A time-resolved infrared vibrational spectroscopic study of the photo-dynamics of crystalline materials.

Time-resolved infrared vibrational spectroscopy is a structurally sensitive probe of the excited-state properties of matter. The technique has found many applications in the study of molecules in dilute solution phase but has rarely been applied to crystalline samples. We report on the use of a sensitive pump-probe time-resolved infrared spectrometer and sample handling techniques for studies of the ultrafast excited-state dynamics of crystalline materials. The charge transfer excited states of crystalline metal carbonyls and the proton transfer of dihydroxyquinones are presented and compared with the solution phase.

Photocrystallographic structure determination of a new geometric isomer of [Ru(NH3)4(H2O)(eta1-OSO)][MeC6H4SO3]2.

The structure of a new metastable geometric isomer of [Ru(NH3)4(H2O)(SO2)][MeC6H4SO3]2 in which the SO2 group is coordinated through a single oxygen in an eta1-OSO bonding mode has been determined at 13 K; the new isomer was obtained as a 36% component of the structure within a single crystal upon irradiation using a tungsten lamp.

1,4,8,11-Tetraazoniacyclotetradecane tetrakis(phenylphosphonate) dihydrate forms hydrogen-bonded sheets.

In the title compound, C(10)H(28)N(4)(4+).4C(6)H(6)O(3)P(-).2H(2)O, the cation lies across a centre of inversion in space group P2(1)/n. The two independent anions and the water molecule are linked by four O-H.O hydrogen bonds [H.O = 1.74-2.15 (3) A, O.O = 2.5482 (14)-3.0438 (16) A and O-H.O = 160-176 (2) degrees ] into sheets containing equal numbers of centrosymmetric R(6)(6)(16) and R(10)(10)(36) rings. The cation lies at the centre of the R(10)(10)(36) ring and is linked to it by eight N-H.O hydrogen bonds [H.O = 1.77-1.98 A, N.O = 2.6756 (15)-2.8168 (16) A and N-H.O = 151-169 degrees ].

4,4'-Trimethylenedipyridinium bis[carboxymethylphosphonate(1-)]: a three-dimensional framework structure built from O-H...O, N-H...O and C-H...O hydrogen bonds.

In the title compound, C(13)H(16)N(2)(2+).2C(2)H(4)O(5)P(-), the cation lies across a twofold rotation axis in space group Fdd2. The anions are linked into molecular ladders by two O-H.O hydrogen bonds [H.O = 1.73 and 1.77 A, O.O = 2.538 (2) and 2.598 (3) A, and O-H.O = 160 and 170 degrees ], these ladders are linked into sheets by a single type of N-H.O hydrogen bond [H.O = 1.75 A, N.O = 2.624 (3) A and N-H.O = 171 degrees ] and the sheets are linked into a three-dimensional framework by a single type of C-H.O hydrogen bond [H.O = 2.48 A, C.O = 3.419 (4) A and C-H.O = 167 degrees ].

meso-5,5,7,12,12,14-Hexamethyl-4,11-diaza-1,8-diazoniacyclotetradecane (S)-malate(2-) methanol disolvate: a chain of rings generated by two pairs of N-H.O hydrogen bonds.

The title compound is a methanol-solvated salt, C(16)H(38)N(4)(2+).C(4)H(4)O(5)(2-).2CH(3)OH, in which the ionic components are linked into chains by two pairs of N-H.O hydrogen bonds [H.O = 1.78-2.21 A, N.O = 2.702 (14)-3.094 (8) A and N-H.O = 160-179 degrees ]. The methanol molecules are pendent from the chain and are linked to it by O-H.O hydrogen bonds [H.O = 1.86 and 1.89 A, O.O = 2.691 (9) and 2.708 (16) A, and O-H.O = 168 and 165 degrees ].

meso-5,5,7,12,12,14-hexamethyl-1,4-diaza-8,11-diazoniacyclotetradecane bis(2-naphthoate) ethanol disolvate: centrosymmetric five-component aggregates linked into sheets by C-H...pi(arene) hydrogen bonding.

The title compound is an ethanol-solvated salt, C(16)H(38)N(4)(2+) x -2C(11)H(7)O(2)(-) x -2C(2)H(6)O, in which the cation lies across a centre of inversion in P2(1)/c. The ions are linked by N-H...O hydrogen bonds [H...O = 1.70 and 2.30 A, N...O = 2.624 (2) and 3.136 (2) A, and N-H...O = 178 and 151 degrees ], and the ethanol molecule is linked to the anion by an O-H...O hydrogen bond [H...O = 1.90 A, O...O = 2.728 (2) A and O-H...O = 171 degrees ], to form a centrosymmetric five-component aggregate. C-H...O hydrogen bonds and aromatic pi-pi-stacking interactions are absent, but the aggregates are linked into sheets by a single C-H...pi(arene) hydrogen bond.

Phosphonopropionic acid as a building block in supramolecular chemistry: salts with organic diamines.

The structures of seven salts formed by phosphonopropionic acid with organic diamines are reported; in these salts, the hydrogen-bonded substructures formed by the anions can be zero-, one- or two-dimensional, while the overall hydrogen-bonded supramolecular structures are three-dimensional. The 1:1 adduct, compound (1), formed between 1,2-bis(4'-pyridyl)ethene and phosphonopropionic acid is a salt, [[(C(12)H(10)N(2))H(2)](2+)].[(C(12)H(10)N(2))].[(C(3)H(6)O(5)P)(-)](2), in which both diamine components lie across centres of inversion in space group P2(1)/c. The anions form hydrogen-bonded head-to-head dimers, and these are linked by the two diamine units into sheets, which are themselves linked by C-H.O hydrogen bonds. With 2,2'-dipyridylamine the acid forms the hydrated salt [[(C(10)H(9)N(3))H](+)].[(C(3)H(6)O(5)P)(-)].H(2)O (2), in which all components are disordered with occupancy 0.5 in space group Fmm2. The anions form head-to-tail dimers, which are linked into sheets by the cations, and the sheets are linked into a three-dimensional framework by the water molecules. The piperazine salt [[(C(4)H(10)N(2))H(2)](2+)].[(C(3)H(5)O(5)P)(2-)] (3) contains simple anion chains linked into a three-dimensional framework by the two independent cations, both of which are centrosymmetric. In the hydrated salt formed by N,N'-dimethylpiperazine, [[(MeNC(4)H(8)NMe)H(2)](2+)].[(C(3)H(6)O(5)P)(-)](2).(H(2)O)(2) (4), head-to-tail anion chains combine with the water molecules to form a three-dimensional framework, which encloses voids that contain the cations. In the 4,4'-bipyridyl adduct [[(C(10)H(8)N(2))H(0.72)](0.72+)].[[(H(0.5)O)(3)PCH(2)CH(2)COOH(0.78)](0.72-)] (5), there is extensive disorder of the H atoms that are bonded to N and O atoms, and the anion chains are linked by the cations into sheets, which are themselves linked by C-H.O hydrogen bonds. In the 1:2 adduct formed with 1,2-bis(4'-pyridyl)ethane, [[(C(12)H(12)N(2))H(2)](2+)].[(C(3)H(6)O(5)P)(-)](2) (6), where the cation lies across an inversion centre, the anions form molecular ladders. These ladders are linked into sheets by the cations, which are themselves linked by C-H.O hydrogen bonds. In the methanol-solvated salt formed with 2,6-dimethylpiperazine, [[(C(6)H(14)N(2))H(2)](2+)].[(C(3)H(6)O(5)P)(-)](2). (CH(4)O)(0.34) (7), the anions form sheets that are linked into a three-dimensional framework by the cations. The supramolecular structures are compared with those of analogous salts formed by phosphonoacetic acid.

The 1:1 adduct of triphenylsilanol and 4,4'-bipyridyl, and three pairwise-concomitant triclinic polymorphs of the 4:1 adduct having Z' = 0.5, 1 and 4.

Crystallization from methanol solution of mixtures of triphenylsilanol and 4,4'-bipyridyl has given a 1:1 adduct (I), Ph(3)SiOH.C(10)H(8)N(2), and three polymorphic 4:1 adducts (II)-(IV), (Ph(3)SiOH)(4).C(10)H(8)N(2). In (I), the components are linked by a single O-H...N hydrogen bond and by a number of C-H...pi(arene) hydrogen bonds to form a continuous three-dimensional structure. Compounds (II)-(IV) are all triclinic, space group P-1, with Z' values of 0.5, 1 and 4, respectively. The basic hydrogen-bonded aggregate is the same in each of (II)-(IV), having a pair of silanol molecules linked to the bipyridyl via O-N...N hydrogen bonds and a further pair of silanol molecules linked to the first pair via O-H...O hydrogen bonds. In (II) there is just one such aggregate lying across a centre of inversion (Z' = 0.5) and in (III) there are two such aggregates, both lying across centres of inversion (Z' = 2 x 0.5 = 1). In (IV) there are six independent aggregates of this type, four of which lie across centres of inversion and two of which lie in general positions, so that Z' = (4 x 0.5) + 2 = 4. While the components in (I) are fully ordered, each of (II)-(IV) exhibits extensive disorder involving both the bipyridyl units and the phenyl rings of the silanol components.

Phosphonoacetic acid as a building block in supramolecular chemistry: salts with organic polyamines.

Phosphonoacetic acid, (HO)(2)P(O)CH(2)COOH, forms adducts with a range of amines. The acid component in these adducts may be the neutral molecule C(2)H(5)O(5)P, the mono-anion (C(2)H(4)O(5)P)(-) or the di-anion (C(2)H(3)O(5)P)(2-). The substructure formed by the acid component takes the form of simple chains in compounds (1)-(3), which are the 1:1 adducts formed with 1,4-diazabicyclo[2.2.2]octane, 4,4'-bipyridyl and 1,3-trimethylenedipiperidine, respectively. These adducts contain C(2)H(5)O(5)P, (C(2)H(4)O(5)P)(-) and (C(2)H(3)O(5)P)(2-), respectively, although (3) is solvated by a mixture of methanol and water. The (C(2)H(4)O(5)P)(-) anion substructure in (4), which is the adduct formed with meso-5,5,7,12,12,14-hexa-C-methyl-1,4,8,11-tetraazacyclotetradecane, is a chain of spiro-fused rings, while the substructure in (5), which is the adduct formed with 2,2'-dipyridylamine, is a chain of edge-fused rings. In (6), the adduct formed with 1,2-bis(4'-pyridyl)ethane, the anion substructure is two-dimensional. The chain substructures are linked by the amine units into two-dimensional structures in (1) and (4) and into three-dimensional frameworks in (2), (3) and (5), while the anion sheets in (6) are likewise linked by the amine units into a three-dimensional framework.

Salts of maleic and fumaric acids with organic polyamines: comparison of isomeric acids as building blocks in supramolecular chemistry.

Maleic acid and fumaric acid both readily form adducts with organic diamines: maleic acid usually forms 2:1 adducts with bases, while fumaric acid usually forms 1:1 adducts, and the supramolecular structures within the two series are not simply related. The 1:2 adducts formed by 1,2-bis(4-pyridyl)ethane and by 4,4'-bipyridyl, respectively, with maleic acid, compounds (1) and (2), are salts [(diamine)H(2)(2+)].[(C(4)H(3)O(4))(-)](2) in which the cations lie across a centre of inversion and a twofold rotation axis, respectively. The ions are linked by N-H...O hydrogen bonds into three-ion aggregates, which are further linked by C-H...O hydrogen bonds into two- and three-dimensional arrays, respectively. In the fumarate salts formed by 2,2'-dipyridylamine (1:1) and 1,4-diazabicyclo[2.2.2]octane (1:2), compounds (3) and (4), the ionic components are linked into molecular ladders. The 1:1 adduct of 4,4'-bipyridyl and fumaric acid, compound (5), contains two neutral components, both of which lie across centres of inversion; these components are linked into chains by a single O-H...N hydrogen bond and thence into sheets by C-H...O hydrogen bonds. The corresponding adduct formed by 1,4-diazabicyclo[2.2.2]octane, compound (6), is a salt that again contains chains linked into sheets by C-H...O hydrogen bonds. In the 1:1 adducts, compounds (7), (8) and (10), that are formed between 1,2-bis(4-pyridyl)ethane, 4,4'-trimethylenedipyridine and hexamethylenetetramine, respectively, with fumaric acid, and in the 1:2 adduct, compound (9), of 2,2'-dipyridylamine and maleic acid, the chains that are generated by the hard hydrogen bonds are linked by C-H...O hydrogen bonds to form, in each case, a single three-dimensional framework. In the 1:1 adduct, compound (11), of 2,2'-bipyridyl and fumaric acid the hydrogen bonds generate two interwoven three-dimensional frameworks.

A triclinic polymorph of benzanilide: disordered molecules form hydrogen-bonded chains.

In the P-1 polymorph of benzanilide or N-phenylbenzamide, C(13)H(11)NO, the molecules are linked into simple C(4) chains by N-H...O hydrogen bonds. The molecules exhibit orientational disorder, but the donor and acceptor in a given hydrogen bond may occur, independently, in either the major or the minor orientation, such that all four possible N-H.O combinations have very similar geometries. The structure of this P-1 polymorph can be related to that of a previously reported C2/c polymorph.

Two polymorphs, with Z' = 1 and 2, of 2-amino-4-chloro-6-morpholinopyrimidine in P21/c, and 2-amino-4-chloro-6-piperidinopyrimidine, which is isomorphous and almost isostructural with the Z' = 2 polymorph.

Crystallization of 2-amino-4-chloro-6-morpholinopyrimidine, C(8)H(11)ClN(4)O, (I), yields two polymorphs, both with space group P2(1)/c, having Z' = 1 (from diethyl ether solution) and Z' = 2 (from dichloromethane solution), denoted (Ia) and (Ib), respectively. In polymorph (Ia), the molecules are linked by an N-H...O and an N-H...N hydrogen bond into sheets built from alternating R(2)(2)(8) and R(6)(6)(40) rings. In polymorph (Ib), one molecule acts as a triple acceptor of hydrogen bonds and the other acts as a single acceptor; one N-H...O and three N-H...N hydrogen bonds link the molecules in a complex chain containing two types of R(2)(2)(8) and one type of R(4)(4)(18) ring. 2-Amino-4-chloro-6-piperidinopyrimidine, C(9)H(13)ClN(4), (II), which is isomorphous with polymorph (Ib), also has Z' = 2 in P2(1)/c, and the molecules are linked by three N-H...N hydrogen bonds into a centrosymmetric four-molecule aggregate containing three R(2)(2)(8) rings.

N,N'-Dithiobisphthalimide-nitrobenzene (2/1): a Pn solvate with localized solvent molecules ordered head-to-tail in channels.

N,N'-Dithiobisphthalimide crystallizes from nitrobenzene solution as a solvate, 2C(16)H(8)N(2)O(4)S(2).C(6)H(5)NO(2), having space group Pn. The bisphthalimide molecules are linked by C-H.O hydrogen bonds and by aromatic pi-pi-stacking interactions, forming a framework enclosing continuous channels running along the [100] direction and accounting for ca 20% of the unit-cell volume. The nitrobenzene molecules lie in these channels, ordered in a head-to-tail fashion and linked to the bisphthalimide framework by C-H.O and C-H.pi(arene) hydrogen bonds.

Self-assembled hydrogen-bonded bilayers in 1,4-diazabicyclo[2.2.2]octane-N-(phosphonomethyl)iminodiacetic acid-water (1/1/1.5).

The title compound is a hydrated salt, 1,4-diazoniabicyclo[2.2.2]octane-N-[(hydroxyphosphinato)methyl]iminiodiacetate-water (1/1/1.5), C(6)H(14)N(2)(2+).C(5)H(8)NO(7)P(2-).1.5H(2)O, in which one of the water molecules lies across a twofold rotation axis in space group P2/n. The ionic components are linked into sheets by a combination of a three-centre N-H...(O)(2) hydrogen bond and two-centre O-H...O and N-H...O hydrogen bonds, and these sheets are pairwise linked by the water molecules into bilayers, by means of further O-H...O hydrogen bonds.

Tetrameric triphenylsilanol, (Ph(3)SiOH)(4), and the adduct (Ph(3)SiOH)(2)-dimethyl sulfoxide, both at 120 K, and the adduct (Ph(3)SiOH)(4)-1,4-dioxan at 150 K: interplay of O[bond]H...O and C[bond]H...pi(arene) interactions.

The structure of tetrameric triphenylsilanol, C(18)H(16)OSi, (I), has been re-investigated at 120 (2) K. The hydroxyl H atoms were readily located and one of the arene rings is disordered over two closely positioned sets of sites. The molecules are linked into cyclic tetramers, having approximate 4 (S(4)) symmetry, via O[bond]H...O hydrogen bonds [H...O 1.81-1.85 A, O...O 2.634 (3)-2.693 (3) A and O[bond]H...O 156-166 degrees ]. At ambient temperature, there are indications of multiple disorder of the phenyl-ring sites. In bis(triphenylsilanol) dimethyl sulfoxide solvate, 2C(18)H(16)OSi x C(2)H(6)OS, (II), the dimethyl sulfoxide component is disordered across a twofold rotation axis in C2/c, and the molecular components are linked by a single O[bond]H...O hydrogen bond [H...O 1.85 A, O...O 2.732 (2) A and O[bond]H...O 172 degrees ] into three-molecule aggregates, which are themselves linked into a single three-dimensional framework by two C[bond]H...pi(arene) interactions. In tetrakis(triphenylsilanol) 1,4-dioxan solvate, 4C(18)H(16)OSi x C(4)H(8)O(2), (III), the 1,4-dioxan component lies across an inversion centre in space group P-1 and centrosymmetric five-molecule aggregates are linked by paired C[bond]H...pi(arene) interactions to form molecular ladders.

N,N'-Dithiobisphthalimide-1,4-dioxan (1/0.6): a C2/c solvate with disordered solvent molecules localized in channels.

N,N'-Dithiobisphthalimide crystallizes from 1,4-dioxan solution as a solvate, 3C(16)H(8)N(2)O(4)S(2) x 1.8C(4)H(8)O(2), having space group C2/c. Four of the 12 C(16)H(8)N(2)O(4)S(2) molecules in the unit cell lie on twofold rotation axes, while the other eight lie in general positions. These molecules are linked by aromatic pi-pi-stacking interactions and by C[bond]H...O hydrogen bonds to form a framework enclosing continuous channels running parallel to the [101] direction, which account for ca 20% of the unit-cell volume. The dioxan molecules lie in these channels disordered across two sets of sites, with one set across an inversion centre and the other across a twofold rotation axis.