Crystal chemistry of complex indium(III) and other M(III) halides, with a discussion of M—Cl bond lengths in complex M(III) chlorides and of the structures of and hydrogen bonding in (NH4)2[InCl5(H2O)], K3InCl6•nH2O, (MeNH3)4[InCl6]Cl, and (Me2NH2)4[InCl6]Cl

1987 ◽  
Vol 65 (7) ◽  
pp. 1527-1556 ◽  
Author(s):  
Osvald Knop ◽  
T. Stanley Cameron ◽  
D. Adhikesavalu ◽  
Beverly R. Vincent ◽  
James A. Jenkins

The crystal chemistry of complex In(III) halides is discussed and compared with that of other Group III elements and Fe(III), with critical comments and analysis of the available information. The cation/anion packing types occurring among A+[M3+X4] halides are classified according to volume per formula unit and the relative ionic sizes of M, X, and A, and the structural trends in this class of compounds are identified. The effect of systematic factors responsible for variation in M(III)—Cl bond lengths is examined in detail. It is shown that the mean M(III)—Cl bond lengths in [MClnLm]ε(M = Al, Ga, Fe, In, Tl; L = Cl or a neutral ligand) complexes can be approximated, to within about 0.02 Ă, by a linear function of the coordination number CN = n + m and the charge ε over the range 3 ≤ CN ≤ 6 and.−3 ≤ ε ≤2. This analytical expression provides a norm for comparing M(III)—Cl bond lengths and demonstrates that the CN is always a more important factor than ε in determining the variation in the mean bond length and that it becomes dominant when M is small. The crystal structure of (Me2NH2)4[InCl6]Cl (P21212, a = 10.156(4) Å, b = 13.007(4) Å, c = 8.751(3) Å, Z = 2) has been determined and those of (NH4)2InCl5(H2O)] (Pnma, a = 13.953(4) Å, b = 10.086(5) Å, c = 7.152(3) Å, Z = 4), K3InCl6•nH2O (I4mm, a = 15.659(8) Å, c = 18.106(5) Å, Z = 14) and (MeNH3)4[InCl6]Cl (P2/n, a = 16.113(3) Å, b = 7.446(2) Å, c = 16.163(4) Å, β = 103.75(2)°, Z = 4) redetermined. The water in K3InCl6•nH2O appears to be in part zeolitic; the hydrate examined contained more water than the monohydrate reported previously. Hydrogen bonding in these and related structures is described and discussed in detail; descriptions of the hydrogen-bonding schemes in (NH4)2[InCl5(H2O)] and (MeNH3)4[InCl6]Cl constitute the main improvement over earlier structure determinations.

1988 ◽  
Vol 43 (2) ◽  
pp. 171-174 ◽  
Author(s):  
Siegfried Pohl ◽  
Wolfgang Saak ◽  
Peter Stolz

(Ph4P)2Mn2Br6 (1) and (Ph3PCH2Ph)2Mn2I6 (2) were prepared from the reaction of manganese dihalide with the corresponding phosphonium halide in CH2Cl2.The structures of 1 and 2 were determined from single crystal X-ray diffraction data.Both compounds crystallize in the triclinic space group P 1 with one formula unit per unit cell.1:a = 998.1(1), b = 1005.7(1), c = 1313.3(2) pm, α = 108.51(1), β = 94.25(1), γ = 100.36(1)°.2: a = 1058.6(2), b = 1236.3(2), c = 1248.4(3) pm, α = 63.53(1), β = 74.15(1), γ = 74.65(1)°.The structures of 1 and 2 exhibit discrete, dimeric anions formed by the fusion of two identical tetrahedral-like units with a common halogen-halogen edge. The mean Mn-Hal bond lengths were found to be 251.8 pm (Mn-Br) and 272.2 pm (Mn-I). The difference between the bridging and terminal Mn-Hal bond lengths is about 12-13 pm in both compounds


1999 ◽  
Vol 63 (1) ◽  
pp. 17-26 ◽  
Author(s):  
U. Kolitsch ◽  
P. G. Slade ◽  
E. R. T. Tiekink ◽  
A. Pring

AbstractThe structure of antimonian dussertite, (AsO4)2(OH,H2O)6, has been refined in space group R3̄m with a 7.410(3), c 17.484(4) Å, Z = 3, to R = 3.2 % and Rw = 3.7 % using 377 observed reflections with I ≥ 3 σ(I). The structure is of the alunite-type and consists of sheets of corner-sharing (Fe3+,Sb5+)O6 octahedra parallel to (0001). The substitution of Sb5+ for Fe3+, and not for As5+, is unambiguously demonstrated not only by the structure refinement but also by electron microprobe analyses and crystal-chemical considerations. The icosahedrally coordinated Ba cations occupy cavities between pairs of octahedral sheets and are surrounded by six O atoms from the AsO4 tetrahedra and six O atoms from the (Fe3+,Sb5+)O6 octahedra. The mean bond lengths for the various coordination polyhedra are As-O 1.684(3) Å, (Fe,Sb)-O 2.004(1) Å, and Ba-O 2.872(2) Å. A hydrogen-bonding network is modelled using bond-valence calculations. The dussertite sample investigated is the first member of the crandallite group found to contain substantial Sb.


1994 ◽  
Vol 72 (5) ◽  
pp. 1273-1293 ◽  
Author(s):  
Pradip K. Bakshi ◽  
Antony Linden ◽  
Beverly R. Vincent ◽  
Stephen P. Roe ◽  
D. Adhikesavalu ◽  
...  

The aim of this investigation is to provide a classification and examples of N—H …π (and also O—H …π) bonds to the aromatic π systems in organic ammonium tetraphenylborates that would serve as reference for X—H …π(arene) bonds in general. To this end the crystal structures of the tetraphenylborates of the following cations have been determined: Me3NH+, Et3NH+, quinuclidinium, DabcoH+, Et(iso-Pr)2NH+ (monohydrate), (Ph3B)NH[—(CH2)2—]2NHMe+ (Me2CO solvate), Me2NH2+ (MeCN and Et2CO solvates), Et2NH2+, (iso-Pr)2NH2+, azoniacycloheptane, guanidinium (monohydrate), MeNH3+, EtNH3+, and 1-adamantammonium (monohydrate). These structures contain a variety of normal, bifurcated, and trifurcated N—H …π bonds as well as normal O—H …π bonds to the phenyl groups of the anion. The X—H …π bonds will form whenever opportunity arises, even though the result may be unfavourable bonding geometry. Branched bonds and orientational disorder represent compromise solutions in situations where the H(X) hydrogens are presented with competing phenyl acceptors or where the general organization of the crystal structure offers unfavourable bonding conditions to these hydrogens. The distributions of the distances from X or H(X) to the centre of the phenyl-ring skeleton are analyzed in detail, as are also those of the mean X … C and H(X)… C distances to the ring carbons.


1978 ◽  
Vol 33 (8) ◽  
pp. 881-883 ◽  
Author(s):  
Wolfgang May ◽  
Hans Georg von Schnering

Abstract By the weak acid interaction of polymeric phosphanes the condensation of ethylendi-amine yields in a small amount bicyclo-[4,4,0]-1,4,6,9-tetraazadecane C6H14N4. The compound crystallizes triclinic in the space group P1̅ with a = 841.6 pm, b - 463.6 pm, c = 529.2 pm, a= 109.05°, β= 108.35°, γ = 84.13° and Z= 1 formula unit per unit cell. The two condensed six-membered rings have chair conformations. The mean N-C bond lengths are 146.0 pm, the bridging C-C bond is 150.3 pm, whereas the other C-C bonds are 155.1 pm. Structure and condensation reaction are discussed.


2004 ◽  
Vol 23 (8) ◽  
pp. 413-419 ◽  
Author(s):  
Cetin Kaymak ◽  
Ela Kadioglu ◽  
Hulya Basar ◽  
Semra Sardas

In this study, genotoxic effects of repeated sevoflurane anaesthesia were investigated in rabbits with or without antioxidant supplementation. Twenty-one New Zealand male rabbits were included in the study and randomized into three groups as: placebo treated (Group I), vitamin E supplemented (Group II) and selenium supplemented (Group III). Vitamin E and selenium were given intraperitoneally for 15 days before anaesthesia treatment. Anaesthesia was administered using 3% sevoflurane in 4 L/min oxygen for a 3-hour period and continued for 3 days. Blood samples were collected before anaesthesia (Sample 1), after the first, second and third days of sevoflurane administration (Sample 2, Sample 3 and Sample 4 respectively) and the last samples were taken 5 days after the last sevoflurane administration (Sample 5). Genotoxic damage was examined using the comet assay. The degree of damage is assessed by grading the cells into three categories of no migration (NM), low migration (LM) and high migration (HM) depending on the fraction of DNA pulled out into the tail under the influence of the electric field. The number of comets in each sample was calculated (1 × number of comets in category NM + 2 × number of comets in category LM + 3 ×number of comets in category HM) and expressed as the total comet score (TCS), which summarizes the damage frequencies. In Group I, a significant increase in the mean TCSs was observed for Samples 3 and 4 as compared with Sample 1. However, there were no significant differences between Samples 1, 2 and 5. The mean TCS of Sample 4 was significantly higher than Sample 1, 2 and 3 in Group II. Group III demonstrated no significant mean TCSs for any experimental conditions. Statistical differences were also observed between the groups with significant P values. This experimental study points out the presence of DNA damage with repeated sevoflurane anaesthesia and the genoprotective role of antioxidant supplementation on DNA damage in mononuclear leukocytes of rabbits by highly sensitive comet assay.


2014 ◽  
Vol 32 (1) ◽  
pp. 30-70 ◽  
Author(s):  
Xiaohong Chen ◽  
David T. Jacho-Chávez ◽  
Oliver Linton

We establish the consistency and asymptotic normality for a class of estimators that are linear combinations of a set of$\sqrt n$-consistent nonlinear estimators whose cardinality increases with sample size. The method can be compared with the usual approaches of combining the moment conditions (GMM) and combining the instruments (IV), and achieves similar objectives of aggregating the available information. One advantage of aggregating the estimators rather than the moment conditions is that it yields robustness to certain types of parameter heterogeneity in the sense that it delivers consistent estimates of the mean effect in that case. We discuss the question of optimal weighting of the estimators.


1998 ◽  
Vol 39 (5) ◽  
pp. 538-542 ◽  
Author(s):  
R. Andresen ◽  
S. Radmer ◽  
D. Banzer

Objective: the clinical value of spinal quantitative CT (sQCT) and the structural patterns of the vertebral bone were studied Material and Methods: sQCT was performed on 246 patients with a mean age of 57 years for whom conventional lateral radiographies of the thoracic and lumbar spine were available. All patients were suffering from back pain of unknown etiology. the bone mineral density (BMD) of the midvertebral section of 3 lumbar vertebral bodies was determined by means of single-energy-(SE)-weighted QCT (85 kV). Spongiosa architecture and density profile analyses were made in the axial images. This was contrasted to BMD values ascertained in SE QCT. the mean BMD was compared to the number of fractures and the patients were divided into three groups: group I — no fracture; group II — one fracture; and group III 1 fracture Results: the mean BMD was: 134.3 (74.1–187.5) mg hydroxyapatite (HA)/ml in group I; 79.6 (58.6–114.3) mg HA/ml in group II; and 52.4 (13.1–79.1)mg HA/ml in group III. A significant deterioration in spongiosa structure was found with increasing demineralization: strongly rarefied patterns predominated in the fracture groups II and III Conclusion: sQCT provides a good risk assessment of the occurrence of vertebral body insufficiency fractures


1960 ◽  
Vol 11 (1) ◽  
pp. 75 ◽  
Author(s):  
M Wodzicka

The monthly wool growth of three groups of rams was studied at Beltsville, Maryland. Group I received natural daylight (at 38° 53' N.) and was shorn monthly. Group II had a 7:17 hours of daylight to hours of darkness rhythm and was shorn every 6 months, once in winter and once in summer. Group III received natural daylight and was likewise shorn every 6 months. The rams of all groups produced more wool in summer than in winter. This difference was significant (P<0.001). The mean body weight and food intake were both greater in the winter months, which indicated that the seasonal rhythm of wool growth was not a consequence of poorer feeding in winter. The rams which were shorn monthly (group I) grew considerably more wool than the other two groups, but the difference was not statistically significant. The short-day treatment of group II did not increase the annual wool production nor decrease the seasonal rhythm of wool growth. The balance of evidence from this and other experiments indicates that temperature rather than light controls the seasonal rhythm of wool growth.


Author(s):  
A. Prasanth Babu ◽  
P. Jagapathi Ramayya ◽  
Y. Nagamalleswari ◽  
Makkena Sreenu ◽  
K. Lakshmi Kavitha

Background: Affections of eye commonly encountered in all the species of animals. If these not treated in time, the vision may be hampered, this may impair the physical ability, utility and productivity of animals leading to economic loss to the animal owners. Corneal dystrophies like basement membrane dystrophy, stromal dystrophy, endothelial dystrophy, corneal erosions and corneal ulcerations etc., seen in the aged buffaloes. The current study was carried out to establish basic data and to provide authentic information to the clinicians on ageing changes in eyes of buffaloes.Methods: The study on age related changes in the cornea was conducted on 63 eye balls of locally available buffaloes of different breeds in and around Proddatur. These buffaloes were categorized into 3 groups based on their age i.e., group I (1-5 yrs), group II (6-10 yrs) and group III (11 yrs and above) buffaloes. The eyeballs were isolated and fixed with Davidson’s fluid. The paraffin sections of cornea were subjected for routine histological study.Result: The mean total thickness (µm) of cornea was increased from group I to III animals and it was 747.22±13.57, 853.33±11.05 and 897.22±8.06. Hence, The mean thickness (µm) of all five layers of cornea increased with advancement of age. Superficial corneal epithelial layer was made up of non keratinized stratified squamous epithelium with 6 to 7 layers at early age and 12-14 layers of cells in adult animals. The mean thickness (µm) of corneal epithelium in group I to III animals was 117.04±3.37, 122.59±2.23 and 133.71±3.55 respectively. Bowman’s membrane of cornea was measured 12.97±0.86, 17.22±0.55 and 18.71±0.68 in group I, II and III animals respectively. The mean thickness (µm) of corneal stroma in group I to III animals was 600.75±10.33, 672.22±10.46 and 690.00±5.32 respectively. This was mainly due to progressive increase in number of collagenous lamellae. The keratocytes became thin in old animals. Thickness of posterior band zone (PBZ) of Descemet’s membrane was increased with advancement of age. The mean thickness (µm) of Descemet’s membrane and endothelium together was in group I, II and III animals was 16.48±0.91, 41.29±2.25 and 54.82±1.44 respectively. The corneal endothelial cells were enlarged and increased in size in old buffaloes. The age related pigmentation was also noticed in epithelium and stroma of cornea in animals of group III. Density of sub basal nerve plexuses between the stroma and the corneal epithelium was not altered with advancement of age.


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