Crystal and molecular structures of three dihalobenzocyclobutenes

Chem. , 1968, 72 (2), pp 668–676. DOI: 10.1021/j100848a048. Publication Date: February 1968. ACS Legacy Archive. Cite this:J. Phys. Chem. 72, 2, 668...
0 downloads 0 Views 1MB Size
668

G. L. HARDGROVE, L. K. TEMPLETON, AND D. H. TEMPLETON

Crystal and Molecular Structures of Three Dihalobenzocyclobutenes'

by George L. Hardgrove,2Lieselotte K. Templeton, and David H. Templeton Department of Chemistry and Lawrence Radiation Laboratory, Uniaersity of California, Berkeley, California 94720 (Received August 16, 2967)

It is shown by single-crystal X-ray diffraction that cis-1,2-dichlorobenzocyclobutene(mp 91-92') is monoclinic, space groupo P2'/c, with unit cell dimensions at 25 and -19500, respectively: a = 8.60(2), 8.48(4) A; b = 11.06(5), 10.95(2) 8; c = 8.78(2), 8.56(2) A ; /3 = 110.5(2)', ll0.9(2)" (estimated error of last digit in parentheses). The corresponding bromide and iodide are orthorhombic, space group Pna21, with unit cell dimensions, respectively: a = 16.18(3), 16.43(3) 8; b = 11.79(2), 12.46(2) i;c = 4.38(1), 4.49(1) i. Atomic positions have been refined by least squares for all three substances, but most accurately for the chloride at low temperature. Except for the bond lengths involving halogen atoms, no significant difference in molecular dimensions is found. In the chloride, the cyclobutene ring is planar rather than skewed. Its plane is the same as that of the benzene ring within 1.5". Average C-C bond distances are 1.39 in the benzene ring, 1.48 8 adjacent to the benzene ring, and 1.58 in the bond between aliphatic atoms. The strain of bond angles extends into the benzene ring, in which C-C-C angles range from 114 to 124". The orthorhombic structures offer striking examples of a difficulty of interpretation in the presence of anomalous dispersion when one has a polar space group, t n effect called the "polar dispersion shift." The average C-C1 bond distance is 1.78 A, C-Br is 1.96 8, and C-I is 2.15 8. We have studied the crystal structures of three cis-l,2-dihalobenzocyclobutenes

crystals of the chloro compound have the molecules packed together in a different way. The structures of all three compounds were first determined at room temperature. We were dissatisfied with the accuracy of the chloro structure, which was poor at least in part because of large and anisotropic thermal motion, and this determination was repeated at - 195' with better results. The early part of the work is described by Hardgrove in his thesis.9 The present paper presents his structure for the bromide, the results of more extensive refinement of the low-temperature chloride structure, and a recalculation of the iodide structure.

where X represents chlorine, bromine, or iodine. These compounds can also be named as cis-7,s-dichlorobicyclo [4.2.0]octa-1,3,5-triene, etc. We were interested in the molecular geometry of this strained ring system and the effect of changing the size of the halogen substituents. This investigation, started in 1958, has been exceptionally fruitful of crystallographic diffiExperimental Section culties and opportunities for error. It was our first experience in use of the full matrix in least-squares The samples were prepared by Professor F. R. Jensen refinement and introduced us to certain complications and Dr. W. E. Coleman, who kindly made them availof polar space groups which are described e l ~ e w h e r e . ~ , ~ A more recent stage of the calculation, made necessary (1) Work done under the auspices of the U. s. Atomic Energy Comby the discovery of a major blunder, revealed one of mission. the first few examples of the "polar dispersion shift" (2) Chemistry Department, St. Olaf College, Northfield, Minn. (3) D. H. Templeton, Acta Cryst., 12, 771 (1959). and its unpleasant consequence^.^-^ (4) D. H.Templeton, 2.Krist., 113, 234 (1960). The present paper presents the structural results, (5) T. Ueki, A. Zalkin, and D. H. Templeton, Acta Cryst., 20, 836 which show an interesting shape for the cyclobutene (1966). ring and incidentally give a confirmation of the assign(6) A. Zalkin, T. E. Hopkins, and D. H. Templeton, Inorg. Chem., 5, 1767 (1966). ment of cis and trans isomers which was made by Jensen (7) D.W.J. Cruickshank and W. S. McDonald, Acta Cryst., 23, 9 and Coleman* on the basis of dipole moments and (1967). isomerization equilibrium constants. (8) F. R. Jensen and W. E. Coleman, J. Org. Chem., 23, 869 (1958). The orthorhombic crystals of the bromo and iodo (9) G. L. Hardgrove, Thesis, University of California, Berkeley, compounds are isomorphous, while the monoclinic 1959. The Journal of Physical Chemistry

CRYSTAL AND MOLECULAR STRUCTURES OF DIHALOBENZOCYCLOBUTENES able to us. They prepared cis-1,2-diiodobenzocyclobutene (CsHsIz, needles, mp 150") as described elsewhere.8 Infrared and ultraviolet spectral analysis showed it to be free of the trans isomer which crystallizes as prisms, mp 62-63". Treatment of the diiodo compound with bromine yielded cis-1,Bdibromobenzocyclobutene (needles, mp 101-102"). I n like manner cis-1,2-dichlorobenzocyclobutene(plates, mp 91-92") was prepared by treatment of the diiodo compound with chlorine water. X-Ray diffraction data were recorded by photographic methods with rotation and Weissenberg techniques using Cu K a radiation, and with the precession technique using Mo K a radiation. A nearly cylindrical crystal of the bromine compound (radius 0.0190.026 mm, elongated along c) was sealed in a thinwalled glass capillary because of its appreciable vapor pressure. A similar crystal of the iodine compound (radius 0.020-0.029 mm) was mounted on the end of a glass fiber. Unit cell dimensions were determined from quartz-calibrated rotation photographs (for c) and from hlcO quartz-calibrated Weissenberg films (for a and b). , The cell dimensions a = 4.913 8 and c = 5.405 8 were assumed for quartz. The standard quartz crystal was checked with an NaCl pattern to an accuracy of one part in 3000. Diffraction intensity data were estimated for multiple-film Weissenberg photographs of the hkO, hkl, hk2, and hk3 layers by visual comparison with an intensity standard. For the bromine and iodine compounds, respectively, 443 and 599 independent reflections were observed, while 170 and 266 others were too weak to be observed in the part of reciprocal space which was investigated. The relative scaling of the Weissenberg layers was based on precession photographs of the h01, hll, and Okl layers. The intensities from the C8HeIz crystal were corrected for absorption by the method of Bond,"J using the tables of Bradley (as reproduced by Klug and Alexander" with the parameter p r = 0.58. For CsH6Brz ( p r = 0.14) absorption was neglected. The sample of C8H&& was recrystallized several times from a hexane-ether solution by slow evaporation at room temperature in order to grow crystals of sufficient size for diffraction experiments. The crystals are plates parallel to (100). Cell dimensions were derived from quartz-calibrated photographs of a crystal aligned on [OlO]; b was determined from a rotation photograph, and the other parameters from the h01 Weissenberg layer. A second crystal, a piece cut from a plate, was sealed in a thin-walled glass capillary and aligned on [ O l l I. Multiple-film Weissenberg photographs were taken through the twelfth layer on the newer "improved" Kodak medical no-screen X-ray film at 25". Factors which adjusted the intensities from various layers to the same scale were based on equivalent reflections which fell on two levels. There were

669

844 independent observed reflections and 303 unobserved in the portion of the reciprocal lattice which was photographed. For the low-temperature measurements, some crystals of CsH&l2 were sealed in a thin-walled glass capillary of 0.2 mm diameter. The sample was melted and recrystallized very slowly in a hot air stream. Several cylindrical single crystals longer than the diameter of the X-ray beam were prepared in the capillary. One of these was aligned on the a axis. The X-ray exposures a t liquid nitrogen temperature were taken using the equipment described by Olovsson and Templeton.'* Gaseous dry nitrogen was obtained from a 100-1. dewar flask of liquid Nz by a constant input of electrical heating. The gas was recooled by passage through a copper coil in another dewar of liquid nitrogen, and finally the cold gas was transferred through a dewar tube onto the capillary. The temperature was measured with a copper-constantan thermocouple and did not vary more than 4" from the lower limit of -195". No phase transition was observed on cooling. Cell dimensions were derived from quartz-calibrated rotation and Okl Weissenberg patterns. The angle P was determined from the upper-layer Weissenberg photographs by the method of angular lag.13 Multiplefilm Weissenberg photographs were taken through the 6kl layer with Ilford Industrial G film. This film showed much less fogging of the background and made weak intensities easier to observe than did the Kodak film then available to us. Intensities were estimated visually for 972 independent reflections, and 209 others were recorded as too weak to be observed. No relative scale factors between layers were determined experimentally; they were adjusted in the leastsquares calculations as described below. S o correction was made for absorption, which is estimated to be unimportant. Fourier calculations were made with Beevers and Lipson strips or with the IBM-701 computer and the program of Dodge.14 The early refinements by least squares used the IBM-650 computer and Senko's LS-I1 program,I5 which neglects nearly all off-diagonal terms. This program was modified for some of the later cycles to permit full-matrix calculations with the help of the IBM-701 for the matrix inversion. The last refinements of the chloride and iodide structures used the IBM-7044 and the unpublished programs of Dr. A. Zalkin, 1965 and 1966 versions. Atomic scattering factors, in each case for neutral (10) W. L. Bond, Acta Cryst., 12, 375 (1959). (11) H. P. Klug and L. E. Alexander, "X-ray Diffraction Procedures," John Wiley and Sons, Inc., New York, N . Y., 1954, p 155. (12) I. Olovsson and D. H. Templeton, Acta Cryst., 12, 827 (1959). (13) M. J. Buerger, "X-ray Crystallography," John Wiley and Sons, Ino., New York, N . Y., 1942, p 377. (14) R. P. Dodge, Thesis, University of California, Berkeley, 1958. (15) M . E. Senko, Thesis, University of California, Berkeley, 1956.

Volume 76, Number 6 February 1968

G. L. HARDGROVE, L. E(. TEMPLETON, AND D. H. TEMPLETON

670

atoms, were taken from Thomas and Urnedal6 for bromine and iodine, from Hoerni and Ibers" for carbon in the bromine compound, and from the International Tables'* for chlorine and for carbon in the chlorine and iodine compounds. For chlorine, 0.3 was added for the real part of the dispersion effect. For iodine, -1.03 was added for the real part and 6.68 for the imaginary part.

Crystal Data Crystals of CsHeBr2 and CsH& are orthorhombic, space group Pna21, with the cell dimensions listed in Table I. With four molecules per cell, the density is Table I

a b C

CaHsBrz

CsHsIz

16.18 f 0 . 0 3 A 11.79 & 0.02 b 4.38 z t 0.01 b

16.43 f 0 . 0 3 b 12.46 f 0.02 b 4.49 & 0 . 0 1 b

calculated to be 2.08 g/ml for the bromide and 2.58 g/ml for the iodide. I n this space group, all atoms are in the general set of positions: x, y, x; - 2 , -yI '/2 2;

'/z

- x, '/z

+ y, '/z +

2;

'/e

+

+

2 , '/2

- y, 2.

Crystals of CsH&lz are monoclinic, space group P21/c, with unit cell dimensions as listed in Table 11. Table I1 - 105O

26O

a b C

B

8.60 i 0.02 8 11.06 & 0 0 . 0 5 A 8 . 7 8 f0 . 0 2 b 110.5' i0 . 2 "

6

8 . 4 8 f0 . 0 4 10.95 k 0 . 0 2 A 8.56 f 0.02 A 110.9" f O . 2 O

With four molecules per cell, the density is calculated to be 1.475 g/ml at 25" and 1.554 g/ml at -195". These data correspond to an average coefficient of volper degree and to average ume expansion of 2 X linear expansion coefficients for the a, b, and c axes, respectively, of 0.6 X 0.4 X and 1.2 X per degree. Each atom is in the general set of posiy, '/2 - x ) . tions: f ( 2 , y, x; - 2 ,

+

Determination of the Orthorhombic Structure The structure of the bromide was determined first. The systematic absences (OkZ absent if k Z = 2n 1, h0Z absent if h = 2n 1) are characteristic of space groups Pna21 and Pnam. The short c axis does not give enough space to permit molecules of the expected shape t o be arranged with mirror symmetry, so Pnam was not considered further. A structure was readily found in Pna21, confirming this space group.

+

The Journal of Physical Chemistry

+

+

The locations of the bromine atoms in the wellresolved [OOl] projection were found readily with a projection of the Patterson function. After refinement of these two atoms, a Fourier projection phased with bromine showed clearly the eight carbon atoms. This structure was refined in two dimensions by least squares. In this polar space group, the x coordinate of one atom is arbitrary. The coordinate of the second bromine atom was determined by some trial and error calculations and was checked by a Patterson projection along [loo]. Coordinates for the carbon atoms were estimated on the basis of the expected molecular geometry and the results of the two-dimensional refinement. This structure, with isotropic thermal parameters, was refined by least squares. Weights were assigned according to Hugheslg as the smaller of IF,I-2 or 14F,I -2, where F , is the limit of detection, except that in any cycle an unobserved reflection was deleted if 1F.l < IF,/. Such a reflection was also excluded from the residual index R = Z l [ F o \ - IFo11/21F01. The subsequent refinements of the other structures with the IBM-650 were done in the same way. Nine cycles of refinement, with the help of two intervening calculations of Fourier sections, reduced R to 0.117 (calculated in the tenth cycle). This was the best agreement which was achieved. After the seventh cycle, hydrogen atoms were introduced at locations expected on the basis of estimated molecular geometry with thermal parameters B = 2.4. No hydrogen parameters were refined. I n further cycles R and Zw(AF) increased slightly, and some parameters oscillated, even when partial-shift rules were introduced. A full matrix was calculated and inverted. When this matrix was used repetitively with new values of Zw bF/bx AF, it yielded slightly different coordinates, but failed to improve the agreement.20 A third set of coordinates was derived from a three-dimensional electron density function, corrected for series termination on the basis of a Fourier synthesis of the calculated structure factors. The three sets of resultss are in agreement within the estimated accuracy. The cause of the lack of convergence is not known, but we suspect that it results from the method of treatment of unobserved reflections, some of which may be omitted from one cycle and be included in the next. The imaginary dispersion correction for bromine, Aj" = 1.5, is small enough that one is likely to have (16) L. H. Thomas and K. Umeda, J . Chem. Phys., 26, 293 (1957). (17) J. A. Hoerni and J. A. Ibers, Acta Cryst., 7, 744 (1954). (18) "International Tables for X-ray Crystallography," Vol. 111, Kynoch Press, Birmingham, 1962,p 202. (19) E. Hughes, J . Am. Chem. SOC.,6 3 , 1737 (1941). (20) This result gave evidence for the necessity of recalculation of the matrix as refinement proceeds, a practice which was generally adopted as soon as larger computers became available.

671

CRYSTAL AND MOLECULAR STRUCTURES OF DIHALOBENZOCYCLOBUTENES Z=.80

difficulty in establishing the polarity of a specimen. Even so, we estimate that neglect of this effect introduces a systematic error (polar dispersion shift6-') into the z coordinates of the carbon atoms of about 0.006 (sign unknown), or 0.03 in position. This error is unimportant relative to the precision of the determination in this case. We list in Table I11 the parameters which gave the best agreement in the diagonal refinements. Further refinement by modern methods would improve the fit, but we doubt that the improvement in accuracy would be sufficient to justify the labor involved. Table 111: Atomic Parameters and Standard Deviations" for C8HGBr2

I

\

\

-

, IA

2.-05

0.1934(3) 0.3389 (3) 0.305 (2) 0.372 (3) 0.414 (3) 0.357(2) 0.369 (2) 0.440 (2) 0.491. (3) 0.488 (2)

0.1812 (4) -0.0269(4) 0.197 (3) 0.108(3) 0.196 (6) 0.275 (3) 0.386 (4) 0.414 (3) 0.320 (4) 0.209 (3)

0,500 0.379 (3) 0.677 (15) 0.601 (13) 0.391(16) 0.469(15) 0.347 ( 15) 0.183 (14) 0.112 (18) 0.240 (12)

6.4(1) 6.5(1) 5.1(2) 5.2(3) 6.3(11) 5.2(2) 4.9(2) 5.4(5) 6 . 6 (17) 4.6(1)

I

,

Figure 1. Section of the electron density function of C8HBBrZ near the carbon atoms. The equation of this plane is 1.5192 0.575~ 0.6652 = 1 (orthorhombic coordinates). The contour interval is 1.0 electron/bs, with zero contour omitted.

+

+

Standard deviations of the least significant digits are given in parentheses; they were estimated by least squares or by the difference between diagonal and full-matrix results, if it was larger.

An oblique section through the electron density function, approximately in the plane of the carbon atoms, is shown in Figure 1. A projection, Figure 2, of the AF synthesis (down the c axis) shows, as its most prominent features, indications of anisotropic thermal motion of the bromine atoms with largest amplitudes in directions transverse to the C-Br bonds. The arrangement of the molecules in the unit cell is shown in Figure 3.

Refinement of the Iodide The iodide is isomorphous with the bromide, and corresponding coordinates differ in no case by as much as 0.04. By an inadvertence, the z coordinates of the iodine atoms were interchanged, an error which turns out to be nearly equivalent to giving wrong z coordinates to atoms C(3), C(4), C(5), and C(8) and connecting them to C(6) and C(7) atoms with correct coordinates but in the wrong unit cell. The frustrating consequences of this blunder need not be recounted here. The details of the earlier conclusionsBconcerning this structure should be disregarded. Several years later the error was detected, and in 1966 this structure was refined by full-matrix least squares. Coordinates correct within 0.04 were derived

U

A

I

-02

Figure 2. Projection, down c, of the AF synthesis for CsHeBrz. The contour interval is 0.5 electron/Wz, with zero contour omitted and negative contours broken.

from the earlier work. Weights were assigned on the basis that standard deviations of observed structure factors (on our final scale) were u = 7,5 or Q = 0.07F0, whichever is larger, for 589 observed and 266 undetected reflections. Ten other reflections, identified by Hardgroveg as very uncertain, were assigned u = 107. This large standard deviation was chosen arbitrarily so that the existing program would report the structure factors and include them in R, without the reflections having any significant effect on the structure. With isotropic thermal parameters, R was reduced to 0.200. Because there was clear evidence of anisotropic thermal motion of the heavy atoms in Fourier functions of the bromide (Figure 2) and the iodide (not shown), further calculations were made with anisoVolume 7.8, Number R February 1968

672

G. L. HARDGROVE, L. K. TEMPLETON, AND D. H. TEMPLETON residuals is slightly larger. The doubt concerning the polarity of the structure is of trivial concern in respect to bond distances and angles involving only carbon atoms, since all these atoms are shifted very similar amounts. The final parameters are listed in Table IV. The polarity implied by the negative signs of z is of no general significance, but refers only to the orientation of the specimen used in this investigation. If the signs of x are taken as positive, then the signs of the thermal parameters B13 and B23 must be changed. Table IV: Atomic Parameters and Standard Deviations“ for C8H&

Figure 3. Unit cell of CsHBBrz, projection down c.

tropic thermal parameters for the iodine atoms; R fell to 0.176. The imaginary dispersion correction was then introduced, and the structure was refined with coordinates corresponding to those listed for the bromide (Table 111) and with the same coordinates but with sign changed on each 2. As expected from our previous experience5 with the polar dispersion shift, the x coordinates of carbon were significantly changed, but the effect on the agreement of observed and calculated structure factors was almost negligible, whether ~ 414 judged by R (0.176 in each case) or by Z W ( A F ) = or 415. Examination of the data showed that the undetected reflections were being given too much weight; they were then assigned zero weight. Further refinement with both polarities yielded R = 0.081, 0.081 (599 reflections), and 0.180, 0.179 (including undetected reflections). The weighted sums of squared residuals were 250 and 252, respectively. This agreement is probably as good as the accuracy of the intensity measurements; the large discrepancies among the undetected reflections are the result of poor sensitivity for detection. The two polarities give coordinates which differ significantly only in the x coordinates of carbon atoms. For the positive signs, these coordinates have magnitudes greater by from 0.028 to 0.038 (average, 0.033 or 0.15 8). The least-squares agreement gives little basis for choice, and we make a choice on chemical grounds. The positive coordinates give C-I distances of 2.24 and 2.21 8, while the negative ones give 2.18 and 2.13 A. The shorter distances are closer to the value listed in “Tables of Interatomic Distances”21 for paraffinic iodides, 2.135 k 0.01 8. We expect this comparison to be valid because our results for the chloride and bromide (averages, 1.78 and 1.96 8) are in agreement with corresponding values in the tables (1.767 and 1.937 8). We choose the negative coordinates on this basis, even though the sum of squared The Journal of Physical Chemistry

Atom

2

U

E

I(1) I(2) C(1) C(2) C(3) C(4) C(5) C(6) C(7) C(8)

0.1922(2) 0.3497(2) 0.316(2) 0.383(3) 0.422(2) 0.366(2) 0.370(3) 0.436(3) 0.494(3) 0.492(2)

0.1937(2) -0.0166(2) 0.216(3) 0.129(4) 0.215(3) 0.294(3) 0.395(3) 0.419(3) 0.345(4) 0.232(3)

-0.500 -0.354 1 ) -0.674 12) -0.569 12) -0.398 10) -0.459 13) -0.382 14) -0.166(13) -0.123(16) -0.216(10)

Atom

1(1) I(2)

BII

Bzz

Bas

B,

BIZ

Bis

12 b

. . .b 3.7(8) 4.4(10) 3.3(8) 3.6(8) 4 . 9 (11) 4.1(9) 5 . 5 ( 12) 3.5(9) Bza

3.7(1) 5.1(1) 4.7(2) -0.7(1) -0.3(2) -0.2(2) 5.6(1) 3.4(1) 4.4(2) -0.3(1) 0.8(2) 0.2(2)

‘ Standard deviations estimated by least squares for the least significant digits are given in parentheses. Anisotropic parameters used. Determination of the Monoclinic Structure The monoclinic structure of the chloride first was solved with the data taken at 25”. The CI-C1 vectors were recognized in the three-dimensional Patterson function. An electron density function with signs determined by the two chlorine atoms showed the eight carbon atoms. Twelve cycles of least squares reduced R to 0.21 with isotr:pic thermal parameters which ranged from 3.9 to 6.8 A2. The bond distances in the benzene ring ranged from C(6)-C(7) = 1.24 to Table V FO

0-10 11-20 21-30 3140 41 up

a

1.85 1.69 2.24 2.71 0.07Fo

(21) H. J. M. Bowen, et al., “Tables of Interatomic Distances and Configuration in Molecules and Ions,” The Chemical Society, London, 1968.

CRYSTAL AND MOLECULAR STRUCTURES OF DIHALOBENZOCYCLOBUTENES

- 195')

Table VI : Atomic Parameters and Standard Deviationsn for CaHeClz (at Atom

21

X

Biib

2

673

Baa

B22

Table VII: Interatomic Distances"

(A)

Chloride

Bromide

Iodide

C(l)-C(2) c m-c (4) C (2)-C (3) c (3)-C (4) c (4)-C ( 5 ) C (5)-C (6) C (6)-C ( 7 ) C (7)-C (8) C (8)-c(3) c (1)-X (I)* c (2)-X (2) x (l)-X (2)

1.584 (10) 1.471(12) 1.490(12) 1.386(9) 1.367 (11) 1,407 ( 11) 1.395 (11) 1.373 (12) 1.392 ( 11) 1.785(8) 1.774(8) 3.197(5)

1.54(7) 1.54 (7) 1.54 (7) 1.35(6) 1.43(7) 1.39 (7) 1.42 (7) 1.43(7) 1.38(7) 1.98(4) 1.94 (4) 3.44(1)

1.63(6) 1.62(6) 1.46 (6) 1.37(5) 1.30(6) 1.48(7) 1.35(7) 1.47 (7) 1.43(6) 2.18(4) 2.13(5) 3.741 (6)

Standard deviations of the least significant digits are given in parentheses. X stands for C1, Br, or I.

'

0 h6.O 72 86

b h,OaO 63 12 6 1115 15L

8 69 66

10 26 11 12 12. 13

111 lL.

16 11

18

3

6

im 5

3 h 7b 4 , 0 81

L 93 113 5

9

11

6 68 69 12 8 15 1 2 9 39 L3 10 3 2 3 2 ll 11. 1 1 2 3 2 2L 13 28 32 I L ZL 16 15 23 23 16 12. 2 17 111 I 18 10. 3 1 68

1 hC;1°6* 2 7* L 3 51 55 b 73 811 5 Ib 1 2 6 19 28 7 2b 2 1 8 20 l b

Table VIII: Bond Angles (degrees)

9 5 6 5 6 I1 I1 h3 LO 10 72

X ( l )-C(I )-C(2)a X(l)-C(l )-C(4) C(2)-C( 1)-c(4) x (21-ci2 )-c ( 1) X(2)-C(2)-C(3) C(1)-c(2)-c(3) c (2)-ct3)-c(4) C(Z)-C(S)-C (8) C (4)-C (3)-C (8) C(1)-C(4)-C( 3) C(l)-C(4)-C(5) c (3)-C(4)-C(5) c(4)-c(5)-C(6) C (5)-C (6)-C (7) C (61-C (7)-C (8) C(7)-C(8)-C(3) Std dev e

116 115 87 118 116 85 94 144 122 94 142 124 114 122 123 115 1

'

Estimated Limit for Detection of an Undetected Reflection) ommvw

Chloride

0 . 9 (1) 0.2 (1) 0 . 7 (1) 0.4 (1) 0.8(3) 0 . 3 (2) 0.7 (2) 0.2 (2) 0.8(2) 0.1(2) 0.5(2) 0.3(2) 0.2(2) 0 . 1 (2) 0.3(3) 0.5(2) 0.5(3) 0.6(2) 1.0(3) -0.3(2) Values of Bll should

Table IX : Observed and Calculated Structure Factor Magnitudes for CsHeBrz. (An Asterisk ( * ) Indicates the

Atoms

Atoms

B2P

BlS

B12

O.OlSO(1) 0.2916(2) 0 . 1 (1) 2.4(1) 2.1(1) 2.9(1) 0.1681(3) 0.2560(2) 0.0603(2) 2.6(1) 2.5(1) 2.7(1) 0 . 5 (1) CW) 0.0796(3) 2.0(3) 0.3(2) 0.4790(6) 0.6217(9) 3.9(5) 1.6(2) C(1) 0.2433(11) 0.3594 (6) 0.5105 (9) 2.2 (3) -0.2 (2) 2.7 (4) 2 . 0 (3) C(2) 0.2005(10) 0.3399(6) 0.5731(8) 3.0(4) 2.1(3) 1.5(2) 0.0(2) (33) 0.3867(10) 2.0(3) -0.1(2) 0.6679(8) 2.4(4) 1.9(3) 0.4223(10) 0.4457(6) C(4) C(5) 0.4184(10) 0.5150(6) 0.2399(9) 2.7(4) 1.8(2) 1,8(2) -0.4(2) 0.5917(7) 0.2509(10) 2.8(4) 2.7(3) 2.5(3) 0.1(3) c(6) 0.2897(11) 2.5(3) 0.2(2) 0.3483(10) 3.2(5) 2.3(3) 0.3250(11) 0.6973(7) C(7) 0.4401(9) 2.5(3) -0.6(3) 0.4860(11) 0.7350(7) 2.8(5) 2.7(3) C(8) Standard deviations estimated by least squares for the least significant digits are given in parentheses. have added an unknown constant because of the lack of experimental scaling of the Weissenberg layers. CUI)

Bromide

120 109 84 118 112 89 91 138 129 96 147 117 122 114 128 109 5

Iodide

117 110 82 121 120 88 97 140 123 92 140 128 113 119 127 109 5

X stands for C1, Br, or I.

12 13 1L 15

12r 1

10 16 lL 1 h 78 J . 0 80 2

lli 15

3 1113 16b

L 22 23 5 PI 132 6 10 13

la

7 LI

8 26 33

9 39 10 11. 11 25 12 Ilr

Lb 12 22 6

13 1 2 1 b

14 2 2 23 15 12. 1 16 1 2 1 2 I 7 11. 2 h.L.0 0

49 50

1130 2 28 3 23 L 26 5 31

6 I

n

9 10 11 12 13 15

156 25 18

26

111 L8 50 75 81 101 7 53 50 20 25 12. L 26 28 121 I 12. L

1 h 21 S . 0 21 2 22 18

3 L

C(7)-C(8) = 1.46 8, values which gave us little confidence in the results. The details of this structure are given by Hardgrove.9 Further refinement was done with the low-tempera-

26 31 121 2

15 10 16 16 1 8 17 Ib 12

101

9

l* li 5 30 35 6 Lo L7 1 28 3b 8 38 36 9 22 2L 10 111 6 11 12. 8 12 16 16 13 26 21 111 I8 20 15 13 111

I

1 IL

2 li7 51 3 1 5 18 L 8. 3 5 li5 L5 6 116 50 1

13 12r 6 llr 12. 5 1 h,loO 101

a

2 82 8 5 3 31 21 L 12 78

5 10. 3 1

li 29 33 6 86 101 8 69 71 1 0 15 17 IL 35 36 16 12. 9

12 13 101 1

8 22 2L

9 19 17 10 18 18 11 13. L 1 2 12. 2 13 12. b lli 11" 5

2 h PO J 8 I03 1 3 12 12 L 27 27 5 6L 71 6 25 27 1 6 1 66 8 b7 119 9 21 13 10 31 38 11 19 29 12 19 19

u

15 18 111 5

1L

16 12+ 11 I 7 11.

18

111

9 I1

1 hL1 ? J b1 2 85 102 3 95 lob L 109 121 5 61 66

0

1 2

3 L

h.8,0 25 19 21 21 16 I9 12. 1 17 2 2 29 27

5 6 11. lo 7 17 8 26 28 9 ll 12 1 0 26 27 11 1 2 u1 1 2 12" b

u

13 13 ll Ilr lM 2 1 h 12. , 9 8 11 2 28 20 3 Ilr 1 2 L 1% 2 5 21 211 6 17 13

1 15 8 8 22 2 2

9 12. 2 l o 121 6

I1 12. 10 1 2 13 10 u 11. 6

ui

13 12

h.1010 0 21 21

1 43 1 12r 2 3 12. 8 2

11 12. 5 28 6 12. 7 23 8 12" 9 12* 10 12.

1 28

3

22 L 8 I

h,ll,O

1 12x 10 2 lb I 3 12 12 L 15 10 5 12. I8 6 121 1 h,12,0 0 12. 1 12. 2 12. 3 12r b 11. 5 Il* h.13.O 1 lM

b

L 1 6

5 5

3

2 I3 11 3 1P 2

b lL

12

6 31 31 7 20 20 8 35 b2 9 16 19 10 30 3L 11 17 11 1 2 21 16 13 18 13 I L 12. 6 1 5 12. 6 16 11. 6 17 10. 3 0 h65 J . 1 68

1 69 12 2 29 31 3 38 L2

L 18 19

5 59 61

6 39 bl 7 30 3li 8 30 29

9 56 60 10 111 6 11 L6 I 8 12 1 11 15 16 17

15

15

12. 8 12. 0 12 12

11.

6

2 56 51 J LI 115

L

50 53 5 113 L6 6 13 9 7 II2 L7 8 28 35 9 19 2 1 10 2 1 21

I1 111 11 12 111 L 13 31 29 lb 12. 15 15 22 11

16

11.

2

5 35 31 6 25 28

12 25 23 13 18 20

9 29 28

I L 11 13 15 lL 12 16 11. 6

hi?lso

1 83 88 2 L7 49 3 35 35

L 26 26

5 37 37 6 w1 k L 1 50 L9 8 28 29 9 31 36 10 12 11

11 I3 13 12 12. 1 1 13 12. B 111 12. b 15 11. L

6

11 12.

12 15 16

13 12.

5

15 I1

6

lli 18 11

o

hjjl.',2 I 20 15 2 2L 30 3 10. 2 L 3L 311 5 19 16 6 26 23

7 12. 9 8 31 33 9 15 1 0 10 32 35 11 111 11 12 16 1L 1v 2 1 2 28 31

3 39 36 Ir 37 37 5 2li 18 6 16 17

I 1L 15

8 12. 3 9 18 11 I? 12. L

0 h!lt'276

I 19 19 2 25 27 3 12 9

L 18 13 5 13 6

6 31 26 I 12r 12 8 M 17 9 12. 8 10

u

8

h,lO,l ' 1 12. 8

2 12" 3 3 23 19 b 121 IO

5 111 12

6 121 I 1 21 2 1 h,ll,l 0 20 1 12 2 15

3 12.

12 16 9

5

L

I2

6

6

12.

11

5 121 2 h,12,1

1 11. 2 IL 3 19 L ll*

5

7 9 17

7 16 1 2

115 111 3 12 15 b ZL 25 5 31 31 6 55 58 1 22 2b 8 25 25

9 33 10 18 11 18 1 2 18 13 11

1 L 14 15 12.

28

21 12

19

L

1

7

1 hj:'ZLi 2 31 318

a5 2 6

!:

60 62 u1 17

1 33 >3

8 16 16 9 28 28 10 121 10 I1 20 18

12 15 13 13 21 17 lli 12. 7 1 5 16 11 0 h,L,2 51 L9

I 56 55 2 12 I 1 3 31 30 k 29 26 5 29 21 6 30 30 7 3b 21 8 11 7 9 38 3 2 10 19 19 11 12.11 12 lb 13 13 1 2 t 7

l h 1%

15

2

llt 8

1" P 3 9 2 36 37

3 L8 w1

Ir 3) >b 5 38 37 6 16 15 I 25 2b

8 2 1 20 9 12. 9

10 12" 12 11 12. 1 3 1 2 111 8 1 3 17 I3 1 L 16 10 1 5 11. 11 0 h,6.2 51 Ir2

0h,13,1 10

5 9

1 37 29 2 25 22 15 15

3

h

2 hiP1'236

L 52 % 6 L8 52 8 LL 38 10 36 35 1 2 22 2b 111 12. L 16

12 1)

1 hjif239 L2

2 32 3 L3 L 51 5 31 6 52 7 21

51 56 31 53 26

5 lb 11 22 21

6

1

8 9 10 11 12

16 9 23 2 1 13 7 1L 9 12" 2 12. 11

13 IL

2

1L 101 10 15 10 3

20 11 5 21 211 6 18 15 7 28 2L 8 26 2L 9 18 16 1 0 19 17 I1 11 111 12 12. I 13 12. 6 1L 11. 2 1 5 10. 5

1 h,7,2 11. 7 2 L i 36

3 11 16 b L8 43

9 10 11 12 13 111

10.

15

10

0 h$!'Z23 1 23 2 1 2 18 19 3 121 6

h 12" 2

5 20 15 6 11 12 7 16 15

111

8 18 9 13

2

10 16 10 11 16 13 12 Il. L

1

1M 1 11 10 1L 12 12 10

13 1L. 6

0 h 18 9 3 J 18

1 L9 L9 2

1 56 58 2

0 hirsp"b9

1 13

o

5

10 12.

16 16 h,Ld

1 3L 38

8 lL 1L 9 33 38 IO 15 11 11 16 13

7 18 13 8 21 20

4

DmomBeNzocxcmwm

3 I2 72 li 32 35

1 29 28 2 19 22

12 39 b1 18 10.

5

91

38 38 9 33 32 l o 2L 20 11 30 33 12 13. 7 8

6

ULCUUTED STRUCIWE FACTORS OF

7

8

3 12 14 h 16 111 5

32 6 81 7 28 a 10. 9 16 10 10

29 I 28

5

16

9

11 13 I 12 IO* 1 13 10. 4

1 h 26 , L J 23 28

2

Ira

22

Le

1 h8.2 13s 6

3

2 2 9 I9 3 16 12 L 23 18

5 3L 32 6 .9 6

5 6 1

:2.10

17 111 12x 9

8 I1 11 9 12. 3 10 I2 8

12a 6

3 121 1 L 12. 1 5 21 13 6 15 3 7 17 12 8 11s L 9 11. 9

1h,ll,Z 12. 2 2 15 9 3 12r 11 h Ib 10 5 11. 11 6 I>* 1 1 . CI 6 8 I2 7 h,12.2 0 Ib 7 1 15 11

1h,U.Z 12 1 h 0,I 2 I9 61 L 59 bL

6 21 20 8 1L 17 10 19 19 12

11

I L .9

u 9

h,lJ 0 35 LO 1 23 2b 2 18 22 3 12 13 L 6r 6 5 22 23 6 1 Y 20 7 11 16 8 18 19

9 ui 11

10 12 11 11 15 11 1 2 10" 2 lJ 101 6

llr

15 i

2

3 k 5

6 7 8

1

20

14

10

6

8 I L 14

9 Ilr 11 10 12 9

11 1 2 11 0

h,lO,2

n 12r 5 1 13 23 2

I

hPll

1 11 16 2 a* 7 3 13 1s b 18 I1 5 20 18

6

16

1 12

11 11 11 1 h&.3 101 9 2 26 25 3 l3 10 L 2b 23 5 15 11

6 lL

IS u1

0 I 2 3

h38 m 7 J3 2 10. 5 22 19

10.

L 13

5

3

8

12 6 6 25 22 7 11 6 8 12 P 9 10. I, 10 9. I

1 h38.3 IL 2 IM 3 17 L lL

5 10 6 111 7 1M 8 10.

1 7 12 15

3

12 6

6

9 13 10 0 hlo. s?2 9

1 101 9 2

3 10. li 10.

20 20 19 18 2L 20 21 2b 28 25 23 2L 2 8 21

I4

7

8 11 5 9 13 10 10 12 9 11 10 3

9r 1

hi;aZs3it,

8

; :6' 9111

10 I 5

8.

5

U

101

5

11 9

1h,lO,J 1 2 10 2

10.

3 15

b

111

0ho1l,3 8. 6

1 11

8

Volume 7.8, Number B February 1068

G. L. HARDGROVE, L. K. TEMPLETON, AND D. H. TEMPLETON

674

Table X: Observed and Calculated Structure Factor Magnitudes (X2) for CsH& (An Asterisk (*) Indicates a Reflection Which Was Assigned Zero Weight. A Question Mark (1) Indicates a Reflection Which Was Assigned Reduced Weight, As Described in the Text) O I S E D V E O LHO C A L C U l l r E O S I R Y C I U R E F I L I O R S I( 2 . 8 1 OF

b 133 129 7 141 l 2 + 8 9b R3 9 I22 111 IO +r I O 11 0 18. 12 92 S l 13 0 18. l b 7 3 7s I5 69 71 16 0 bl I7 47 5, 10

0 0

1')

11 0

11.1.

0 182 IT)

P 105 I 0 5

99 98 I 1 116 119 12 I24 125 I 3 131 I43 I. I 8 78 15 Sb 63 Lh 0 30. 17 0 18 0 6.

+,*

1'1

0

20

45

13

1 ILL IbO I I Lb 3 I63 158 lb 50

6q

45 I1 0 R.L.

119

320

I12 21. Ib 63 122

IO Ll I2

0

IO.

30 I7

35

2

K,L*i3, 2 n F O O ILL I 0 I7 2 60 6 0

3

9 i r 8 159

IO 116 113 I 1 5) 50 12 LO SI I3 0 12, Ib S I bb

9

13

b8

I* 15

.6

I6

27.

I7 10

I9

FOE I C 4 1 289 307

0 73 0

5b

0

3.*

36

55 31

34 0

7 LI

0

26. 301

30 L2 0 Pl

21. 71 22. $8

1-1. I , 3

b5 193 113 5I .o 58 sr 0 I. 0 2St 0 15. 43 40

KIL.

I 24 20 3 k33 5 1 2 1 h7

q. I

12' bb

3, 0

75

X.L.;

21. 36 33

IO 0 2,. I 1 15) I I I

6,

a 'zna i

26

6

H

4

0

32

b I50 l 3 b ? 251 2 b 8 I 1 1 1 I03 9 8, I8

I a 3 3 230

18

Yb 0 0 20.

i

7 12* 120

I7

74 51 26.

MIL. 5. 0 n FOB FCA 1 111 97 2 92 9 l 1 n a. 3i 3 i 5 2 1 8 209

6 300 '97

9 212 10 301) I 1 11) 12 6 1 13 0 Ib II I5 bh IO I22

32. bb

L 5

18 19

2

20 b3

19

m

W

r

16 I7

" 5

66

19 92 0 75 73

I5 49 3b

30. 39

1,L. 2. 0 FOB FC4 0 5 b 52

6

8

I+ 15 lh

1 381 4 2 9 7 2 139 132 3 bd 65 1 I16 L B O S I 5 6 1bO h 233 2 2 4 236 II 0 P.

IO

ii

I2

I2 5 b 5 1

91

i: ii

11

k, 0 II P O I F C 1 Kiln

0'

9

I.

0 313 310

3 2 b I 256

75

IO

21.

2 103 IO+

I

I

5 b 7

Y FOB F C 1

L 367 369 5 131 109 6 2,, 229 I 2 8 1 20, 8 51 3r

01100fll)EN10CYCLOBUIEN€

I. 3

".I.

Y FOB I ; C I

0 218 I 8 2

I LO1

2 105 3 n8 b

0

5

131 b 88 I 39 8 16

b. 0

U F O I fCA

II

o

iz.

10 11

1,11121 3 H &OR I C & I 0 22 2 0 1. 3 36 3 3 $ 0 5. 5 2B ? I b 32 %k

6

r

45 '1

97

7

62

8 9

81

"I

8

21

IO I ?1

0 4kq1

26.

n m a FCI

I9

IP? Bb

3,

IT 72

81

F08 FCL

86 8 , 2 1 3 1 I17 3 I50 LEI b 88 12 5 122 121

81 15.

B1 9 I l * 111

0 2 9 0 301 I 73 75 2 l b l Lb9

"1

91

o

11.

n 251

I3

SI

I* I5

'83

0

)a 51 ,I.

*I

Kv1.11,

0 43 I 65 I n 3

4 5

0 3, ir

I 4

I3 3

'5

$8

12.

IO* IO

Ya.76

0 n

Figure 5. Unit cell of CsHsClZ.

W Ym.13

IA

,

Figure 4. Section of the electron density function of CsHeClz at 195' near the carbon atoms. The equation of this plane is -2.5592 5 . 1 9 9 ~ 6.5712 = 1 (monoclinic coordinates). The contour interval is 1.0 eleotron/AB, with zero contour omitted and negative contours broken.

-

-

+

ture data. Eleven cycles of least squares, with hydrogen atoms included in the last three at calculated positions, reduced R to 0.11 and yielded much more The Journal of Physical Chembtry

satisfactory bond distances. This structure is described by H a r d g r ~ v e . ~Later experience with other problems suggested that more extensive refinement would be desirable. The data were assigned weights on the basis of standard deviations of structure factors derived by a study of the discrepancies of F , and F, given by Nardgrove.9 For 967 observed reflections, these standard deviations are listed in Table V. For 215 undetected reflections, F, was taken as zero and its (r as the estimated limit for detection. The above data are on Hardgrove's scale; adjustment of the scale factor in

CRYSTAL AND MOLECULAR STRUCTURES OF DIHALOBENZOCYCLOBUTENES

675

Table XI: Observed and Calculated Structure Factors ( X 2 ) for CaHaClr 0 8 S f I V C O AN0 CALCULA7liO I 7 l U C 7 U E FLC70*S I X 2.01 Or DIEnlDDatrtOOIClDllVK?E H.K. 0, 0 L 108 FCh 2 36 -3,

2 3 4

28 51

4

5

38 -38

6

8

53

52 $6 - 4 2 38 -37

nom.

L FOB f C A 1 b h 70 2 172-lLl 3 36 38

lO8-lOk b1 -63 b * k -39

4

5

7 8 9

IO

59

58

I7 -I5 28 - 2 5 IS 20

0. 2 L IO8 FCL 0 25 28 1131-132 2 251-250 H,I.

3

+ 5

b 7 8

v IO

b

bb

7

8 I5 I 7 -18

8

0. I

8

7

42 kI I 5 -1, 25 2 k

23

28 52 23

b3

0, 8 L FOO FCL 0 85 87 I 51 -53 2 23 2 1 3 0 -1 k 3) 35 5 IT -13 6 P I -33 7 0 -1 8 19 -1) "11.

H.X. 0 , 'L L FOB FCA I 23 - 2 3

2 3 k 5

6 7

17 - I 7 I7 I 8

6b -7b

19 -15 0 k 30 25

-3

0

36

35

0

-3 33

36

L FOB FC1 0 21 -23

2 I

k

3 8 -35 5 7 -0 32 2 9

O

5

0

L

O

1 -2

5

0111 L COO FCA 1 0 2 30 3 2 3 0 3 W.K.

-*

b L I O 8 ICA 0 201 206 *,I. 0,

0, 3 L I O 8 FCA 9 17 - l P H,K.

n.i. o,

L

I 101 FCa I 2

3 4 5 b 7

8 9

70 -73 3, - 3 1 59 53

0 b

-9 3 1 -35 0 5 36 -40 O k

0, 5 L FOI FCL

O

1

2 3 k

.e

5 h 1 8 9

kP -52

-69

I5

16

IO -67 O 3 42 4 3 19 -2k 2 1 -19

MIX- 0. b C FOB F C A 0 0 I2 I 78 -7b 2 74 -75 3 28 29 4

5

6

7 8

5 b

O

P

25 - 2 1 49 4 9

Horn. 0112 L FOB FCA 0 32 3 5 I 6 2 -,2 I I1 10 3 I9 I 8 4

5

I5

13 8 -10

7

n w I

b

13 21 23

0 21

n,m- o.

II

-7 -6

4

-3 -2 -1 0

I

2

3

4 5

b 7 8 9

. b 8

85 - 7 9 0 16

49 -44

*,K. I, I L F Q I FCL -10 0 -5 -9 I 7 -20 -8 25 2 4 -7

-b -5 -2

-I

0

38 3k

k0

36 36 - 3 h P I -94

b2 4 5 8 3 -7b

I IZV-l30

-7

k 5

b 7 8 9

88 - 8 3

LO 43 55 -55 I 7 -12 0 -8 0

1

17 I 7 25

3b 3b I 3 -10 53 -5b 0 -I 0

24

-6

b8 -bb 5 9 -63 91 -90 I 7 -+7 0 -0 2 1 -22 I P -Ik 0 -5 8 91

9 86

0 -8 21 -21 0 -2

nII. I , 3 L FOB F C I -10 0 -6 28 - 2 5 -9 -8 0 -b -7 0 7 -6 70 -69

59 -4 0 -3 0 - 2 36 -I 121 I 8P 2 7k

4 5

-I -7

-39 I32 -86

71

3

5 1 54 4 42 I I I 21 - I 7 b 0 -6 7 0 -6 1 0 -k 9 0 -1 ".I. I, 6

L FOB -10 11 -9 0 -8 I7 -7 2 1 -b 59

-5 -L

38 bl

-3

b9

-2

-I

FC1 -7

-I -1b -21 -55 k0 60

50 25 2 5 6 S 75

0

74

I 2

15 - I 5

6

I. o

n.i.

L FOS FC1 -10 0 -1 -8 0 -2 -6 36 -3b

2 3

7 L 1 0 1 FCL I I 5 14

-I

-5

3

21 21

21

L FOB FCA -10 28 2 b -e 0 0

-5

n m o.10 I

n,li= 1, 2

5 6

7 8 9

21 0

20 -1 53 - 5 1 0

6

8 8 2 1 -23 .I -48 2 1 20

n m

I. 5

-8 -7

?b -5

-*

-I

0

I

2 3 4 5

I3

-b

-5 -b

-3

-2 -1 0

6

68

b4

7

0

-9 3

1

I 2 3

-1

-2 -1

0

I 2 3

k 5 b 7 8 9

b

7

55

41 53 -411 2 3 -2b 0 -8 25 26

21 I3

21 I2

0

-1 0

I

2 3 b

6

-1 70 7' 32 - 3 0 3b -33 LOO 93 0 7 0

O h I 23 -20 8 32 28 7 8

0 0

7

-I

I, n

(I.K.

1 FOB FCI -8

0

-5

-7

I3 -12

-b -5

0 -11 L 2 40

-4

32

-3 -2 -1 0

I5 -11 2 1 27

34

0 -10

bl

I

bo

'10 - 6 2 0 1

2

3

I9 -21 31 - 3 5

5

19 21 0 12 21 - 2 3

4 6

7

-I

0

I

0 8 b2 0 0 0

ion-103 6 0 -3 8 5 9 -b2 2, I L FBI I C 1 -10 0 0 -9 8 -7 -8 I3 I I - 1 97 9 3 I(,#*

0 lI7-12b I 123-117 2 8 1 -7, 3 53 k 9 I 6 8 -58

b

7 8 9

. 5

b

0 36 32

0 3 I 5 -17 I 9 -17 15 I 5

n

-2

0 117-132

I

2

3 6

5 b 7 8

9

53 50 81 80 32 -30 23 -21

0

5

19 88 2 8 -27 E IO 8 1

-: 1

-6

29 28

IO

5

II

0

-1

b

o

b

7 8

HtK. 2 9 3 L FO8 FCA -10 I 5 -18 -P -8

-7

23 -zb 38 -35 2 1 -19

0 -2 25 -2k

2, + L FOR FCI

n,n* -9 -8

5- -50

21 13

IO I5

-7

I P 19 36 -3h -5 21 2 3 -6 1 3 3 I41

-b -3 -2 -1

1 2

3

+ 5

'10 - 3 9 91 9, 8 -9 51 (7

21

22

Jb 3 5 55 - 5 2 b8 -b2

7

I, 50 0 -1 0 -2

I

2 3 -2b

n , w 2. 5 L FO8 F C A -9 0 1 4 +2 38 '7 I 1 -17 -6 97 9b -5 21 23 -4 0 3 -3 3b - b 2 -2 28 2 8 -1 bd 62 0 95 -96 1 68 -62 2 S I -53 3 b? I7 4 2 8 -29 6

7 8

0

6

23 -21 19 23

*,I. 2. 6 L PO8 FCA -9

-8

-7

nrw

2, 2 1 FOR FCA -10 0 -5 -9 I 5 -I3 -8 I 7 L5 - 7 23 -23 -I2 -6 42 -bO -3 - 5 I 3 -15 11 -61 -k IT 15 -3 2 -4 7 - 2 148-151 -2 - 1 25 -22 9

6 Ik 15 - I T

;3 I: 0

I5 - I 2 30 - 2 5 I 5 -16

+

nIn. I.IO

0

I8

0 -I0 0 -1 30 -2, 1 7 -15

,

L Fn8 I C 1 -7 23 -2k -6 0 -9 -5 0 7 -k 0 -9 - 3 25 -32 -2 38 -50

-I

19 23

L TO8 FCL -IO k0 -39 -9 8 0 -8 I 0 2 8 -3, 2 7k BO

1, 9 L F08 FCA I7 15 -6 0 3 -5 0 'I) -4 23 22 - 3 2 5 -2. -2 21 22 -I 0 -6 0 85 - 3 7

5

4

1 2 -IO

-I

UBI* 2, 0

WvK.

3

15

-b 101-113 - 3 5 3 -53 - 2 67 45 - 1 IO8 I 0 3 0 bb b3 I 66 - 6 1 2 I W s5 3 I7 1T

6

-7

I3

0

L 108 f C 4 -2 I5 15

5

I

I5 23 21

-b 28 -30 - 5 100 IO1

n.i= 1 ~ 1 3 0

k

7

I, -92

-+

-3 -2

1, 7

-.

b

L7 -53

H.K. I , I ~ L FO1 FC1 -5 k 6 37

L FOI FCL - 8 1 5 -3 -7 8 12 -b 32 - 3 1 -5 0 5 2 5 -23

I5

21

0

W.X.

0 L 81 8 3 28 - 2 8 67 I b

I9

lb 21 -I7 29

6

22

15 0

-,

I9

28

2

23

-I

H.X.

21 27 25 -29 12 -75 I7 Ib zn -32 k k 10 23 -21

-3 -2

1 FOR F C 4 -9 0 -11 -8

1.11 L 1 0 8 FCA -b 25 - 2 3 -5 0 -5 0 -1 -3 0 8 -2 0 IS -1 0 11 0 0 -1 I I7 I5 2 k2 k6 3 0 -6 . 0 1 5 0 -10

I I -3 2 1 23 2 1 -21 I3 -IO 30 30

-9

-b

-5

-4

-3 -2 -I 0

I

2

3

4 5 h 7

n.*.

I1

17

67 5 1 21 -19 5q "5 2 1 -19

,,-b2

I7 -17 93 -91 0

5

76 -75 38 39 23 22 15 -11 32 32 I7 l a I7 b5 23 -23 2. 7

L 108 I C A 11 -7 -*-I 32 -29 -1

-b -5

I 1 -11 I1 -16 21 20

-4

b l -59

-3 -2

67 - k 3 42 k2 25 27 2 1 20 $9 -50 89 85

-1 0

I 2

3

6

k 5

8

2

I3

30 30 0 -9 21 - 2 1 2 1 -20

b I

II

u

IIO ion I 46 .I3 2 I1 6 3 47 -51 b I3 I3 5 0 -1 6 21 -22 7 0 -?

n,X.

2, 8 L FO8 FCh -8 11 5

3 2 -29

-7

I9 -16 IO 30 SI Y2

-h

-1 -I

-J -2 -I

40 -40 42 41 0 -0

2Y

0

I

2 3 5

b

7

*,&* 4. 4 1 1 0 8 FCP 'IO 0 -r -1 0 -R 6 -IO -5 17 - 1 7 -6 19 - I 2 - 3 2 1 I' -2 *I 90 -1 25 - 2 5 0 34 -3, I I 3 -13 2 23 -27

*,I. 1. I L FOB FCA -10 I 1 I9

-v

2

I PI-IOI

0

I

IO

-+

17

2 3

I8

51 -53 19 - 5 1

.' 21

5 b 7

b4

20 $2

36

3J

1

23

L

-*b

29

3

n,m. 2. 9 H I I S 31 2 L FOR FCL L I O 8 FCA -1 IT l k -IO 8 -13 -f I 3 -6 -9 15 15 -6 42 + 3 21 1L -5 8 I3 -2 I5 2 1 4 2 3 -I+ - 1 I P - 3 I5 -16 0 76 -85 -2 23 20 I I 3 -9 -1 30 3 1 2 1 2 1 11" 0 59 -b2 3 21 I 3 1 3G -3b I kP 53

-*

21 -23 25 24 30 7 2 8 0 7 8 -12

2

3 4

5 6

M,K. 2ilO L FOB I C 1

-7

-6

28 -26 I 7 -17

-3

28

-4

I5 -12 23 -23 I 1 -b 11 -8 +2 -60

-3 -2 -1 0

I

2 3 6

26

23 25 15 IO I 7 -1' I9 21

I II Sb

h

I1 31

Hen* 2,11

L P O I IC1 -6

-3 -2 -1 0

32 -30 0 4 28 25 3 2 29

25 - 2 4 21 - 2 2 bl I1 I1 I5 I 7 0 -6

I

2 3

59

I 5

n,m. 2.12

L P O 8 FCA -3 3b 3 2 8 12 -3 0 -3

-* -2

-1 0

I

23

2. 30 -29 II I k

2

3

17 I 5 I5 13 b -IO

0

I

J

6

0 -3 4 7 -6h

5 b 1

38 -63 I 7 1')

-*

0 0

1 7

7 8

I7 8

I+ II

-2 -1 0

3, I 1 0 1 ICL 6 -9 2 3 2, k0 - 3 8 I 5 -13

I

-3

HIS.

1 -9

-8

-7 -6

-5 -4

-3

-2 -1 0

I

2 3 k 5

b 7 LI

0 53

0

2

5' -1

3

L

-1

0

5

0 I7

-1 -?

-1

-b

-5 -6

-3 -2

-1

0 I

38 - k l k -5

2

3

-T

-6 -5 -4

-3 -2 -I 0

I

2

3 k 5

b 7

19 32

+,

U.K.

4

3, 4 L FOO FCA - I O 28 -20 -9

I3 -12 32 -32 42 $4 68 -75

5 6

I"

-6

23

2. I 3 -12

-5

13 - 1 1 0 -3

-4

-3 -2

-I 0

I 2

-7

-b

0,

-5

kP -kb

-6

I b -7k 34 IO 32 30

-3 -2 -1 0

8 1 .I -19 21 -23 2 1 -17

I

I 7 -lb 13 1 1 I 3 -14 34 3 1 32 -30

3

II

I

25

5

8

2

3

I , -40 0 -0 0 b IO I 6 I 3 -11 I 3 -11 25 25 1 -6

I3 3'

13 -5 I

e n

4 0 -2 I 1'1 I S

7

8 13 I 1 2.13 FD8 FCA n.K. 3. 5 2 5 -21 L 101 FCA 2 3 2 s 'IO 28 2b 0 -3 -9 II 1 3b -61 -8 I7 IS O 4 -7 1 3 - 6

b

I1

-7

.,

8 L F O 1 FCA -8 0 I -7 IP I8 -6 44 62 H.K.

101 F C A

-I

15 -1' I5 , I

5

0

-7

0

-6 -5

-7

13 -12 70 72 I 4 *d 23 ?I 2 1 -?I

-4

-3 -2 -1 0 I 2

30

8

L 101 I C . I! 8 -7 I T 16 -6 4 2 10 -1 n -6 -6 2 1 21 -3 I 3 -2 21 -I5 -1 2 1 2 1 0 4 -10 I $0 - 1 2 2 42 -.I 3 30 30

b.10

L FOR F C 1 -7 15 I 3 -b 11 - 1 2

-*-- 1I -2 -I 0 1

?I '21 38 - 3 I I 59 18 0 -2 0 -2 I1 I

2 3

I1 IO 0

20

L

23

20

I

-Q

.

HIN. + ? I 1 L FOM I C & -6

'

",X. 'i, L f0" F C I -10 23 2' -9 0 -6 -8 0 3

5

-7 -h

-I 0

I 2

3

22

I5 -13

io

LO

b -I 19 -1" I P -22

H d - bg12 I FO* FCA -5 32 -31 -I b 9 -3 13 I 3 -2 I 3 13 -1 0

I 2

3,

-1

I 2 io+-iir 3 2 8 22 I 17 I 6 5 I1 P b I 1 -19

&

u

HIK. 5 , 5 L E O I IC&

28 -2*

-1

21 13 17 0

-b

6 0 -16

w- 5. o O

b

1

2 L O O -98 31 3 3 b 0 -b

4

w.

5. I L 1 0 0 FCA I 3 19 0 6 -1 0 h -2 51 -&E -1 23 -29 0 34 -30 I $7' k 8 2 I 3 I3 3 IS -19 k 30 32 I * * h 19 l b

-10 -9

I5

Ik

-10 -9

21 P

18 -2

-53

-5

49

-b

30 - 2 8

-3

51

-2 -1 0

I

2 3 k 5 b

FOB fCA II P

.e

50 76 - 1 7

32 -36 I I -16 15 I n 0 -1

b

-5

+7 0

k8 -3 31

28

0

2

3

I

2 1 -19 21 -20

-6 0 - 3 30

2

26 51 -50 10 -27 0 6

I3 I2 I 3 -14 0 17

-2 I6

H,K.

5.10 1 FOB I C 4 -7 8 IO -b 19 -19 '5 0 -b -4 I 3 - I 4 -3 0 b 72 0 8 -1 2 1 17 0

I

?

-L

-3 -2

-I

0

I 2

3 k 5

b

59 -*5 b -3 3 1 -37 36 -31 I 3 IO 32 35

0 6 3+ -37 0 3 23 2 1

, i 5

I,,

I

15 -12 0 ,-I 0 3

2

3 L

0 1 28 -2b 25 24

-b 8 -b I-) 8 -10 Y b2 *8 -3 I7 I7 -2 I5 -1. -1 2 1 -24 0 23 25

17 -16 I -9

I1 - l b

65

I

23 - 2 2 I 3 I1

2 3 b

53 0

-7

0

L* 7

Il-lI 0 -1 0 5 23 -23

19

D 8

-3 -h

YiK.

-.

%IbI 3 L 1011 F C I -10 13 -11

-7

-.,

-7

a-b

-5 -k -1

0 I 2

3 b 5

a -5 I7 I6 I7 I3 I9 I 8 2 1 -19

re -.a

8 7 8 -13 I 7 20

42 -,z I5 I 5 O

2

0

-5

3

I1

10

be10

*.K.

L 108 FCL

-,b -5 -4

b

II

2

-9

I3

I 3 -I5 0

-3 -2 0 -I I7 0 3b I 21 *,I(.

II

-+

-1 I5 35 -21 9

b.11

L PO8 FCL -5 0 I -4 32 3 1

H,K. 3 - 1 2 L FOB FC1 0 I7 - I 3 H i K . 6. 0 L FOB FCA -10 32 31 -8 0 5 0 I 7 -1b

-+ -3

59 -59 0 -k

-1 0

$

I1

1 FOR I C & -1 I t I, -7 30 2 9 -h R -6 -5 I -6 - b 5J 51 - 3 2 3 20 -2 0 -I - 1 2 1 -22 0 I1 I

b, 8 L FOB FCA 0 4 0 b -6 2 1 2, -5 0 -I -9 I3 -I2 II Ib -8 I 3 -IO - 3 3 1 -3s -7 I 3 11 - 2 2 3 -2. -6 I 5 I5 - I 0 -6 -5 36 4, 0 I I -11 -6 4 2 ' 2 I 8 -8 -3 3k 30 2 30 - 2 8 -2 I5 IC 3 23 20 -1 4 2 -36 0 0 -3 HI