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Crystal engineering of hybrid inorganic-organic systems based upon complexes with dissymmetric compartmental ligands
17 November 2009
Marius Andruh and colleagues design supramolecular heterometallic systems based on Schiff-base ligands

Green tea prevents kidney stones
13 November 2009
Drinking green tea can help prevent the formation of large kidney stones claim Chinese scientists
Crystal engineering in molecular magnetism
17 September 2009
Check out the latest developments on crystal engineering in molecular magnetism in CrystEngComm’s issue 10, 2009
Contents list for CrystEngComm, issue 12, 2009
Front cover
CrystEngComm, 2009, 11, 2555
DOI: 10.1039/b922619m

Inside front cover
CrystEngComm, 2009, 11, 2556
DOI: 10.1039/b922620f
Contents and Highlights in Chemical Technology
CrystEngComm, 2009, 11, 2557
DOI: 10.1039/b922494g
Highlight
Crystal engineering of hybrid inorganic–organic systems based upon complexes with dissymmetric compartmental ligands
Marius Andruh, Diana G. Branzea, Ruxandra Gheorghe and Augustin M. Madalan,
CrystEngComm, 2009, 11, 2571
DOI: 10.1039/b909476h

The manuscript describes and summarizes the work on heterometallic o-vanillin-based Schiff base complexes. The versatility of mono- and heterobinuclear complexes with dissymmetric compartmental ligands in designing molecular and supramolecular heterometallic systems is illustrated.
Communications
Solid state crystal-to-crystal transformation from a monomeric structure to 1-D coordination polymers on anion exchange,
Mojtaba Khanpour and Ali Morsali,
CrystEngComm, 2009, 11, 2585
DOI: 10.1039/b908362f

Yellow crystals of monomeric structure [Zn(bpdh)2(H2O)4](NO3)2·2bpdh (1) convert on heating at ca. 160 °C under grinding and mixing with KSCN or NaN3 to white and orange 1D coordination polymers, [Zn(µ-bpdh)2(NCS)2]n (2) and [Zn(µ-bpdh)2(N3)2]n (3), respectively.
A new anionic acceptor, 2-sulfo-3,5,6-trichloro-1,4-benzoquinone and its charge-transfer salts
Hiroki Akutsu, Jun-ichi Yamada, Shin'ichi Nakatsuji and Scott S. Turner,
CrystEngComm, 2009, 11, 2588
DOI: 10.1039/b909519e

A novel anionic acceptor, 2-sulfo-3,5,6-trichloro-1,4-benzoquinone, being a weaker acceptor by 0.16 V than chloranil provided one TTF and two BEDT-TTF salts.
A novel 3D Mn(II) coordination polymer involving 4,4
-dipyridylsulfide and 4,4
-dipyridyltrisulfide obtained by in situ ligand formation from 4,4
-dipyridyldisulfide
Lu-Fang Ma, Li-Ya Wang and Miao Du,
CrystEngComm, 2009, 11, 2593
DOI: 10.1039/b914827m

A novel Mn(II) coordination framework, {[Mn(mip)(dps)](dpts)0.5}2n, has been successfully solvothermally synthesized by in situ generation of dps and dpts ligands from the dpds precursor through a cleavage of the S–S and S–C bonds.
A new layered aluminoborate [Zn(dien)2][{Al(OH)}{B5O9F}] templated by transition metal complexes
Jian Zhou, Shou-Tian Zheng, Mingyi Zhang, Guang-Zhen Liu and Guo-Yu Yang,
CrystEngComm, 2009, 11, 2597
DOI: 10.1039/b909693k

A new acentric layer [{Al(OH)}{B5O9F}2-]n templated by a chiral mer-[Zn(dien)2]2+ cation is further stacked in -AAA- fashion to result in a noncentrosymmetric structure.
Polymerisation of a Cu(II) dimer into 1D chains using high pressure
Stephen A. Moggach, Kyle W. Galloway, Alistair R. Lennie, Pascal Parois, Niall Rowantree, Euan K. Brechin, John E. Warren, Mark Murrie and Simon Parsons,
CrystEngComm, 2009, 11, 2601
DOI: 10.1039/b912707k

When the complex [Cu2(OH)(citrate)(guanidine)2]- is exposed to a pressure of 2.9 GPa the coordination of the Cu centres changes from [4 + 1] to [4 + 2]. On increasing the pressure to 4.2 GPa some of the Cu centres become [4 + 1]-coordinate again.
A step-heating procedure for the synthesis of high-quality FePt nanostars
Shengtai He, Isabel Garcia, Juan Gallo and Soledad Penadés,
CrystEngComm, 2009, 11, 2605
DOI: 10.1039/b909022n

With a step-heating procedure, high-quality FePt nanostars were synthesized by confined decomposition of Fe(acac)2 and reduction of Pt(acac)2. Water soluble FePt nanostars were prepared by ligand exchange for its potential aqueous applications.
The first crystallographic observation of up to the third hydration layer of Cu(II) ion in an unusual
water-cation layer
templated by an Anderson polyoxometallate
Mahammad Ali, Daipayan Dutta, Surajit Biswas, Jaromir Marek and Atish Dipankar Jana,
CrystEngComm, 2009, 11, 2608
DOI: 10.1039/b910732k

First crystallographic observation of hydrated Cu(II) ion with three hydration layers depicted in red, yellow and blue.
An unusual 3D polycatenane motif generated by the 2D
2D parallel
3D parallel interpenetration of (4,4) sheets
Huadong Guo, Dongfang Qiu, Xianmin Guo, Stuart R. Batten and Hongjie Zhang,
CrystEngComm, 2009, 11, 2611
DOI: 10.1039/b913747e

A fascinating 3D polycatenane-like metal–organic framework with two kinds of helical chains was reported, in which the helical chains exhibit multiple interweaving modes based on the unusual 2D
2D parallel
3D parallel interpenetration.
CdSnO3 micro-cubes with porous architecture: synthesis and gas-sensing properties
Yanfen Cao, Zhixuan Cheng, Jiaqiang Xu, Yuan Zhang and Qingyi Pan,
CrystEngComm, 2009, 11, 2615
DOI: 10.1039/b914809d

CdSnO3 micro-cubes with porous architecture were obtained exclusively via a simple co-precipitation method at 80 °C for 6 hours, with which a good response to ethanol vapor in ppb was observed.
Drug-containing coordination and hydrogen bonding networks obtained mechanochemically
Dario Braga, Fabrizia Grepioni, Vânia André and M. Teresa Duarte,
CrystEngComm, 2009, 11, 2618
DOI: 10.1039/b913433f

Coordination and hydrogen bonding networks of the antibiotic 4-aminosalicylic acid and of the nootropic drug piracetam with silver and nickel cations have been prepared mechanochemically; in the case of silver, solid-state and solution reactions afforded different crystalline materials.
Papers
Facile shape-controlled synthesis of luminescent europium benzene-1,3,5-tricarboxylate architectures at room temperature
Kai Liu, Hongpeng You, Yuhua Zheng, Guang Jia, Lihui Zhang, Yeju Huang, Mei Yang, Yanhua Song and Hongjie Zhang,
CrystEngComm, 2009, 11, 2622
DOI: 10.1039/b905924p

The metal–organic framework Eu(1,3,5–BTC)·6H2O superstructures were prepared at room temperature for the first time. The splitting growth mechanism and luminescent properties were investigated in detail. These unique hierarchical architectures may have potential applications in building minioptoelectronic devices.
Synthesis, crystal structure and magnetic properties of two 3-D gadolinium complexes
Zheng-Bo Han, Guo-Xin Zhang, Ming-Hua Zeng, Chun-Hua Ge, Xiao-Hong Zou and Guang-Xi Han,
CrystEngComm, 2009, 11, 2629
DOI: 10.1039/b905663g

Two new gadolinium coordination polymers, [Gd(tci)(H2O)]·DMF·2H2O (1) and [Gd(bci)(H2O)]·2H2O (2) feature interesting 3D metal–organic frameworks, a pair of Gd centers are bridged by two µ-O atoms of the carboxylate groups to form an infinite linear chain. The magnetic studies indicate that there exist antiferromagnetic interactions in 1 and ferromagnetic interactions in 2.
Knowledge-based H-bond prediction to aid experimental polymorph screening
Peter T. A. Galek, Frank H. Allen, László Fábián and Neil Feeder,
CrystEngComm, 2009, 11, 2634
DOI: 10.1039/b910882c

Potential H-bond likelihoods are predicted and used to assess structural stability. An illustration of the method's potential automatically points toward the well-known polymorphism of the drug ritonavir (Norvir
), and identifies the relative stability of form II over form I.
Structural diversity of lanthanide coordination polymers with 2,2
-biquinoline-4,4
-dicarboxylate
Jie Zhou, Shaohua Yan, Daqiang Yuan, Xiangjun Zheng, Licun Li and Linpei Jin,
CrystEngComm, 2009, 11, 2640
DOI: 10.1039/b911100j

Eight lanthanide complexes based on the 2,2
-biquinoline-4,4
-dicarboxylate ligand have been synthesized with different synthetic strategies and characterized by single-crystal X-ray diffraction. The result shows they have three types of structures, which may be attributed to the properties of lanthanide ions and the ligands.
Role of
-hydroxycarboxylic acids in the construction of supramolecular assemblies of nickel(II) complexes with nitrogen donor coligands
Partha Halder, Biswarup Chakraborty, Priya Ranjan Banerjee, Ennio Zangrando and Tapan Kanti Paine,
CrystEngComm, 2009, 11, 2650
DOI: 10.1039/b904939h

The supramolecular assembly of six nickel(II) complexes of
-hydroxycarboxylic acids using nitrogen donor coligands is studied. All the complexes form one-dimensional H-bonded polymers built by the monomeric nickel(II) building blocks.
Probing the influence of pH dependent citric acid towards the morphology of rock salt: a computational study
Md Abdul Shafeeuulla Khan, Anik Sen and Bishwajit Ganguly,
CrystEngComm, 2009, 11, 2660
DOI: 10.1039/b909765a

A detailed computational study is presented on the role of conformations of citric acid and its dissociated forms on the morphological change of sodium chloride, employing MESP and slab model calculations.
Pressure-controlled aggregation in carboxylic acids. A case study on the polymorphism of bromochlorofluoroacetic acid
Roman Gajda, Andrzej Katrusiak and Jeanne Crassous,
CrystEngComm, 2009, 11, 2668
DOI: 10.1039/b910409g

Depending on the pressure, CBrClFCOOH freezes as two polymorphs: in the orthorhombic phase
molecules form unusual zigzag catemers, whereas the monoclinic phase
is built of centrosymmetric dimers, typical of carboxylic acids.
Titania polymorphs derived from crystalline titanium diboride
Gang Liu, Hua Gui Yang, Chenghua Sun, Lina Cheng, Lianzhou Wang, Gao Qing (Max) Lu and Hui-Ming Cheng,
CrystEngComm, 2009, 11, 2677
DOI: 10.1039/b909191m

Due to its capability of controllably releasing titanium species, TiB2 was chosen as a precursor for synthesizing phase tunable (rutile/anatase/brookite) titania with different morphologies (nanocones/bipyramids/spherical nanoparticles) under hydrothermal treatment.
Morphology-controlled ZnO particles from an ionic liquid precursor
Zhonghao Li, Qian Yu, Yuxia Luan, Guangshan Zhuang, Runhua Fan, Rui Li and Chengguo Wang,
CrystEngComm, 2009, 11, 2683
DOI: 10.1039/b910551b

The ionic liquid precursor tetraethylammonium hydroxide (TEAH) acting as the reactant precursor and the solvent is demonstrated to be effective for synthesis of ZnO particles with controlled morphologies.
Different solvates of two isomeric dicarboxylic acids with pyridine and quinoline
Devendra Singh and Jubaraj B. Baruah,
CrystEngComm, 2009, 11, 2688
DOI: 10.1039/b911084d

Two different polymorphs of solvates of 2-[7-(2-carboxy-phenyl)-1,3,6,8-tetraoxo-3,6,7,8-tetrahydro-1H-benzo[lmn][3,8]phenanthrolin-2-yl]-benzoic acid with pyridine.
Turbine-like structured silica transcribed simply by pre-structured crystallites of linear poly(ethyleneimine) bounded with metal ions
Hiroyuki Matsukizono, Pei-Xin Zhu, Norimasa Fukazawa and Ren-Hua Jin,
CrystEngComm, 2009, 11, 2695
DOI: 10.1039/b909023c

Hierarchical silica was constructed by the transcription of linear poly(ethyleneimine) precipitates from various metal salts aq. These coexisting metal salts serve as inhibitors of crystallization of the polymers to develop easily various morphologies depending on the crystallization conditions.
A structural survey of metal
heteroaromatic supramolecular synthons for metal = tellurium, tin, and gold
Edward R. T. Tiekink and Julio Zukerman-Schpector,
CrystEngComm, 2009, 11, 2701
DOI: 10.1039/b910209d

The introduction of a nitrogen atom into an aromatic ring is shown to increase the likelihood of supramolecular structures sustained by Au
interactions.
Dehydration and rehydration behavior of a trinodal topological 3-D framework of Cd(II) benzimidazole-5,6-dicarboxylate
Yong-Ru Liu, Lei Li, Tao Yang, Xing-Wen Yu and Cheng-Yong Su,
CrystEngComm, 2009, 11, 2712
DOI: 10.1039/b909772d

A new 3-D structural model has been established from a Cd(II) coordination polymer which shows a trinodal (3,4,5)-connected net topology. A study in de/rehydration processes of this coordination polymer reveals reversible single-crystal-to-single-crystal, crystal-to-crystal and irreversible crystal-to-amorphous transformations.
ds-Block metal ions catalyzed decarboxylation of pyrazine-2,3,5,6-tetracarboxylic acid and the complexes obtained from hydrothermal reactions and novel water clusters
Ai-Hong Yang, Ying-Ping Quan, Hong-Ling Gao, Su-Rong Fang, Yan-Ping Zhang, Li-Hua Zhao, Jian-Zhong Cui, Jian-Hui Wang, Wei Shi and Peng Cheng,
CrystEngComm, 2009, 11, 2719
DOI: 10.1039/b911939f

Higher temperature lower pH and ds-block metal ions can promote the decarboxylation of pyrazinetetracarboxylic acid under hydrothermal conditions. The novel T5(0)A0 water tape and S-shaped (H2O)10 cluster are observed in the obtained complexes.
Metal–organic frameworks with six- and four-fold interpenetration and their photoluminescence and adsorption property
Jing Xu, Zheng-Shuai Bai, Man-Sheng Chen, Zhi Su, Shui-Sheng Chen and Wei-Yin Sun,
CrystEngComm, 2009, 11, 2728
DOI: 10.1039/b904784k

Two novel 3D coordination polymers {[ZnL2]·4H2O}n and {[Cu(HL)2(H2O)2]Cl2}n [HL = 1-(imidazol-1-yl)-4-(imidazol-4-yl)benzene] with a different degree of interpenetration were synthesized, and their stabilities, luminescent and adsorption properties are investigated.
Protonated 3-amino-1,2,4-triazole templated luminescent lanthanide isophthalates with a rare (3,6)-connected topology
Pei-Xiu Yin, Zhao-Ji Li, Jian Zhang, Lei Zhang, Qi-Pu Lin, Ye-Yan Qin and Yuan-Gen Yao,
CrystEngComm, 2009, 11, 2734
DOI: 10.1039/b907107e

The paper presents a series of isomorphous lanthanide isophthalates, [Ln(ip)2(H2O)]·(HAmTAZ) (Ln = La (1), Sm (2), Tb (3); ip = isophthalate, AmTAZ = 3-amino-1,2,4-triazole), templated by protonated HAmTAZ+ cations.
The uranyl tetrachloride anion as a tecton in the assembly of U(VI) hybrid materials
Nicholas P. Deifel and Christopher L. Cahill,
CrystEngComm, 2009, 11, 2739
DOI: 10.1039/b911470j

Reported are seven compounds containing the [UO2Cl4]2- tecton. Four of these demonstrate the application of the NH
Cl2M supramolecular synthon to the assembly of actinide bearing hybrid materials.
Facile synthesis of highly uniform octahedral LuVO4 microcrystals by a facile chemical conversion method
Guang Jia, Hongpeng You, Lihui Zhang, Yuhua Zheng, Kai Liu, Yeju Huang and Hongjie Zhang,
CrystEngComm, 2009, 11, 2745
DOI: 10.1039/b911499h

Uniform octahedral LuVO4 microcrystals have been successfully prepared through a designed two-step hydrothermal method. The LuVO4
:
Ln3+ (Ln = Eu, Dy, Sm, and Er) phosphors show strong light emissions with different colors coming from different activator ions under ultraviolet excitation or low-voltage electron beam excitation.
Solvothermal assembly of a mixed-valence Cu(I,II) cyanide coordination polymer [Cu(II)Cu(I)2(µ-Br)2(µ-CN)2(bdmpp)]n by C–C bond cleavage of acetonitrile
Ling-Ling Li, Lei-Lei Liu, Zhi-Gang Ren, Hong-Xi Li, Yong Zhang and Jian-Ping Lang,
CrystEngComm, 2009, 11, 2751
DOI: 10.1039/b903972d

Dissolving CuBr and 2,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)pyridine (bdmpp) in MeCN followed by the C–C cleavage of MeCN at solvothermal conditions afforded an unique mixed-valence Cu(I,II) cyanide coordination polymer [Cu(II)Cu(I)2(µ-Br)2(µ-CN)2(bdmpp)]n.
Structural variability of Cd(II) and Co(II) mixed-ligand coordination polymers: effect of ligand isomerism and metal-to-ligand ratio
Feng-Yun Cui, Kun-Lin Huang, Yan-Qing Xu, Zhan-Gang Han, Xi Liu, Ying-Nan Chi and Chang-Wen Hu,
CrystEngComm, 2009, 11, 2757
DOI: 10.1039/b907606a

Three isomeric 2-amino-4,6-dipyridylpyrimidine ligands were firstly introduced in the mixed-ligand system. The influence of the metal-to-ligand ratio and ligand isomerism on the coordination structure and supramolecular assembly was investigated.
Controlled large-scale fabrication of sea sponge-like ZnO nanoarchitectures on textured silicon
Maria Elena Fragalŕ, Alessandro Di Mauro, Grazia Litrico, Filippo Grassia, Graziella Malandrino and Gaetano Foti,
CrystEngComm, 2009, 11, 2770
DOI: 10.1039/b914541a

Textured silicon micropattern drives ZnO growth on all the {111} exposed faces, resulting in 3D sea sponge-like ZnO nanoarchitectures. Each individual ZnO nanorod has a perfect hexagonal surface throughout its length, with diameter <100 nm and preferentially grows in 1D direction. A strong green luminescence is associated to crystal surface nanoarchitectures.
Novel sonochemical assisted hydrothermal approach towards the controllable synthesis of ZnO nanorods, nanocups and nanoneedles and their photocatalytic study
Sambhaji S. Warule, Nilima S. Chaudhari, Bharat B. Kale and Mahindra A. More,
CrystEngComm, 2009, 11, 2776
DOI: 10.1039/b909916f

ZnO nanocups, self assembled nanorods and nanowires have been synthesized by a facile sonochemical method. Tetrapods of ZnO nanorods, nanotubes and nanoneedles were synthesized by a novel sonochemical assisted hydrothermal method. The nanocups and nanoneedles showed an excellent photocatalytic activity as compared to bulk and other ZnO morphologies.
Construction of hybrid d10 metal–organic frameworks by flexible aromatic dicarboxylate and N-donor ligands
:
syntheses, structures and physical properties
Guang-Xiang Liu, Kun Zhu, Huan-Min Xu, Sadafumi Nishihara, Rong-Yi Huang and Xiao-Ming Ren,
CrystEngComm, 2009, 11, 2784
DOI: 10.1039/b916280c

Assembly of Zn(II) and Cd(II) salts with two flexible aromatic dicarboxylate acids and a series of rationally selected N-donor ligands of different size, conformation and degrees of freedom results in the formation of six distinct coordination polymers. The solid-state photoluminescence properties of the complexes have been explored.
Selective etching of gold nanorods by ferric chloride at room temperature
Renxian Zou, Xia Guo, Jian Yang, Dandan Li, Feng Peng, Lei Zhang, Hongjuan Wang and Hao Yu,
CrystEngComm, 2009, 11, 2797
DOI: 10.1039/b911902g

We report a chemical etching reaction of gold nanorods induced by ferric chloride at room temperature.
Anion-controlled assemble of C–H
X hydrogen bonded helical tubes or catemers by crescent imidazolium salts
Kwang-Ming Lee, Jack C. C. Chen, Chao-June Huang and Ivan J. B. Lin,
CrystEngComm, 2009, 11, 2804
DOI: 10.1039/b911665f

Crescent imidazolium cations could convergently form helical tubes with Br- and NO3-, or divergently form 1-D catemers with PF6- and BF4- anions respectively.
Additions and Corrections
CrystEngComm, 2009, 11, 2810
DOI: 10.1039/b922492k




