Mercuric Bis(N‐imino‐methyl‐formamidate), Hg(Imf)2

Single crystals of mercuric bis(N‐imino‐methyl‐formamidate), Hg(Imf)₂, were obtained from aqueous solutions of 1,2,4‐triazole and Hg(NO₃)₂·2H₂O. The crystal structure [monoclinic, P2₁/c (no. 14), a = 499.6(2), b = 1051.2(4), c = 711.1(3) pm, β = 117.55(1)°, Z = 2, R₁ for 890 reflections with I₀>2σ(I₀): 0.0369] contains linear centrosymmetric Hg(Imf)₂ molecules with Hg–N distances of only 203.5(7) pm. Two plus two intra‐ and intermolecular nitrogen atoms add to an effective coordination number of 6.     

M(benzo‐18‐crown‐6)I4 (M = Cd,Hg): Tetraiodide,Iodide–Iodine Adduct,or an Inclusion Compound of Iodine in MI2@(benzo‐18‐crown‐6)?

M(benzo‐18‐crown‐6)I₄ (M = Cd, Hg) are obtained as red columnar crystals from the reactions of benzo‐18‐crown‐6 (b18c6), cadmium and mercury iodide, respectively, and iodine in molar ratios of 1:1:2 in acetonitrile. They both crystallize with the orthorhombic crystal system, P2₁2₁2₁, a = 833.7(1), b = 1610.9(1), c = 1846.8(1) pm, V = 2480.3(1) 10⁶·pm³, Z = 4, for M = Cd and a = 823.4(1), b = 1616.5(1), c = 1866.1(1) pm, V = 2483.8(2) 10⁶·pm³ for M = Hg. The crystal structures consist of [M(b18c6)]I₂ molecules which are connected to a slightly lengthened iodine molecule via a secondary contact, according to the formulation I₂@[MI₂@(b18c6)].     

Pb(18‐crown‐6)Cl2 and Hg(18‐crown‐6)I2: Molecular Dihalides Trapped in a Crown Ether

Pb(18‐crown‐6)Cl₂ and Hg(18‐crown‐6)I₂ are obtained as transparent colourless crystals of needle and hexagonal shape, respectively, by isothermal evaporation of their dichloromethane solutions. Pb(18‐crown‐6)Cl₂ crystallizes with the trigonal crystal system [ , no. 148, a = b = 1176.3(2), c = 1191.8(3) pm, V = 1428.2(5) 10⁶·pm³, Z = 3] whereas Hg(18‐crown‐6)I₂ crystallizes with the orthorhombic crystal system (Pnma, no. 62, a = 1613.9(2) pm, b = 2822.2(5) pm, c = 841.3(1) pm, V = 3832(1)10⁶·pm³, Z = 8). Both compounds are characterized by linear MX₂ (HgI₂ or PbCl₂) molecular units which are encrypted by the crown ether. In both cases, the divalent metal ion resides in the middle of the crown ether resulting in a hexagonal bipyramidal coordination environment for the metal cations. The molecular symmetry comes close to D_3d. Hg(18‐crown‐6)I₂ and Pb(18‐crown‐6)Cl₂ differ in the way the single MX₂@18‐crown‐6 units are packed. Whereas the Hg(18‐crown‐6)I₂ molecules are arranged in a (distorted) cubic closest packing, the Pb(18‐crown‐6)Cl₂ molecules adopt a hexagonal closest packing.     

An Unusual Mixed‐Anionic Iodine‐Rich Polyiodide: [Rb(crypt‐2,2,2)]4(I5)2(I8)

Black crystals of [Rb(crypt‐2,2,2)]₄(I₅)₂(I₈) were obtained from a dichloromethane/ethanol solution of RbI, I₂ and Kryptofix‐2,2,2®. The crystal structure (monoclinic, P2₁/c (no. 14), a = 1250.1(1), b = 2555.2(2), c = 2313.4(3) pm, β = 121.45(1)°, V = 6309.9(11)·10⁶ pm³, Z = 2) consists of [Rb(crypt‐2,2,2)]⁺ cations leaving three‐dimensional channels for the V‐shaped (I₅)^? and Z‐shaped (I₈)^2? anions which are isolated from each other.     

Crystal Structure of the Mixed‐Valent Basic Mercury Nitrate HgI2(NO3)2·HgII(OH)(NO3)·HgII(NO3)2·4HgIIO [= Hg8O4(OH)(NO3)5]

Light‐yellow single crystals of the mixed‐valent mercury‐rich basic nitrate Hg₈O₄(OH)(NO₃)₅ were obtained as a by‐product at 85 °C from a melt consisting of stoichiometric amounts of (Hg^I₂)(NO₃)₂·2H₂O and Hg^II(OH)(NO₃). The title compound, represented by the more detailed formula Hg^I₂(NO₃)₂·Hg^II(OH)(NO₃)·Hg^II(NO₃)₂·4Hg^IIO, exhibits a new structure type (monoclinic, C2/c, Z = 4, a = 6.7708(7), b = 11.6692(11), c = 24.492(2) Å, β = 96.851(2)°, 2920 structure factors, 178 parameters, R1[F² > 2σ(F²)] = 0.0316) and is made up of almost linear [O‐Hg^II‐O] and [O‐Hg^I‐Hg^I‐O] building blocks with typical Hg^II‐O distances around 2.06Å and a Hg^I‐O distance of 2.13Å. The Hg₂²⁺ dumbbell exhibits a characteristic Hg‐Hg distance of 2.5079(7) Å. The different types of mercury‐oxygen units form a complex three‐dimensional network exhibiting large cavities which are occupied by the nitrate groups. The NO₃^? anions show only weak interactions between the nitrate oxygen atoms and the mercury atoms which are at distances > 2.6Å from one another. One of the three crystallographically independent nitrate groups is disordered.     

Metal Derivatives of 1,3‐Imidazolidine‐2‐thione with Divalent d10 Metal Ions (Zn–Hg) : Synthesis and Structures

Reactions of divalent Zn‐Hg metal ions with 1,3‐imidazolidine‐2‐thione (imdtH₂) in 1 : 2 molar ratio have formed monomeric complexes, [Zn(η¹‐S‐imdtH₂)₂(OAc)₂] ( 1 ), [Cd((η¹‐SimdtH₂)₂I₂] ( 2 ), [Cd(η¹‐S‐imdtH₂)₂Br₂] ( 3 ), and [Hg(η¹‐S‐imdtH₂)₂I₂] ( 4 ). Complexes 1 – 4 , have been characterized by elemental analysis (C, H, N), spectroscopy (IR, ¹H, NMR) and x‐ray crystallography ( 1 ‐ 4 ). Hydrogen bonding between oxygen of acetate and imino hydrogen of ligand, {N(2)–H(2C)···O(2)^#} in 1 , ring CH and imino hydrogen, {C(2A)–H(2A)···Br(2)^#} in 3 have formed H‐bonded dimers. Similarly, the interactions between molecular units of complexes 2 and 4 have yielded 2D polymers. The polymerization occurs via intermolecular interactions between thione sulfur and imino hydrogen, {N(2)–H(2)···S(1)^#}, imino hydrogen and the iodine atom, {NH(1)···I(2)^#} in 2 and imino hydrogen – iodine atom {N(2A)–H(2A)···I(2)} and I···I interaction in 4 . Crystal data: [Zn(η¹‐S‐imdtH₂)₂(OAc)₂] ( 1 ), C₁₀H₁₈N₄O₄S₂Zn, orthorhombic, Pbcn, a = 9.3854(7) Å, b = 12.4647(10) Å, c = 13.2263(11) Å; V = 1547.3(2) ų, Z = 4, R = 0.0280 [Cd((η¹‐S‐imdtH₂)₂I₂] ( 2 ), C₆H₁₂CdI₂N₄S₂, orthorhombic, Pnma, a = 13.8487(10) Å, b = 14.4232(11) Å, c = 7.0659(5) Å; Z = 4, V = 1411.36(18) ų, R = 0.0186.     

Isolated Triiodide and Pentaiodide Anions in the Crystal Structure of [Rb(Dibenzopyridino‐18‐Crown‐6)2]2(I3)(I5)

Red shiny crystals of [Rb(dibenzopyridino‐18‐crown‐6)₂]₂(I₃)(I₅) were obtained from a dichloromethane/ethanol solution of RbI, I₂ and dibenzopyridino‐18‐crown‐6. Triclinic, , a = 1494.3(1), b = 1534.1(1), c = 2412.9(2) pm, α = 76.95(1), β = 83.58(1), γ = 68.67(1)°, V = 5016.7(7) 10⁶·pm³, Z = 2. The crystal structure consists of [Rb(dbp18c6)₂]⁺ cations leaving suitable three‐dimensional channels for the linear I₃⁻ and V‐shaped I₅⁻ anions which are isolated from each other.     

Synthesis and Crystal Structure of [(1‐(Phenyltriazenido)‐2‐(phenyltriazeno)benzene)(nitrato)mercury(II)], {Hg[PhN3C6H4N3(H)Ph](NO3)}, a Complex with Weak Metal‐Arene π‐Interactions

The reaction of PhN₃(H)C₆H₄N₃(H)Ph with Hg(NO₃)₂ in THF in the presence of triethylamine yields {Hg[PhN₃C₆H₄N₃(H)Ph](NO₃)} as a yellow powder that can be recrystallized from THF/acetone. The crystals belong to the monoclinic system, space group P2₁ with the cell dimensions a = 9.639(2), b = 5.412(1), c = 19.675(4) Å, β= 97.47(3)°, V = 1017.7 (4) ų, Z = 2. The crystal structure determination (2668 unique reflections with [I>2σ(I)], 262 parameters, R₁ = 0.0393) shows that the structure consists of mononuclear complexes. Hg atoms are linearly coordinated by one N_α atom of the triazenide unit of the planar ligand [Hg‐N(1) = 2.101(8) Å] and an O atom of the NO₃^— ion [Hg‐O(1) = 2.11(1) Å]. Additional weak Hg‐N contacts [Hg‐N(4) = 2.662(9) and Hg‐N(3) = 2.851(9) Å] and an intramolecular hydrogen bond between the triazenide hydrogen and an O atom of the nitrate group are observed [N(6)‐H(6)···O(2) = 2.92(2) Å]. The complexes are stacked to infinite chains by metal‐arene π‐interactions. Each Hg atom is coordinated by the terminal phenyl rings of two neighboring complexes [Hg‐C from 3.40(1) to 4.10(1) Å] in a η² fashion.     

Iodoplumbate mit vier‐ und fünffach koordinierten Pb2+‐Ionen

Iodoplumbates with Tetra‐ and Penta‐coordinated Pb²⁺ Ions In contrast to all known iodoplumbates with octahedrally coordinated Pb²⁺ ions, square pyramidal geometry is observed in the iodoplumbate chains of (Pr₄N)[PbI₃] ( 1 ) and [Mg(dmf)₆][PbI₃]₂ ( 2 ), whereas the isolated anions in (Ph₄P)₂[Pb₂I₆] ( 3 ) and [Bu₃N–(CH₂)₃–NBu₃][PbI₄] ( 4 ) contain tetra‐coordinated lead atoms. (Pr₄N)[PbI₃] ( 1 ): a = 910.86(6), b = 1221.46(7), c = 1907.7(1) pm, V = 2122.5(2) · 10⁶ pm³, space group P2₁2₁2₁; [Mg(dmf)₆][PbI₃]₂ ( 2 ): a = 891.24(9), b = 1025.34(7), c = 1234.82(9) pm, α = 92.938(8), β = 106.457(8), γ = 98.100(7)°, V = 1066.4(2) · 10⁶ pm³, space group P1; (Ph₄P)₂[Pb₂I₆] ( 3 ): a = 1174.5(1), b = 722.29(7), c = 3104.8(4) pm, β = 100.50(1)°, V = 2589.8(5) · 10⁶ pm³, space group P2₁/n; [Bu₃N–(CH₂)₃–NBu₃][PbI₄] ( 4 ): a = 2178.3(1), b = 1008.63(5), c = 1888.3(1) pm, β = 110.003(5)°, V = 3898.6(4) · 10⁶ pm³, space group P2/c.     

Kristallstrukturen „supramolekularer”︁ (Benzo‐18‐krone‐6)kaliumtetrathiocyanatometallate: Ein dimerer Komplex {[K(Benzo‐18‐krone‐6)]2[Hg(SCN)4]}2 und zwei isomere Komplexe [K(Benzo‐18‐krone‐6)][Cd(SCN)3] mit kettenförmigen Trithiocyanatocadmat‐Anionen

Crystal Structures of „Supramolecular”︁ Benzo‐18‐crown‐6 Potassium Tetrathiocyanato Metallates: A Dimeric Complex {[K(Benzo‐18‐crown‐6)]₂[Hg(SCN)₄]}₂ and Two Isomeric Complexes [K(Benzo‐18‐crown‐6)][Cd(SCN)₃] Containing Trithiocyanato Cadmate Anions with Chain Structures By reaction of potassium thiocyanatomercurate(II) complexes with benzo‐18‐crown‐6 (2,3‐benzo‐1,4,7,10,13,16‐hexaoxacyclooctadec‐2‐ene) crystals of {[K(benzo‐18‐crown‐6)]₂[Hg(SCN₄)]}₂ ( 1 ) were obtained. 1 crystallizes monoclinic, space group P2₁/n (non‐standard setting of P2₁/c), a = 1737.35(2), b = 1377.16(2), c = 1984.12(3) pm, β = 100.637(1)°, Z = 2. With potassium tetrathiocyanatocadmate(II) two modifications of a complex [K(benzo‐18‐crown‐6)][Cd(SCN)₃] ( 2 , 3 ), of different symmetry were formed. 2 crystallizes monoclinic, P2₁/c, a = 1158,31(3), b = 1096,55(2), c = 2028,46(2) pm, β = 99,5261(2)°, Z = 4, 3  orthorhombic, P2₁cn, a = 1105,95(3), b = 1413,07(4), c = 1617,10(5) pm, Z = 4. 1 has a dimeric structure, built up from a dication K₂(benzo‐18‐crown‐6)₂]²⁺ and two [K(benzo‐18‐crown‐6)]⁺ cations, which are bridged by two [Hg(SCN)₄]^2– anions. In 2 and 3 triply bridged infinite [{Cd(SCN)₃^–}_n] zigzag chains, stretching along screw axes, are to be found as anions. In 2 these chains exist in two conformations related by inversion symmetry, whereas in 3 only one form can be found. [K(benzo‐18‐crown‐6)]⁺ cations are linked to the anion chains via K · · · S interactions of different lengths.     

Darstellung von Organylquecksilber(II)‐di(methansulfonyl)amiden und Kristallstruktur von Ph–Hg–N(SO2Me)2

Polysulfonylamines. CXXIV. Preparation of Organylmercury(II) Di(methanesulfonyl)amides and Crystal Structure of Ph–Hg–N(SO₂Me)₂ Four N,N‐disulfonylated organylmercury(II) amides R–Hg–N(SO₂Me)₂, where R is Me, ⁱPr, Me₃SiCH₂ or Ph, were obtained on treating the appropriate chlorides RHgCl with AgN(SO₂Me)₂, and characterized by ¹H and ¹³C NMR spectra. In the crystal structure of the phenyl compound (orthorhombic, space group Pbca, Z = 8, X‐ray diffraction at –95 °C), the molecule exhibits a covalent and significantly bent C–Hg–N grouping [bond angle 172.7(3)°; Hg–C 204.0(8), Hg–N 209.1(7) pm]. One sulfonyl oxygen atom forms a short intramolecular Hg…O contact [296.1(5) pm] and simultaneously catenates glide‐plane related molecules via a second Hg…O interaction 297.6(5) pm], thus conferring upon Hg^II the effective coordination number 4 and a geometrically irregular coordination polyhedron (bond angles from 173 to 54°).     

Copper(I) π‐Complexes with 2‐Butyne‐1,4‐diol. Synthesis and Crystal Structure of Na[CuCl2(HOCH2C≡CCH2OH)]·2H2O

Crystals of anionic Na[CuCl₂(HOCH₂C≡CCH₂OH)]·2H₂O π‐complex have been synthesized by interaction of 2‐butyne‐1,4‐diol with CuCl in a concentrated aqueous NaCl solution and characterized by X‐ray diffraction at 100 K. The crystals are triclinic: space group , a = 7.142(3), b = 7.703(3), c = 10.425(4) Å, α = 105.60(3), β = 99.49(3), γ = 110.43(3)°, V = 495.9(4) ų, Z = 2, R = 0.0203 for 3496 reflections. The structure is built of discrete [CuCl₂(HOCH₂C≡CCH₂OH)]^? anionic stacks and polymeric cations among the stacks. The Cu^I atom adopts trigonal planar coordination of two Cl^? anions and the C≡C bond of 2‐butyne‐1,4‐diol, Cu–(C≡C) distance is equal to 1.903(3) Å. Na⁺ cations environment is octahedral and consists of O and Cl atoms. The crystal packing is governed by strong hydrogen bonds of O–H···Cl and O–H···O types.     

Schwache Sn…I‐Wechselwirkungen in den Kristallstrukturen der Iodostannate [SnI4]2– und [SnI3]–

Weak Sn…I Interactions in the Crystal Structures of the Iodostannates [SnI₄]^2– and [SnI₃]^– Iodostannate complexes can be crystallized from SnI₂ solutions in polar organic solvents by precipitation with large counterions. Thereby isolated anions as well as one, two or three‐dimensional polymeric anionic substructures are established, in which SnI₃^– and SnI₄^2– groups are linked by weak Sn…I interactions. Examples are the iodostannates [Me₃N–(CH₂)₂–NMe₃][SnI₄] ( 1 ), (Ph₄P)₂[Sn₂I₆] ( 2 ), [Me₃N–(CH₂)₂–NMe₃][Sn₂I₆] ( 3 ), [Fe(dmf)₆][SnI₃]₂ ( 4 ) and (Pr₄N)[SnI₃] ( 5 ), which have been characterized by single crystal X‐ray diffraction. [Me₃N–(CH₂)₂–NMe₃][SnI₄] ( 1 ): a = 671.6(2), b = 1373.3(4), c = 2046.6(9) pm, V = 1887.7(11) · 10⁶ pm³, space group Pbcm;(Ph₄P)₂[Sn₂I₆] ( 2 ): a = 1168.05(6), b = 717.06(4), c = 3093.40(10) pm, β = 101.202(4)°, V = 2541.6(2) · 10⁶ pm³, space group P2₁/n;[Me₃N–(CH₂)₂–NMe₃][Sn₂I₆] ( 3 ): a = 695.58(4), b = 1748.30(8), c = 987.12(5) pm, β = 92.789(6)°, V = 1199.00(11) · 10⁶ pm³, space group P2₁/c;[Fe(dmf)₆][SnI₃]₂ ( 4 ): a = 884.99(8), b = 1019.04(8), c = 1218.20(8) pm, α = 92.715(7), β = 105.826(7), γ = 98.241(7), V = 1041.7(1) · 10⁶ pm³, space group P1;(Pr₄N)[SnI₃] ( 5 ): a = 912.6(2), b = 1205.1(2), c = 1885.4(3) pm, V = 2073.5(7) · 10⁶ pm³, space group P2₁2₁2₁.     

Synthesis and Characterization of Three Zinc Phosphonates Based on 5‐Phosphonoisophthalic Acid, (HO2C)2C6H3PO3H2

Three new Zn‐phosphonates based on 5‐phosphonoisophthalic acid, (HO₂C)₂C₆H₃PO₃H₂ (H₄L), [Zn₂(H₂O)(O₂C)₂C₆H₃PO₃] · H₂O ( 1 ), Zn₂(H₂O)₂(O₂C)₂C₆H₃PO₃ ( 2 ), and KZn[H(O₂C)₂C₆H₃PO₃] ( 3 ) have been hydrothermally synthesized and characterized by single‐crystal X‐ray diffraction ( 1 : triclinic, , a = 742.49(3) pm, b = 846.37(4) pm, c = 992.84(4) pm, α = 80.936(2)°, β = 81.574(2)°, γ = 73.139(3)°, V = 586.28(4) · 10⁶ pm³, R1 = 0.0583, wR2 = 0.1347 (for I > 2σ(I)); 2 : monoclinic, P2₁/m, a = 464.78(9) pm, b = 1329.2(3) pm, c = 974.5(3) pm, β = 95.80(3)°, V = 599.0(2) · 10⁶ pm³, R1 = 0.0395, wR2 = 0.1086 (for I > 2σ(I)); 3 : monoclinic, P2₁/c, a = 501.9(1) pm, b = 2489.9(5) pm, c = 946.2(5) pm, β = 105.38(3)°, V = 1140.0(7) · 10⁶ pm³, R1 = 0.0365, wR2 = 0.0848 (for I > 2σ(I))). The title compounds 1 and 2 have the same chemical composition but exhibit different structures and are therefore polymorphs. Thus, in compound 1 , isolated ZnO₄‐tetrahedra, and in 2 , infinite double‐chains of corner‐sharing ZnO₆ polyhedra are observed. In, KZn[H(O₂C)₂C₆H₃PO₃] ( 3 ) K⁺‐ions have been incorporated into the structure leading to the formation of a bimetallic inorganic‐organic hybrid compound.     

Molekül‐ und Kristallstruktur von Quecksilber(II)‐α‐Amino‐γ‐methylmercapto‐butyrat,Hg(Met)2

Molecular and Crystal Structure of Mercuric α‐Amino‐γ‐methyl‐mercapto‐butyrate, Hg(Met)₂ The mercuric salt of deprotonated methionine, Hg(Met)₂, was obtained as colourless needles from aqueous solutions of methionine and HgCl₂ or HgO, respectively. The crystal structure (monoclinic, P2₁, Z = 2, a = 984, 2(2), 507, 96(6), c = 1574, 2(3) pm, β = 93, 05(2)°; R_all = 0, 055) exhibits formula‐like molecules with strong Hg—N coordination at a distance of 216 pm; one oxygen atom adds to a chelate like N—Hg—O coordination. Stacking of these molecules adds two oxygen atoms of different methionate anions to an effective 2+2+2 ?octahedral”? coordination around the mercuric ion. Thereby a layer structure parallel (001) is formed with the methyl‐mercapto function on top and bottom of these layers.     

Kristallstrukturen der iso‐Thiocyanatoberyllate (Ph4P)2[Be(NCS)4] und (Ph4P)4[{Be2(NCS)4(μ‐NCS)2}{Be2(NCS)6(μ‐H2N2C2S2)}]

Bis(tetraphenylphosphonium) hexachloridodiberyllate, (Ph₄P)₂[Be₂Cl₆], reacts with excess trimethylsilyl‐iso‐thiocyanate to give a mixture of colourless single crystals of (Ph₄P)₂[Be(NCS)₄] ( 1 ) and (Ph₄P)₄[{Be₂(NCS)₄(μ‐NCS)₂}{Be₂(NCS)₆(μ‐H₂N₂C₂S₂)}] ( 2 ), which can be separated by selection. Both complexes were characterized by X‐ray diffraction. Compound 1 can be prepared without by‐products by treatment of (Ph₄P)₂[BeCl₄] with excess Me₃SiNCS in dichloromethane solution. 1 : Space group I4₁/a, Z = 4, lattice dimensions at 100(2) K: a = b = 1091.2(1), c = 3937.1(3) pm, R₁ = 0.0474. The [Be(NCS)₄]^2– ion of 1 forms tetragonally distorted tetrahedral anions with Be–N distances of 168.4(2) pm and weak intermolecular S ··· S contacts along [100] and [010]. 2 ·4CH₂Cl₂: Space group P , Z = 1, lattice dimensions at 100(2) K: a = 919.5(1), b = 1248.3(1), c = 2707.0(2) pm, α = 101.61(1) °, β = 95.08(1) °, γ = 94.52(1) °, R₁ = 0.103. Compound 2 contains two different anionic complexes in the ratio 1:1. In {Be₂(NCS)₄(μ‐NCS)₂}^2–, the beryllium atoms are connected by (NCS)^– bridging groups forming centrosymmetric eight‐membered Be₂(NCS)₂ rings with distances Be–N of 168(1) pm and Be–S of 235.2(9) pm. The second anion {Be₂(NCS)₆(μ‐H₂N₂C₂S₂)}^2– consists of two {Be(NCS)₃}^– units, which are linked by the nitrogen atoms of the unique dimeric cyclo‐addition product of HNCS with Be–N distances of 179(1) pm.     

Polysulfonylamine. CLXXVIII Onium‐Salze des Benzol‐1,2‐di(sulfonyl)amins (HZ): Eine zweite Kristallform des Ammonium‐Salzes NH4Z·H2O und Kristallstruktur des Bis(triphenylphosphoranyliden)ammonium‐Salzes [Ph3PNPPh3]Z

Polysulfonylamines. CLXXVIII. Onium Salts of Benzene‐1,2‐di(sulfonyl)amine (HZ): A Second Crystal Form of the Ammonium Salt NH₄Z·H₂O and Crystal Structure of the Bis(triphenylphosphoranylidene)ammonium Salt [Ph₃PNPPh₃]Z A dimorphic form of NH₄Z·H₂O, where Z^? is N‐deprotonated ortho‐benzenedisulfonimide, has been obtained and structurally characterized (previously known form 1A : monoclinic, P2₁/c, Z′ = 1; new polymorph 1B : monoclinic, P2₁/n, Z′ = 1). Both structures are dominated by an abundance of classical hydrogen bonds N⁺–H/O–H···O=S/OH₂, whereby the anionic N^? function does not act as an acceptor. The major difference between the dimorphs arises from the topology of the hydrogen bond network, which is two‐dimensional in 1A , leading to a packing of discrete lamellar layers, but three‐dimensional in 1B . Moreover, the latter network is reinforced by a set of weak C–H··O/N hydrogen bonds, whereas the layered structure of 1A displays only one independent C–H···O bond, providing a link between adjacent layers. The compound [Ph₃PNPPh₃]Z ( 2 , monoclinic, P2₁/c, Z′ = 1) is the first structurally authenticated example of an ionic Z^? derivative in which the cation contains neither metal bonding sites nor strong hydrogen bond donors. This structure exhibits columns of anions, surrounded by four parallel columns of cations, giving a square array. The large cations are associated into a three‐dimensional framework via weak C–H···C(π) interactions and an offset face‐to‐face phenyl interaction, while the anions occupy tunnels in this framework and are extensively bonded to the surrounding cations by C–H···O/N^? hydrogen bonds and C–H···C(π) interactions.     

[Be3(μ3‐O)3(MeCN)6{Be(MeCN)3}3](I)6 – ein Berylliumkomplex mit Cyclo‐(Be3O3)‐Kern und sein Hydrolyseprodukt [Be(H2O)4](I)2·2MeCN

Single crystals of [Be₃(μ₃‐O)₃(MeCN)₆{Be(MeCN)₃}₃](I)₆·4CH₃CN ( 1 ·4CH₃CN) were obtained in low yield by the reaction of beryllium powder with iodine in acetonitrile suspension, which probably result from traces of beryllium oxide containing the applied beryllium metal. The compound 1 ·4CH₃CN forms moisture sensitive, colourless crystal needles, which were characterized by IR spectroscopy and X‐ray diffraction (Space group Pnma, Z = 4, lattice dimensions at 100(2) K: a = 2317.4(1), b = 2491.4(1), c = 1190.6(1) pm, R₁ = 0.0315). The hexaiodide complex cation 1 ⁶⁺consists of a cyclo‐Be₃O₃ core with slightly distorted chair conformation, stabilized by coordination of two acetonitrile ligands at each of the beryllium atoms and by a {Be(CH₃CN)₃}²⁺ cation at each of the oxygen atoms. This unique coordination behaviour results in coplanar OBe₃ units with short Be–O distances of 155.0 pm and 153.6 pm on average of bond lengths within the cyclo‐Be₃O₃ unit and of the peripheric BeO bonds, respectively. Exposure of compound 1 ·4CH₃CN to moist air leads to small orange crystal plates of [Be(H₂O)₄]I₂·2CH₃CN ( 3 ·2CH₃CN). According to the crystal structure determination (Space group C2/c, Z = 4, lattice dimensions at 100(2) K: a = 1220.7(1), b = 735.0(1), c = 1608.5(1) pm, β = 97.97(1)°, R₁ = 0.0394), all hydrogen atoms of the dication [Be(H₂O)₄]²⁺ are involved to form O–H ··· N and O–H ··· I hydrogen bonds with the acetonitrile molecules and the iodide ions, respectively. Quantum chemical calculations (B3LYP/6‐311+G**) at the model [Be₃(μ₃‐O)₃(HCN)₆{Be(HCN)₃}₃]⁶⁺ show that chair and boat conformation are stable and that the distorted chair conformation is stabilized by packing effects.     

N-(4-甲基苯甲酰氨基) N’-[5-(2-三氟甲基苯基)-2-呋喃甲酰硫脲的合成、晶体结构测定与生物活性测定

本文首次合成标题化合物N-(4-甲基苯甲酰氨基)-N’-[5-(2-三氟甲基苯基)-2-呋喃甲酰硫脲。化合物(C21H16F3N3O3S, Mr = 447.43)单晶经测定为单斜晶体,空间群为P -1。在晶体中,存在一些分子内和分子间的相互作用,分子间还有C—H···π 的相互作用,这可能导致晶体更稳定的原因。目标产物的结构经IR, H NMR和元素分析测定确证。初步生物活性测试表明,部分化合物对棉花枯萎病、黄瓜灰霉病、苹果轮纹病和棉花炭疽病有较好的选择性杀菌活性;部分目标化合物有较好的除草活性。     

Three structures containing (E)‐1,2‐bis­(benzimidazol‐2‐yl)ethene groups

Two of the title compounds, namely (E)‐1,2‐bis­(1‐methyl­benzimidazol‐2‐yl)ethene, C₁₈H₁₆N₄, (Ib), and (E)‐1,2‐bis­(1‐ethyl­benzimidazol‐2‐yl)ethene, C₂₀H₂₀N₄, (Ic), consist of centrosymmetric trans‐bis­(1‐alkyl­benzimidazol‐2‐yl)ethene mol­ecules, while 3‐eth­yl‐2‐[(E)‐2‐(1‐ethyl­benzimidazol‐2‐yl)­ethen­yl]benzimidazol‐1‐ium perchlorate, C₂₀H₂₁N₄⁺·ClO₄⁻, (II), contains the monoprotonated analogue of compound (Ic). In the three structures, the benzimidazole and benzimidazolium moieties are essentially planar; the geometric parameters for the ethene linkages and their bonds to the aromatic groups are consistent with double and single bonds, respectively, implying little, if any, conjugation of the central C=C bonds with the nitro­gen‐containing rings. The C—N bond lengths in the N=C—N part of the benzimidazole groups differ and are consistent with localized imine C=N and amine C—N linkages in (Ib) and (Ic); in contrast, the corresponding distances in the benzimidazolium cation are equal in (II), consistent with electron delocalization resulting from protonation of the amine N atom. Crystals of (Ib) and (Ic) contain columns of parallel mol­ecules, which are linked by edge‐over‐edge C—H⋯π overlap. The columns are linked to one another by C—H⋯π inter­actions and, in the case of (Ib), C—H⋯N hydrogen bonds. Crystals of (II) contain layers of monocations linked by π–π inter­actions and separated by both perchlorate anions and the protruding eth­yl groups; the cations and anions are linked by N—H⋯O hydrogen bonds.