organic compounds
Table 3
Hydrogen-bonding geometry (A, ) for (IIIb).
compound (V), data collection: P3 (Siemens, 1989); cell re®nement:
P3. For all three compounds, data reduction: SHELXTL-Plus
(Sheldrick, 1994); program(s) used to solve structure: SHELXS97
(Sheldrick, 1990); program(s) used to re®ne structure: SHELXL97
(Sheldrick, 1997); molecular graphics: SHELXTL-Plus; software
used to prepare material for publication: SHELXL97.
ꢀ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
N3ÐH3BÁ Á ÁS1i
0.86
2.55
3.402 (2)
170
Symmetry code: (i) 1 x; 1 y; 2 z.
We thank the NASA Alliance for Nonlinear Optics for
support (NAG8-1708) and NASA for funding via cooperative
agreement NCC8-194-B.
Table 4
Selected geometric parameters (A, ) for (V).
ꢀ
Ê
S1ÐC18
S1ÐC19
N2ÐC17
N3ÐC18
N3ÐC20
1.7342 (18)
1.712 (2)
1.146 (2)
1.307 (2)
1.383 (2)
C3ÐC15
1.448 (2)
1.358 (2)
1.434 (3)
1.471 (2)
1.362 (3)
C15ÐC16
C16ÐC17
C16ÐC18
C19ÐC20
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: BM1472). Services for accessing these data are
described at the back of the journal.
C18ÐS1ÐC19
C18ÐN3ÐC20
C2ÐC3ÐC15
C16ÐC15ÐC3
C15ÐC16ÐC17
C15ÐC16ÐC18
C17ÐC16ÐC18
N2ÐC17ÐC16
88.93 (9)
111.08 (15)
124.00 (16)
131.52 (17)
124.43 (16)
120.34 (16)
115.21 (16)
177.5 (2)
N3ÐC18ÐC16
N3ÐC18ÐS1
C16ÐC18ÐS1
C20ÐC19ÐS1
C19ÐC20ÐN3
C19ÐC20ÐC21
N3ÐC20ÐC21
123.25 (16)
114.59 (13)
122.16 (14)
111.09 (14)
114.30 (17)
126.89 (17)
118.81 (17)
References
Allen, F. H. & Kennard, O. (1993). Chem. Des. Autom. News, 8, 1, 31±37.
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor,
R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1±19.
Allinger, N. L., Yuh, Y. H. & Lii, J.-H. (1989). J. Am. Chem. Soc. 111, 8551±
8566.
Antipin, M. Yu., Barr, T. A., Cardelino, B. H., Clark, R. D., Moore, C. E.,
Myers, T., Penn, B., Romero, M., Sanghadasa, M. & Timofeeva, T. V. (1997).
J. Phys. Chem. B, 101, 2770±2781.
C11ÐN1ÐC12ÐC13
C15ÐC16ÐC18ÐN3
104.1 (2)
4.4 (3)
N3ÐC20ÐC21ÐC26
3.4 (3)
Antipin, M. Yu., Timofeeva, T. V., Clark, R. D., Nesterov, V. N., Dolgushin,
F. M., Wu, J. & Leyderman, A. (2001). J. Mater. Chem. 11, 351±358.
Antipin, M. Yu., Timofeeva, T. V., Clark, R. D., Nesterov, V. N., Sanghadasa,
M., Barr, T. A., Penn, B., Romero, L. & Romero, M. (1998). J. Phys. Chem.
A, 102, 7222±7232.
Brunskill, J. S. A., De, A., Ewing, D. F. & Welch, A. J. (1984). Acta Cryst. C40,
493±495.
Enraf±Nonius (1989). CAD-4 Software. Version 5.0. Enraf±Nonius, Delft, The
Netherlands.
Data collection
Syntex P21 diffractometer
ꢂ/2ꢂ scans
h = 24 ! 24
k = 21 ! 1
4942 measured re¯ections
4540 independent re¯ections
3066 re¯ections with I > 2ꢄ(I)
Rint = 0.037
l = 0 ! 8
2 standard re¯ections
every 98 re¯ections
intensity decay: 3%
Kuzyk, M. C. & Dirk, C. W. (1998). Characterization Techniques and
Tabulations for Organic Nonlinear Optical Materials, p. 894. New York:
Marcel Dekker Inc.
ꢂmax = 27.1ꢀ
Lii, J.-H. & Allinger, N. L. (1989). J. Am. Chem. Soc. 111, 8566±8575.
Nalwa, H. S. & Miyata, S. (1997). Nonlinear Optics of Organic Molecules and
Polymers, p. 885. Boca Raton: CRC Press.
Nesterov, V. N., Antipin, M. Yu., Timofeeva, T. V. & Clark, R. D. (2000). Acta
Cryst. C56, 88±89.
Nesterov, V. N., Shestopalov, A. M., Sharanin, Yu. A., Aitov, I. A., Shklover,
V. E., Struchkov, Yu. T. & Litvinov, V. P. (1991). Izv. Akad. Nauk SSSR Ser.
Khim. pp. 896±902. (In Russian.)
Re®nement
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.043
wR(F2) = 0.112
S = 0.92
4540 re¯ections
272 parameters
H-atom parameters constrained
w = 1/[ꢄ2(Fo2) + (0.068P)2]
where P = (Fo2 + 2Fc2)/3
(Á/ꢄ)max = 0.001
3
Ê
Áꢅmax = 0.30 e A
3
Ê
0.32 e A
Áꢅmin
=
Sanghadasa, M., Barr, T. A., Wu, B., Clomenil, D., Tong, Y., Bhat, K. N., Clark,
R. D. & Penn, B. G. (1996). Proc. SPIE, 2853, 37±45.
Sheldrick, G. M. (1990). Acta Cryst. A46, 467±473.
Sheldrick, G. M. (1994). SHELXTL-Plus. PC Version 5.02. Siemens Analytical
X-ray Instruments Inc., Madison, Wisconsin, USA.
È
Sheldrick, G. M. (1997). SHELXL97. University of Gottingen,
Germany.
Siemens (1989). P3. Siemens Analytical X-ray Instruments Inc., Madison,
Wisconsin, USA.
Timofeeva, T. V., Nesterov, V. N., Antipin, M. Yu., Clark, R. D., Sanghadasa,
M., Cardelino B. H., Moore, C. E. & Frazier, D. O. (2000). J. Mol. Struct. 519,
225±241.
Wang, Z., Nesterov, V. N., Borbulevych, O. Ya., Clark, R. D., Antipin, M. Yu. &
Timofeeva, T. V. (2001). Acta Cryst. C57, 1343±1348.
Zyss, J. (1994). Molecular Nonlinear Optics: Materials, Physics, and Devices,
p. 479. New York: Academic Press/Harcourt Brace and Jovanovich.
Molecular mechanics calculations were carried out using MM3
(Allinger et al., 1989; Lii & Allinger, 1989). EFISH measurements of
hyperpolarizability for the three compounds in solution were
performed using the methods described by Sanghadasa et al. (1996)
and Antipin et al. (1997). H atoms were placed geometrically; for
(IIIa) and (V), those attached to sp2, methyl and methylene C atoms
Ê
were set at distances of 0.95, 0.98 and 0.99 A, respectively. For (IIIb),
Ê
the corresponding distances were 0.93, 0.96 and 0.97 A. For methyl H
atoms, Uiso(H) = 1.5Ueq(C), and for all other H atoms, Uiso(H) =
1.2Ueq(C).
For compounds (IIIa) and (IIIb), data collection: CAD-4 Software
(Enraf±Nonius, 1989); cell re®nement: CAD-4 Software. For
ꢁ
Acta Cryst. (2002). C58, o72±o75
Vladimir N. Nesterov et al.
C18H13N3, C18H15N3S and C26H19N3S o75