This note explains the relationship (as well as the absence of a relationship) between chiral space groups and chiral molecules (which have absolute configurations).For a chiral molecule,which must crystallize in a chiral space group,the outcome of the absolute configuration determination must be linked to some other properties of the chiral crystal such as its optical activity for the observation to the relevant. 相似文献
1 INTRODUCTION Although the incorrect assignment of the space groups of crystal structures has been addressed in a number of reports, instances of crystal structures refined in incorrect symmetry turn up even in the recent literature[1~4]. A simple method of space group revision makes use of the published atomic coordinates and temperature factors to simulate the diffraction intensities; the structure is then 搒olved?in the correct space group from the simulated hkl-F2 data[5] and an O… 相似文献
The structure factors of any crystal structure can be simulated from its atomic coordinates (and temperature factors) in a SHELXL-97 run on a dummy hkl in which only the scale factor is refined. The squares of the structure factors are retrieved from thefcf, and such simulated data are used in the revision of the space groups of several incorrectly-refined crystal structures. Two cases, a P1 to Pl- revision and a chemically-incorrect structure that is refined in a correct space group, are discussed. 相似文献
Higher‐dimensional crystals have been studied for the last thirty years. However, most practicing chemists, materials scientists, and crystallographers continue to eschew the use of higher‐dimensional crystallography in their work. Yet it has become increasingly clear in recent years that the number of higher‐dimensional systems continues to grow from hundreds to as many as a thousand different compounds. Part of the problem has to do with the somewhat opaque language that has developed over the past decades to describe higher‐dimensional systems. This language, while well‐suited to the specialist, is too sophisticated for the neophyte wishing to enter the field, and as such can be an impediment. This Focus Review hopes to address this issue. The goal of this article is to show the regular chemist or materials scientist that knowledge of regular 3D crystallography is all that is really necessary to understand 4D crystal systems. To this end, we have couched higher‐dimensional composite structures in the language of ordinary 3D crystals. In particular, we developed the principle of complementarity, which allows one to identify correctly 4D space groups solely from examination of the two 3D components that make up a typical 4D composite structure. 相似文献
Communication: Phenoxycarbonyloxymethyl ethylene carbonate 4 was synthesized from glycerol carbonate and phenyl chloroformate. Polyurethanes with pendant hydroxyl groups were obtained from polycondensation reactions of this AA* monomer with diamines. These polymers contain primary as well as secondary hydroxyl groups. The obtained polyurethanes are amorphous materials. The glass transition temperature decreases with increasing number of methylene groups between the urethane groups.
As the number of methylene groups increases between the urethane groups, the glass transition temperature of the polymer decreases. 相似文献
An algorithm has been developed for calculating radii, direction vectors, and coordination numbers (c.n.) for an arbitrary number of coordination spheres (CS) of the diamond lattice. It is established that the space of CS of the diamond lattice has imaginary CS in addition to real ones. The imaginary CS are defined by a direction vector, one of the components of which is an imaginary value. The coordination numbers of such CS are zero. For a great number of tabulated CS, we have studied the hierarchies of structural groups (motifs), forming in the space of coordination spheres and determining the X-ray spectra of lattice CS, the crystallomorphological growth forms of diamond crystals, and the forms of diamond fragmentation induced by thermal destruction and melting. 相似文献
A family of macrocyclic compounds are described, together with their precursors. These cycles are composed of icosahedral carboranes linked via their carbon vertices through 1,3-trimethylene, alpha,alpha'-1,3-xylylene, or alpha,alpha'-2,6-lutidylene groups. The compounds cyclo-(1,3-trimethylene-1',2'-closo-1',2'-C(2)B(10)H(10))(4) (6a), cyclo-(1,3-trimethylene-1',2'-closo-9',12'-dimethyl-1',2'-C(2)B(10)H(8))(4) (6b), cyclo-(1,3-trimethylene-1',2'-closo-1',2'-C(2)B(10)H(10))(3) (9), cyclo-(alpha,alpha'-1,3-xylylene-1',2'-closo-1',2'-C(2)B(10)H(10))(2) (11a), cyclo-(alpha,alpha'-1,3-xylylene-1',7'-closo-1',7'-C(2)B(10)H(10))(2) (11b), cyclo-(alpha,alpha'-1,3-xylylene-1',7'-closo-9',10'-dimethyl-1,7-C(2)B(10)H(8))(2) (11c), cyclo-(alpha,alpha'-1,3-xylylene-1',2'-closo-1',2'-C(2)B(10)H(10))(4) (12), cyclo-(alpha,alpha'-1,3-xylylene-1',7'-closo-1',7'-C(2)B(10)H(10))(3) (13), cyclo-(alpha,alpha'-2,6-lutidylene-1',7'-closo-1',7'-C(2)B(10)H(10))(2) (19), and cyclo-(alpha,alpha'-2,6-lutidylene N-oxide-1',7'-closo-1',7'-C(2)B(10)H(10))(2) (20) have been synthesized. The structures of 6a, 6b, 9, 11a, 11b, 11c, 12, and 19 have been determined by X-ray crystallography. Crystal data: for 6a, triclinic, space group P&onemacr;, a = 11.131(2) ?, b = 12.642(2) ?, c = 12.996(2) ?, alpha = 84.383(6) degrees, beta = 65.884(6) degrees, gamma = 97.292(5) degrees, Z = 1, R = 0.079; for 6b, monoclinic, space group P2(1)/a, a = 13.500(2) ?, b = 31.141(3) ?, c = 13.831(2) ?, beta = 99.90(1) degrees, Z = 2, R = 0.097; for 11a, monoclinic, space group C2/c, a = 14.5682(8) ?, b = 14.5046(8) ?, c = 16.1998(8) ?, beta = 95.631(2) degrees, Z = 4, R = 0.081; for 11b, monoclinic, space group P2(1)/n, a = 11.650(2) ?, b = 10.606(2) ?, c = 11.730(2) ?, beta = 104.951(6) degrees, Z = 2, R = 0.069; for 11c, orthorhombic, space group Pbca, a = 12.532(2) ?, b = 14.271(2) ?, c = 18.143(3) ?, Z = 4, R = 0.076; for 19, orthorhombic, space group Pcab (No. 61, standard setting Pbca), a = 11.0428(6) ?, b = 11.3785(6) ?, c = 22.533(1) ?, Z = 4, R = 0.074. 相似文献
A new diamine monomer containing benzimidazole‐5‐sulfonic acid has been synthesised. It has been reacted, alone or mixed with diaminodiphenyl ether, with naphthalenic dianhydride to attain polynaphthalimides in which the sulfonic acid functionality is borne by pendant benzimidazole groups. The presence of sulfonic and benzimidazole groups greatly affected the physical properties of the polyimides as the novel polymers were found to be soluble in polar organic solvents and exhibited a lower thermal resistance than their non‐sulfonated counterparts. The polymer films exhibited good mechanical properties with tensile strength in the range 100–120 MPa and with moduli in the range 2.2–3.1 GPa. Sulfonic and benzimidazole groups significantly enhanced the hydrophilicity of the copolyimides, which showed water uptake up to 39%.
A method for highly precise and high‐resolution imaging and location of oxygen‐containing groups on the walls of carbon nanotubes (CNTs) is presented. The soft‐chemistry approach is used by means of tagging oxygen‐containing groups on the surface of CNTs with EuIII through coordinate covalent bonds. EuIII ions bonded to oxygen‐containing groups are observed by high‐angle annular dark‐field scanning TEM.
Polymers bearing activated aziridine groups are attractive precursors to α‐substituted‐β‐amino‐functionalized materials due to the enhanced reactivity of the pendant aziridine functionalities toward ring‐opening by nucleophiles. Two aziridine‐containing styrenic monomers, 2‐(4‐vinylphenyl)aziridine (VPA) and N‐mesyl‐2‐(4‐vinylphenyl)aziridine (NMVPA), were polymerized under a variety of reversible deactivation radical polymerization conditions. Low‐catalyst‐concentration atom transfer radical polymerization (LCC‐ATRP) and reversible addition‐fragmentation chain‐transfer (RAFT) polymerization were ineffective at producing well‐defined polymers from VPA due to side reactions between the aziridine functionalities and the agents controlling the polymerizations (catalysts or chain transfer agents). PolyVPA produced under nitroxide‐mediated polymerization (NMP) conditions had narrow molecular weight distribution at low to moderate conversions of monomer, but branched and eventually cross‐linked polymers were formed at higher conversions due to ring‐opening reactions of the aziridine groups. Most of these undesirable side reactions were eliminated by attaching a methanesulfonyl (mesyl) group to the aziridine nitrogen atom, and well‐defined linear homopolymers with targeted molecular weights were realized from NMVPA under RAFT and NMP conditions; however, side reactions between the aziridine groups and the catalyst in LCC‐ATRP still occured and the polymerization was uncontrolled using this technique.
The properties of graphdiyne (GDY), such as energy gap, morphology, and affinity to alkali metals, can be adjusted by including electron-withdrawing/donating groups. The push–pull electron ability and size differences of groups play a key role on the partial property adjusting of GDY derivatives MeGDY, HGDY, and CNGDY. Cyano groups (electron-withdrawing) and methyl groups (electron-donating) decrease the band gap and increase the conductivity of the GDY network. The cyano and methyl groups affects the aggregation of GDY, providing a higher number of micropores and specific surface area. These groups also endow the original GDY additional advantages: the stronger electronegativity of cyano groups increase the affinity of GDY frameworks to lithium atoms, and the larger atomic volume of methyl groups increases the interlayer distance and provides more storage space and diffusion tunnels. 相似文献
The space group of [(H2O)(C3H4N2)(O2CCH=CHCO2Zn)]n, which was originally described in the acentric Pc space group (Liu et al., Chin. J. Struct. Chem. 2004, 23, 160~163), is re-described in the centric P21/c space group.The crystal structure of (H2O)(C3H4N2)O2C-CH=CHCO2Zn was refined in the acentric Pc space group on 266 variables to R = 0.037 for the 1926 of the 2067 obeying the I > 2σ criterion[1]. The structure is better described in the centric P21/c space group (Table 1) as the two indepen-dent formula units are related by a center of symmetry. The 21 screw axis is must be pre-sent, as noted from the systematically absent 0k0 (k = 2n + 1) reflections in the 3302 reflections that were simulated[2, 3] from the published cell dimensions and atomic coordinates. Crystallo-graphica[4] estimates the hemisphere of reflections to be 3302, so that only a little more than the minimum monoclinic data must have been collec-ted in the study. A revision from Pc to P21/c is not particularly common[5] as the P21/c space group is uniquely determined from systematic absences. The polymeric chain propagates linearly along the c-axis of the unit cell (Fig. 1). 相似文献
1 INTRODUCTION Resorcinarene-derived cavitands come in a varietyof subclasses, from shallower bowls to deeper vases,with the depth of the binding cavity reflecting thelength of the bridging group between the resorcinolresidues[1, . Methylene-bridged resorcinarenes are 2]used to construct several important and well establi-shed types of host compounds, including carcerandsand hemicarcerands, reversible capsules, and ho-lands[3~6]. Methylene-bridged tetramethylbowl cavi-tands p… 相似文献