The crystal engineering design strategy facilitates supramolecular synthesis of 13 new crystalline phases of carbamazepine (CBZ), an analgesic and anticonvulsant with known problems related to solubility and polymorphism. CBZ forms supramolecular complexes with the following molecules, all of which are complementary to CBZ in terms of hydrogen bonding and can therefore act as cocrystal formers:  acetone (1a); DMSO (1b); benzoquinone (1c); terephthalaldehyde (1d); saccharin (1e); nicotinamide (1f); acetic acid (1g); formic acid (1h); butyric acid (1i); trimesic acid (1j); 5-nitroisophthalic acid (1k); adamantane-1,3,5,7-tetracarboxylic acid (1l); and formamide (1m). Two distinct strategies based upon selection of complementary hydrogen-bond functionalities and previously known supramolecular synthons were utilized:  strategy I exploits the exofunctional nature of the carboxamide dimer as either a hydrogen-bond donor or a hydrogen-bond acceptor and thereby retains the carboxamide dimer that is present in all previously isolated forms of CBZ; strategy II perturbs the carboxamide homosynthon by forming a heterosynthon between the carboxamide moiety of CBZ and the carboxylic acid moieties. The latter approach profoundly modifies crystal packing and should therefore affect the physical and pharmaceutical properties of CBZ. A full analysis of crystal packing and a discussion of what these results might mean in the broader context of crystal engineering and pharmaceutical solids is presented.

X-ray analysis has revealed that 4,4′-bipyridine, 1,2-bis(4-pyridyl)ethylene, and hexamethylenetetramine form donor-acceptor complexes with 1,4-diiodobenzene, 1,4-diiodotetrafluorobenzene, and tetraiodoethylene in which the N‚‚‚I distance is longer than that for the corresponding I 2 complexes. As opposed to the corresponding I 2 complexes that are molecular adducts, these complexes have extended structures and longer N‚‚‚I distances. Steric and electronic effects influence the strength of the N‚‚‚I interaction and the crystal packing. An additional complex of 1,2-bis(4-pyridyl)ethane and 1,4-dibromotetrafluorobenzene has also been investigated for comparison of N‚‚‚I and N‚‚‚Br interactions.

The carboxylic acid-pyridine supramolecular heterosynthon can be exploited to predictably generate binary crystalline phases involving rac-ibuprofen, rac-flurbiprofen or aspirin.

A novel anionic metal-organic cube (MOC-1), [Ni(8)(HImDC)(12)](8-), has been synthesized by metal-ligand directed assembly of eight tri-connected Ni nodes and twelve doubly deprotonated bis(bidentate) imidazoledicarboxylic acid ligands (HImDC).

Chemical investigation of five Antarctic macroalgae whose tissues and crude extracts displayed ecologically relevant feeding deterrence in field bioassays was performed. Eleven compounds were characterized from the three red algae studied, of which four (1-3 and 9) were previously unreported, and four compounds were found from two brown algae, two (12 and 14) of which are new natural products. Several of these pure compounds have been individually investigated in ecological and/or pharmacological bioassays.

The self-assembly of [Cu2(dicarboxylate)2]4 nanoscale secondary building units (nSBUs) into coordination polymers can occur in such a way that a range of calix-like atropisomers can exist. Eight compounds have been prepared and crystallographically characterized via reaction between Cu(NO3)2 and angular dicarboxylate ligands:  {[Cu2(bdc)2(py)2]4•guest} n (1a), {[Cu2(bdc)2(py)2]4•4nitrobenzene•2EtOH} n (1b), {[Cu2(bdc)2(4-pic)2]4•4o-dichlorobenzene} n (2), {[Cu2(5-OEt-bdc)2(py)2]4•8H2O} n (3), {[Cu2(5-OPr-bdc)2(py)2]4•guest } n (4), {[Cu2(pdc)2(py)2]4•4MeOH} n (5), {[Cu2(pdc)2(4-pic)2]4•4H2O} n (6), and {[Cu2(tdc)2(MeOH)2]4•4naphthalene•8MeOH} n (7). The following atropisomers, all of which have also been observed in calixarenes, were observed:  (a) cone (1a, 3, and 4); (b) partial cone (1b); (c) 1,2-alternate (2 and 5−7); and (d) 1,3-alternate (1a, 3, and 4). The similarities and differences between the crystal structures of 1−7 are detailed herein.

The bis(aryl)diacetylenes 1,4-bis(3-quinolyl)-1,3-butadiyne (1), 1,4-bis(4-isoquinolyl)-1,3-butadiyne (2), and 1,4-bis(3-pyridyl)-1,3-butadiyne (3) form strongly halogen bonded complexes with organic iodides, including tetraiodoethylene (TIE), 1,4-diiodotetrafluorobenzene (F4DIB), and 1,4-diiodooctafluorobutane (F8DIBut). The crystal structures for the new donor, 2, as well as for six complexes, 1·TIE, 1·F4DIB, 2·TIE, 2·F4DIB, 3·(F4DIB)2, and 3 2· (F8DIBut)2, are reported. Extended chain structures consisting of donor and acceptor molecules are observed in all cases, except that of 3 2·(F8DIBut)2, which forms a molecular adduct. In most cases, the complexes segregate into columns of donors and acceptors, as is typical for this class of complexes. However, 1·F4DIB displays an unusual “crosshatched” pattern with each acceptor directly above the diacetylene moiety of another donor along the b-axis. In addition to 1·F4DIB, 3 2·(F8DIBut)2 also exhibits packing that does not consist of segregated stacks (i.e., the acceptor in the chain sits on top of one end of the donor and the uncomplexed F4DIB sits on top of the other end). Neither diacetylene 2, nor any of the complexes, pack in a manner that would allow for topotactic polymerization of the diacetylene moiety.

2-Mercapto-1-methylimidazole (mmim) forms complexes with organic iodides, 1,4-diiodotetrafluorobenzene (p-F4DIB), tetraiodoethylene (TIE), and 1,2-diiodotetrafluorobenzene (o-F4DIB), in which there are remarkably similar N−H···S hydrogen bonding and S···I halogen bonding patterns. Extended chains of alternating donor (mmim) and acceptor (p-F4DIB and TIE) molecules are formed through divalent I···S···I interactions. These chains are joined into double strands through N−H···S interactions that link two mmim molecules into a dimer. In the third complex, N−H···S bound dimers are linked into infinite chains through S···I interactions involving a pair of o-F4DIB molecules. Thermal analysis indicates that decomposition in both of the F4DIB complexes proceeds through total loss of acceptor, while decomposition of the TIE complex involves a combination of acceptor loss and acceptor reaction. Melting in the o-F4DIB complexes appears to be preceded by a solid-state rearrangement or premelting phenomenon that is not observed in the other two complexes. Crystal data for mmim· p-F4DIB:  monoclinic space group, C2/c (no. 15), a = 26.915(3) Å, b = 7.9216(6) Å, c = 14.2630(4) Å, β = 105.618(1)°, V = 2928.7(4) Å3, Z = 8, ρcalc = 2.34 g/cm3. Crystal data for mmim·TIE:  monoclinic space group, C2/c (no. 15), a = 20.1789(12) Å, b = 10.7824(10) Å, c = 14.5072(2) Å, β = 118.767(1)°, V = 2766.9(3) Å3, Z = 8, ρcalc = 3.10 g/cm3. Crystal data for mmim· o-F4DIB:  triclinic space group, P1̄ (no. 2), a = 7.4987(7) Å, b = 8.1906(12) Å, c = 11.6512(12) Å, α = 83.245(4)°, β = 84.695(3)°, γ = 86.135(3)°, V = 706.35(14) Å3, Z = 2, ρcalc = 2.43 g/cm3.