inorganic hybrid materials with novel structures and special properties is of current interest. Sulfur-oxygen-metal linkages provide the possibility of using sulfate tetrahedra as building units to form new solid-state materials. A series of novel organically templated metal sulfates of 2-aminopyridinium (2ap) with aluminium(III), cobalt(II), magnesium(II), nickel(II) and zinc(II) were obtained from the respective aqueous solutions and studied by single-crystal X-ray diffraction. The compounds crystallize in centrosymmetric triclinic unit cells in three structure types: type 1 for 2-aminopyridinium hexaaquaaluminium(III) bis(sulfate) tetrahydrate, (C5H7N2)[Al(H2O)6](SO4)2·4H2O, (I); type 2 for bis(2-aminopyridinium) tris[hexaaquacobalt(II)] tetrakis(sulfate) dihydrate, (C5H7N2)2[Co(H2O)6]3(SO4)4·2H2O, (II), and bis(2-aminopyridinium) tris[hexaaquamagnesium(II)] tetrakis(sulfate) dihydrate, (C5H7N2)2[Mg(H2O)6]3(SO4)4·2H2O, (III); and type 3 for bis(2-aminopyridinium) hexaaquanickel(II) bis(sulfate), (C5H7N2)2[Ni(H2O)6](SO4)2, (IV), and bis(2-aminopyridinium) hexaaquazinc(II) bis(sulfate), (C5H7N2)2[Zn(H2O)6](SO4)2, (V). The templating role of the 2ap cation in all of the reported crystalline substances is governed by the formation of characteristic charge-assisted hydrogen-bonded pairs with sulfate anions and the presence of π-π interactions between the cations. Additionally, both coordinated and uncoordinated water molecules are involved in hydrogen-bond formation. As a consequence, extensive three-dimensional hydrogen-bonding patterns are formed in the reported crystal structures. [ABSTRACT FROM AUTHOR]

The design and synthesis of tripodal ligands 1-3 based upon the N-methyl-1,3,5-benzenetricarboxamide platform appended with three aryl urea arms is reported. This ligand platform gives rise to highly preorganized structures and is ideally suited for binding SO42- and H2PO4- ions through multiple hydrogen-bonding interactions. The solid-state crystal structures of 1-3 with SO42- show the encapsulation of a single anion within a cage structure, whereas the crystal structure of 1 with H2PO4- showed that two anions are encapsulated. We further demonstrate that ligand 4, based on the same platform but consisting of two bis-urea moieties and a single ammonium moiety, also recognizes SO42- to form a self-assembled capsule with [4:4] SO42-:4 stoichiometry in which the anions are clustered within a cavity formed by the four ligands. This is the first example of a self-sorting self-assembled capsule where four tetrahedrally arranged SO42- ions are embedded within a hydrophobic cavity. [ABSTRACT FROM AUTHOR]

A coordination polymer constructed from the ligand 2, 2′-bipyridine-5, 5′-carboxylate (Bpydc) with hybrid functional groups and the co-ligand SO42- was synthesized and structurally characterized by single-crystal X-ray diffraction. It shows an intriguing structure of parallel infinite Mn-SO4 double chains resulting from the coordination of SO42- groups to central MnII atoms. Further linkage of the Bpydc ligands with the Mn-SO4 double chains gave rise to a three-dimensional pillar-layer framework, in which the Mn-SO4 double chains act as pillars and the Bpydc ligands form the layers. Two types of hydrogen bonds are observed between the SO42- and carboxylate groups. The assembly of the Bpydc ligand and the SO42- co-ligand with central MnII atoms results in a binodal (3, 5)-connected network with a rare 3, 5T1 topology, confirming the feasibility of this strategy in constructing novel architectures. The formation of the dense pillar-layer framework sustained by Mn-SO4 double chains and hydrogen bonds enhances the stability of this coordination polymer and results in a high thermal stability up to 400°C. [ABSTRACT FROM AUTHOR]

We report a new sulfate receptor, anchored onto 2,5-diketopiperazine units, which results in the formation of two types of supramolecules; one in which the sulfate ion guest fits snugly into extended cavities and the other in which the guest is sandwiched between layers. In each case, the anion is held by six hydrogen bonds from the host. 1H NMR spectroscopic solution studies enabled the construction of Job plots, and calculation of stoichiometry and association constants. These findings are of possible significance in drug design and for construction of combinatorial libraries. [ABSTRACT FROM AUTHOR]

The title compound, [Sr7(C7H3NO4)6(SO4)(H2O)6] n, has been synthesized by an ionothermal method using the ionic liquid 1-ethyl-3-methylimidazolium ([Emim]Br) as solvent, and characterized by elemental analysis, energy-dispersive X-ray spectroscopy, IR and single-crystal X-ray diffraction. The structure of the compound can be viewed as a three-dimensional coordination polymer composed of Sr2+ cations, pyridine-2,6-dicarboxylate anions, sulfate anions and water molecules. The compound not only exhibits a three-dimensional structure with a unique coordination mode of the sulfate anion, but also features the first example of a heptanuclear strontium(II) coordination polymer. The structure is further stabilized by O-H...O hydrogen bonds and π-π stacking interactions. [ABSTRACT FROM AUTHOR]

Infrared spectra of K2NiSeO42·6H2O and NH42NiSeO42·6H2O containing SO42ions and those of K2NiSO42·6H2O and K2NiSeO42·6H2O containing NH4ions are presented and discussed in the region of ν3and ν1of the sulfate ions and in the region of ν4of the NH4ions, respectively. The SO42ions matrixisolated in the selenate matrices approximately 1 mol exhibit three bands for ν3and one band for ν1in agreement with the low site symmetry C1of the host selenate ions. The NH4guest ions included in the potassium sulfate matrix are characterized also with three bands for ν4. However, the ammonium ions in NH42NiSeO42·6H2O as well as those included in K2NiSeO42·6H2O display four infrared bands corresponding to ν4due probably to some kind of disorder of the ammonium ions. The extent of energetic distortion of the isomorphously included sulfate ions as deduced from the values of Δν3and Δνmaxis commented. The spectroscopic experiments reveal that the SO42guest ions are weaker distorted in the selenate matrices as compared to the same ions in the neat sulfates due to the larger unitcell volumes of the selenate compounds. The band positions of the water librations in the host potassium compounds are affected by the included ammonium cations. The formation of hydrogen bonds between the NH4guest ions and the XO42host ions leads to a decrease in the proton acceptor capabilities of the anions and as a result the hydrogen bonds weaken on going from the neat potassium compounds to the mixed crystals. © 2010 WILEYVCH Verlag GmbH & Co. KGaA, Weinheim [ABSTRACT FROM AUTHOR]

The features of hydrogen bonds in DsrD protein from sulfate-reducing bacteria have been investigated by neutron protein crystallography. The function of DsrD has not yet been elucidated clearly, but its X-ray crystal structure revealed that it comprises a winged-helix motif and shows the highest structural homology to the DNA-binding proteins. Since any neutron structure of a DNA recognition protein has not yet been obtained, here detailed information on the hydrogen bonds in the winged-helix-motif protein is given and the following features found. (i) The number of hydrogen bonds per amino acid of DsrD is relatively fewer than for other proteins for which neutron structures were determined previously. (ii) Hydrogen bonds are localized between main-chain and main-chain atoms; there are few hydrogen bonds between main-chain and side-chain atoms and between side-chain and side-chain atoms. (iii) Hydrogen bonds inducted by protonation of specific amino acid residues (Glu50) seem to play an essential role in the dimerization of DsrD. The former two points are related to the function of the DNA-binding protein; the three-dimensional structure was mainly constructed by hydrogen bonds in main chains, while the side chains appeared to be used for another role. The latter point would be expected to contribute to the crystal growth of DsrD. [ABSTRACT FROM AUTHOR]

The asymmetric unit of the title compound, C4H8N4O2+·-C4H7N4O+SO42-·HSO4-, contains one half of an O—H⋯O hydrogen-bonded dimer-like unit, viz. a C4H8N4O2+·-C4H7N4O+ unit and one half of an SO42-·HSO4- unit. Each of these dimeric units lies on an inversion centre, with the O-bound H atoms disordered across inversion centres. The cations and part of the anions are arranged in layers parallel to the (-120) plane through a combination of N—H⋯O, N—H⋯S and O—H⋯S hydrogen bonds. [ABSTRACT FROM AUTHOR]

In the title compound, [Mg(C2H5NO2)2(H2O)4][Mg(H2O)6]-(SO4)2, the MgII atoms of both dications lie on inversion centres, and each of them is in an octahedral coordination environment. The glycine molecule exists in the zwitterionic form. The [Mg(H2O)6]2+ and [Mg(C2H5NO2)2-(H2O)4]2+ dications pack as alternate layers parallel to the ab plane, with the sulfate anions lying between them. The ions are linked to form a three-dimensional network by O—H⋯O and N—H⋯O hydrogen bonds. [ABSTRACT FROM AUTHOR]

In the crystal structures of the title compounds, hexa­aqua­cobalt(II) tetra­aqua­diglycinato­cobalt(II) bis(sulfate), [Co(H2O)6][Co(C2H5NO2)2(H2O)4](SO4)2, (I), poly[diaqua-μ3-glycinato-di-μ4-thio­sulfato-tetra­sodium(I)], [Na4(C2H5NO2)(S2O3)2(H2O)2] n, (II), and poly[μ2-glycinato-μ4-thio­sulfato-dipotassium(I)], [K2(C2H5NO2)(S2O3)] n, (III), all atoms are located on general positions, except the Co atoms in (I), which are located on inversion centres. In (I), hydrogen bonds play an important role, while the alkali thio­sulfate compounds are characterized by three-dimensional frameworks of polyhedra. Relations to other compounds of glycine and metal sulfates are commented on. [ABSTRACT FROM AUTHOR]

In the title coordination polymer, [Cd2(SO4)2(C13H8N4)(H2O)2] n, there are two crystallographically independent CdII centres with different coordination geometries. The first CdII centre is hexacoordinated by four O atoms of four sulfate ligands, one water O atom and one N atom of a 1 H-imidazo[4,5- f][1,10]phenanthroline (IP) ligand, giving a distorted octahedral coordination environment. The second CdII centre is heptacoordinated by four O atoms of three sulfate ligands, one water O atom and two N atoms of one chelating IP ligand, resulting in a distorted monocapped anti-trigonal prismatic geometry. The symmetry-independent CdII ions are bridged in an alternating fashion by sulfate ligands, forming one-dimensional ladder-like chains which are connected through the IP ligands to form two-dimensional layers. These two-dimensional layers are linked by interlayer hydrogen bonds, leading to the formation of a three-dimensional supramolecular network. [ABSTRACT FROM AUTHOR]

In the structure of the novel zinc complex catena-poly[[diaqua(4-hydroxybenzohydrazide)zinc(II)]-μ-sulfato], [Zn(SO4)(C7H8N2O2)(H2O)2] n, the complex cations are linked by sulfate counter-ions into helical polymeric chains extending along the b axis. Each helix is stabilized by six intrachain hydrogen bonds involving stronger O-H...O (1.83-2.06 Å) and weaker N-H...O (2.20-2.49 Å) interactions. The ZnII atom displays a distorted octahedral geometry formed by the 4-hydroxybenzohydrazide ligand, two water molecules and two SO42− ions, which is very similar to the metal-atom environment in a previously reported CoII complex [Zasłona, Drożdżewski & Kubiak (2010). J. Mol. Struct. 982, 1-8], especially the Zn-O and Zn-N bond lengths of 2.0453 (12)-2.1602 (9) and 2.1118 (12) Å, respectively. [ABSTRACT FROM AUTHOR]

The article focuses on a single-crystal study of the organic compound streptidinium sulfate monohydrate. It notes that the order of the components of the compound are in double helices that are based on hydrogen bonds. It adds that the streptidinium cation is needed for the transport of two positive charges required for the stoichoimetry of the crystal. Under the study, an attempt to crystallize a molecular complex of streptomycin sulfate with the use of p-sulfonatocalix[4]-arene resulted in the formation of streptidine crystals.

The title compound, Eu2(SO4)3·8H2O, crystallizes in space group C2/ c, with one of the anions lying on a twofold rotation axis and the other in a general position, and is best formulated as [Eu(H2O)4/1(SO4)3/3(SO4)1/2]2, where one of the anions lies across a twofold axis. The coordination environment of EuIII consists of four water mol­ecules and four sulfate ions. All the water mol­ecules and sulfate ions are involved in hydrogen-bonding interactions. The structure is similar to that previously determined at 293 K [Wei & Zheng (2003). Z. Kristallogr. New Cryst. Struct. 218, 277–278], but the cell parameters and the interatomic distances are more precise in the present determination. [ABSTRACT FROM AUTHOR]

In the title compound, [Zn(SO4(C18H12N6)(H2O)2]·2H2O, the metal complex is monomeric, with an octahedral ZnII centre coordinated by the tridentate ligand 2,4,6-tris(2-pyridyl)-1,3,5triazine (tpt), two aqua molecules and a monodentate sulfate ion. A complex hydrogen-bonding scheme is built up out of the profuse availability of donors and acceptors (O-H···O/N and C-H···O) which, in addition to π-π interactions between tpt groups, define a three-dimensional assembly. [ABSTRACT FROM AUTHOR]

The title compound, [Cu(C2H6OS)6](HSO4)2, is composed of discrete [Cu(C2H6OS)6]2+ cations and HSO4− anions. The Cu atom is located on a centre of inversion. Two HSO4− anions are connected via hydrogen bonds, forming a centrosymmetric dimer. [ABSTRACT FROM AUTHOR]

The title compound, (C10H10N2)[Co(H2O)6](SO4)2, consists of 4,4′-bipyridinium dications, hexa­aqua­cobalt(II) cations and sulfate anions that are linked by hydrogen bonds into a network structure. Six water mol­ecules are coordinated to the Co atom and the geometry is octahedral. The bipyridinium cation has site symmetry 2 and the Co atom lies on a position of site symmetry 2/ m. [ABSTRACT FROM AUTHOR]

The title compound, 2C4H8N3O+·SO42−, crystallizes with two creatininium cations and one sulfate anion in the asymmetric unit. Cations and anions dimerize through N—H...O hydrogen bonds forming R22(8) ring motifs. Furthermore, these rings are connected via N—H...O hydrogen bonds, leading to C22(6) and C22(8) chain motifs. These interactions lead to a parallel set of hydrogen-bonded lamellar aggregations propagating along the c axis of the unit cell. Another cation is situated above these sheets, leading to a grid-like structure. [ABSTRACT FROM AUTHOR]

The title crystal structure, {[Cu(SO4)(C6H6N2O)(H2O)2]·H2O}6, is a monoclinic polymorph of the previously reported triclinic structure [Sieroń & Bukowska-Strzyżewska (1999). Acta Cryst. C 55, 491–494] in which sulfate ligands bridge six-coordinate Cu atoms, generating an extended one-dimensional chain structure along [010]. Neighboring chains are connected by N—H⋯O(sulfate) hydrogen bonds into ladders, which are further connected into two-dimensional layers perpendicular to the [100] direction by N—H⋯O(water) and O(water)—H⋯O hydrogen bonds. These layers are connected by O—H⋯O hydrogen bonds into a three-dimensional network. [ABSTRACT FROM AUTHOR]

The two independent Zr atoms in the asymmetric unit of the title structure, (C2H10N2)5[Zr(SO4)5(H2O)][Zr(SO4)4(H2O)2], are both eight-coordinate. In the docedahedral aqua­penta­sulfatozirconate(IV) hexa­anion, three of the sulfate groups are monodentate, whereas the other two chelate to the metal atom. In the square-anti­prismatic diaqua­tetra­sulfato­zircon­ate(IV) tetra­anion, two of the sulfate groups are monodentate and two are bidentate. Two of the five 1,2-ethanediammonium cations lie about crystallographic centres of inversion. The cations and anions are linked into a three-dimensional network architecture by hydrogen bonds. [ABSTRACT FROM AUTHOR]

In the structure of the title compound, 2C5H7N2+·SO42−, the S atom of the sulfate anion lies on a twofold axis. The structure is stabilized by an extensive network of N—H⋯O hydrogen bonds. [ABSTRACT FROM AUTHOR]

In 2,2′-bipyridinium thio­cyanate, C10H9N2+·NCS−, the cations are disordered over two sets of sites with occupancies of 0.845 (2) and 0.155 (2). The ions are linked into simple chains by a combination of N—H⋯N and C—H⋯N hydrogen bonds, regardless of the orientation of the cation. In 2,2′-bipyridinium picrate, C10H9N2+·C6H2N3O7−, the bond distances in the anion indicate a markedly non-classical electronic structure; the component ions are linked by a combination of six independent hydrogen bonds, viz. one of N—H⋯O type and five of C—H⋯O type, into a complex chain containing five distinct types of ring. The ions in 2,2′-bipyridinium hydrogensulfate, C10H9N2+·HSO4−, are linked by a combination of five hydrogen bonds, viz. one each of O—H⋯O and N—H⋯O types, and three of C—H⋯O type, into complex sheets built from two one-dimensional substructures, each in the form of a complex chain of rings. [ABSTRACT FROM AUTHOR]

The crystal structure of dibrucinium sulfate­(VI) hepta­hydrate, 2C23H27N2O4+·SO42−·7H2O, has been determined. The components are packed in layers. Puckered brucinium sheets are separated by layers consisting of hydrogen-bonded disordered sulfate(VI) anions and water mol­ecules. Both layers, the cationic together with the anionic/water, are linked by N—H+⋯O− and O—H⋯O hydrogen bonds. [ABSTRACT FROM AUTHOR]

The cation and anion of the title compound, (C7H10N)2[Mn(SO4)2(H2O)4], are linked by hydrogen bonds into a three-dimensional network structure. The Mn atom of the anion lies on a centre of inversion in an octa­hedral coordination geometry of water and sulfate ligands. [ABSTRACT FROM AUTHOR]