H. Bock et al.
FULL PAPER
Its solution in THF (90 mL) was cooled to
758C; iodine (9.8 g,
1,8-Diiodonaphthalene: 1,8-Iodonaphthylamine hydrochloride (6.3 g,
24 mmol) was dissolved in conc. HCl (71 mL) and cooled to 18C; under
stirring NaNO2 (1.46 g, 21 mmol) was added in small portions. On addition
of KI (5.5 g, 33 mmol), the yellow-brown solution of the diazonium
chloride turned into the red one of diazonium iodide. After heating the
mixture for 2 h on a waterbath, nitrogen evolution ceased; the crude
product was recrystallized from methanol to yield orange-brown needles
(m.p. 1098C).
38.5 mmol) was added, and the mixture stirred at room temperature for
17 h. After quenching with water added dropwise (20 mL) the solution was
extracted twice with ether (each 50 mL); the combined ether phases were
washed first with 40% NaHSO3 solution and then four times with water
(each 50 mL). The ether solution dried over MgSO4 and evaporated yields
1,10-diiodophenanthrene as a light brown product, which can be recrystal-
lized at 208C after addition of n-hexane (m.p. 188 ± 1938C).
Crystal structure determination for 1,8-diiodonaphthalene: 1,8-Diiodo-
naphthalene, orange-brown needles, C10H6I2 (Mr 379.95), a 1283.8(2),
Crystal structure determination for 1,10-diiodophenanthrene: 1,10-Diio-
dophenanthrene, brown blocks, C14H8I2 (Mr 430), a 877.2(1), b
b 1540.2(2), c 1599.9(2) pm, a 77.16(1), b 72.64(1), g 82.26(1)8,
877.4(1), c 1658.2(1) pm, a 105.03(1)8, b 100.28(1)8, g 90.15(1)8,
3
V 2935.9 Â 106 pm3 (T 200 K), 1ber 2.579 gcm , triclinic, P1 (No. 2),
Å
3
V 1211.2 Â 106 pm3 (T 150 K), 1ber 2.358 gcm , triclinic, P1 (No. 2),
Å
Z 12, F(000) 2064.0. w ± q scan on a four-circle diffractometer Siemens/
Stoe AEDII, MoKa radiation, m 6.37 mm 1, all data corrected for Lorentz
and polarization effects and absorption correction established by PSI-scan
measuring 10 reflections in steps of 108. In the range 3 ꢂ 2q ꢂ 528 are
measured 9962 reflections, of which 9251 independent and 7766 used for
refinement (Rint 0.0863). Structure solution with direct methods using
SHELXS-86, refinement with SHELXL-93, 650 parameters, w 1/
[s2(F2o) (0.0614P)2 20.76P], R 0.0408 for 7766 Fo > 4s(Fo), wR2
Z 4, F(000) 792.0, w ± q scan on a Siemens P4 four-circle diffractometer,
MoKa radiation, m 5.16 mm 1, all data corrected for Lorentz and polar-
ization effects and absorption correction established by DIFABS.[32] Range
3 ꢂ 2q ꢂ 668; 9728 reflections, of which 8936 independent and 8185 used for
refinement (Rint 0.0211). Structure solution with direct methods by means
of SHELXS-86, refinement with SHELXL-93, 290 parameters, w 1/
[s2(F2o) (0.0298P)2 2.49P], R 0.0401 for 8185 Fo > 4s(Fo), wR2
0.0979 for all 9728 reflections, GoF 1.231, residual density: 1.45/
1.20 e 3. All heavy centers were refined with anisotropic displacement
parameters and all hydrogens located from the difference map, positioned
ideally, and refined with isotropic displacement parameters using the riding
model ([Uiso 1.2Ueq(C ± H/CH2)]; [Uiso 1.5Ueq(C ± H/CH3)]).
0.1152 for all 9962 reflections, GoF 1.057, residual density: 3.33/
3
2.14 e
. All heavy centers were refined by means of anisotropic
displacement parameters and all hydrogens located from the difference
map, positioned ideally, and refined with isotropic displacement parame-
ters using the riding model ([Uiso 1.2Ueq(C ± H/CH2)]; [Uiso 1.5Ueq(C ±
H/CH3)]).
2,2'-Diiodobiphenyl:[10] Biphenyl (4.7 g, 30.5 mmol) was stirred under
argon in n-butyllithium in n-hexane solution (1.6m, 46 mL, 74 mmol) and
then heated to 608C for 3 h. After standing at room temperature for 10 h,
the mixture was cooled to 208C, the resulting light yellow solid filtered
off, pure THF (20 mL) added and the red solution cooled to 758C. Under
argon, iodine (15 g, 59 mmol) was added, and the dark brown solution
allowed to warm up to room temperature and stirred for 2 h. On shaking
the mixture with ether and 40% NaHSO3 solution, it turned orange.
Washing with water to neutral pH and evaporation yielded a dark oil, from
which on addition of n-hexane a light yellow solid precipitated. Crystals of
2,2'-diiodobiphenyl are best obtained by a 7-day sublimation at 708C and
10 mbar (m.p. 1098C).
Crystallographic data (excluding structure factors) for the structures
reported in this paper have been deposited with the Cambridge Crystallo-
graphic Data Centre as supplementary publication no. CCDC-101284.
Copies of the data can be obtained free of charge on application to CCDC,
12 Union Road, Cambridge CB21EZ, UK (Fax: (44)1223-336-033;
e-mail: deposit@ccdc.cam.ac.uk).
Density functional calculations are performed at the B3LYP level[34±36] with
631G** basis sets[37±39] for centers H and C. For iodine, the effective core
potential known from the literature[40] was modified to extend the valence
basis set to (4s,4p). The uncontracted gaussians were simultaneously
optimized for the I atom (at the B3LYP level), the polarization d function
(a 0.246, optimized for HI) added and the valence basis set contracted to
double-zeta 31G* quality. The resulting basis set for iodine fits the 6-31G**
basis set of the other atoms. All molecules studied were totally geometry-
optimized. To compute the rotational potential energy surface of 1,1'-
diiodobiphenyl, the central (H)C-C-C-C(H) torsion angle was varied in 108
steps and all the other parameters optimized.
Crystal structure determination for 2,2'-diiodobiphenyl: 2,2'-Diiodobi-
phenyl, yellow rods, C12H8I2 (Mr 405.98), a 767.4(1), b 1412.7(2), c
2212.4(2) pm, a b g 908, V 2398.5 Â 106 pm3 (T 200 K), 1ber
2.249 gcm 3, orthorhombic, Pbca (No. 61), Z 8, F(000) 1488.0, w ± q
scan on a Siemens/Stoe AEDII four-circle diffractometer, MoKa radiation,
m 5.21 mm 1, all data corrected for Lorentz and polarization effects and
empirical absorption correction established by XEMP (min. transm.
0.730, max transm. 0.993).[33] Range 3 ꢂ 2q ꢂ 528; 3215 reflections, of
which 2322 independent and 1755 used for refinement (Rint 0.0117).
Structure solution with direct methods using SHELXS-86, refinement with
SHELXL-93, 128 parameters, w 1/[s2(Fo2) (0.0259P)2 3.27P], R
0.0246 for 1755 Fo > 4s(Fo), wR2 0.0645 for all 3215 reflections, GoF
1.042, residual density: 0.90/ 0.65 e 3. All centers were refined with
anisotropic displacement parameters and all hydrogens located from the
difference map, positioned ideally, and refined with isotropic displacement
Acknowledgements: Our investigations have been generously supported
by the Deutsche Forschungsgemeinschaft, the State of Hesse, the Hoechst
Corporation and the Fonds der Chemischen Industrie.
Received: August 20, 1997 [F798]
[1] H. Bock, Z. Havlas, D. Hess, C. Näther, Angew. Chem. 1998, 110, 518;
Angew. Chem. Int. Ed. Engl. 1998, 37, 502.
[2] For an overview, see: H. Bock, K. Ruppert, C. Näther, Z. Havlas, H.-F.
Herrmann, C. Arad, I. Göbel, A. John, J. Meuret, S. Nick, A.
Rauschenbach, W. Seitz, T. Vaupel, B. Solouki, Angew. Chem. 1992,
104, 594; Angew. Chem. Int. Ed. Engl. 1992, 31, 550.
[3] X. Qiao, D. M. Ho, R. A. Pascal, Jr., Angew. Chem. 1997, 109, 1588;
Angew. Chem. Int. Ed. Engl. 1997, 36, 1531.
[4] F. P. van Remoortere, F. P. Boer, J. Am. Chem. Soc. 1970, 92, 3355.
[5] See, for example, The Crystal as a Supramolecular Entity (Ed.: G. R.
Desiraju), Wiley, Chichester, 1996.
parameters using the riding model ([Uiso 1.2Ueq(C ± H/CH2)]; [Uiso
1.5Ueq(C ± H/CH3)]).
1,8-Diiodonaphthalene:[13] The compound is prepared in two steps via 1,8-
iodonaphthylamine hydrochloride (see Scheme 3).
1,8-Iodonaphthylamine hydrochloride: A hot solution of 1,8-naphthylendi-
amine (15 g, 95 mmol) in conc. HCl (200 mL) was poured into water
(1400 mL); the solution was filtered and cooled by adding ice (300 g).
Subsequently, H2SO4 (15 mL) and NaNO2 (6.7 g, 97 mmol) were added
under constant stirring and after cooling the temperature to well below
58C. The product was filtered off, dried at 10 2 mbar and suspended in HI
(100 g, 781 mmol). Under constant stirring, copper metal (4 g, 63 mmol)
was added in small portions and the reaction mixture heated for 2 h on a
waterbath. Under vigorous liberation of nitrogen, a black crystalline
product formed, which could be recrystallized from hot ethanol to yield
grey needles of 1,8-iodonaphthylamine hydrochloride. This was purified by
refluxing with diethyl ether for 2 h, drying the filtered solution with K2CO3
and precipitating the hydrochloride salt with aqueous HCl. Recrystalliza-
tion from hot ethanol yielded light gray needles (m.p. 186 ± 1898C).
[6] Representative examples are: a) R2Si CR2 with R Si(CH3)3,
adamantyl: A. G. Brook, J. W. Harris, J. Lemmon, M. El Sheikh, J.
Am. Chem. Soc. 1979, 101, 83; b) H2C NH: H. Bock, R. Dammel,
Angew. Chem. 1987, 99, 503; Angew. Chem. Int. Ed. Engl. 1987, 26,
489; R2Si NSiR3 with R C(CH3)3: N. Wiberg, K. Schurz, G. Reber,
G. Müller, J. Chem. Soc. Chem. Commun. 1986, 591; c) supermesityl
ligands ((H3C)3C)3H2C6, e.g. for RP PR: M. Yoshifuji, I. Shima, N.
Inamoto, K. Hirotsu, T. Higuchi, J. Am. Chem. Soc. 1981, 103, 4587.
[7] a) L. Pauling, Die Natur der Chemischen Bindung (The Nature of the
Chemical Bond), Verlag Chemie, Weinheim, 1962, p. 242 ± 247; b) A.
684
ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1998
0947-6539/98/0404-0684 $ 17.50+.50/0
Chem. Eur. J. 1998, 4, No. 4
Bock, Hans
