Low-dimensional hydrogen-bonded structures in the 1:1 and 1:2 proton-transfer compounds of 4,5-dichlorophthalic acid with the aliphatic Lewis bases triethylamine, diethylamine, n-butylamine and piperidine

The structures of proton-transfer compounds of 4,5-dichlorophthalic acid (DCPA) with the aliphatic Lewis bases triethylamine, diethylamine, n-butylamine and piperidine, namely triethylaminium 2-carboxy-4,5-dichlorobenzoate C~6~H~16~N^+^ C~8~H~3~Cl~2~O~4~^-^ (I), diethylaminium 2-carboxy-4,5-dichlorobenzoate C~4~H~12~N^+^ C~8~H~3~Cl~2~O~4~^-^ (II), bis(n-butylaminium) 4,5-dichlorophthalate monohydrate 2(C~4~H~12~N^+^) C~8~H~2~Cl~2~O~4~^2-^ . H~2~O (III) and bis(piperidinium) 4,5-dichlorophthalate monohydrate 2(C~5~H~12~N^+^) C~8~H~2~Cl~2~O~4~^2-^ . H~2~O (IV)have been determined at 200 K. All compounds have hydrogen-bonding associations giving in (I) discrete cation-anion units, linear chains in (II) while (III) and (IV) both have two-dimensional structures. In (I) a discrete cation-anion unit is formed through an asymmetric R2/1(4) N+-H...O,O' hydrogen-bonding association whereas in (II), one-dimensional chains are formed through linear N-H...O associations by both aminium H donors. In compounds (III) and (IV) the primary N-H...O linked cation-anion units are extended into a two-dimensional sheet structure via amide N-H...O(carboxyl) and ...O(carbonyl) interactions. In the 1:1 salts [(I) and (II)], the hydrogen 4,5-dichlorophthalate anions are essentially planar with short intramolecular carboxylic acid O-H...O(carboxyl) hydrogen bonds [O...O, 2.4223(14) and 2.388(2)A respectively]. This work provides a further example of the uncommon zero-dimensional hydrogen-bonded DCPA-Lewis base salt and the one-dimensional chain structure type, while even with the hydrate structures of the 1:2 salts with the primary and secondary amines, the low dimensionality generally associated with 1:1 DCPA salts is also found.

2-(2,4-dinitrobenzyl)pyridinium 2-hydroxy-3,5-dinitrobenzoate

In the structure of the title compound, the salt C12H10N3O4+ C7H3N2O72-, the cations and the anions are linked by a single N+-H...O(carboxyl) hydrogen bond, the discrete cation-anion unit having no intermolecular associations other than weak cation--anion aromatic ring pi--pi interactions [ring centroid separation, 3.7320(14)A] and a number of weak inter-unit aromatic C-H...O contacts.

The modulation of outdoor running speed : the influence of gradient

This thesis aimed to investigate the way in which distance runners modulate their speed in an effort to understand the key processes and determinants of speed selection when encountering hills in natural outdoor environments. One factor which has limited the expansion of knowledge in this area has been a reliance on the motorized treadmill which constrains runners to constant speeds and gradients and only linear paths. Conversely, limits in the portability or storage capacity of available technology have restricted field research to brief durations and level courses. Therefore another aim of this thesis was to evaluate the capacity of lightweight, portable technology to measure running speed in outdoor undulating terrain. The first study of this thesis assessed the validity of a non-differential GPS to measure speed, displacement and position during human locomotion. Three healthy participants walked and ran over straight and curved courses for 59 and 34 trials respectively. A non-differential GPS receiver provided speed data by Doppler Shift and change in GPS position over time, which were compared with actual speeds determined by chronometry. Displacement data from the GPS were compared with a surveyed 100m section, while static positions were collected for 1 hour and compared with the known geodetic point. GPS speed values on the straight course were found to be closely correlated with actual speeds (Doppler shift: r = 0.9994, p < 0.001, Δ GPS position/time: r = 0.9984, p < 0.001). Actual speed errors were lowest using the Doppler shift method (90.8% of values within ± 0.1 m.sec -1). Speed was slightly underestimated on a curved path, though still highly correlated with actual speed (Doppler shift: r = 0.9985, p < 0.001, Δ GPS distance/time: r = 0.9973, p < 0.001). Distance measured by GPS was 100.46 ± 0.49m, while 86.5% of static points were within 1.5m of the actual geodetic point (mean error: 1.08 ± 0.34m, range 0.69-2.10m). Non-differential GPS demonstrated a highly accurate estimation of speed across a wide range of human locomotion velocities using only the raw signal data with a minimal decrease in accuracy around bends. This high level of resolution was matched by accurate displacement and position data. Coupled with reduced size, cost and ease of use, the use of a non-differential receiver offers a valid alternative to differential GPS in the study of overground locomotion. The second study of this dissertation examined speed regulation during overground running on a hilly course. Following an initial laboratory session to calculate physiological thresholds (VO2 max and ventilatory thresholds), eight experienced long distance runners completed a self- paced time trial over three laps of an outdoor course involving uphill, downhill and level sections. A portable gas analyser, GPS receiver and activity monitor were used to collect physiological, speed and stride frequency data. Participants ran 23% slower on uphills and 13.8% faster on downhills compared with level sections. Speeds on level sections were significantly different for 78.4 ± 7.0 seconds following an uphill and 23.6 ± 2.2 seconds following a downhill. Speed changes were primarily regulated by stride length which was 20.5% shorter uphill and 16.2% longer downhill, while stride frequency was relatively stable. Oxygen consumption averaged 100.4% of runner’s individual ventilatory thresholds on uphills, 78.9% on downhills and 89.3% on level sections. Group level speed was highly predicted using a modified gradient factor (r2 = 0.89). Individuals adopted distinct pacing strategies, both across laps and as a function of gradient. Speed was best predicted using a weighted factor to account for prior and current gradients. Oxygen consumption (VO2) limited runner’s speeds only on uphill sections, and was maintained in line with individual ventilatory thresholds. Running speed showed larger individual variation on downhill sections, while speed on the level was systematically influenced by the preceding gradient. Runners who varied their pace more as a function of gradient showed a more consistent level of oxygen consumption. These results suggest that optimising time on the level sections after hills offers the greatest potential to minimise overall time when running over undulating terrain. The third study of this thesis investigated the effect of implementing an individualised pacing strategy on running performance over an undulating course. Six trained distance runners completed three trials involving four laps (9968m) of an outdoor course involving uphill, downhill and level sections. The initial trial was self-paced in the absence of any temporal feedback. For the second and third field trials, runners were paced for the first three laps (7476m) according to two different regimes (Intervention or Control) by matching desired goal times for subsections within each gradient. The fourth lap (2492m) was completed without pacing. Goals for the Intervention trial were based on findings from study two using a modified gradient factor and elapsed distance to predict the time for each section. To maintain the same overall time across all paced conditions, times were proportionately adjusted according to split times from the self-paced trial. The alternative pacing strategy (Control) used the original split times from this initial trial. Five of the six runners increased their range of uphill to downhill speeds on the Intervention trial by more than 30%, but this was unsuccessful in achieving a more consistent level of oxygen consumption with only one runner showing a change of more than 10%. Group level adherence to the Intervention strategy was lowest on downhill sections. Three runners successfully adhered to the Intervention pacing strategy which was gauged by a low Root Mean Square error across subsections and gradients. Of these three, the two who had the largest change in uphill-downhill speeds ran their fastest overall time. This suggests that for some runners the strategy of varying speeds systematically to account for gradients and transitions may benefit race performances on courses involving hills. In summary, a non – differential receiver was found to offer highly accurate measures of speed, distance and position across the range of human locomotion speeds. Self-selected speed was found to be best predicted using a weighted factor to account for prior and current gradients. Oxygen consumption limited runner’s speeds only on uphills, speed on the level was systematically influenced by preceding gradients, while there was a much larger individual variation on downhill sections. Individuals were found to adopt distinct but unrelated pacing strategies as a function of durations and gradients, while runners who varied pace more as a function of gradient showed a more consistent level of oxygen consumption. Finally, the implementation of an individualised pacing strategy to account for gradients and transitions greatly increased runners’ range of uphill-downhill speeds and was able to improve performance in some runners. The efficiency of various gradient-speed trade- offs and the factors limiting faster downhill speeds will however require further investigation to further improve the effectiveness of the suggested strategy.

Bis(4-carbamoylpiperidinium)biphenyl-4,4'-disulfonate

In the title isonipecotamide salt 2C6H13N2O+.C12H8O6S22-,the asymmetric unit comprises one biphenyl-4,4'-disulfonate dianion which lies across a crystallographic inversion centre and another in a general position [dihedral angle between the two phenyl rings is 37.1(1)deg], together with three isonipecotamide cations. Two of these cations give a cyclic homomeric amide-amide dimer interaction [graph set R2/2(8)],the other giving a similar dimeric interaction but across an inversion centre, both dimers then forming lateral cyclic R2/4(8) pyrimidinium N-H...O interactions. These units are linked longitudinally to the sulfonate groups of the dianions through piperidinium N-H...O hydrogen bonds, giving a three-dimensional framework structure.

4-Carbamoylpiperidinium acetate monohydrate

In the structure of the title compound, C6H13N2O+ C2H3O2- . H2O, the amide H atoms of the cations form centrosymetric cyclic hydrogen-bonding associations incorporating two water molecules [graph set R^2^~4~(8)], which are conjoint with cyclic water-bridged amide-amide associations [R^4^~4~(12)] and larger R4/4(20) associations involving the water molecule and the acetate anions, which bridge through the piperidinium H donors, giving an overall three-dimensional framework structure.

4-Carbamoylpiperidinium phenylacetate hemihydrate

In the structure of the title compound, C6H13N2O+ C8H7O2- . 0.5H2O, the asymmetric unit comprises two isonipecotamide cations, two phenylacetate anions and a water molecule of solvation. The hydrogen-bonding environments for both sets of ion pairs are essentially identical with the piperidinium and amide 'ends' of each cation involved in lateral heteromolecular hydrogen-bonded cyclic N---H...O associations [graph set R2/2(11)] which incorporate a single carboxyl O-atom acceptor. These cyclic motifs enclose larger R5/5(21) cyclic systems forming sheet substructures which lie parallel to (101) and are linked across b by the single water molecule via water O---H...O(carboxyl) associations to give a two-dimensional duplex-sheet structure

Anhydrous 1:1 proton-transfer compounds of isonipecotamide with picric acid and 3,5-dinitrosalicylic acid: 4-carbamoylpiperidinium 2,4,6-trinitrophenolate and two polymorphs of 4-carbamoylpiperidinium 2-carboxy-4,6-dinitrophenolate

The structures of the anhydrous 1:1 proton-transfer compounds of isonipecotamide (4-carbamoylpiperidine) with picric acid and 3,5-dinitrosalicylic acid, namely 4-carbamoylpiperidinium 2,4,6-trinitrophenolate, C6H13N2O8+ C6H2N3O7- (I) and 4-carbamoylpiperidinium 2-carboxy-4,6-dinitrophenolate, C6H13N2O8+ C7H3N2O7-: two forms, the monoclinic alpha-polymorph (II) and the triclinic beta-polymorph (III) have been determined at 200 K. All compounds form hydrogen-bonded structures, one-dimensional in (II), two-dimensional in (I) and three-dimensional in (III). In (I), the cations form centrosymmetric cyclic head-to-tail hydrogen-bonded homodimers [graph set R2/2(14)] through lateral duplex piperidinium N---H...O(amide) interactions. These dimers are extended into a two-dimensional network structure through further interactions with anion phenolate-O and nitro-O acceptors, including a direct symmetric piperidinium N-H...O(phenol),O(nitro) cation--anion association [graph set R2/1(6)]. The monoclinic polymorph (II) has a similar R2/1(6) cation-anion hydrogen-bonding interaction to (I) but with an additional conjoint symmetrical R1/2(4) interaction as well as head-to-tail piperidinium N-H...O(amide) O hydrogen bonds and amide N-H...O(carboxyl) hydrogen bonds, give a network structure which include large R3/4(20) rings. The hydrogen bonding in the triclinic polymorph (III) is markedly different from that of monoclinic (II). The asymmetric unit contains two independent cation-anion pairs which associate through cyclic piperidinium N-H...O,O'(carboxyl) interactions [graph set R2/1(4)]. The cations also show the zig-zag head-to-tail piperidinium N-H...O(amide) hydrogen-bonded chain substructures found in (II) but in addition feature amide N-H...O(nitro) and O(phenolate) and amide N-H...O(nitro) associations. As well there is a centrosymmetric double-amide N-H...O(carboxyl) bridged bis(cation-anion) ring system [graph set R2/4(8)] in the three-dimensional framework. The structures reported here demonstrate the utility of the isonipecotamide cation as a synthon with previously unrecognized potential for structure assembly applications. Furthermore, the structures of the two polymorphic 3,5-dinitrosalicylic acid salts show an unusual dissimilarity in hydrogen-bonding characteristics, considering that both were obtained from identical solvent systems.

4-Carbamoylpiperidinium 5-nitrosalicylate

In the structure of the title compound, C6H13N2O+ C7H4NO5-, the isonipecotamide cations and the 5-nitrosalicylate anions form hydrogen-bonded chain substructures through head-to-tail piperidinium N---H...O(carboxyl) hydrogen bonds and through centrosymmetric cyclic head-to-head amide-amide hydrogen-bonding associations [graph set R2/2(8)]. These chains are cross linked by amide N---H...O~carboxyl~ and piperidinium N-H...O(nitro) associations to give a two-dimensional sheet structure.

Raman spectroscopy of hydrogene-arsenate group (AsO3OH) in solid-state compounds: cobalt mineral phase burgessite Co2(H2O)4[AsO3OH]2•H2O

Raman spectrum of burgessite, Co2(H2O)4[AsO3OH]2.H2O was studied, interpreted and compared with its infrared spectrum. The stretching and bending vibrations of (AsO3) and As-OH units together with the stretching, bending and libration modes of water molecules and hydroxyl ions were assigned. The range of O-H...O hydrogen bond lengths was inferred from the Raman and infrared spectra of burgessite. The presence of (AsO3OH)2- units in the crystal structure of burgessite was proved in agreement with its recently solved crystal structure. Raman and infrared spectra of erythrite inferred from the RRUFF database are used for comparison.

4-Carbamoylpiperidinium 2-carboxybenzoate-benzene-1,2-dicarboxylic acid (1/1)

In the structure of the title salt adduct, C6H13N2O+ C8H5O4- . C8H6O4, the asymmetric unit comprises one isonipecotamide cation, a hydrogen phthalate anion and a phthalic acid adduct molecule and form a two-dimensional hydrogen-bonded network through head-to-tail cation-anion-adduct molecule interactions which include a cyclic heteromolecular amide--carboxylate motif [graph set R2/2(8)], conjoint cyclic R2/2(6) and R3/3(10) piperidinium N-H...O(carboxyl) associations, as well as strong carboxylic acid O-H...O(carboxyl) hydrogen bonds.

Pseudo-merohedral twinning in the structure of the hydrated 1:1 proton-transfer compound of 5-sulfosalicylic acid with 4-aminopyridine

The structure of the pseudo-merohedrally twinned crystal of the 1:1 proton-transfer compound of 5-sulfosalicylic acid (3-carboxy-4-hydroxybenzenesulfonic acid) with 4-aminopyridine: 4-aminopyridinium 3-carboxy-4-hydroxybenzenesulfonate sesquihydrate has been determined at 180 K and the hydrogen-bonding pattern is described. Crystals of the compound are monoclinic with space group P21/c, with unit cell dimensions a = 35.2589(8), b = 7.1948(1), c = 24.5851(5) Å, β = 110.373(2)o, and Z = 16. The monoclinic asymmetric unit comprises four cation-anion pairs and six water molecules of solvation with only the pyridinium cations having pseudo-symmetry as a result of inter-cation aromatic ring π-π stacking effects. Extensive hydrogen bonding gives a three-dimensional framework structure.

Review of Dr. Richard Shapcott's International Ethics : A Critical Introduction. 2010. London: Polity Press. ISBN-13: 978-0-7456-3142-4.

This work by Richard Shapcott is, as the title provides, an introduction to international ethics. By taking a quick glance at the table of contents (see Figure 1) we see that he has systematically divided this particular discourse into its normative areas of concern (in other words its major areas of argument or research). When reading, we also see that a great deal of work has gone into the publication because the narrative is flowing, the arguments continuous, and because the tone of the work maintained its critical position throughout.

Diiodidobis[4-(-nitrobenzyl)pyridine-kN']zinc

In the structure of title compound [ZnI2(C12H10N2O2)2] from the reaction of 4-(4-nitrobenzyl)pyridine with zinc(II) iodide, the asymmetric unit contains two independent discrete distorted tetrahedral complex units [Zn-I range, 2.5472(8)-2.5666(7)A; Zn-N range, 2.044(4)-2.052(4)A], which are essentially identical conformationally and exist in the crystal structure as a racemic twin.