Equatorial Sites Research Articles

Ethyl 2-[2-(2,4-diphenyl-3-azabicyclo[3.3.1]nonan-9-ylidene)hydrazin-1-yl]-4-methyl-1,3-thiazole-5-carboxylate dimethylformamide monosolvate

In the title mol­ecule, C27H30N4O2S·C3H7NO, the fused piperidine and cyclo­hexane rings adopt a twin chair conformation and the phenyl groups occupy equatorial sites. The phenyl rings make a dihedral angle of 40.74 (2)°. In the crystal, the di­methyl­formamide solvent mol­ecule is connected to the main mol­ecule by an N—H⋯O hydrogen bond. An additional N—H⋯O hydrogen bond connects mol­ecules into chains along [100]. Pairs of weak C—H⋯O hydrogen bonds connect inversion-related chains. The ethyl group was refined as disordered over two sets of sites with an occupancy ratio of 0.660 (17):0.340 (17).

A mixed-addenda Nb/W polyoxometalate containing dimeric Dawson subunit: Synthesis, structure, and characterization

A mixed-addenda Nb/W polyoxometalates, K4Na4[H6P2W12Nb4O59(NbO2)2]2·48H2O (1), has been isolated under acidic condition. The single crystal structural analysis showed that the six vacant sites of the lacunary {P2W12} precursor are occupied by six Nb atoms, two at the polar sites and four at the equatorial sites to form a {P2W12Nb6} mixed-addenda subunit. Two {P2W12Nb6} subunits are joined together in an inversion mode by two Nb–O–Nb bridges from the Nb atoms at equatorial sites to form a dimeric unit, which can be considered as a Nb12 core wrapped by two lacunary {P2W12} polyoxoanions. It is notable that the terminal peroxo groups bonded niobium atoms in the Nb12 core are only partially eliminated during the formation of the dimeric unit.

Joint experimental and computational 17O solid state NMR study of Brownmillerite Ba2In2O5

Structural characterization of Brownmillerite Ba2In2O5 was achieved by an approach combining experimental solid-state NMR spectroscopy, density functional theory (DFT) energetics, and GIPAW NMR calculations. While in the previous study of Ba2In2O5 by Adler et al. (S. B. Adler, J. A. Reimer, J. Baltisberger and U. Werner, J. Am. Chem. Soc., 1994, 116, 675-681), three oxygen resonances were observed in the (17)O NMR spectra and assigned to the three crystallographically unique O sites, the present high resolution (17)O NMR measurements under magic angle spinning (MAS) find only two resonances. The resonances have been assigned using first principles (17)O GIPAW NMR calculations to the combination of the O ions connecting the InO4 tetrahedra and the O ions in equatorial sites in octahedral InO6 coordination, and to the axial O ions linking the four- and six-fold coordinated In(3+) ions. Possible structural disorder was investigated in two ways: firstly, by inclusion of the high-energy structure also previously studied by Mohn et al. (C. E. Mohn, N. L. Allan, C. L. Freeman, P. Ravindran and S. Stølen, J. Solid State Chem., 2005, 178, 346-355), where the structural O vacancies are stacked rather than staggered as in Brownmillerite and, secondly, by exploring structures derived from the ground-state structure but with randomly perturbed atomic positions. There is no noticeable NMR evidence for any substantial occupancy of the high-energy structure at room temperature.

Time-transgressive North Atlantic productivity changes upon Northern Hemisphere glaciation

[1] Marine biological export productivity declined in high-latitude regions in the North Pacific and Southern Ocean 2.7 million years ago, in parallel with the intensification of Northern Hemisphere glaciation. Here we present data from the North Atlantic, which show a similar but time-transgressive pattern of high-latitude productivity decline from 3.3 to 2.5 Ma, with productivity decreasing first at 69°N, hundreds of thousands of years before it declined at 58°N. We propose that the cumulative data are best explained by an equatorward migration of the westerly winds, which caused a southward shift in the zone of Ekman divergence and upwelling-associated major nutrient supply over this time interval. We suggest that a similar equatorward migration of the westerly winds may also help explain the productivity changes observed in other high-latitude regions, particularly the Southern Ocean. At 2.7 Ma, equatorial and temperate Atlantic sites began to show orbitally paced productivity pulses, consistent with a shoaling and meridional contraction of the nutrient-poor “warm sphere” that characterizes the low latitude upper ocean. This timing coincides with observed productivity changes in Southern Ocean, consistent with previous findings that the Southern Ocean exerts a strong influence on the fertility of the low-latitude Atlantic. Finally, we propose that the unique basin geometry of the North Atlantic caused deep water formation in this region to remain relatively stable despite equatorward migration of winds and ocean fronts.

A humped latitudinal phylogenetic diversity pattern of orchid bees (Hymenoptera: Apidae: Euglossini) in western Amazonia: assessing the influence of climate and geologic history

Amazonian rainforests are among the most species‐rich terrestrial habitats on Earth. The aim of this study was to analyze phylogenetic diversity (PD) patterns of orchid bee assemblages along a latitudinal gradient of 15° from northern Peru to central Bolivia and to relate them to climatic factors and geological history. We expanded an existing phylogeny of orchid bees and analyzed the PD of 15 orchid bee assemblages along a latitudinal gradient using mean pair‐wise phylogenetic distance. The resulting pattern was correlated to climatic factors and elevation. We found a hump‐shaped pattern of PD that peaked in central Peru and decreased towards the equatorial and especially towards the southern, subtropical sites. The decrease in PD towards higher latitudes is a common pattern found in many taxa, which in our case correlates with increasing climatic seasonality. However, the decrease towards the equatorial sites is unusual and may be related to a particular historic event: the northern sites with low PD are situated in the area of the former Lake Pebas, which covered western Amazonia until 3 mya. After the lake disappeared orchid bees mainly belonging to two distantly related species groups apparently colonized the region and diversified, which led to the comparatively low observed PD. In contrast, in central Peru, no in situ radiations were detected, hence the assemblages were composed of species from diverse phylogenetic lineages. Additionally, we identified multiple phylogenetically independent radiations of regionally restricted Euglossa species along the latitudinal gradient that, according to a published, dated phylogeny, diversified roughly 3–1 mya. The hump‐shaped latitudinal pattern of PD of the orchid bees of western Amazonia thus appears to have resulted from a preponderance of early divergent lineages in central Peru and of young radiations from distantly related clades colonizing higher latitudes, possibly triggered by historic climate fluctuations and major geological events.

6,6′-Bis(1,1-dimethylethyl)-4,4′-dimethyl-2,2′-methylenediphenolato-κ2O,O′]dichlorido(9H-fluoren-9-ol-κO)titanium(IV)–fluorene–diethyl ether (1/0.5/1)

The title adduct, [TiCl2(C23H30O2)(C13H10O]·0.5C13H10·C4H10O, is a monomer with a trigonal–bypyramidal coordination sphere of the TiIV atom in which the ligand O atoms of the bidentate diphenolate anion are located in both apical and equatorial positions. Chloride ligands occupy the remaining two equatorial sites of the trigonal bypyramid with the fluoren-9-ol O atom occupying the other apical site. The hy­droxy group H atom of this latter group is hydrogen bonded to an O atom of a non-coordinating diethyl ether mol­ecule. The title compound also contains a further fluorene solvent mol­ecule, which lies across a centre of symmetry and which is equally disordered over an inversion centre.

Equatorial 150 km echoes and daytime F region vertical plasma drifts in the Brazilian longitude sector

Abstract. Previous studies showed that conventional coherent backscatter radar measurements of the Doppler velocity of the so-called 150 km echoes can provide an alternative way of estimating ionospheric vertical plasma drifts during daytime hours (Kudeki and Fawcett, 1993; Chau and Woodman, 2004). Using observations made by a small, low-power 30 MHz coherent backscatter radar located in the equatorial site of São Luís (2.59° S, 44.21° W; −2.35° dip lat), we were able to detect and monitor the occurrence of 150 km echoes in the Brazilian sector. Using these measurements we estimated the local time variation of daytime vertical ionospheric drifts in the eastern American sector. Here, we present a few interesting cases of 150 km-echoes observations made by the São Luís radar and estimates of the diurnal variation of vertical drifts. These cases exemplify the variability of the vertical drifts in the Brazilian sector. Using same-day 150 km-echoes measurements made at the Jicamarca Radio Observatory in Peru, we also demonstrate the variability of the equatorial vertical drifts across the American sector. In addition to first estimates of the absolute vertical plasma drifts in the eastern American (Brazilian) sector, we also present observations of abnormal drifts detected by the São Luís radar associated with the 2009 major sudden stratospheric warming event.

Light-Enhanced Displacement of Methyl Acrylate from Iron Carbonyl: Investigation of the Reactive Intermediate via Rapid-Scan Fourier Transform Infrared and Computational Studies

The thermal displacement of methyl acrylate from Fe(CO)4(η(2)-CH2=CHCOOMe) by phosphine ligands is a relatively slow reaction requiring several hours at elevated temperatures. In the present study, it is observed that photolysis of the tetracarbonyl complex with UV light activates the process such that the reaction is complete within a few seconds. This rate enhancement is due to the formation of an intermediate η(4) complex where the organic C=O and C=C units of methyl acrylate occupy axial and equatorial coordination sites on the Fe center, respectively, following photochemical CO loss. The displacement of methyl acrylate from this photolytically generated intermediate is facile with a remarkably low barrier of 8.7 kcal/mol. Density functional theory calculations support these experimental observations.

Measurements of ozone and its precursor nitrogen dioxide and crop yield losses due to cumulative ozone exposures over 40 ppb (AOT40) in rural coastal southern India

Measurements of ground level ozone (O3), nitrogen dioxide (NO2) and meteorological parameters (air temperature, relative humidity and wind speed and direction) has been made for 3 years from March 2007 to February 2010 at Nagercoil (8.2°N, 77.5°E, 23 m above sea level), an equatorial rural coastal site of southern India. The monthly average of daytime maximum of O3 concentrations ranged from 28 to 50 parts per billion (ppb) with an annual average of 19.8 ppb. Similarly, monthly average of NO2 concentration ranged from 3.4 ppb to 7.7 ppb with an annual average of 5.3 ppb. The monthly variation of meteorological parameters shows the little changes being a coastal site. The estimated summer crops yield losses by 1.1–15.6 % from present O3 concentration level associated with AOT40 index 3.1–5 ppm h.

Unusual Redox Chemistry of Ytterbium Carbazole–Bis(oxazoline) Compounds: Oxidative Coupling of Primary Phosphines by an Ytterbium Carbazole–Bis(oxazoline) Dialkyl

The 1,8-bis(4′,4′-dimethyloxazolin-2′-yl)-3,6-di-tert-butylcarbazole anion (Czx) forms monomeric, six-coordinate halide complexes of Yb(II), (Czx)Yb(X)(THF)2 (X = I (2), Cl (3)), by metathesis of YbX2 with NaCzx (1) or Na/Hg reduction of (Czx)Yb(Cl)2(THF). The crystal structure of 1 reveals a polymeric chain structure in which the oxazoline ring bridges to the Na+ of an adjacent unit. The iodo complex 2 serves as a precursor to divalent silylamide, alkyl, and phosphide complexes, (Czx)Yb(X)(THF)n (4, X = N(SiMe3)2, n = 1; 5, X = CH(SiMe3)2, n = 1; 7a, X = 2,4,6-Me3C6H2PH, n = 2; 7b, X = 2,4,6-Pri3C6H2PH, n = 2). The X-ray structure of 4 reveals a distorted-trigonal-bipyramidal geometry with the Czx ligand occupying two axial sites and one equatorial site in a pseudo-mer coordination mode. In contrast to the typical metathesis chemistry observed with LiCH(SiMe3)2, an unusual oxidation occurs when 2 or 3 is treated with LiCH2SiMe3 to generate the previously isolated trivalent alkyl (Czx)Yb(CH2SiMe3)2. Trivalent Yb complexes with the Czx ligand also display unusual redox chemistry: rapid reduction to the Yb(II) phosphides 7a,b is observed on treatment of mer,cis-(Czx)Yb(Cl)2(THF) with ArPH– Na+ (6a,b) or, equivalently, on treatment of (Czx)Yb(CH2SiMe3)2 with ArPH2. In both cases, oxidative coupling of the phosphide or phosphine was observed to form meso- and rac-biphosphines, ArPH–PHAr (Ar = 2,4,6-Me3C6H2 (9a), 2,4,6-Pri3C6H2 (9b)).

Interaction of Insulin-Enhancing Vanadium Compounds with Human Serum holo-Transferrin

The interaction of VO(2+) ion and four insulin-enhancing compounds, [VO(ma)2], [VO(dhp)2], [VO(acac)2], and cis-[VO(pic)2(H2O)], where Hma, Hdhp, Hacac, and Hpic are maltol, 1,2-dimethyl-3-hydroxy-4(1H)-pyridinone, acetylacetone, and picolinic acid, with holo-transferrin (holo-hTf) was studied through the combined application of electron paramagnetic resonance (EPR) and density functional theory (DFT) methods. Since in holo-hTf all of the specific binding sites of transferrin are saturated by Fe(3+) ions, VO(2+) can interact with surface sites (here named sites C), probably via the coordination of His-N, Asp-COO(-), and Glu-COO(-) donors. In the ternary systems with the insulin-enhancing compounds, mixed species are observed with Hma, Hdhp, and Hpic with the formation of VOL2(holo-hTf), explained through the interaction of cis-[VOL2(H2O)] (L = ma, dhp) or cis-[VOL2(OH)](-) (L = pic) with an accessible His residue that replaces the monodentate H2O or OH(-) ligand. The residues of His-289, His-349, His-473, and His-606 seem the most probable candidates for the complexation of the cis-VOL2 moiety. The lack of a ternary complex with Hacac was attributed to the square-pyramidal structure of [VO(acac)2], which does not possess equatorial sites that can be replaced by the surface His-N. Since holo-transferrin is recognized by the transferrin receptor, the formation of ternary complexes between VO(2+) ion, a ligand L(-), and holo-hTf may be a way to transport vanadium compounds inside the cells.

Structural and spectral studies of diorganotin(IV) complexes containing bis-tridentate N,N-bis(4-oxo-4-phenylbutan-2-ylidene)oxalohydrazide ligand

Three new symmetrical binuclear diorganotin(IV) complexes with the symmetrical bis-tridentate Schiff base, N,N-bis(4-oxo-4-phenylbutan-2-ylidene)oxalohydrazide, (R2Sn)2[Ph–C(O)CH–C(Me)N–NC(O)–C(O)N–NC(Me)–CHC(O)−Ph] (R = Ph: Ia; R = Me: Ib; R = n-Bu: Ic) have been synthesized by reaction with corresponding diorganotin(IV) dichloride at room temperature in methanol in presence of triethylamine. The complexes have been characterized by elemental analyses, IR, 1H, 13C, 15N and 119Sn NMR spectroscopy. Two dimensional H,H-COSY, NOESY, H,C-COSY, gs(gradient selected)-HMQC and gs-HMBC techniques were applied in order to assign proton and carbon chemical shifts unambiguously. The δ(119Sn) values for the complexes Ia–Ic are −320.1, −181.9 and −150.7 ppm respectively, indicating pentacoordinated tin centres. The C–Sn–C angles calculated from 1J(119Sn, 13C) for Ia, 1b and Ic are found to be 135.6°, 133.85° and 135.0° respectively. From the 2J(119Sn, 1H) value, the Me–Sn–Me angle for Ib is found to be 130.46°. From NMR spectra a distorted trigonal-bipyramidal geometry at each tin centre is proposed. The structures of the complexes have been confirmed by single crystal X-ray diffraction analysis of one representative compound Ia. The ligand, N,N-bis(4-oxo-4-phenylbutan-2-ylidene)oxalohydrazide (H4L) coordinates to the metal centre in enolate form via the phenolic O, imino N and enolic O atoms. The X-ray structure indicates that the coordination geometry of tin atoms are intermediate between trigonal bipyramid and a square pyramid. The oxygen atoms are in axial positions while the imino nitrogen atom of the ligand and two phenyl groups occupy the equatorial sites.

Catena-Poly[{μ-N′-[2-(carboxylatomethoxy)benzylidene]-2-hydroxybenzohydrazidato}(methanol-κO)nickel(II)

In the title compound, [Ni(C16H12N2O5)(CH3OH)]n, the unique NiII ion is coordinated in a distorted octa­hedral environment by three O atoms and one N atom from a symmetry-unique ligand in the equatorial sites. Coordination of the axial sites is provided by an O atom of a symmetry-unique methanol ligand and an O atom of a carboxyl­ate group from a symmetry-related ligand, thus generating a one-dimensional polymer parallel to [010]. In the crystal, O—H⋯N hydrogen bonds and π–π inter­actions, with a centroid–centroid distance of 3.693 (2) Å, form a two-dimensional network parallel to (100). In addition, weak C—H⋯O and C—H⋯N hydrogen bonds complete a three-dimensional network. An intra­molecular O—H⋯O hydrogen bond is also observed.

Bis[O,O′-bis(4-tert-butylphenyl) dithiophosphato-κ2S,S′]bis(pyridine-κN)lead(II)

In the title compound, [Pb(C20H26O2PS2)2(C5H5N)2], the PbII ion is coordinated by two S,S′-bidentate anions and two pyridine mol­ecules. The PbN2S4 coordination geometry approximates to a penta­gonal bipyramid with one equatorial site vacant. The N atoms occupy the axial sites. One of the pyridine mol­ecules is disordered over two sets of sites in a 0.907 (7):0.093 (7) ratio and one of the tert-butyl groups is disordered over two sets of sites in a 0.534 (6):0.466 (6) ratio. An intra­molecular C—H⋯O inter­action occurs in one of the ligands. In the crystal, pairs of short Pb⋯S contacts [3.4018 (11) Å] generate a centrosymmetric dimeric assembly with the distant S atom lying in the region of the vacant coordination site of the metal atom. No directional packing inter­actions occur.

A re-investigation of arsenoacetic acid, (AsCH2COOH)n

Detailed spectroscopic data have been obtained for arsonoacetic acid, As(CH2COOH)O3H2, and its barium and sodium salts. The X-ray crystal structure of the free acid is isomorphous with phosphonoacetic acid. Reduction gave the As(I) compound arsenoacetic acid, (AsCH2COOH)n which was shown by ESI-MS to contain cyclic species based on As–As bonds, with n mainly 3–6. The X-ray crystal structure of the hexamer was determined as the pyridine solvate and shown to have a hexacyclic As6 ring in a puckered chair conformation, with –CH2COOH groups in equatorial sites, each H-bonded to a pyridine molecule in the lattice.

Three transition-metal complexes with the macrocyclic ligandmeso-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (L): [Cu(ClO4)2(L)], [Zn(NO3)2(L)] and [CuCl(L)(H2O)]Cl

The three transition-metal complexes, (meso-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-κ⁴N)bis(perchlorato-κO)copper(II), [Cu(ClO₄)₂(C₁₈H₄₀N₄)], (I), (meso-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-κ⁴N)bis(nitrato-κO)zinc(II), [Zn(NO₃)₂(C₁₈H₄₀N₄)], (II), and aquachlorido(meso-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-κ⁴N)copper(II) chloride, [CuCl(C₁₈H₄₀N₄)(H₂O)]Cl, (III), are described. The molecules display a very similarly distorted 4+2 octahedral environment for the cation [located at an inversion centre in (I) and (II)], defined by the macrocycle N₄ group in the equatorial sites and two further ligands in trans-axial positions [two O-ClO₃ ligands in (I), two O-NO₂ ligands in (II) and one chloride and one aqua ligand in (III)]. The most significant difference in molecular shape resides in these axial ligands, the effect of which on the intra- and intermolecular hydrogen bonding is discussed. In the case of (I), all strong hydrogen-bond donors are saturated in intramolecular interactions, while weak intermolecular C-H∙∙∙O contacts result in a three-dimensional network. In (II) and (III), instead, there are N-H and O-H donors left over for intermolecular interactions, giving rise to the formation of strongly linked but weakly interacting chains.

What drives the seasonality of photosynthesis across the Amazon basin? A cross-site analysis of eddy flux tower measurements from the Brasil flux network

We investigated the seasonal patterns of Amazonian forest photosynthetic activity, and the effects thereon of variations in climate and land-use, by integrating data from a network of ground-based eddy flux towers in Brazil established as part of the ‘Large-Scale Biosphere Atmosphere Experiment in Amazonia’ project. We found that degree of water limitation, as indicated by the seasonality of the ratio of sensible to latent heat flux (Bowen ratio) predicts seasonal patterns of photosynthesis. In equatorial Amazonian forests (5° N–5° S), water limitation is absent, and photosynthetic fluxes (or gross ecosystem productivity, GEP) exhibit high or increasing levels of photosynthetic activity as the dry season progresses, likely a consequence of allocation to growth of new leaves. In contrast, forests along the southern flank of the Amazon, pastures converted from forest, and mixed forest-grass savanna, exhibit dry-season declines in GEP, consistent with increasing degrees of water limitation. Although previous work showed tropical ecosystem evapotranspiration (ET) is driven by incoming radiation, GEP observations reported here surprisingly show no or negative relationships with photosynthetically active radiation (PAR). Instead, GEP fluxes largely followed the phenology of canopy photosynthetic capacity (Pc), with only deviations from this primary pattern driven by variations in PAR. Estimates of leaf flush at three non-water limited equatorial forest sites peak in the dry season, in correlation with high dry season light levels. The higher photosynthetic capacity that follows persists into the wet season, driving high GEP that is out of phase with sunlight, explaining the negative observed relationship with sunlight. Overall, these patterns suggest that at sites where water is not limiting, light interacts with adaptive mechanisms to determine photosynthetic capacity indirectly through leaf flush and litterfall seasonality. These mechanisms are poorly represented in ecosystem models, and represent an important challenge to efforts to predict tropical forest responses to climatic variations.

Tetraammine(carbonato-κ2O,O′)cobalt(III) perchlorate

In the title complex, [Co(CO3)(NH3)4]ClO4, both the cation and anion lie on a mirror plane. The CoIII ion is coordinated by two NH3 ligands and a chelating carbonato ligand in the equatorial sites and by two NH3 groups in the axial sites, forming a distorted octa­hedral geometry. In the crystal, N—H⋯O hydrogen bonds connect the anions and cations, forming a three-dimensional network.

Experimental Visualization of the Diffusional Pathway of Oxide Ions in a Layered Perovskite-type Cobaltite PrBaCo2O5+δ

Layered perovskite-type cobaltite PrBaCo2O5+δ is an oxide-ion and electronic mixed conductor with high oxide-ion conductivity and is promising for potential use in SOFC (solid oxide fuel cell) cathodes and oxygen membranes. The crystal structure and oxide-ion diffusional pathway of PrBaCo2O5+δ at 596 and 1000 °C have been investigated by in situ high-temperature neutron powder diffraction and a maximum-entropy method (MEM)-based nuclear-density analysis. The oxide ions of PrBaCo2O5+δ two-dimensionally and anisotropically diffuse through equatorial and deficient apical oxygen sites along the ⟨101⟩ directions in the Pr–Co–O ion-conducting slab.

Two solvatomorphic forms of a copper complex formulated as Cu(L1)(ClO4)2·1.2H2O and Cu(L1)(ClO4)2, whereL1is 3,10-C-meso-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane

Two copper complex solvatomorphs, namely (3,10-C-meso-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane)bis(perchlorato-κO)copper(II) 1.2-hydrate, [Cu(ClO4)2(C18H40N4)]·1.2H2O, (I), and (3,10-C-meso-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane)bis(perchlorato-κO)copper(II), [Cu(ClO4)2(C18H40N4)], (II), are described and compared with each other and with a third, already reported, anhydrous diastereomer, denoted (III). Both compounds present very similar centrosymmetic coordination environments, with the Cu(II) cation lying on an inversion centre in a distorted 4+2 octahedral environment, defined by the macrocyclic N4 group in the equatorial sites and two perchlorate groups in trans-axial positions [one of the perchlorate ligands in (I) is partially disordered]. The most significant difference in molecular shape is seen in the orientation of the perchlorate anions, and the influence of this on the intramolecular hydrogen bonding is discussed. The (partially) hydrated state of (I) favours the formation of chains along [011], while the anhydrous character of (II) and (III) promotes loosely bound structures with low packing indices.