catena‐Poly[sodium(I)‐μ‐tetra­ethoxy­borato]

The title compound, [Na(C₈H₂₀BO₄)]_n, has twofold crystallographic symmetry, with the Na⁺ cations bound by four O atoms [Na—O = 2.251 (3) Å]. The tetra­ethoxy­borate anion acts as a bridging ligand to form one‐dimensional polymers running along the twofold crystal axis. The crystal was treated as a racemic twin.     

Poly[tetrasodium(I)‐tetra‐μ2‐bis(butane‐1,4‐diyldioxy)borato‐μ2‐1,4‐butane­diol]

In the title compound, [Na₄(C₈H₁₆BO₄)₄(C₄H₁₀O₂)]_n, there are two coordination types for the four independent Na⁺ cations: two Na⁺ cations bond to six diolate O atoms [Na—O = 2.305 (2)–2.609 (2) Å], while the other two are five‐coordinate via one 1,4‐butane­diol [2.289 (2) and 2.349 (3) Å] and four diolate O atoms [2.295 (2)–2.408 (2) Å]. Corresponding to this, there are three‐ and four‐coordinate diolate O atoms, the latter bridging Na atoms. The 1,4‐butane­diol mol­ecules lie on inversion centres. The boron stereochemistry shows minor local perturbations from its usual tetrahedral state [B—O = 1.457 (4)–1.503 (4) Å]. The resulting polymer packs as sheets parallel to the (10) plane crosslinked by the butane­diol mol­ecules. The structure was solved using data from a multiple crystal.     

Bis(acesulfamato‐κ2O4,N)bis­(3‐methyl­pyridine)copper(II)

In the crystal structure of the title compound {systematic name: bis­[6‐methyl‐1,2,3‐oxa­thia­zin‐4(3H)‐one 2,2‐dioxide(1−)‐κ²N³,O⁴]bis­(3‐meth­yl­pyridine)copper(II)}, [Cu(C₄H₄NO₄S)₂(C₆H₇N)₂], the Cu^II centre resides on a centre of symmetry and has an octa­hedral geometry that is distorted both by the presence of four‐membered chelate rings and because of the Jahn–Teller effect. The equatorial plane is formed by the N atoms of two methyl­pyridine ligands and by the more basic O atoms of the acesulfamate ligands, while the weakly basic N atoms of these ligands are in elongated axial positions with a misdirected valence. The crystal is stabilized by two inter­molecular C—H⋯O inter­actions involving the methyl and CH groups, and the sulfonyl O atoms of the acesulfamate group.     

Synthesis,crystal structure and optical properties of a new beryllium borate,CsBe4(BO3)3

A novel beryllium borate CsBe₄(BO₃)₃ has been grown in crystals by high-temperature flux method using spontaneous nucleation technique for the first time. The crystal structure of this compound was determined by single crystal X-ray diffraction analysis. It crystallizes in the orthorhombic space group Pnma with lattice parameters a = 8.3914(5) Å, b = 13.3674(7) Å, c = 6.4391(3) Å, Z = 4, V = 722.28(7) Å³. The crystal takes the same structure type as Rb analog based on the units of BO₃ triangles and BeO₄ tetrahedrons, displaying a three-dimensional tunnel structure with Cs atoms filling in the cages. The IR spectrum confirms the presence of BO₃ groups and the UV–vis–IR diffuse reflectance spectrum exhibits this compound has a short UV cut-off edge below 200 nm. Band structures and density of states were calculated.     

Bismuth octaborate,Bi2B8O15

In the title compound, Bi₂B₈O₁₅, the Bi atom is coordinated to five or six O atoms. The B atoms exhibit two kinds of hybridization, sp² and sp³, seen in the BO₃ triangles and BO₄ tetrahedra, respectively. Three BO₃ triangles are connected to form a B₃O₆ planar ring. All atoms in the structure are connected together to form an infinite three‐dimensional network.     

Pb2BO3Cl: A Tailor‐Made Polar Lead Borate Chloride with Very Strong Second Harmonic Generation

A meticulously designed, polar, non‐centrosymmetric lead borate chloride, Pb₂BO₃Cl, was synthesized using KBe₂BO₃F₂ (KBBF) as a model. Single‐crystal X‐ray diffraction revealed that the structure of Pb₂BO₃Cl consists of cationic [Pb₂(BO₃)]⁺ honeycomb layers and Cl^? anions. Powder second harmonic generation (SHG) measurements on graded polycrystalline Pb₂BO₃Cl indicated that the title compound is phase‐matchable (type I) and exhibits a remarkably strong SHG response, which is approximately nine times stronger than that of potassium dihydrogen phosphate, and the largest efficiency observed in materials with structures similar to KBBF. Further characterization suggested that the compound melts congruently at high temperature and has a wide transparency window from the near‐UV to the mid‐IR region.     

Synthese und Kristallstruktur von Terbium(III)‐meta‐Oxoborat Tb(BO2)3 (≡ TbB3O6)

Synthesis and Crystal Structure of Terbium(III) meta‐Oxoborate Tb(BO₂)₃ (≡ TbB₃O₆) The terbium meta‐oxoborate Tb(BO₂)₃ (≡ TbB₃O₆) is obtained as single crystals by the reaction of terbium, Tb₄O₇ and TbCl₃ with an excess of B₂O₃ in gastight sealed platinum ampoules at 950 °C after three weeks. The compound appears to be air‐ and water‐resistant and crystallizes as long, thin, colourless needles which tend to growth‐twinning due to their marked fibrous habit. The crystal structure of Tb(BO₂)₃ (orthorhombic, Pnma; a = 1598.97(9), b = 741.39(4), c = 1229.58(7) pm; Z = 16) contains strongly corrugated oxoborate layers {(BO₂)^‐} built of vertex‐linked [BO₄]^5‐ tetrahedra (d(B‐O) = 143 ‐ 154 pm, ?(O‐B‐O) = 102‐115°) which spread out parallel (100). The four crystallographically different Tb³⁺ cations all exhibit coordination numbers of eight towards the oxygen atoms (d(Tb‐O) = 228‐287 pm). The corresponding metal cation polyhedra [TbO₈]¹³⁺ too convene to layers (composition: {(Tb₂O₁₁)^16‐}) which are likewise oriented parallel to the (100) plane.     

Zwei Fluoridborate des Gadoliniums: Gd2F3[BO3] und Gd3F3[BO3]2

Two Fluoride Borates of Gadolinium: Gd₂F₃[BO₃] and Gd₃F₃[BO₃]₂ By flux‐supported solid‐state reaction of Gd₂O₃ and GdF₃ with B₂O₃ (flux: CsCl, molar ratio: 1 : 1 : 1 : 6, sealed tantalum capsule, 700 °C, 7 d) the new gadolinium fluoride borate Gd₂F₃[BO₃] (monoclinic, P2₁/c; a = 1637.2(1), b = 624.78(4), c = 838.04(6) pm, β = 93.341(8)°; V_m = 64.418(6) cm³/mol, Z = 8) was obtained as colourless, prismatic, face‐rich single crystals. The four crystallographically different Gd³⁺ cations (CN = 9) are all capped square‐antiprismatically surrounded by fluoride and oxide anions, in which the latter represent always components of isolated trigonal planar [BO₃]^3— anions. The six crystallographically independent F^— anions all reside in more or less planar coordination of three Gd³⁺ cations. Thus the constitution of Gd₂F₃[BO₃] can be described as a sequence of alternating layers each of the composition Gd[BO₃] and GdF₃ parallel (100), respectively. The crystal structures of Gd₂F₃[BO₃] and the shortly published Gd₃F₃[BO₃]₂ (monoclinic, C2/c; a = 1253.4(1), b = 623.7(1), c = 836.0(1) pm, β = 97.404(6)°; V_m = 97.571(9) cm³/mol, Z = 4) are compared with each other. Due to the structural analogies between these two gadolinium fluoride borates, a disorder model of the boron atoms frequently found for Gd₂F₃[BO₃] is able to be transferred to Gd₃F₃[BO₃]₂ as well.     

Poly[bis(μ2‐2‐aminopyrazine‐κ2N1:N4)(μ2‐nitrato‐κ2O:O)(nitrato‐κ2O,O′)disilver(I)]: an achiral two‐dimensional coordination polymer forming chiral crystals

The solution reaction of AgNO₃ and 2‐aminopyrazine (apyz) in a 1:1 ratio gives rise to the title compound, [Ag₂(NO₃)₂(C₄H₅N₃)₂]_n, (I), which possesses a chiral crystal structure. In (I), both of the crystallographically independent Ag^I cations are coordinated in tetrahedral geometries by two N atoms from two apyz ligands and two O atoms from nitrate anions; however, the Ag^I centers show two different coordination environments in which one is coordinated by two O atoms from two different symmetry‐related nitrate anions and the second is coordinated by two O atoms from a single nitrate anion. The crystal structure consists of one‐dimensional Ag^I–apyz chains, which are further extended by μ₂‐κ²O:O nitrate anions into a two‐dimensional (4,4) sheet. N—H...O and C_apyz—H...O hydrogen bonds connect neighboring sheets to form a three‐dimensional supramolecular framework.     

Synthesis, crystal structure, spectrum properties, and electronic structure of a novel non-centrosymmetric borate, BiCd3(AlO)3(BO3)4

A novel non-centrosymmetric borate, BiCd₃(AlO)₃(BO₃)₄, has been prepared by solid state reaction methods below 750 °C. Single-crystal XRD analysis showed that it crystallizes in the hexagonal group P6₃ with a=10.3919(15) Å, c=5.7215(11) Å, Z=2. In its structure, AlO₆ octahedra share edges to form 1D chains that are bridged by BO₃ groups through sharing O atoms to form the 3D framework. The 3D framework affords two kinds of channels that are occupied by Bi³⁺/Cd²⁺ atoms only or by Bi³⁺/Cd²⁺ atoms together with BO₃ groups. The IR spectrum further confirmed the presence of BO₃ groups. Second-harmonic-generation measurements displayed a response of about 0.5×KDP (KH₂PO₄). UV-vis diffuse reflectance spectrum showed a band gap of about 3.19 eV. Solid-state fluorescence spectrum exhibited the maximum emission peak at around 390.6 nm. Band structure calculations indicated that it is an indirect semiconductor.     

Bis(acesulfamato‐κ2N3,O4)bis­(2‐amino­pyrimidine‐κN1)copper(II)

In the crystal structure of the title compound, bis­(2‐amino­pyrimidine‐κN¹)bis­[6‐meth­yl‐1,2,3‐oxathia­zin‐4(3H)‐one 2,2‐dioxide(1−)‐κ²N³,O⁴]copper(II), [Cu(C₄H₄NO₄S)₂(C₄H₅N₃)₂], the first mixed‐ligand complex of acesulfame, the Cu^II centre resides on a centre of symmetry and has an octa­hedral geometry that is distorted both by the presence of four‐membered chelate rings and by the Jahn–Teller effect. The equatorial plane is formed by the N atoms of two amino­pyrimidine (ampym) ligands and by the weakly basic carbonyl O atoms of the acesulfamate ligands, while the more basic deprotonated N atoms of these ligands are in the elongated axial positions with a strong misdirected valence. The crystal is stabilized by pyrimidine ring stacking and by inter­molecular hydrogen bonding involving the NH₂ moiety of the ampym ligand and the carbon­yl O atom of the acesulfamate moiety.     

Synthesis,Crystal Structure,and Electrochemical Behaviour of an Azido μ‐bridged Ni2+ Complex

A homo‐dinuclear Ni^II complex was prepared from 2, 6‐bis(3, 5‐dimethylpyrazolyl)pyridine (Me₄‐bpp) and azide ions in nonaqueous media. It was characterized by single crystal X‐ray structural analysis, IR spectroscopy, and elemental analysis. In addition, the electrochemical properties of the compound were determined with cyclic voltammetry in DMF. The title compound crystallizes in the P2₁/n monoclinic space group, with unit cell parameters a = 8.978(1), b = 12.459(1), c = 17.764(1) Å, ß =100.603(3)°, V = 1953.0(3) ų, Z = 2. The Ni²⁺ ion has a distorted octahedral environment involving three nitrogen atoms of the Me₄‐bpp ligand, two nitrogen atoms from the bridged azide group, and one nitrogen atom from the terminal azide group. The Ni···Ni distance is 3.273(5) Å.     

HP‐CsB5O8: Synthesis and Characterization of an Outstanding Borate Exhibiting the Simultaneous Linkage of All Structural Units of Borates

The new cesium pentaborate HP‐CsB₅O₈ is synthesized under high‐pressure/high‐temperature conditions of 6 GPa and 900 °C in a Walker‐type multianvil apparatus. The compound crystallizes in the orthorhombic space group Pnma (Z=4) with the parameters a=789.7(1), b=961.2(1), c=836.3(1) pm, V=0.6348(1) nm³, R₁=0.0359 and wR₂=0.0440 (all data). The new structure type of HP‐CsB₅O₈ exhibits the simultaneous linkage of trigonal BO₃ groups, corner‐sharing BO₄ tetrahedra, and edge‐sharing BO₄ tetrahedra including the presence of threefold‐coordinated oxygen atoms. With respect to the rich structural chemistry of borates, HP‐CsB₅O₈ is the second structure type possessing this outstanding combination of the main structural units of borates in one compound. The structure consists of corrugated chains of corner‐ and edge‐sharing BO₄ tetrahedra interconnected through BO₃ groups forming octagonal channels. Inside these channels, cesium is 13+3‐fold coordinated by oxygen atoms. ¹¹B MQMAS NMR spectra are analyzed to estimate the isotropic chemical shift values and quadrupolar parameters. IR and Raman spectra are obtained and compared to the calculated vibrational frequencies at the Γ‐point. The high‐temperature behavior is examined by means of temperature‐programmed powder diffraction.     

[O2Pb3]2(BO3)Br: An Oxidoborate Oxide Bromide with the ∞1[O2Pb3] Double Chains Based on Edge‐sharing OPb4 Tetrahedra

Through extensive research on the PbO / PbBr₂ / B₂O₃ system, a new single crystal of yellow lead‐containing oxyborate bromine, [O₂Pb₃]₂(BO₃)Br, was grown from the melt. It crystallizes in the centrosymmetric space group Cmcm (no. 63) of the orthorhombic system with the following unit cell dimensions: a = 9.5748(8) Å, b = 20.841(2) Å, c = 5.7696(5) Å, and Z = 4. The whole structure is characterized by an infinite one‐dimensional (1D) _∞¹[O₂Pb₃] double chain, which is based on the OPb₄ oxocentered tetrahedra and considered as the derivative of the continuous sheet of OPb₄ tetrahedra from the tetragonal modification of α‐PbO. The 1D _∞¹[O₂Pb₃] double chains are further bridged by the BO₃ units through common oxygen atoms to form two‐dimensional (2D) _∞¹[[(O₂Pb₃)(BO₃)] layers, with Br atoms situated between the layers. IR spectroscopy, UV/Vis/NIR diffuse reflectance spectroscopy, and thermal analysis were also performed on the reported material.     

An alkoxide cluster with 18 Li+ ions encapsulating two borate anions, [(tBuO)12Li18(BO3)2]

The title compound, bis­(borato)­dodeca(tert‐butoxo)­octa­deca­lithium, [Li₁₈(BO₃)₂(C₄H₉O)₁₂], is formulated conveniently as [{(^tBuOLi)₃(Li₃BO₃)}₂(^tBuOLi)₆]. A central 12‐membered ring and two outer six‐membered rings are formed by alternating Li⁺ cations and alkoxide O atoms. Sandwiched between the central ring and each of the outer rings is a planar array of three further Li⁺ cations surrounding a [BO₃]³⁻ anion. Thus, the mol­ecule consists of a cationic [Li₁₈(O^tBu)₁₂]⁶⁺ cage encapsulating two borate anions. This compound is the first example of a structurally characterized polynuclear lithium borate, and a rare case of a lithium alkoxide cage with nuclearity greater than eight. All the alkoxide ligands are triply bridging, and the lithium ions have trigonal‐planar, trigonal‐pyramidal and fourfold coordination, all with major distortions from regular coordination geometry.     

Bis(μ‐5‐carboxybenzene‐1,3‐dicarboxylato‐κ2O1:O3)bis[(2,2′‐bi‐1H‐imidazole‐κ2N3,N3′)zinc]

The title compound, [Zn₂(C₉H₄O₆)₂(C₆H₆N₄)₂], consists of two Zn^II ions, two 5‐carboxybenzene‐1,3‐dicarboxylate (Hbtc²⁻) dianions and two 2,2′‐bi‐1H‐imidazole (bimz) molecules. The Zn^II centre is coordinated by two carboxylate O atoms from two Hbtc²⁻ ligands and by two imidazole N atoms of a bimz ligand, in a distorted tetrahedral coordination geometry. Two neighbouring Zn^II ions are bridged by a pair of Hbtc²⁻ ligands, forming a discrete binuclear [Zn₂(Hbtc)₂(bimz)₂] structure lying across an inversion centre. Hydrogen bonds between carboxyl H atoms and carboxylate O atoms and between imidazole H atoms and carboxylate O atoms link the binuclear units. These binuclear units are further extended into a three‐dimensional supramolecular structure through extensive O—H...O and N—H...O hydrogen bonds. Moreover, the three‐dimensional nature of the crystal packing is reinforced by the π–π stacking. The title compound exhibits photoluminescence in the solid state, with an emission maximum at 415 nm.     

含能配合物[Zn(DAT)6](ClO4)2(DAT＝1,5-二氨基四唑)的合成、晶体结构及性质

采用直接法合成了新型高氮含能配合物[Zn(DAT)₆](ClO₄)₂(DAT＝1,5-二氨基四唑), 并用元素分析、傅立叶变换红外光谱对其结构进行了表征. 利用缓慢蒸发溶剂法培养出其单晶, 采用X射线单晶衍射仪测定其晶体结构, 结果表明该晶体属于三方晶系, 空间群, a＝b＝1.18398(9) nm, c＝0.65700(10) nm, γ＝120°, V＝0.79760(15) nm³, Z＝1. 在目标配合物的最小不对称单元中有1个Zn^2＋, 6个DAT分子和2个. 来自6个DAT分子的6个N原子分别与中心Zn^2＋配位, 形成一个六配位、非中心对称的畸变八面体结构. 用差示扫描量热分析、热重-微分热重分析结合红外光谱研究了标题化合物的热分解机理以及分解反应动力学参数. 测定了标题配合物的感度性能, 结果表明标题配合物具有一定的摩擦感度.     

A twofold interpenetrating three‐dimensional CdII coordination framework: poly[[μ2‐1,3‐bis(2‐methyl‐1H‐imidazol‐1‐yl)benzene](μ3‐5‐nitrobenzene‐1,3‐dicarboxylato)cadmium(II)]

A twofold interpenetrating three‐dimensional Cd^II coordination framework, [Cd(C₈H₃NO₆)(C₁₄H₁₄N₄)]_n, has been prepared and characterized by IR spectroscopy, elemental analysis, thermal analysis and single‐crystal X‐ray diffraction. The asymmetric unit consists of a divalent Cd^II atom, one 1,3‐bis(2‐methyl‐1H‐imidazol‐1‐yl)benzene (1,3‐BMIB) ligand and one fully deprotonated 5‐nitrobenzene‐1,3‐dicarboxylate (NO₂‐BDC²⁻) ligand. The coordination sphere of the Cd^II atom consists of five O‐donor atoms from three different NO₂‐BDC²⁻ ligands and two imidazole N‐donor atoms from two different 1,3‐BMIB ligands, forming a distorted {CdN₂O₅} pentagonal bipyramid. The NO₂‐BDC ligand links three Cd^II atoms via a μ₁‐η¹:η¹ chelating mode and a μ₂‐η²:η¹ bridging mode. The title compound is a twofold interpenetrating 3,5‐connected network with the {4².6⁵.8³}{4².6} topology. In addition, the compound exhibits fluorescence emissions in the solid state at room temperature.     

A new orthoborate,Sr3Ga3(BO3)4O(OH)

The crystal structure of tristrontium trigallium tetraborate oxide hydro­xide has been determined by X‐ray diffraction using a crystal grown by hydro­thermal crystallization of a strontium gallo‐borate glass. It represents a new orthoborate structure type built of complex layers formed by BO₃ triangles sharing corners with Ga₂O₇ tetrahedral dimers and GaO₄OH square pyramids. The Sr atoms occupy both inter‐ and intralayer sites.     

Experimental and quantum chemical calculational studies on N‐[4‐(3‐Methyl‐3‐phenyl‐cyclobutyl)‐thiazol‐2‐yl]‐N′‐pyridin‐3ylmethylene‐hydrazine

The title molecule, N‐[4‐(3‐Methyl‐3‐phenyl‐cyclobutyl)‐thiazol‐2‐yl]‐N′‐pyridin‐3ylmethylene‐ hydrazine (C₂₀ H₂₀ N₄ S₁), was characterized by ¹H‐NMR, ¹³C‐NMR, IR, UV‐visible, and X‐ray determination. In addition to the molecular geometry from X‐ray experiment, the molecular geometry, vibrational frequencies and gauge including atomic orbital ¹H‐ and ¹³C‐NMR chemical shift values of the title compound in the ground state have been calculated using the Hartree‐Fock and density functional method (B3LYP) with 6‐31G(d, p) basis set. The calculated results show that optimized geometries can well reproduce the crystal structural parameters. By using time‐dependent density functional theory method, electronic absorption spectrum of the title compound has been predicted. © 2011 Wiley Periodicals, Inc.