Hydro/solvothermal synthesis and structures of new zinc phosphates of varying dimensionality

Hydro/solvothermal reactions of ZnO, HCl, H(3)PO(4), 1,4-diazacycleheptane (homopiperazine), and H(2)O under a variety of conditions yielded three new organic-inorganic hybrid materials, [C(5)N(2)H(14)][Zn(HPO(4))(2)].xH(2)O (x = approximately 0.46), I, [C(5)N(2)H(14)][Zn(3)(H(2)O)(PO(4))(2)(HPO(4))], II, and [C(5)N(2)H(14)][Zn(2)(HPO(4))(3)].H(2)O, III. While I has a one-dimensional structure, II possesses a two-dimensional layered structure, and III has a three-dimensional structure closely related to the ABW zeolitic architecture. All the compounds consist of vertex linking of ZnO(4), PO(4), and HPO(4) tetrahedral units. The fundamental building unit, single four-membered ring (S4R), is present in all the cases, and the observed differences in their structures result from variations in the connectivity between the S4R units. Thus I has a corner-shared S4R forming an infinite one-dimensional chain, II has two corner-shared chains fused through a 3-coordinated oxygen atom forming a strip and a layer with eight-membered apertures, and III has S4R units connected via oxygen atoms to give rise to channels bound by eight T atoms (T = Zn, P) in all crystallographic directions. Crystal data: I, monoclinic, space group = P2(1)/n (No. 14), a = 8.6053(3) A, b = 13.7129(5) A, c = 10.8184(4) A, beta = 97.946(1) degrees, V = 1264.35(8) A(3), Z = 4; II, monoclinic, space group = P2(1)/c (No. 14), a = 11.1029(1) A, b = 17.5531(4) A, c = 8.2651(2) A, beta = 97.922(2) degrees, V = 1595.42(5) A(3), Z = 4; III, monoclinic, space group = P2(1) (No. 4), a = 8.0310(2) A, b = 10.2475(3) A, c = 10.570(3) A, beta = 109.651(1) degrees, V = 819.24(3) A(3), Z = 2.     

Synthesis, characterization, and chiral properties of CoIII2AgI3 pentanuclear, CoIII4ZnII4 octanuclear, and CoIII mononuclear complexes with aza-capped hexadentate-N3S3 thiolate ligands: crystal structures of

The reaction of an S-bridged Co2(III)Ag3(I) pentanuclear complex, [Ag3[Co(aet)3]2][BF4]3 (aet = NH2CH2CH2S-), with paraformaldehyde in basic acetonitrile, followed by adding aqueous ammonia, produced an aza-capped Co2(III)-Ag3(I) complex, [Ag3[Co(L)]2]3+ ([1]3+) (L = N(CH2NHCH2CH2S-)3). The crystal structure of [1]3+ was determined by X-ray crystallography. [1][PF6]3 x H2O, empirical formula C18H44Ag3Co2F18N8OP3S6, crystallizes in the tetragonal space group 142m with a = 13.012(1) A, c = 24.707(2) A, and Z = 4. In [1]3+ the two aza-capped [Co(L)] units are linked by three Ag(I) atoms, such that the two Co(III) atoms are encapsulated in a macrobicyclic metallocage, [Ag3(I)(L)2]3-. [1]3+ was converted to an aza-capped Co4(III)Zn4(II) octanuclear complex, [Zn4O[Co(L)]4]6+ ([2]6+), by reaction with I- in the presence of Zn2+ and ZnO in water. The crystal structure of [2]6+ was also determined by X-ray crystallography. [2][PF6]6 x 8H2O, empirical formula C36H100Co4F36N16O9P6S12Zn4, crystallizes in the monoclinic space group P2(1/n) with a = 14.33(7) A, b = 25.67(10) A, c = 24.83(6) A, beta = 101.3(3) degrees , and Z = 4. In [2]6+ each of four [Co(L)] units is bound to each trigonal Zn3(II) face of the tetrahedral [Zn4(II)O]6+ core, such that each Co(III) atom is encapsulated in a macrobicyclic [Zn4(II)O(L)] fragment. Treatment of [2]6+ with a basic aqueous solution resulted in a cleavage of the Zn-S bonds to produce an aza-capped Co(III) mononuclear complex, [Co(L)] ([3]), from which [1]3+ is readily reproduced by the reaction with Ag+ in water. All the reactions were found to proceed with retention of the absolute configuration (delta or lambda) of the Co(III) chiral centers; deltadelta-[1]3+, deltadeltadeltadelta-[2]6+, and A-[3] were derived from deltadelta-[Ag3[Co(aet)3]2]3+. The contributions to circular dichroism (CD) from the triple helicity in [1]3+, besides from the asymmetric N and S donor atoms and the Co(III) chiral centers in [1]3+ and [2]6+, were estimated by comparing the CD spectra of deltadelta-[1]3+, deltadeltadeltadelta-[2]6+, and delta-[3].     

Formation of one-, two-, and three-dimensional open-framework zinc phosphates in the presence of a tetramine

Five new open-framework zinc phosphates, encompassing the entire hierarchy of open-framework structures, have been synthesized hydrothermally in the presence of triethylenetetramine. The structures include one-dimensional ladders, two-dimensional layers, and three-dimensional structures as well as a zinc phosphate where the amine acts as a ligand. [C6N4H22]0.5[Zn(HPO4)2] (I): monoclinic, space group P2(1)/c (no. 14), a = 5.2677(1) A, b = 13.3025(1) A, c = 14.7833(1) A, beta = 96.049 degrees, Z = 4. [C6N4H22]0.5[Zn2(HPO4)3] (II): triclinic, space group P1 (no. 2), a = 7.515(1) A, b = 8.2553(1) A, c = 12.911(1) A, alpha = 98.654(1) degrees, beta = 101.274(1) degrees, gamma = 115.791(1) degrees, Z = 2. [C6N4H22]0.5[Zn2P2O8] (III): triclinic, space group P1 (no. 2), a = 8.064(1) A, b = 8.457(1) A, c = 9.023(1) A, alpha = 111.9(1) degrees, beta = 108.0(1) degrees, gamma = 103.6(1) degrees, Z = 2. [C6N4H22]0.5[Zn3(PO4)2(HPO4)] (IV): triclinic, space group P1 (no. 2), a = 5.218(1) A, b = 8.780(1) A, c = 16.081(1) A, alpha = 89.3(1) degrees, beta = 83.5(1) degrees, gamma = 74.3(1) degrees, Z = 2. [C6N4H20]0.5[Zn4P4O16] (V): monoclinic, space group P2(1)/c (no. 14), a = 9.219(1) A, b = 15.239(1) A, c = 10.227(1) A, beta = 105.2(1), Z = 4. The structure of I is composed of ZnO4 and HPO4 tetrahedra, which are edge-shared to form four-membered rings, which, in turn, form a one-dimensional chain (ladder). In II, these ladders are fused into a layer. The structures of III and IV comprise networks of ZnO4 and PO4 tetrahedra forming three-dimensional architectures. In V, the amine molecule coordinates to the Zn and acts as a pillar supporting the zinc phosphate layers, which possess infinite Zn-O-Zn linkages. The 16-membered one-dimensional channel in IV and the ZnO3N pillar, along with infinite Zn-O-Zn linkages in V, are novel features. The structure of the open-framework zinc phosphates is found to depend sensitively on the relative concentrations of the amine and phosphoric acid, with high concentrations of the latter favoring structures with lower dimensions.     

Syntheses and structures of two low-dimensional beryllium phosphate compounds: [C5H14N2]2[Be3(HPO4)5].H2O and [C6H18N2]0.5[Be2(PO4)(HPO4)OH].0.5H2O

The first two low-dimensional beryllium phosphates, [C5H14N2]2[Be3(HPO4)5].H2O (BePO-CJ29) and [C6H18N2]0.5[Be2(PO4)(HPO4)OH].0.5 H2O (BePO-CJ30), have been successfully synthesized under mild hydrothermal/solvothermal conditions. BePO-CJ29 is built up from strict alternation of BeO4 and HPO4 tetrahedra forming a unique one-dimensional double chains with 12-ring apertures. There are pseudo-10-ring apertures enclosed by two double chains through H-bonds. BePO-CJ29 can also be viewed as a pseudo 2-D layered structure stabilized by strong H-bonds. The diprotonated 2-methylpiperazium cations are located at three positions (i.e., inside the 12-ring aperture, inside the pseudo-10-ring aperture, and in the interlayer of the inorganic pseudo-layers. BePO-CJ30 is constructed by the alternation of Be-centered tetrahedra (including BeO4 and HBeO4) and P-centered tetrahedra (including PO4 and HPO4) resulting in a two-dimensional layered structure parallel to the (0 1 1) direction. The complex layer is composed of coupled 4.8 net sheets. The diprotonated 1,6-hexandiamine cations and water molecules reside in the interlayer regions and interact with the inorganic layers through H-bonds. Crystal data are as follows: [C5H14N2]2[Be3(HPO4)5].H2O (BePO-CJ29), triclinic, P1 (No. 2), a = 8.1000(9) A, b = 8.4841(14) A, c = 19.665(2) A, alpha = 89.683(10) degrees, beta = 78.182(8) degrees, gamma = 87.932(9) degrees, V = 1321.9(3) A3, Z = 2, R1 = 0.0523 (I > 2sigma(I)), and wR2 = 0.1643 (all data); [C6H18N2]0.5[Be2(PO4)(HPO4)OH].0.5 H2O (BePO-CJ30), orthorhombic, Pccn (No. 56), a = 26.01(4) A, b = 8.431(12) A, c = 9.598(13) A, V = 2105(5) A3, Z = 8, R1 = 0.0833 (I > 2sigma(I)), and wR2 = 0.2278 (all data).     

Three-dimensional open-framework cobalt(II) phosphates by novel routes

Two new three-dimensional open-framework cobalt phosphates, [C2N2H10]2[Co4(PO4)4]H2O, I, and [C4N3H16]3-[Co6(PO4)5(HPO4)3]H2O, II, have been prepared by the reaction of amine phosphates with Co2+ salts. I could also be prepared by the reaction of the cobalt tris amine complex with H3PO4. The crystal data for I and II are as follows: phosphate I, orthorhombic, space group P2(1)2(1)2(1) (no. 19), a = 10.277 (1) A, b = 10.302 (1) A, c = 18.836 (1) A, V = 1994.2 (2) A3, Z = 4; phosphate II, monoclinic, space group P2(1)/c (No. 14), a = 31.950 (1) A, b = 8.360 (1) A, c = 15.920 (1) A, beta = 96.6 (1) degrees V = 4223.4 (2) A3, Z = 4. The structures of both I and II are constructed from alternating CoO4 and PO4 tetrahedra. The connectivity leads to the formation of eight-membered channels in all the crystallographic directions resembling the aluminosilicate zeolite, merlinoite in the case of I and to a rather large, one-dimensional 16-membered channel in II. Strong hydrogen-bond interactions involving the amine and framework oxygen are present in both I and II.     

具有开放骨架结构氟化磷酸钛的水热合成及分子动力学辅助确定骨架中模板剂的位置

在水热体系中,制备了一个具有三维开放骨架结构的氟化磷酸钛化合物Ti₄(PO₄)4(HPO₄)₂F₂.[(CH₃)₂N(CH₂)₂NH₃][H₃O](简称TP-J3J=Jilinuniversity).用X射线粉末衍射、元素分析、热重分析和X射线单晶衍射对其进行了表征.单晶结构分析表明,该化合物属于三斜晶系,P1空间群,晶胞参数a=0.6353(1)nm,b=0.8699(2)nm,c=1.1069(2)nm,α=93.94(3),β=90.13(3),γ=107.96(3),V=0.5804(2)nm³,Z=2,R₁=0.0391,wR₂=0.0959,GOF=1.052.TP-J3的骨架结构可以看作是由次级结构单元(SBU)[Ti₂(PO₄)₂(HPO₄)F]通过氧桥共顶点相连构筑而成的,在a和c方向形成了两种不同的八元环孔道,两种孔道相互交叉,形成了一种“类笼”结构.通过计算模拟确定双质子化的模板剂存在于“类笼”中,模板剂与骨架原子之间存在强烈的氢键作用,可稳定骨架的结构.     

A novel organic-inorganic hybrid based on an 8-electron-reduced Keggin polymolybdate capped by tetrahedral, trigonal bipyramidal, and octahedral zinc: synthesis and crystal structure of (CH3NH3)(H2bipy)[Zn4(bipy)3(H2O)2MoV8MoVI4O36)(PO4)].4H2O

Hydrothermal reaction of H(3)PO(3), CH(3)NH(2), zinc(II) acetate, 4,4'-bipyridine (bipy), and (NH(4))(6)Mo(7)O(24).4H(2)O at 180 degrees C led to a novel organic-inorganic layered hybrid, [CH(3)NH(3)][H(2)bipy][Zn(4)(bipy)(3)(H(2)O)(2)Mo(V)(8)Mo(VI)O(36)(PO(4))].4H(2)O (1). Its structure was established by single-crystal X-ray diffraction. It crystallizes in the monoclinic space group P2(1)/c with cell parameters of a = 17.3032(2), b = 17.8113(3), and c = 23.4597 (4) A, beta = 106.410(1) degrees, V = 6935.6(2) A(3), and Z = 4. The structure of compound 1 features a novel 2D layer built from the 8e-reduced tetracapped Keggin [Zn(4)Mo(12)O(36)(PO(4))](3)(-) anions, which are further interconnected by bridging bipy ligands. The four zinc(II) ions are in tetrahedral, trigonal bipyramidal, and octahedral coordination geometries, respectively.     

Novel zinc phosphate topologies defined by organic ligands

Six new zinc phosphates [C18H20N4][Zn4(HPO4)4(H2PO4)2(C18H18N4)3].2H2O (1), [Zn4(HPO4)4(C18H18N4)3].4H2O (2), [Zn3(HPO4)3(H2PO4)(C22H22N8)0.5(C22H24N8)0.5] (3), [Zn2(HPO4)2(C18H16N4)] (4), [Zn(HPO4)(C18H14N2)] (5), and [Zn2(HPO4)2(C12H10N4)] (6) have been synthesized under mild hydrothermal conditions in the presence of 1,4-bis(N-benzimidazolyl)butane (L1), 1,2,4,5-tetrakis(imidazol-1-ylmethyl)benzene (L2), 1,4-bis(imidazol-1-ylmethyl)naphthalene (L3), 9-(imidazol-1-ylmethyl)anthracene (L4), and 1,4-bis(1-imidazolyl)benzene (L5), respectively, and their structures were determined by X-ray crystallography. Compound 1 exhibits a unique inorganic motif of isolated 8-rings interconnected by L1. Compound 2, also formed from L1, contains a previously unobserved chain structure composed of edge-sharing 4-rings and 8-rings. Compound 3, prepared from L2, possesses an unusual one-dimensional framework, which is composed of vertex-sharing 4-rings and triple fused 4-rings. The inorganic portions of 4, 5, and 6 each adopt a layer structure. The sheets in 4 and 5 have a 4.8(2) topology, and in 6, a 6(3) topology is observed. The zinc atoms in compounds 1-6 are all tetrahedrally coordinated by a combination of phosphate groups and organic ligands. Potential relationships between the inorganic motifs reported in the present study are identified. These are indicative of a possible pattern of self-assembly of zinc and phosphorus tetrahedra and indicative of the role of the organic ligands in the formation of hybrid structures.     

新型层状磷酸铝[Al6P8O32][(C2H5)2NHCH2CH2NH3]2·[C2H5NH2CH2CH2NH2C2H5] 的合成、表征及其共模板作用

在溶剂热体系中,以N,N-二乙基乙二胺为结构导向剂,合成了Al/P为3/4的层状磷酸铝[Al6P8O32][(C2H5)2NHCH2CH2NH3]2·[C2H5NH2CH2CH2NH2C2H5]单晶,并通过X射线单晶衍射结构分析.XRD,ICP,元素分析,差热-热重分析等手段进行了表征.该化合物属单斜晶系,P2(1)/c空间群,晶胞参数:a=0.90945(2)nm,b=1.46424(4)nm,c=1.87572(5)nm,β=102.672(2)°,Z=4.其阴离子层由AlO4四面体和PO3(=O)四面体单元交替连接构成,形成四、六、八元环拓扑结构,无机层以ABAB方式堆积,两种质子化的有机胺分子N,N-二乙基乙二胺及其重排产物N,N′-二乙基乙二胺填充在层间.用分子动力学模拟方法,考察了标题化合物中有机胺与无机层间的相互作用,讨论了这两种有机胺的共模板作用.     

Tunable N-substitution in zwitterionic benzoquinonemonoimine derivatives: metal coordination, tandemlike synthesis of zwitterionic metal complexes, and supramolecular structures

Full details on a very efficient transamination reaction for the synthesis of zwitterionic N,N-dialkyl-2-amino-5-alcoholate-1,4-benzoquinonemonoiminium derivatives [C6H2(=NHR)2(=O)2] 5-16 are reported. The molecular structures of zwitterions 5 (R=CH3) in 5.H2O, 13 (R=CH2CH2OMe), 15 (R=CH2CH2NMe2), and of the parent, unsubstituted system [C6H2(=NH2)2(=O)2] 4 in 4.H2O have been established by single-crystal X-ray diffraction. This one-pot preparation can be carried out in water, MeOH, or EtOH and allows access to new zwitterions with N-substituents bearing functionalities such as -OMe (13), -OH (9-12), NR1R2 with R1 = or not equal R2 (14-16) or an alkene (8), leading to a rich coordination chemistry and allowing fine-tuning of the supramolecular arrangements in the solid state. As previously described for 15, which reacted with Zn(acac)2 to afford the octahedral Zn(II) complex [Zn[C6H2(NCH2CH2NMe2)O(O)(NHCH2CH2NMe2)]2] (20), ligands 13 and 16 with coordinating "arms" afforded with Zn(acac)2 the 2:1 adducts [Zn[C6H2(NCH2CH2X)O(=O)(NHCH2CH2NX)]2] 19 (X=OMe) and 21 (X=NHEt), with N2O4 and N4O2 donor sets around the octahedral Zn(II) center, respectively. Furthermore, zwitterions 15 and 16 reacted with ZnCl2 to give the stable, crystallographically characterized Zn(II) zwitterionic complexes [ZnCl2[C6H2(NCH2CH2NR1R2)O(=O)(NHCH2CH2NHR1R2)]] 22 (R1=R2=Me) and 23 (R1=Et, R2=H) by means of an unprecedented, tandemlike synthesis in which 1) the two pendant amino groups of the organic benzoquinonemonoimine zwitterionic precursor favor metal coordination and proton transfer and 2) the saturated linker prevents pi-conjugation between the charges. The nature of the structural arrangements in the solid state for both inorganic (20, 22, 23) and organic (5, 9, 13, and 15) molecules is determined by subtle variations in the nature of the N-substituent on the zwitterion precursor.     

Kinetic and mechanistic investigations of hydrothermal transformations in zinc phosphates

The room-temperature crystallization of [C(6)N(2)H(18)][Zn(HPO(4))(H(2)PO(4))(2)], an organically templated zinc phosphate containing [Zn(2)(HPO(4))(2)(H(2)PO(4))(4)](4)(-) molecular anions, and its transformation to compounds containing either one- or two-dimensional inorganic components, [C(6)N(2)H(18)][Zn(3)(H(2)O)(4)(HPO(4))(4)], [C(4)N(2)H(12)][Zn(HPO(4))(2)(H(2)O)], or [C(3)N(2)H(6)][Zn(4)(OH)(PO(4))(3)], under hydrothermal conditions were studied in-situ using energy-dispersive X-ray diffraction. The ability to collect data during reactions in a large volume ( approximately 23 mL) Teflon-lined autoclave under real laboratory conditions has allowed for the elucidation of kinetic and mechanistic information. Kinetic data have been determined by monitoring changes in the integrated peak intensities of Bragg reflections and have been modeled using the Avrami-Erofe'ev expression. The crystallization of [C(6)N(2)H(18)][Zn(HPO(4))(H(2)PO(4))(2)] is a diffusion-controlled process, while nucleation is increasingly more important in determining the overall rate of the formation of [C(6)N(2)H(18)][Zn(3)(H(2)O)(4)(HPO(4))(4)], [C(4)N(2)H(12)][Zn(HPO(4))(2)(H(2)O)], and [C(3)N(2)H(6)][Zn(4)(OH)(PO(4))(3)]. The transformation of [C(6)N(2)H(18)][Zn(HPO(4))(H(2)PO(4))(2)] to [C(4)N(2)H(12)][Zn(HPO(4))(2)(H(2)O)] and [C(3)N(2)H(6)][Zn(4)(OH)(PO(4))(3)] occurs via a dissolution-reprecipitation mechanism, while the transformation to [C(6)N(2)H(18)][Zn(3)(H(2)O)(4)(HPO(4))(4)] may be the first observation of a direct topochemical conversion of one organically templated solid to another under hydrothermal conditions.     

Synthesis,structural and spectroscopic properties of two new ethylenediamine-templated gallophosphate-oxalate layered materials

Two new layered gallophosphate-oxalate materials have been prepared hydrothermally using ethylenediamine and oxalic acid as structure-directing agents. The compounds (C2N2H10)2[Ga2(C2O4)2(HPO4)3].H2O 1 and (C2N2H10)3- [Ga4(C2O4)4(HPO4)4(H2PO4)2] 2 are closely related, consisting of anionic double chains built of alternating paris of GaO6 and HPO4 polyhedra. These double chains are linked via bridging HPO4 or H2PO4 tetrahedra to form corrugated layers containing eight-membered rings. The oxalate group acts as a bidentate ligand to each of the GaO6 octahedron. The corrugated layers are held together by strong to weak hydrogen-bonding interactions between oxalate groups, water and diprotonated ethylenediamine molecules, and the framework components. The compounds were characterized by single-crystal X-ray diffraction, thermogravimetric analysis, and infrared and Raman spectroscopy. Crystal data for 1: monoclinic, space group P21/C (No. 14), a = 6.355(1) A, b = 39.362(8) A, c = 9.249(2) A, beta = 106.7(1) degrees, Z = 2. Crystal data for 2: triclinic, space group P1 (No. 2), a = 8.730(1) A, b = 11.575(1) A, c = 11.696(1) A, alpha = 115.12(1) degree, beta = 90.07(1) degree, gamma = 111.23(1) degree, Z = 2.     

Coordination polymers and hybrid networks of different dimensionalities formed by metal sulfites

In our effort to explore the use of the sulfite ion to design hybrid and open-framework materials, we have been able to prepare, under hydrothermal conditions, zero-dimensional [Zn(C12H8N2)(SO3)].2H2O, I (a = 7.5737(5) A, b = 10.3969(6) A, c = 10.3986(6) A, alpha = 64.172(1) degrees , beta = 69.395(1) degrees , gamma = 79.333(1) degrees , Z = 2, and space group P), one-dimensional [Zn2(C12H8N2)(SO3)2(H2O)], II (a = 8.0247(3) A, b = 9.4962(3) A, c = 10.2740(2) A, alpha = 81.070(1) degrees , beta = 80.438(1) degrees , gamma = 75.66(5) degrees , Z = 2, and space group P), two-dimensional [Zn2(C10H8N2)(SO3)2].H2O, III (a = 16.6062(1) A, b = 4.7935(1) A, c = 19.2721(5) A, beta = 100.674(2) degrees , Z = 4, and space group C2/c), and three-dimensional [Zn4(C6H12N2)(SO3)4(H2O)4], IV (a = 11.0793(3) A, c = 8.8246(3) A, Z = 2, and space group P42nm), of which the last three are coordination polymers. A hybrid open-framework sulfite-sulfate of the composition [C2H10N2][Nd(SO3)(SO4)(H2O)]2, V (a = 9.0880(3) A, b = 6.9429(2) A, c = 13.0805(5) A, beta = 91.551(2) degrees , Z = 2, and space group P21/c), with a layered structure containing metal-oxygen-metal bonds has also been described.     

New framework connectivity patterns in templated networks: the creatinine zinc phosphites C4N3OH7.ZnHPO3, C4N3OH7.Zn(H2O)HPO3, and (C4N3OH7)2.ZnHPO3.H2O

The syntheses, crystal structures, and properties of C(4)N(3)OH(7).ZnHPO(3), C(4)N(3)OH(7).Zn(H(2)O)HPO(3), and (C(4)N(3)OH(7))(2).ZnHPO(3).H(2)O are reported. These new creatinine zinc phosphites are built up from networks of vertex-sharing HPO(3) pseudopyramids and various types of ZnO(2)N(2), ZnO(3)N, and ZnO(2)N(H(2)O) tetrahedra, resulting in extended structures of different dimensionalities (as sheets, clusters, and chains, respectively). They demonstrate the structural effect of incorporating "terminal" (nonnetworking) Zn-N and Zn-OH(2) moieties into zinc centers. Crystal data: C(4)N(3)OH(7).ZnHPO(3), triclinic, P1 (No. 2), a = 8.9351(4) A, b = 9.5011(4) A, c = 9.9806(4) A, alpha = 87.451(1) degrees, beta = 85.686(1) degrees, gamma = 89.551(1) degrees, Z = 4; C(4)N(3)OH(7).Zn(H(2)O)HPO(3), monoclinic, P2(1)/c (No. 14), a = 10.1198(7) A, b = 7.2996(5) A, c = 13.7421(9) A, beta = 107.522(1) degrees, Z = 4; (C(4)N(3)OH(7))(2).ZnHPO(3).H(2)O, triclinic, P1 (No. 2), a = 10.7289(6) A, b = 10.9051(6)A, c = 13.9881(8) A, alpha = 89.508(1) degrees, beta = 74.995(1) degrees, gamma = 74.932(1) degrees, Z = 4.     

Diazo complexes of rhenium: preparations and crystal structures of the bis(dinitrogen), [Re(N2)2(PPh(OEt)2)4][BPh4] and methyldiazenido [ReCl(CH3N2)(CH3NHNH2)(PPh(OEt)2)3][BPh4] derivatives

Depending on experimental conditions and the nature of the hydrazine, the reactions of ReCl3P3 [P = PPh(OEt)2] with RNHNH2 (R = H, CH3, tBu) afford the bis(dinitrogen) [Re(N2)2P4]+ (2+), dinitrogen ReClN2P4 (3), and methyldiazenido [ReCl(CH3N2)(CH3NHNH2)P3]+ (1+) derivatives. In contrast, reactions of ReCl3P3 [P = PPh(OEt)2, PPh2OEt] with arylhydrazines ArNHNH2 (Ar = Ph, p-tolyl) give the aryldiazenido cations [ReCl(ArN2)(ArNHNH2)P3]+ (4+) and [ReCl(ArN2)P4]+ (7+) and the bis(aryldiazenido) cations [Re(ArN2)2P3]+ (5+, 6+). These complexes were characterized spectroscopically (IR; 1H and 31P NMR), and the BPh4 complexes 1, 2, and 7 were characterized crystallographically. The methyldiazenido derivative [ReCl(CH3N2)(CH3NHNH2)(PPh(OEt)2)3][BPh4] (1) crystallizes in space group P1 with a = 15.396(5) A, b = 16.986(5) A, c = 11.560(5) A, alpha = 93.96(5) degrees, beta = 93.99(5) degrees, gamma = 93.09(5) degrees, and Z = 2 and contains a singly bent CH3N2, group bonded to an octahedral central metal. One methylhydrazine ligand, one Cl- trans to the CH3N2, and three PPh(OEt)2 ligands complete the coordination. The complex [Re(N2)2(PPh(OEt)2)4][BPh4] (2) crystallizes in space group Pbaa with a = 23.008(5) A, b = 23.367(5) A, c = 12.863(3) A, and Z = 4. The structure displays octahedral coordination with two end-on N2 ligands in mutually trans positions. [ReCl(PhN2)(PPh(OEt)2)4][BPh4] (7) crystallizes in space group P2(1)/n with a = 19.613(5) A, b = 20.101(5) A, c = 19.918(5) A, beta = 115.12(2) degrees, and Z = 4. The structure shows a singly bent phenyldiazenido group trans to the Cl- ligand in an octahedral environment. The dinitrogen complex ReClN2P4 (3) reacts with CF3SO3CH3 to give the unstable methyldiazenido derivative [ReCl(CH3N2)P4][BPh4]. Reaction of the methylhydrazine complex [ReCl(CH3N2)(CH3NHNH2)P3][BPh4] (1) with Pb(OAc)4 at -30 degrees C results in selective oxidation of the hydrazine, affording the corresponding methyldiazene derivative [ReCl(CH3N=NH)(CH3N2)P3][BPh4] (8). In contrast, treatment with Pb(OAc)4 of the related arylhydrazines [ReCl(ArN2)(ArNHNH2)P3][BPh4] (4) [P = PPh(OEt)2] gives the bis(aryldiazenido) complexes [Re(ArN2)2P3][BPh4] (5). Possible protonation reactions of Br?nsted acids HX with all diazenides, 1, 4, 5, 6, and 8, were investigated and found to proceed only in the cases of the bis(aryldiazenido) complexes 5 and 6, affording, with HCl, the octahedral [ReCl(ArN=NH)(ArN2)P3][BPh4] or [ReCl(Ar(H)NN)(ArN2)P3][BPh4] (10) (Ar = Ph; P = PPh2OEt) derivative.     

二十元环超大孔磷酸亚磷酸锌锰的合成与结构

本文以1,3-环己二甲胺[1,3-Cyclohexanebis(methylamine), CHBMA]为模板剂, 采用水热法合成了微孔磷酸亚磷酸锌锰 [H2CHBMA][Zn1.5Mn(HPO3)2(PO4)]·H2O(命名为TJPU-3Mn), 单晶结构解析显示该化合物为首个与超大孔磷酸铝JDF-20具有相同拓扑结构的微孔晶体, 沿c方向具有二十元环超大孔道, 孔道中的CHBMA分子均为顺式构象, 有望用于分离和识别CHBMA异构体.     

Synthesis, structure, and polymorphism studies in amine-templated open-framework zinc phosphites

Five new zinc phosphites, [C10N4H26][Zn2(HPO3)4].2H2O, 1, [C10N4H26][Zn5(H2O)4(HPO3)6].4H2O, 2, [C10N4H26][Zn4(HPO3)6].2H2O, 3, [C10N4H26][Zn4(HPO3)6].2H2O, 4, and [Zn2(HPO3)2(C10N4H24)], 5, were synthesized employing solvo/hydrothermal reactions in the presence of 1,4-bis (3-aminopropyl) piperazine (APPIP). Single crystal X-ray diffraction studies indicate that all the compounds form a hierarchy of structures. While the structures 1 and 2 are low-dimensional, 3-5 have three-dimensional connectivity. ZnO4 and HPO3 units form a 4-membered ring and are connected through their corners forming a one-dimensional chain structure in 1. 2 has one-dimensional ladders connected by ZnO2(H2O)4 octahedral units forming a layer with 4- and 8-membered apertures. Compounds 3 and 4 have similar molecular formulae and connectivity, which makes them polymorphic in nature. The amine molecules exist in gauche and all-trans form in 3 and 4, respectively. The amine molecule binds with the zinc center in 5 and acts as a pillar between the two zinc phosphite layers. The present study outlines the possible role of synthesis parameters for the isolation of a number of different structures by employing a single amine molecule, APPIP. The observation of polymorphic structures along with the interconvertibilities of one of the phases is important and noteworthy. The 31P chemical shifts observed in NMR studies, consistent with the single crystal data, have been correlated with the valence sum values of the oxygen that are bound with the distinct phosphorus.     

C(4)N(3)OH(7).Zn(H2O)HPO4, a neutral zincophosphate cluster

C(4)N(3)OH(7).Zn(H(2)O)HPO(4), built up from 4-rings of ZnO(2)(H(2)O)N and HPO(4) tetrahedra, is the first neutral, molecular, zincophosphate cluster. The unit-cell packing involves numerous O-H...O and N-H...O hydrogen bonds and pi...pi stacking interactions. Crystal data: C(4)N(3)OH(7).Zn(H(2)O)HPO(4), M(r) = 292.49, triclinic, P1 (No. 2), a = 9.2956(5) A, b = 11.2077(6) A, c = 19.8319(12) A, alpha = 80.314(1) degrees, beta = 78.829(1) degrees, gamma = 89.241(1) degrees, V = 1997.7(2) A(3), Z = 4.     

Design and crystal structures of triple helicates with crystallographic idealized D3 symmetry: the role of side chain effect on crystal packing

Novel crystallographic D3-symmetric binuclear triple molecular helices [Co2L(1)3][BF4]4 (1), [Zn2L(1)3][BF4]4 (2), [Mn2L(1)3][BF4]4 (3), [Co2L(2)3][BF4]4 (4), [Zn2L(2)3][BF4]4 (5), and [Mn2L(2)3][BF4]4 (6) have been achieved to establish the side chain effect on molecular packing, where L1 is [(C5H4N)C(CH3)=N-(C6H4)-]2CH2 and L2 is [(C5H4N)C(CH3)=N-(C6H4)-]2O, respectively. Crystal structure analyses show that each helix crystallizes in a hexagonal crystal system with space group Pc1 and the general axis of the helix occupies the crystallographic 3-fold axial position with the other three crystallographic 2-fold symmetries perpendicular to it. Each metal center is bound to three pyridylimine units to attain C3 pseudooctahedral coordination geometry with respective equivalent metal-N (CH=N) and metal-N (pyridyl) bonds. It is speculated that the existence of the methyl group might minimize the potential intermolecular interactions, which would be the essential factor controlling the helices formed in idealized crystallographic D3 symmetry. Moreover, crystallographic idealized C3-symmetric helicates [Co2L(3)3][BF4]4 (7), [Zn2L(3)3][BF4]4 (8), [Ni2L(3)3][BF4]4 (9), and [Cu2L(3)3][BF4]4 (10) were also structurally characterized for comparison, where L3 is [(C5H4N)C(CH3)=N-]2. All the results indicate that the existence of the methyl group in the side chain of aromatic ligands could effectively reduce the potential - intermolecular interactions and the side chain effect of the methyl group in crystal packing is robust enough to be exchanged from one network structure to another, which ensures the generality and predictability of the crystallographic idealized symmetry formation to a certain extent.     

Hydrothermal Synthesis, Crystal Structure and Fluorescent Property of a Novel Mo(Ⅴ) Phosphate [Zn(Mov6P4O31H10)2(C4H14N3)2]·2C4H13N3·8H2O

A new molybdenum phosphate [Zn(Mov6P4O31H10)2(C4H14N3)2]·2C4H13N3·8H2O 1 (C4H13N3 = diethylenetriamine) has been synthesized under hydrothermal condition. Single-crystal X-ray diffraction reveals that compound 1 crystallizes in the monoclinic, space group P21/n, a =13.1679(3), b = 22.1240(6), c = 13.6146(3) (A), β = 103.4847(7)°, V = 3856.95(16) (A)3,C16H90N12O70P8ZnMo12, Mr = 3035.41, Z = 2, Dc = 2.614 g/cm3, μ = 2.483 mm-1, F(000) = 2968, S = 1.014, the final R = 0.0196 and wR = 0.0506 for 7486 observed reflections (I ＞ 2σ(Ⅰ)). Compound 1 consists of two identical rings of six edge-sharing MoO6 octahedra interconnected by one ZnO6 octahedron, whereas the PO4 tetrahedra which share their apices with the MoO6 octahedra are only located on one side of each Mo6 ring. The 2-charge of polyanion [Zn(Mov6P4O31H10)2]2- unit is compensated in the crystal by two mono-protonated diethylenetriamines (C4H14N3)+. By hydrogen bonding interactions the polyanion of compound 1 is interconnected to form pseudo three dimensional molybdophosphate. Other characterizations by elemental analyses, IR spectrum and fluorescent spectrum are also described.