Mendeleev Commun., 2013, 23, 289–291
atoms in O–N–N geminal system, unusual elongating of N–N+
bond and shortening of N–OMe bond in salt 13.
O(6)
S(1)
O(4)
C(4)
C(7)
C(2)
C(5)
O(3)
C(8)
C(6)
O(2)
C(1)
This work was supported by the Russian Foundation for Basic
Research (grant no. 13-03-90460) and Ukrainian Foundation for
Fundamental Research (grant no. F-53/105-2013).
N(2)
N(1)
C(9)
O(5)
C(11)
C(10)
O(1)
Online Supplementary Materials
Supplementary data associated with this article can be found
in the online version at doi:10.1016/j.mencom.2013.09.018.
C(3)
Figure 2 Molecular structure of compound 7. Selected bond lengths (
N(1)–N(2) 1.379(4), N(1)–O(3) 1.414(4), N(1)–C(1) 1.398(5), N(2)–C(4)
.411(4), C(1)–O(1) 1.196(4), C(4)–O(4) 1.193(4), N(2)–S(1) 1.723(3);
selectedbondangles (°): N(2)–N(1)–O(3) 112.1(3), N(2)–N(1)–C(1) 118.0(3),
O(3)–N(1)–C(1)111.6(3),N(1)–N(2)–S(1)119.0(2),N(1)–N(2)–C(4)120.2(3),
C(4)–N(2)–S(1) 120.8(2).
Å
):
References
1
2
3
V. G. Shtamburg, A.V. Tsygankov, O. V. Shishkin, R. I. Zubatyuk, B. V.
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1
In compound 7 the O(3)–C(3) bond has sp-orientation toward
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69.1(3)°]. The LpN(1) and LpN(2) have mutual orthogonal
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¶
The XRD data for compound 13 (Figure 3) revealed that
+
N(1)–N(2) bond is elongated to 1.483(3) Å compared to N–N
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1
+
bond length in hydrazine (1.466 Å) and N–N bond length in
salt 17 [1.466(2) Å].22 The length of N(1)–N(2)+ bond in salt
1
661.
1
3 is similar to the N–N bond length in tetramethoxyhydrazine
1
1
0 S. A. Glover, G. Mo and A. Rauk, Tetrahedron, 1999, 55, 3413.
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4
(
1.484 Å). In compound 13 the N(1)–O(1)Me bond is strongly
shortened [1.391(3) Å] compared to that in compound 17
2
2
[1.4142(16) Å]. The N(1) atom is strongly pyramidal, Sß
is 312°. This is in accordance with significant geminal non-
12 J. J. Cambell and S. A. Glover, J. Chem. Res. (S), 1999, 8, 474.
13 J. J. Cambell and S. A. Glover, J. Chem. Res. (M), 1999, 8, 2075.
1
equivalence of N–OCH R protons in H NMR spectra of hydra-
2
1
4 R. J. Crawford and R. Raap, J. Org. Chem., 1963, 28, 2419.
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Thus, the study of structures of compounds 5, 7 and 13
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1
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9
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1
1
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O(3B)
O(4A)
4
23 (Izv. Akad. Nauk SSSR, Ser. Khim., 1981, 449).
O(3A)
1
1
2
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O(2)
Cl(1)
O(1)
C(1)
O(4B)
O(5B)
O(5A)
N(1)
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N(2)
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2
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C(2)
C(4)
C(3)
2
Figure 3 Molecular structure of compound 13. Selected bond lengths (Å):
N(1)–N(2) 1.483(3), O(1)–N(1) 1.391(3), O(1)–C(1) 1.446(4), N(2)–C(2)
1
.491(3), N(2)–C(3) 1.500(4), N(2)–C(4) 1.481(4); selected bond angles (°):
O(1)–N(1)–N(2) 107.12(19), N(1)–O(1)–C(1) 109.1(3), N(1)–N(2)–C(2)
13.4(2), N(1)–N(2)–C(3) 102.9(2).
1
Received: 30th May 2013; Com. 13/4128
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