J. Phys. Chem., 1996, 100(35), , DOI: /jp952328y

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J. Phys. Chem., 1996, 100(35), 14625-14629, DOI:10.1021/jp952328y Terms & Conditions Electronic Supporting Information files are available without a subscription to ACS Web Editions.

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1 J. Phys. Chem., 1996, 100(35), , DOI: /jp952328y Terms & Conditions Electronic Supporting Information files are available without a subscription to ACS Web Editions. The American Chemical Society holds a copyright ownership interest in any copyrightable Supporting Information. Files available from the ACS website may be downloaded for personal use only. Users are not otherwise permitted to reproduce, republish, redistribute, or sell any Supporting Information from the ACS website, either in whole or in part, in either machinereadable form or any other form without permission from the American Chemical Society. For permission to reproduce, republish and redistribute this material, requesters must process their own requests via the RightsLink permission system. Information about how to use the RightsLink permission system can be found at Copyright 1996 American Chemical Society

2 I TABLE Si, Part 1: Total Experimental Intensities, I(s), 19-cm Camera Distance (9.50 s A-1, with Data intervals As = 0.25 A-1; the Table Develops Horizontally)

4 TABLE S1, Part 2: Total Experimental Intensities, I(s), 50-cm Camera Distance (1.875 s A-1, with Data Intervals As = A-1; the Table Develops Horizontally)

6 TABLE S2: Selected Geometrical Parametersa and R Factors from Refinements A-C parameter refinements A B Cb D 2 h model C2v model r(c1-c2) (4) (4) (4) r(c2-c3)c r(c1-c7) 1.428(1) 1.429(1) 1.429(1) r(c7-c9) (6) (6) (6) LC2-Cl-C (13) (22) (13) Re d R e (12) a Bond distances (ra) are given in angstroms, angles in degrees. Least-squares standard deviations are given in parentheses as units in the last digit. b In refinement C the molecule was assumed to exist as a mixture of four rigid conformers, differing only in the extent of symmetric out-of-plane bending of the ethynyl groups (see text). C In all refinements the parameters AI(C-C) = r(c2-c3) - r(c1-c2), r(c2-h2), A (C-H) = r(c2-h2) - r(c9-h9), and LC3-C2-H2 were assumed. dbending angle of the substituent. e R = (Y w[iobs - Icalcl 2 / Y WIobs 2 )1/2

7 TABLE S3: Molecular Parameters of p-diethynylbenzene from Electron Diffractiona (Unabridged Version of Table 2) Distances and Mean Amplitudes of Vibration (A)b atom multiplicity ra 1 coupling pair scheme d exp. calc.c C1-C (4) (5) i C2-C (4)e i C1-C (1)e i C2-H f 0.077(1) ii C9-H e ii C7=C ( 6 )e C1...C (1)e (6) iii C1...C (5)e 0.064(2) iv C2...C (3)e iv C2...C ( 3 )e iii C7...C (1)e iii C7...C (1)e 0.066(2) v C7...C ( 3 )e 0.071(4) vi C9...C ( 1 )e 0.048(2) vii C9...C (1)e 0.101(3) viii C9... C (2)e 0.094(4) ix C9...C (3)e 0.066(5) x C7... C8 1 5, 64 6 ( 4 )e 0.062(8) xi

8 C7...C1O ( 6 )e 0.085(8) xli C9...C1O 8.049(9)e 0.093(19) xiii C1... H ( 1 )e 0.091(4) xiv C1...H (1)e viii C1...H (1)e V Cl ( 2 )e g C2... H (1)e xiv C2... H (3)e V C2... H (3)e viii C2... H (1)e' 0.151(14) xv C2... H1O 5.930(2)e g C7... H (1)e' vii C7... H (1)e' x-v C7... H (1)e' ii C7...H1O 7.920(7)e xiii C9... H (1)e' viii C9... H (2)e xi C9...H1O 9.118(11)ef

9 0 Angles (deg) and Differences between Bond Distances (A) L C2-C1-C (2) A 2 (C-C)k (16) LC3-C2-H h A3(C-C) (6) 9i 6.8(12) A(C-H)m h Ai(C-Cy h a Refinement B. Least-squares standard deviations are given in parentheses as units in the last digit. b The H... H distances are not shown; their amplitudes have been assumed at A. c From molecular mechanics calculations (MM3 force field). d The roman numerals indicate the groups within which the amplitudes were refined with constant differences between them. e Dependent parameter. fassumed from an electron diffraction study of benzene. g Assumed from molecular mechanics calculations. h Assumed from ab initio MP2/6-3 1G*(f.c.) calculations. I Bending angle of the substituent. J AI(C-C) = r(c2-c3) - r(c1-c2). k A 2 (C-C) = r(c1-c7) - r(c1-c2). 1 A3(C-C) = r(c7-c9) - r(c1-c2). ma (C-H) = r(c2-h2) - r(c9-h9).

10 9 TABLE S4: Correlation Matrix Elements with Absolute Values Greater than 0. 5 a i j Xy (i j) r(c1-c2) A 2 (C-C)b LC2-C1-C6 8 C (C1-C2) 1(C1...C3) (C1-C2) S19d (C1...C3) S19d (C9... C3) 1(C2...H9) 0.56 a From refinement B. b A2(C-C) = r(c1-c7) - r(c1-c2). C Bending angle of the substituent. d Scale factor for the 19-cm data set.

11 10 TABLE S5: Length (A) of the Carbon-Carbon Triple Bond in Alkynesa from Electron Diffraction Studies Molecule rg(c-c)b Acetylenec 1-Butyned Dimethylacetylene (2-butyne tert-butylacetyleneg Vinylacetyleneh Divinylacetylene' CyclopropylacetyleneW Cyclopropylacetylenek 4-Pentyn-1-ol Diacetylene m 1,5-Hexadiynen Ethynylbenzeneo p-diethynylbenzenep Diphenylacetyleneq ± (1)e ± ± 0.005e ± (2)e 1.209(2) ± (2)e ± (1)e ± ± (2)e a Cyclic alkynes have not been included. b Total errors are given as error limits. Least-squares standard deviations are given in parentheses as units in the last digit.

12 11 c Morino, Y.; Kuchitsu, K.; Fukuyama, T.; Tanimoto, M. Acta Crystallogr., Sect. A 1969, 25, S 127. See also footnotesf and m. d Bastiansen, 0.; Bakken, P.; Kloster-Jensen, E.; Samdal, S.; Traetteberg, M. 1 Mol. Struct. 1995, 352/353, 77. e Calculated from the published ra distance. ftanimoto, M.; Kuchitsu, K.; Morino, Y. Bull. Chem. Soc. Jpn. 1969, 42, g Haase, J.; Zeil, W. Z. Naturforsch., Teil A 1969, 24, h Fukuyama, T.; Kuchitsu, K.; Morino, Y. Bull. Chem. Soc. Jpn. 1969, 42, 379. 'Almenningen, A.; Gogstad, E.; Hagen, K.; Schei, H.; Stilevik, R.; Thingstad, 0.; Traetteberg, M. 1 Mol. Struct. 1984, 116, 131. J Klein, A. W.; Schrumpf, G. Acta Chem. Scand, Ser. A 1981, 35, 431. k Tamagawa, K.; Hilderbrandt, R. L. J. Phys. Chem. 1983, 87, Traetteberg, M.; Bakken, P.; Seip, R.; LUittke, W.; Knieriem, B. Acta Chem. Scand, Ser. A 1988, 42, 584. m Tanimoto, M.; Kuchitsu, K.; Morino, Y. Bull. Chem. Soc. Jpn. 1971, 44, 386. n Traetteberg, M.; Bakken, P.; Seip, R.; Cyvin, S. J.; Cyvin, B. N.; Hopf, H. J Mol. Struct. 1979, 51, Schultz, G.; Nagy, T.; Portalone, G.; Ramondo, F.; Hargittai, I.; Domenicano, A. Struct. Chem. 1993, 4, 183. P This work. q Abramenkov, A. V.; Almenningen, A.; Cyvin, B. N.; Cyvin, S. J.; Jonvik, T.; Khaikin, L. S.; Rpmming, C.; Vilkov, L. V. Acta Chem. Scand, Ser. A 1988, 42, 674.

J. Am. Chem. Soc., 1996, 118(17), , DOI: /ja953373m

J. Am. Chem. Soc., 1996, 118(17), 4090-4093, DOI:10.1021/ja953373m Terms & Conditions Electronic Supporting Information files are available without a subscription to ACS Web Editions. The American Chemical