CRYSTAL STRUCTURES AND TRIBOLUMINESCENT ACTIVITIES OF SAMARIUM(III) COMPLEXES

Abstract

The triboluminescence spectra and crystal structures of 1,2-dimethylpyridinium tetrakis(2-thenoyltrifluoroacetonato)samarium(III) (1) and 1,2,6-trimethylpyridinium tetrakis(2-thenoyltrifluoroacetonato)samarium(III) (2) were determined. The triboluminescent maximums are similar to those of the photoluminescence. Complex 1 is centrosymmetric and the triboluminescent emission may correlate with the disorder of all S atoms, all CF₃ groups and the cation. The triboluminescent activity of complex 2 may correlate with its noncentrosymmetric space group. Complex 1 crystallizes in the monoclinic space group P2₁/a with cell parameters a = 19.874(2) Å, b = 22.922(2)Å, c = 21.188(1)Å, β = 108.126(6)°, V = 9173(1)ų; Z = 8; R = 0.0758 and R_w = 0.1315. Complex 2 crystallizes in the monoclinic space group Pn with cell parameters a = 11.2808(6)Å, b = 11.0199(5)Å c c = 18.4336(9)Å, β = 108.126(6)° V = 2285.28(19)ų; Z = 4; R = 0.0347 and R_w = 0.0900. All the structures were refined by full-matrix least squares methods.     

CRYSTAL STRUCTURE AND THERMAL ANALYSIS OF A 4,4′-BIPY-BRIDGED BINUCLEAR ZINC(II) COMPLEX, 2[R2NCS2]2 · Zn(4,4′-BIPY) (R=PIPERIDYL)

Abstract

The crystal structure of the title complex 2[R₂NCS₂]₂ · Zn(4,4′-bipy) (R = Piperidyl), 1, revealed that it consists of dimers made up from two crystallographically independent molecules. Each zinc atom in 1 forms a 5-coordinate pseudo-square-based pyramidal arrangement (with four Zn-S and one Zn-N interactions). Bondlengths to Zn with the coordinating atoms are comparable to those in other Zn(II) dithiocarbamate complexes. The piperidine ring has a chair conformation. To allow improved packing, the title complex molecules form an approximately linear arrangement extending along both a and b. TGA showed that 1 is decomposed in two close steps to produce ZnS as identified by residual weight. The complex 1 crystallizes in the monoclinic space group C2/c with cell parameters: a = 22.021(5), b = 22.215(3), c = 17.537(2) Å, β = 93.49(2)°, V = 8563(3) ų and Z = 8. The structure was refined by full-matrix least-squares methods to R = 0.067, R_w = 0.114.     

SYNTHESIS OF ONE-AND TWO-DIMENSIONAL ZINC AND CADMIUM COMPLEXES WITH 4, 4′-BIPY

Abstract

The zinc(II) and cadmium(II) complexes [Zn(4, 4′-bipy)(SCN)₂]_∞ 1 and [Cd(4, 4′-bipy)-(SCN)₂]_n 2 have been synthesized and their crystal structures determined by X-ray crystallography. Complex 1 is monoclinic, space group C2/c, with a = 18.076(5), b = 5.190(1), c = 17.315(4)Å; β = 115.54(2), V = 1465.8(8)ų, calculated density 1.530gcm^?3, Z = 4. In this compound, the rod-like ligand 4, 4′-bipy bridges Zn(II) centres, and the NCS groups are terminally coordinated. (N-Zn-N) is 108.5°, resulting in the formation of a zigzag Zn-bipy-Zn chain. These chains are arranged in parallel fashion. The 4, 4′-bipy ligands of adjacent layers are separated by 3.95 (Å). Complex 2 is monoclinic, space group C2/c, a = 11.902(2), b = 11.745(2), c = 10.500(2)Å; β = 109.71(3), V = 1381.8(4)ų calculated density 1.849gcm^?3, Z = 4. In this structure, the cadmium(II) ion is slightly distorted octahedral and the SCN groups act as doubly bridging ligands connecting cadmium atoms to form zigzag chains, separated by 4, 4′-bipy to create two-dimensional planes.     

Syntheses and crystal structures of two maleonitriledithiolate complexes containing the 1-(R-benzyl)pyrazinium cation (R = 4′-nitro or 4′-bromo)

The complexes [NO₂BzPz]₂[Ni(mnt)₂] (1) and [BrBzPz]₂[Pd(mnt)₂] (2) have been prepared by reaction of Na₂mnt, NiCl₂·6H₂O or PdCl₂, and the corresponding 1-(R-benzyl)pyrazinium bromide salt (R = 4′-nitro, R = 4′-bromo). Crystallographic data for 1: monoclinic, P2₁/n, a = 7.3494(15), b = 15.223(3), c = 15.054(3)?Å, β = 102.42(3)°, V = 1644.8(6)?ų, Z = 2. Data for 2: monoclinic, P2₁/n, a = 7.399(2), b = 19.024(4), c = 12.224(2)?Å, β = 94.62(3)°, V = 1715.0(7)?ų, Z = 4. In both complexes, the [M(mnt)₂]^2? anion has a centre of symmetry at the metal atom and two cations are related to each other by the symmetry centre. The [M(mnt)₂]^2? anion exhibits a quasi-planar structure in both complexes, which show similar crystal packing.     

THE CRYSTAL AND MOLECULAR STRUCTURE OF Ru3(CO)9(PPh3)3

Abstract

The synthesis of tertiary phosphine and phosphite substituted derivatives of M₃(CO)₁₂ {M = Ru(1a) Os(1b)} is discussed and the X-ray crystal and molecular structure of the tris-triphenylphosphine substituted ruthenium cluster Ru₃(CO)₉(PPh₃)₃ (2a) is reported. Complex 2a crystallises in the monoclinic space group P2₁/n with cell parameters a = 14.180(9), b = 21.644(14), c = 18.248(10) Å, β = 92.52(5)°, V = 5595(6) Å ³, Z = 4. The structure was solved by full-matrix least-squares methods based on F ². The refinement converged at R1 = 0.0564, wR2 = 0.2125 for 4857 observed data [F > 4σ(F)].     

REACTIONS OF CuX (X = SCN AND CN) WITH 2-BENZOYLPYRIDINE. SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF [9-OXO-INDOLO[1,2-a] PYRIDINIUM] DITHIOCYANATOCUPRATE(I) AND POLYMERIC μ-CYANO(2-BENZOYLPYRIDINE) COPPER(I)

Abstract

When a mixture of excess CuSCN and 2-benzoylpyridine (2-Bzpy) stands in an ethanolic medium for about ten days in contact with air, the intramolecular oxidative cyclization of 2-Bzpy occurs with formation of the ionic compound [9-oxo-indolo[1,2-a]pyridinium]⁺ [Cu(SCN)₂]^? (1). In contrast, interaction of CuCN and 2-Bzpy in ethanol leads to formation of the polymer [Cu(CN)(2-Bzpy)]_n (2). The reaction of Cu(II) and 2-Bzpy in presence of excess SCN^? in ethanol affords (1) and the green monomer [Cu(SCN)₂(2-Bzpy)₂] (4). These complexes, along with the 1:1 CuSCN complex of 2-Bzpy (3) are studied by IR, Raman and electronic spectroscopic methods and X-ray structural analysis of (1) and (2). Crystals of (1) are monoclinic, space group P2₁/n (No. 14), with a = 5.887(1), b = 36.142(7), c = 7.083(1) Å, B = 109.56(1)°, Z = 4, and R_F = 0.033 for 2487 observed MoKα data, (2) monoclinic, space group P2₁/c (No. 14), a = 14.393(3), b = 8.881(2), c = 9.287(2) Å, B = 103.80(3)°, Z = 4, and R_F = 0.036 for 2030 observed MoKα data. The structure of (1) consists of a packing of [9-oxo-indolo [1,2-a]pyridinium]⁺ cations and [Cu(SCN)₂]^? anions. Puckered layers are formed by the [Cu(SCN)₂]^? component with four-coordinate Cu(I) and one tridentate μ(N,S,S)-thiocyanato ligand. Complex (2) features distorted tetrahedral Cu(I) geometry, formed by a bidentate chelating 2-Bzpy and linear C- and N-bonded bidentate cyano groups, which link adjacent copper centers to form zigzag chains extending along the c axis. Complexes (1) and (2) do not fluoresce at room temperature.     

STRUCTURE AND PROPERTIES OF N,N-DI-n-BUTYLDITHIOCARBAMATO-1, 2-DICYANOETHENE-1, 2-DITHIOLATO-GOLD(III)

Abstract

The crystal and molecular structure and some spectral data of the compound N,N-di-n-butyldithiocarbamato-1, 2-dicyanoethene-1, 2-dithiolato-gold(III), AuS₂CN(C₄H₉)₂S₂C₂(CN)₂, are reported. The crystal structure has been determined from a three-dimensional single-crystal X-ray diffraction study. The orthorombic cell, space group Pbca, with a=14.066(3), b=28.980(2) and c=9.192(2) Å, contains eight formula units. Intensity data were collected on an automatic diffractometer. The structural parameters were refined by full-matrix least-squares methods to a conventional R-factor of 0.047 for 1587 independent non-zero reflections. The structure determination proved the compound to be a mixed dithiocarbamato-dithiolato complex, Au(dtc)(mnt), (dtc=N,N-di-n-butyl-dithiocarbamate, mnt=maleonitriledithiolate ≡ 1, 2-dicyanoethene-1, 2-dithiolate), as expected from spectral data. The gold atom is in approximately square-planar coordination, however, deviations from mm2 (C_2#) symmetry are considerable. Au-S bond distances in the dtc-moiety (2.329(5) Å and 2.324(5) Å) are significantly longer than those in the mnt-moiety (2.303(5) Å and 2.284(5) Å). The molecules are packed pairwise around inversion centres with relatively short intermolecular S-S distances.     

SYNTHESIS AND STRUCTURES OF DICHLOROTETRAKIS-(PHENYLTHIOUREA) CADMIUM(II) AND CATENA-BIS(THIOCYANATE) BIS(PHENYLTHIOUREA)CADMIUM(II)

Abstract

Two new cadmium(II) complexes with phenylthiourea (PTU), namely Cd(PTU)₄Cl₂ (1) and [Cd₂(NCS)₂(μ₂-SCN)₂(PTU)₂(μ₂-PTU)₂] _n (2), have been prepared and characterized structurally by X-ray diffaction. Complex 1 crystallizes in the monoclinic space group C2/c, with a = 27.057(13), b = 8.108(3), c = 16.751(8) Å, β = 114.46°, V = 3345(3) ų, Z = 4. Complex 2 crystallizes in the triclinic space group P-1, with a = 9.336(3), b = 14.686(5), c = 16.911(5) Å, α = 71.36(2), β = 84.31(2), γ = 72.470(10)°, V = 2095.0(12) ų Z = 4. The structural analysis shows that each metal atom in both the mononuclear complex 1 and polynuclear complex 2 is octahedrally coordinated by four sulfur atoms and two chloro ligands or two nitrogen atoms from the thiocyanate groups, respectively. The PTU ligand can serve as either a monodentate ligand or a μ₂-bridging ligand upon coordination to a metal atom.     

SYNTHESIS AND CHARACTERIZATION OF THE FORMAL Ni(III) AND Cu(III) COORDINATION COMPLEXES OF THE NEW 1,2-DITHIOLENE, 1,4-BUTANEDIYLDITHIOETHYLENE-1,2-DITHIOLATE

Abstract

The new 1,2-dithiolene, 1,4-butanediyldithioethylene-1,2-dithiolate, has been isolated. In addition, new monoanionic bis-complexes with nickel and copper have been prepared and isolated. The formal Ni(III) complex crystallizes in the orthorombic space group, P_bca, with a = 9.762(9), b = 12.53(2), and c = 23.166(3) Å, with 4 molecules in the unit cell. The structure was refined to an R = 9.01% (R_w = 8.95%). The formal Cu(III) complex crystallizes in the monoclinic space group, C_2/c, with a = 25.567(6), b = 8.011(3), c = 14.504(3) Å, and β = 106.17(2)° with 4 molecules in the unit cell. The structure refined to R = 4.2% with R _w = 4.3%. Comparisons to similar 1,2-dithiolenes suggest this ligand produces only modest structural and electronic differences when compared to the 1,3-propanediyldithioethylene-1,2-dithiolate complexes. The oxidation (to a neutral complex) and reduction (to a dianion) for the Ni(III) and Cu(III) complexes show large differences from those of maleonitriledithiolate. Other physical data are presented as well.     

Synthesis,crystal structure,and characterization of a new high-dimensional phosphomolybdate architecture built from silver-complex fragments and hexa-connected P2Mo5 clusters

A new 3-D organic–inorganic hybrid phosphomolybdate, [Ag(bipy)]₄(H₂P₂Mo₅O₂₃) · 3H₂O (1) (bipy = 4,4′-bipyridine) has been hydrothermally synthesized and characterized by elemental analyses, IR, TG, and fluorescent properties. Compound 1 crystallizes in the monoclinic space group C2/c with a = 23.830(5), b = 21.030(4), c = 24.501(5) Å, β = 110.38(3)°, V = 11510(4) ų, Z = 8, and R ₁ (wR ₂) = 0.0507 (0.1210). It contains unique 3-D metal organic frameworks based on silver-complex fragments and hexa-connected P₂Mo₅ clusters via covalent bonds and represents the highest connection numbers of P₂Mo₅ clusters to date.     

PRECURSORS OF HEXA-AZAMACROCYCLES. SYNTHESIS AND X-RAY STRUCTURE OF 2,9-DIAMINOPHENANTHROLINEBISACETATE-Co(II) AND 6,6′-DIAMINOBIPYRIDINE-BISACETATE-M(II) (M = Ni,Cu)

Abstract

The synthesis, conventional characterisations and x-ray structures of the following monomeric complexes are given for 2,9-diaminophenanthroline-bisacetate-cobalt(II) ( A ) and 6,6′-diaminobipyridine-bisacetate-M(II) (M = nickel( C ) and copper( B )). Complex A crystalizes in the monoclinic, C2/c space group with a=12.813(6), b = 10.218(3), c= 13.811(5), Å; β= 118.17(2)°; Z=4; V=1549(2) ų. A total of 1787 unique reflections with F > 6σ(F) were refined to values of R and R_w 0.0461 and 0.0774, respectively. Complex B crystallizes in the triclinic, P-1 space group with a=10.099(5), b=10.257(5), c=8.015(11), Å; α=112.98(2), β=93.13(2), γ=92.960(2),°; Z=2; V = 761(1), ų. A total of 2603 unique reflections with F > 3.00σ(F) were refined to values of R and R_w 0.0764 and 0.1022, respectively. Complex C crystallizes in the monoclinic, P2₁/n space group with a=8.124(5), b=10.343(6), c=18.724(11), β=98.36(2),°; Z=4; V=1556(1), ų. A total of 2537 unique reflections with F > 3.00σ(F) were refined to values of R and R_w 0.0689 and 0.0975, respectively. The structures consist of six-coordinate [M(CH₃COO)₂(L)] (L=2,9-diaminophenanthroline or 6,6′-diaminobipyridine) discrete monomeric neutral species, although in the Cu(II) compound the elongation of two long Cu—O bonds, due to the Jahn-Teller effect, makes the metal essentially four-coordinate. In the Ni and Co compounds the acetate acts as a bidentate ligand. The diamino ligands are coordinated by the pyridine nitrogen atoms. The IR spectra of the complexes have been recorded and are discussed in relation to the crystal structure and the acetate coordination mode.     

Synthesis,structure and physical properties of nickel bis(dithiolene) complexes with different cations

A series of new complexes of multi-sulfur 1,2-dithiolene ligands, [Ru(bipy)₃][Ni(L)₂]₂ (bipy?=?2,2′-bipyridine; L?=?pddt (6,7-dihydro-5H-1,4-dithiepin-2,3-dithiolate), dddt (5,6-dihydro-1,4-dithiin-2,3-dithiolate)), have been synthesized and characterized. One typical complex, [Ru(bipy)₃][Ni(pddt)₂]₂·2H₂O (1), crystallized in an acentric space group of P2₁2₁2₁, with the cell dimensions of a?=?8.634(1), b?=?14.560(1), c?=?49.889(5)?Å, α?=?β?=?γ?=?90°, and Z?=?4. It consists of alternating columns of cations and anions along the a direction. The structure was refined by full matrix least squares methods to R ₁?=?0.0340, wR ₂?=?0.0670. Magnetic studies on [Ph₂Cr][Ni(dddt)₂] are also reported.     

Syntheses and crystal structures of Zn(II) and Co(II) complexes with ofloxacin and enoxacin

[Zn(Ofl) · (H₂O)] · 2H₂O (1) and [Co(Enox)₂] · 4H₂O (2) were obtained by hydrothermal reactions. The solid-state structures have been characterized by IR spectroscopy and single crystal X-ray diffraction analyses. Complex 1 crystallizes in the triclinic system, space group P 1, with lattice parameters a = 9.2923(5), b = 11.3432(6), c = 17.7722(10) Å, α = 92.839(3), β = 94.826(3), γ = 91.909(3)°, V = 1863.01(18) ų, Z = 2, D _Calcd = 1.494 mg m^?3. The coordination environment around Zn²⁺ is a slightly distorted square pyramid. Complex 2 crystallizes in the triclinic system, space group P2(1)/c, with lattice parameters a = 5.97980(10), b = 21.4183(3), c = 13.1539(2) Å, V = 100.2810(10), Z = 2, D _Calcd = 1.526 mg m^?3, Co(II) ion is a distorted octahedral geometry.     

STRUCTURES OF PYRIDINE CARBOXYLATE COMPLEXES OF COBALT(II) AND COPPER(II)

Abstract

The syntheses and crystal structures of [Co(nic)₂(H₂O)₄] (1). [Co(iso)₂(H₂O)₄] (2). [Cu(nic)₂(H₂O)₄] (3), and [Cu(iso)₂(H₂O)₄] (4) (nic = nicotinate; iso = isonicotinate) are reported. Complex 1 crystallizes in monoclinic, space group C2/m with cell parameters a =14.150(4). b = 6.883(2)., c = 8.497(2) Å, β= 118.28(2)° and Z = 2. The other crystals. 2. 3. and 4. are all triclinic, Pī; a = 9.777(3), b = 6.348(4), c = 6.888(3)Å, a= 113.10(6)., β= 110.55(3). γ = 97.61(5)°, and Z=l for 2; a = 7.0281(4), b = 7.7176(6), c = 8.6978(7)Å, a = 68.103(7), β = 68.526(5), γ = 62.550(6)°, and Z=1 for 3; a = 9.1807(4), b = 6.3334(3), c = 6.8871(3)Å, a= 108.213(4), β = 99.433(4), γ= 105.190(4)°, and Z= 1 for 4. The arrangements around the metal ions are trans-octahedra with two pyridyl nitrogens and two aqua oxygens in the equatorial positions and two aqua oxygens in the axial positions, although the Cu(II) complexes show a larger Jahn-Teller distortion.     

ANIONIC COORDINATION COMPLEXES OF Mo AND W WHICH CRYSTALLIZE FROM LIQUID CLATHRATE MEDIA WITH OXONIUM ION-CROWN ETHER CATIONS

Abstract

The complexes [H₃O⁺·18-crown-6][MoOCl₄(H₂O)^?], 1, and [H₂O·aza-18-crown-6·(H⁺)] [MoOCl₄(H₂O)^?], 3, were synthesized from a mixture of Mo(CO)₆, HCl(g), H₂O and either 18-crown-6 for 1 or mono-aza-18-crown-6 for 3, in toluene. For complex 4, [H₂O·aza-18-crown-6·(H⁺)]₂[WOCl₄(H₂O)^?][Cl^?], reaction conditions were as for 3 except W(CO)₆ was used in place of Mo(CO)₆. Similarly, for complex 2, [H₃O⁺·18-crown-6][WOBr₄(H₂O)^?], W(CO)₆ and HBr were used in the reaction mixture. These reactions were promoted by UV radiation and formed liquid clathrates almost immediately upon reaction. X-ray crystal structures were performed on each compound. Complex 1 crystallizes in the triclinic space group P/i with a = 10.206(1), b = 10.486(1), c = 11.701(1) Å, α = 71.11(1), β = 74.60(1), γ = 75.08(1)°, and D _c = 1.649 g cm^?3 for Z = 2. Refinement based on 3925 observed reflections led to a final R value of 0.078. Complex 2 crystallizes in the monoclinic space group P2₁/c with a = 9.710(1), b = 19.824(1), c = 12.399(1) Å, β = 104.58(1)°, and D _c = 2.369 g cm^?3 for Z = 4. Refinement based on 2008 observed reflections led to a final R value of 0.090. Complex 3 crystallizes in the orthorhombic space group Pnmn with a = 16.927(1), b = 12.226(1), c = 11.167(1) Å, and D _c = 1.598 g cm^?3 for Z = 4. Refinement based on 1486 observed reflections led to a final R value of 0.040. Complex 4 crystallizes in the monoclinic space group C2/m with a = 11.761(2), b = 12.096(2), c = 14.966(1) Å, β = 132.91(1)°, and D _c = 1.502 g cm^?3 for Z = 4. Refinement based on 2021 observed reflections led to a final R value of 0.051. In all cases the metal coordination sphere was essentially octahedral with the water ligand trans to the oxo species.     

Coordination chemistry of organometallic polydentate ligand Reactive chemistry of the tridentate ligand trans‐Fe(Ph2PQu‐P)2‐(CO)3 [PhzPQu=2‐diphenyl‐phosphino‐4‐methylquinoline] and molecular structure of [Fe(CO)3(μ‐Ph2PQu)2HgI]+ [HgI3]

Reaction of a new type of bidentate ligand PhPQu [PhPQu = 2‐diphenylphosphino‐4‐methylquinoline] with Fe(CO)₅ in butanol gave trans‐Fe(FpPQu‐P)(CO)₃ (1). Compound 1, which can act as a neutral tridentate organometallic ligand, was reacted with I B, II B metal compounds and a rhodium complex to give six binuclear complexes with Fe? M bonds, Fe(CO)₃ (μ‐Ph₂PQu)MX_n (2–7) [M= Zn(II), Cd(II), Hg(II), Cu(I), Ag(I), Rh(I)], and an ion‐pair complex [Fe(CO)₃ (μ‐Ph₂PQu)₂HgI][HgI₃]^? (8). The structure of 8 was determined by X‐ray crystallography. Complex 8 crystallizes in the space group P‐1 with a = 1.0758(3), b = 1.6210(4), c=1.7155(4)nm; a=75.60(2), β=71.81(2), γ=81.78(2)° and Z = 2 and its structure was refined to give agreement factors of R=0.050 and R_w = 0.057. The Fe‐Hg bond distance is 0.2536nm.     

Syntheses and Crystal Structures of Cadmium Complexes with Thiophenedicarboxylate and Bipyridine‐like Ligands

Two new coordination polymers [Cd(tdc)(bpy)(H₂O)]_n ( 1 ) and [Cd(tdc)(phen)]_n ( 2 ) (H₂tdc = thiophene‐2,5‐dicarboxylic acid, bpy = 2,2′‐bipyridine and phen = 1,10‐phenanthroline) have been synthesized under hydrothermal condition. Their crystal structures have been established by X‐ray single‐crystal diffraction. Complex 1 crystallizes in the orthorhombic space group Fdd2 with a = 14.757(7), b = 45.38(2), c = 10.518(5) Å, V = 7044(6) ų, Z = 16; 2 in the monoclinic space group P2₁/c with a = 7.262(1), b = 21.970(2), c = 10.051(1) Å, β = 105.01(1)°, V = 1548.8(2) ų, Z = 4. Both of them are double‐stranded chains and further assembled into three‐dimensional networks by π‐π stacking interactions. 1 and 2 are stable in air, and show blue photoluminescence at 415 nm and 410 nm, respectively.     

Thallium silver chalcogenides of the orderedanti-PbCl2-structure type

TlAgS, TlAgSe and TlAgTe crystallize with the orderedanti-PbCl₂-structure type, space group Pnma,Z=4. The lattice constants are: TlAgS:a=722.8(3).b=446.6(1),c=833.1(2)pm. TlAgSe:a=747.56(3),b=463.75(2),c=869.0(1) pm. TlAgTe:a=775.9(1),b=486.8(1),c=877.3(2) pm. The crystal structure of TlAgSe was refined from single crystal diffractometer data to a conventionalR-factor of 0.045. The relationship with the BaCu₂S₂-structure type is discussed.On leave from Institute of Inorganic Chemistry, University of Vienna A-1090, Wien, Austria     

Synthesis and Crystal Structures of Two Zinc(II) Complexes with the Tripodal Ligand Tris(2-Benzimidazolymethyl)Amine

This article reports the synthesis and crystal structures of two new mononuclear Zinc(II) complexes, [Zn₂(NTB)₂(N₃)₂](NO₃)₂·2CH₃OH (1) and [Zn₂(NTB)₂(SCN)₂](NO₃)₂·2CH₃OH·H₂O (2). Complex 1 crystallizes in the triclinic system, space group P&1macr;, a=13.743(4), b=14.374(4), c=14.443(5) Å; α=77.053(5), β=81.824(5), γ=88.959(6)°; Z=2; R1=0.0418, wR2=0.0889. Complex 2 also crystallizes in the triclinic system, space group P&1macr;, a=12.203(10), b=14.430(12), c=18.541(15)Å; α=72.712(15), β=85.039(15), γ=73.610(14); Z=2; R1=0.0771, wR2=0.1288. In both cases the central zinc(II) metal ions are coordinated to the four nitrogen atoms of NTB and a nitrogen atom of N^- ₃(1) or SCN^-(2) to form distorted trigonal bipyramidal coordination spheres.     

Inclusion Properties and Crystal Structure of Clathrates Constructed Based on “π-sandwich”

Abstract

Inclusion behavior of structurally similar host compounds, 1,4-bis[1-(9-anthryl)-3-propen-1-on-3-yl]benzene (1) and 1,4-bis[3-(9-anthryl)-3-propen-1-on-1-yl]benzene (2), has been studied. Both hosts preferred cyclic, non-branched small molecules as a guest component, to yield 1:2 clathrates specifically. X-ray powder diffraction studies revealed that those 1:2 clathrates of 1 and 2 were respectively isostructural. X-ray analyses of (1)(THF)₂ (P 1, a = 10.910(2), b = 19.656(5), c = 9.172(4) Å, α = 95.58(3), β = 93.67(2), γ = 103.30(2)°, D _calc = 1.195 g cm^?3, Z = 2, and R = 0.067 for 8644 observed reflections) and (2)(1,4-dioxane)₂, (P2₁/n, a = 5.661(1), b = 17.971(3), c = 18.619(3) Å, β = 91.37(2)°, D _calc = 1.254 g cm^?3, Z = 2, and R = 0.097 for 4353 observed reflections) illuminated that their guest preference should be ascribed to the commonly observed π-sandwich” structure, in which guest molecules are enclathrated between two anthracene planes of the host molecules.