research communications
Crystal structures of 4-(2/3-methoxyphenoxy)phthalonitrile
aDepartment of Inorganic Chemistry, Ivanovo State University of Chemistry and Technology, Ivanovo, Russian Federation, bDepartment of Fine Tune Synthesis, Ivanovo State University of Chemistry and Technology, Ivanovo, Russian Federation, and cSector of X-ray Diffraction Research, Razuvaev Institute of Metalloorganic Chemistry, Nizhnii Novgorod, Russian Federation
*Correspondence e-mail: erzunov_da@isuct.ru
The syntheses and crystal structures are reported of 4-phenoxy-substituted phthalonitriles with methoxy groups in the ortho- and meta-positions of the terminal benzene rings, respectively, namely, 4-(2-methoxyphenoxy)phthalonitrile and 4-(3-methoxyphenoxy)phthalonitrile, both C15H10N2O2. The https://journals.iucr.org/e/issues/2023/03/00/molecular structure was determined using the single-crystal X-ray diffraction method. It is shown that short contacts play a more decisive role in the molecular packing compared to van der Waals interactions.
1. Chemical context
Phthalonitriles are a class of organic compounds with high thermal and oxidative stability (Laskowski et al., 2016). That destruction only takes place at high temperatures facilitates using these molecules as building blocks for polymer composite materials with a high degree of cross-linking (Wang et al., 2019). In addition, phthalonitriles are among the most promising precursors for the preparation of phthalocyanine complexes of various structures based on building blocks derived from them.
Phthalocyanines, as a result of their structural features and the possibility of introducing almost any functional moieties to their periphery, have found wide application in areas of societal and industrial importance such as catalysis, optics, medicine, light industry, etc. (Botnar et al., 2020, 2021). Substituted phthalocyanines, which attract the most attention, however, are obtained from phthalonitriles with various fragments in the 3 and 4 positions.
Thus, it is of general interest to obtain functionally substituted meta- and ortho-substitution, respectively, which have been prepared for the synthesis of the corresponding substituted phthalocyanines. X-ray diffraction data for the ortho-isomer are already described in the literature (Agar et al., 2007). However, no discussion is provided of the influence of the structure of the substituted nitrile on the crystal-packing stabilization. The presence of oxygen atoms in the composition of the molecules leads to the formation of interesting intermolecular interactions, which are discussed in this communication.
and to study their properties. Here, we report the crystal structures of methoxyphenoxyphthalonitriles with the methoxy group in the2. Structural commentary
Both substituted and 2. The phthalonitrile (A, C7–C12 atoms) and phenoxy (B, C1–C6 atoms) rings are oriented at dihedral angles of 66.61 (5) and 83.84 (11)° in the cases of meta- and ortho-substitution, respectively. For both the C13, C14, N1, N2 and O1 atoms are practically coplanar to the A ring with a maximum deviation of 12° in the case of the C13N1 fragment. The O1, O2, and C15 atoms and the B rings are essentially coplanar. The plane of the methoxy group (C15/O2) and its B-ring pivot atom (C3 or C2) is at an angle to the B-ring plane of only 2.21 (6)° (meta) or 1.43 (15)° (ortho). The torsion angles (C15—O2—C3—C2 for meta and C15—O2—C2—C1 for ortho) are 1.32 (15) and −179.1 (2)°, respectively.
crystallize as solvent-free crystals; the structures are illustrated in Figs. 13. Supramolecular features
In 4-(2-methoxyphenoxy)phthalonitrile, stabilization of the intermolecular packing is realized mainly through the formation of hydrogen bonds between the donor C8—H8A group of the A ring with the cyano group (C14≡N2) acceptor attached to the A ring of an adjacent molecule (C8—H8A⋯N2; symmetry operator: x + , −y + , −z + 1; Fig. 3, Table 1). The formation of a weaker but bifurcated intermolecular hydrogen-bonding interaction C11—H11⋯O1/O2(− + x, − y, 1 − z) is also found in this structure, which additionally supports the packing. In the case of 4-(3-methoxyphenoxy)phthalonitrile, because of the favorable spatial arrangement of two A rings of neighboring molecules, stabilization occurs largely through respective π–π interactions. The planes of the A rings of two neighboring molecules are parallel to each other, but offset (angle between the ring normal and the centroid vector is 22.6° with a slippage of 1.41 Å). The distance between the centers of the A rings is 3.6632 (6) Å (centroid–centroid distance). These geometric characteristics imply the presence of a significant intermolecular π–π attraction (Janiak, 2000). The hydrogen atom of the aromatic C11—H11 moiety of one and the O1 oxygen atom of the adjacent molecule may be engaged in additional bidirectional contacts (Fig. 4), which support the π–π interaction as well as its slippage. In both cases, a number of weaker hydrogen-bonding contacts are observed, comprising additional contributions to the stabilization of the crystal structures. Thus, the packing of the ortho-isomer exhibits in total eight intermolecular hydrogen-bonding interactions, while for the meta-isomer, in addition to the π–π interaction, five hydrogen bonds are observed (Tables 1, 2, Fig. 5). The resulting crystal packings for the title 4-(2/3-methoxyphenoxy)phthalonitriles are shown in Figs. 6 and 7.
4. Database survey
A survey of the CSD (Groom et al., 2016) using ConQuest version 2022 3.0 (Bruno et al., 2002) for closely related 4-(phenoxy)phthalonitriles with ether-functionalized substituents on the phenoxy moiety in the ortho- and meta-positions results in only two and one hits, respectively. The ortho-isomers are a phthalonitrile dimer bridged by the o-phenoxy moiety (refcode: NAGJEN; Köç et al., 2016), and the same molecule as the one reported here (refcode: JEVNII; Ağar & Ocak İskeleli, 2007). The meta-isomer is also a phthalonitrile dimer now bridged by the m-phenoxy moiety (refcode: HAMVIB; Deveci et al., 2004). Notably, with regard to the phthalonitrile dimers, π–π-stacking is observed for the meta-isomer but not for the ortho-isomer; the same observation was made for the two title compounds.
5. Synthesis and crystallization
Materials and physical methods: All reagents were purchased from Sigma–Aldrich. Reaction progress was monitored by
(TLC) on silica-gel plates.Synthesis of substituted phthalonitriles: 4-nitrophthalonitrile and 2/3-methoxyphenol in a 1:1 molar ratio were placed in a flask and dissolved in DMF. Further, after complete dissolution of the reagents, 1 mol of potassium carbonate and 1/3 portion of water (in relation to DMF) were added to the mixture. The reaction mass was stirred at 353–363 K for 2.5 h, after which it was cooled to 278 K and poured into a threefold excess (by volume) of 15% aqueous NaCl solution. The precipitate was filtered off, recrystallized from 50% aqueous 2-propanol solution and then dried at 343 K. As a result, light crystals of 4-(2-methoxyphenoxy) phthalonitrile (75%) and 4-(3-methoxyphenoxy) phthalonitrile (89%) were obtained, respectively. Crystals were obtained by slow evaporation of solvent from a
of phthalonitriles in chloroform.6. Refinement
Crystal data, data collection and structure . All hydrogen atoms were placed in calculated positions and were refined using a riding model [Uiso(H) = 1.5Ueq(C) for CH3 groups and Uiso(H) = 1.2Ueq(C) for other groups).
details are summarized in Table 3
|
Supporting information
https://doi.org/10.1107/S2056989023000518/yz2027sup1.cif
contains datablocks o-C15H10N2O2, m-C15H10N2O2, global. DOI:Structure factors: contains datablock m-C15H10N2O2. DOI: https://doi.org/10.1107/S2056989023000518/yz2027m-C15H10N2O2sup2.hkl
Structure factors: contains datablock o-C15H10N2O2. DOI: https://doi.org/10.1107/S2056989023000518/yz2027o-C15H10N2O2sup3.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989023000518/yz2027o-C15H10N2O2sup6.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989023000518/yz2027m-C15H10N2O2sup6.mol
Supporting information file. DOI: https://doi.org/10.1107/S2056989023000518/yz2027m-C15H10N2O2sup7.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989023000518/yz2027o-C15H10N2O2sup7.mol
For both structures, data collection: APEX3 (Bruker, 2003); cell
SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: Mercury (Macrae et al., 2020).C15H10N2O2 | Dx = 1.354 Mg m−3 |
Mr = 250.25 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 9781 reflections |
a = 7.7329 (3) Å | θ = 2.7–30.1° |
b = 8.2536 (3) Å | µ = 0.09 mm−1 |
c = 19.2301 (7) Å | T = 100 K |
V = 1227.35 (8) Å3 | Prism, colorless |
Z = 4 | 0.24 × 0.24 × 0.07 mm |
F(000) = 520 |
Bruker D8 Quest (CMOS) diffractometer | 2616 reflections with I > 2σ(I) |
Radiation source: microfocus tube | Rint = 0.046 |
ω scans | θmax = 28.3°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −10→10 |
Tmin = 0.903, Tmax = 0.971 | k = −11→11 |
19395 measured reflections | l = −25→25 |
3035 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.095 | w = 1/[σ2(Fo2) + (0.0385P)2 + 0.3865P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max < 0.001 |
3035 reflections | Δρmax = 0.21 e Å−3 |
173 parameters | Δρmin = −0.32 e Å−3 |
0 restraints | Absolute structure: Flack x determined using 931 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Primary atom site location: dual |
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 | ||
O1 | 0.6870 (2) | 0.31404 (19) | 0.64727 (8) | 0.0195 (4) | |
O2 | 0.9772 (2) | 0.4854 (2) | 0.66084 (9) | 0.0268 (4) | |
N1 | 0.4498 (4) | 0.9100 (3) | 0.50573 (12) | 0.0377 (6) | |
N2 | 0.3018 (3) | 0.6112 (3) | 0.36049 (11) | 0.0244 (5) | |
C1 | 0.7085 (3) | 0.4120 (3) | 0.70640 (12) | 0.0172 (5) | |
C2 | 0.8609 (3) | 0.5003 (3) | 0.71355 (12) | 0.0193 (5) | |
C3 | 0.8807 (3) | 0.5958 (3) | 0.77286 (13) | 0.0235 (5) | |
H3A | 0.982511 | 0.658542 | 0.779084 | 0.028* | |
C4 | 0.7515 (3) | 0.5990 (3) | 0.82256 (12) | 0.0249 (6) | |
H4A | 0.765466 | 0.665266 | 0.862552 | 0.030* | |
C5 | 0.6029 (3) | 0.5081 (3) | 0.81540 (12) | 0.0242 (5) | |
H5A | 0.516618 | 0.509974 | 0.850546 | 0.029* | |
C6 | 0.5809 (3) | 0.4138 (3) | 0.75631 (12) | 0.0210 (5) | |
H6A | 0.478840 | 0.351196 | 0.750360 | 0.025* | |
C7 | 0.6104 (3) | 0.3826 (3) | 0.59041 (11) | 0.0160 (5) | |
C8 | 0.5802 (3) | 0.5471 (3) | 0.58379 (11) | 0.0166 (5) | |
H8A | 0.611760 | 0.619803 | 0.619924 | 0.020* | |
C9 | 0.5027 (3) | 0.6041 (3) | 0.52311 (11) | 0.0174 (5) | |
C10 | 0.4544 (3) | 0.4968 (3) | 0.46957 (11) | 0.0170 (5) | |
C11 | 0.4861 (3) | 0.3315 (3) | 0.47775 (12) | 0.0178 (5) | |
H11A | 0.454353 | 0.257754 | 0.442035 | 0.021* | |
C12 | 0.5635 (3) | 0.2752 (3) | 0.53775 (12) | 0.0180 (5) | |
H12A | 0.584819 | 0.162514 | 0.543185 | 0.022* | |
C13 | 0.4736 (3) | 0.7744 (3) | 0.51398 (12) | 0.0235 (5) | |
C14 | 0.3705 (3) | 0.5595 (3) | 0.40833 (12) | 0.0187 (5) | |
C15 | 1.1358 (3) | 0.5737 (4) | 0.66790 (16) | 0.0365 (7) | |
H15A | 1.209911 | 0.552231 | 0.627585 | 0.055* | |
H15B | 1.195310 | 0.539339 | 0.710413 | 0.055* | |
H15C | 1.110784 | 0.689945 | 0.670515 | 0.055* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0259 (9) | 0.0151 (8) | 0.0175 (8) | 0.0017 (7) | −0.0029 (7) | −0.0003 (6) |
O2 | 0.0213 (8) | 0.0321 (10) | 0.0270 (9) | −0.0034 (8) | 0.0053 (8) | 0.0023 (8) |
N1 | 0.0639 (18) | 0.0183 (11) | 0.0310 (12) | 0.0001 (11) | −0.0236 (13) | −0.0027 (10) |
N2 | 0.0281 (11) | 0.0235 (11) | 0.0216 (11) | 0.0009 (10) | −0.0029 (10) | −0.0021 (9) |
C1 | 0.0213 (11) | 0.0130 (10) | 0.0172 (11) | 0.0032 (10) | −0.0023 (10) | 0.0017 (9) |
C2 | 0.0193 (11) | 0.0204 (11) | 0.0183 (11) | 0.0025 (10) | 0.0003 (9) | 0.0067 (10) |
C3 | 0.0216 (12) | 0.0234 (13) | 0.0255 (12) | −0.0002 (11) | −0.0092 (11) | 0.0033 (10) |
C4 | 0.0317 (14) | 0.0266 (13) | 0.0165 (12) | 0.0070 (12) | −0.0083 (10) | −0.0031 (10) |
C5 | 0.0267 (13) | 0.0280 (13) | 0.0177 (11) | 0.0067 (12) | 0.0025 (10) | 0.0004 (10) |
C6 | 0.0197 (11) | 0.0193 (12) | 0.0241 (12) | 0.0019 (10) | −0.0016 (10) | 0.0053 (10) |
C7 | 0.0137 (10) | 0.0174 (11) | 0.0168 (10) | −0.0005 (9) | 0.0038 (9) | 0.0016 (9) |
C8 | 0.0192 (11) | 0.0162 (11) | 0.0144 (10) | −0.0032 (9) | 0.0003 (9) | −0.0029 (9) |
C9 | 0.0183 (11) | 0.0150 (11) | 0.0187 (11) | −0.0016 (9) | 0.0010 (10) | −0.0004 (9) |
C10 | 0.0162 (10) | 0.0183 (11) | 0.0164 (10) | −0.0011 (10) | 0.0009 (9) | −0.0026 (9) |
C11 | 0.0162 (11) | 0.0183 (11) | 0.0191 (11) | −0.0029 (9) | 0.0020 (9) | −0.0042 (9) |
C12 | 0.0175 (11) | 0.0123 (11) | 0.0243 (12) | 0.0000 (9) | 0.0028 (10) | −0.0015 (9) |
C13 | 0.0320 (14) | 0.0208 (13) | 0.0175 (11) | −0.0029 (11) | −0.0098 (11) | −0.0038 (10) |
C14 | 0.0196 (11) | 0.0167 (11) | 0.0199 (12) | −0.0030 (9) | 0.0021 (10) | −0.0054 (9) |
C15 | 0.0195 (12) | 0.0447 (17) | 0.0451 (17) | −0.0050 (13) | 0.0056 (12) | 0.0081 (14) |
O1—C7 | 1.366 (3) | C6—H6A | 0.9500 |
O1—C1 | 1.405 (3) | C7—C8 | 1.384 (3) |
O2—C2 | 1.360 (3) | C7—C12 | 1.394 (3) |
O2—C15 | 1.434 (3) | C8—C9 | 1.394 (3) |
N1—C13 | 1.145 (3) | C8—H8A | 0.9500 |
N2—C14 | 1.145 (3) | C9—C10 | 1.408 (3) |
C1—C6 | 1.377 (3) | C9—C13 | 1.434 (3) |
C1—C2 | 1.393 (3) | C10—C11 | 1.395 (3) |
C2—C3 | 1.395 (3) | C10—C14 | 1.441 (3) |
C3—C4 | 1.382 (4) | C11—C12 | 1.381 (3) |
C3—H3A | 0.9500 | C11—H11A | 0.9500 |
C4—C5 | 1.379 (4) | C12—H12A | 0.9500 |
C4—H4A | 0.9500 | C15—H15A | 0.9800 |
C5—C6 | 1.388 (3) | C15—H15B | 0.9800 |
C5—H5A | 0.9500 | C15—H15C | 0.9800 |
C7—O1—C1 | 117.45 (17) | C7—C8—C9 | 118.8 (2) |
C2—O2—C15 | 116.7 (2) | C7—C8—H8A | 120.6 |
C6—C1—C2 | 122.1 (2) | C9—C8—H8A | 120.6 |
C6—C1—O1 | 119.1 (2) | C8—C9—C10 | 120.9 (2) |
C2—C1—O1 | 118.8 (2) | C8—C9—C13 | 120.1 (2) |
O2—C2—C1 | 116.0 (2) | C10—C9—C13 | 119.0 (2) |
O2—C2—C3 | 126.0 (2) | C11—C10—C9 | 119.1 (2) |
C1—C2—C3 | 118.0 (2) | C11—C10—C14 | 121.5 (2) |
C4—C3—C2 | 119.8 (2) | C9—C10—C14 | 119.4 (2) |
C4—C3—H3A | 120.1 | C12—C11—C10 | 120.0 (2) |
C2—C3—H3A | 120.1 | C12—C11—H11A | 120.0 |
C5—C4—C3 | 121.5 (2) | C10—C11—H11A | 120.0 |
C5—C4—H4A | 119.2 | C11—C12—C7 | 120.4 (2) |
C3—C4—H4A | 119.2 | C11—C12—H12A | 119.8 |
C4—C5—C6 | 119.3 (2) | C7—C12—H12A | 119.8 |
C4—C5—H5A | 120.4 | N1—C13—C9 | 179.0 (3) |
C6—C5—H5A | 120.4 | N2—C14—C10 | 178.6 (2) |
C1—C6—C5 | 119.3 (2) | O2—C15—H15A | 109.5 |
C1—C6—H6A | 120.4 | O2—C15—H15B | 109.5 |
C5—C6—H6A | 120.4 | H15A—C15—H15B | 109.5 |
O1—C7—C8 | 123.6 (2) | O2—C15—H15C | 109.5 |
O1—C7—C12 | 115.53 (19) | H15A—C15—H15C | 109.5 |
C8—C7—C12 | 120.9 (2) | H15B—C15—H15C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3A···O2i | 0.95 | 2.95 | 3.629 (3) | 129 |
C5—H5A···N2ii | 0.95 | 2.66 | 3.394 (3) | 134 |
C5—H5A···N1iii | 0.95 | 2.90 | 3.557 (3) | 128 |
C5—H5A···O1iv | 0.95 | 2.96 | 3.453 (3) | 113 |
C8—H8A···N2v | 0.95 | 2.69 | 3.469 (3) | 140 |
C11—H11A···O2vi | 0.95 | 2.82 | 3.735 (3) | 161 |
C11—H11A···O1vi | 0.95 | 2.75 | 3.546 (3) | 142 |
C12—H12A···N1vii | 0.95 | 2.44 | 3.199 (3) | 137 |
Symmetry codes: (i) −x+2, y+1/2, −z+3/2; (ii) −x+1/2, −y+1, z+1/2; (iii) −x+1, y−1/2, −z+3/2; (iv) −x+1, y+1/2, −z+3/2; (v) x+1/2, −y+3/2, −z+1; (vi) x−1/2, −y+1/2, −z+1; (vii) x, y−1, z. |
C15H10N2O2 | Z = 2 |
Mr = 250.25 | F(000) = 260 |
Triclinic, P1 | Dx = 1.371 Mg m−3 |
a = 8.0609 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.4672 (4) Å | Cell parameters from 9781 reflections |
c = 9.9999 (4) Å | θ = 2.7–30.1° |
α = 104.638 (1)° | µ = 0.09 mm−1 |
β = 95.078 (1)° | T = 100 K |
γ = 110.570 (1)° | Prism, colorless |
V = 606.31 (4) Å3 | 0.45 × 0.30 × 0.27 mm |
Bruker D8 Quest (CMOS) diffractometer | 3040 reflections with I > 2σ(I) |
Radiation source: microfocus tube | Rint = 0.017 |
ω scans | θmax = 29.6°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −11→11 |
Tmin = 0.903, Tmax = 0.971 | k = −11→11 |
10029 measured reflections | l = −13→13 |
3395 independent reflections |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0528P)2 + 0.2143P] where P = (Fo2 + 2Fc2)/3 |
3395 reflections | (Δ/σ)max < 0.001 |
173 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.27 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 | ||
O1 | 0.56496 (10) | 0.59440 (10) | 0.80203 (7) | 0.01795 (16) | |
O2 | 0.87906 (10) | 0.47550 (9) | 1.17760 (7) | 0.01716 (16) | |
N1 | 0.95411 (13) | 0.23336 (15) | 0.44743 (10) | 0.0277 (2) | |
N2 | 0.46049 (13) | −0.06002 (13) | 0.21559 (10) | 0.0253 (2) | |
C1 | 0.69339 (13) | 0.64698 (13) | 0.92463 (10) | 0.01494 (18) | |
C2 | 0.72490 (12) | 0.52173 (12) | 0.97939 (9) | 0.01389 (18) | |
H2A | 0.668855 | 0.398795 | 0.929816 | 0.017* | |
C3 | 0.84135 (13) | 0.58336 (12) | 1.10919 (9) | 0.01423 (18) | |
C4 | 0.92411 (14) | 0.76450 (13) | 1.18106 (10) | 0.01779 (19) | |
H4A | 1.004512 | 0.805311 | 1.269112 | 0.021* | |
C5 | 0.88827 (14) | 0.88403 (13) | 1.12324 (11) | 0.0203 (2) | |
H5A | 0.943632 | 1.007075 | 1.172592 | 0.024* | |
C6 | 0.77200 (14) | 0.82629 (13) | 0.99356 (10) | 0.0186 (2) | |
H6A | 0.747571 | 0.908341 | 0.953705 | 0.022* | |
C7 | 0.55405 (13) | 0.45928 (12) | 0.68822 (9) | 0.01418 (18) | |
C8 | 0.70450 (12) | 0.42664 (12) | 0.65164 (9) | 0.01438 (18) | |
H8A | 0.820847 | 0.493469 | 0.709832 | 0.017* | |
C9 | 0.67994 (12) | 0.29370 (12) | 0.52775 (9) | 0.01387 (18) | |
C10 | 0.50752 (12) | 0.19245 (12) | 0.44232 (9) | 0.01434 (18) | |
C11 | 0.35970 (13) | 0.22881 (13) | 0.48119 (10) | 0.01664 (19) | |
H11A | 0.242865 | 0.161880 | 0.423787 | 0.020* | |
C12 | 0.38297 (13) | 0.36220 (13) | 0.60321 (10) | 0.01613 (19) | |
H12A | 0.282369 | 0.387620 | 0.629065 | 0.019* | |
C13 | 0.83370 (13) | 0.26098 (14) | 0.48459 (10) | 0.0185 (2) | |
C14 | 0.48277 (13) | 0.05290 (13) | 0.31588 (10) | 0.01762 (19) | |
C15 | 0.79525 (14) | 0.28892 (13) | 1.10841 (11) | 0.0189 (2) | |
H15A | 0.829282 | 0.225820 | 1.168675 | 0.028* | |
H15B | 0.835383 | 0.260815 | 1.018882 | 0.028* | |
H15C | 0.663676 | 0.252294 | 1.090253 | 0.028* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0233 (4) | 0.0224 (4) | 0.0123 (3) | 0.0155 (3) | 0.0020 (3) | 0.0032 (3) |
O2 | 0.0211 (3) | 0.0165 (3) | 0.0143 (3) | 0.0086 (3) | 0.0001 (3) | 0.0046 (3) |
N1 | 0.0205 (4) | 0.0418 (6) | 0.0197 (4) | 0.0167 (4) | 0.0019 (3) | 0.0014 (4) |
N2 | 0.0272 (5) | 0.0235 (5) | 0.0203 (4) | 0.0083 (4) | 0.0016 (4) | 0.0019 (3) |
C1 | 0.0167 (4) | 0.0193 (4) | 0.0115 (4) | 0.0094 (3) | 0.0045 (3) | 0.0051 (3) |
C2 | 0.0156 (4) | 0.0145 (4) | 0.0126 (4) | 0.0073 (3) | 0.0041 (3) | 0.0034 (3) |
C3 | 0.0163 (4) | 0.0164 (4) | 0.0124 (4) | 0.0081 (3) | 0.0049 (3) | 0.0052 (3) |
C4 | 0.0195 (4) | 0.0176 (5) | 0.0135 (4) | 0.0060 (4) | 0.0021 (3) | 0.0022 (3) |
C5 | 0.0246 (5) | 0.0141 (4) | 0.0198 (5) | 0.0064 (4) | 0.0047 (4) | 0.0027 (4) |
C6 | 0.0240 (5) | 0.0170 (4) | 0.0184 (4) | 0.0105 (4) | 0.0063 (4) | 0.0068 (4) |
C7 | 0.0187 (4) | 0.0165 (4) | 0.0110 (4) | 0.0097 (3) | 0.0042 (3) | 0.0059 (3) |
C8 | 0.0139 (4) | 0.0178 (4) | 0.0123 (4) | 0.0070 (3) | 0.0019 (3) | 0.0050 (3) |
C9 | 0.0136 (4) | 0.0179 (4) | 0.0122 (4) | 0.0078 (3) | 0.0025 (3) | 0.0056 (3) |
C10 | 0.0148 (4) | 0.0164 (4) | 0.0126 (4) | 0.0063 (3) | 0.0022 (3) | 0.0055 (3) |
C11 | 0.0126 (4) | 0.0212 (5) | 0.0167 (4) | 0.0060 (3) | 0.0022 (3) | 0.0076 (4) |
C12 | 0.0150 (4) | 0.0222 (5) | 0.0160 (4) | 0.0100 (4) | 0.0055 (3) | 0.0090 (3) |
C13 | 0.0170 (4) | 0.0247 (5) | 0.0127 (4) | 0.0096 (4) | 0.0003 (3) | 0.0026 (3) |
C14 | 0.0159 (4) | 0.0196 (5) | 0.0166 (4) | 0.0060 (3) | 0.0012 (3) | 0.0062 (4) |
C15 | 0.0244 (5) | 0.0160 (4) | 0.0181 (4) | 0.0099 (4) | 0.0029 (4) | 0.0058 (3) |
O1—C7 | 1.3658 (11) | C6—H6A | 0.9500 |
O1—C1 | 1.3959 (11) | C7—C12 | 1.3939 (14) |
O2—C3 | 1.3669 (11) | C7—C8 | 1.3942 (13) |
O2—C15 | 1.4303 (12) | C8—C9 | 1.3914 (12) |
N1—C13 | 1.1464 (14) | C8—H8A | 0.9500 |
N2—C14 | 1.1468 (14) | C9—C10 | 1.4067 (13) |
C1—C6 | 1.3782 (14) | C9—C13 | 1.4404 (13) |
C1—C2 | 1.3954 (13) | C10—C11 | 1.3946 (13) |
C2—C3 | 1.3915 (13) | C10—C14 | 1.4384 (13) |
C2—H2A | 0.9500 | C11—C12 | 1.3834 (13) |
C3—C4 | 1.3975 (13) | C11—H11A | 0.9500 |
C4—C5 | 1.3835 (14) | C12—H12A | 0.9500 |
C4—H4A | 0.9500 | C15—H15A | 0.9800 |
C5—C6 | 1.3934 (15) | C15—H15B | 0.9800 |
C5—H5A | 0.9500 | C15—H15C | 0.9800 |
C7—O1—C1 | 120.56 (7) | C9—C8—C7 | 118.33 (8) |
C3—O2—C15 | 117.05 (7) | C9—C8—H8A | 120.8 |
C6—C1—C2 | 122.83 (9) | C7—C8—H8A | 120.8 |
C6—C1—O1 | 116.08 (8) | C8—C9—C10 | 121.08 (8) |
C2—C1—O1 | 120.80 (8) | C8—C9—C13 | 119.63 (8) |
C3—C2—C1 | 117.62 (8) | C10—C9—C13 | 119.28 (8) |
C3—C2—H2A | 121.2 | C11—C10—C9 | 119.29 (8) |
C1—C2—H2A | 121.2 | C11—C10—C14 | 119.99 (8) |
O2—C3—C2 | 123.86 (8) | C9—C10—C14 | 120.72 (8) |
O2—C3—C4 | 115.26 (8) | C12—C11—C10 | 120.09 (9) |
C2—C3—C4 | 120.85 (9) | C12—C11—H11A | 120.0 |
C5—C4—C3 | 119.61 (9) | C10—C11—H11A | 120.0 |
C5—C4—H4A | 120.2 | C11—C12—C7 | 119.99 (9) |
C3—C4—H4A | 120.2 | C11—C12—H12A | 120.0 |
C4—C5—C6 | 120.85 (9) | C7—C12—H12A | 120.0 |
C4—C5—H5A | 119.6 | N1—C13—C9 | 178.59 (10) |
C6—C5—H5A | 119.6 | N2—C14—C10 | 178.88 (11) |
C1—C6—C5 | 118.24 (9) | O2—C15—H15A | 109.5 |
C1—C6—H6A | 120.9 | O2—C15—H15B | 109.5 |
C5—C6—H6A | 120.9 | H15A—C15—H15B | 109.5 |
O1—C7—C12 | 115.57 (8) | O2—C15—H15C | 109.5 |
O1—C7—C8 | 123.07 (8) | H15A—C15—H15C | 109.5 |
C12—C7—C8 | 121.20 (9) | H15B—C15—H15C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···N2i | 0.95 | 2.64 | 3.5839 (13) | 175 |
C8—H8A···O2ii | 0.95 | 2.47 | 3.3447 (11) | 153 |
C11—H11A···N1iii | 0.95 | 2.62 | 3.2718 (13) | 126 |
C12—H12A···N1iii | 0.95 | 2.74 | 3.3325 (13) | 121 |
C12—H12A···O2iv | 0.95 | 2.67 | 3.5343 (12) | 151 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+2, −y+1, −z+2; (iii) x−1, y, z; (iv) −x+1, −y+1, −z+2. |
Funding information
Funding for this research was provided by: Russian Science Foundation (grant No. 22-73-10158 to Arthur Vashurin).
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