Crystalline complexes of N,N'-ditritylurea (DTU) and N-tritylurea (NTU) hosts with molecular guests

This paper reports crystalline complexes of the new hosts N,N'-ditritylurea (DTU) and N-tritylurea (NTU) with various uncharged molecular guests. The crystal structures of the following complexes were elucidated by single crystal X-ray diffraction analysis at 115^oK: (I) 1:1 DTU-propanamide — space group C2/c, a=15.839Å, b=9.088Å, c=24.584Å, =111.05^o, Z=4; (II) 1:1 DTU-ethyl N-acetylglycinate — space group P1, a=9.010Å, b=10.800Å, c=19.810 Å, =105.29^o =94.33^o, =93.03^o, Z=2; (III) 2:1 NTU-N, N-dimethylformamide — space group Cc, a=29.614Å, b=8.906Å, c=16.127Å, =121.04^o, Z=4. The three crystal structures are stabilized mainly by a cooperative effect of hydrogen bonding between amide fragments displaced along the shortest axis of each crystal. This interaction occurs between host and guest in complexes I and II, and between host and host in complex III. The latter also represents a cage-type clathrate in which the guest molecules are accommodated in voids between the hydrophobic fragments of four neighboring NTU hosts. On the other hand, complexes of DTU are characterized by a more specific interaction between the two components, each guest molecule being inserted between two adjacent hosts (related by translation) and strongly bound to them via hydrogen bridges. These results illustrate a useful concept in the design of molecular species which can be potential hosts upon crystallization with neutral molecular guests. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82022 (7 pages).     

Crystallographic studies of the molecular complexes ofE,E-1[p-dimethylaminophenyl]-5-[o-hydroxyphenyl]-penta-1,4-dien-3-one 9DHDK) with chloroform (1:0.4),m-dinitrobenzene (1:1) andp-dimethylaminobenzaldehyde (1:1); the Heilbron complexes

Crystal structures are reported for the molecular complexes ofE,E-1-[p-dimethylaminophenyl]-5-[o-hydroxyphenyl]-penta-1,4-dien-3-one (DHDK) with chloroform,m-dinitrobenzene andp-dimethylaminobenzaldehyde. The three complexes (first reported by I. M. Heilbron and J. S. Buck [1] in 1921) have different structures. In DHDK·0.4 CHCl₃ (triclinic,a=12.086(6),b=10.323(5),c=8.015(4) Å, =94.58(6), =103.58(6), =110.10(6)^o,Z=2,P (assumed)), the host molecules are linked by two hydroxyl carbonyl hydrogen bonds to form centrosymmetric pairs, with the disordered CHCl₃ molecules contained in cavities left between the molecule pairs. The complex is a clathrate. In DHDK·m-dinitrobenzene (triclinic,a=21.787(9),b-13.850(5),c=7.759(4) Å, =88.25(5), =84.70(5), =88.86(5)^o,P ,Z=4) the DHDK molecules are linked in ribbons through head-to-waist hydroxyl-carbonyl hydrogen bonds. The guest molecules are contained in sinuous channels left between the DHDK ribbons; the host and guest molecules are approximately coplanar. Successive planes are mutually shifted so that the guest molecules are enclosed above and below by host molecules. This is a new structural type, with features resembling those of channel inclusion complexes. In DHDK·p-dimethylaminobenzaldehyde (monoclinic,a=22.331(9),b=12.238(5),c=8.904(4) Å, =92.99(5)^o,Z=4,P2₁/n) the host molecules are arranged so as to leave channels of approximately rectangular cross-sections in which the guest molecules are accommodated. Additional stabilization is achieved by hydrogen bonding between host hydroxyl and guest carbonyl groups. This is a channel-inclusion complex. In the chloroform andp-dimethylaminobenzaldehyde complexes the host molecule has thes-trans, trans conformation but in them-dinitrobenzene complex its conformation iss-cis, trans.Dedicated to Professor Friedrich Cramer on the occasion of his 60th birthday Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication NO. SUP 90076 (13 pages). To obtain copies, see page ii of this issue.Molecular Compounds and Complexes, Part XIV. For Part XIII, see [25].     

New synthesis and complexing properties ofp-tert-butyldihomooxacalix[4]arene. Structure of its 1∶2 complex with tetrahydrofuran

A new method is described for the synthesis of isolatedp-tert-butyldihomooxacalix[4]arene (CALO) with a 24% yield. The ability of CALO to form complexes in the solid state with small neutral molecules has been studied; the potential guests were common solvents bearing various chemical functions. The powder obtained after evaporation of the solvent has been characterized by the X-ray powder diffraction technique. Analysis of the patterns shows the non-complexation of linear alkanes and alcohols, but formation of complexes when the guest is cyclic or when it bears an amine or a ketone function. As illustration of the possible arrangement of molecules in complexes, the structure of the 1:2 complex with tetrahydrofuran (THF) is presented: the crystals are monoclinic, space groupP2₁/c,a=9.459(2) Å,b=17.286(2) Å,c=30.469(6) Å, =92.52(2)^o,V=4977(2) ų,Z=4,D _c=1.099 Mg m^–3, =1.54178 Å, =5.6 cm^–1,R=0.086 for 3590 reflections withF>4 (F); one of the THF molecules is inside the cavity of the macrocycle, while the other, in the interhost space, exhibits disorder. In the CALO molecule, three out of the fourtert-butyl groups are disordered which may induce the disorder of the THF molecule. Supplementary Data: relating to this article are deposited with the British Library: Supplementary Publication No. Sup. 82191 (29 pages).     

Diaqua[N,N-di(2-carboxyethyl)-o-anisidinato]copper(II) Dihydrate [Cu(o-Andp)(H2O)2] · 2H2O: Synthesis and Crystal Structure

Crystals of [Cu(o-Andp)(H₂O)₂] · 2H₂O (where o-Andp^2–is -anisidine-N,N-di-3-propionate) were synthesized and studied using X-ray diffraction analysis. The crystals are triclinic: a= 12.063(1) Å, b= 12.483(3) Å, c= 13.586(2) Å, = 91.29(1)°, = 111.67(1)°, = 104.00(1)°, V= 1830.5(5) ų, space group P , Z= 2, and R= 0.0528 for 5965 reflections with I2(I). The two crystallographically independent complexes are isostructural. The tetragonal–bipyramidal coordination of copper(III) involves three O atoms, the N atom of the tetradentate ligand o-Andp^2–, and two O atoms from water. The aminodipropionate group of the ligand (average Cu–O 1.939 Å and Cu–N 2.051 Å) and one of the coordinated water molecules (Cu–O(w) 1.991 Å) lie in the equatorial plane. The second water molecule (Cu–O(w) 2.32 Å) and the methoxy O atom of o-Andp^2–(Cu–O 2.37 Å) are in the apical positions of the bipyramid.     

Urea-water-anion Lattices Part 1. Crystal structures of (C2H5)4N+X−·(NH2)2CO·2 H2O (X=Cl,Br, CN), an isomorphous series of layer-type inclusion complexes

The title ternary complexes (1, X=Cl;2, X=Br;3, X=CN) have been prepared and characterized by X-ray crystallography. Crystal data: space groupP2₁/n,Z=4;1,a=7.505(2),b=14.556(4),c=14.453(3) Å, =98.13(2)^o, andR _F=0.088 for 1831 observed MoK data;2,a=7.483(1),b=14.643(6),c=14.443 Å, =98.25(2)^o, andR _F=0.113 for 923 data;3,a=7.490(2),b=14.646(5),c=14.594(5) Å, =98.85(5)^o, andR _F=0.082 for 915 data. In the isomorphous crystal structure of1 and2, ordered (C₂H₅)₄N⁺ cations are sandwiched between puckered layers matching the (020) family of planes, each being constructed from the cross-linking of planar zigzag chains of hydrogen-bonded urea molecules by the water molecules and halide ions. Compound3 has the same structure except that its cyanide group is disordered. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82066 (30 pages).Operated under contract DE-AC02-76CH00016 with the U.S. Department of Energy, Office of Basic Energy Science.     

Studies on clathrasils VIII. Nonasils-[4158], 88SiO2 · 8M8 · 8M9 · 4M20: Synthesis,thermal properties,and crystal structure

Nonasils-[4¹5⁸], 88SiO₂·8M⁸·8M⁹·4M²⁰, have been synthesized with 2-methylpyrrolidine, hexamethyleneimine, 2-(aminomethyl)-tetrahydrofuran, 1,2-diaminocyclohexane, 2-methylpiperidine, 2-methylpiperazine, 1-aminobutane, 2-aminobutane, and 2-aminopentane as guest molecules, M²⁰. The samples have been prepared from aqueous silicate solutions which were sealed in silica tubes and heated at about 200°C for several weeks. These clathrasils crystallize in space groupFmmm. For the nonasil with 2-aminopentane as the guest molecule and the unit cell dimensionsa _o=22.232(6) Å,b ₀=15.058(4) Å, andc _o=13.627(4) Å, the structure has been refined using 550 non-equivalent single crystal reflexions to a reliability factorR _w =0.125. The 3-dimensional 4-connected silica host framework has three types of cage-like voids, [5⁴6⁴], [4¹5⁸], and [5⁸6¹²], the latter housing the structure-controlling guest molecules, M²⁰. The non-spherical shape of the guest molecules is the most important factor for the formation of nonasils-[4¹5⁸]. On heating nonasils-[4¹5⁸] up to 950°C the organic guest species are driven out and the pure silica form of nonasil is obtained.Part of this study was presented at the 24th Jahrestagung der AGKr, Cologne, 1985 [1]. For part VII see [4].     

Inclusion complexes of the natural product gossypol. Recognition by gossypol of halogeno methanes. Structure of the dichloromethane complex of gossypol and single crystal conservation after decomposition

The structures of gossypol complexes are extremely sensitive to the halogenomethane present as the guest; e.g. changing the number of Cl atoms in chloromethane derivatives changes the structure of the gossypol complex. The crystals of C₃₀H₃₀O₈·CH₂Cl₂ are monoclinic, space groupC2/c,a=21.320(4),b=19.199(6),c=15.765(2)Å, =113.05(2)^o,V=5916(2)ų,Z=8,D _x=1.35 g/cm³,T=295 K. The structure has been solved by direct methods and refined to the finalR value of 0.084 for 1828 reflections. In the structure H-bonded gossypol molecules form columns, generating channels in the structure which are filled by guest molecules. After decomposition (desolvation) monocrystals of the complexes are conserved without destruction, in which there are rather wide and empty channels though slightly smaller than in the complex. An attempt is made to explain some peculiarities of the behavior of the gossypol polymorph formed on the basis of its structure with empty channels. Supplementary data relevant to this article have been deposited with the British Library Publication No. SUP 82165 (17 pages).     

1-Aminoadamantane as guest molecule in dodecasil 1H: an X-ray crystallographic study

Dodecasil 1H, 34SiO₂ · 3M¹² · 2M¹² · 1M²⁰ with M¹², M¹²=N₂ and M²⁰=1-aminoadamantane, is hexagonal witha=13.825(2) Å,c=11.189(2) Å and crystallizes in space groupP6/mmm. With 767 unique reflexions the structure has been refined to a weighted reliability factorR _w =0.054. The three-dimensional four-connected host framework is built by corner sharing [SiO₄] tetrahedra and shows three types of cagelike voids, [5¹²] cages, [4³5⁶6³] cages and [5¹²6⁸] cages, the latter housing the 1-aminoadamantane guest molecule. Difference Fourier synthesis (obs)-(calc(Si,O)) delineate the guest molecules within the different types of cage. Residual electron densities reveal positional disorder of the 1-aminoadamantane guest molecule. Four crystallographically different preferred orientations for the 1-aminoadamantane guest molecule are found.     

Preparation and x-ray structure determination of penta-and tetracyano-oxomolybdenum(IV) anions. The influence of water on their reactivity

Summary Several penta-and tetracyanooxomolybdenum(IV) anions have been synthesized containing different numbers of H₂O molecules, either coordinated or present as crystallisation molecules. The influence of these molecules on the reactivity of the complex, especially towards O₂, is discussed. Three compounds were characterized by x-ray structure determination. [Mo(O)(CN)₅(H₂O)₂(MeCN)₂][PPh₄]₄Cl belongs to triclinic space group P-1 witha=13.146(3) Å,b=16.944(5) Å,c=21.761(6) Å, =84.72(2)°, =87.15(2)° and =85.25(2)°. The volume of the unit cell is 4678(6)ų withz=2. The structure was refined to R=6.5%. [Mo(O)(CN)₄(H₂O)·6H₂O][PPh₄]₂ belongs to monoclinic space group P2₁/n witha=15.313(2)Å,b=19.983(3)Å,c=17.006(2)Å, =100.51(2)°. The volume of the unit cell is 5117(3)ų withz=4. The structure was refined to R=8.7%. [Mo(O)(CN)₄(MeCN)](PH₃)₂N]₂ belongs to triclinic space group P-1 witha=13.770(4)Å,b=16.292(5)Å,c=16.889(5)Å, =73.23(2)°, =72.02(2)° and =71.57(2)°. The volume of the unit cell is 3342(3)ų withz=2. The structure was refined to R=7.2%.     

Crystal and Molecular Structures of (Dibenzo-18-Crown-6)(Nitrato-O,O")-Tetrahydrofuranpotassium, [K(DB18C6)(THF)(NO3)]

The (dibenzo-18-crown-6)(nitrato-O,O")tetrahydrofuranpotassium complex [K(DB18C6)(THF)(NO₃)] (I) was synthesized and studied using X-ray diffraction analysis. The crystals are orthorhombic: a= 9.608 Å, b= 9.926 Å, c= 27.234 Å, Z= 4, space group P2₁2₁2₁. The structure was solved by the direct method and refined by the least-squares method in the anisotropic approximation to R= 0.099 over all 2620 measured independent reflections (CAD4 automated diffractometer, MoK radiation). Complex Iin the crystal exists as individual host–guest molecules, the K⁺cation (CN 9) being located in the DB18C6 macrocycle cavity and being coordinated to its six oxygen atoms and to two oxygen atoms of the nitrato ligand on one side of the macrocycle and to the THF oxygen atoms on the other side. The DB18C6 molecule in Ihas a butterfly conformation with approximate C _2V symmetry.     

Synthesis, structure of [H3dien]·(MF6)·H2O (M=Cr, Fe) and Fe Mössbauer study of [H3dien]·(FeF6)·H2O

Single crystals of [H₃dien]·(FeF₆)·H₂O (I) and [H₃dien]·(CrF₆)·H₂O (II) are obtained by solvothermal synthesis under microwave heating. I is orthorhombic (Pna2₁) with a=11.530(2) Å, b=6.6446(8) Å, c=13.787(3) Å, V=1056.3(2) Å³ and Z=4. II is monoclinic (P2₁/c) with a=13.706(1) Å, b=6.7606(6) Å, c=11.3181(9) Å, β=99.38(1)°, V=1034.7(1) Å³ and Z=4. The structure determinations, performed from single crystal X-ray diffraction data, lead to the R₁/wR₂ reliability factors 0.028/0.066 for I and 0.035/0.102 for II. The structures of I and II are built up from isolated FeF₆ or CrF₆ octahedra, water molecules and triprotonated amines. In both structures, each octahedron is connected by hydrogen bonds to six organic cations and two water molecules. The iron-based compound is also characterized by ⁵⁷Fe Mössbauer spectrometry: the hyperfine structure confirms the presence of Fe³⁺ in octahedral coordination and reveals the existence of paramagnetic spin fluctuations.     

Synthesis and crystal structure of a cubane-like molybdenum copper sulphur bromide cluster [MoCu3S3Br(SCH2CH2S)(PPh3)3]·MeCN

Summary [MoCu₃S₃Br(SCH₂CH₂S)(PPh₃)₃]·MeCN, MW=1382.78, space group Pl, has the triclinic cell parametersa=12.272(11),b=13.172(7),c=20.363(3)Å, =106.26(3)^o, =95.64(5)^o, =65.79(6)^o; Z=2, V=2881.4ų. Dc=1.55 g cm^–3. MoK radiation. =0.71073Å, =22.8 cm^–1. F(000)=1348. R=0.69 for 4964 observed unique reflections [I>3(I)]. There are some distortions in the cubane-like MoCu₃S₃Br core, with three form Mo–Cu bonds. The Mo atom is bound by chelating SCH₂CH₂S and three ₃-S atoms.     

Three-dimensional molecular network, [{Cu(dps)2(SO4)}·3H2O·DMF]n, and its different third-order NLO performance (dps=4,4′-dipyridyl sulfide)

A new three-dimensional non-interpenetrating coordination polymer, [{Cu(dps)₂(SO₄)}·3H₂O·DMF]_n (1) (dps=4,4′-dipyridyl sulfide) was synthesized and structurally characterized. 1 crystallizes in triclinic system, space group P−1 with cell parameters of a=10.9412(1) Å, b=11.8999(1) Å, c=12.5057(1) Å, V=1400.7(3) Å³, Z=2, D_c=1.573 g cm⁻³, F(0 0 0)=686, μ=1.059 mm⁻¹. R₁=0.0436, wR₂=0.1148. In the polymeric architecture, serve as bridging coligands to connect highly puckered [Cu₂(dps)₂]_n frameworks resulting in a 3D motif containing channels for guest molecule inclusion. Quantum chemistry calculation shows that the third-order NLO properties of polymer 1 are controlled by groups and dps ligands, and metal ions have less influence on the third-order NLO properties.     

Topologically novel copper molybdate phases based on 3,4′-dipyridylketone: Hydrothermal synthesis, structural characterization, and magnetic properties

Hydrothermal treatment of CuCl₂·2H₂O, MoO₃, and 3,4′-dipyridylketone (3,4′-dpk) in 1:1:2 mole ratio afforded the new mixed metal oxide phases [Cu₂(MoO₄)₂(3,4′-dpk)(H₂O)] (1) or [Cu₄(3,4′-dpk)₄(Mo₈O₂₆)] (2), depending on the pH of the initial reaction mixture. Compound 1 possesses unique one-dimensional (1-D) [Cu₂(MoO₄)₂(H₂O)]_n ribbons constructed from the linkage of {Cu^II₄O₆} tetrameric units through isolated [MoO₄]^2- tetrahedra. These ribbons in turn are connected into a two-dimensional (2-D) coordination polymer structure by tethering 3,4′-dpk ligands. Compound 2, containing monovalent copper ions, manifests an unprecedented “X-rail” 1-D extended structure with (6²8)₄(6⁶) topology formed from the bracketing of discrete [β-Mo₈O₂₆]^4- anions by four chains. The variable temperature magnetic susceptibility behavior of 1 was fit to a linear tetramer model, with g=2.03(3), J₁=25.8(7) cm^-1 and J₂=−46(1) cm^-1. Antiferromagnetic inter-tetramer interactions (zJ′=−0.21(3) cm^-1) were also evident. Crystallographic data: 1 monoclinic, P2₁/c, a=10.3911(11) Å, b=6.9502(6) Å, c=22.958(2) Å, β=100.658(7)°, V=1629.5(3) Å³, R₁=0.1256, and wR₂=0.2038; 2 triclinic, a=10.9000(3) Å, b=11.7912(4) Å, c=13.5584(4) Å, α=102.482(2)°, β=102.482(2)°, γ=117.481(2)°, V=1450.98(8) Å³, R₁=0.0428, and wR₂=0.0630.     

Crystalline inclusion compounds of tetrabenzo-18-crown-6 with uncharged organic molecules. Solid-state structure of the nitroethane complex

Tetrabenzo-18-crown-6 (1) shows distinct solid-state inclusion properties towards a number of OH-acidic, CH-acidic and low-polar uncharged organic molecules. The single crystal X-ray analysis of the inclusion complex between1 and EtNO₂ (11) is reported. Crystals are monoclinic,P2₁/c, witha=12.887(1),b=19.365(2),c=10.776(1) Å, =96.33(2)^o,D _c=1.321g cm^–1,Z=4. The host macroring has a conformation similar to a dentist's-chair. The complex is stabilized mainly by C–H...O type interactions involving the methyl group of the EtNO₂ guest molecule which is highly disordered. The nitroethane guests are trapped in channels formed by the host macrocycles. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82150 (11 pages)     

Synthesis and single crystal structures of ternary phosphides Li4SrP2 and AAeP (A=Li, Na; Ae=Sr, Ba)

Two new (NaSrP, Li₄SrP₂) and two known (LiSrP, LiBaP) ternary phosphides have been synthesized and characterized using single crystal X-ray diffraction studies. NaSrP crystallizes in the non-centrosymmetric hexagonal space group (#189, a=7.6357(3) Å, c=4.4698(3) Å, V=225.69(2) Å³, Z=3, and R/wR=0.0173/0.0268). NaSrP adopts an ordered Fe₂P structure type. PSr₆ trigonal prisms share trigonal (pinacoid) faces to form 1D chains. Those chains define large channels along the [001] direction through edge-sharing. The channels are filled by chains of PNa₆ face-sharing trigonal prisms. Li₄SrP₂ crystallizes in the rhombohedral space group (#166, a=4.2813(2) Å, c=23.437(2) Å, V=372.04(4) Å³, Z=3, and R/wR=0.0142/0.0222). In contrast to previous reports, LiSrP and LiBaP crystallize in the centrosymmetric hexagonal space group P6₃/mmc (#194, a=4.3674(3) Å, c=7.9802(11) Å, V=131.82(2) Å³, Z=2, and R/wR=0.0099/0.0217 for LiSrP; a=4.5003(2) Å, c=8.6049(7) Å, V=150.92(2) Å³, Z=2, and R/wR=0.0098/0.0210 for LiBaP). Li₄SrP₂, LiSrP, and LiBaP can be described as Li₃P derivatives. Li atoms and P atoms make a graphite-like hexagonal layer, . In LiSrP and LiBaP, Sr or Ba atoms reside between layers to substitute for two Li atoms of Li₃P, while in Li₄SrP₂, Sr substitutes only between every other layer.     

Structural study of the 1:1 clathrate of an asymmetric calix[4]arene and acetone

The crystal and molecular structure of the 1:1 clathrate of the asymmetric calix[4]arene,1, and acetone has been determined by X-ray analysis. The crystal data are: tetragonal, space groupP4/n,a=b=12.574(6),c=12.572(6) Å,V=1988(2) ų,Z=2,D _x =1.111 g cm^–3,D _m =1.108 g cm^–3. Least-squares refinement based on 1131 observed reflections withF ₀>3(F ₀) and anisotropic temperature factors led toR=0.096. In spite of the molecular asymmetric calixarene1 the crystal structure has high symmetry, because a part of the host and guest molecules are in disordered states.     

Reactivity of cyclopalladated compounds derived from biphenyl-2-ylamine towards carbon monoxide, butyl isocyanide and alkynes

The reactivity of the dimeric cyclopalladated compounds derived from biphenyl-2-ylamine (μ-X)₂[κ²-N2′,C1-1-Pd-2-{(2′-NH₂C₆H₄)C₆H₄}]₂ [X = OAc (1), X = Cl (2)] towards unsaturated organic molecules is reported. Compound 1 reacted with carbon monoxide and ^tbutyl isocyanide producing phenanthridin-6(5H)-one and N-tert-butylphenanthridin-6-amine in 63% and 88% yield, respectively. Compound 2 reacted separately with diphenylacetylene and 3-hexyne, affording the mononuclear organopalladium compounds [κ²-N2″,C1-η²-C2,C3- 1-Pd{(R-CC-R)₂-2′-(2″-NH₂C₆H₄)C₆H₄}Cl] [R = Ph (5), R = Et (6)] in 50-60% yield, which derived from the insertion of two alkyne molecules into the C-Pd σ bonds of 2. The crystal structure of compounds 5 and 6 has been determined. Compound 5 crystallized in the monoclinic space group P2₁/n with a = 13.3290(10) Å, b = 10.6610(10) Å and c = 22.3930(10) Å and β = 100.2690(10)°. Compound 6 crystallized in the triclinic space group with a = 7.271(7) Å, b = 10.038(3) Å and c = 16.012(5) Å, and α = 106.79(3)°, β = 96.25(4)° and γ = 99.62(4)°. The crystal structures of 5 and 6 have short intermolecular Pd-Cl?H-N-Pd non-conventional hydrogen bonds, which associated the molecules in chains in the first case and in dimers in the second.     

Coordination chemistry of alkali and alkaline earth cations: Crystal structure of rubidium (benzo-15-crown-5)2NO3·H2O

The complex Rb(B15C5)₂NO₃·H₂O is monoclinic,P2_1/c,a=12.695(3),b=19.471(3),c=12.991(2)Å, =99.60(2)^o,V=3166 ų,D _c =1.473 g/cm³ (163 K),D _c =1.434 g/cm³ (298 K),D _o =1.44 g/cm³ (298 K),T=163K,Z=4, MoK=0.71069 Å, 2(4^o–53^o), =16.43 cm^–1,F(000)=1424. FinalR for the 4588 observed reflections (F>3) is 0.062. All ten oxygens of the two benzo-crowns are shown to coordinate to the rubidium ion (Rb...O,2.92 to 3.07 Å) forming a charge-separated sandwich. The nearest nitrate oxygen is displaced 6.51 Å from the rubidium ion and is hydrogen bonded to a water molecule. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82028 (28 pages)     

Hydrogen bonding in 2-hydroxybenzoic, 2-hydroxythiobenzoic,and 2-hydroxydithiobenzoic acid. A structural and spectroscopic study

Summary X-ray structural data are reported for 2-hydroxythiobenzoic acid (T=200 K;P2₁/a;a=14.903(5) Å,b=5.203(3) Å,c=9.114(6) Å, =92.40(4)°;Z=4;R=0.049) and 2-hydroxydithiobenzoic acid (T=297 K;P2₁/a;a=14.416(3) Å,b=13.447(3) Å,c=3.947(1) Å, =90.96(2)°;Z=4;R=0.047). In 2-hydroxythiobenzoic acid, each two molecules form cyclic dimersvia S-H...O=C hydrogen bonds, analogous to the association pattern of 2-hydroxybenzoic acid. In 2-hydroxydithiobenzoic acid, the molecules are linked to chains by S-H...O(H)-C hydrogen bonds. Solid state IR, and solution IR and NMR spectroscopic data of 2-hydroxybenzoic acid, 2-hydroxythiobenzoic acid, and 2-hydroxydithiobenzoic acid are summarized. The main characteristics of the intramolecularly associated phenolic O-H groups of the three title compounds are for the solids, for solutions (CCl₄), and _OH=10.21, 10.53, 12.20 ppm for solutions (CCl₄:CDCl₃=5:1).Dedicated to Prof.O. Olaj on the occasion of his 60^th birthday