research communications
Bromination of bis(pyridin-2-yl) diselenide in methylene chloride: the H-pyridine-2-selenenyl dibromide and its cycloadduct with cyclopentene (3aSR,9aRS)-2,3,3a,9a-tetrahydro-1H-cyclopenta[4,5][1,3]selenazolo[3,2-a]pyridinium bromide
and crystal structures of 1aR.E. Alekseev Nizhny Novgorod State Technical University, Minin St, 24, Nizhny Novgorod, 603950 , Russian Federation, and bInorganic Chemistry Department, Peoples' Friendship University of Russia (RUDN University), 6 Miklukho-Maklay St., Moscow 117198, Russian Federation
*Correspondence e-mail: vnkhrustalev@gmail.com
1H-Pyridine-2-selenenyl dibromide, C5H5NSeBr2, 1, is a product of the bromination of bis(pyridin-2-yl) diselenide in methylene chloride recrystallization from methanol. Compound 1 is essentially zwitterionic: the negative charge resides on the SeBr2 moiety and the positive charge is delocalized over the pyridinium fragment. The C—Se distance of 1.927 (3) Å is typical of a single bond. The virtually linear Br—Se—Br moiety of 178.428 (15)° has symmetrical geometry, with Se—Br bonds of 2.5761 (4) and 2.5920 (4) Å, and is twisted by 63.79 (8)° relative to the pyridinium plane. The Se atom forms an intermolecular Se⋯Br contact of 3.4326 (4) Å, adopting a distorted square-planar coordination. In the crystal, molecules of 1 are linked by intermolecular N—H⋯Br and C—H⋯Br hydrogen bonds, as well as by non-covalent Se⋯Br interactions, into a three-dimensional framework. (3aSR,(9aRS)-2,3,3a,9a-Tetrahydro-1H-cyclopenta[4,5][1,3]selenazolo[3,2-a]pyridinium-9 bromide, C10H12NSe+·Br−, 2, is a product of the cycloaddition reaction of 1 with cyclopentene. Compound 2 is a salt containing a selenazolopyridinium cation and a bromide anion. Both five-membered rings of the cation adopt envelope conformations. The dihedral angle between the basal planes of these rings is 62.45 (11)°. The Se atom of the cation forms two additional non-covalent interactions with the bromide anions at distances of 3.2715 (4) and 3.5683 (3) Å, attaining a distorted square-planar coordination. In the crystal, the cations and anions of 2 form centrosymmetric dimers by non-covalent Se⋯Br interactions. The dimers are linked by weak C—H⋯Br hydrogen bonds into double layers parallel to (001).
1. Chemical context
Selenium-containing molecules have attracted significant attention from chemical and medicinal scientists because of their wide range of biological activities, such as antitumor effects, cardiovascular protection, antibacterial or antiviral effects (Banerjee & Koketsu, 2017; Zhang et al., 2017; Álvarez-Pérez et al., 2018; Miao et al., 2018). However, the chemistry of organoselenium compounds has not been sufficiently developed in comparison with that of organosulfur compounds because of the instability of most Se-containing compounds (Ninomiya et al., 2011). Thus, the synthesis, isolation and structural characterization of selenium-containing substances is essential for the further development of potential medicines.
Earlier, the product of bromination of bis(pyridin-2-yl) diselenide in methylene chloride was described by Japanese researchers (Toshimitsu et al., 1984). This compound had a melting point of 388–390 K and was assigned as 2-pyridylselenenyl bromide based on the elemental analysis and IR spectroscopic data.
However, as a result of our multiple experiments on the bromination of bis(pyridin-2-yl) diselenide under similar conditions, a product with a melting point of 373–375 K was obtained. We isolated a compound with the same melting point as that previously obtained by the Japanese authors only after recrystallization from methanol. In our opinion, it is the lower melting point product that is the 2-pyridylselenenyl bromide 1*. The product having a higher melting point was isolated by us and then structurally characterized by X-ray analysis to be 1H-pyridine-2-selenenyl dibromide 1 (Fig. 1).
Previously we have developed an approach to the synthesis of [1,3]thia(selen,tellur)azolo[3,2-a]pyridin-4-ium derivatives via heterocyclization of unsaturated compounds and 2-pyridinesulfenyl, selenenyl and tellurenyl chlorides with ring closure through the nitrogen atom of the pyridyl fragment (Borisov et al., 2010, 2012a,b,c). In this case, our studies have paid particular attention to clarifying the structural characteristics of the reagents used (Borisov et al., 2010; Khrustalev et al., 2014, 2016). Determination of the factors providing the stability of organochalcogenyl halides is known to be an urgent challenge in general (Khrustalev et al., 2014, 2016). The structural features of 2-pyridine-selenenyl and -tellurenyl chlorides have been described by us in detail (Borisov et al., 2010; Khrustalev et al., 2014, 2016). Moreover, we have proposed a probable mechanism of the reaction including the interaction of selenenyl bromide 1* with methanol producing hydrogen bromide and methyl selenite (Fig. 2) (Garratt & Kabo, 1980; Reich & Jasperse, 1988). Furthermore, the subsequent addition of hydrogen bromide to selenenyl bromide 1* gives 1H-pyridine-2-selenenyl dibromide 1 (Fig. 3).
We have also succeeded in involving 1H-pyridine-2-selenenyl dibromide 1 in the cycloaddition reaction with cyclopentene. The product of this reaction was identified as 2,3,3a,9a-tetrahydro-1H-cyclopenta[4,5][1,3]selenazolo[3,2-a]pyridinium-9 bromide (2) by X-ray diffraction (Fig. 4).
2. Structural commentary
Compound 1, C5H5NSeBr2, is essentially zwitterionic: a negative charge resides on the SeBr2 moiety and a positive charge is delocalized over the pyridinium fragment (Fig. 5). The C2—Se1 distance of 1.927 (3) Å is typical for a single bond [in comparison, the lengths of the C=Se bonds in related compounds are 1.817 (7) Å (Husebye et al., 1997), 1.8236 (11) Å (Mammadova et al., 2011) and 1.838 (2) Å (Mammadova et al., 2012)]. The N1—C2 and N1—C6 bond lengths are almost equal to each other because of the aromaticity of the cyclic system. The virtually linear Br1—Se1—Br2 moiety of 178.428 (15)° has a symmetrical geometry with Se—Br bonds of 2.5761 (4) and 2.5920 (4) Å and is twisted by 63.79 (8)° relative to the pyridinium plane. The slight elongation of the Se1—Br2 bond in comparison with the Se1—Br1 bond is explained by the involvement of the Br2 atom in the intermolecular secondary Se1⋯Br2(x, − y, + z) interaction [3.4326 (4) Å]. Thus, the selenium atom adopts a distorted square-planar coordination.
Compound 2, C10H12NSeBr, is a salt containing a selenazolopyridinium cation and a bromide anion (Fig. 6). The five-membered heterocycle of the cation adopts a flattened with the C3A carbon atom deviating by 0.274 (3) Å from the plane through the other ring atoms. The cyclopentane fragment has the usual with the C2 carbon atom deviating from the plane through the other ring atoms by 0.648 (4) Å. The dihedral angle between the basal planes of the two five-membered rings of the cation is 62.45 (11)°. The selenium atom of the cation forms two additional non-covalent interactions with the bromide anions at distances of 3.2715 (4) Å [Se4⋯Br1(x, 1 + y, z)] and 3.5683 (3) Å [Se4⋯Br1(1–x, 1–y, –z)], affording a distorted square-planar coordination.
Cation 2 has two asymmetric C3A and C9A carbon atoms. The crystal of the compound is racemic with the following relative configurations of the centers – rac-3aSR,9aRS.
3. Supramolecular features
In the crystal of 1, molecules are linked by intermolecular N—H⋯Br and C—H⋯Br hydrogen bonds (Table 1) as well as by the non-covalent Se⋯Br interactions (see above) into a three-dimensional framework (Fig. 7).
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In the crystal of 2, the cations and anions are linked by Se⋯Br interactions, forming centrosymmetric dimers (Fig. 8). The dimers are linked by weak C—H⋯Br hydrogen bonds (Table 2) into double layers parallel to (001) (Fig. 9).
4. Database survey
A search of the Cambridge Structural Database (CSD, Version 5.40; Groom et al., 2016) for zwitterionic molecules containing the T-shaped SeBr2 fragment yielded 22 such compounds. In 16 of them, the hypervalent SeBr2 fragments have asymmetric geometries, with the difference in the two Se—Br bond lengths more than or close to 0.1 Å, which is explained by intermolecular non-covalent interactions in the crystals. Moreover, 12 out of these 16 crystal structures revealed the presence of intermolecular non-covalent Se⋯Br interactions with distances of 3.3374 (5)–3.556 (1) Å.
Remarkably, the intermolecular non-covalent Se⋯Br interaction of 3.2715 (4) Å observed in the crystal of 2 is the strongest one found in the compounds of this type – between the diorganyl selenide unit and the bromide anion.
5. Synthesis and crystallization
2-Pyridineselenenyl bromide (1*). A solution of bromine (0.32 g, 2 mmol) in ethylene chloride (10 ml) was added to a solution of bis(pyridin-2-yl)diselenide (0.628 g, 2 mmol) in methylene chloride (10 ml) at room temperature. After 30 min, the solvent was removed under vacuum. The residue was washed with diethyl ether. Yield 0.93 g (98%), bright-yellow powder, m.p. 373–375 K. Analysis calculated for C5H4BrNSe (%): C, 25.35; H, 1.70; N, 5.91. Found (%): C, 25.31; H, 1.68; N, 5.89.
1H-Pyridine-2-selenenyl dibromide (1). Compound 1* was recrystallized from methanol. Yield 0.59 g (92%), orange crystals, m.p. 388–390 K. Analysis calculated for C5H5Br2NSe (%): C, 18.89; H, 1.59; N, 4.41. Found (%): C, 18.81; H, 1.55; N, 4.37.
2,3,3a,9a-Tetrahydro-1H-cyclopenta[4,5][1,3]σelenazolo[3,2-a]pyridinium-9 bromide (2). A solution of cyclopentene (0.034 g, 0.5 mmol) in ethyl acetate (5 ml) was added to a solution of 1 (0.159 g, 0.5 mmol) in ethyl acetate (10 ml) at room temperature. The reaction mixture was kept at room temperature for 24 h, then the solvent was removed under vacuum. The crude white solid was recrystallized from methylene chloride. Single crystals suitable for X-ray were obtained by recrystallization from methylene chloride. Yield 0.133 g (87%), white powder, m.p. 463–465 K. Analysis calculated for C10H12BrNSe (%): C, 39.29; H, 3.91; N, 4.52. Found (%): C, 39.38; H, 3.97; N, 4.59. 1H NMR (DMSO-d6, 400 MHz, 302 K): δ = 8.98 (d, 1H, H8, J = 6.3 Hz), 8.20 (m, 2H, H5, H6), 7.74 (ddd, 1H, H7, J = 8.9 Hz, J = 5.8 Hz, J = 3.2 Hz), 5.78 (td, 1H, H9a, J = 8.4 Hz, J = 3.9 Hz), 4.66 (m, 1H, H3a), 2.34, 2.09, 1.71 (m, 6H, 3CH2).
6. Refinement
Crystal data, data collection and structure . The hydrogen atom of the NH-group in 1 was localized in the difference-Fourier map and refined isotropically with fixed displacement parameters [Uiso(H) = 1.2Ueq(N)]. The other hydrogen atoms in 1 and 2 were placed in calculated positions with C—H = 0.95–1.00 Å and refined using a riding model with fixed isotropic displacement parameters [Uiso(H) = 1.5Ueq(C) for the CH3-groups and 1.2Ueq(C) for the other groups].
details are summarized in Table 3Supporting information
https://doi.org/10.1107/S2056989019004997/yk2121sup1.cif
contains datablocks global, 1, 2. DOI:Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S2056989019004997/yk21211sup2.hkl
Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S2056989019004997/yk21212sup3.hkl
For both structures, data collection: APEX2 (Bruker, 2005); cell
SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C5H5Br2NSe | F(000) = 584 |
Mr = 317.86 | Dx = 2.612 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.0971 (6) Å | Cell parameters from 4271 reflections |
b = 12.6116 (10) Å | θ = 2.8–32.6° |
c = 8.7325 (7) Å | µ = 14.44 mm−1 |
β = 114.975 (1)° | T = 120 K |
V = 808.36 (11) Å3 | Prism, orange |
Z = 4 | 0.20 × 0.20 × 0.15 mm |
Bruker APEXII CCD diffractometer | 2426 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.051 |
φ and ω scans | θmax = 32.6°, θmin = 2.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −12→12 |
Tmin = 0.063, Tmax = 0.104 | k = −18→19 |
12425 measured reflections | l = −13→13 |
2959 independent reflections |
Refinement on F2 | Primary atom site location: difference Fourier map |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.032 | Hydrogen site location: mixed |
wR(F2) = 0.074 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0302P)2 + 0.5977P] where P = (Fo2 + 2Fc2)/3 |
2959 reflections | (Δ/σ)max = 0.001 |
85 parameters | Δρmax = 1.37 e Å−3 |
0 restraints | Δρmin = −1.06 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.26838 (4) | 0.03212 (2) | 0.84166 (3) | 0.01817 (8) | |
Br2 | −0.14496 (4) | 0.29163 (3) | 0.38147 (4) | 0.01989 (8) | |
Se1 | 0.06027 (4) | 0.16227 (2) | 0.61494 (3) | 0.01433 (7) | |
N1 | 0.1263 (4) | 0.0928 (2) | 0.3377 (3) | 0.0161 (5) | |
H1 | 0.012 (6) | 0.079 (3) | 0.298 (5) | 0.019* | |
C2 | 0.2053 (4) | 0.1389 (2) | 0.4909 (4) | 0.0143 (5) | |
C3 | 0.3877 (4) | 0.1667 (3) | 0.5524 (4) | 0.0205 (6) | |
H3 | 0.4467 | 0.1997 | 0.6598 | 0.025* | |
C4 | 0.4837 (4) | 0.1459 (3) | 0.4561 (4) | 0.0214 (6) | |
H4 | 0.6089 | 0.1643 | 0.4981 | 0.026* | |
C5 | 0.3971 (5) | 0.0985 (3) | 0.2989 (4) | 0.0218 (6) | |
H5 | 0.4616 | 0.0839 | 0.2323 | 0.026* | |
C6 | 0.2157 (4) | 0.0729 (3) | 0.2415 (4) | 0.0200 (6) | |
H6 | 0.1533 | 0.0412 | 0.1335 | 0.024* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.01837 (14) | 0.02401 (16) | 0.01174 (12) | 0.00296 (10) | 0.00598 (10) | 0.00250 (10) |
Br2 | 0.01919 (14) | 0.02324 (16) | 0.01808 (14) | 0.00366 (11) | 0.00869 (11) | 0.00614 (11) |
Se1 | 0.01580 (13) | 0.01724 (14) | 0.01117 (12) | −0.00047 (10) | 0.00690 (10) | −0.00082 (9) |
N1 | 0.0186 (11) | 0.0173 (12) | 0.0115 (10) | −0.0010 (9) | 0.0056 (9) | −0.0011 (9) |
C2 | 0.0159 (12) | 0.0165 (13) | 0.0112 (11) | 0.0006 (10) | 0.0065 (10) | 0.0012 (10) |
C3 | 0.0202 (14) | 0.0254 (16) | 0.0157 (13) | −0.0041 (11) | 0.0075 (11) | −0.0051 (11) |
C4 | 0.0194 (14) | 0.0283 (17) | 0.0186 (14) | 0.0005 (12) | 0.0102 (12) | 0.0028 (12) |
C5 | 0.0270 (15) | 0.0257 (16) | 0.0187 (14) | 0.0070 (12) | 0.0155 (12) | 0.0037 (12) |
C6 | 0.0276 (14) | 0.0204 (15) | 0.0123 (12) | 0.0038 (12) | 0.0087 (11) | −0.0004 (10) |
Br1—Se1 | 2.5761 (4) | C3—C4 | 1.390 (4) |
Br2—Se1 | 2.5920 (4) | C3—H3 | 0.9500 |
Se1—C2 | 1.927 (3) | C4—C5 | 1.386 (5) |
N1—C6 | 1.344 (4) | C4—H4 | 0.9500 |
N1—C2 | 1.347 (4) | C5—C6 | 1.375 (5) |
N1—H1 | 0.86 (4) | C5—H5 | 0.9500 |
C2—C3 | 1.387 (4) | C6—H6 | 0.9500 |
C2—Se1—Br1 | 88.76 (9) | C4—C3—H3 | 120.2 |
C2—Se1—Br2 | 89.69 (8) | C5—C4—C3 | 120.1 (3) |
Br1—Se1—Br2 | 178.428 (15) | C5—C4—H4 | 119.9 |
C6—N1—C2 | 123.1 (3) | C3—C4—H4 | 119.9 |
C6—N1—H1 | 119 (3) | C6—C5—C4 | 118.6 (3) |
C2—N1—H1 | 118 (3) | C6—C5—H5 | 120.7 |
N1—C2—C3 | 118.4 (3) | C4—C5—H5 | 120.7 |
N1—C2—Se1 | 118.5 (2) | N1—C6—C5 | 120.2 (3) |
C3—C2—Se1 | 123.1 (2) | N1—C6—H6 | 119.9 |
C2—C3—C4 | 119.6 (3) | C5—C6—H6 | 119.9 |
C2—C3—H3 | 120.2 | ||
C6—N1—C2—C3 | −0.3 (4) | C2—C3—C4—C5 | 0.5 (5) |
C6—N1—C2—Se1 | −179.9 (2) | C3—C4—C5—C6 | 0.1 (5) |
N1—C2—C3—C4 | −0.4 (5) | C2—N1—C6—C5 | 0.9 (5) |
Se1—C2—C3—C4 | 179.2 (2) | C4—C5—C6—N1 | −0.8 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Br1i | 0.86 (4) | 2.50 (4) | 3.305 (3) | 156 (3) |
C5—H5···Br1ii | 0.95 | 2.92 | 3.790 (3) | 153 |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y, −z+1. |
C10H12NSe+·Br− | Z = 2 |
Mr = 305.07 | F(000) = 296 |
Triclinic, P1 | Dx = 1.993 Mg m−3 |
a = 6.3333 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.0515 (7) Å | Cell parameters from 4390 reflections |
c = 9.5807 (7) Å | θ = 2.3–32.7° |
α = 111.350 (1)° | µ = 7.57 mm−1 |
β = 93.657 (2)° | T = 120 K |
γ = 93.543 (1)° | Prism, colourless |
V = 508.35 (7) Å3 | 0.30 × 0.20 × 0.20 mm |
Bruker APEXII CCD diffractometer | 3156 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.029 |
φ and ω scans | θmax = 32.7°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −9→9 |
Tmin = 0.115, Tmax = 0.154 | k = −13→13 |
7982 measured reflections | l = −14→14 |
3711 independent reflections |
Refinement on F2 | Primary atom site location: difference Fourier map |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.080 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0431P)2 + 0.1817P] where P = (Fo2 + 2Fc2)/3 |
3711 reflections | (Δ/σ)max = 0.001 |
118 parameters | Δρmax = 0.64 e Å−3 |
0 restraints | Δρmin = −1.05 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.57452 (3) | 0.30220 (3) | 0.11384 (2) | 0.01988 (7) | |
C1 | 1.3458 (4) | 1.1581 (3) | 0.4167 (3) | 0.0220 (4) | |
H1A | 1.3149 | 1.1019 | 0.4855 | 0.026* | |
H1B | 1.5016 | 1.1718 | 0.4139 | 0.026* | |
C2 | 1.2526 (4) | 1.3189 (3) | 0.4669 (3) | 0.0227 (4) | |
H2A | 1.3228 | 1.3911 | 0.4237 | 0.027* | |
H2B | 1.2658 | 1.3710 | 0.5780 | 0.027* | |
C3 | 1.0180 (4) | 1.2722 (3) | 0.4033 (3) | 0.0243 (5) | |
H3A | 0.9389 | 1.2208 | 0.4619 | 0.029* | |
H3B | 0.9463 | 1.3656 | 0.4012 | 0.029* | |
C3A | 1.0408 (3) | 1.1551 (3) | 0.2450 (2) | 0.0166 (4) | |
H3C | 1.0710 | 1.2169 | 0.1796 | 0.020* | |
Se4 | 0.79630 (3) | 0.99892 (2) | 0.14860 (2) | 0.01599 (6) | |
C4A | 0.9599 (3) | 0.8444 (3) | 0.1826 (2) | 0.0162 (4) | |
C5 | 0.8875 (4) | 0.6872 (3) | 0.1569 (3) | 0.0193 (4) | |
H5 | 0.7437 | 0.6487 | 0.1212 | 0.023* | |
C6 | 1.0290 (4) | 0.5881 (3) | 0.1845 (3) | 0.0213 (4) | |
H6 | 0.9816 | 0.4813 | 0.1696 | 0.026* | |
C7 | 1.2422 (4) | 0.6449 (3) | 0.2342 (3) | 0.0212 (4) | |
H7 | 1.3406 | 0.5773 | 0.2520 | 0.025* | |
C8 | 1.3054 (3) | 0.7997 (3) | 0.2566 (3) | 0.0191 (4) | |
H8 | 1.4499 | 0.8392 | 0.2880 | 0.023* | |
N9 | 1.1641 (3) | 0.8974 (2) | 0.2342 (2) | 0.0158 (3) | |
C9A | 1.2350 (3) | 1.0656 (3) | 0.2576 (2) | 0.0163 (4) | |
H9A | 1.3328 | 1.0679 | 0.1803 | 0.020* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.01950 (11) | 0.01593 (11) | 0.02337 (11) | −0.00059 (8) | −0.00022 (8) | 0.00698 (8) |
C1 | 0.0221 (10) | 0.0198 (10) | 0.0187 (10) | −0.0016 (8) | −0.0044 (8) | 0.0022 (8) |
C2 | 0.0232 (10) | 0.0180 (10) | 0.0197 (10) | −0.0035 (8) | −0.0023 (8) | −0.0001 (8) |
C3 | 0.0215 (10) | 0.0216 (11) | 0.0208 (10) | 0.0006 (8) | 0.0003 (8) | −0.0023 (8) |
C3A | 0.0171 (9) | 0.0145 (9) | 0.0154 (8) | 0.0003 (7) | −0.0011 (7) | 0.0026 (7) |
Se4 | 0.01420 (10) | 0.01455 (10) | 0.01694 (10) | 0.00013 (7) | −0.00074 (7) | 0.00368 (8) |
C4A | 0.0154 (8) | 0.0153 (9) | 0.0145 (8) | 0.0005 (7) | 0.0009 (7) | 0.0018 (7) |
C5 | 0.0193 (9) | 0.0157 (9) | 0.0195 (9) | −0.0025 (7) | 0.0007 (7) | 0.0034 (8) |
C6 | 0.0258 (10) | 0.0166 (10) | 0.0209 (10) | 0.0007 (8) | 0.0013 (8) | 0.0066 (8) |
C7 | 0.0238 (10) | 0.0191 (10) | 0.0222 (10) | 0.0060 (8) | 0.0029 (8) | 0.0083 (8) |
C8 | 0.0181 (9) | 0.0204 (10) | 0.0183 (9) | 0.0034 (8) | 0.0003 (7) | 0.0066 (8) |
N9 | 0.0156 (7) | 0.0147 (8) | 0.0153 (7) | 0.0004 (6) | 0.0007 (6) | 0.0039 (6) |
C9A | 0.0156 (8) | 0.0147 (9) | 0.0158 (8) | −0.0009 (7) | −0.0005 (7) | 0.0031 (7) |
C1—C2 | 1.527 (3) | Se4—C4A | 1.898 (2) |
C1—C9A | 1.542 (3) | C4A—N9 | 1.347 (3) |
C1—H1A | 0.9900 | C4A—C5 | 1.396 (3) |
C1—H1B | 0.9900 | C5—C6 | 1.385 (3) |
C2—C3 | 1.542 (3) | C5—H5 | 0.9500 |
C2—H2A | 0.9900 | C6—C7 | 1.403 (3) |
C2—H2B | 0.9900 | C6—H6 | 0.9500 |
C3—C3A | 1.523 (3) | C7—C8 | 1.367 (3) |
C3—H3A | 0.9900 | C7—H7 | 0.9500 |
C3—H3B | 0.9900 | C8—N9 | 1.356 (3) |
C3A—C9A | 1.536 (3) | C8—H8 | 0.9500 |
C3A—Se4 | 1.961 (2) | N9—C9A | 1.492 (3) |
C3A—H3C | 1.0000 | C9A—H9A | 1.0000 |
C2—C1—C9A | 104.40 (19) | N9—C4A—C5 | 119.8 (2) |
C2—C1—H1A | 110.9 | N9—C4A—Se4 | 114.19 (16) |
C9A—C1—H1A | 110.9 | C5—C4A—Se4 | 125.99 (16) |
C2—C1—H1B | 110.9 | C6—C5—C4A | 118.9 (2) |
C9A—C1—H1B | 110.9 | C6—C5—H5 | 120.6 |
H1A—C1—H1B | 108.9 | C4A—C5—H5 | 120.6 |
C1—C2—C3 | 102.42 (19) | C5—C6—C7 | 120.2 (2) |
C1—C2—H2A | 111.3 | C5—C6—H6 | 119.9 |
C3—C2—H2A | 111.3 | C7—C6—H6 | 119.9 |
C1—C2—H2B | 111.3 | C8—C7—C6 | 118.7 (2) |
C3—C2—H2B | 111.3 | C8—C7—H7 | 120.7 |
H2A—C2—H2B | 109.2 | C6—C7—H7 | 120.7 |
C3A—C3—C2 | 101.23 (18) | N9—C8—C7 | 120.7 (2) |
C3A—C3—H3A | 111.5 | N9—C8—H8 | 119.6 |
C2—C3—H3A | 111.5 | C7—C8—H8 | 119.6 |
C3A—C3—H3B | 111.5 | C4A—N9—C8 | 121.68 (19) |
C2—C3—H3B | 111.5 | C4A—N9—C9A | 117.87 (18) |
H3A—C3—H3B | 109.3 | C8—N9—C9A | 120.34 (18) |
C3—C3A—C9A | 106.34 (17) | N9—C9A—C3A | 109.62 (17) |
C3—C3A—Se4 | 115.96 (15) | N9—C9A—C1 | 112.33 (18) |
C9A—C3A—Se4 | 108.73 (14) | C3A—C9A—C1 | 105.39 (17) |
C3—C3A—H3C | 108.5 | N9—C9A—H9A | 109.8 |
C9A—C3A—H3C | 108.5 | C3A—C9A—H9A | 109.8 |
Se4—C3A—H3C | 108.5 | C1—C9A—H9A | 109.8 |
C4A—Se4—C3A | 87.21 (9) | ||
C9A—C1—C2—C3 | 38.3 (2) | Se4—C4A—N9—C9A | −0.1 (2) |
C1—C2—C3—C3A | −44.9 (2) | C7—C8—N9—C4A | −3.3 (3) |
C2—C3—C3A—C9A | 34.7 (2) | C7—C8—N9—C9A | −179.5 (2) |
C2—C3—C3A—Se4 | 155.69 (16) | C4A—N9—C9A—C3A | 11.0 (2) |
C3A—Se4—C4A—N9 | −7.96 (16) | C8—N9—C9A—C3A | −172.69 (19) |
C3A—Se4—C4A—C5 | 172.9 (2) | C4A—N9—C9A—C1 | 127.8 (2) |
N9—C4A—C5—C6 | −0.5 (3) | C8—N9—C9A—C1 | −55.9 (3) |
Se4—C4A—C5—C6 | 178.57 (17) | C3—C3A—C9A—N9 | 109.6 (2) |
C4A—C5—C6—C7 | −1.3 (3) | Se4—C3A—C9A—N9 | −15.9 (2) |
C5—C6—C7—C8 | 0.9 (3) | C3—C3A—C9A—C1 | −11.5 (2) |
C6—C7—C8—N9 | 1.4 (3) | Se4—C3A—C9A—C1 | −137.02 (15) |
C5—C4A—N9—C8 | 2.8 (3) | C2—C1—C9A—N9 | −136.01 (19) |
Se4—C4A—N9—C8 | −176.36 (16) | C2—C1—C9A—C3A | −16.7 (2) |
C5—C4A—N9—C9A | 179.04 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···Br1i | 0.95 | 2.91 | 3.728 (2) | 145 |
C9A—H9A···Br1ii | 1.00 | 2.82 | 3.614 (2) | 137 |
Symmetry codes: (i) x+1, y, z; (ii) x+1, y+1, z. |
Acknowledgements
The publication has been prepared with the support of the RUDN University Program `5–100'.
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