Hydrothermal Syntheses and Crystal Structures of Six Complexes Constructed from 1,3,5-Benzenetricarboxylic Acid and 4'-(4-Pyridyl)-2,2':6',2''-terpyridine Mixed Ligands

Six new transition metal complexes, [Zn（HBTC）（PYTPY）]n·n PYTPY（1）, [Cu（HBTC）（PYTPY）]n·n PYTPY（2）, [Co（HBTC）（PYTPY）]n·n DMF（3）, [Mn（HBTC）（PYTPY）]n·n DMF（4）, [Cd（HBTC）（PYTPY）（H2O）]n·2nH2O（5）, and [Co（HBTC）（PYTPY）（H2O）2]（6）,（H3BTC = 1,3,5-benzenetricarboxylic acid, PYTPY = 4＇-（4-pyridyl）-2,2＇：6＇,2＇＇-terpyridine, DMF = N,N？-dimethylformamide）, have been synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. Complexes 1~5 all feature one-dimensional chain structures, and complex 6 exhibits a zero-dimensional structure. Complexes 1~5 present three-dimensional（3D） supramolecular frameworks via π-π stacking interactions, whenas 6 has also a 3D supramolecular structure assembled by hydrogen bonding. Meanwhile, complexes 1 ~ 6 exhibit the thermal stabilities and photoluminescent properties.

Hydrothermal Synthesis,Crystal Structure and Magnetic Properties of a Novel Cobalt Complex Based on Biphenyl-3,3',4,4'-tetracarboxylate

A novel cobalt complex,[Co2（bptc）（bix）1.5]（1,H4bptc=3,3＇,4,4＇-biphenyltetra-carboxylic acid,bix = 1,4-bis（imidazol-1-ylmethyl）benzene）,has been hydrothermally prepared and characterized by IR spectroscopy,elemental analysis and single-crystal X-ray diffraction.The crystal is of triclinic system,space group P1 with a=10.770（7）,b=12.245（8）,c=13.514（9）,α=102.829（8）,β=107.734（8）,γ=98.833（9）°,C37H27N6O8Co2,Mr=801.51,V=1607.5（18）3,Dc=1.656g/cm3,F（000）=818,μ=1.100mm-1,Z=2,the final R = 0.0694 and wR = 0.1543 for 3034 observed reflections（I2σ（I））.In the title complex,the two Co（Ⅱ） ions are in different coordination environments with distorted octahedral and trigonal bipyramidal geometries,respectively.The Co atoms are linked together through hexadentate bptc ligands,giving rise to 2D layers which are bridged by the bix ligands into a 3-D supramolecular network.Magnetic susceptibilities of 1 reveal weak antiferromagnetic exchange interactions between the adjacent Co（Ⅱ） ions.

Synthesis and Crystal Structure of N-tert-butyl-N′-(2,4-dichlorobenzoyl)-N- [1-(4-chlorophenyl)-1, 4-dihydro-6-methylpyridazine-4-oxo-3-carbonyl] hydrazine

The title compound N-tert-butyl-N(-(2,4-dichlorobenzoyl)-N-[1-(4-chlorophenyl)- 1,4-dihydro-6-methylpyridazine-4-oxo-3-carbonyl]hydrazine [(C23H_21N4O3Cl3)2·1.5H_2O, Mr = 1042.60] was prepared by the reaction of 1-(4-chlorophenyl)-1,4-dihydro-4-oxo-6- methylpyridazine-3-carboxylic acid with chloroformate ethyl ester, then with N′-tert-butyl-N- (2,4-dichlorobenzoyl) hydrazine in the present of triethylamine. The crystal structure has been determined by X-ray diffraction. The crystal belongs to Monoclinic, space group P21/c, with unit cell constants a =11.4948(9), b=12.7495(10), c=35.854(3) ?, β =92.964(2)°, Z=4, V=5247.6(7) ?3, Dc = 1.320 Mg/m3, F(000) = 2156 , μ (MoKa)= 0.385, R = 0.0661, wR = 0.1875, for 9151 observed reflections( I >2σ(I)). The structure is a dimer linked by intermolecular hydrogen bond which can be observed between N(1)- H...O(6), N(5)- H...O(3). The distances are 2.068 and 2.027? respectively.

Morphology, Growth Process and Symmetry of {0001} Face on Yb:YAl_3(BO_3)_4 Crystal

The {0001} face develops on the habit of self-frequency doubling laser crystal Yb: YAI3(B03)4 (YbYAB) only under high growth rate condition, and its morphology is rough. To study the growth mechanism of {0001} face, we have observed the growth morphology on {0001} polishing section by atomic force microscopy (AFM). A series of AFM images captured in different growth durations on the {0001} polishing section reflect the crystal growth process. It is shown that the growth morphology on the {0001} polishing section was rough with many hillocks at the first growth stage, and it can become smooth finally, although the growth morphology on the {0001} face developed naturally on YbYAB crystal habit is always rough. On the smooth {0001} surface formed at the last growth stage, there are some triangular pits. This fact is different from that of hillocks in most crystal growth morphologies. AFM can easily distinguish the pits or hillocks on the surface, but differential interfere contrast microscopy (DIC) can not do. The orientation of the triangular pits is just the opposite to the triangular {0001} faces. The chemical etching pattern is also composed of this kind of triangular pits. These growth morphology and etching pattern of the {0001} faces show 3m symmetry, but the point group of YbYAB crystal is 32. The symmetric contradiction between morphology and point group does not exist for quartz, although which has the same point group as YbYAB. From quartz {0001} surface morphology we can distinguish the right form or left form of the crystal, but from YbYAB {0001} surface morphology we can not do. The reason for the symmetric contradiction between YbYAB {0001} surface morphology and its point group is not known yet.

Synthesis and Crystal Structure of a Novel Ethyl 5-(4-(2-Phenylacetamido)phenyl)-1H-pyrazole-3-carboxylate as an Acrosin Inhibitor

The title compound （ethyl5-（4-（2-phenylacetamido）phenyl）-lH-pyrazole-3-carboxylate, C20H19N3O3） was synthesized by the reaction of Claisen condensation, cyclization, reduction and acylation. The structure was characterized by X-ray diffraction, MS, NMR and IR. It belongs to the monoclinic system, space group C2/c with a = 22.723（9）, b = 9.324（4）, c = 18.890（8） A, β = 114.259（6）°, V = 3649（3） A^3, Dc = 1.272 Mg·m^3, Z = 8, Mr = 349.38, p = 0.087 mm^-1, F（000） = 1472, the final R = 0.0615 and wR = 0.1643. The biological test shows that the title compound has a moderate acrosin inhibition activity.

Synthesis and Crystal Structure of Ethyl 3-(4-Chlorophenyl)-3,4-dihydro-6-methyl-4-oxo-2-(pyrrolidin-1-yl)furo[2,3-d]pyrimidine-5-carboxylate

The crystal structure of the title compound ethyl 3-（4-chlorophenyl）-3,4-dihydro-6- methyl-4-oxo-2-（pyrrolidin-1-yl）furo[2,3-d]pyrimidine-5-carboxylate （C20H20ClN3O4, Mr= 401.84） has been prepared and determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/n with a = 20.6215（9）, b = 8.5311（4）, c = 21.6886（9） A^°, β = 91.607（1）°, V = 3814.0（3）A^°^3, Z = 8, Dc = 1.400 g/cm^3, F（000） = 1680, μ = 0.233 mm^-1, R = 0.0718 and wR = 0.1545 for 6717 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals two crystallographically independent molecules in the asymmetric unit.

Growth and Characteristic of YbAl_3(BO_3)_4 Crystal

YbAl3(BO3)4 crystal of good optical quality was grown by the flux method. The structure of YbAl3(BO3)4 crystal was determined by single-crystal X-ray diffraction. The experiment shows that YbAl3(BO3)4 belongs to the double bo-rates with a trigonal structure. The space group is R32 and its unit cell constants were measured to be a = 0.92965 nm, c=0.72129 nm, V = 0.53673 nm3, Z=3. The transmittance spectra were measured. The cut-off of YbAl3(BO3)4 crystal is 216 nm, and there are two absorption peaks located at 940 and 975 nm from 190 nm to 2600 nm. The thermal properties of YbAl3(BO3)4 crystal were studied for the first time. The average thermal expansion coefficients were determined to be 2×10-6/℃, 9.5×10-6/℃along a- and c- direction. The specific heat of YbAl3(BO3)4 crystal was measured to be 0.6695 J·(g·℃) -1 at room temperature . All results indicate that the YbAl3(BO3)4 crystal is an excellent stoichioimet-ric laser material.

Growth and Spectroscopic Properties of Nd^(3+):Sr_3Gd_2(BO_3)_4 Crystal

This paper reports the growth, X-ray diffraction and spectroscopy of Nd3＋：Sr3Gd2（BO3）4 crystal. A Nd3＋：Sr3Gd2（BO3）4 crystal with dimensions of φ20 × 45 mm3 has been grown by the Czochralski method. Nd3＋：Sr3Gd2（BO3）4 crystal belongs to the orthorhombic system, space group Pnma （D2h） with a = 0.7401, b = 1.604 and c = 0.8755 nm. The absorption and emission spectra of Nd3＋：Sr3Gd2（BO3）4 were investigated. The absorption cross section oa is 3.11 × 10^-20cm2 at 808 nm. The absorption transition at 808 nm has an FWHM of 14 nm. The luminescence lifetime τf is 51.7 μs. The emission cross section oc at 1064 nm wavelength is 1.09 × 10^-19 cm2.

Synthesis,Crystal Structure and Antiproliferative Activity of Ethyl 1-(Phenylcarbamoyl)-2-3,4,5-trimethoxyphenyl)cyclopropanecarboxylae

Many small-molecule compounds have been evaluated with potential antiproliferative activities. Ethyl 1-（phenylcarbamoyl）-2-（3,4,5-trimethoxyphenyl）cyclopropanecarboxylate, one novel cyclopropylamide analogue of combretastatin-A4（CA-4）, has been synthesized and its crystal structure was characterized by X-ray single-crystal diffraction. The crystal belongs to monoclinic, space group P21/n, with a = 15.0263（3）, b = 7.6574（2）, c = 19.4117（4）, β = 111.9010（10）o, V = 2072.36（8）3, Z = 4, C22H24NO6, Mr = 398.42, Dc = 1.277 Mg/cm3, F（000） = 844, λ（MoKα） = 1.54178 , μ = 0.770 mm–1, R = 0.0546 and wR = 0.1889 for 3319 observed reflections（I 〉 2σ（I））. Meanwhile, the compound revealed potential antiproliferative activities in several cancer cells in vitro.

Synthesis and Crystal Structure of 2-Ethoxycarbonylmethyl-8-chloro-3a,4-dihydro-3a-methyl-chromeno[4,3-c]pyrazol-3(2H)-one

The crystal structure of the title compound 2-ethoxycarbonylmethyl-8-chloro-3a,4-dihydro-3a-methyl-chromeno[4,3-c]pyrazol-3（2H）-one（C15H15ClN2O4,Mr = 322.74） has been prepared and determined by single-crystal X-ray diffraction.The crystal is of orthorhombic,space group Pccn with a = 16.7246（10）,b = 19.6626（12）,c = 9.3013（6） ,V = 3058.7（3） 3,Z = 8,Dc = 1.402 g/cm3,μ = 0.269 mm-1,F（000） = 1344,the final R = 0.0506 and wR = 0.1464 for 2568 reflections with I 〉 2σ（I）.In addition,disordered C（14） and C（15） atoms exist in the crystal structure.

Yb∶YAl_3(BO_3)_4 晶体形貌与生长速度的关系

观察测量了不同生长速度 (相应于不同降温速度 )自发成核生长的Yb∶YAl3(BO3) 4 晶体形貌。粒度较大 ( >2mm)的晶体不管降温速度快慢形态都很简单 ,只发育六方柱 { 112 0 }和菱面体 { 10 11} ;粒度较小 ( <2mm)的晶体形态随降温速度增快而变复杂 ,发育一些罕见的高指数晶面。说明在生长速度较快的条件下 ,在晶体生长早期 ,一些高能面发育 ,在晶体生长后期已尖灭了 ,晶体生长的大部分时间是在低能面 { 112 0 }和 { 10 11}上进行的。对比了不同生长条件下晶面的粗糙度 ,随着降温速度的增快 ,六方柱面 { 112 0 }和菱面体面 { 10 11}由光滑变粗糙 ,顶面 { 0 0 0 1}永远是粗糙的。从晶体结构上定性地探讨了 3种晶面的杰克逊因子α及生长机理。

Facile Synthetic Method and Crystal Structure of 2,3,3',4'-Biphenyltetracarboxylic Dianhydride

A facile method for the synthesis of 2,3,3＇,4＇-biphenyltetracarboxylic dianhydride（a-BPDA） was reported,which comprises the steps of the dehalogenative coupling of dimethyl 4-chlorophthalate（4-DMCP） and dimethyl 3-chlorophthalate（3-DMCP） catalyzed by low-cost（Ph 3 P） 2 NiCl 2,the hydrolysis of tetra-ester and the dehydration of tetra-acid.In contrast to the conventional methods,this method has the advantage of low cost,convenient manipulation,available condition,high purity and good overall yield.Moreover,the single crystal structure of a-BPDA was analyzed by X-ray diffraction method.The X-ray data suggest that a-BPDA is a rigid,non-coplanar and non-linear structure.It contains three crystallographically independent molecules,in which the dihedral angles of the two linked phenyl rings are 44.75（4）°,46.37（3）° and 42.32（3）°,respectively.The title molecule is governed by a stronger intermolecular interaction in contrast to van der Waals interaction because of the special positions of anhydride groups.

Synthesis,Characterization and Crystal Structure of 3-o-Fluorophenyl-6-(4-decarboxydehydroabietyl)-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole

Three novel 1,2,4-triazolo[3,4-b]-1,3,4-thiadiazoles were designed,synthesized and characterized by IR,NMR and APCI-MS.3-o-Fluorophenyl-6-（4-decarboxydehydroabietyl）-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole（6a,C28H31FN4S） was structurally determined by single-crystal X-ray diffraction.The crystal belongs to the orthorhombic system,space group P212121 with a=6.0153（14）,b=12.2577（19）,c=34.055（3）A,V=2511.0（7）A^3,Z=4,Mr=474.63,Dc=1.255Mg/m^3,λ=0.71073 A,μ（MoKα）=0.160 mm^-1,F（000）=1008,the final R=0.0555 and wR=0.1248 for 3094 observed reflections with I〉2σ（I）.There are six rings in the crystal structure of the title compound.The dihedral angle between 1,2,4-triazole and 1,3,4-thiadiaole rings is 1.4o,and that between 1,2,4-triazole and benzene ring D 25.5o.

Synthesis,Crystal Structure and Anti-tumor Activity of Ethyl 3-(4-methoxyphenyl)-4-oxo-3,3a,4,6-tetrahydro-1H-furo[3,4-c]pyran-3a-carboxylate

The title compound（ethyl 3-（4-methoxyphenyl）-4-oxo-3,3a,4,6-tetrahydro-1H-furo[3,4-c]pyran-3a-carboxylate） has been synthesized,and its crystal structure was characterized by X-ray single-crystal diffraction.The crystal belongs to monoclinic,space group P21/n,with a = 10.124（4）,b = 11.754（4）,c = 13.792（5） ,β = 111.533（3）o,V = 1526.6（10） 3,Z = 4,C17H19O6,Mr = 319.32,Dc = 1.389 g/cm3,F（000） = 676,λ（MoKα） = 0.71073 ,μ = 0.105 mm-1,R = 0.0660 and wR = 0.2027 for 2993 observed reflections（I 2σ（I））.The compound shows potent anti-tumor activity in vitro.

Ln_7O_6(BO_3)(PO_4)_2∶Eu(Ln=La,Gd,Y)的VUV-UV激发和辐射发光

本文报道了Ln7O6(BO3) (PO4 ) 2 ∶Eu(Ln =La ,Gd ,Y)在VUV UV区的激发光谱及Eu3 + 在可见区的发射光谱。其激发光谱包括基质在真空紫外区的激发带和激活剂离子在紫外区的Eu3 + O2 -电荷迁移带 ,随La3 + ,Gd3 + ,Y3+ 离子半径逐渐减小 ,Eu3 + O2 -电荷迁移带的重心位置逐渐向高能量方向移动 ,Gd7O6(BO3) (PO4 ) 2 ∶Eu和Y7O6(BO3) (PO4 ) 2 ∶Eu在真空紫外区的吸收与Eu3+ O2 -电荷迁移带位于紫外区的吸收的比值要高于在La7O6(BO3) (PO4 ) 2 ∶Eu中的这个比值。激发能可被基质吸收 ,传递给激活剂离子 ,得到Eu3 + 的红光发射。在Gd7O6(BO3) (PO4 ) 2 ∶Eu中 ,5D0 →7F1的发射强度较强 ,在Y7O6(BO3) (PO4 ) 2 ∶Eu中 ,5D0→7F2 和5D0 →7F3的跃迁较强。

Er^(3+),Yb^(3+)∶YAl_3(BO_3)_4晶体的光谱性质研究

采用助熔剂法生长了Er3 + ,Yb3 + 共掺的YAl3 (BO3 ) 4 晶体 ,测量了晶体的室温吸收谱。由此吸收谱 ,根据Judd Ofelt理论计算了Er3 + 在Er3 + ,Yb3 + ∶YAl3 (BO3 ) 4 晶体中的强度参数、自发辐射几率、积分发射截面等参数。强度参数为Ω2 =2 .4 4× 10 -2 0 cm2 、Ω4=2 .0 0× 10 -2 0 cm2 、Ω6=6 .10× 10 -2 0 cm2 。研究了晶体的荧光特性 ,并在 976nm激光泵浦下得到了上转换绿色荧光。

Synthesis and CrystalStructure of Dicesiumtrans-Dicarbonatotetraaquom agnesium ,Cs_2[Mg(CO_3)_2(H_2O)_4]

The title compound, Cs 2[Mg(CO 3) 2(H 2O) 4], was synthesized by the dropwise addition of an aqueous solution of Mg(NO 3) 2 to a stirred aqueous Cs 2CO 3/CsHCO 3 solution. A colorless needle shaped crystal was formed by slow evaporation. The crystal structure was established on the basis of the single crystal X ray diffraction data. Cs 2[Mg(CO 3) 2(H 2O) 4] crystallized in the orthorhombic space group Pbca (No. 61) with a =0.658 4(1) nm, b =1.257 9(1) nm, c =1.301 3(1) nm, \{ V =1.077 8 nm 3, Z =4, D x=2.971 g·cm -3 , μ =69.20 cm -1 , F (000)=888, T =298 K, final R =0.029 and R w=0.024 for 1 037 observed reflections. The crystal consists of Cs + cations and the complex trans [Mg(CO 3) 2(H 2O) 4] 2- anions with each Mg atom coordinated by the six oxygens of two carbonate groups and four water molecules [ d (Mg_O)=0.203 6(4), 0.207 4(4), 0.213 4(4) nm]. The complex trans [Mg(CO 3) 2(H 2O) 4] 2- anions are arranged in a strongly compressed bcc pattern. A 3D network was formed through the intermolecular hydrogen bonds. The Cs + cations are located in cavities, each being surrounded by nine oxygens of five complex anions with d (Cs_O)=0.306 1-0.348 8 nm. The CO 2- 3 group reveals a lowering of D 3h symmetry due to site and coordination effects, but not any observable deviation from co planarity [ d (C_O)=0.127 2(6), 0.127 5(7) , 0.130 5(6) nm and O_C_O=119.6(5)°, 120.1(5)°, 120.4(5)°].

Synthesis and Crystal Structure of 5-Diazo-4-ethoxycarbonyl-3-methylthio Pyrazol

The crystal of the title compound, 5-diazo-4-ethoxycarbonyl-3-methylthio pyrazole, has been prepared and determined by X-ray diffraction. The crystal belongs to the monoclinic system, space group C2/c with a = 29.174(8), b = 4.7592(12), c = 15.956(4) ? b = 117.632(4), C7H8N4O2S, Mr = 212.23, V = 1962.7(9) ?, Z = 8, Dx = 1.436 g/cm3, S = 1.000, m(MoKa) = 0.31 mm-1, T = 298(2) K, F(000) = 880, R = 0.0658 and wR = 0.1741 for 1091 independent reflections with I ≥ 2s(I). The crystal of the title compound is formed with p-p interactions through electrostatic attractions. Moreover, no HSO4- exists in the crystal structure. Therefore, only diazo pyrazole was obtained rather than either diazonium salt of the corresponding pyrazole or diazoaminopyrazole when 5-amino-4-ethoxycarbonyl-3-methylthio pyrazole was diazotized with sodium nitrite, catalyzed by sulfuric acid at 0 ℃.

GdAl_3(BO_3)_4:Eu^(3+)荧光粉的光致发光特性

用硝酸盐热分解法合成了单相粉末样品Gd1-xEuxAl3(BO3)4(0≤x≤1)。研究了Eu3+在GdAl3(BO3)4中的紫外和真空紫外光谱性质。GdAl3(BO3)4:Eu3+中稀土离子占据非中心对称的格位,Eu3+在其中的特征发射以5D0→7F2电偶极跃迁为主。在147nm激发下GdAl3(BO3)4:Eu3+呈色坐标为(0.645,0.330)的强红光发射,说明是非常有前途的PDP用红色发光材料。在GdAl3(BOa)4:Eu3+的真空紫外光谱中观察到两个峰,158nm的激发带归属于BO3基团的吸收,258nm处的激发带为Eu3+→O2-的电荷转移跃迁带。在147nm激发下,GdAl3(BO3)4:Eu3+的红光发射强度随着Eu3+浓度的增加而减弱,而在258nm激发下随Eu3+浓度的增大Eu3+的红光发射增强,说明它们发光的机理不同。

Growth and Crystal Structure of YbAl_3(BO_3)_4

The compound YbAl3(BO3)4 belongs to huntite, space group R32 with cell parameters: a = 9.251(2), c = 7.189(3) ? Z = 3, Dc = 4.574 g/cm3, F(000) = 675.0, V = 532.84 3, ?= 13.63 mm-1, (MoK? = 0.71073 ? Mr = 489.22, (YbAl3B4O12), the final R = 0.0286 and wR = 0.0710. The Yb3+ ion occupies the trigonal prismatic site and the Al3+ ion occupies the octahedral site. There are two sets of (BO3)3- planar triangles. The Yb3+ ions are connected by means of YbOAl[B(2)]Yb with the distance 5.854 ?