三维孔道结构(H3 NCH2 CH2 NH3)2(H3 NCH2 CH2 NH2)[VⅢ(H2O)2(VⅣ O)8(OH)4(H(P,B)O4)4((P,B)O4)4(H2O)2]·3H2O的水热合成及晶体化学研究 --(2)晶体结构与晶体化学

在单晶X射线衍射实验的基础上,对孔道结构化合物V9P8-en的类质同象物V9(P,B)8-en的晶体结构和晶体化学进行了深入研究.结果表明,该化合物的晶体学数据为:P2(1)/n,a=1.43134(9)nm,b=1.01256(6)nm,c=1.83156(12)nm,β=90.280(2)°,V=2.6545(3)nm3,Z=2,R=0.0540,wR2=0.1551.结构中,沿着三个结晶轴方向发育复杂而规整的三维孔道,最大孔径达1.83nm(∥b轴),质子化乙二胺和水分子居于孔道中.硼部分替代四面体配位的磷,替代率为B8:P8=0.1838:7.8162;其中B与{P-OH}位P的替代量大于与[P-O]位P的替代量.相对于V9P8-en来说,V9(P,B)8-en的晶胞参数发生了变化,导致b轴增长(1.0150→1.0256nm)和c轴缩短(1.8374→1.8316nm),同时β角变小(90.39→90.278(2)°).二者的化学计量比也不同,体现在结构与孔容的关系、电荷平衡、满足亲水-疏水作用的结晶水的数量及有机模板分子的赋存状态等方面都有差异.     

三维孔道结构(H3NCH2CH2NH3)2(H3NCH2CH2NH2)[VⅢ(H2O)2(VⅣO)8(OH)4(H(P,B)O4)4(P,B)O4)4(H2O)2]·3H2O的水热合成及晶体化学研究——(1)水热合成与产物表征

为了探讨化学成份对VPO体系孔道结构化合物结构稳定性的影响,根据酸碱平衡原理进行了合成实验设计;利用V2O5、H3PO4、H3BO3等简单的无机前驱物、乙二胺作结构导向剂,水热法合成了孔道结构钒硼磷酸盐化合物(H3NCH2CH2NH3)2(H3NCH2CH2NH2)[VⅢ(H2O)2(VⅣO)8(OH)4(H(P,B)O4)4((P,B)O4)4(H2O)2]·3H2O(简称V9(P,B)8-en).典型的反应起始物摩尔比为n(V2O5):n(H3BO3):n(H3PO4):n(en):n(H2O)=0.89:3.50:3.50:3.60:265(pH值为6.5),在175℃、自生压力条件下恒温晶化6.5d(最终pH值为5.9).通过电子探针、粉末X射线衍射、红外吸收光谱、原子占位度修正等方法,对产物的化学成份、物相及其结构等进行了实验研究.证实V9(P,B)8-en为V9P8-en的类质同象化合物,不同晶粒中B与P的含量有差别,B与P之比为O.1:7.9～2.54:5.46(原子比),但恒有V:(P+B)≈9:8.表明通过合理设计和控制合成条件,可在保持V9P8-en基本结构不变的前提下通过同晶取代引入新的化学成份,并由此探讨成份与结构稳定性的关系.     

Synthesis and structure of (NH4)3[UO2(C3H2O4)2(NCS)] · 2H2O

Malonate-thiocyanate complex (NH₄)₃[UO₂(C₃H₂O₄)₂(NCS)] · 2H₂O is synthesized and studied by X-ray diffraction. The compound crystallizes in the monoclinic system: a = 13.9983(4) Å, b = 8.1947(2) Å, c = 16.4678(4) Å, β = 100.846(1)°, space group Cc, Z = 4, and R = 0.0158. The main structural units of the crystal are mononuclear [UO₂(C₃H₂O₄)₂(NCS)]^3? groups belonging to the AB ₂ ⁰¹ M ₁ crystal chemical group of uranyl complexes (A = UO ₂ ²⁺ , B ⁰¹ = C₃H₂O ₄ ^2? , M ¹ = NCS^?). Discrete uranium-containing groups are connected by electrostatic interactions with ammonium ions and by hydrogen bonds. Some specific structural features of crystals containing [UO₂(L)₂(NCS)]^3? complexes, where L is the oxalate or malonate ion, are discussed.     

Crystal structure of NH3(CH2)2NH3BiCl5·2H2O

The ethylenediammonium pentachlorobismuthate(III) dihydrate salt is monoclinic with the following unit cell dimensions: a = 10.902(8)Å, b = 7.926(6)Å, c = 15.199(6)Å, = 96.40(1)°, space group P2₁/n with Z = 4. The structure shows a layer arrangement parallel to the axis: planes of the [Bi₂Cl₁₀]^4– bioctahedra alternate with planes of [NH₃(CH₂)₂NH₃]²⁺ dications. The [Bi₂Cl₁₀]^4– bioctahedra are connected through O(W)–H··· Cl hydrogen bonds, so that infinite unidimensional chains of composition [Bi₂Cl₁₀(H₂O)₂] _n ^4n– are formed in the structure parallel to the axis. These chains are themselves interconnected by means of the N–H···Cl bonds originating from the [NH₃(CH₂)₂NH₃]²⁺ entities, forming a three-dimensional network.     

Synthesis, Structure and Properties of (H2NCH2CH2NH3)3 {(VO)6 [B10O16 (OH)6]2} · 11H2O

Abstract A new polyoxovanadoborate cluster (H₂NCH₂CH₂NH₃)₃ {(VO)₆[B₁₀O₁₆(OH)₆]₂} · 11H₂O was prepared by hydrothermal technique and characterized by single crystal X-ray diffraction analysis, IR and TGA. The crystal of the new compound belongs to monoclinic system, space group C2/c with a = 20.198(1) ?, b = 13.4476(8) ?, c = 21.602(1) ?, β = 97.067(1)°, V = 5822.8(5) ?³, Z = 4, D _c = 1.956 g cm⁻³, M = 1714.4, μ = 1.066 mm⁻¹, S = 1.905, R = 0.059, R _w = 0.0966. Index Abstract A new polyoxovanadoborate cluster (H2NCH2CH2NH3)3{(VO)6 [B10O16(OH)6]2} · 11H2O was prepared by hydrothermal technique and characterized by single crystal X-ray diffraction analysis, IR and TGA.      

NH4 HB4 O7·3H2 O为硼源添加剂高温高压合成金刚石研究

为了研究金刚石中硼元素含量对合成金刚石的颜色与热稳定性的影响.以石墨粉体和Fe70Ni30合金触媒为原料,NH4HB4O7·3H2O为硼源添加剂,采用静态高温高压技术合成出金刚石.利用体视显微镜观察合成金刚石 的颜色;AES检测金刚石中B元素的含量;TG-DSC进行热稳定性分析.结果表明:合成金刚石的初始氧化温度均超过837℃,最高达到917.8℃;1200℃时热失重率在59;～96;之间,放热峰值在893～1144 ℃之间;随着硼元素含量的增加,合成金刚石的颜色由淡黄色逐渐向黑色转变,热稳定性提高.     

三维孔道结构钒磷酸盐[H3N(CH2)3NH3]2[H3N(CH2)3NH2][H2N(CH2)3NH2]-[V(H2O)2(VO)8(OH)4(PO4)4(HPO4)4]·4H2O的水热合成和结构表征

以1,3-丙二胺为模板,水热合成了三维孔道结构钒磷酸盐[H3N(CH2)3NH3]2[H3N(CH2)3NH2][H2N(CH2)3NH2][V(H2O)2(VO)8(OH)4(PO4)4(HPO4)4]·4H2O(DAP-V9P8).用单晶X射线衍射、红外光谱和热重法对该化合物的晶体结构进行了表征.DAP-V9P8的无机骨架由[VO5]、[VO6]、[PO4]和[HPO4]通过共顶点连接而成.孔道中充填的丙二胺分子随所处结晶学位置不同,有三种完全不同的分子构象.其中,位于//b轴直径达1.82nm椭圆形孔道中心的丙二胺分子碳链呈独特的直线状分布.晶体学参数:a=1.4820(9)nm,b=1.0255(4)nm,c=1.8181(9)nm,β=90.391(8)°;P21/n(No.14);R1=0.0772,wR2=0.2004(I＞(2σI)).与等结构的其它化合物进行了系统的结构比较.     

New Crystals in the CsHSO4–CsH2PO4–NH4H2PO4–H2O System

Crystallography Reports - The phase equilibria in the CsHSO4–CsH2PO4–NH4H2PO4–H2O four-component aqueous salt system have been studied. The crystallization ranges and solubilities...     

Cyclic dithiophosphate salts [Et3NH+[(OCH2CMe2CH2O)P(S)S]− and [Et3NH]+[CH2{6-t-Bu-4-Me-C6H4O}2P(S)S]−

X-ray structures of the cyclic dithiophosphate salts [Et₃NH]⁺[(OCH₂CMe₂CH₂O)P(S)(S)]^– (1) and [Et₃NH]⁺[CH₂{6-t-Bu-4-Me-C₆H₄O}₂P(S)S]^– (2) have been determined. Crystal data for 1: Tetragonal, P4₂/m, a = 13.416(7), b = 13.416(2), c = 9.153(2) Å, and Z = 4. Crystal data for 2 = Monoclinic, P2₁/c, a = 19.1112(17), b = 14.649(9), c = 22.7166(19) Å, = 102.883(7)°, and Z = 8. The six- and eight-membered rings in 1 and 2 have chair and boat-chair conformations respectively. Both of these compounds show weak N—H······S hydrogen bonds; interestingly, in 2 both two-center and three-center hydrogen bonds are observed in the solid state.     

孔道结构铁磷酸盐（C4H12N2）2[Fe6（HPO4）2（PO4）6（H2O）2]·H2O的水热合成及热变化过程研究

在与前人不同的条件下水热合成了孔道结构铁磷酸盐（C4H12N2）2[Fe6（HPO4）2（PO4）6（H2O）2]·H2O。用ICP、有机元素分析仪、TG-DTA、变温XRD、变温FT-IR等分析技术对其成份、物相和热变化过程进行了系统研究。结果表明,室温～330℃,化合物失去吸附水,有机模板哌嗪开始氧化脱氢;330～380℃,哌嗪环破坏,大部分有机模板和结晶水脱除,化合物结构骨架明显破坏;470℃化合物完全非晶化;650℃形成FePO4和Fe4（P2O7）3新物相。哌嗪起到平衡电荷和支撑结构的作用。哌嗪环破坏并脱除是导致结构破坏的根本原因。     

Crystal structure of triethylentetraammonium bis monohydrogenmonophosphate dihydrate, [NH3(CH2)2NH2(CH2)2NH2(CH2)2NH3](HPO4)2 · 2H2O

The salt triethylentetraammonium bis monohydrogenmonophosphate dihydrate is monoclinic with the following unit cell dimensions: a = 8.462(1), b = 10.500(1), c = 9.520 Å, = 99.297(1)°, space group P2₁/n with Z = 2. The structure was solved by the Patterson method and refined to final R value of 0.043 for 1590 independent reflections. The structure consists of infinite parallel two-dimensional [ 01] planes built of mutually connected ions and water molecules by strong O—H···O and N—H···O hydrogen bonding.     

Crystal structure of N-benzylmethylammonium dihydrogen-monophosphate monohydrate, [C6H5CH2NH2CH3]H2PO4·H2O

The salt N-benzylmethylammonium dihydrogenmonophosphate monohydrate is monoclinic with the following unit cell dimensions: a = 6.356(1)Å, b = 8.385(7)Å, c = 11.472(5)Å, = 104.32(1)°, space group P2₁ with Z = 2. The structure consists of infinite parallel two-dimensional [110] planes built of mutually connected ions and water molecules by strong O–H···O and N–H···O hydrogen bonding. There are no contacts other than normal van der Waals interactions between the layers.     

NH4HB4O7·3H2O为硼源添加剂高温高压合成金刚石研究

为了研究金刚石中硼元素含量对合成金刚石的颜色与热稳定性的影响。以石墨粉体和Fe70Ni30合金触媒为原料,NH4HB4O7·3H2O为硼源添加剂,采用静态高温高压技术合成出金刚石。利用体视显微镜观察合成金刚石的颜色;AES检测金刚石中B元素的含量;TG—DSC进行热稳定性分析。结果表明：合成金刚石的初始氧化温度均超过837℃,最高达到917．8℃;1200℃时热失重率在59％-96％之间,放热峰值在893—1144℃之间;随着硼元素含量的增加,合成金刚石的颜色由淡黄色逐渐向黑色转变,热稳定性提高。     

Database Survey of Single-and-Half Phosphorus–Oxygen Bonds in Salts with the C2PO2 Segment: Crystal Structure of [NH2C5H4NH][(C6H5)2P(O)(O)]⋅2H2O

Crystallography Reports - For structures with a C2PO2 skeleton, a comparison of “single-and-half” phosphorus–oxygen bonds with single and double phosphorus–oxygen bonds is...     

新型磷酸钒孔道结构化合物(H3NCH2CH2NH3)3[(VO)4(PO4)2(HPO4)4]的表征及热性能研究

利用五氧化二钒、磷酸作前驱物,乙二胺作模板,水热法合成了新型孔道结构磷酸盐化合物(H3NCH2CH2NH3)3[(VO)4(PO4)2(HPO4)4].借助红外光谱(FT-IR)、热分析(TG-DTA)、粉晶X 射线衍射(XRD)及扫描电镜(SEM)等手段,对该化合物晶体在受热条件下的孔容脱除、结构变化及热相变特征等进行了系统研究.从晶体化学角度对其成分、结构及热稳定性之间的关系进行了探讨.指出应通过优化模板、元素替代等方法减弱模板分子与无机骨架间的键联强度及改善基本结构骨架的牢固性,进一步提高其热稳定性.     

Crystal structure of triethylentetraammonium bis monohydrogen-monophosphate dihydrate β-NH3(CH2)2NH2(CH2)2NH2(CH2)2NH3(HPO4)2·2H2O

The salt triethylentetraammonium bis monohydrogen-monophosphate dihydrate is orthorhombic Pbca with unit cell dimensions a = 8.963(2), b = 10.326(2), c = 17.381(4)Å; Z = 4; D_m = 1.540 g cm^–3; D _x = 1.562 g cm^–3. The examination of the structure shows a layer arrangement parallel to the axis: planes of [HPO₄]^2– tetrahedra alternate with planes of [(NH₃(CH₂)₂NH₂CH₂)₂]⁴⁺. The [HPO₄]^2– tetrahedra are connected through O(W)s--H···O hydrogen bonds, so that infinite chains of the composition [HPO₄(H₂O)]_n ^2n– are formed in the structure parallel to the axis. The structure of this compound is built from [HPO₄]^2– anions, [(NH₃(CH₂)₂NH₂CH₂)₂]⁴⁺ cations and zeolitic water molecules connected by hydrogen bonds.     

层状结构钒磷酸盐（pipzH2）2[（VO）3（HPO4）2（PO4）2]·H2O的水热合成及热稳定性研究

水热合成了钒磷酸盐体系中少有的结构中具有多面体共棱连接的层状孔道结构化合物（pipzH2）2[（VO）3（HPO4）2（PO4）2]·H20的纯相。用ICP、单晶XRD、TG-DTA、粉晶XRD和SEM对产物进行了表征。结果表明，化合物在空气中开始失重的温度为274℃，随着温度的升高，化合物中有机分子分解，同时伴随着重结晶过程，但晶体的外观形貌保持不变直至有机部分分解殆尽。相变过程分析和与模板相同的（pipzH2）0.5[（VO）（PO4）]的热稳定性对比研究表明，有机模板的稳定性及分解过程不但影响化合物的热稳定性和热变化过程，还影响原晶体微形貌的保持；无机骨架结合的牢固程度在很大程度上影响化合物的热稳定性。     

Hydrothermal synthesis and X-ray structure: A reduced titanic molybdenum(V) phosphate (NH3CH2CH2NH2)5Na [Ti2Mo12O30(PO4)(HPO4)4(H2PO4)3]⋅6H2O

A novel titanic molybdenum(V) phosphate (NH₃CH₂CH₂NH₂)₅Na [Ti₂Mo₁₂O₃₀(PO₄) (HPO₄)₄(H₂PO₄)₃]6H₂O crystallizes in the triclinic space group P1 with a = 12.057(3) Å, b = 14.668(2) Å, c = 21.2680(10) Å, = 80.840(10)°, = 82.960(10)°, = 76.65(2)°, and D _c = 2.707 g cm^–3 for Z = 2, Refinement based on 12,037 observed reflections led to R = 0.0609. The result of single crystal x-ray diffraction revealed the presence of a tunnel and two crystallographically independent clusters in the solid state structure. The plane layers in its solid-state structure are interconnected in-sheet (axial) through multipoint hydrogen bonding between the ethylenediamine nitrogen atoms and the cluster oxygen atoms.     

[Co(H2O)6](C18H15O4SO3)2·4H2O的合成和晶体结构

以芒柄花素为先导化合物,合成了水溶性的[Co(H2O)6](C18H15O4SO3)2·4H2O,并采用IR, 1H NMR, TG-DTA, XRD和单晶X射线衍射法对其结构进行了表征.单晶X射线衍射结果表明:[Co(H2O)6]2+、C18H15O4SO 3和H2O之间存在多种氢键,形成晶体结构中的亲水区.异黄酮骨架间反平行排列,面对面和边对面芳香堆积作用同时存在于其中,构成晶体结构中的疏水区.磺酸根是连接亲水区和疏水区的桥梁.氢键、芳香堆积作用以及阴阳离子之间的静电引力共同将标题化合物组装成具有三维网络结构的超分子.