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Objective: To investigate the chemical constituents from the stems and branches of Sorbaria arborea., Methods: The chemical constituents were isolated and purified by silica gel column chromatography, Sephadex LH-20 column chromatography and recrystallization. Their structures were identified by physicochemical properties and spectra analysis., Results: Ten compounds were isolated and identified as ursolic acid (1), cucurbitacin F (2), (-) -epicatechin (3), daucosterol (4), arbutin (5), 3-O-β-anthemisol (6), 2,6-dimethoxy-p-hydroquinone-4-O-β-D-glucopyranoside (7), lupeol (8), betulin (9) and lup-20 (29) -en-3β, 30-diol (10)., Conclusion: All the compounds are isolated from this plant for the first time, and compounds 1, 6 - 8 and 10 are obtained from Sorbaria genus for the first time.

The asymmetric unit of the title Co(II) complex, [Co(C13H8BrN2O)2], contains two independent mol-ecules (A and B). In both mol-ecules, the Co(II) cation is N,O-chelated by two 2-(1H-benzimidazol-2-yl)-4-bromo-phenolate anions in a distorted tetra-hedral geometry. In mol-ecule A, both chelating rings display an envelope conformation, with the flap Co atom lying 0.614 (6) and 0.483 (6) Å from the mean planes of the remaining atoms. In mol-ecule B, both chelating rings are approximately planar, the maximum deviations being 0.039 (4) and 0.076 (3) Å. In the crystal, mol-ecules are linked by classical N-H⋯O hydrogen bonds and weak C-H⋯O and C-H⋯Br hydrogen bonds into a three-dimensional supra-molecular network. Extensive π-π stacking is observed between nearly parallel aromatic rings of adjacent mol-ecules with centroid-centroid distances in the range 3.407 (3)-3.850 (4) Å.

There are two mol-ecules in the asymmetric unit of the title compound, C20H14Br2N2. In the first, the dihedral angles between the mean plane of the benzimidazole group and those of the 4-bromo-benzyl and 4-chloro-phenyl groups are 50.72 (17) and 71.29 (16)°, respectively, while the corresponding angles in the second mol-ecule are 42.09 (16) and 89.05 (17)°. The 4-bromo-benzyl and 4-bromo-phenyl groups make an angle of 68.1 (2) and 85.1 (21)° with each other in the two mol-ecules. In the crystal, weak C-H⋯N and C-H⋯Br hydrogen bonds link the mol-ecules along the c-axis direction. Br⋯Br inter-actions [3.5733 (9)Å] are also observed.

The structure of the title compound [systematic name: bis(adamantan-1-aminium) tetrachloridozincate(II)-1,4,7,10,13,16-hexaoxacyclooctadecane-water (1/1/1)], (C(10)H(18)N)(2)[ZnCl(4)] x C(12)H(24)O(6) x H(2)O, consists of supramolecular rotator-stator assemblies and ribbons of hydrogen bonds parallel to [010]. The assemblies are composed of one protonated adamantan-1-aminium cation and one crown ether molecule (1,4,7,10,13,16-hexaoxacyclooctadecane) to give an overall [(C(10)H(18)N)(18-crown-6)](+) cation. The -NH(3)(+) group of the cation nests in the crown and links to the crown-ether O atoms through N-H...O hydrogen bonds. The 18-crown-6 ring adopts a pseudo-C(3v) conformation. The second adamantan-1-aminium forms part of ribbons of adamantan-1-aminium-water-tetrachloridozincate units which are interconnected by O-H...Cl, N-H...O and N-H...Cl hydrogen bonds via three different continuous rings with R(5)(4)(12), R(4)(3)(10) and R(3)(3)(8) motifs.

The reaction of propane-1,3-diamine hydrochloride, 18-crown-6 and zinc(II) chloride in methanol solution yields the title complex salt [systematic name: propane-1,3-diaminium tetrachloridozincate(II)-1,4,7,10,13,16-hexaoxacyclooctadecane (1/1)], (C(3)H(12)N(2))[ZnCl(4)] x C(12)H(24)O(6), with an unusual supramolecular structure. The diprotonated propane-1,3-diaminium cation forms an unexpected 1:1 supramolecular rotator-stator complex with the crown ether, viz. [C(3)H(12)N(2)(18-crown-6)](2+), in which one of the -NH(3)(+) substituents nests in the crown and interacts through N-H...O hydrogen bonding. The other -NH(3)(+) group interacts with the [ZnCl(4)](2-) anion via N-H...Cl hydrogen bonding, forming cation-crown-anion ribbons parallel to [010].

In the cation of the title compound, C(9)H(11)N(2)O(4) (+)·ClO(4) (-), the conformation is stabilized by an intra-molecular N-H⋯O hydrogen bond. In the crystal packing, centrosymmetrically related cations inter-act through inter-molecular O-H⋯O hydrogen bonds involving the carb-oxy groups, forming dimers. The dimers and the perchlorate anions are further linked into layers parallel to the ab plane by C-H⋯O and N-H⋯O hydrogen-bonding inter-actions.

In the title salt, C(9)H(12)NO(2) (+)·NO(3) (-), the cation and anion are linked by a bifurcated N-H⋯(O,O) hydrogen bond. The crystal packing is stabilized by inter-molecular N-H⋯O, O-H⋯O and C-H⋯O hydrogen bonds, which connect neighbouring cations and anions, resulting in a two-dimensional network.

The title compound, C(8)H(8)N(4), possesses crystallographic mirror symmetry, with four C atoms lying on the reflecting plane, which bis-ects the phenyl and tetra-zole rings. It is composed of a planar r.m.s. deviation (0.0012 Å) tetra-zole ring which is nearly coplanar with the benzene ring, the dihedral angle being 2.67 (9)°. In the crystal, symmetry-related mol-ecules are linked by inter-molecular N-H⋯N hydrogen bonds. The mol-ecules stack along [100] with a π⋯π inter-action involving the phenyl and tetra-zole rings of adjacent mol-ecules [centroid-centroid distance = 3.5639 (15) Å]. The H atom of the N-H group is disordered over two sites of equal occupancy. The methyl H atoms were modelled as disordered over two sets of sites of equal occupancy rotated by 60° with respect to each other.

The crystal structure of the title compound, C(6)H(10)N(2) (2+)·2Cl(-), has been reported previously in the non-standard setting P2(1)/a [Genet (1965 ▶). Bull. Soc. Fr. Miner. Crist.88, 463-470], with an R value of 0.16. The current redetermination improves significantly the precision of the geometric parameters. In the crystal packing, cations and anions are linked by inter-molecular N-H⋯Cl and C-H⋯Cl hydrogen bonds into a three-dimensional network.

The title mol-ecule, C(9)H(9)N(3)O(4), syhthesized from 1H-pyrazole-3,5-dicarboxylic acid and 2-bromo-acetonitrile, is approximately planar; the inter-planar angles between the pyrazole ring and the mean planes of the two carboxylate units and the cyanomethyl unit are 4.49 (10), 5.56 (9) and 5.03 (19)°, respectively. In the crystal, inversion dimers linked by pairs of weak C-H ⋯O bonds occur, and the packing is further stabilized by aromatic π-π stacking [centroid-centroid separation = 3.793 (4) Å].

In the title compound, H(3)O(+)·C(8)H(5)O(5) (-), neighbouring cations and anions are linked by O-H⋯O hydrogen bonds, forming a one-dimensional chain framework along [001]. The crystal structure is further stabilized by π-π inter-actions, with centroid-centroid distances of 3.734 (3) Å.

In the mol-ecule of the title compound, C(19)H(15)N(5), the dihedral angles formed by the plane of the triazole ring with those of the 2-pyridyl, 4-pyridyl and p-tolyl rings are 28.12 (10), 34.62 (10) and 71.43 (9)°, respectively. The crystal structure is consolidated by C-H⋯π hydrogen-bonding inter-actions and by π-π stacking inter-actions, with a centroid-centroid distance of 3.794 (4) Å.

In the title compound, C(9)H(12)NO(2) (+)·ClO(4) (-), an intra-molecular N-H⋯O inter-action results in the formation of a six-membered ring having a twisted chair conformation. In the crystal structure, inter-molecular O-H⋯O, N-H⋯O and C-H⋯O inter-actions link the mol-ecules into a network. A weak C-H⋯π inter-action is also found.

The structure of title compound, C(8)H(8)ClN(2) (+)·Cl(-), comprises discrete ions which are inter-connected by N-H⋯Cl hydrogen bonds, leading to a neutral one-dimensional network in [001]. This hydrogen bonding appears to complement π-π stacking inter-actions [centroid-centroid distances 3.768 (2) and 3.551 (2) Å] and helps to stabilize the structure further.

We report on a multi-technique investigation of the supramolecular organisation of N,N-diphenyl oxalic amide under differently dimensioned environments, namely three-dimensional (3D) in the bulk crystal, and in two dimensions on the Ag(111) surface as well as on the reconstructed Au(111) surface. With the help of X-ray structure analysis and scanning tunneling microscopy (STM) we find that the molecules organize in hydrogen-bonded chains with the bonding motif qualitatively changed by the surface confinement. In two dimensions, the chains exhibit enantiomorphic order even though they consist of a racemic mixture of chiral entities. By a combination of the STM data with near-edge X-ray absorption fine-structure spectroscopy, we show that the conformation of the molecule adapts such that the local registry of the functional group with the substrate is optimized while avoiding steric hindrance of the phenyl groups. In the low coverage case, the length of the chains is limited by the Au(111) reconstruction lines restricting the molecules into fcc stacked areas. A kinetic Monte Carlo simulated annealing is used to explain the selective assembly in the fcc stacked regions.

The title compound, C(11)H(11)NO, was synthesized by the reaction of 2-(bromo-meth-yl)benzonitrile and acetyl-acetone in the presence of KOH. In the crystal packing, mol-ecules are linked by inter-molecular N-H⋯O hydrogen bonds into chains running parallel to the b axis. Centrosymmetrically-related chains inter-act further through weak C-H⋯π inter-actions.

The title compound, C(16)H(10)N(2)O(8)·2C(3)H(7)NO, was synthesized by the reductive condensation reaction of 5-nitro-isophthalic acid in the presence of NaOH. The tetra-acid mol-ecule, which has a crystallographically imposed centre of symmetry, adopts an E configuration with respect to the azo group. In the crystal packing, mol-ecules are linked through inter-molecular O-H⋯O and C-H⋯O hydrogen-bonding inter-actions, forming chains propagating in [20].

The title compound, [CdCl(2)(C(6)H(8)N(2))](n), is a coordination polymer prepared by the hydro-thermal reaction of cadmium chloride and o-diamino-benzene. The cadmium cation, located on an inversion center, is octa-hedrally coordinated by four Cl atoms at equatorial sites and two N atoms from two ligands at the axial sites. Cd atoms are bridged by Cl atoms, forming extended chains parallel to [010]. Neighboring chains are connected by N-H⋯Cl hydrogen bonds.

The title compound, [CdCl(2)(C(9)H(11)NO(2))](n), is a coordination polymer prepared by the hydro-thermal reaction of cadmium(II) chloride and 3-amino-3-phenyl-propanoic acid. Geometric parameters are in the usual ranges. The cadmium cation is octa-hedrally coordinated by four Cl atoms at equatorial sites and two O atoms from two ligands at the axial sites. The material is composed of one-dimensional extended polymeric chains in which two Cl atoms bridge Cd atoms. The crystal structure is stabilized by an intra-molecular N-H⋯O hydrogen bond.

The title compound, [Cd(2)(C(8)H(4)N(4)O(2))(2)(H(2)O)(2)](n), is a coordination polymer prepared by the hydro-thermal reaction of cadmium(II) chloride and 2-(1H-tetra-zol-5-yl)benzoic acid. Two types of coordinated cadmium cations exist in the structure. One is located on a twofold axis and is coordinated by four O and two N atoms from four symmetry-related ligands, forming a trigonal-prismatic coordination polyhedron. The other is located on an inversion center and is octa-hedrally coordinated by two N and two O atoms from two ligands in equatorial sites, and two water mol-ecules in axial sites. The organic ligand bridges three Cd atoms, through a carboxyl-ate group and two N atoms of the tetra-zolate unit. This mode of coordination results in a two-dimensional framework. The crystal structure is stabilized by inter-molecular O-H⋯O and O-H⋯N hydrogen bonds.

The title compound, C(32)H(20)N(2)O(6), was synthesized by the reaction of 1,1'-binaphthyl-2,2'-diol and 4-nitro-phenol in the presence of K(2)CO(3). The two naphthalene systems make a dihedral angle of 73.70 (5)°. The crystal packing involves mol-ecules connected by C-H⋯O hydrogen bonds into a chain along the c axis.

A new tetra-dentate chiral Schiff base ligand, C(26)H(30)N(2)O(2), has been synthesized by the reaction of 1-phenyl-butane-1,3-dione with (1S,2S)-(-)-1,2-diamino-cyclo-hexane. The chiral centers in the mol-ecule have the same S configuration, since the absolute configuration was determined by that of the starting reagent (1S,2S)-(-)-1,2-diamino-hexane. The cyclo-hexane ring is in a chair conformation, and the substituents are equatorial in the most stable conformation (trans-cyclo-hexyl). The crystal structure is stabilized by two intra-molecular O-H⋯N hydrogen bonds and a weak C-H⋯π inter-action.

The title coordination polymer, [Zn(C(8)H(4)N(4)O(2))(H(2)O)](n), was prepared by the hydro-thermal reaction of zinc nitrate and 2-(1H-tetra-zol-5-yl)benzoic acid. Two types of coordinated zinc cations exist in the structure. One is tetra-hedrally coordinated by two O and two N from two ligands, the other is octa-hedrally coordinated by two N and two O from two ligands at equatorial sites and by two O atoms of water mol-ecules at axial sites, resulting in a two-dimensional framework. The crystal structure is stabilized by intra-molecular O-H⋯O and O-H⋯N hydrogen bonds.

A new tetra-dentate chiral Schiff base ligand, C(16)H(26)N(2)O(2), has been synthesized by the reaction of acetyl-acetone with (1R,2R)-(-)-1,2-diamino-cyclo-hexane. Both of the mol-ecules in the asymmetric unit are of the same chirality (R configuration), since the absolute configuration was determined by the starting reagent (1R,2R)-(-)-1,2-diamino-cyclo-hexane. The six-membered cyclo-hexane ring is in a chair conformation, and the substituents are equatorial in the most stable conformation (trans-cyclo-hexyl). At the ring substituents, large conjugated -C=N-CH=C-OH systems exist, resulting from the original ketone converted into the enol form. With H atoms excluded, the atoms of each substituent lie in the same plane. The two mol-ecules in the asymmetric unit have almost the same structure, with slight differences in the torsion angles between the substituents and the cyclo-hexane ring; the corresponding N(1)-(C-C-C)(cyclo-hexa-ne) torsion angles are -177.2 (3) and 179.3 (4)° in one mol-ecule and -176.5 (3) and 178.4 (4)° in the other. Two intra-molecular O-H⋯N hydrogen bonds exist in each mol-ecule.

The title compound, C(9)H(7)N(5), was synthesized by reaction of 4-(bromomethyl)benzonitrile and 2H-tetrazole in the presence of KOH. The relative orientation of the planar tetra-zole ring and the methyl-benzonitrile moiety is (-)-anti-clinal. The crystal packing is dominated by van der Waals inter-actions.

Hydrothermal (deuteratothermal) reaction of L-ethyl lactate (Lig-Et) with Eu(ClO(4))(3)6 H(2)O gives colorless block crystals of [Eu(Lig)(2)(X(2)O)(2)][ClO(4)] (1, X=H; 2, X=D) both of which possess a two-dimensional laminar homochiral framework. Single-crystal dielectric measurements reveal that 1 and 2 display a giant dielectric anisotropy approximately exceeding 100 and large isotopic effect with about 54 % enhancement along the a axis. Their ferroelectric features further confirm this respect. Crystal parameters: 1, C(6)H(14)ClO(12)Eu, M(r)=465.58, monoclinic, C(2), a=8.6786(6), b=8.3965(6), c=10.2153(7) A, beta=92.040(1) degrees , V=743.92(9) A(3), Z=2, rho(calcd)=2.079 Mg m(-3), R(1)=0.0508, wR(2)=0.1239, mu=4.448 mm(-1), S=1.043; Flack=0.04(5). 2: C(6)H(10)D(4)ClO(12)Eu, M(r)=469.61, monoclinic, C(2), a=8.689(2), b=8.410(2), c=10.224(3) A, beta=92.057(4) degrees , V=746.7(3) A(3), Z=2, rho(calcd)=2.089 Mg m(-3), R(1)=0.0465, wR(2)=0.1150, mu=4.432 mm(-1), S=1.058; Flack=0.02(5).

Colorless block crystals of MOF (metal-organic framework) 1 and 2 were prepared in respective yields of 65 and 60% by thermal treatment of HQA (HQA=6-methoxyl-(8S,9R)-cinchonan-9-ol-3-carboxylic acid) with ZnBr(2) in either H(2)O or D(2)O and 2-butanol at 70 degrees C for 1-2 days. The MOFs 1 and 2 are isostructural, one-dimensional chains in which the local coordination geometry around the Zn center can be best described as a slightly distorted tetrahedron defined by two bromine atoms, one nitrogen atom of quinoline from HQA, and an oxygen atom of carboxylate from HQA. The nitrogen atom of the quinuclidine of HQA is protonated in a zwitterionic form. The MOFs 1 and 2 crystallize in a polar point group (C(2), space group P2(1)) which belongs to ferroelectric active compounds. MOFs 1 and 2 display both ferroelectric behavior and large dielectric constants. Interestingly, at low frequency range the dielectric response to water can achieve an approximate increase of more than 600%. Crystal parameters: 1: C(20)H(28)Br(2)NO(7)Zn, M=619.62, monoclinic, P2(1), a=9.5711(8), b=12.0486(10), c=11.1972(9) A, alpha=gamma=90, beta=98.4(2) degrees , V=1277.39(18) A(3), Z=2, rho(cald)=1.611 mg m(-3), R(1)=0.0499, wR(2)=0.0982, mu=4.126 mm(-1), S=1.015, Flack value=0.032(13); 2: C(20)H(22)D(6)Br(2)NO(7)Zn, M=625.66, monoclinic, P2(1), a=9.5650(9), b=12.0392(11), c=11.1973(10) A, alpha=gamma=90, beta=98.44(2) degrees, V=1275.5(2) A(3), Z=2, rho(cald)=1.629 mg m(-3), R(1)=0.0543, wR(2)=0.1072, mu=4.133 mm(-1), S=1.056, Flack value=0.025(17).

Tetrazole compounds have been studied for more than one hundred years and applied in various areas. Several years ago Sharpless and his co-workers reported an environmentally friendly process for the preparation of 5-substituted 1H-tetrazoles in water with zinc salt as catalysts. To reveal the exact role of the zinc salt in this reaction, a series of hydrothermal reactions aimed at trapping and characterizing the solid intermediates were investigated. This study allowed us to obtain a myriad interesting metal-organic coordination polymers that not only partially showed the role of the metal species in the synthesis of tetrazole compounds but also provided a class of complexes displaying interesting chemical and physical properties such as second harmonic generation (SHG), fluorescence, ferroelectric and dielectric behaviors. In this tutorial review, we will mainly focus on tetrazole coordination compounds synthesized by in situ hydrothermal methods. First, we will discuss the synthesis and crystal structures of these compounds. Their various properties will be mentioned and we will show the applications of tetrazole coordination compounds in organic synthesis. Finally, we will outline some expectations in this area of chemistry. The direct coordination chemistry of tetrazoles to metal ions and in situ synthesis of tetrazole through cycloaddition between organotin azide and organic cyano group will be not discussed in this review.

The syntheses and luminescent properties of three novel zinc coordination polymers containing tetrazolyl ligands are described. In situ [2+3] cycloaddition reactions of acetonitrile or p-tolylnitrile with sodium azide in the presence of Zn(ClO(4))(2) as a Lewis acid (Demko-Sharpless tetrazole synthesis method) under hydrothermal (solvothermal) reaction conditions gave [Zn(CH(3)CN(4))(2)](3)(H(2)O) (1) and [Zn(4-MPTZ)(2)] (3) [4-MPTZ = 5-(4-methylphenyl)tetrazole], respectively. On the other hand, [Zn(HCN(4))(2)] (2) was obtained by directly reacting tetrazole with Zn(OAc)(2) under hydrothermal reaction conditions. The structure of 1 shows a super-diamond-like topological network with a diamond subunit as a connecting node. For 2, a diamond-like topological network is also found, but it is 2-fold interpenetrated. The structure of 3 reveals a 2D layered network with a hexagonal net, with the adjacent layers in the network stacked in an ABAB sequence. Photoluminescence studies revealed coordination polymers 1, 2, and 3 exhibit strong blue fluorescent emissions at lambda(max) = 396, 418, and 397 nm, respectively, in the solid state at room temperature.

The homochiral inorganic-organic hybrid compound (H(3)NHPA)(SnCl(3))(2)(H(2)O)(3) [1, (S)-4-(4'-aminophenyl)-2-aminobutanoic acid diammonium trichloride stannite triaqua] has a TGS (triglycine sulfate)-like structure. Preliminary investigation suggests a possible ferroelectric behavior with a saturation spontaneous polarization (P(s)) of ca. 3.5 microC.cm(-)(2), which is slightly greater than that of TGS (P(s) = 3.0 microC.cm(-)(2)).

The molten reaction of 2-naphthol, 4-(aminomethyl)pyridine, and 4-pyridinecarboxaldehyde at about 180 degrees C yields trans-2,3-dihydro-2,3-di(4'-pyridyl)benzo[e]indole (1) which possesses two chiral centers, rather than an expected Betti-type reaction product with only one chiral carbon center. The same reactions, using 3-pyridinecarboxaldehyde, 4-cyanobenzaldehyde, or 3- cyanobenzaldehyde instead of 4-pyridinecarboxaldehyde produce the related compounds trans-2,3-dihydro-2-(4'-pyridyl)-3-(3"-pyridyl)benzo[e]indole (2), trans-2,3-dihydro-2-(4'-pyridyl)-3-(4"-cyanophenyl)benzo[e]indole (3), and trans-2,3-dihydro-2-(4'-pyridyl)-3-(3"-cyanophenyl)benzo[e]indole (4), respectively. This reaction proceeds with a high degree of stereoselectivity with a trans/cis ratio of about 98:2 at elevated temperature. Compounds 1, 2, and 4 crystallize in a noncentrosymmetric space group (Pca2(1), Pca2(1), and Cc), while compound 3 has a chiral space group (P2(1)). These successfully acentric packing arrangements are probably due to the molecule bearing both two chiral centers and potential hydrogen-bonding groups. Furthermore, the reaction of racemic 6-hydroxy-2'-methyl-2-naphthaleneacetic acid with ethyl-2-cyano-1-(4'-pyridyl)acrylic acetate in the presence of piperidine gives 1-pyridyl-2-ethoxycarbonyl-3-amino-1H-naphtho[2,1-b]pyran-2'-methylacetic acid (5), which likewise crystallizes in a chiral space group. All of compounds are second harmonic generation (SHG) active, and have a very strong SHG response approximately about 8.0, 5.0, 12.0, 6.0, and 1.4 (for 1-5 compounds) times that of urea. Ferroelectric property measurements indicate that compounds 1, 2, 4, and 5 may display ferroelectric behavior.

The reaction of Cu(CH(3)CN)(4)ClO(4) with 2-pyridylacrylic acid (2-HPYA) affords an unusual mixed-valence Cu(I)-Cu(II) 3-D framework ([Cu(II)(2-PYA)(2)](3).[Cu(I)(2-PYA)](2).(H2O)(2))n (1) with a novel topology which features Cu(II) dimeric units (or paddle-wheel unit). The almost perpendicular coordinating direction between the N atom of pyridyl and the O atom of carboxylate groups may be responsible for the formation of such a novel network.

Under hydrothermal (solvothermal) reaction conditions chiral compounds 1, 2, and 3 and one acentric compound 4 were obtained by the reaction of Zn(2+) or Cd(2+) with racemic 3-(3-pyridyl)-3-aminopropionic acid (rac-HPAPA). Compounds 1 and 2 crystallized in chiral space group P2(1)2(1)2(1). At 105 degrees C, racemic 3-pyridyl-3-aminopropionic acid (rac-HPAPA) reacted with Zn(ClO4)(2).6 H2O and dehydrogenated in situ to form the first chiral coordination polymer [Zn[(E)-3-C(5)H4N-C(NH2)=CH-COO]]ClO4 (1) with a beta-dehydroamino acid. Beyond 120 degrees C, the reaction of rac-HPAPA with Zn(ClO4)(2).6 H2O deaminates in situ to form chiral coordination polymer [Zn[(E)-3-C5H4N-CH=CH-COO](OH)] (2). At relatively low temperatures (70 degrees C), the solvothermal reaction of Zn(NO3)(2).6 H2O with rac-HPAPA in methanol does not lead to any change in the ligand and results in the formation of a chiral (P2(1)2(1)2(1)) coordination polymer [Zn(papa)(NO3)] (3). The same reaction of Cd(ClO4)(2).6 H2O with HPAPA also does not lead to any change in ligand and results in the formation of noncentric (Cc) coordination polymer [Cd(papa)(Hpapa)]ClO4.H2O (4). The network topology of both 1 and 3 is 10,3a, while 2 has a diamondoid-like (KDP-like, KDP=potassium dideuterophosphate) network. Particularly interesting from a topological perspective is that 4 has an unprecedented three-dimensional network. Compounds 1, 2, 3, and 4 are all second harmonic generation (SHG) active with 1 exhibiting the strongest response, while only 4 also displays good ferroelectric properties.

The reactions of (S)-3-cyanophenylalanine with NaN(3) in the presence of H(2)O and Lewis acids (ZnCl(2) and CdCl(2)) afford two unprecedented 3D homochiral networks, mono[(S)-5-(3-tetrazoyl)-phenylalaninato]zinc(II) (1) and mono[(S)-5-(3-tetrazoyl)-phenylalaninato]cadmium(II) monoaqua(II) (2), respectively. The two compounds are isostructural with noninterpenetrated SrAl(2) topology. The structure of these coordination polymers gives new insight into Sharpless' reaction of chiral 5-substituted 1H-tetrazole and homochiral supramolecular array constructions.

The reaction of Cu(I)(CH(3)CN)(4)BF(4) with 4-pyridylacrylic acid (4-HPYA) affords an unprecedented 8-fold interpenetrating diamondoid-like coordination polymer network [Cu(I)(3)(4-PYA)(2)(H(2)O)(BF(4)) ] (1) with a Cu(+)(4)(CO(2))(4) cluster as connecting node. The interpenetration in metal coordination polymers is the highest degree ever found within diamondoid nets containing a cluster as connecting note. Its fluorescent property was also reported.

The reactions of 2-, 3-, and 4-cyanopyridine with NaN(3) in the presence of H(2)O and Lewis acid (ZnCl(2)) afford discrete monomer, (2-PTZ)(2)Zn(H(2)O)(2) (1), 3D diamondoid-like network (3-PTZ)(2)Zn (2), and 2D layered network (4-PTZ)Zn(OH)(H(2)O) (3), respectively (PTZ = 5-(pyridyl)tetrazolato). Their solid state structures and natures give new insight into the Sharpless reaction of 5-substituted 1H-tetrazole. Interestingly, 2 crystallizes in a noncentrosymmetric space group and its powdered sample is second-harmonic generation active.