Synthesis and structure of alkyl-α-arylamino-β-bromo-β- nitroacrylates, new functionalized β-nitroenamines

Article abstract of DOI:10.1134/S1070363211020162

New bromonitroenamine compounds, alkyl-2-arylamino-3-bromo-3- nitroacrylates, were synthesized and characterized using IR, UV, ¹H and ¹³C NMR spectroscopy, and X-ray analysis. Their molecules were found to have the E-configuration an

Full text of DOI:10.1134/S1070363211020162

ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 2, pp. 376–384. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © V.M. Berestovitskaya, S.V. Makarenko, K.S. Kovalenko, I.A. Litvinov, D.B. Krivolapov, A.D. Shevchenko, 2011, published in
Zhurnal Obshchei Khimii, 2011, Vol. 81, No. 2, pp. 277–286.
Synthesis and Structure
of Alkyl-α-arylamino-β-bromo-β-nitroacrylates,
New Functionalized β-Nitroenamines
V. M. Berestovitskayaa, S. V. Makarenkoa, K. S. Kovalenkoa,
I. A. Litvinovb, D. B. Krivolapovb, and A. D. Shevchenkoa
a Herzen Russian State Pedagogical University, nab. r. Moiki, 48, St. Petersburg, 191186 Russia
e-mail: kohrgpu@yandex.ru
b Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center,
Russian Academy of Sciences, Kazan, Tatarstan, Russia
Received May 6, 2010
Abstract—New bromonitroenamine compounds, alkyl-2-arylamino-3-bromo-3-nitroacrylates, were synthesized
1
and characterized using IR, UV, H and 13C NMR spectroscopy, and X-ray analysis. Their molecules were
found to have the E-configuration and to exist as highly conjugated structures. According to the X-ray analysis,
in the ethyl-3-bromo-2-(p-bromophenylamino)-3-nitroacrylate molecule the bromonitroenamine moiety is
almost planar, the ester group is located completely out of the C=C double bond plane, amino hydrogen and
nitro oxygen atoms form an intramolecular hydrogen bond.
DOI: 10.1134/S1070363211020162
β-Nitroenamines [1] containing β-halogen atom in
the geminal position to the nitro group are poorly
known [2–6], and the compounds including an
additional electron-withdrawing group are unknown at
all. However, the structure of a number of halogen-
containing nitroenamines are of interest not only from
a theoretical point of view (as objects for studying the
structure of sterically hindered unsaturated compounds
and the transfer of electronic effects in a conjugated
systems), but also in the practical aspect (as potential
biologically active substances, whose representatives
have already been patented as insecticides and
pesticides [7, 8]).
produce brightly colored crystalline α-arylamino-β-
bromo-β-nitroacrylates III–IX in yields of 54–87%.
1
ROOC
Br
ROOC
Br
NO2
Br
2
3
2 H2N−Ar
−ArNH2
HBr
N
NO2
Ar
H
III−IX
I, II
R = Me (I), Et (II); R = Me, Ar = p-Br-C6H4 (III), p-Me-
C6H4 (V), p-EtO-C6H4 (VII), α-naphthyl (IX); R = Et, Ar =
p-Br-C6H4 (IV), p-Me-C6H4 (VI), p-EtO-C6H4 (VIII).
Alkyl-α-aryl-β-bromo-β-nitroacrylates
can
be
Such mild conditions of this reaction are logical,
considering activating effect of an additional acceptor,
the ester group, on the multiple C=C bond of
dihalogen-substituted nitroacrylate. The closest
analogs, α,β-dibromo-β-nitrostyrenes, are known to
react with the primary arylamines in boiling benzene
[5].
considered both as halogen-containing nitroenamines
and the derivatives of β-nitroacrylic acid ester. The
latter is used for the synthesis of some practically
important alkaloids and antibiotics [9–12].
The approach to the synthesis of arylaminobromo-
nitroacrylates was found to be simple enough. The
reaction of α,β-dibromo-β-nitroacrylates I, II obtained
previously [13] with a twofold excess of the primary
arylamine proceeds efficiently at room temperature in
a solution of anhydrous benzene for 10–45 min to
The studied reaction occurs apparently by the
SNVin mechanism via the formation of the inter-
mediate bipolar ion, allowing the rotation around the
376

SYNTHESIS AND STRUCTURE OF ALKYL-α-ARYLAMINO-β-BROMO-β-NITROACRYLATES
377
bond C2-C3, and the formation of the end-product as E-
or Z-isomer. The formation of not only inter-, but
intramolecular hydrogen bond involving the NH-group
and the nitro or ester functions is theoretically possible
for both configurations. The tautomeric transformation
enamine↔imine is not excluded [1].
O−
N+
O−
N+
1
O−
O
Br
N+
ROOC
NO2
Br
ROOC
ROOC
ROOC
2
3
−
C
C
Br
Br
C
Br
+
+
+
O−
Br
Ar
Ar
Ar
NH2
NH2
NH2
Br
Br
−
O
H2N
Ar
Br
N+
ROOC
C
O
−HBr
O−
Ar
N
H
OR
OR
ROOC
Ar
Br
ROOC
Ar
Br
ROOC
Ar
Br
H
NO2
Br
NO2
NO2
Br
O
O
H
H
N
NO2
N
Ar
N+ O−
N
N
N
H
Ar
H O
E-configuration
Z-configuration
Enamine
Imine
The structure of the synthesized α-arylamino-β-
bromo-β-nitroacrylates III–IX was established on the
basis of 1Н, 13C–{1H} NMR, IR, and UV spectroscopy
105.2 (=CBrNO2) and 141.8 ppm (=CHN) are assigned
[3] to the vinyl carbons, while in the case of 1-nitro-
2,2-di-(4-chlorophenylamino)-1-chloroethene they are
at 106.4 (=CClNO2) and 149.3 ppm (=CNN) [14].
1
(Tables 1, 2). The Н and 13C–{1H} NMR spectra
(DMSO-d6) of compounds III–IX contain one set of
signals for all structural fragments and suggest the
configurational homogeneity of the substances (Table 1).
For example, in the spectrum of III there is a singlet
signal of methoxy protons at 3.63 ppm, doublets of the
protons of p-substituted aromatic ring at 7.13–7.15 and
7.56–7.58 ppm, as well as a broad signal of the NH-
proton at 10.17 ppm.
The infrared and electronic spectra (Table 2) of
aminobromonitroacrylates III–IX indicate a significant
contribution to the electronic structure of the charge
separation [1, 15].
ROOC
Br
ROOC
Br
N+
H
NOO−
Ar
Ar
N
H
NO2
The 13C–{1H} NMR spectra (Table 1) of com-
pounds III–IX contain the signals of carbon atoms of
the alkyl substituents of ester groups [53.71–54.15
ppm (CH3) and 13.73–14.12, 63.20–63.47 ppm
(C2H5)], the aromatic ring (115.10–158.76 ppm), as
well as downfield signals of the carbon of alkoxy-
carbonyl group (161.04–161.77 ppm). The signals at
148.65–151.07 ppm can be attributed to the carbon
atom C2. The carbon atom C3 containing the nitro
group and bromine atom is observed as a low-intensity
broad signal at 100.04–105.99 ppm only in the spectra
of compounds III, IV, VI, VIII, IX. Their location is
consistent with the published data for structurally
similar analogs [3, 14]. For example, in the spectrum
of 1-bromo-1-nitro-2-phenylaminoethene the signals at
Their IR spectra contain vibration bands of C=O
bond (1752–1735 cm–1) of the ester group [16] and a
set of bands belonging to the vibrations of
nitroenamine fragment: a strong band of conjugated
multiple bonds C=C and C=N at 1608–1556 cm–1 [1],
intense overlapping bands originating from the ionized
nitro group at 1301–1271, 1253–1203, and 1179–
1114 cm–1 [17], and broad bands of the free and bound
amino groups at 3348–3188 cm–1 [16]. Note that the IR
spectra in going from the liquid phase (chloroform
solution) to the solid (KBr pellets) slightly differ. For
example, the amino group appears not as several bands
(as in chloroform), but as a single broad band of
moderate intensity. Also the position of the vibration
band of carbonyl group attracts attention: the band is
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 2 2011

378
BERESTOVITSKAYA et al.
Table 1. Yields, melting points, and 1H, 13C NMR spectral data of arylaminobromonitroacrylates III–IX
NMR spectrum, δ, ppm, DMSO-d6
Comp.
no.
Yield,
%
mp,
R
Ar
1Hа
13Cb
NH OCH3 (OС2Н5) C2 (С3)
°С
OMe (OEt)
3.63
Ar
Ar
C=O
Me p-BrС6Н4
Et p-BrС6Н4
Me p-MeС6Н4
Et p-MeС6Н4
Me p-EtOС6Н4
Et p-EtOС6Н4
Me α-Naphthyl
68
83
54
81
87
68
79
145–146
7.13–7.15, 10.17
7.56–7.58
54.15
148.65 120.61, 127.27, 161.77
(105.99) 132.64, 137.21
III
IV
88–89 (1.02, 4.06) 7.14–7.16, 10.15 (13.73, 63.46)
7.56–7.58
149.06 120.71, 127.76, 161.04
(105.68) 132.51, 137.15
122–123
3.59
7.06–7.08, 10.16
7.17–7.19
53.95
149.57 125.49, 130.12, 161.75
135.03, 137.66
V
61–63 (0.99, 4.04) 7.08–7.09, 10.10 (13.78, 63.20)
7.17–7.19
149.84 125.96, 129.99, 161.06
(104.21) 134.95, 137.78
VI
133–135
3.57
6.89–6.91, 10.10
7.10–7.12
53.89
150.05 115.10, 127.52, 161.68
129.91, 158.34
VII
VIII
IX
94–95 (0.98, 3.99) 6.89–6.91, 10.07 (14.12, 63.47)
7.11–7.14
150.73 115.34, 128.31, 161.35
(103.86) 130.15, 158.76
139–141
3.38
7.37–7.60, 10.43
7.88–7.96
53.71
151.07 123.67, 125.75, 161.71
(100.04) 127.46, 127.60,
128.61, 129.48,
130.30, 133.71,
133.98
a
1
In the H NMR spectra of compounds V and VI the methyl protons of p-tolyl moiety appear as singlets at 2.27 and 2.26 ppm,
respectively, and ethyl protons of p-ethoxyphenylamine fragment (VII and VIII) are observed as a triplet at 1.28 ppm and a quadruplet
at 3.99–4.04 ppm. b In the 13C NMR spectra of compounds V and VI the methyl carbon atoms p-tolyl group appear at 21.10 ppm, and the
ethyl carbon atoms of p-ethoxyphenylamine moiety in the spectra of compounds VII and VIII are observed as the signals at 9.15–15.37
and 63.86–64.22 ppm.
located in a region characteristic of C=O bond not
involved in hydrogen bonding [16].
the form of nitroenamine with cis-arranged arylamino
and nitro groups [1]. The latter form quasi-six-
membered ring due to the intramolecular hydrogen
bonding. As stated above, in the compounds III–IX
the intra- and intermolecular hydrogen bonds forma-
tion involving NH- and NO2 or NH- and COOR
groups also is possible. A convincing conclusion about
the fine structure of these compounds was made on the
basis of the X-ray analysis of ethyl α-(p-bromoaniline)-
β-bromo-β-nitroacrylate IV (Figs. 1–4, Tables 3, 4).
The electronic spectra of arylaminobromonitro-
acrylates III–IX contain intense long-wave absorption
at λmax 380–383 nm (ε 16000–17700). The observed
slight red shift compared with the model α-(p-bromo-
phenylamino)-β-nitroacrylate of the similar structure
(λmax 365 nm, ε 17800 [1, 18]) is apparently due to
some contribution of the bromine atom to the electron
distribution in the molecules.
Thus, the spectral data obtained confirm nitro-
enamine structure and show that the synthesized
arylaminobromonitroacrylates are highly polarized
structures. However, these data do not permit a valid
conclusion about the geometry of these compounds
and the nature of the hydrogen bonding.
Compound IV forms monoclinic crystals (space
group P21/c) with one independent molecule in the
asymmetric part of the unit cell (Fig. 1). By these data,
the molecule of compound IV in the crystal has E-
configuration, and the presence of the bulky bromine
atom in the gem-position to the nitro group hinders
significantly the coplanar arrangement of the ester
group in the double bond plane [torsion angle
The published data indicate preferential existence
of similar structures but without the ester function in
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SYNTHESIS AND STRUCTURE OF ALKYL-α-ARYLAMINO-β-BROMO-β-NITROACRYLATES
Table 2. IR and electronic spectral data of arylaminobromonitroacrylates III–IX
379
UV spectrum,
DMSO
IR spectrum, ν, cm–1
Comp.
no.
R
Ar
phase
С=О
С=С, С=N
NOO−
NH
λmax, nm
ε
Me p-BrС6Н4
CHCl3 1752 m 1590 m, 1583 m, 1288 m, 1253 m
1570 s
3348 w, 3238 w. br
382
380
381
17700
15950
16200
III
IV
V
KBr
1735 m 1593 m, 1571 s, 1285 m, 1271 s, 1234 m, 3287 m
1564 s 1210 m
Et p-BrС6Н4
CHCl3 1748 m 1591 m, 1582 m, 1288 m, 1250 m
1569 s
3347 w, 3236 w. br
KBr
1745 s 1592 m, 1581 m, 1283 m, 1249 s
1564 s
3189 m
Me p-MeС6Н4 CHCl3 1751 m 1573 s
1290 s
3348 w
KBr
1742 s 1590 m, 1556 s
1298 m, 1252 s, 1230 m, 3206 m
1207 s
Et p-MeС6Н4 CHCl3 1749 m 1571 s
1289 m, 1251 m
3348 w, 3230 w. br
380
383
381
380
16100
16300
16400
17900
VI
Me p-EtOС6Н4 KBr
Et p-EtOС6Н4 KBr
1750 s 1608 m, 1556 s
1748 s 1605 m, 1558 s
1301 m, 1248 s, 1209 s
1294 s, 1246 s, 1203 s
3237 m
3216 m
VII
VIII
IX
Me α-Naphthyl CHCl3 1752 m 1578 m, 1570 s
1290 m, 1273 s, 1251 m, 3341 w, 3224 w. br
1228 m
KBr
1751 s 1576 m, 1558 s
1278 s, 1246 s, 1220 s
3188 m
C3C2C1O3 is 102.8(6)°], whereas the corresponding
torsion angle O6C6C1C2 in the model ethyl 2-(p-
bromoaniline)-3-nitroacrylate is –46.13° (Fig. 1) [18].
The nitroenamine fragment in the molecule of IV is
almost planar [the torsion angle is –0.2(8)°] that favors
the efficient conjugation of the lone electron pair of
aniline nitrogen atom with the π-bond and the nitro
group. This is seen in the increase in the С3–С2 bond
length 1.365(7) Å (1.337Å in nitroethylene molecule
[19]) and in the decrease in the length of the bonds
С3–N1 1.435(7), C2–N2 1.335(6) Å compared with the
usual value (1.45–1.47 Å) in the nitroethene molecules
[19–21]. Some geometric parameters are given in
Table 4.
0.83(3), d(H2···O12) 1.93(4), d(N2···O12) 2.615(6) Å,
∠(N2–H2···O12) 139(5)°; intermolecular, N2–H2···O12' (1 – x,
–y, 1 – z), d(N2–H2) 0.83(3), d(H2···O12') 2.49(4),
d(N2···O12') 3.222(5) Å, ∠(N2–H2···O12') 148(4)°. The
intermolecular hydrogen bonding results in the
formation of centrosymmetric dimers (Fig. 2).
Thus, the studied reaction can be used as a
convenient approach to the new alkyl α-arylamino-β-
bromo-β-nitroacrylates, which are of interest as
potential biologically active compounds. Both the
spectral characteristics (in solution and solid phase)
and the X-ray analysis data of the ethyl 3-bromo-2-(p-
bromophenylamino)-3-nitroacrylate allow the confident
conclusion on the E-configuration for this series of
compounds. Based on the X-ray analysis data we
established that the steric hindrances in the molecule of
these compounds are overcame mainly by the location
of the ester group out of the plane of the double bond,
while the relative planarity of nitroenamine fragment is
retained.
In the crystal were found the intra- and inter-
molecular hydrogen bonds of NH···O type. It should be
noted that the hydrogen atom H2 and the oxygen atom
O12 are involved into the formation of bifurcated
hydrogen bonds. Parameters of the hydrogen bonds are
the following: intramolecular N2–H2···O12, d(N2–H2)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 2 2011

380
BERESTOVITSKAYA et al.
Fig. 1. General view of compound VI.
EXPERIMENTAL
13С NMR spectra were registered on a Jeol ECX-400A
spectrometer operating at 100.525 (13С) and
399.782 MHz (1Н) using the signals of the residual
protonated solvents as reference signals. The UV
spectra were recorded on a Shimadzu UV2401PC
spectrophotometer in quartz cell (l 0.1 cm) in DMSO.
The reaction progress was monitored by TLC method
on Silufol UV-254 plates with detecting on a
chromatoscope.
The IR spectra were taken on a Shimadzu
IRPrestige-21 Fourier-spectrometer from chloroform
solutions (с 0.1–0.001 M) or pellets with KBr. The 1Н,
Study of single crystal of IV was made in the
Laboratory of diffraction analysis methods at the
Arbuzov Institute of Organic and Physical Chemistry.
X-Ray diffraction analysis of compound IV was
performed at 20º on a Bruker Smart APEX2 automated
diffractometer (MoKα irradiation, graphite mono-
chromator, ω-scanning). The extinction was accounted
for semiempirically using SADABS program [22]. The
structures were solved by the direct method by SIR
program [23] and refined first in isotropic and then
anisotropic approximation by SHELXL-97 program
package [24]. Hydrogen atoms were placed in the
calculated position and refined using the rider model.
The hydrogen atom at the nitrogen atom N2 was
localized from differential Fourier charts and refined in
the isotopic approximation. All calculations were
Fig. 2. Hydrogen bonds in the crystal of IV (dotted line).
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SYNTHESIS AND STRUCTURE OF ALKYL-α-ARYLAMINO-β-BROMO-β-NITROACRYLATES
381
Fig. 3. Molecular organization and hydrogen bonds in the crystal of IV (projection of the plane b0c).
Fig. 4. Molecular arrangement and hydrogen bonds in the crystal of IV (projection of the plane a0c).
performed using WinGX [25] and APEX2 program
package [26]. Figure and analysis of hydrogen bonds
was made by means of PLATON program [27].
Conditions of the X-ray diffraction studies and
crystallographic parameters are given in Table 3. The
atomic coordinates and complete structural data are
deposited at Cambridge Crystallographic Data Center.
The starting alkyl 2,3-dibromo-3-nitroacrylates I
and II were prepared by the described procedure [13].
Methyl 3-bromo-2-(p-bromophenylamino)-3-nitro-
acrylate (III). To a solution of 0.32 g of methyl 2,3-
dibromo-3-nitroacrylate I in 8 ml of anhydrous
benzene was dropwise added a solution of 0.38 g of p-
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382
BERESTOVITSKAYA et al.
Table 3. Crystallographic data of the structure IV
Ethyl 3-bromo-2-(p-bromophenylamino)-3-nitro-
acrylate (IV) was prepared similarly from 0.34 g of
ethyl 2,3-dibromo-3-nitroacrylate II and 0.38 g of p-
bromoaniline in 13 ml of anhydrous benzene
(maintained for 20 min). Yield 0.37 g (83%), dark
yellow crystals, mp 88–89°С (methanol). Found, %: C
33.58; H 2.80; N 7.14. С11H10Br2N2O4. Calculated, %:
C 33.53; H 2.56; N 7.11.
Parameter
Color, habit
Value
Colorless prisms
C11H10Br2N2O4
Monoclinic
P21/с
Empirical formula
Crystal system
Space group
Methyl 3-bromo-3-nitro-2-(p-toluidine)acrylate
(V) was prepared similarly from 0.68 g of methyl 2,3-
dibromo-3-nitroacrylate I and 0.50 g of p-toluidine in
40 ml of anhydrous benzene (maintained for 20). After
the solvent removal the oily pale yellow residue was
treated with n-hexane. Yield 0.40 g (54%), yellow
crystals, mp 122–123°С (n-hexane). Found, %: N 8.89.
С11H11BrN2O4. Calculated, %: N 8.76.
Unit cell parameters
a 10.2136(18),
b 8.0502(14),
c 17.278(3) Å;
α 90.00°,
β 98.240(2)°,
γ 90.00°
Volume, Å3
Z
1405.9(4)
4
Ethyl
3-bromo-3-nitro-2-(p-toluidine)acrylate
Molecular weight
dcalc, g cm–3
394.03
1.862
57.76
(VI) was prepared similarly from 0.68 g of ethyl 2,3-
dibromo-3-nitroacrylate II and 0.48 g of p-toluidine in
45 ml of anhydrous benzene (maintained for 20 min).
Yield 0.60 g (81%), yellow crystals, mp 61-63°С (n-
hexane). Found, %: N 8.37. С12H13BrN2O4. Calculated,
%: N 8.51.
Extinction coefficient,
µМо, cm–1
F(000)
768
Interval θ
2.01 ≤ θ ≤ 26.00
Methyl 3-bromo-3-nitro-2-(p-ethoxyphenylamine)-
acrylate (VII) was prepared similarly from 0.48 g of
methyl 2,3-dibromo-3-nitroacrylate I and 0.43 ml of p-
ethoxyphenylamine in 25 ml of anhydrous benzene
(maintained for 10 min). Yield 0.48 g (87%), mp 133–
135°С (methanol). Found, %: C 42.19; H 3.93; N 7.98.
С12H13BrN2O5. Calculated, %: C 41.76; H 3.80; N
8.10.
R(int)
0.0354
Indices measurement interval
–12 ≤ h ≤ 12
–9 ≤ k ≤ 9
–21 ≤ l ≤ 21
Number of measured reflections/
independent
7652/2687
1649
Number of reflections with
I > 2σ(I)
Ethyl 3-bromo-3-nitro-2-(p-ethoxyphenylamine)
acrylate (VIII) was prepared similarly from 0.49 g of
ethyl 2,3-dibromo-3-nitroacrylate II and 0.42 ml of p-
ethoxyphenylamine in 20 ml of anhydrous benzene
(maintained for 10 min). After the solvent removal the
residue was treated with diethyl ether. Yield 0.38 g
(68%), yellow crystals, mp 94–97°С (methanol).
Found, %: N 7.73, С13H15BrN2O5. Calculated, %: N
7.80.
Final values of divergence
factors
R
ob 0.0498
Rwob 0.1105
all 0.0935
R
Rwall 0.1308
Fitting parameters
Δ/σ
1.028
0.005
176
Number of refined parameters
Methyl 3-bromo-2-(α-naphthylamino)-3-nitro-
acrylate (IX) was prepared similarly from 0.60 g of
methyl 2,3-dibromo-3-nitroacrylate I and 0.60 g of α-
naphthylamine in 30 ml of anhydrous benzene
(maintained for 45 min). After the solvent removal the
oily residue was treated with methanol. Yield 0.58 g
(79%), yellowish green crystals, mp 139–141°С
(methanol). Found, %: N 7.92. С14H11BrN2O4.
Calculated, %: N 7.98.
bromoaniline in 9 ml of anhydrous benzene. The reac-
tion mixture was maintained for 15 min at vigorous
stirring. p-Bromoaniline hydrobromide was filtered
off, and the solvent was removed. The oily residue was
treated with isopropanol. Yield 0.28 g (68%), dark
yellow crystals, mp 145–146°С (methanol). Found, %:
C 31.60; H 2.39; N 7.08. С10H8Br2N2O4. Calculated,
%: C 31.61; H 2.12; N 7.37.
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SYNTHESIS AND STRUCTURE OF ALKYL-α-ARYLAMINO-β-BROMO-β-NITROACRYLATES
383
Table 4. Selected geometrical parameters: bond lengths (d, Å), bond angles (ω, deg) and torsion angles (τ, deg) in IV
Bond
C3–C2
d, Å
1.365(7)
1.435(7)
1.873(5)
1.335(6)
1.534(7)
ω, deg
Bond
C4–O4
d, Å
Bond
d, Å
1.485(7)
1.416(7)
1.904(5)
1.308(6)
1.197(6)
ω, deg
N1–O11
N1–O12
N2–H2
C4–C5
1.209(6)
1.220(5)
0.828(19)
1.422(9)
C3–N1
C3–Br1
C2–N2
C2–C1
C6–N2
C9–Br9
C1–O4
C1–O3
Angle
Angle
Angle
ω, deg
110.5(5)
124.4(5)
118.8(4)
116.8(4)
115.9(4)
108.9(6)
τ, deg
C2C3N1
123.3(4)
121.9(4)
114.7(4)
126.2(5)
116.8(4)
116.9(4)
τ, deg
O3C1O4
128.4(5)
130.0(4)
121.1(5)
117.5(5)
123.4(5)
120.3(5)
τ, deg
O4C1C2
C2C3Br1
N1C3Br1
N2C2C3
C2N2C6
O11N1O12
O11N1C3
O12N1C3
C1O4C4
O3C1C2
C7C6N2
N2C2C1
C11C6N2
C3C2C1
C10C9Br9
Angle
C5C4O4
Angle
Angle
N1C3C2N2
Br1C3C2N2
N1C3C2C1
Br1C3C2C1
N2C2C1O3
C3C2C1O3
N2C2C1O4
C3C2C1O4
–0.2(8)
C7C8C9Br9
Br9C9C10C11
N2C6C11C10
C2C3N1O11
Br1C3N1O11
N2C6C7C8
C5C4O4C1
C2C1O4C4
179.9(4)
179.6(4)
–176.3(5)
179.6(5)
3.5(7)
C2C3N1O12
Br1C3N1O12
C3C2N2C6
C1C2N2C6
C7C6N2C2
C11C6N2C2
O3C1O4C4
–0.5(8)
175.7(4)
–175.0(5)
0.9(7)
–176.6(4)
175.0(5)
–10.2(8)
149.6(5)
–34.0(8)
–5.2(8)
–72.5(6)
102.8(6)
110.3(5)
–74.4(6)
176.1(5)
–146.3(6)
171.7(4)
Pavlova, I.V., Zh. Obshch. Khim., 2001, vol. 71, no. 3,
p. 466.
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