Manifestations of noncovalent bonding in the solid state. 6. [H₄(cyclam)]⁴⁺ (cyclam = 1,4,8,11-tetraazacyclotetradecane) as a template for crystal engineering of network hydrogen-bonded solids

Abstract

A series of salts of composition [H,(cyclam)]X~rlH,O, where cyclam = 1,4,8,1 l-tetraazacyclotetradecane and X = 4C1-(I-, 11 = 4). 4Br-(2, n = 4). 41-(3,17 = x), 4C10,-(4, tz = 2), 4CNS-(5, n = 2), 2S04'-(6, rz = 6), and @-CH,C,H,S03-) (7, rz = 0) have been prepared and crystal structures of 1,2,4,5,6, and 7 have been determined by single crystal X-ray crystallography. 1,2,3,4, and 7 were prepared by crystallizing cyclam with a large excess of the corresponding acid whereas the thiocyanate, 5, and the sulphate, 6, salts were prepared by metathesis of the perchlorate salt, 4, with KCNS and K2S04, respectively. Crystal data: 1: orthorhombic, Przrlb, n = 7.7962 (16) , and 7 exhibit extensive network hydrogen bonding between the anions, cations, and, if appropriate, water molecules of crystallization. The dimensionality of the hydrogen-bonded networks is dependent upon the nature of the anion and the number of water molecules of crystallization since the cation adapts a centrosymmetric exodentate conformation in all six salts.Keywords: crystal engineering, cyclams, network hydrogen bonding.Resume : On a prtpart une strie de sels de composition [H,(cyclam))]X.nH,O, dans lesquels cyclam = 1,4,8,11 -tttraazacyclotCtradCcane et X = 4 Cl-(11 = 4), 4 Br-(2, n = 4), 41-(3, n = x), 4 C10,-(4, n = 2), 4CNS-(5,n = 2), 2 SO: -(6, n = 6) et 4@-CH,C,H,SO<) (7, n = 0) et on a determine les structures cristallines des composts 1,2,4,5,6 et 7 par diffraction des rayons X. On a prtpart les composts 1,2,3,4 et 7 par cristallisation du cyclame avec un grand exces de I'acide correspondant alors que l'on a prepare les sels de thiocyanate, 5, et de sulfate, 6, par mttathkse du perchlorate. 4, avec respectivement du KCNS et du K,S04. Les donntes cristallines sont les suivantes. Author to whom correspondence may be addressed. Telephone: (902)

Liquid crystals derived from multi-cationic azamacrocyclic alkylsulphates

“…The d-spacings vary linearly with the number of carbon atoms in the alkyl chains according to the equation d (Å )~8.5 ¡0.5 z1.82 ¡0.04 n at 100 ‡C (figure 2). The Y-intercept, which is a measure of the thickness of the polar sublayer, is very close to the crystallographically determined distance between the sulphate groups in the hydrophilic layer of the cyclam tosylate salt [18] and therefore the tetraaza groups are almost orthogonal in the polar sublayer.…”

“…For the tetraaza derivatives in the crystalline phase, the spectra of the compounds contain in the N-H stretching region four bands at 3130, 3244, 3376 and 3465 cm 21 that are in agreement with those reported in the literature for guanidinium benzensulphonate [19] or for guanidinium benzene sulphonates [20], suggesting the formation of a hydrogen-bonded pattern between the sulphate and the amino groups. Although not explicitly stated in the literature, these bands can be assigned to the symmetric [16,18]. At temperatures just above the thermal transition detected by DSC, the absorption bands in the infrared spectra decrease in intensity, becoming broader while retaining their peak positions.…”

“…The protonated amino groups are directed away from the macrocycle, being located as far away as possible from each other to minimize electrostatic interactions [16]. As a result of the tendency to adopt this conformation, the molecule can simultaneously hydrogen bond up to eight different hydrogen bond acceptors such as carboxylate or sulphate groups [16][17][18]. Additionally in the case of the cyclam tosylate salt, the tosyl moieties arrange themselves to form hydrophobic regions above and below the hydrogen-bonded sheet comprising the polar layer [18].…”

4,11-Diaza-1,8-diazoniacyclotetradecane dichloride hemihydrate

“…For the crystal structure of [H 2 (cyclam)](ClO 4 ) 2 , see: Nave & Truter (1974). For the crystal structures of [H 4 (cyclam)]XÁ-nH 2 O [X = Cl 4 , Br 4 , (ClO 4 ) 4 , (SCN) 4 , (SO 4 ) 2 or (p-CH 3 C 6 H 4 SO 3 ) 4 ], see: Robinson et al (1989); Subramanian & Zaworotko (1995).…”

A Comparative Study of the Effect of Different Stabilizers on the Critical Quality Attributes of Self-Assembling Nano Co-Crystals

“…Crystal engineering is described as the exploitation of non-covalent interactions between molecular or ionic components for the rational design of solid-state materials [2,3]. The application of crystal engineering in pharmaceutics is usually related to understanding polymorphism and its associated properties.…”