Preparation,Crystal Structure and Theoretical Calculation of N-（Pyrimidin-2-yl）-N＇-methoxycarbonyl-thiourea

The compound, N-（pyrimidin-2-yl）-N＇-methoxycarbonyl-thiourea, has been synthesized. The single crystal structure has been determined by an X-ray diffractometer. The crystal belongs to triclinic with space group P-1 and a=0.72152（4） nm, b=0.8056（4） nm, c=0.90772（5） nm, α= 105.141（4）°, β=94.588（4）°, γ= 115.415（4）°, F（000）= 220, the unit cell volume V=0.45704（4） nm^3, the molecule number in one unit cell Z=2, the absorption coefficient μ=0.333 mm^-1, the calculated density Dc= 1.542 g/cm^3. The theoretical investigation of the title compound was carried out with B3LYP/6-311G, HF/6-311G and MP2/6-311G methods, and the atomic charges and natural bond orbital analysis were also discussed.     

Synthesis and Crystal Structure of 2-Amino-4- chloro-5-（4-methylbenzyl）-6-methylpyrimidine

The title compound 2-amino-4-chloro-5-(4-methylbenzyl)-6-methylpyrimidine (C26H28Cl2N6, Mr = 495.44) has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. The crystal belongs to monoclinic, space group P21/c with a = 14.892(7), b = 6.129(3), c = 14.889(7) , β = 109.795(8)°, V = 1278.7(10) 3, Z = 2, F(000) = 520, Dc = 1.287 g/cm3, μ = 0.280 mm-1, the final R = 0.0577 and wR = 0.1589 for 1357 observed reflections with I > 2σ(I). A total of 6091 reflections were collected, of which 2257 were independent (Rint = 0.033). The X-ray analysis reveals that the chlorine atom and methyl of the title compound are disordered.     

Synthesis and Crystal Structure of 4-（4,6-Dimethoxylpyrimidin-2-yl）- 3-thiourea Carboxylic Acid Ethyl Ester

4-（4,6-Dimethoxyl-pyrimidin-2-yl）-3-thiourea carboxylic acid ethyl ester was synthesized by the reaction of 2-amino-4,6-dimethoxyl pyrimidine, potassium thiocyanate and methyl chloroformate in ethyl acetate. Single crystals suitable for X-ray measurement were obtained by recrystallization with the solvent of dimethyl formamide at room temperature. The crystal structure was determined by X-ray diffraction analysis. Crystallographic data： C10H14N4O4S, M, = 286.31, monoclinic, space group C2/c with a = 2.5309（3）, b = 0.67682（6）, c = 1.74237（19） nm, β = 114.744（3）°, V= 2.7106（5） nm3, Dc = 1.403 g/cm3, p = 0.225 mm-1, F（000） = 1200, Z= 8, R= 0.0514 and wR= 0.1529.     

Crystal Structure and DFT Studies of a Triazole Derivative： 4- （ 2-Hydrobenzylideneamino ） -3- （ 1,2,4-triazol-4-ylmethyl） 1H-1, 2,4-triazole-5 （4H） -thione

A novel triazole derivative 4-(2-hydrobenzylideneamino)-3-(1,2,4-triazol-4-ylmethyl)-1H-1,2,4-triazole-5(4H)-thione(1) was synthesized and characterized using elemental analysis, FTIR, and 1H NMR, and its crystal structure was determined via X-ray single crystal diffraction analysis. Crystal data: monoclinic, P2(1)/c, a=0.83335(9) nm, b=1.49777(16) nm, c=1.14724(12) nm, β =107.990(2)°, D=1.470 Mg/m3, and Z=4. The geometries and the vibrational frequencies were determined using the density functional theory(DFT) method at the B3LYP/ 6-31G level. To demonstrate the accuracy of the reaction route of compound 1, one of the important intermediates was also tested using the same method. The structural parameters of the two compounds calculated using the DFT study are close to those of the crystals, and the harmonic vibrations of the two compounds computed via the DFT method are in good agreement with those in the observed IR spectral data. The thermodynamic properties of the title compound were calculated, and the compound shows a good structural stability at normal temperature. The test results of biological activities show that it has a certain bactericidal ability.     

1,3-二甲基-2-二茂铁甲基苯并咪唑碘盐的合成、表征、晶体结构及量子化学计算

A novel benzimidazole derivative, 1,3-dimethyl-2-ferrocenylmethylbenzimidazolium iodide （1） was synthesized and characterized by elemental analysis, MS, IH NMR and IR spectra. Its crystal structure was determined by X-ray single crystal diffraction, and the title compound belongs to monoclinic system with space group P2（1）/c. According to the crystal structure, the quantum chemistry calculation was performed by Gaussian 03 program, and full geometry optimizations of the title compound were carried out with DFT method at B3LYP/6-31G level. Its structure, stability, frontier molecular orbital components and net charge distribution were discussed.     

Synthesis and Structural Characterization of 1,4-Di（2-methoxyphenyl）-2,5-piperazinedione

A new derivative of 2,5-piperazinedione, 1,4-di（2-methoxyphenyl）-2,5-piperazinedione （I）, was synthesized by the cyclocondensation reaction of N-2-methoxyphenyl chloroacetamide, and its structure was characterized by elemental analysis, IR, ^1H NMR and single crystal X-ray diffraction method. The crystal belongs to monoclinic system, space group P21/c with unit cell dimensions a=0.56934（10） nm, b=1.3880（2） nm, c=1.00329（17） nm, β= 90.376（3）°, V= 0.7928（2） nm^3, Z=2, Dc = 1.367 g·cm^-3,μ = 0.98 cm^-1, R and wR being 0.0606 and 0.1564 respectively for 1549 unique reflections with 1247 observed reflections [I〉2σ（I）]. The molecule has a crystallographically imposed symmetry center. The three rings in the molecule are each coplanar with their attached groups, excluding methyl H atoms and the H atoms attached to the piperazinedione ring, while the whole molecule is not planar, with dihedral angles of 74.7（1）° between the piperazinedione and each of the two aromatic rings. The crystal structure is stabilized by van der Waals and dipole-dipole forces.     

Crystal Structure and Biological Activities of N-（5-（4-Chloro-2-（trifluoromethyl）phenyl）furan-2-carbonyl）-N＇-（4,6,dimethylpyrimidin-2-yl）thiourea

The new title compound N-（5-（4-chloro-2-（trifluoromethyl）phenyl）furan-2-carbon-yl）- N＇-（4,6-dimethylpyrimidin-2-yl）thiourea （C19H14C1F3N4O2S） has been synthesized, and its crystal structure and biological behaviors were studied. The title compound crystallizes in the monoclinic system, space group P21/c with a = 7.932（5）, b = 33.46（2）, c = 7.556（5） A, β = 98.058（9）°, V = 1986（2） A^3 Mr = 454.85, Z = 4, Dc = 1.521 g/cm^3, μ = 0.349 mm^-1 and F（000） = 928. The structure was solved by direct methods and refined to R = 0.0724 and wR= 0.1429 for 3494 observed reflections （I 〉 2σ（I））. Intermolecular hydrogen bonds along the b axis together with the continuous π-π interactions construct the three-dimensional architecture of the title compound. The preliminary biological tests show definite herbicidalactivity for the title compound.     

{Na2[μ2-(C6H4O2)2](C6H4OOH)2}4-的结构及其在固态合溶液中的NMR比较

The new compound （NH3CH2CH2NH3）2{Na2[μ2-（C6H4O2）2]（C6H4OOH）2} has been synthesized and characterized by elemental analysis, IR, UV, NMR and single crystal X-ray diffraction. The yellow crystals crystallized in the triclinic system with space group P-1 and a=0.6091（2） nm, b= 1.0274（3） nm, c= 1.2466（4） nm, α=89.073（6）°, β=89.376（6）°, γ=78.873（5）°, V=0.7653（4） nm^3, Z= 1, R1=0.0568, wR2=0.1198. Every sodium ion coordinates in trigonal prismatic fashion with two O atoms from a terminal chelating catecholato ligand and four O atoms from bridging P2 catecholato ligands, Two neighboring NaO6 trigonal prisms are face-shared and centrosymmetric with regard to the inversion center consisting of four tri-bridging O atoms to form a binuclear cluster {Na2[μ2-（C6H4O2）2]}^2- anion. The comparison of ^13C NMR spectrum of tlie complex in solid state with that in solution indicated that the rapid exchange between the bridging [μ2-（C6H4O2]^2- and terminal [C6H4OOH]^- ligands was present in solution.     

Synthesis and Crystal Structure of 2,5-Di- （pyridin-3-yl）-1,3,4-oxadiazolendium Nitrate

In order to continue our studies on the synthesis, properties and coordination of s-tetrazine, 3,6-di-(pyridin-3-yl)-s-tetrazine (II, 3-dptz) was synthesized and characterized by 1H- NMR, MS and IR spectra. And the coordination reaction of 3-dptz with nitrate of Cu(II) was studied. 3-dptz reacting with CuII salt [Cu(NO3)2·2H2O] generates a new salt, nitrate of 2,5-di-(pyridin-3- yl)-1,3,4-oxadiazolene (III). III was determined by IR spectra and single-crystal X-ray diffraction to give the following crystal data: space group P21/c, a = 4.9112(1), b = 8.4101(3), c = 29.499(1) , β = 93.266(2)o, V = 1216.44(7) nm3, Mr = 287.24, Z = 4, Dc = 1.568 g/cm3,μ= 0.122 mm-1, F(000) = 592, R = 0.0430 and wR = 0.1240. The results show that III is composed of one cation and one nitrate anion. The cation consists of one H+ and one 2,5-di-(pyridin-3-yl)-1,3,4-oxadiazol molecule, with the former being attached to the latter via electrovalent bond with N3 atom. And the O(42) atom in the nitrate anion is disordered. Intra- and intermolecular H-bonds are observed in the crystal of the title compound. The mechanism of metal-assisted decomposition was also discussed briefly.     

Crystal Structure, Photoluminescence and Theoretical Studies of Diethyl 4,5-di（thienyl）- 3,6-bis（trimethylsilyl）phthalate

The crystal structure of the title compound, diethyl 4,5-di（thienyl）-3,6-bis（trime- thylsilyl）phthalate （C26H3404S2Si2, Mr = 530.83）, has been determined by single-crystal X-ray diffraction. The crystal belongs to the orthorhombic system, space group Pccn with a = 43.008（5）, b = 10.9000（12）, c = 11.9357（14） A, V= 5595.3（11） A3, Z = 8, F（000） = 2256, Dc= 1.260 mg/m3, p = 0.305 mm-1, T = 113（2） K, S = 1.090, R = 0.0413 and wR = 0.0969 for 5952 observed reflections with 1 〉 2o（/）. The benzene ring system is planar and makes dihedral angles of 63.7（2） and 72.5（4） with the two thienyl rings A （C（23）-C（26）, S（2）） and B （C（19）-C（22）, S（1））, respectively. The UV-vis absorption and fluorescence of the title compound were discussed. The molecular structure of the title compound has been optimized using DFT method at the B3LYP/6-31G（d） level. The computational results showed that the optimized geometer parameters are consistent well with the experiment data. The vertical ionization potential, vertical electron affinity and frontier orbitals were also discussed.     

N-(4-甲基苯甲酰氨基) N’-[5-(2-三氟甲基苯基)-2-呋喃甲酰硫脲的合成、晶体结构测定与生物活性测定

本文首次合成标题化合物N-(4-甲基苯甲酰氨基)-N’-[5-(2-三氟甲基苯基)-2-呋喃甲酰硫脲。化合物(C21H16F3N3O3S, Mr = 447.43)单晶经测定为单斜晶体,空间群为P -1。在晶体中,存在一些分子内和分子间的相互作用,分子间还有C—H···π 的相互作用,这可能导致晶体更稳定的原因。目标产物的结构经IR, H NMR和元素分析测定确证。初步生物活性测试表明,部分化合物对棉花枯萎病、黄瓜灰霉病、苹果轮纹病和棉花炭疽病有较好的选择性杀菌活性;部分目标化合物有较好的除草活性。     

配位聚合物[Cu(pa)(vim)2]n的合成、晶体结构和电化学性质研究

本文合成了一种新型配位聚合物[Cu(pa)(vim)2]n(pa为邻苯二甲酸阴离子,vim为1-乙烯基-1H-咪唑),并用x射线单晶衍射仪和元素分析表征了其单晶结构。晶体属单斜晶系,C2/c空间群,晶胞参数分别为：a＝1.6527(3) nm, b＝0.81800(16) nm, c＝1.4463(3) nm, β＝113.19(3)°, V＝1.7973(7) nm3, Z＝4, Dc＝1.537 g?cm－3。 [I＞2σ(I)]时：R1＝0.0476, wR2＝0.1235,对所有数据：R1＝0.0693, wR2＝0.1355。配合物的结构中存在沿着c轴的zigzag聚合链。每个铜原子位于晶体中心,与两个N原子和两个O原子进行配位,形成了扭曲的平面结构。电化学研究表明在配合物中Cu2+/Cu+的氧化还原是一个单电子的准可逆过程。     

新颖双核钐硫酚化合物[(THF)3I2Sm(m-SAr)]2 (Ar = Ph, 4-Me2NC6H4)的合成与化合物[(THF)3I2Sm(m-S-4-Me2NC6H4)]2的晶体结构

Reactions of SmI2 in THF with ArSSAr produced two binuclear samarium thiolate complexes [（THF）3I2- Sm（μ-SAr）]2 [Ar=Ph （1）, 4-Me2NC6H4 （2）] in high yields. The structure of 2 was characterized by single crystal X-ray crystallography. The crystal of 2 belongs to the triclinic system with space group P 1 and a=0.95705（13） nm, b= 1.22287（14） nm, c= 1.26450（14） nm, a=64.194（11）°, B=78.491（13）°, y=76.176（12）°, V= 1.2860（3） nm^3, Z= 1,μ=4.783 mm^-1, Dc= 1.964 Mg/m^3, M= 1521.19, S= 1.046, R1=0.0358, wR2=0.0910. X-ray analysis revealed that 2 is a thiolate-bridged dimer in which each Sm atom adopts a distorted pentagonal bipyramidal coordi- nation geometry.     

An experimental and theoretical approach to the molecular structure of 3‐{[4‐(3‐Methyl‐3‐phenyl‐cyclobutyl)‐thiazol‐2‐yl]‐hydrazono}‐1,3‐dihydro‐ indol‐2‐one

The title molecule, 3‐{[4‐(3‐methyl‐3‐phenyl‐cyclobutyl)‐thiazol‐2‐yl]‐hydrazono}‐1,3‐dihydro‐indol‐2‐one (C₂₂H₂₀N₄O₁S₁), was prepared and characterized by ¹H NMR, ¹³C NMR, IR, UV–visible, and single‐crystal X‐ray diffraction. The compound crystallizes in the monoclinic space group P21 with a = 8.3401(5), b = 5.6976(3), c = 20.8155(14) Å, and β = 95.144(5)°. Molecular geometry from X‐ray experiment and vibrational frequencies of the title compound in the ground state has been calculated using the Hartree–Fock with 6‐31G(d, p) and density functional method (B3LYP) with 6‐31G(d, p) and 6‐311G(d, p) basis sets, and compared with the experimental data. The calculated results show that optimized geometries can well reproduce the crystal structural parameters, and the theoretical vibrational frequencies values show good agreement with experimental data. Density functional theory calculations of the title compound and thermodynamic properties were performed at B3LYP/6‐31G(d, p) level of theory. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012     

新颖有机/无机杂化配位聚合物[(DBU-H)(PbI3)]n的合成、晶体结构和量子化学研究

The coordination polymer [（DBU-H）（PbI3）]n（DBU=catena-（1,8-diazabicyclo[5,4,0]-undec-7-ene） was synthesized by self-assembly reaction of DBU and PbI2 at room temperature with pH=6.0 and structurally characterized by means of X-ray single crystal diffraction. It crystallizes in monoclinic system with space group P21/c and crystal parameters a = 1.1940（2） nm, b = 1.7409（4） nm, c = 0.81347（16） nm, β= 100.32（3）°, chemical formula C9H17N213Pb and Mr=741.15, V= 1.6635（6） nm^3, Z=4, Dc=2.959 g/cm^3, F（000）= 1304,μ（Mo Kα）= 15.687 mm^-1, the final R=0.0389 and wR=0.0635 for 2279 observed reflections with 1〉2σ（I）. Structure analysis shows that the inorganic anion chain consists of distorted PbI6 octahedra, which shares the same faces with adjacent PbI6 units to form one-dimensional infinite chains along the c-axis. Anion chains are surrounded by protonated （DBU-H）^＋ cations. Anion chains and cations are in combination with each other by static attracting forces in the crystal to form so-called organic-inorganic hybrid structure. According to the crystal structure data, quantum chemical calculation with DFT at B3LYP level was used to reveal the electronic structure of title compound.     

Molecular Structure and a Density Functional Theoretical Study on 2‐Nitroimino‐5‐Nitro‐Hexahydro‐1,3,5‐Triazine (NNHT)

2‐Nitroimino‐5‐nitro‐hexahydro‐1,3,5‐triazine (NNHT), was synthesized and its structure was determined by single‐crystal X‐ray diffraction. The crystal is monoclinic, space group P2₁/c with crystal parameters of a = 9.4031(13) Å, b = 8.5891(12) Å, c = 9.0200(13) Å, β = 91.213(2)°, V = 728.33(18) ų, Z = 4, F(000) = 392, D_c = 1.734 g/cm³. The experimental geometry of NNHT was input to Gaussian‐03W program and optimized using DFT‐B3LYP/6‐311++G** method. The IR frequencies and NMR chemical shift were carried out and compared well with those of the experimental. The atomic net charges and the population analysis are discussed. The heat of formation (HOF) for NNHT was evaluated by designing an isodesmic reaction. The detonation velocity (D) and detonation pressure (P) were estimated by using the well known Kamlet‐Jacobs equation, based on the theoretical HOF.     

4,6-二甲氧基-2-[甲氧脲基硫代脲基]嘧啶的合成、晶体结构和理论计算

利用2-氨基-4,6-二甲氧基嘧啶在干燥条件下与硫氰酸钾、氯甲酸甲酯在乙酸乙酯溶液中反应制得4-(4,6-二甲氧基嘧啶-2-基)-3-硫代脲酸甲酯, 在二甲基甲酰胺溶液中培养出单晶, 通过X射线单晶结构分析法测定分子结构和晶体结构, 晶体属单斜晶系, 空间群为C2/m, 晶胞参数为: a＝1.6672(3) nm, b＝0.66383(12) nm, c＝1.1617(2) nm, β＝109.275(2)°, V＝1.2136(4) nm³, D_c＝1.490 g/cm³, μ＝0.281 mm^－1, F(000)＝568, Z＝4, R₁＝0.0341, wR₂＝0.1042. 运用Gaussian 03程序, 在6-311G的基组水平上, 用HF, MP2以及B3LYP三种计算方法对标题化合物进行了几何全优化, 并对其成键情况及自然键轨道(NBO)进行了分析.     

Synthesis of 1‐Methyl‐3‐aryl‐substituted Titanocene and Zirconocene Dichlorides and Crystal Structure of Bis[η5‐1‐methyl‐3‐(α, α‐dimethylbenzyl) cyclopentadienyl] titanium Dichloride

The syntheses of a series of l‐methyl‐3‐aryl‐substituted titanocene and zirconocene dichlorides are reported. These complexes are synthesized by the reaction of 2‐ and 3‐methyl‐6, 6‐dimethylfulvenes (1:4) with aryllithium, followed by the reaction with TiCl₄·2THF, ZrCl₄ and (CpTiCl₂)₂O respectively, to give complexes 1–5. The complex [η⁵‐1‐methyl‐3‐(α, α‐dimethylbenzyl) cyclopentadienyl] titanium dichloride has been studied by X‐ray diffraction. The red crystal of this complex is monoclinic, space group P2_t/C with unit cell parameters: a =6.973(6) × 10^?1 nm, b =36.91(2) × 10^?1 nm, c = 10.063(4) × 10^?1 nm, α=β= γ = 93.35(5)°, V = 2584(5) × 10^?3 nm³ and Z = 4. Refinement for 1004 observed reflections gives the final R of 0.088. There are four independent molecules per unit cell.     

Mechanistic Insights into an Unexpected Carbon Dioxide Insertion Reaction through the Crystal Structures of Carbamic Diphenylthiophosphinic Anhydride and l‐[(4‐Nitrophenyl)‐sulfonyl]‐trans‐2,5‐pyrrolidinedicarboxylic Acid Methyl Ester

The crystal structures of an unexpected carbon dioxide inserted carbamidiphenylthiophosphinic anhydride and l‐[(4‐nitrophenyl) sulfonyl]‐trans‐2, 5‐pyrrolidinedicarboxylic acid methyl ester were determined by X‐ray analysis. They crystallized in the space group P2₁(#4) with a =0.9550(2), b = 0.9401(4), c= 1.2880(2) nm, β= 107.74°, V= 1.1013 (5) nm³, D_caled= 1.349 g/cm³, Z = 2 and P2₁2₁2₁(# 19) with a = 1.4666(2), b = 0.7195(2), c = 1.6339(2) nm, V = 1.7240(7) nm³, D_caled = 1.434 g/cm³, Z = 4, respectively. Through the investigation of these two crystal structures, the mechanistic insights into this unexpected carbon dioxide insertion in the reaction of trans‐2,5‐disubstituted pyrrolidine with diphenylthiophosphoryl chloride in the presence of potassium carbonate were disclosed.