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0.1312. CCDC 175139 175141 contain the supplementarycrystallo-
graphic data for this paper. These data can be obtained free of charge
Crystallographic Data Center, 12, Union Road, Cambridge CB21EZ,
UK; fax: (44)1223-336-033; or deposit@ccdc.cam.ac.uk).
[16] R. Blom, T. Br¸ck, O. J. Scherer, Acta Chem. Scand. 1989, 43, 458
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[17] O. J. Scherer, T. Br¸ck, G. Wolmersh‰user, Chem. Ber. 1988, 121,
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[18] Mean deviation from planarity: 0.0098(6) ä (4), 0.0293(9) ä (5),
0.0350 (20) ä (6).
[3] a) M. Scheer, E. Herrmann, Z. Chem. 1990, 29, 41 55; b) O. J.
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[4] In the reaction with MeHg , [(triphos)CoP3HgMe]PF6 was obtained:
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[10] O. J. Scherer, T. Br¸ck, G. Wolmersh‰user, Chem. Ber. 1989, 122,
2049 2054.
Structure and Synthesis of the Natural
Heptachloro-1'-methyl-1,2'-bipyrrole (Q1)
Jun Wu, Walter Vetter,* Gordon W. Gribble,*
John S. Schneekloth, Jr., David H. Blank, and
Helmar Gˆrls
A number of anthropogenic organohalogen compounds
such as polychlorinated biphenyls (PCBs), polychlorinated
dibenzo-p-dioxins (PCDDs), and chlorinated pesticides
(DDT, toxaphene, lindane, and others) are recognized as
persistent, bioaccumulative, and toxic chemicals.[1] The ma-
jorityof these substance classes are ubiquitouslydistributed in
the environment, and long-term exposure is one of the major
threats to humans and wildlife from these substances.[2] The
scientific interest in anthropogenic halogenated compounds is
reflected in the fate of these contaminants and related
compounds in the environment, which was reported on in
more than 1000 publications in the past 40 years.
More than 3600 naturallyoccurring organohalogens have
been identified to date.[3] The total amount of these com-
pounds is not known, but is probablyhigher than currently
known.[4] It was thought that these natural products are
neither persistent nor lipophilic, and thus do not accumulate
in the lipids of higher organisms. This hypothesis is currently
under reconsideration, as recent work has resulted in the
detection of a series of unknown halogenated compounds that
[11] B. Rink, O. J. Scherer, G. Wolmersh‰user, Chem. Ber. 1995, 128, 71
74.
[12] a) O. J. Scherer, T. Mohr, G. Wolmersh‰user, J. Organomet. Chem.
1997, 529, 379 385; b) C. Hoffmann, O. J. Scherer, G. Wolmersh‰user,
J. Organomet. Chem. 1998, 559, 219 222; c) B. Koch, O. J. Scherer, G.
Wolmersh‰user, Z. Anorg. Allg. Chem. 2000, 626, 1797 1802.
[13] a) M. Detzel , T. Mohr, O. J. Scherer, G. Wolmersh‰user, Angew.
Chem. 1994, 106, 1142 1144; Angew. Chem. Int. Ed. Engl. 1994, 33,
1110 1112; b) M. Detzel, G. Friedrich, O. J. Scherer, G. Wolmer-
sh‰user, Angew. Chem. 1995, 107, 1454 1456; Angew. Chem. Int. Ed.
Engl. 1995, 34, 1321 1223; for NMR spectroscopic evidence for
h5:h2:h1 coordination of 3 see: c) G. Friedrich, Dissertation, Universi-
t‰t Kaiserslautern, 1995; M. Detzel, Dissertation, Universit‰t Kaiser-
slautern, 1995; d) O. J. Scherer, S. Weigel, G. Wolmersh‰user, Chem.
Eur. J. 1998, 4, 1910 1916.
[14] Because to their insolubility, no NMR spectroscopic investiga-
tion could be carried out. Solid-state NMR investigations are in
progress.
[15] Crystal structure analyses of 4 6 were performed on STOE IPDS
diffractometers with MoKa radiation (l 0.71073 ä) for 5 and AgKa
radiation (l 0.56087 ä) for 4 and 6. The structures were solved by
direct methods with the program SHELXS-97,[19a] and full-matrix
least-squares refinement on F 2 in SHELXL-97[19b] was performed with
anisotropic displacements for non-hydrogen atoms. Hydrogen atoms
were located in idealized positions and refined isotropicallyaccording
to the riding model. 4 ¥ 0.5 CH2Cl2: C10.5H16Cl2CuFeP5, Mr 487.37,
crystal dimensions 0.20 Â 0.14 Â 0.04 mm3, monoclinic, space group
C2/c (No. 15), a 20.184(4), b 16.885(3), c 13.860(3) ä, b
[*] Priv.-Doz. Dr. W. Vetter, Dr. J. Wu
Lehrbereich Lebensmittelchemie
Friedrich-Schiller-Universit‰t Jena
Dornburger Strasse 25, 07743 Jena (Germany)
Fax : (49)3641-949-652
129.33(3)8,
T 203(2) K,
Z 8,
V 3653.7(13) ä3,
1calcd
1.772 MgmÀ3
,
m 1.382 mmÀ1
, 3831 independent reflexes (Rint
0.0365, 2qmax 428), 3128 observed with Fo 4s (Fo), 190 parameters,
R1 0.0370, wR2 0.0974. 5: C10H15BrCuFeP5, M 489.37, crystal
dimensions 0.20 Â 0.20 Â 0.01 mm3, tetragonal, space group P421c
Prof. Dr. G. W. Gribble, J. S. Schneekloth, Jr., Dr. D. H. Blank
Department of Chemistry, 6128 Burke Laboratory
Dartmouth College
≈
(No. 114), a b 12.147(2), c 21.859(4) ä, T 200(1) K, Z 8,
V 3225.2(9) ä3, 1calcd 2.016 MgmÀ3, m 5.170 mmÀ1, 3152 inde-
pendent reflexes (Rint 0.0777, 2qmax 528), 2681 observed with Fo
4s (Fo), 168 parameters, R1 0.0345, wR2 0.0809. 6: C10H15CuFeIP5,
Mr 536.36, crystal dimensions 0.10 Â 0.10 Â 0.10 mm3, tetragonal,
Hanover, NH 03755 (USA)
Fax : (1)603-646-3946
≈
space group P421m (No. 113); a b 12.372(2), c 11.241(2) ä, T
Priv.-Doz. Dr. H. Gˆrls
203(1) K, Z 4, V 1720.6(5) ä3, 1calcd 2.071 MgmÀ3
,
m
Institut f¸r Anorganische und Analytische Chemie
Friedrich-Schiller-Universit‰t Jena
Lessingstrasse 8, 07743 Jena (Germany)
2.258 mmÀ1, 8297 independent reflexes (Rint 0.1663, 2qmax 408),
1475 observed with Fo 4s (Fo); 94 parameters, R1 0.0496, wR2
1740
¹ WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002
1433-7851/02/4110-1740 $ 20.00+.50/0
Angew. Chem. Int. Ed. 2002, 41, No. 10