Structures of four- and six-coordinate monomers of [N,N′-bis(5-chlorosalicylidene)-1,3-diaminopropane]nickel(II)

[N,N-Bis(5-chlorosalicylidene)-1,3-diaminopropane]nickel(II) [Ni(C₁₇H₁₄N₂O₂Cl₂)] 1 and [N,N-Bis(5-chlorosalicylidene)-1,3-diaminopropane]nickel(II) dihydrate [Ni(C₁₇H₁₄N₂O₂Cl₂).2(H₂O)] 2 were synthesized, and their crystal structures were determined. Compound 1 is monoclinic, space group C2/c, a = 21.063(4), b = 8.151(1), c = 9.421(2) Å, = 94.16(1)°, V = 1613.2(5) ų, Z = 4 and D_c = 1.680 g cm^–3. Compound 1 contains a crystallographic twofold axis, and the whole molecule is not planar. The two Schiff base moieties, which in themselves are planar, are twisted with respect to one another. The least-squares planes through each half of the molecule are inclined at an angle of 29.1(1)°. The Ni atom is in a square-planar environment. The Ni—N and Ni—O distances are 1.958(2) and 1.910(2) Å, respectively. Compound 2 is orthorhombic, space group Pnma, witha = 7.892(1), b = 23.396(2), c = 9.992(1) Å, V = 1846.3(3) ų, Z = 4 and D_c = 1.597 g cm^–3. Compound 2 has crystallographic mirror symmetry, and again, the whole molecule is not planar. The two planar Schiff base moieties inclined at an angle of 38.7(1)°. The Ni atom is in a distorted octahedral geometry and coordinated by the donor atoms of the ligand in the horizontal plane, and the coordination sphere is completed by O atoms of two water molecules.     

Synthesis and crystal structure of (S, S, S, S)-N, N′-bis[N-(P-toluenesulfonamido)-1,2-diphenylethyl]ethylenediamine

(S, S, S, S)-N,N′-bis[N-(p-toluenesulfonamido)-1,2-diphenylethyl] ethylenediamine (C₄₄H₄₆N₄O₄S₂), has been synthesized and structurally characterized by elemental analysis, ¹H-NMR, MS, IR and single-crystal X-ray diffraction. The title compound contains four chiral centers with C atoms in S configuration. Molecules are connected to one another by hydrogen bonds between sulfonamide nitrogen and sulfonyl oxygen to form chains alone a axis.     

Structure of N,N′-bis[3-(aminocarbonyl)propyl]sulfamide

The title compound, C₈H₁₈N₄O₄S, possesses C₂ symmetry, with the S atom lying on a twofold rotational axis in the unit cell. The sulfamide group of each molecule forms four identical hydrogen bonds with those of its four neighboring molecules, resulting in a rhombic two-dimensional hydrogen bonded network. This network assembles in the third dimension via hydrogen bonds between the primary amide groups of the substituents that extend from the 2D sulfamide sheets. The primary amide groups form a hydrogen-bonded eight-membered cyclic dimer around a two-fold rotational axis. These cyclic dimers are linked into a ribbon-like network via hydrogen bonding interaction between the trans-H and the carbonyl of the amide groups. The compound crystallizes in C2/ca with a = 8.6162(1), b = 57716(1), c = 24.8344(b) Å, = 96.298(1)°, D _calc = 1.441 g cm^–3, and Z = 4.     

Crystal structure and spectroscopic study of bis{1,3-bis[3-(5-amino-1,2,4-triazolyl)]triazenido-N′4,N2,N″4}nickel(II) tetrahydrate

The title compound [Ni(batt)₂]·4H₂O, in which Hbatt is 1,3-bis[3-(5-amino-1,2,4-triazolyl)]triazene, has been prepared and its crystal structure determined by X-ray diffraction methods. The compound crystallizes in the tetragonal space group I4/m (a = 10.5645(8) Å, c = 9.1336(6) Å, and Z = 2). The Ni(batt)₂ molecule has local 4¯ symmetry, but it is located on a crystallographic 4/m site and is disordered over the mirror plane. The ligand batt^– is tridentate with nitro-type coordination of the triazenido group and N⁴ coordination of the two outer triazolyl substituents. The complex has a distorted octahedral geometry with meridional configuration of the two nearly planar batt^– ligands. The geometry of the tridentate cavity is examined and a comparison is made with the Ni-terpyridyl system, which shows similar coordination around the nickel center. The FTIR, micro-Raman, and UV-vis spectra are analyzed in relation with the structure.     

Synthesis and crystal structure of trans-bis(O, O′-diisopropylthiophosphoryl-1H-imidazole-N3) bis(O,O′-diisopropyldithiophosphato) nickel(II) complex: Ni[N3-ImSP(OiPr)2]2[S2P(OiPr)2]2 (Im = imidazole; iPr = isopropyl)

The mononuclear complex, Ni[N³-ImSP(OiPr)₂]₂[S₂P(OiPr)₂]₂ (Im = imidazole; iPr = isopropyl), was unexpectedly obtained in a reaction of bis(O,O-diisopropyl-dithiophosphato) nickel(II) complex with imidazole ligand, and its structure was determined by X-ray crystallography. It crystallizes in the triclinic system, space group P , with lattice parameters a = 12.437(3) Å, b = 13.181(3) Å, c = 8.4580(17) Å, = 93.16(3)°, = 101.93(3)°, = 65.26(3)°, and Z = 1. The Ni atom has almost perfect octahedral coordination geometry and is coordinated by two N atoms of imidazole from two O,O-diisopropylthiophosphoryl-1H-imidazole ligands in axial positions and four S atoms from two (O,O-diisopropyldithiophosphato) anions which act as bidentate ligands forming a four-membered chelate ring in the equatorial plane. The Ni—S bond distances are 2.469(1) and 2.507(1) Å, and the Ni—N bond distances are 2.097(2) Å. The IR spectra data are in agreement with the structural data.     

Synthesis and Crystal Structure of Bis-(N,N′-dibenzylethane-1,2-diamine) cobalt(II) acetate

Abstract  

Bis-(N,N′-dibenzylethane-1,2-diamine) cobalt(II) acetate has been synthesized and the crystal structure determined. The compound crystallizes in the space group P2₁/c, a = 8.3212(6) ?, b = 11.8774(8) ?, c = 17.3643(12) ?, β = 98.1850(10)°, V = 1698.7(2) ?³, Z = 2. The complex occupies a crystallographic inversion center. The cobalt is in a distorted octahedral environment likely due to steric influences of the acetate groups.     

Synthesis and structural characterization of [VS4(CuPPh3)4Br]·CH2Cl2

Heating a solid mixture of (NH₄)₃VS₄, CuCl, PPh₃, and NEt₄Br at 100°C for 10 h and extraction with CH₂Cl₂ yielded [VS₄(CuPPh₃)₄Br]·CH₂Cl₂. Crystallographic data: Triclinic, P1¯, a = 15.189(3), b = 20.093(6), c = 12.031(3) Å, = 102.39(2), = 100.05(2), = 82.86(2)°, V = 3517(3) ų, and Z = 2. The configuration of the VS₄Cu₄Br core can be described as a distorted cubane with an additional face. The V atom has retained the tetrahedral geometry of the free [VS₄]^3– moiety. The four Cu atoms have three different coordination environments, strongly distorted tetrahedral, nearly trigonal planar, and strictly trigonal planar. The infrared, electronic, and ⁵¹V NMR spectra have also been reported.     

Structure of bis(O,O′-diisopropyldithiophosphato-S,S′) (1,10-phenanthroline-N1,N10)zinc(II) complex, [Zn(phen)(S2P(OiPr)2)2]

The crystal and molecular structure of [Zn(phen)(S₂P(OiPr)₂)₂] (Phen = 1,10-phenanthroline) has been determined by X-ray crystallography. It crystallizes in the Monoclinic system, space group C2/c, with lattice parameters a = 19.315(4), b = 10.438(2), c = 16.567(3)Å, = 102.89 (3)°, and Z = 4. The complex has C₂ symmetry. The coordination geometry of each Zn atom, by two S atoms from two (O,O-diisopropyldithiophosphato) anions and by two N atoms from phenanthroline ligand, is that of a slightly distorted tetrahedron [Zn—S 2.2914(8)Å Zn—N 2.111(2)Å]. The Zn···S distances to the noncoordinated S atoms are long: 3.5276 Å, which are indicated that there are much weaker interactions between them.     

Synthesis, crystal structure, and properties of the adduct of bis(O,O′-diisopropyl dithiophosphato)nickel(II) with pyridine [Ni(i-Pr2dtp)2(py)2]

A new adduct bis(pyridine)-bis(O,O-diisopropyl dithiophosphato-S,S)nickel(II), [Ni(i-Pr₂dtp)₂(py)₂] (dtp = dithiophosphate, py = pyridine) has been obtained by re-crystallization from CH₃COCH₃. The crystal and molecular structure of the title complex has been determined by X-ray crystallography. It crystallizes in the monoclinic system, space group P2₁/c, with lattice parameters a = 6.4890(13) Å, b = 16.386(3) Å, c = 14.830(3) Å, = 99.74(3)°, V = 1554.1(5) ų, and Z = 2. The crystal structure consists of discrete molecules of [Ni(i-Pr₂dtp)₂(py)₂], which displays a slightly distorted octahedral geometry for the NiS₄N₂ chromophore. Two O,O-diisopropyl dithiophosphate ions act as bidentate ligands with their S atoms coordinated to Ni atom. Each forms a four-membered chelate ring in the equatorial plane. The N atoms from two pyridine ligands are axially coordinated to the Ni atom. The Ni S bond distances are 2.4492(8) Å and 2.5711(9) Å, and the Ni bond distances are 2.127(3) Å. Thermal analyses show that the thermal decomposition of this adduct is so unstable that loss of two pyridine ligands begins at about 65°C. Electronic and IR spectra data is in agreement with the structural data.     

The structure of N,N′-bis(2-hydroxyphenyl)butanediamide

The structure of N,N-bis(2-hydroxyphenyl)butanediamide has been determined. The molecule consists of two 2-hydroxyphenyl moieties which are attached (at the 2 position) to the two nitrogens of the butanediamide. The compound C₁₆H₁₆N₂O₄ crystallizes in the monoclinic space group P2₁/c witha=5.576(1),b=4.8853(6),c=25.397(6) Å and =90.58(1)°.     

Synthesis and structure of an unusual complex formed between 1,2-bis(3′-pyridyl)ethyne and C-methyl calix[4]resorcinarene

The X-ray crystal structure of the complex formed between 1,2-bis(3-pyridyl)ethyne and C-methylresorcinarene is described. The structure (C₄₅H₄₇N₃O₁₂) is monoclinic with a = 11.8086(7), b = 31.2037(17), c = 11.2933(6) Å, = 101.9330(10)° and space group P2₁/c. The structure reveals that the resorcinarene adopts the common bowl-shaped conformation however the four intramolecular hydrogen bonds are arranged asymmetrically. One of the pyridyl rings sits inside the resorcinarene and is hydrogen bonded to two adjacent resorcinarenes.     

Synthesis,Crystal Structure and Thermal Behavior of a New Polynitrile N,N,N′,N′-tetra(2-cyanoethyl)-1,4-bis(3-aminopropyl)piperazine

Abstract  

A new polynitrile, N,N,N′,N′-tetra(2-cyanoethyl)-1,4-bis(3-aminopropyl)piperazine, was synthesized by the nucleophilic addition reaction of 1,4-bis(3-aminopropyl)piperazine and acrylonitrile for the first time. The title compound was characterized by elemental analysis, IR spectrum, and its crystal structure determined by X-ray single-crystal diffraction. The compound crystallizes in the monoclinic system with space group P2 ₁/c and a = 8.6195(12), b = 9.300(14), c = 16.221(2) ?, β = 97.824(2)°, V = 1288.2(3) ?³, D _c  = 1.064 g cm⁻³, M _r  = 412.59, Z = 2, F(000) = 448, μ = 0.067 mm⁻¹. The TG–DTA analysis revealed that the title compound possesses relatively good thermal stability under 220 °C.     

Synthesis, spectroscopy, and X-ray structure of the polymer catena-[bis(azido-N)-copper(II)-μ-bis(2-benzimidazolyl)butane]

The title compound, catena-[bis(azido-N)-copper(II)-(bis(2-benzimidazolyl)butane), [Cu(C₁₈H₁₈N₄)(N₃)₂]_n, was obtained from the reaction of the ligand bis(2-benzimidazolyl)butane and Cu(N₃)₂. The x-ray crystal structure is reported. The compound crystallizes in the monoclinic space group P2₁/c with a = 8.2524(10), b = 12.765(5), c = 9.1125(15) Å, = 106.423(12)°, Z = 2. The Cu(II) ions are square-planar coordinated with trans-oriented end-on binding azido ligands. The structure is a polynuclear chain with the benzimidazole bridging at each end. In addition a N_(ligand)-H···N_(azido) H-bridge [N_(ligand)···N_(azido) = 2.994(7) Å] is present, resulting in a pseudo 2-dimensional lattice. The characteristic azido infrared vibrations are found at 2060 and 2077 cm^–1 (_as(N₃)) and 1284 and 1297 cm^–1 ((N₃)).     

Synthesis and crystal structure of the perchlorate salt of diprotonated N,N′-bis(1-methylimidazole-2-methyl)1,5-diazacyclooctane

The diprotonated perchlorate salt of a new 1,5-diazacyclooctane (DACO) mesocycle functionalized by two imidazole pendants, N,N-bis(1-methylimidazole-2-methyl)-1,5-diazacyclo-octane (C₁₆H₂₈N₆Cl₂O₈), has been synthesized and the structure determined by X-ray diffraction analysis. The title compound crystallizes in the monoclinic system, space group P2₁/c with a = 11.964(2), b = 13.251(3), c = 14.741(3) Å, = 106.00(3)°, Mr = 503.34, V = 2246(1) ų, Z = 4. The crystal structure of the title compound reveals that the DACO ring is also folded up into the chair/boat configuration, which is consistent with the configuration in most of the transition metal complexes of DACO and its derivatives. The two imidazole pendants of the compound are in cis position with a dihedral angle of 16.0(4)°.     

Synthesis and structural characterization of [Co(tren)(Tsal)]ClO4·H2O and [Ni(pn)(py)2(NCS)2]

Complexes [Co(tren)(Tsal)]ClO₄·H₂O 1 and [Ni(pn)(py)₂(NCS)₂] 2, (tren = tris(2-aminoethyl)amine, Tsal = thiosalicylate ion, pn = 1, 2-diamino propane and py = pyridine) have been synthesized and structurally characterized. Both complexes crystallize in the monoclinic space group C2/c with a = 21.3340(6), b = 11.7754(2), c = 14.8076(5) Å, = 100.3831(10)°, Z = 8 (1), and a = 7.2573(8), b = 17.8810(11), c = 15.2681(12) Å, = 101.170(2)°, Z = 4 (2). The metal atoms in both cases have distorted octahedral geometry. In 1, the tren ligand is quadridentate and Tsal is bidentate chelate. In 2, the pn ligand forms a bidentate chelate with the NCS ligands in trans positions. Complex 1 is diamagnetic whereas 2 shows paramagnetism with a magnetic moment of 3.10 B. M.     

Crystal and molecular structure of the spin-crossover complex bis(pyridine) [N,N′-ethylenebis (3-carboxysalicylaldimine)] cobalt (II)

The average structure of the title compound, Co(H₂fsa₂en)(py)₂, which has been shown previously to exhibit a thermally induced high-spin low-spin crossover, has been investigated by single-crystal X-ray diffraction. This structure has been solved in the monoclinic space groupC2/c (No. 15), with cell dimensionsa=16.641(5),b=9.496(4),c=16.329(6) Å, and=95.47(3)°;V=2569(3) ų,M _r =571.46,Z=4,D _x =1.478 mg m^–3; MoK radiation (graphite crystal monochromator),=0.71073 Å,(MoK)=7.138 cm^–1;T=295 K andR=0.081 for 681 observed [I>3(I)] independent reflections. The cobalt(II) ion resides on a twofold axis in an elongated octahedral environment, the length of the apical bond (formed with pyridine) being 2.262(12) Å and the mean length of the equatorial bonds (formed with the Schiff base) 2.079(12) Å. These values are consistent with the magnetic behavior, which suggested a distorted surrounding for the metal atom. The packing is essentially governed by the parallelism of the salicylaldimine ligands. The two pyridine rings of the molecule are twisted by ~98° on each side of the basal plane; they are probably affected by orientational disorder or, if ordered, they might be described in a superstructure not yet established.     

Crystal structures of bis(cyanido)bis(N,N′-diethylthiourea-κS) mercury(II) and bis(cyanido)bis(N,N′-dipropylthiourea-κS) mercury(II)

Two mercury(II) complexes containing cyanide and, N,N′-diethylthiourea (detu) and N,N′-dipropylthiourea (dprtu) ligands, [(detu)₂Hg(CN)₂] (1) and [(dprtu)₂Hg(CN)₂] (2), respectively, have been prepared and characterized by X-ray crystallography. In the both complexes Hg atom lies on a 2-fold rotation axis, and is coordinated to the sulfur atoms of two thiourea ligands and to two cyanide carbon atoms. Both have a distorted tetrahedral environment with bond angles about the Hg atoms in the range of 93.41(4)°–146.75(19)°. In the crystal structures symmetry related molecules are linked via N-H-N hydrogen bonds resulting in the formation of a two-dimensional network in 1, while in 2 a double stranded one-dimensional chain is formed.     

Synthesis and crystal structure of [{V3(μ-Cl)4(μ 3-Cl) (μ 3-OH)(thf)2(teeda)}2]·2(thf) (teeda = N,N,N′N′-tetraethylethane-1,2-diamine)

The title complex was prepared from the reaction of [V₂(-Cl)₃(thf)₃]₂[Zn₂Cl₆] with N,N,NN-tetraethylethane-1,2-diamine (teeda) in refluxing thf and its crystal structure exhibits two triangulo-[V₃(-Cl)₃(-Cl)( ₃-OH)(thf)₂(teeda)]⁺ cations bridged by two chlorides. The molecular structure (monoclinic, space group P2 ₁/n, Z = 2, a = 11.8005(7) Å, b = 18.7492(14) Å, c= 15.6253(9) Å, = 103.600(4) shows each vanadium site in a distorted octahedral geometry. V1 and V2 have two thf molecules bounded in cis configuration, and V3 completes the hexa-coordination with the diamine teeda. Main bond distances are 2.5149(12) Å for V(1)--Cl(1), 2.062(3) Å for V(1)- ₃-O(3), 2.5554(12) Å for V(1)- ₃-Cl(4), 2.140(3) Å for V(1)–O(1)(thf), 2.243(4) Å for V(3)–N(1)(teeda), and 3.0437(9) for V(1)···V(2).