THE CRYSTAL STRUCTURES OF AMMONIUM AND SODIUM 2-AMINO-3,5-DICHLOROBENZOATES

Abstract

The crystal structures of ammonium and sodium 2-amino-3,5-dichlorobenzoates were determined by the X-ray diffraction method. The ammonium salt crystallizes in the monoclinic system (space group P2₁/c) with a = 13.941(3), b = 9.128(3), c = 7.349(2) Å, β = 90.80(3)° and Z = 4. The structure consists of an ammonium cation hydrogen bonded to a carboxylate oxygen of the 2-amino-3,5-dichlorobenzoate anion. The sodium salt of 2-amino-3,5-dichlorobenzoic acid crystallizes in the triclinic system (space group P 1) with a = 8.033(2), 6 = 8.944(2), c = 17.350(3) Å, α = 76.72(3)°, β = 79.69(3)°, γ = 72.54(3)° and Z = 4. The compound is a polymer in which the sodium ions are coordinated by carboxylate oxygen atoms of the organic ligand and water molecules in an octahedral arrangement. IR spectra of the salts are discussed.     

Crystal structure and triboluminescence of the [Tb(BTFA)2(NO3)(TPPO)2] complex

The crystal structure of the [Tb(BTFA)₂(NO₃)(TPPO)₂] complex (TPPO is triphenylphosphine oxide, BTFA is benzoyltrifluoracetone), which exhibits strong triboluminescence, has been established by X-ray crystallography. The crystals are triclinic: a = 11.668(3) Å, b = 11.700(3) Å, c = 12.512(3) Å, α = 65.161(4°), β = 79.120(4)°, γ = 61.860(4)°, space group P1, Z = 1. The central terbium(III) atom coordinates two oxygen atoms from two triphenylphosphine oxide molecules (Tb-O, 2.264(3) and 2.273(3) Å), two oxygen atoms from the nitrate group (Tb-O, 2.460(3) and 2.476(3) Å), and four oxygen atoms from two benzoyltrifluoroacetonate groups (Tb-O, 2.329(3), 2.399(3), 2.351(3), and 2.367(3) Å). The coordination polyhedron of the Tb(III) atom is a distorted dodecahedron. The photoluminescence and triboluminescence spectra of the [Tb(BTFA)₂(NO₃)(TPPO)₂] complex are identical and caused by the f-f luminescence of Tb³⁺.     

Synthesis, molecular structure and intramolecular aromatic-ring stacking interaction of a novel binuclear Cu(Ⅱ) complex with 1, 10-phenanthroline and phenylacetate

The complex [Cu(phen)2(POAc)3]ClO·4H2O has been synthesized and investigated by elemental analysis, IR spec-troscopy and X-ray diffraction methods, where phen = 1,10-phenanthroline, POAc = phenylacetate group). The complex crystallizes in the triclinic space group PI with two molecules in a unit cell of dimensions a = 1.0579(2) nm, b = 1.2423(3) nm, c = 1.9190(4) nm, α = 71.84(1)°, β = 80.50(2)°, γ = 88.60(1)°, V = 2.3625(9) nm3, R = 0.0407 and Rw = 0.0656. The complex results from bridging of two Cu(phen)2 units by three carboxylate groups, and each Cu2 ion is in a distorted square pyramidal geometry with two nitrogen atoms of phen and three carboxylate oxygen atoms of POAc. It has been showed that intramolecular stacking interactions occur between the phenyl moieties of POAc and aromatic rings of phen, leading to a novel molecule structure with two coordinating modes of carboxylate ligands, of which two phenylacetates are μ2-carboxylate-O-bridging ligands, and the other is a μ2-carboxylate-     

Synthesis and crystal structure of a 3-d polymeric cobalt(II) and sodium complex with pyrazine-2-carboxylate as a bridging ligand

A complex with a three-dimensional structure {[Na₃Co(pyz)₃(H₂O)₄(ClO₄)₂]} _n (pyz = pyrazine-2-carboxylate anion) has been synthesized and its crystal structure determined by X-ray crystallography. The complex crystallizes in a triclinic system with a space group Pī and a = 8.598(11), b = 11.382(15), c = 14.496(19)?Å, α = 87.79(2), β = 88.21(2), γ = 82.08(2)°. The Co(II) ion is located in a distorted octahedral environment with three oxygen atoms and three nitrogen atoms, from the three pyr ligands. Na(1) ion is coordinated by four oxygen atoms and two nitrogen atoms, in which O(1), O(2), O(2A), N(4A) and N(6A) come from ligand pyr while O(15) comes from H₂O. Na(2) and Na(3) ions are each coordinated by six oxygen atoms. Through coordination of the bridging ligand pyr with Co(II) and Na(I) a three-dimensional net structure is formed.     

Crystal structure,and thermal and magnetic properties of 2,4-dinitrobenzoatoterbium(III) complex

The Tb(III) complex containing 2,4-dinitrobenzoate (2,4-DNB), Tb(2,4-DNB)₃(H₂O)₂]?·?C₂H₅OH has been synthesized and its crystal structure analyzed by X-ray diffraction methods. The complex crystallizes in the triclinic space group P 1, as a linear polymeric chain in which terbium ions are bridged by carboxylate groups. The eight-coordinate Tb ion with six carboxylate groups and two water molecules forms a slightly distorted square antiprism. Thermal and magnetic properties of the terbium complex were also studied.     

Synthesis,Crystal Structure and Fluorescence of A 1-D Polymeric Zinc(Ii) Complex with Pyrazine-2-Carboxylate as a Bridging Ligand

A one-dimensional chain complex {[Zn(pyz)(SCN)(H₂O)₂]·H₂O}_∞ (pyz = pyrazine-2-carboxylic anion) has been synthesized and its crystal structure determined by X-ray crystallography. The complex crystallizes in an orthorhombic system and the space group is P2 ₁2₁2₁ with a = 6.873(3), b = 9.847(4), c = 16.466(7) Å. The Zn(II) ion is located in a distorted octahedral environment with two oxygen atoms O(3) and O(4) from terminal ligands of two water molecules, another oxygen atom O(1) from the carboxylate group of pyz, and three nitrogen atoms, N(1), and N(2A) from two different pyz and N(3) from a terminal thiocyanate anion, in which a chelated five-membered ring is formed by coordination of O(1) and N(1) to the Zn(1) atom. Therefore, an infinite zigzag chain consisting of Zn(II) ions and pyz anions is constructed and the chains are linked together with hydrogen bonding from coordinated and uncoordinated water molecules. The fluorescence spectra for the bridging ligand Na(pyz) and the complex were measured at room temperature in aqueous solution and in the solid state.     

A Novel Cu(Ⅱ） Complex with 2,2′-Bipyridyl and L-Methioninate -synthesis,Characterization,Molecular Structure and Stability

The ternary Cu(II) complex with 2,2′‐bipyridyl (bipy) and L‐methioninate (L‐Met) has been synthesized and characterized by elemental analysis, molar conductivity, UV‐Vis spectra, IR spectra and pH‐potentiometric titration methods. The structure of the complex [Cu(L‐Met) (bipy) (H₂O)]ClO₄ · 3/8H₂O was characterized by the X‐ray diffraction analysis. It crystallizes in the triclinic system, space group P1 with four molecules in a unit cell of dimensions, a = 0.7656(2) nm, b = 1.3142(3) nm, c = 2.0596(4) nm, α = 97.70(3)°, β = 97.96(3)°, γ = 94.33(3)°, V= 2.0244(8) nm³, R₁, = 0.0441 and wR₂ = 0.0678. The crystal contains four crystllographically independent [Cu(L‐Met) (bipy) (H₂O)]⁺ complexes (Cu1—Cu4), having a distorted square‐pyramidal geometry with the same coordinated atoms around each copper center. The base plane is occupied by two nitrogen atoms of one bipy, the amino nitrogen atom and one carboxylate oxygen atom from each independent L‐Met moiety, and one water oxygen at an axial position. Cu1 and Cu3 are essentially enantiomers of Cu2 and Cu4. The four molecules are packed with each other by intermolecular hydrogen‐bonding and aromatic‐ring stacking interactions.     

Hydrothermal Synthesis and Structure of a New 3D Lanthanide—Carboxylate Framework,[La（btec）1／2（H2btec）1／2（H2O）]n（H4btec=1,2,4,5—Benzeneteracarboxylic acid）

The title complex, [La(btec)_1/2(H₂btec)_1/2 (H₂O)]_n (H₄btec= 1, 2,4,5‐benzenetetracarboxylic acid) (1) was synthesized by the hydrothermal reaction of 1,2,4,5‐benzenetetracarboxylic dianhydride with La(NO₃)₃·6H₂O in H₂O, and crystallizes in the triclinic system, space group P‐1 with a = 0.64403(3) nm, b = 0.94500(4) nm, c = 0.96380(5) nm, a = 88.535(2)°, β = 100.314(2)°, γ = 76.6470(10)°, V = 1.60968(10) nm³, Z = 2, and final R = 0.0274, R_w = 0.0735. In 1, each La(m) ion is coordinated by eight oxygen atoms from six carboxylate groups and one coordinated water molecule. Two different coordination modes of H₄btec were present in the structure, one of which contains two protonated carboxylate groups to balance the charge.     

A novel dimeric complex of dysprosium with pyridine-3-carboxylic acid: structure and photophysical properties

A dimeric complex [Dy(NIC)₃(H₂O)₂]₂ (HNIC = pyridine-3-carboxylic acid) has been synthesized. X-ray analysis reveals that it forms a novel dimeric structure through bridged oxygen atoms of carboxylate groups. The title complex crystallizes in space group P2₁/c, with a = 9.560(3), b = 11.601(4), c = 17.731(5)?Å, β = 91.572(4)°, V = 1965.7(10)?ų, D _c = 1.909?Mg/m³, Z = 2, F(000) = 1100, GOF = 0.956, R ₁ = 0.0248. Photophysical properties have been studied with ultraviolet absorption, excitation and emission spectra. The complex exhibits strong blue emission.     

Synthesis,Characterization and Molecular Structure of Ternary Cu(II) Complex with 1, 4, 8, 9‐Tetraazatriphenylene and L‐Phenylaninate

The complex [Cu(L‐Phe)(TATP)(H₂O)]ClO₄.0.5H₂O has been synthesized and investigated by elemental analysis, molar conductivity, spectroscopic and X‐ray diffraction methods, where TATP= 1,4,8,9‐tetraazatriphenylene and L‐phe = L‐phenylaninate group. The complex crystallizes in the triclinic space group PI with two molecules in a unit cell of dimensions a=0.5730(l), b = 1.0190(2), c = 2.1430(4), α= 97.50 (1)°, β = 95.33(3)°, γ= 102.85(1)°, V= 1.1998(4) nm³, R₁ = 0.0360, wR₂ = 0.0400. The crystal contains two independent [Cu(L‐Phe) (TATP)(H₂O)]⁺ complexes Cu1 and Cu2, having essentially the same distorted square‐pyramidal structure, where each Cu(II) ion coordinates two nitrogen atoms of TATP and the amino nitrogen and carboxylate oxygen atoms of L‐Phe in the equatorial positions and one water oxygen at an axial position.     

A new 3s–3d heterometallic polymer containing N‐methyliminodiacetic acid: synthesis,structure and characterization

A new complex {[Na₂(H₂O)₃(µ‐L)₂Cu]₄}_∞ (L = N‐methyliminodiacetic acid) has been synthesized and structurally characterized. The complex crystallizes in the monoclinic, space group C2/c, with the unit cell parameters a = 16.556(3) Å, b = 8.0622(13) Å, c = 12.671(2) Å, α = 90°, β = 95.849(2)°, γ = 90°. The central metal Cu (II) ion is coordinated with two nitrogen atoms and four oxygen atoms belonging to two ligands. Simultaneously, the sodium is six‐coordinated with oxygen atoms coming from the ligand and water molecule; the sodium atoms related are bridged by oxygen atoms, forming a sodium chain. The structure consists of CuL₂ moieties linked by sodium chain via the exo oxygen atoms of two ligands, forming a novel three‐dimensional structure. Moreover, elemental analysis, IR, UV‐vis, ESR spectroscopy and thermal stability were determined. Copyright © 2007 John Wiley & Sons, Ltd.     

Crystal structures of two Ca(II) complexes with imidazole-4,5-dicarboxylate and water ligands

The structure of compound I: poly-diaqua(μ-imidazole-4,5-dicarboxylato-N,O; -O′; -O′′, -O′′′) calcium(II) monohydrate [Ca(C₅H₂N₂O₄)(H₂O)₂·H₂O] is built of molecular sheets in which imidazole-4,5-dicarboxylate ligands bridge the metal ions using both carboxylate groups, each bidentate. Ca(II) is coordinated by six oxygen atoms and one hetero-ring nitrogen atom distributed at the apices of a capped tetragonal bipyramid. The basal plane of the pyramid is formed by two carboxylate oxygen atoms [d(Ca–O2?=?2.374(1)?Å, d(Ca–O4)?=?2.412(1)?Å] and two water oxygen atoms [d(Ca–O5)?=?2.384(1)?Å, d(Ca–O6)?=?2.455(1)?Å], the capped position is occupied by the carboxylate oxygen atom O3 [d(Ca–O3)?=?2.325(1)?Å], the hetero-ring nitrogen atom [d(Ca–N2)?=?2.523(1)?Å] and the carboxylate oxygen atom O4 [d(Ca–O2)?= 2.412(1)?Å] form the apices of the prism. The solvation water molecule plays a significant role in a framework of hydrogen bonds responsible for the stability of the crystal. The structure of compound II: trans-tetraquadi(H-imidazole-4,5-dicarboxylato-N,O) calcium(II) monohydrate, [Ca(C₅H₃N₂O₄)₂(H₂O)₄·H₂O] consists of monomers in which the Ca(II) ion is located on a centre of symmetry. The coordination around the Ca(II) is a strongly deformed pentagonal bipyramidal with the imidazole-4,5-dicarboxylate (4,5-IDA) ligands in the trans arrangement forming a dihedral angle of 68.3°. An imidazole-ring nitrogen atom [d(Ca–N)?=?2.632(2)?Å] and one carboxylate O atom [d(Ca–O)?=?2.531(2)?Å] from each ligand coordinate to the metal ion. The coordination is completed by four water oxygen atoms [d(Ca–O)?=?2.393(2)?Å] and [d(Ca–O)?=?2.367(2)?Å]. The coordinated water molecules act as hydrogen bond donors and acceptors to the unbonded carboxylate oxygen atoms in adjacent monomers giving rise to a three-dimensional molecular network.     

Preparation and Molecular Structure of Binuclear Nickel (I) Complex Bridged by 1,2,4, 5‐Benzenetetracarboxylato Tetravalent Anion

The title complex [(H₂O)₂(IMI)₃Ni(TCB)Ni(IMI)₃‐(H₂O)₂] H₂O (TCB = 1,2,4,5‐benzenetetracarboxylato te‐travalent anion; IMI = imidazole) has been prepared by the reaction of Ni(IMI)₃(Ac)₂ and TCB in aqueous solution. The crystal structure has been determined by single‐crystal X‐ray diffraction method. It crystallizes in the monoclinic system, space group P2₁/c(# 14), a = 1.2714(4) nm, b = 0.9411 (3) nm, c = 1.5869(4) nm, β= 108.54(2)°, V= 1.8001(9) nm³, Z = 2. The main feature of the crystal structure is a symmetric binuclear unit made up of two slightly distorted coordination octahedrons, which are bridged by TCB in monodentate fashion to each metal ion. Moreover three nitrogen atoms from three imidazoles, three oxygen atoms from two water molecules and one carboxylate group of TCB coordinated to a nickel (I) ion are found on a face of the octahedron respectively, so the octahedron is a facial isomer.     

Hydrothermal Syntheses,Crystal Structures,and Luminescent Properties of Three Organic‐Lanthanide Complexes with 3‐Hydroxycinnamic Acid

Three new homodinuclear lanthanide(III) complexes [Ln₂(L)₆(2,2′‐bipy)₂] [Ln = Tb^III ( 1 ), Sm^III ( 2 ), Eu^III ( 3 ); HL = 3‐hydroxycinnamic acid (3‐HCA); 2,2′‐bipy = 2,2′‐bipyridine] were synthesized and characterized by IR spectroscopy, elemental analyses, and X‐ray diffraction techniques. Complexes 1 – 3 crystallize in triclinic system, space group P$\bar{1}$ . In all complexes the lanthanide ions are nine‐coordinate by two nitrogen atoms from the 2,2′‐bipy ligand and seven oxygen atoms from one chelating L ligands and four bridging L ligands, forming distorted tricapped trigonal prismatic arrangements. The lanthanide(III) ions are intramolecularly bridged by eight carboxylate oxygen atoms forming dimeric complexes with Ln ··· Ln distances of 3.92747(15), 3.9664(6), and 3.9415(4) Å for complexes 1 – 3 , respectively. The luminescent properties in the solid state of HL ligand and Eu^III complex are also discussed.     

A Novel One-Dimensional Copper(II) Complex of a Carboxymethylated Tricyclic Azacrown Ether Derivative Linked by Hydrogen Bonding

The complex [CuL]·H₂O(H₂L=4,13-dioxa-1,7,10,16-tetraaza-1,16:7,10-bis(ethylene)-9,18-diacetic acid cyclooctadecane-8,17-dione) has been synthesized and structurally characterized. It crystallizes in the triclinic system, space group P1 with a=9.0111(7), b=9.4371(7), c=14.3092(11)Å, a=89.846(2), β=81.871(2), γ=65.616(2)°, V=1095.05(14)&Aringsup3;, and Z=1. The structure of the complex consists of two different CuL coordination moieties in which six-coordinated copper ions each have different coordination environments. In both CuL moieties, copper ions are coordinated to two tertiary nitrogen and four oxygen atoms, two from the crown ether ring and two from the pendant carboxylate groups. These two different CuL moieties are linked alternately by water molecules to form an infinite one-dimensional chain structure through hydrogen bonding between the water molecule and the uncoordinated oxygen atom of the carboxyl group.     

Synthesis,Crystal Structure and Magnetism of A 1-D Polymeric Manganese(II) Complex with 2-Hydroxyl-2-Hydroxylate-Malonate as Bridging Ligand

A one-dimensional chain complex {Na[MnL(H₂O)₂]} _n (L = 2-hydroxyl-2-hydroxylate-malonate trivalent anion) has been synthesized and its crystal structure determined by X-ray crystallography. In the complex each Mn ion is located in a distorted octahedral environment with two oxygen atoms O(7) and O(8) from terminal ligands of two H₂O molecules, and four other coordinating oxygen atoms O(1), O(5), O(3A) and O(6A) from two bridging ligands, respectively. Each bridging ligand provides four coordinating oxygen atoms, in which O(6) comes from the hydroxylate, O(5) from the hydroxyl, and O(1) and O(3) from two carboxylate groups, respectively. The O(1) and O(5) atoms coordinate to one Mn ion and the O(3) and O(6) atoms coordinate to another Mn ion; a one-dimensional chain is thereby constructed. The variable-temperature magnetic susceptibility of the complex was measured in the 4–300 K range. The magnetic coupling parameter is consistent with an antiferromagnetic exchange and generates the antiferromagnetic coupling parameter, 2J=–0.0544 cm^–1.     

Crystal Structure and Luminescence of a Europium Coordination Polymer {[Eu(p-MOBA)_3·2H_2O]·0.5H_2O· 0.5(4,4′-bipy)}_∞

ＩｎｔｒｏｄｕｃｔｉｏｎＭｏｎｏｎｕｃｌｅａｒ ,ｄｉｎｕｃｌｅａｒａｎｄｐｏｌｙｍｅｒｉｃｔｙｐｅｓｏｆｃｒｙｓ ｔａｌｓｔｒｕｃｔｕｒｅｓｆｏｒｌａｎｔｈａｎｉｄｅｃｏｍｐｌｅｘｅｓｗｉｔｈｂｅｎｚｏｉｃａｃｉｄａｎｄｉｔｓｄｅｒｉｖａｔｉｖｅｓｈａｖｅｂｅｅｎｏｂｔａｉｎｅｄｂｅｃａｕｓｅｏｆｔｈｅｖａｒｉ ａｔｉｏｎｏｆｂｒｉｄｇｉｎｇｆｏｒｍｓｆｏｒｃａｒｂｏｘｙｌａｔｅｇｒｏｕｐａｎｄｃｏｏｒｄｉｎａ ｔｉｏｎａｂｉｌｉｔｙｏｆｄｉａｍｍｉｎｅｌｉｇａｎｄｓ ,ｓｕｃｈａｓ 1,10 ｐｈｅｎａ…     

The coordination properties of aminobenzoate ligands in complexes with alkali metals

The crystal structures of sodium 4-amino-2-hydroxybenzoate dihydrate [NaL·2H₂O, L?= C₆H₃(NH₂)(OH)COO] and potassium 2-aminobenzoate monohydrate [KL*·H₂O, L*?=?C₆H₄(NH₂)COO] were determined by X-ray diffraction methods. The compound NaL·2H₂O crystallizes in the monoclinic system, space group P2₁/c with a?=?8.820(2), b?=?14.632(3), c?=?6.948(2)?Å, β?=?97.88(3)°. The structure consists of sodium ion pairs joined together by tridentate 4-amino-2-hydroxybenzoate moieties creating a polymeric chain. In the metal centres, two water molecules bridge the sodium atoms. Five oxygen atoms and one nitrogen atom form a distorted octahedral environment. The compound KL*·H₂O crystallizes in the monoclinic system, space group P2₁/c with a?=?14.684(3), b?=?7.618(2), c?=?7.512(2)?Å, β?=?96.95(3)°. The structure consists of octacoordinated potassium atoms bonded with three water molecules and five carboxylate oxygen atoms. Water molecules appear as bridging ligands. The 2-aminobenzoate ligand acts as a pentadentate ligand with the molecular network stabilized by hydrogen bonds. Among the polymeric chains in both structures appear noncovalent interactions of type N?H···X.     

有机锡1,1′-亚甲基双(1H-吡唑-4-甲酸酯)的合成、结构与抗肿瘤活性

通过1,1′-亚甲基双(1H-吡唑-4-甲酸)(CH2(PzCO2H)2)与R3SnOH或(R3Sn)2O的反应,合成了4个有机锡1,1′-亚甲基双(1H-吡唑-4-甲酸酯)衍生物(CH2(PzCO2SnR3)2,R=Ph(1),环己基(2),Et(3),n-Bu(4))。通过红外和核磁对这些配合物进行了详细的结构表征。配合物1和3的X射线单晶衍射分析表明,这2个配合物中的吡唑氮原子均没有参与配位,但它们的羧酸根却表现出明显不同的配位方式。配合物1中羧酸根为单齿配体,且该配合物表现为简单双核结构;配合物3中羧酸根为双齿配体,其通过羧基的桥式双齿配位方式形成具有32元大环结构单元的二维配位高分子。初步的生物活性测试表明,这些有机锡衍生物对MCF-7和A549细胞具有很好的体外细胞毒性。     

Synthesis,crystal structure and magnetism of a 1-D polymeric manganese(II) complex with pyrazine-2-carboxylate as bridging ligand

A one-dimensional chain complex {[Mn(pyz)(SCN)(H₂O)₂] · H₂O} (pyz = pyrazine-2-carboxylic anion) has been synthesized and its crystal structure determined by X-ray crystallography. In the complex each Mn ion is located in a distorted octahedral environment with two oxygen atoms O(3), O(4) from terminal ligands of two water molecules, another oxygen atom O(1) from the carboxylate group of pyz, and three nitrogen atoms N(1), N(2A) from two different pyz units and N(3) from the terminal ligand thiocyanate anion, in which a chelated five-membered ring is formed by coordination of O(1) and N(1) to the Mn(1) atom. Thus, an infinite zigzag chain consisting of Mn and pyz is constructed and the chains are linked together by hydrogen bonding from coordinated and uncoordinated water molecules, the sulfur atom of thiocyanate and the carboxylate oxygen of pyz. The variable-temperature magnetic susceptibility of the complex was measured in the 4–300 K range. The magnetic coupling parameter is consistent with an antiferromagnetic exchange between the two manganese(II) centers and the data fit a binuclear magnetic exchange model based on the Hamiltonian operator (H = –2JS ₁ S ₂, S ₁ = S ₂ = 5/2), giving the antiferromagnetic coupling parameter of 2J = –0.17 cm^–1. This is the first pyrazine-2-carboxylic anion bridging complex dealing with the magnetic interaction study.