Piperazine–4,4'-Sulfonyldiphenol (1/2): a Self-Assembled Channel Structure

Self Cite

104

Phenylphosphonic acid–4,4′-bipyridyl (1/1), (1), C6H7O3P.C10H8N2, triclinic, P1¯, a = 6.9026 (8), b = 9.7086 (9), c = 12.201 (2) Å, α = 77.138 (9), β = 74.345 (10), γ = 75.477 (8)°, with Z = 2, is a salt, C10H9N2 +.[C6H5PO2(OH)]−, containing singly protonated 4,4′-bipyridyl cations: the cations and anions are linked by N—H...O and C—H...O hydrogen bonds in an R^{2}_{2}(7) motif and these aggregates are linked into centrosymmetric R^{2}_{2}(8) dimers by O—H...O hydrogen bonds; the dimer units are linked into chains by C—H...O hydrogen bonds. Phenylphosphonic acid–piperazine (2/1), (C6H7O3P)2.C4H10N2 (2), monoclinic, P21/n, a = 6.0042 (9), b = 19.746 (3), c = 8.651 (2) Å, β = 105.63 (2)°, with Z = 2, is a salt, C4H12N2 2+. [{C6H5PO2(OH)}−]2, containing doubly protonated piperazine: the anions are linked by O—H...O hydrogen bonds into centrosymmetric R^{2}_{2}(8) dimers and these dimers are linked to the centrosymmetric cations by N—H...O hydrogen bonds: each cation is hydrogen-bonded to four different anion dimers and each anion dimer is hydrogen-bonded to four different cations; the overall structure consists of two-dimensional sheets built from R^{4}_{6}(16) and R^{4}_{4}(18) rings. Phenylphosphonic acid–1,4-diazabicyclo[2.2.2]octane (2/1), (3), (C6H7O3P)2.C6H12N2, monoclinic, P21/n, a = 6.3607 (3), b = 21.8300 (11), c = 14.5965 (9) Å, β = 92.558 (6)°, with Z = 4, is a salt in which one nitrogen of the diamine is fully protonated and the other is partially protonated: the anionic components are linked into C(4) chains by O—H...O hydrogen bonds, and these chains are cross-linked via the diamines by means of N—H...O and O—H...N hydrogen bonds. The resulting sheets built from R^{8}_{8}(34) rings are linked by C—H...O hydrogen bonds into a three-dimensional framework.

Section: Molecular Dimensions and Conformationssupporting

confidence: 51%

Chain, Sheet and Framework Structures in the Adducts of Phenylphosphonic Acid with 4,4'-Bipyridyl (1/1), Piperazine (2/1) and 1,4-Diazabicyclo[2.2.2]octane (2/1)

Ferguson¹,

Glidewell²,

Gregson³

et al. 1998

Self Cite

104

“…Since the independent rotations of the two aryl rings relative to the central C 2 SO 2 core of this molecular building block do not alter the positions of the hydroxyl O atoms relative to this central core, then all points in the resulting two-dimensional conformational space should be accessible without affecting the intermolecular hydrogen bonding. However, the structures of compounds (5), (6) and (7) reported here, along with those of pure O 2 S(C 6 H 4 OH) 2 (Glidewell & Ferguson, 1996), as well as the adducts of this bisphenol with HMTA and its salts with piperazine (Coupar et al, 1996b) and cyclam (Ferguson et al, 1998a), show very clear conformational preferences. So, far from the conformations being randomly distributed, there is a clear preference for conformations in which one or both of the aryl rings are virtually coplanar with a neighbouring CÐS O fragment, with the formation of nearly planar S(5) HÐCÐCÐS O ring motifs.…”

Section: Molecular Dimensions and Conformationsmentioning

confidence: 68%

“…In the presence of more basic amines, proton transfer from the bisphenol to the amine is possible (Coupar et al, 1996b;Ferguson et al, 1998b). The resulting formation of the phenolate anion HOC 6 H 4 SO 2 C 6 H 4 O À leads to a radically different mode of supramolecular aggregation: instead of chains built of alternating bisphenol and amine molecules, linked by neutral OÐHÁ Á ÁN hydrogen bonds, the dominant mode of aggregation is that of phenolate anions linked together by means of the much stronger ionic (Aakero È y & Seddon, 1993;Gilli et al, 1994) OÐHÁ Á ÁO À hydrogen bonds.…”

Section: Introductionmentioning

confidence: 99%

“…The resulting formation of the phenolate anion HOC 6 H 4 SO 2 C 6 H 4 O À leads to a radically different mode of supramolecular aggregation: instead of chains built of alternating bisphenol and amine molecules, linked by neutral OÐHÁ Á ÁN hydrogen bonds, the dominant mode of aggregation is that of phenolate anions linked together by means of the much stronger ionic (Aakero È y & Seddon, 1993;Gilli et al, 1994) OÐHÁ Á ÁO À hydrogen bonds. In the 2:1 compound formed with piperazine, which is in fact the salt [H 2 N(CH 2 ) 4 NH 2 ] 2+ Á-2HOC 6 H 4 SO 2 C 6 H 4 O À (Coupar et al, 1996b), pairs of phenolate anions form R 2 2 (24) rings. The rings are joined together by the cations, by means of ionic N + Ð HÁ Á ÁO S and N + ÐHÁ Á ÁO À ÐC hydrogen bonds, to form stacks which enclose linear channels.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Crystal engineering using bisphenols: interwoven ladders, sheet and framework structures in the binary adducts of 4,4′-sulfonyldiphenol with pyrazine (2/1), 4,4′-bipyridyl (1/1), trans-1,2-bis(4-pyridyl)ethene (1/1), 1,2-bis(4-pyridyl)ethane (1/1) and 4,4′-trimethylenedipyridine (1/1), and in 4,4′-sulfonyldiphenol–4,4′-trimethylenedipiperidine–water (2/2/1)

Ferguson

Glidewell

Gregson

et al. 1999

The structures of six hydrogen-bonded adducts of 4,4'-sulfonyldiphenol with heteroaromatic amines have been determined. In 4,4'-sulfonyldiphenol-pyrazine (2/1) the pyrazine molecules lie across centres of inversion. The bisphenol molecules are linked into C(8) chains parallel to [100] by means of O-H.O=S hydrogen bonds, and antiparallel pairs of these chains are cross-linked by the pyrazine molecules, via O-H.N hydrogen bonds, to form molecular ladders containing R(6)(6)(50) rings between the rungs of the ladders. Each ladder is interwoven with two neighbouring ladders, thus producing a continuous two-dimensional sheet. The structure of 4,4'-sulfonyldiphenol-4,4'-bipyridyl (1/1) consists of spiral C(2)(2)(21) chains parallel to [010] containing alternating bisphenol and bipyridyl molecules linked by O-H.N hydrogen bonds: these chains are linked by two types of C-H.O hydrogen bonds which form C(5) chains along [001] and C(2)(2)(10) chains along [101], thus generating two interconnected nets characterized in the one case by a chequerboard pattern of R(6)(6)(44) and R(6)(6)(52) rings, and in the other by a single type of R(6)(6)(46) ring. 4,4'-Sulfonyldiphenol-trans-1,2-bis(4-pyridyl)ethene (1/1) [systematic name: 4,4'-sulfonyldiphenol-trans-4,4'-vinylenedipyridine (1/1)] and 4,4'-sulfonyldiphenol-1,2-bis(4-pyridyl)ethane (1/1) [systematic name: 4,4'-sulfonyldiphenol-trans-4,4'-ethylenedipyridine (1/1)] are isomorphous: the 1,2-bis(4-pyridyl)ethene component exhibits orientational disorder, corresponding approximately to a 180 degrees rotation of ca 23% of the molecules about the N.N vector; in each compound the structure is built from C(2)(2)(23) chains of alternating bisphenol and bis(pyridyl) molecules connected by O-H.N hydrogen bonds, running parallel to [112] and generated by translation. The [112] chains are linked by C-H.O hydrogen bonds which generate C(2)(2)(12) chains parallel to [101], so forming a two-dimensional net built from R(6)(6)(50) rings. The structure of 4,4'-sulfonyldiphenol-4,4'-trimethylenedipyridine (1/1) consists of C(2)(2)(24) chains parallel to [100] generated by translation and consisting of alternating bisphenol and bis(pyridyl) molecules linked by O-H.N hydrogen bonds. Pairs of such chains are coiled together to form double helices, and pairs of such double helices, of opposite hand, are linked together by paired C-H.O hydrogen bonds in R(2)(2)(10) rings to form pairs of interwoven ladders in which the C(2)(2)(24) chains form the uprights and the R(2)(2)(10) rings form the rungs, between which are R(6)(6)(50) rings: an R(2)(2)(10) ring belonging to one ladder lies at the centre of an R(6)(6)(50) ring belonging to the other. 4,4'-Sulfonyldiphenol-4,4'-trimethylenedipiperidine-water (2/2/1) is a salt, 2C(13)H(27)N(2)(+).2C(12)H(9)O(4)S(-).H(2)O, containing two independent singly protonated diamine cations, two independent bisphenolate anions, and neutral water molecules. The two independent diamine cations are linked by N-H.N hydrogen bonds into C(2)(2)(24) chains running parallel to [0...

“…Where both the bis-phenol and the diamine have some degree of conformational flexibility, the chains can coil, sometimes giving multiple helices, while in other examples the overall structure is controlled by soft hydrogen bonds : the suggestion has been made (Ferguson, Bell et al, 1997) that soft hydrogen bonds will be of little significance when the conformational flexibility of the chain components is reduced to a minimum, leading to a prediction of quasi-linear chains of extreme simplicity in such cases. In adducts of poly-phenols with secondary amines the N--H bonds can themselves also act as hydrogen-bond donors, as in the piperazine adducts with 4,4'-thiodiphenol, where there are hydrogen bonds of N H---yr(arene) type (Coupar et al, 1996b) and with 4,4'-sulfonyldiphenol and 1,1,1-tris(4-hydroxyphenyl)ethane, in both of which there are N--H..-O hydrogen bonds (Coupar et al, 1996c;Ferguson, Bell et aL, 1997). Similarly, in the adducts of piperazine and of 2,5-dimethylpiperazine with phenol itself (Loehlin et al, 1994) When NH2 groups are present, considerable structural complexity can result: in the adduct of the bisprimary amine 1,2-diaminoethane with phenol, of composition (C6H5OH)E.HENCH2CH2NH2 and containing equal numbers of NH 2 and OH groups, each NH2 and each OH group act as both a single donor and a single acceptor of hydrogen bonds, and the resulting structure is built from two-dimensional hydrogenbonded sheets (Loehlin et al, 1994).…”

Section: Introductionmentioning

confidence: 99%

Formation of One-Dimensional Chains, Two-Dimensional Bilayers and a Three-Dimensional Diamondoid Architecture in Hydrogen-Bonded Adducts of 4,4'-Biphenol with 1,4-Diazabicyclo[2.2.2]octane and 1,2-Diaminoethane

Ferguson¹,

Glidewell²,

Gregson³

et al. 1998

Self Cite

In 4,4′-biphenol–1,4-diazabicyclo[2.2.2]octane (1/1), C12H10O2.C6H12N2 (1), monoclinic, C2/c, a = 12.1510 (9), b = 6.3202 (4), c = 21.051 (2) Å, β = 98.875 (10)° with Z = 4, the biphenol units lie across twofold rotation axes and the diamine units are disordered across centres of inversion. The molecular components are linked by means of O—H...N hydrogen bonds into zigzag chains with graph set C^{2}_{2}(16) running parallel to the [201] direction; the chains are not coiled and there are no interactions between neighbouring chains. In 4,4′-biphenol–1,2-diaminoethane–methanol (2/1/1), (C12H10O2)2.C2H8N2.CH4O (2), triclinic, P1¯, a = 9.4592 (7), b = 10.6311 (10), c = 12.2085 (14) Å, α = 91.812 (9), β = 93.091 (6), γ = 90.652 (6)° with Z = 2, there are seven independent hydrogen bonds of O—H...O, O—H...N and N—H...O types and each oxygen and each nitrogen acts as a single donor and single acceptor of hydrogen bonds. The four independent components are linked by means of O—H...O and O—H...N hydrogen bonds into a linear aggregate, and further O—H...N and O—H...O hydrogen bonds generate chains in the [011] direction containing alternating biphenol and diamine units, and in the [021] direction containing methanol and pairs of biphenol molecules. These two types of chain intersect to form a continuous two-dimensional net, graph set R^{10}_{10}(62), with biphenol molecules at the nodes: pairs of these nets are linked into bilayers by N—H...O hydrogen bonds, but the nets are not interwoven. In 4,4′-biphenol–1,2-diaminoethane (1/1), C12H10O2.C2H8N2 (3), monoclinic, P21/a, a = 8.2121 (5), b = 5.3401 (3), c = 14.6014 (9) Å, β = 99.962 (7)° with Z = 2, each of the components lies across a centre of inversion. The O atoms act as single donors and double acceptors of hydrogen bonds and the N atoms as double donors and single acceptors, so that both oxygen and nitrogen are effectively four-coordinate; all the hydrogen bonds are of O—H...N or N—H...O type. Chains built from N—H...O and O—H...N hydrogen bonds run parallel to [100] and [010] and the intersection of these gives two-dimensional nets built from R^{6}_{6}(12) rings: these nets are linked by the —C6H4C6H4— and —CH2CH2— spacer units into a continuous three-dimensional diamondoid structure.