Dimorphs

Boron trioxide is not particularly soluble in water but it slowly dissolves to form both dioxo(HB02)(meta) and trioxo(H3B03) (ortho) boric acids. It is a dimorphous oxide and exists as either a glassy or a crystalline solid. Boron trioxide is an acidic oxide and combines with metal oxides and hydroxides to form borates, some of which have characteristic colours—a fact utilised in analysis as the "borax bead test , cf alumina p. 150. Boric acid. H3BO3. properly called trioxoboric acid, may be prepared by adding excess hydrochloric or sulphuric acid to a hot saturated solution of borax, sodium heptaoxotetraborate, Na2B407, when the only moderately soluble boric acid separates as white flaky crystals on cooling. Boric acid is a very weak monobasic acid it is, in fact, a Lewis acid since its acidity is due to an initial acceptance of a lone pair of electrons from water rather than direct proton donation as in the case of Lowry-Bronsted acids, i.e. 

C,H,CH,- —C-NH,j The compound separates in either, sometimes as both, of two dimorphic forms, m.p. 150° and 175° respectively. The former may be converted into the higher m.p. form by dissolving It in alcohol and seeding with crystals of the form, m.p. 175° the low m.p. form when warmed to 175° gives, after sohdification, a m.p. of 175°. Both dimorphic forms give identical derivatives with carboxyUc acids and sulphonic acids (see Sections 111,85 and IV,33). 

Method 1. Dissolve 76 g. of thiourea in 200 ml. of warm water in a 750 ml. or 1 litre round-bottomed flask. Dilute the solution with 135 ml. of rectified spirit and add 126-5 g. of benzyl chloride. Heat the mixture under reflux on a water bath until the benzyl chloride dissolves (about 15 minutes) and for a further 30 minutes taking care that the mixture is well shaken from time to time. Cool the mixture in ice there is a tendency to supersaturation so that it is advisable to stir (or shake) the cold solution vigorously, when the substance crystallises suddenly. Filter off the sohd at the pump. Evaporate the filtrate to about half bulk in order to recover a further small quantity of product. Dry the compound upon filter paper in the air. The yield of hydrochloric acid filter off the sohd which separates on cooling. Concentrate the filtrate to recover a further small quantity. The yield of recrystalhsed salt, m.p. 175° is 185 g. some of the dimorphic form, m.p. 150°, may also separate. 

Natural titanium is reported to become very radioactive after bombardment with deuterons. The emitted radiations are mostly positrons and hard gamma rays. The metal is dimorphic. The hexagonal alpha form changes to the cubic beta form very slowly at about 88O0C. The metal combines with oxygen at red heat, and with chlorine at 550oC. 

Tripotassium hexakiscyanoferrate [13746-66-2] K2[Fe(CN)g], forms anhydrous red crystals. The crystalline material is dimorphic both orthorhombic and monoclinic forms are known. The compound is obtained by chemical or electrolytic oxidation of hexacyanoferrate(4—). K2[Fe(CN)g] is soluble in water and acetone, but insoluble in alcohol. It is used in the manufacture of pigments, photographic papers, leather (qv), and textiles and is used as a catalyst in oxidation and polymerisation reactions. 

Since there are no volatile components this halophosphate phosphor is prepared with close to the stoichiometric amounts of SrHPO, SrCO, CaCO, BaCO, SrCl2, or NH Cl and EU2O2. The blend is fired under an atmosphere containing 1—2% hydrogen at 1100°C. A small excess of chloride provides some fluxing action and gives weU-formed crystals of apatite. The chlorapatites are dimorphous one modification is hexagonal and the other monoclinic. 

Manganese(III) Oxides. The sesquioxide, Mn202, exists in dimorphic forms. The a-Mri202 exists in nature as the mineral bixbyite. 

Steroid Hormones and Neurosteroids. Steroids (qv) can affect neuroendocrine function, stress responses, and behavioral sexual dimorphism (78,79) (see Steroids). Mineralocorticoid, glucocorticoid, androgen, estrogen, and progesterone receptors are localized in the brain and spinal cord. In addition to genomic actions, the neurosteroid can act more acutely to modulate the actions of other receptors or ion channels (80). Pregnenolone [145-13-17, ( ) dehydroepiandosterone [53-43-0] C H2 02 (319) are excitatory neurosteroids found in rat brain, independent of adrenal... 

Properties. o-Nitiotoluene [88-72-2] is a clear yeUow liquid. The solid is dimorphous and the melting points of the a- and P-forms ate —9.55 and —3.85 C, respectively. o-Nitrotoluene is infinitely soluble in benzene, diethyl ether, and ethanol. It is soluble in most organic solvents and only slightly soluble in water (0.065 g in 100 g of water at 30°C). The physical properties of o-nitrotoluene are hsted in Table 9. 

Alkali Metal Perchlorates. The anhydrous salts of the Group 1 (lA) or alkah metal perchlorates are isomorphous with one another as well as with ammonium perchlorate. Crystal stmctures have been determined by optical and x-ray methods (38). With the exception of lithium perchlorate, the compounds all exhibit dimorphism when undergoing transitions from rhombic to cubic forms at characteristic temperatures (33,34). Potassium perchlorate [7778-74-7] KCIO, the first such compound discovered, is used in pyrotechnics (qv) and has the highest percentage of oxygen (60.1%). 

Properties and Reactions. Phosphoms sulfochloride [3982-91-0] (thiophosphoryl chloride), PSCI3, is a colorless fuming Hquid andis made by the reaction of phosphoms trichloride with sulfur and by the reaction of PCI3 with P2S3. Phosphoms sulfochloride is dimorphic in the soHd state. It reacts with water, forming either phosphoric acid or dichlorothiophosphoric acid [14500-94-8] depending on the reaction conditions. 

H. P. Klug and L. E. Alexander in 3i-Taj Diffraction ProceduresforPoljcrystalline and dimorphous Materials 2nd ed., John Wiley Sons, New York, 1974. 

Silver nitrate forms colorless, rhombic crystals. It is dimorphic and changes to the hexagonal rhombohedral form at 159.8°C. It melts at 212°C to a yellowish Hquid which solidifies to a white, crystalline mass on cooling. An alchemical name, lunar caustic, is stiU appHed to this fused salt. In the presence of a trace of nitric acid, silver nitrate is stable to 350°C. It decomposes at 440°C to metallic silver, nitrogen, and nitrogen oxides. Solutions of silver nitrate are usually acidic, having a pH of 3.6—4.6. Silver nitrate is soluble in ethanol and acetone. 

Silver Sulfide. Silver sulfide, Ag2S, forms as a finely divided black precipitate when solutions or suspensions of most silver salts are treated with an alkaline sulfide solution or hydrogen sulfide. Silver sulfide has a dimorphic crystal stmcture. Transition from the rhombic (acanthite) to the cubic (argentite) form occurs at 175°C. Both crystal stmctures are found in nature. 

Antimony Trioxide. Antimony(III) oxide (antimony sesquioxide) [1309-64-4] Sb203, is dimorphic, existing in an orthorhombic modification valentinite [1317-98-2] is colorless (sp gr 5.67) and exists in a cubic form and senarmontite [12412-52-17, Sb O, is also colorless (sp gr 5.2). The cubic modification is stable at temperatures below 570°C and consists of discrete Sb O molecules. The molecule is similar to that of P40 and As O and consists of a bowed tetrahedron having antimony atoms at each corner united by oxygen atoms lying in front of the edges. This solid crystallizes in a diamond lattice with an Sb O molecule at each carbon position. 

Antimony Tribromide and Triiodide. Antimony(III) bromide [7789-61-9] SbBr, is a colorless, crystalline soHd having a pyramidal dimorphic molecular stmcture and an acicular (a-SbBr ) and a bipyramidal (P-SbBr ) habit. 

Ketoconazole is active against dermatophytes (Microsporum, Trichophyton Tpidermophyton) yeasts Candida species, Cyptococcus) and the dimorphous... 

Cadmium Sulfide. CdS [1306-23-6] is dimorphic and exists ia the sphalerite (cubic) and wurtzite (hexagonal) crystal stmctures (40). At very high pressures it may exist also as a rock-salt stmcture type. It is oxidized to the sulfate, basic sulfate, and eventually the oxide on heating ia air to 700°C, especially ia the preseace of moisture (9). 

Alkenoic acids also have polymorphic crystalline forms. For example, both oleic and elaidic acids are dimorphic with melting points of 13.6 and 16.3°C for oleic, and 43.7 and 44.8°C for elaidic acid (14). 

The mammalian and avian immune systems function similarly both incorporate humoral and cell-mediated cytotoxic mechanisms, " and are thought to share a 160m year old relationship with the reptilian immune system. The immune system of mammals shows sexual dimorphism " a greater immune response is normally observed in females, which has been attributed to differences in steroid hormone concentration. In the toad Bufo regularis, sexual dimorphism of the immune system is also apparent. ... 

By a modified Bischler-Napieralsky reaction, 6 -nitrophenylaceto-jS-3 4-methylenedioxyphenylethylamide, resulting from the condensation of -3 4-methylenedioxyphenylethylamine with 2-nitrophenylacetyl chloride, was converted into 6 nitro-l-benzyl-6 7-methylenedioxy-3 4-dihydroisoquinoline. The methiodide of the latter was reduced with zinc and hydrochloric acid to 6 -amino-l-benzyl-2-methyl-6 7-methylenedioxy-1 2 3 4-tetrahydro/soquinoline dihydrochloride, which by the Pschorr ring-closure reaction, produced dZ-roemerine (IV, p. 317), m.p. 85-7°. By treatment in succession with d- and Z-tartaric acids, the dZ-base was resolved into Z- and tZ-forms. Synthetic Z-roemerine is dimorphic, m.p. 85-7° and 102°, and has [aju — 79-9° (EtOH), these constants being in good agreement with those of the natural base. 

Under similar conditions, but with palladised charcoal as catalyst, solasodine forms a dihydro-derivative, C27H45O2N, m.p. 208-5-210-5°, [a] ° — 63-5° (CHCI3), and in presence of platinic oxide, a tetrahydro-derivative, C27H4,02N, which is dimorphic, m.p. 292-5°, and 285-291°, [air - 4-94° (CHCI3). 

This table shows that the similarity of the two aglycones is most marked in their salts, but they do not appear to be dimorphic forms giving identical salts, for the melting-points of the bases are unchanged after sublimation, the rotations of the two bases in solution are different, though those of the two hydrochlorides are identical within the limits of experimental error, and all attempts at interconversion of the two bases... 

Several carboxylates, both simple salts and complex anions, have been prepared often as a means of precipitating the An ion from solution or, as in the case of simple oxalates, in order to prepare the dioxides by thermal decomposition. In K4[Th(C204)4].4Fl20 the anion is known to have a 10-coordinate, bicapped square antipris-matic structure (Fig. 31.8b). -diketonates are precipitated from aqueous solutions of An and the ligand by addition of alkali, and nearly all are sublimable under vacuum. [An(acac)4], (An = Th, U, Np, Pu) are apparently dimorphic but both structures are based on an 8-coordinate, distorted square antiprism. 

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