CRYSTALLOGRAPHIC D A T A
103. lsovanillin (3-Hydroxy-4-methoxybenzaldehyde) HARRY A. ROSE Lilly Research Laboratories, Indianapolis 6. Ind.
AxialRatio. a:h:e = 0.6341:1:0.4~91. Interfacial Angle (Polar). 110 A 110 = 64" 20' (x-ray). Beta Angle. 97' 30'. Cleavage. The crystals show very good cleavage partrallel to the 201 plane. Twinning. 101.
CHO
dCH, Structural Formula for lrovanillin
X-Ray Powder Diffraction Data d
crystals of isovanillin consisting of 010 blades and 001 plates may he obtained by orystallization from water. Although the study of venillin ( 1 ) showed several polymorphic forms, no polymorphism was found for isovanillin.
G
OOD
i 9
.
Jt%lod.)
7.1
7,7
7.12 6.71 6.37 5.26 5.02
.14 .71 .37 .25 .04
4.62 4.22 4.04 3.91 3.66
0.27 0.07
.62 .22 .03 6.~0.3.90 3.66
3.46 3.33 3.24 3.12 3.03
0.07 0.20 0.67 0.13 0.03
2.817 2.652 2.511 2.473 2.226
0.03 0.03 0.07
2 093
2 012
1 903
la",
121
031
13i 201 211 140 112
3.45 3.32 3.23 3.12 3.04
0.03 0.07
0 03 0 03 0 07
I
b#:9730' 39-13'
I
rl C
C
1
b-
'1 110
Figure 1. Sublimed crystals of isovanillin obtained on cover slip while heating a few milligrams of sample
__-
-__
(T} p+,
The x-ray powder diffraction data were obtained using a camera. 114.6 mm. in diameter with chromium radiation and vanadium filter. A wave-lenpth value of 2.2886 A. was used in the calculations. The determination of the space group as P2da was based on a and e axis rotation patterns and a aero layer Weissenberg pattern with b axis rotation. These patterns showed that h01 was present only with h even and that OkO was present only with k even.
Figure 2. Orthographic projection of isovanillin
X-RAYDIFFEACTION UATA Cell Dimensions. a = 8.51 A,, b = 13.42 A,, c = 6.43 A. . Formula Weights per Cell. 4. Formula. Weight. 152.1. Density. 1.401 grams per cc. (displacement), 1.390 grams per cc. (x-ray). Space Group. CZh - P2,Ia.
CRYSTAL MORPEOLOGY Crystal System. Monoclinic. Form and Hahit.. Blades lying an 010 elongated parallel to a and plates lying on 001. The blade8 are terminated hy the prism (1101.
267
OFTLGAL PROPERTIES Refractive Indices (5893 A,. 25" C.1.
a =
1.450. 8 = 1.680,
, ,. Dispersion. Strong, r > u. Optic Axial Plane. 010. Acute Bisectrix. a. Extinction. a A a = 39' 15' in ohtuse 8. FU~ION B ~ n a m o a . Isovanillin melts a t 114-5" C. with sub-
limation but no decomposition. The sublimate is well formed (Fipure 1) and shows dates lying on 010 with (110), 11011,
LITERATURE CITED
(1) Mecrone, IV. C.. ANAL.C n m 22, ~ 500 (1950).
104. D-fructose 2,4-Dinitrophenylhydrazone Dioxane Solvate FRANCIS T. JONES, D A L E R. BLACK, and LAWRENCE M. \xlHlTE Wertern Utilization Research Branch, Agricultural Research Service,, U. 5. Department of Agriculture, Albany 10, Calif.
r THE
preparation of D-fructose 2,4-dinitrophenylhydrasone
1 dioxane solvate (CaHt6N4Op.C,HsOe)hits been described by
White and Seeor ( 1 , 8 ) . Their yellow crystalline preparations were used in this study. Fresh preparations were used in order to avoid a surface film of decomposed material. Fresh surfaces obtained by fracturing the cryntals could be used for refractive index determinations. The tips appeared different from the blade in some cases.
Form and Habit. Loose clusters of slender blades or noedles tapering to shows crys elongation Fi re 2 &I 'e inconspicuous. Tdnning 'was not observed gterfacial Angles. No angles could be measured, although the cross sectiasn shown in Figure 2 is approximately correct. X-RAYDIE 'FRACTION DATA Space Group. Probably D: - P2,2,2,, but possibly 0: P 2 M , since only the first four orders of 001 observed. Also observed fi rst 14 orders of h00 and first 10 orders of OkO. Cell Dimiensmns. a = 20.669 A., b = 20.788 A,, c = 4.788 A. Axial Ratio. a:b:c = 0.9943:1:0.2303. Formula Weights per Unit Cell. 4(4.061 calculated). Formula Weight. 448.38. Density. 1.4693 grams per cc. (density gradient tube). ~~
~~~
~~~~
~
~
~
~
~
~
~
OFTICAL PROPERTIES Refractive Indices (5893 4.;2 i " '2.). a = 1.593 i 0.001. = 1.872 i 0.004. B = 1.607 A 0.002. Optic Axial Angles (5893 A,; 27' C.). 2E = 42 4z 2'; 2V = 26' calculated from 2E and 8 ; 2V = 29' calculated from a@-,.
-,
>b' " i :"< Y=1.872 C I
Figure 1. D-Fructose 2,4-dinitmphenylhydrazone dioxane solvate
(ZWX)
-4 crystal mounted on a goniometer head was used for x-ray diffraction. The same mounted crystal was used for the observatioo of the relstionship between crystallographic axe8 and optical properties. I n spite of many attempts t o grow large crystals, the crystal faces were always too small to give observable reflections on the optical goniometer.
CRYSTAL MORPHOLOGY Crystal System. Orthorhombic, Class 6 bisphenoidal, enantiomorphic.
Figure 2. Orthographic projection of typical crystal of fructose 2,4-dinitrophenylhydrazone dioxane solvate
