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1.
Paul K. Baker Marit van Kampen Christina Roos Julia Spaeth 《Transition Metal Chemistry》1994,19(2):165-168
Summary Equimolar quantities of [MI2(CO)3(NCMe)2] (M = Mo or W) and C3H4N2 (pyrazole) react in CH2C12 at room temperature to give the iodo-bridged dimers [M(μ-I) (CO)3(C3H4N2)]2 (1) and (2). Two equivalents of C3H4N2 react with [MI2(CO)3(NCMe)2] (M = Mo or W) to give the bis(pyrazole) complexes [MI2(CO)3(C3H4N2)2] (3) and (4) in good yield. Three and four equivalents of pyrazole react with [MoI2(CO)3(NCMe)2] to give the cationic complexes [MoI(CO)3(C3H4N2)3]I (5) and [MoI(CO)2(C3H4N2)4]I (6), respectively. The mixed ligand complexes [MI2(CO)3(C3H4N2)L] (M = Mo or W; L = PPh3, AsPh3 or SbPh3) (7)-(12) are prepared by reacting equimolar amounts of [MI2(CO)3(NCMe)2] and L in CH2C12 at room temperature, followed by an in situ reaction with one equivalent of C3H4N2. The MoSnCl3 complex [MoCl(SnCl3)(CO)3(C3H4N2)2] (13) is prepared in an analogous manner using acetone as the solvent, whilst the mixed ligand compound [MoCl(SnQ3)(CO) 3(C3H4N2)(PPh3)] (14) was prepared by treating the dimeric complex [Mo(μ-Cl)(SnCl3)(CO)3(PPh3)]2 with two equivalents of C3H4N2. All the new complexes were characterised by elemental analysis (carbon, hydrogen and nitrogen), i.r. and 1H n.m.r. spectroscopy. 相似文献
2.
Synthesis and studies on some five-coordinate ruthenium(II) complexes, viz. [Ru(MPh3)(C6H5CHO)2Cl2] and [Ru(MPh3)2(CO)Cl2] (where M = P or As) have been described. Reactions of [Ru(MPh3)(C6H5CHO)2Cl2] with N,N-dimethylformamide, dimethylsulphoxide and pyridine and of [Ru(MPh3)2(CO)Cl2] with pyridine are described. 相似文献
3.
Summary Reactions of glyoxal bis(morpholineN-thiohydrazone), H2gbmth, with NiCl2·6H2O, Ni(OAc)2·4H2O, Ni(acac)2· H2O, CuCl2·2H2O, Cu(OAc)2·H2O, Cu(acac)2, CoCl2· 6H2O, Co(OAc)2·4H2O and Co(acac)2·2H2O yield complexes of the type [M(gbmth)], [M=NiII, CuII or CoII]. Diacetyl reacts with morpholineN-thiohydrazide in the presence of nickel salts to yield [NiII(dbmth)], [NiII(dmth)(OAc)]H2O and [NiII(Hdmth)(NH3)Cl2] involving N2S2 and NSO donor ligands. Copper and cobalt complexes of N2S2 and NSO donor ligands with compositions [CuII(dbmth)], [CoII(dbmth)]·4H2O and [CoII(H2dbmth)]Cl2, have been isolated. The compounds have been characterised by elemental analyses, magnetic moments, molar conductance values and spectroscopic (electronic and infrared) data. 相似文献
4.
Janice M. Rubin‐Preminger Leonid Kozlov Israel Goldberg 《Acta Crystallographica. Section C, Structural Chemistry》2008,64(2):m83-m86
The title compound, [CoCl(C12H8N2)2(H2O)]Cl·[CoCl2(C12H8N2)2]·6H2O, is the first example of a new 1:1 cocrystal of the octahedral [CoCl2(phen)2] and [CoCl(phen)2(H2O)]+·Cl− complexes (phen is 1,10‐phenanthroline). The latter form heterochiral dimers held by strong π–π stacking interactions via their phenathroline ligands, which confirms that π stacking is an important and reliable synthon in supramolecular design. In addition, the crystal structure is networked by H2O...H2O, H2O...Cl− and H2O...Cl hydrogen bonds, which interconnect the different units of the cobalt complexes. 相似文献
5.
Diimido, Imido Oxo, Dioxo, and Imido Alkylidene Halfsandwich Compounds via Selective Hydrolysis and α—H Abstraction in Molybdenum(VI) and Tungsten(VI) Organyl Complexes Organometal imides [(η5‐C5R5)M(NR′)2Ph] (M = Mo, W, R = H, Me, R′ = Mes, tBu) 4 — 8 can be prepared by reaction of halfsandwich complexes [(η5‐C5R5)M(NR′)2Cl] with phenyl lithium in good yields. Starting from phenyl complexes 4 — 8 as well as from previously described methyl compounds [(η5‐C5Me5)M(NtBu)2Me] (M = Mo, W), reactions with aqueous HCl lead to imido(oxo) methyl and phenyl complexes [(η5‐C5Me5)M(NtBu)(O)(R)] M = Mo, R = Me ( 9 ), Ph ( 10 ); M = W, R = Ph ( 11 ) and dioxo complexes [(η5‐C5Me5)M(O)2(CH3)] M = Mo ( 12 ), M = W ( 13 ). Hydrolysis of organometal imides with conservation of M‐C σ and π bonds is in fact an attractive synthetic alternative for the synthesis of organometal oxides with respect to known strategies based on the oxidative decarbonylation of low valent alkyl CO and NO complexes. In a similar manner, protolysis of [(η5‐C5H5)W(NtBu)2(CH3)] and [(η5‐C5Me5)Mo(NtBu)2(CH3)] by HCl gas leads to [(η5‐C5H5)W(NtBu)Cl2(CH3)] 14 und [(η5‐C5Me5)Mo(NtBu)Cl2(CH3)] 15 with conservation of the M‐C bonds. The inert character of the relatively non‐polar M‐C σ bonds with respect to protolysis offers a strategy for the synthesis of methyl chloro complexes not accessible by partial methylation of [(η5‐C5R5)M(NR′)Cl3] with MeLi. As pure substances only trimethyl compounds [(η5‐C5R5)M(NtBu)(CH3)3] 16 ‐ 18 , M = Mo, W, R = H, Me, are isolated. Imido(benzylidene) complexes [(η5‐C5Me5)M(NtBu)(CHPh)(CH2Ph)] M = Mo ( 19 ), W ( 20 ) are generated by alkylation of [(η5‐C5Me5)M(NtBu)Cl3] with PhCH2MgCl via α‐H abstraction. Based on nmr data a trend of decreasing donor capability of the ligands [NtBu]2— > [O]2— > [CHR]2— ? 2 [CH3]— > 2 [Cl]— emerges. 相似文献
6.
Olga M. Nazarenko Eduard B. Rusanov Alexander N. Chernega Konstantin V. Domasevitch 《Acta Crystallographica. Section C, Structural Chemistry》2013,69(3):232-236
In poly[[bis(μ‐4,4′‐bi‐1H‐pyrazole‐κ2N2:N2′)bis(3‐carboxyadamantane‐1‐carboxylato‐κO1)cobalt(II)] dihydrate], {[Co(C12H15O4)2(C6H6N4)2]·2H2O}n, (I), the Co2+ cation lies on an inversion centre and the 4,4′‐bipyrazole (4,4′‐bpz) ligands are also situated across centres of inversion. In its non‐isomorphous cadmium analogue, {[Cd(C12H15O4)2(C6H6N4)2]·2H2O}n, (II), the Cd2+ cation lies on a twofold axis. In both compounds, the metal cations adopt an octahedral coordination, with four pyrazole N atoms in the equatorial plane [Co—N = 2.156 (2) and 2.162 (2) Å; Cd—N = 2.298 (2) and 2.321 (2) Å] and two axial carboxylate O atoms [Co—O = 2.1547 (18) Å and Cd—O = 2.347 (2) Å]. In both structures, interligand hydrogen bonding [N...O = 2.682 (3)–2.819 (3) Å] is essential for stabilization of the MN4O2 environment with its unusually high (for bulky adamantanecarboxylates) number of coordinated N‐donor co‐ligands. The compounds adopt two‐dimensional coordination connectivities and exist as square‐grid [M(4,4′‐bpz)2]n networks accommodating monodentate carboxylate ligands. The interlayer linkage is provided by hydrogen bonds from the carboxylic acid groups via the solvent water molecules [O...O = 2.565 (3) and 2.616 (3) Å] to the carboxylate groups in the next layer [O...O = 2.717 (3)–2.841 (3) Å], thereby extending the structures in the third dimension. 相似文献
7.
《Journal of Coordination Chemistry》2012,65(13):1113-1122
Naphthaldimines containing N2O2 donor centers react with platinum(II) and (IV) chlorides to give two types of complexes depending on the valence of the platinum ion. For [Pt(II)], the ligand is neutral, [(H2L1)PtCl2]·3H2O (1) and [(H2L3)2Pt2Cl4]·5H2O (3), or monobasic [(HL2)2Pt2Cl2]·2H2O (2) and [(HL4)2Pt]·2H2O (4). These complexes are all diamagnetic having square-planar geometry. For [Pt(IV)], the ligand is dibasic, [(L1)Pt2Cl4(OH)2]·2H2O (5), [(L2)Pt3Cl10]·3H2O (6), [(L3)Pt2Cl4(OH)2]·C2H5OH (7) and [(L4)Pt2Cl6]·H2O (8). The Pt(IV) complexes are diamagnetic and exhibit octahedral configuration around the platinum ion. The complexes were characterized by elemental analysis, UV-Vis and IR spectra, electrical conductivity and thermal analyses (DTA and TGA). The molar conductances in DMF solutions indicate that the complexes are non-ionic. The complexes were tested for their catalytic activities towards cathodic reduction of oxygen. 相似文献
8.
The complexes trans-[PdCl2L2] {L = P-t-Bu (benzyl)2 or P-t-Bu2 (benzyl)} are shown to undergo internal metallation with difficulty to give complexes of the type [Pd2Cl2(PC)2] {(P′C) = C6H4CH2P-t-Bu (benzyl) and (″C) = C6H4CH2P-t-Bu2}. The ligand P-t-Bu2 (benzyl) undergoes metallation more readily than P-t-Bu(benzyl)2. The bridging chlorides of the binuclear complex [Pd2Cl2(P″C)2] are replaced by bromide or iodide and the bridges may be split by various ligands to give mononuclear species. 相似文献
9.
E. V. Lider V. N. Elokhina L. G. Lavrenova Yu. G. Shvedenkov L. A. Sheludyakova E. V. Peresypkina 《Russian Journal of Coordination Chemistry》2007,33(1):37-44
Novel oligonuclear complexes of Co(II), Ni(II), and Cu(II) with 4-(3,4-dichlorophenyl)-1,2,4-triazole (L) of the composition [M3L10(H2O)2](NO3)6 (M = Co(II), Ni(II)), [Ni3L6(H2O)6]Hal6 (Hal = Cl?, Br?), and [Cu5L16(H2O)2](NO3)10 · 2H2O were synthesized and studied by magnetic susceptibility, electronic and IR spectroscopy, and powder X-ray diffraction methods. All the above complexes are X-ray amorphous. Antifer-romagnetic exchange interactions between the M2+ ions were discovered in the [Co3L10(H2O)2](NO3)6 and [Ni3L10(H2O)2](NO3)6 complexes, whereas ferromagnetic exchange interactions were observed in the complexes [Ni3L6(H2O)6]Cl6, [Ni3L6(H2O)6]Br6, and [Cu5L16(H2O)2](NO3)10 · 2H2O. 相似文献
10.
For the complexes (CH8N4)2[CuCl6], (C2H9N5)2[CuCl6] · 2H2O, and (CH8N4O)4[CuCl6]Cl4, where (CH8N4)2+, (C2H9N5)2+, and (CH8N4O)2+ are the aminoguanidinium, biguanidium, and carbohydrazidium cations, respectively, IR and Raman spectra were taken and analyzed in the region of Cu—Cl vibrations. Polarization measurements of the Raman spectra of (CH8N4O)4[CuCl6]Cl4 single crystals were performed with the purpose of assigning the vibrations to symmetry types. Vibration spectra were calculated for the hexachlorocuprate ion in the given series of compounds, and the spectra of the examined complexes were compared with spectra of the previously known compounds incorporating the hexachlorocuprate(II) ion. 相似文献
11.
A new series of complexes is synthesized by template condensation of glyoxal and oxalyldihydrazide in methanolic medium in
the presence of divalent cobalt, nickel, copper, zinc and cadmium salts forming complexes of the type: [M(C8H8N8O4)X2] where M = Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and X = Cl−1, Br−1, NO
3
−1
, OAc−1. The complexes have been characterized with the help of elemental analyses, conductance measurements, magnetic susceptibility
measurements, electronic, n.m.r., infrared and far infrared spectral studies. On the basis of these studies, a six coordinate
octahedral geometry for these complexes has been proposed. The biological activities of the metal complexes have been tested
in vitro against a number of pathogenic bacteria to assess their inhibiting potential. Most of the compounds have been found to exhibit
remarkable antibacterial activities. 相似文献
12.
J. Nicolas Roedel Roman Bobka Bernd Neumann Birgit Weber Peter Mayer Ingo‐Peter Lorenz Prof. Dr. 《无机化学与普通化学杂志》2007,633(8):1171-1177
The synthesis and characterization of mononuclear tetrakis‐aziridine nickel(II ) and copper(II ) complexes as well as of a dinuclear bis‐aziridine copper(II ) complex are described. The reactions of anhydrous MCl2 (M = NiII, CuII) with aziridine (= az = C2H4NH, C2H3MeNH, CH2CMe2NH) in CH2Cl2 at room temperature in a 1:5 and 1:2 molar ratio, respectively, afforded the tetrakis‐aziridine complexes [M(az)4Cl2] (M = Ni, Cu) or the dimeric bis‐aziridine complex [Cu(az)2Cl2]2. After purification, all of the complexes were fully characterized. The single crystal structure analysis revealed two different coordination modes. Whereas both nickel(II ) complexes can be classified as showing an elongated octahedral structure, copper(II ) complexes show either an elongated octahedral or a square pyramidal arrangement forming dimers with chlorido bridges in axial positions. Furthermore, the results of magnetic measurements of the nickel(II ) and copper(II ) compounds are presented. 相似文献
13.
Summary N-Cyano-N-methyl-N(2-[(5-methyl-1H-imidazol-4-yl)-methylthio] ethyl) guanidine cimetidine (CM), complexes with CoII, NiII and CuII are described. The compounds are of stoichiometry [M(CM)2]SO4 · nH2O [M = CoII, NiII or CuII; n = 3,3 or 4, respectively], [M(CM)2](ClO4)2 [M = CoII or NiII], [M(CM)2]Cl2 · nH2O [M=CoII, NiII or CuII; n = 1, 2, or 2, respectively] and [Cu(CM)SO4] · 2H2O. The electronic spectra of the compounds in solid state, magnetic susceptibilities and i.r. and e.p.r. spectra were studied. Octahedral environments are proposed for the complexes: [M(CM)2]SO4·nH2O, [M(CM)2](ClO4)2, [Ni(CM)2]Cl2 · 2H2O, [Cu(CM)2]Cl2 · 2H2O and [Cu(CM)SO4] · 2H2O and a tetrahedral structure for [Co(CM)2]Cl2 · H2O. 相似文献
14.
L. N. Ambroladze Ts. D. Turkadze I. Z. Moseshvili 《Russian Journal of Inorganic Chemistry》2008,53(5):714-717
Complexes of Co(II) with hydantoin (L, C3H4N2O2) have been synthesized. The complexes had the following compositions: [CoL2(OH2)2](NO3)2 · 2H2O, [CoL2(OH2)2]Cl2 · 3H2O, and [CoL2(OH2)2]SO4 · 2H2O. The individual character of the synthesized compounds are proved by the study of the IR absorption spectra (400–4000 cm?1) of all the compounds and the initial ligand, as well as the X-ray diffraction patterns, thermograms, and thermogravigrams of the synthesized compounds. The coordination modes of the ligand and acido groups are revealed. The properties of the synthesized compounds are characterized. 相似文献
15.
Murat Aydemir Akın Baysal Feyyaz Durap Bahattin Gümgüm Saim Özkar Leyla Tatar Yıldırım 《应用有机金属化学》2009,23(11):467-475
The reactions of thiophene‐2‐(N‐diphenylphosphino)methylamine, Ph2PNHCH2‐C4H3S, 1 and thiophene‐2‐[N,N‐bis(diphenylphosphino)methylamine], (Ph2P)2NCH2‐C4H3S, 2, with MCl2(cod) (M = Pd, Pt; cod = 1,5‐cyclooctadiene) or [Cu(CH3CN)4]PF6 yields the new complexes [M(Ph2PNHCH2‐C4H3S)2Cl2], M = Pd 1a, Pt 1b, [Cu(Ph2PNHCH2‐C4H3S)4]PF6, 1c, and [M(Ph2P)2NCH2‐C4H3S)Cl2], M = Pd 2a, Pt 2b, {Cu[(Ph2P)2NCH2‐C4H3S]2}PF6, 2c, respectively. The new compounds were isolated as analytically pure crystalline solids and characterized by 31P‐, 13C‐, 1H‐NMR and IR spectroscopy and elemental analysis. Furthermore, the solid‐state molecular structures of representative palladium and platinum complexes of bis(phosphine)amine, 2a and 2b, respectively, were determined using single crystal X‐ray diffraction analysis. The palladium complexes were tested as potential catalysts in the Heck and Suzuki cross‐coupling reactions. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
16.
Synthesis and Structure of (N,)C,N‐chelated Organoantimony(III) and Bismuth(III) Cations and Isolation of Their Adducts with Ag[CB11H12] 下载免费PDF全文
Iva Vránová Milan Erben Roman Jambor Aleš Růžička Robert Jirásko Libor Dostál 《无机化学与普通化学杂志》2016,642(21):1212-1217
The treatment of N,C,N‐chelated antimony(III) and bismuth(III) chlorides [C6H3‐2,6‐(CH=NR)2]MCl2 [R = tBu and M = Sb ( 1 ) or Bi ( 2 ); R = Dmp and M = Sb ( 3 ) or Bi ( 4 )] (Dmp = 2,6‐Me2C6H3) with one molar equivalent of Ag[CB11H12] led to a smooth formation of corresponding ionic pairs {[C6H3‐2,6‐(CH=NR)2]MCl}+[CB11H12]– [R = tBu and M = Sb ( 7 ) or Bi ( 8 ), R = Dmp and M = Sb ( 9 ) or Bi ( 10 )]. Similarly, the reaction of C,N‐chelated analogues [C6H2‐2‐(CH=NDip)‐4,6‐(tBu)2]MCl2 [M = Sb ( 5 ) or Bi ( 6 ), Dip = 2′,6′‐iPr2C6H3] gave compounds {[C6H2‐2‐(CH=NDip)‐4,6‐(tBu)2]MCl}+[CB11H12]– [M = Sb ( 11 ) or Bi ( 12 )]. All compounds 7 – 12 were characterized with 1H, 11B and 13C{1H} NMR spectroscopy, ESI‐mass spectrometry, IR spectroscopy, and molecular structures of 7 – 9 and 12 were determined by the help of single‐crystal X‐ray diffraction analysis. In contrast, all attempts to cleave also the second M–Cl bond in 7 – 12 using another molar equivalent Ag[CB11H12] remained unsuccessful. Nevertheless, the reaction between 7 (or 8 ) and Ag[CB11H12] produced unprecedented adducts of both reagents namely {[C6H3‐2,6‐(CH=NtBu)2]SbCl}22+[Ag2(CB11H12)4]2– ( 13 ) and {[C6H3‐2,6‐(CH=NtBu)2]BiCl}+[Ag(CB11H12)2]– ( 14 ) in a reproducible manner. The molecular structures of these sparingly soluble compounds were determined by single‐crystal X‐ray diffraction analysis. 相似文献
17.
During alternating‐current electrochemical synthesis of copper(I) π‐complex of [CuCl{C6H4N3(C3H5)}] composition, starting from ethanol solution, containing CuCl2·2H2O and 1‐allylbenzotriazole, green crystals of intermediate [CuII3Cl6{C6H4N3(C3H5)}4] ( I ) compound has been obtained upon 24 h. After some days these crystals transform into red ones of [CuII2Cl4{C6H4N3(C3H5)}3] ( II ). Both compounds were X‐Ray structurally investigated. Crystals of I are triclinic, sp.gr. a = 9.1329(9), b = 10.0352(4), c = 12.239(3) Å, α = 76.443(13), β = 84.470(14), γ = 76.808(7)°, V = 1060.5(3) Å3, R = 0.0414 for 3311 reflections. II : monoclinic, C2/c, a = 13.828(1), b = 15.044(2), c = 10.702(1) Å, β = 91.36(1)°, V = 2225.7(4) Å3, R = 0.050 for 1495 reflections. In both compounds each benzotriazole core coordinates two copper atoms using two nitrogen atoms in 2 and 3 positions. Isolated Cu3Cl6 fragments in I are condensed along [001] direction into infinite chains [CuCl2]n in II. Finally, red crystals of II transform into colorless ones of the earlier studied copper(I) π‐complex of CuCl·C6H4N3(C3H5) composition. 相似文献
18.
Pradipta Kumar Basu Concepción López Mercè Font-Bardía 《Journal of organometallic chemistry》2009,694(22):3633-441
The syntheses and characterization of two novel ferrocene derivatives containing 3,5-diphenylpyrazole units of general formula [1-R-3,5-Ph2-(C3N2)-CH2-Fc] {Fc = (η5-C5H5)Fe(η5-C5H4) and R = H (2) or Me (3)} together with a study of their reactivity with palladium(II) and platinum(II) salts or complexes under different experimental conditions is described. These studies have allowed us to isolate and characterize trans-[Pd{1-Me-3,5-Ph2-(C3N2)-CH2-Fc]}2Cl2] (4a) and three different types of heterodimetallic complexes: cis-[M{1-Me-3,5-Ph2-(C3N2)-CH2-Fc]}Cl2(dmso)] {M = Pd (5a) or Pt (5b)}, the cyclometallated products [M{κ2-C,N-[3-(C6H4)-1-Me-5-Ph-(C3N2)]-CH2-Fc}Cl(L)] with L = PPh3 and M = Pd (6a) or Pt (6b) or L = dmso and M = Pt (8b) and the trans-isomer of [Pt{1-Me-3,5-Ph2-(C3N2)-CH2-Fc]}Cl2(dmso)] (7b). In compounds 4a, 5a, 5b and 7b, the ligand behaves as a neutral N-donor group; while in 6a, 6b and 8b it acts as a bidentate [C(sp2,phenyl),N(pyrazole)]− group. A comparative study of the spectroscopic properties of the compounds, based on NMR, IR and UV-Visible experiments, is also reported. 相似文献
19.
Bernhard Miller Janina Altman Christian Leschke Walter Schunack Karlheinz Sünkel Jrg Knizek Heinrich Nth Wolfgang Beck 《无机化学与普通化学杂志》2000,626(4):978-984
Dinuclear Palladium(II), Platinum(II), and Iridium(III) Complexes of Bis[imidazol‐4‐yl]alkanes The reaction of bis(1,1′‐triphenylmethyl‐imidazol‐4‐yl) alkanes ((CH2)n bridged imidazoles L(CH2)nL, n = 3–6) with chloro bridged complexes [R3P(Cl)M(μ‐Cl)M(Cl)PR3] (M = Pd, Pt; R = Et, Pr, Bu) affords the dinuclear compounds [Cl2(R3P)M–L(CH2)nL–M(PR3)Cl2] 1 – 17 . The structures of [Cl2(Et3P)Pd–L(CH2)3L–Pd(PEt3)Cl2] ( 1 ), [Cl2(Bu3P)Pd–L(CH2)4L–Pd(PBu3)Cl2] ( 10 ), [Cl2(Et3P)Pd–L(CH2)5L–Pd(PEt3)Cl2] ( 3 ), [Cl2(Et3P)Pt–L(CH2)3L–Pt(PEt3)Cl2] ( 13 ) with trans Cl–M–Cl groups were determined by X‐ray diffraction. Similarly the complexes [Cl2(Cp*)Ir–L(CH2)nL–Ir(Cp*)Cl2] (n = 4–6) are obtained from [Cp*(Cl)Ir(μ‐Cl)2Ir(Cl)Cp*] and the methylene bridged bis(imidazoles). 相似文献
20.
Evgen V. Govor Andrey B. Lysenko Konstantin V. Domasevitch 《Acta Crystallographica. Section C, Structural Chemistry》2008,64(5):m201-m204
New coordination compounds with the 4,4′‐bi‐1,2,4‐triazole ligand (btr), namely tetraaqua‐2κ4O‐di‐μ2‐4,4′‐bi‐1,2,4‐triazole‐1:2κ2N1:N1′;2:3κ2N1:N1′‐hexachlorido‐1κ3Cl,3κ3Cl‐trizinc(II), [Zn3Cl6(C4H4N6)2(H2O)4], (I), and poly[cadmium(II)‐μ2‐4,4′‐bi‐1,2,4‐triazole‐κ2N1:N2‐di‐μ2‐chlorido], [CdCl2(C4H4N6)]n, (II), reveal an unprecedented molecular zwitterionic structure for (I) and a polymeric two‐dimensional layer structure for (II). Differences between these products, which involve the formation of either charge‐separated chlorometallate/aquametal fragments or complementary organic and inorganic bridges, are attributable to the hardness–softness characters of the metal cations. In (I), two N1,N1′‐bidentate btr molecules connect one [Zn(H2O)4]2+ cation and two [ZnCl3]− anions into a linear trizinc motif (the Zn atom of the cation occupies a centre of inversion in an N2O4 coordination octahedron, whereas the Zn atom of the anion possesses a distorted tetrahedral Cl3N environment). In (II), the distorted vertex‐sharing CdCl4N2 octahedra are linked into binuclear [Cd2(μ2‐Cl)(μ2‐btr)2]3+ fragments by unprecedented N1:N2‐bidentate btr double bridges and bridging chloride ligands, while the additional chloride anions are also bridging, providing further propagation of the fragments into a two‐dimensional network [Cd—Cl = 2.5869 (2)–2.6248 (7) Å]. 相似文献