ANALYTICAL CHEMISTRY
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Radiation Protection,provisional draft of paper on ssfe handling of rsdioisotopes. (3) Symposium on Design of Radioohemistry Laboratories, Division of Chemical Education. Ind. Eny. Chenz.. 41, 227-50 (1949).
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R ~ C E I V E DApril
23. 1948.
Work supported in part by the Offiae of ~ s v a l
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HIS, the twelfth in the series of crystal descriptions, oompletes the first yew of publication. Although only fifteen of the thousands of common and important compounds have been published, it is hoped that the data presented will he useful in themselves and as an aid in eventual complete structure determinations. It is further hoped that means can he found in the near future to increase the number of descriptions published each month. During the past year several people have been kind enough to point out inconsistencies and errors in the published data. The major corrections required, however, are in the indexing of the powder lines. T h e principal errors include listing of reflections
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forbidden by the space group. Table I gives the correct index values for those compounds involved. The authors are grateful to I. Fankuchen for bringing these to their attention. They have also found, as a result of checking, that a and care reversed in the description of paminoambenzene. This does not, however, affect the other data, which were calculated with the correct a and e. In future, index values will not be given for powder data hecause they are not in themselves analytical data and do not aid in cross checking other orystallographio data which are published in this series.
15. Benzalaminophenol ~ - c H = N - O - O H Structural formula
Figure 1. p-Benzalaminophenol C m f d s from sublimation on mimacops slide Ribht. Fu~ioopreparation Left.
Bemalitminophenol crystallizes readily from alcohol, either by oooling or by dilution a t room temperature with water. .The crystals thus obtained are apparently identical with each other m d with crystals obtained by sublimation or from fusion-no differences could be found microscopic$ly, although powder diffraction data were slightly differentfor a sublimed sample and for crystals obtained by dilution of an alcohol solution (see below). The crystals used for x-ray diffraction were prepared by vacuum maerasublimation; the crystals for optical crystallography and morphology were recrystallieed from alcohol.
V O L U M E 2 1 , NO. 2, F E B R U A R Y 1 9 4 9 Table I. Adipic Acid d Index 6.82 001 4.67 202,202 4.49 4.13 oi i,'o i 1 3.79 3.52 260 3.45 002 3.31 2io 2.86 2.53 020 2.51 201 2.41 120 2.32 2.26 663 2.19 ... 2.14 2 10 220 2.04 022 1.92 ... 1.87 202 1.80 222 1.76 400 1.71 004 1.50 222 1.45 420 1.42 024 1.40 1.28 640 1.24 402 1.22 240
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Indexing of Powder Lines (Corrected)
trans-hzobenzene d Index 7.03 002 5.59 200 5.33 011 5.12 110 4.88 4.62 663 4.54 111 4.47 012 4.30 4.18 4.02 210 .. 3.82 3.75 , . 3.67 202 3.51 004 3.39 3.29 3.19 ... 3.09 ... 3.00 2.88 626 2.80 005,400 2.68 022 2.57 220 2.51 204 2.45 ... 2.34 006 2.27 222
p-Methylaminophenol Sulfate p-ilminoazobenzene Thiamine Hydrochloride d Index d Index d Index 9.33 200 9.05 101 ... 7.79 7.37 111 002 6.86 6.51 002 5.87 301,010 5.25 202, Q l l , 110 200 5.80 5.60 110 4.97 5.42 021 111 5.44 01 1 221 4.56 4.86 202 400 4.66 210,012 111 4.31 4,683 4.43 112 4.17 4.363 103 T21 311,402 4.02 3.99 112,211 4.056 500,013 3.76 3.55 400,303 246 3.829 004,303 3.66 3.28 3,403 204 212 204 3.48 2.93 3.201 204 002 3.37 2.79 3,122 020 012,312 3.09 600 2.60 2,889 400,112 022,220 2.92 020,005 2.48 2.787 022.420 222 2.81 2.44 220 042 2.684 2.74 221 2.39 2.559 360 222 2.67 2.31 206, 603 2.495 440 006 2.61 2.19 222 442 420 2.400 2.49 420 2.12 2,333 222 $05 2.43 2.07 2,259 206 2.37 505;422 %42,'460 2.01 2.196 224,422 2.33 1.96 2.156 333,462 800 2.28 024 1.87 003 505 2.106 2.25 224 1.79 2,062 023 2.20 505,224 1.76 2.015 550,033 io6 2.13 620 1.73 008,033,330 ... 2.08 900,424 1.63 408 ... ... 2.03 424,622 ... ... ,.. .. 1.95 030,130 ... ... , . ,.. 1.88 026 .. .. ... ... 1.84 033 Because the beta angle for p-methylaminophenol sulfate is almost 90' no effort has been made t o differentiate between positive a n d negative h. 911 hk values for this compound then m a y be hkl.
CRYSTAL MORPHOLOGY (determined by W. c. McCrone). Crystal System. Monoclinic Form and Habit. The crystals prepared by sublimation are usually elongated parallel to a and show the clinopinacoid [ 0101, basal pinacoid [ O O l ] , and prism [110]. Crystals from alcohol may show additional dome forms and are usually not elongated. AxialRatio. a:b:c = 0.839:1:0.434. Interfacial Angles ( p l a r ) . 110 A 110 = 73". Betailngle. 11g1/2 * 118.6" (x-ray). Twinning Plane. 106. Color and Pleochroism. The crystals are a light yellow when pure and show slight pleochroism with strongest absorption along 2 and least absorption along X. X-RAY DIFFRACTION DATA(determined by J. F. Whitney and I. Corvin). Cell Dimensions. a = 12.54; 6 = 14.93; c = 6.48. Formula Weights per Cell. 4. Formula Weight. 197.23. Density. 1.303 (buoyancy); 1.25 (x-ray).
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d 8.74 7.48 6.46(s) 5.94 5.43(r) 5.25 4,85(r) 4.73(r) 4.46 4.19(s) 4.06(s) 3.91 3.661 3,514 3,333 3.233 3.152 3,076 2.886
Principal Lines 1/11 d 0.09 Very weak 0.10 0.24 Very weak, unresolved 0.73 Very weak Very weak 1.00 0.66 0.27 0.30 0.82 Very weak Very weak 0.155(s), very weak(r) 0.38 0.42 0.10
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s, sublimed. recrystallized from alcohol. 411 lines except those noted are present in both sublimed and recrystallized samples. T,
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Figure 2.
Orthographic Projection of Typical Crystal of p-Benzalaminophenol
OPTICALPROPERTIES (deter5ined by W. C. McCrone). Refractive Indices (5893A.; 25" C.), ~r = 1.698 * 0.002. B = 1.736 =t0.002. y = 1.84 * 0.01. Optic Axial Angles (5893A.; 25' C . ) , 2V = 63". Dispersion. v> r, very strong. Optic Axial Plane. 010. Sign of Double Refraction. Positive. Acute Bisectrix. y A a = 34" in obtuse beta. Extinction. ahc = 3' (blue); 5' (yellow) in obtuse beta. Molecular Refraction ( R ) (5893A.; 25" C.), I j / ~ r p y= 1.756. R(ca1cd.) = 61.3. R(obsd.) = 62.1. FUSION DATA(determined by W. C. McCrone). p-Benzalaminophenol melts a t 183 C. without decomposition. If heated slowly, however, excellent crystals can be collected by sublimation on the underside of the cover glass. These crystals show 001,010, and 110 and lie on 010 with a 60" profile angle or 001 with a 100" profile angle. The melt supercools readily but eventually solidifies spontaneously, albeit very slowly a t room temperature. The crystal form is spherulitic a t low temperatures; however, a t higher temperature the crystals are larger and grow parallel over large areas. A meltback gives rapid crystallization of broad rods, some crystals showing brilliant purple polarization colors indicating very high dispersion. The off-center optic axis interference figure shows a high 2E, very strong inclined dispersion, positive sign of double refraction, and S X . outside the field. Some rods show oblique extinction and a flash figure.
