research communications
tert-butyl-4-hydroxyphenyl)-3-phenyl-4,5-dihydro-1H-pyrazole-1-carboxamide
and Hirshfeld surface analysis of 5-(3,5-di-aOrganic Chemistry Department, Baku State University, Z. Khalilov str. 23, Az, 1148 Baku, Azerbaijan
*Correspondence e-mail: rayten5071@mail.ru
In the title compound, C24H31N3O2, the mean plane of the central pyrazole ring [r.m.s. deviation = 0.095 Å] makes dihedral angles of 11.93 (9) and 84.53 (8)°, respectively, with the phenyl and benzene rings. There is a short intramolecular N—H⋯N contact, which generates an S(5) ring motif. In the crystal, pairs of N—H⋯O hydrogen bonds link inversion-related molecules into dimers, generating an R22(8) ring motif. The Hirshfeld surface analysis indicates that the most significant contribution involves H⋯H contacts of 68.6%
Keywords: crystal structure; pyrazole; carboxamide; 3,5-di-tert-butyl-4-hydroxyphenyl; N—H⋯O hydrogen bonds; inversion dimer.
CCDC reference: 1934997
1. Chemical context
Compounds containing the pyrazole ring system, considered to be a pharmacologically important active scaffold, possess diverse biological activities such as antimicrobial, anti-inflammatory, analgesic, anticonvulsant, anticancer, anthelmintic, antioxidant and herbicidal (Ansari et al., 2017; Karrouchi et al., 2018; Mamedov et al., 2017). Such compounds have been the subject of NMR investigations of hydrogen bonding and keto–enol in solution (Mamedov et al., 2013, 2015). The structural properties of a series of compounds derived from 2,6-di-tert-butylphenol have been characterized in the solid state (Asgarova et al., 2011a,b, 2019; Khalilov et al., 2018a,b). Non-covalent bond donor/acceptor properties of pyrazoles or related N-compounds are crucial in the organization of supramolecular architectures in the solid state and hence their solubility, etc. (Ma et al., 2017; Maharramov et al., 2010; Mahmoudi et al., 2016, 2017a,b, 2018a,b,c; Mahmudov et al., 2014, 2019; Shikhaliyev et al., 2018). As part of a further study of this class of compounds, the and Hirshfeld surface analysis of the title compound, 5-(3,5-di-tert-butyl-4-hydroxyphenyl)-3-phenyl-4,5-dihydro-1H-pyrazole-1-carboxamide, are reported on herein.
2. Structural commentary
As shown in Fig. 1, the title molecule contains three rings, pyrazole ring A (N19/N20/C16–C18; twisted conformation on bond C16-C17), phenyl ring B (C21–C26) and benzene ring C (C1–C6), with rings B and C being inclined to the mean plane of the central pyrazole ring A [r.m.s deviation = 0.095 Å] by 11.93 (9) and 84.53 (8)°, respectively. In the >NC(=O)NH2 group, atoms N20, C27, O29 and N28 are coplanar, with N19—N20—C27—N28 and N19—N20—C27—O29 torsion angles of 4.0 (2) and −176.1 (1)°. All bond lengths and angles are comparable with those found for closely related structures, for example, methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Li et al., 2014), 2,6-di-tert-butyl-4-methylphenol (Iimura et al., 1983), 2,6-di-tert-butyl-4-(3-chloro-2-hydroxypropyl)phenol (Asgarova et al., 2011a) and 4-[3-(benzylamino)-2-hydroxypropyl]-2,6-di-tert-butylphenol (Asgarova et al., 2011b). In the molecule, there is an N—H⋯N short contact, which generates an S(5) ring motif (Table 1).
3. Supramolecular features and Hirshfeld surface analysis
In the crystal, pairs of N—H⋯O hydrogen bonds link inversion-related molecules into dimers, generating an (8) ring motif (Table 1; Fig. 2). No C—H⋯π or π-π interactions are present in the (PLATON; Spek, 2009).
The Hirshfeld surface analysis (Spackman & Jayatilaka, 2009) was generated by CrystalExplorer17 (Turner et al., 2017) and comprises dnorm surface plots and two-dimensional fingerprint plots (Spackman & McKinnon, 2002). A dnorm surface plot of the title compound mapped using a standard surface resolution with a fixed colour scale of −0.5426 (red) to 1.7721 a.u. (blue) is shown in Fig. 3. The dark-red spots on the dnorm surface arise as a result of the N—H⋯O hydrogen bonds (Table 1), while the other weaker intermolecular interactions appear as light-red spots. The bright-red spots indicate their roles as the respective donors and/or acceptors; they also appear as blue and red regions corresponding to positive and negative potentials on the Hirshfeld surfaces mapped over electrostatic potential (Spackman et al., 2008; Jayatilaka et al., 2005), as shown in Fig. 4.
The shape-index of the Hirshfeld surface is a tool to visualize π–π stacking interactions by the presence of adjacent red and blue triangles; if there are no adjacent red and/or blue triangles then there are no π–π interactions. Fig. 5 clearly indicates that there are no π–π interactions present in the the crystal of the title compound, as also indicated by the analysis of the using PLATON (Spek, 2009). Fig. 6a shows the two-dimensional fingerprint of the sum of the contacts contributing to the Hirshfeld surface represented in normal mode. These represent both the overall two-dimensional fingerprint plot and those delineated into H⋯H (68.6%), C⋯H/H⋯C (18.3%), H⋯O/O⋯H (7.1%) and H⋯N/N⋯H (4.1%) contacts (Fig. 6b–e). The most significant contribution to the Hirshfeld surface is from H⋯H contacts (68.6%; Fig. 5b).
The large number of H⋯H, C⋯H/H⋯C, H⋯O/O⋯H and H⋯N/N⋯H contacts suggest that van der Waals interactions and hydrogen bonding play the major roles in the crystal packing (Hathwar et al., 2015).
4. Synthesis and crystallization
To a solution of of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-1-phenylprop-2-en-1-one (1.2 mmol) in 10 ml ethanol was added semicarbazide hydrochloride (1.26 mmol). The mixture was refluxed for 3 h and then cooled to room temperature. The title compound, that precipitated as colourless single crystals, was collected by filtration and washed with an ethanol–water (1:1) mixture (yield 56%, m.p. 525 K). 1H NMR (300 MHz, DMSO-d6) : 1.38 (s, 18H, 6CH3); 3.05 (dd, 1H, CH2, 3JH-H = 4.8, 2JH-H =17.7,); 3.75 (dd, 1H, CH2, 3JH-H = 12, 2JH-H = 17.7), 5.35 (dd, 1H, CH2, 3JH-H = 4.8, 2JH-H = 11.7); 6.51 (s, 2H, NH2); 6.87 (s, 1H, OHar); 6.96 (s, 2H, 2Ar-H); 7.41–7.83 (m, 5H, 5Ar-H). 13C NMR (75 MHz, DMSO-d6): 30.79 (6CH3), 34.94 (2Ctert), 43.00 (CH2), 60.32 (CH), 121.79 (2CHar), 126.90 (2CHar), 129.39 (2CHar), 130.02 (CHar), 132.18 (Car), 134.96 (Car), 139.67 (Car), 151.13(N=Ctert), 153.23 (O—Car) 155.56 (NC=O).
5. Refinement
Crystal data, data collection and structure . Hydrogen atoms of the amino group were located in a difference-Fourier map and refined freely. The hydroxy H atom (H15) was included in the calculated position (AFIX 147; O-H = 0.84 Å) and refined with Uiso(H) = 1.5Ueq(O). All the C-bound H atoms were placed in calculated positions and refined using a riding model: C—H = 0.95–1.00 Å with Uiso(H) = 1.2Ueq(C).
details are summarized in Table 2As reported previously (cf. Cambridge Structural Database; Groom et al., 2016) short H⋯H contacts (< 2.0 Å), involving the hydroxy H atom and the methyl H atoms of the 3,5-di-tert-butyl-4-hydroxyphenyl moiety, were observed.
Supporting information
CCDC reference: 1934997
https://doi.org/10.1107/S205698901901243X/eb2022sup1.cif
contains datablocks I, Global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901901243X/eb2022Isup2.hkl
Data collection: APEX2 (Bruker, 2003); cell
SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009).C24H31N3O2 | Z = 2 |
Mr = 393.52 | F(000) = 424 |
Triclinic, P1 | Dx = 1.209 Mg m−3 |
a = 6.095 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.215 (4) Å | Cell parameters from 7006 reflections |
c = 17.995 (8) Å | θ = 2.3–27.5° |
α = 84.781 (15)° | µ = 0.08 mm−1 |
β = 85.688 (15)° | T = 150 K |
γ = 76.012 (15)° | Plate, colorless |
V = 1081.1 (8) Å3 | 0.20 × 0.16 × 0.13 mm |
Bruker APEXII CCD diffractometer | 3573 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.093 |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | θmax = 28.0°, θmin = 2.3° |
Tmin = 0.976, Tmax = 0.982 | h = −8→8 |
27614 measured reflections | k = −13→13 |
5128 independent reflections | l = −23→23 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.055 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.163 | w = 1/[σ2(Fo2) + (0.0884P)2 + 0.1168P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
5128 reflections | Δρmax = 0.34 e Å−3 |
278 parameters | Δρmin = −0.20 e Å−3 |
0 restraints | Extinction correction: (SHELXL-2018/3; Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: dual | Extinction coefficient: 0.045 (10) |
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 | ||
O15 | 0.9461 (2) | 0.44716 (13) | 0.91734 (7) | 0.0566 (4) | |
H15 | 1.033732 | 0.369748 | 0.919753 | 0.085* | |
O29 | 0.8119 (2) | 0.43979 (12) | 0.57125 (7) | 0.0481 (3) | |
N19 | 0.3611 (2) | 0.72589 (13) | 0.58893 (7) | 0.0346 (3) | |
N20 | 0.5033 (2) | 0.59925 (13) | 0.60307 (7) | 0.0370 (3) | |
N28 | 0.7453 (3) | 0.64582 (18) | 0.50555 (9) | 0.0523 (4) | |
H28A | 0.882 (4) | 0.625 (2) | 0.4835 (13) | 0.067 (7)* | |
H28B | 0.659 (4) | 0.732 (2) | 0.5038 (12) | 0.063 (6)* | |
C1 | 0.8395 (2) | 0.35284 (15) | 0.81126 (8) | 0.0317 (3) | |
C2 | 0.8169 (3) | 0.46205 (15) | 0.85614 (8) | 0.0344 (3) | |
C3 | 0.6665 (2) | 0.58842 (15) | 0.84134 (8) | 0.0314 (3) | |
C4 | 0.5350 (2) | 0.60223 (15) | 0.77960 (8) | 0.0313 (3) | |
H4 | 0.429397 | 0.685704 | 0.768849 | 0.038* | |
C5 | 0.5536 (2) | 0.49774 (14) | 0.73326 (8) | 0.0293 (3) | |
C6 | 0.7058 (2) | 0.37542 (15) | 0.74962 (8) | 0.0314 (3) | |
H6 | 0.719460 | 0.304401 | 0.717703 | 0.038* | |
C7 | 1.0061 (3) | 0.21512 (15) | 0.82845 (9) | 0.0355 (4) | |
C8 | 0.9502 (4) | 0.1510 (2) | 0.90606 (11) | 0.0568 (5) | |
H8A | 0.795804 | 0.137693 | 0.908130 | 0.085* | |
H8B | 0.961692 | 0.210912 | 0.944383 | 0.085* | |
H8C | 1.057342 | 0.063409 | 0.915125 | 0.085* | |
C9 | 0.9923 (4) | 0.11345 (18) | 0.77254 (12) | 0.0586 (6) | |
H9A | 0.838694 | 0.098943 | 0.775293 | 0.088* | |
H9B | 1.100388 | 0.027416 | 0.784629 | 0.088* | |
H9C | 1.029174 | 0.148899 | 0.721901 | 0.088* | |
C10 | 1.2512 (3) | 0.2323 (2) | 0.82225 (13) | 0.0581 (5) | |
H10A | 1.354990 | 0.145275 | 0.835704 | 0.087* | |
H10B | 1.265658 | 0.298983 | 0.856270 | 0.087* | |
H10C | 1.288924 | 0.263391 | 0.770813 | 0.087* | |
C11 | 0.6506 (3) | 0.70679 (16) | 0.89082 (9) | 0.0368 (4) | |
C12 | 0.8800 (3) | 0.7458 (2) | 0.88750 (12) | 0.0533 (5) | |
H12A | 0.924088 | 0.769747 | 0.835484 | 0.080* | |
H12B | 0.995181 | 0.669096 | 0.907726 | 0.080* | |
H12C | 0.866678 | 0.823474 | 0.917172 | 0.080* | |
C13 | 0.4760 (3) | 0.83347 (17) | 0.86389 (11) | 0.0509 (5) | |
H13A | 0.519650 | 0.862799 | 0.812705 | 0.076* | |
H13B | 0.469798 | 0.905832 | 0.896767 | 0.076* | |
H13C | 0.326834 | 0.812938 | 0.864961 | 0.076* | |
C14 | 0.5774 (4) | 0.6689 (2) | 0.97178 (10) | 0.0533 (5) | |
H14A | 0.569824 | 0.744823 | 1.002283 | 0.080* | |
H14B | 0.687629 | 0.589255 | 0.991622 | 0.080* | |
H14C | 0.427997 | 0.648596 | 0.973155 | 0.080* | |
C16 | 0.4155 (2) | 0.51573 (15) | 0.66436 (8) | 0.0318 (3) | |
H16 | 0.417377 | 0.425207 | 0.646982 | 0.038* | |
C17 | 0.1694 (3) | 0.59885 (16) | 0.67369 (9) | 0.0358 (4) | |
H17A | 0.062980 | 0.553619 | 0.653335 | 0.043* | |
H17B | 0.124746 | 0.613620 | 0.726873 | 0.043* | |
C18 | 0.1762 (3) | 0.73077 (15) | 0.62880 (8) | 0.0318 (3) | |
C21 | −0.0090 (3) | 0.85374 (15) | 0.62682 (8) | 0.0339 (3) | |
C22 | −0.2214 (3) | 0.84869 (19) | 0.65965 (10) | 0.0443 (4) | |
H22 | −0.244531 | 0.766713 | 0.684641 | 0.053* | |
C23 | −0.3989 (3) | 0.9624 (2) | 0.65606 (11) | 0.0540 (5) | |
H23 | −0.543486 | 0.957730 | 0.678261 | 0.065* | |
C24 | −0.3679 (4) | 1.0824 (2) | 0.62059 (11) | 0.0559 (5) | |
H24 | −0.490868 | 1.159998 | 0.618221 | 0.067* | |
C25 | −0.1580 (4) | 1.08977 (18) | 0.58852 (10) | 0.0526 (5) | |
H25 | −0.136101 | 1.172570 | 0.564262 | 0.063* | |
C26 | 0.0211 (3) | 0.97629 (17) | 0.59169 (9) | 0.0421 (4) | |
H26 | 0.165500 | 0.981990 | 0.569754 | 0.050* | |
C27 | 0.6958 (3) | 0.55571 (17) | 0.55953 (8) | 0.0364 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O15 | 0.0598 (8) | 0.0483 (8) | 0.0558 (8) | 0.0115 (6) | −0.0335 (7) | −0.0142 (6) |
O29 | 0.0416 (7) | 0.0390 (7) | 0.0552 (7) | 0.0044 (5) | 0.0052 (5) | −0.0021 (5) |
N19 | 0.0345 (7) | 0.0325 (7) | 0.0321 (6) | 0.0012 (5) | −0.0051 (5) | 0.0004 (5) |
N20 | 0.0347 (7) | 0.0341 (7) | 0.0346 (7) | 0.0038 (6) | −0.0014 (5) | 0.0040 (5) |
N28 | 0.0468 (9) | 0.0471 (9) | 0.0509 (9) | 0.0039 (7) | 0.0122 (7) | 0.0060 (7) |
C1 | 0.0278 (7) | 0.0277 (7) | 0.0364 (8) | 0.0002 (6) | −0.0051 (6) | −0.0013 (6) |
C2 | 0.0324 (8) | 0.0331 (8) | 0.0357 (8) | −0.0012 (6) | −0.0106 (6) | −0.0023 (6) |
C3 | 0.0300 (7) | 0.0275 (7) | 0.0356 (7) | −0.0042 (6) | −0.0035 (6) | −0.0029 (6) |
C4 | 0.0288 (7) | 0.0253 (7) | 0.0371 (7) | −0.0013 (6) | −0.0056 (6) | 0.0009 (5) |
C5 | 0.0271 (7) | 0.0280 (7) | 0.0316 (7) | −0.0045 (6) | −0.0037 (6) | 0.0006 (5) |
C6 | 0.0307 (7) | 0.0279 (7) | 0.0342 (7) | −0.0031 (6) | −0.0043 (6) | −0.0036 (6) |
C7 | 0.0319 (8) | 0.0293 (8) | 0.0403 (8) | 0.0038 (6) | −0.0082 (6) | −0.0012 (6) |
C8 | 0.0649 (13) | 0.0419 (10) | 0.0526 (11) | 0.0039 (9) | −0.0012 (9) | 0.0082 (8) |
C9 | 0.0647 (12) | 0.0359 (9) | 0.0659 (12) | 0.0164 (9) | −0.0251 (10) | −0.0144 (8) |
C10 | 0.0343 (9) | 0.0522 (11) | 0.0808 (14) | 0.0033 (8) | −0.0065 (9) | −0.0010 (10) |
C11 | 0.0372 (8) | 0.0305 (8) | 0.0420 (8) | −0.0035 (6) | −0.0070 (7) | −0.0073 (6) |
C12 | 0.0489 (11) | 0.0490 (11) | 0.0676 (12) | −0.0172 (9) | −0.0082 (9) | −0.0148 (9) |
C13 | 0.0564 (11) | 0.0323 (9) | 0.0596 (11) | 0.0044 (8) | −0.0117 (9) | −0.0130 (8) |
C14 | 0.0617 (12) | 0.0520 (11) | 0.0436 (10) | −0.0063 (10) | 0.0000 (9) | −0.0113 (8) |
C16 | 0.0302 (7) | 0.0288 (7) | 0.0350 (7) | −0.0033 (6) | −0.0073 (6) | 0.0002 (6) |
C17 | 0.0290 (8) | 0.0358 (8) | 0.0409 (8) | −0.0043 (6) | −0.0092 (6) | 0.0025 (6) |
C18 | 0.0311 (7) | 0.0335 (8) | 0.0296 (7) | −0.0028 (6) | −0.0078 (6) | −0.0028 (6) |
C21 | 0.0353 (8) | 0.0339 (8) | 0.0298 (7) | −0.0003 (6) | −0.0085 (6) | −0.0045 (6) |
C22 | 0.0351 (9) | 0.0435 (10) | 0.0512 (10) | −0.0024 (7) | −0.0059 (7) | −0.0036 (7) |
C23 | 0.0362 (9) | 0.0607 (12) | 0.0585 (11) | 0.0057 (8) | −0.0069 (8) | −0.0123 (9) |
C24 | 0.0552 (12) | 0.0488 (11) | 0.0515 (11) | 0.0191 (9) | −0.0180 (9) | −0.0130 (8) |
C25 | 0.0709 (13) | 0.0349 (9) | 0.0442 (9) | 0.0049 (9) | −0.0136 (9) | −0.0006 (7) |
C26 | 0.0491 (10) | 0.0379 (9) | 0.0354 (8) | −0.0022 (7) | −0.0059 (7) | −0.0016 (6) |
C27 | 0.0326 (8) | 0.0388 (8) | 0.0345 (8) | −0.0009 (7) | −0.0029 (6) | −0.0048 (6) |
O15—C2 | 1.3776 (19) | C10—H10B | 0.9800 |
O15—H15 | 0.8400 | C10—H10C | 0.9800 |
O29—C27 | 1.233 (2) | C11—C13 | 1.529 (2) |
N19—C18 | 1.282 (2) | C11—C14 | 1.534 (3) |
N19—N20 | 1.3859 (18) | C11—C12 | 1.539 (3) |
N20—C27 | 1.364 (2) | C12—H12A | 0.9800 |
N20—C16 | 1.480 (2) | C12—H12B | 0.9800 |
N28—C27 | 1.345 (2) | C12—H12C | 0.9800 |
N28—H28A | 0.88 (3) | C13—H13A | 0.9800 |
N28—H28B | 0.91 (2) | C13—H13B | 0.9800 |
C1—C6 | 1.395 (2) | C13—H13C | 0.9800 |
C1—C2 | 1.410 (2) | C14—H14A | 0.9800 |
C1—C7 | 1.544 (2) | C14—H14B | 0.9800 |
C2—C3 | 1.407 (2) | C14—H14C | 0.9800 |
C3—C4 | 1.395 (2) | C16—C17 | 1.540 (2) |
C3—C11 | 1.546 (2) | C16—H16 | 1.0000 |
C4—C5 | 1.392 (2) | C17—C18 | 1.515 (2) |
C4—H4 | 0.9500 | C17—H17A | 0.9900 |
C5—C6 | 1.386 (2) | C17—H17B | 0.9900 |
C5—C16 | 1.523 (2) | C18—C21 | 1.472 (2) |
C6—H6 | 0.9500 | C21—C22 | 1.393 (2) |
C7—C9 | 1.531 (2) | C21—C26 | 1.397 (2) |
C7—C8 | 1.538 (3) | C22—C23 | 1.383 (2) |
C7—C10 | 1.541 (3) | C22—H22 | 0.9500 |
C8—H8A | 0.9800 | C23—C24 | 1.377 (3) |
C8—H8B | 0.9800 | C23—H23 | 0.9500 |
C8—H8C | 0.9800 | C24—C25 | 1.380 (3) |
C9—H9A | 0.9800 | C24—H24 | 0.9500 |
C9—H9B | 0.9800 | C25—C26 | 1.387 (2) |
C9—H9C | 0.9800 | C25—H25 | 0.9500 |
C10—H10A | 0.9800 | C26—H26 | 0.9500 |
C2—O15—H15 | 109.5 | C12—C11—C3 | 109.96 (13) |
C18—N19—N20 | 108.15 (13) | C11—C12—H12A | 109.5 |
C27—N20—N19 | 121.43 (13) | C11—C12—H12B | 109.5 |
C27—N20—C16 | 124.77 (13) | H12A—C12—H12B | 109.5 |
N19—N20—C16 | 113.61 (12) | C11—C12—H12C | 109.5 |
C27—N28—H28A | 116.5 (15) | H12A—C12—H12C | 109.5 |
C27—N28—H28B | 118.7 (14) | H12B—C12—H12C | 109.5 |
H28A—N28—H28B | 122 (2) | C11—C13—H13A | 109.5 |
C6—C1—C2 | 116.81 (13) | C11—C13—H13B | 109.5 |
C6—C1—C7 | 121.23 (13) | H13A—C13—H13B | 109.5 |
C2—C1—C7 | 121.95 (13) | C11—C13—H13C | 109.5 |
O15—C2—C3 | 117.36 (13) | H13A—C13—H13C | 109.5 |
O15—C2—C1 | 119.80 (13) | H13B—C13—H13C | 109.5 |
C3—C2—C1 | 122.84 (13) | C11—C14—H14A | 109.5 |
C4—C3—C2 | 116.96 (13) | C11—C14—H14B | 109.5 |
C4—C3—C11 | 121.73 (13) | H14A—C14—H14B | 109.5 |
C2—C3—C11 | 121.31 (13) | C11—C14—H14C | 109.5 |
C5—C4—C3 | 122.16 (13) | H14A—C14—H14C | 109.5 |
C5—C4—H4 | 118.9 | H14B—C14—H14C | 109.5 |
C3—C4—H4 | 118.9 | N20—C16—C5 | 111.58 (12) |
C6—C5—C4 | 118.82 (13) | N20—C16—C17 | 100.20 (11) |
C6—C5—C16 | 119.48 (13) | C5—C16—C17 | 115.44 (13) |
C4—C5—C16 | 121.69 (13) | N20—C16—H16 | 109.7 |
C5—C6—C1 | 122.39 (14) | C5—C16—H16 | 109.7 |
C5—C6—H6 | 118.8 | C17—C16—H16 | 109.7 |
C1—C6—H6 | 118.8 | C18—C17—C16 | 102.79 (13) |
C9—C7—C8 | 106.08 (16) | C18—C17—H17A | 111.2 |
C9—C7—C10 | 107.04 (16) | C16—C17—H17A | 111.2 |
C8—C7—C10 | 110.82 (15) | C18—C17—H17B | 111.2 |
C9—C7—C1 | 111.32 (13) | C16—C17—H17B | 111.2 |
C8—C7—C1 | 111.35 (13) | H17A—C17—H17B | 109.1 |
C10—C7—C1 | 110.08 (14) | N19—C18—C21 | 121.19 (14) |
C7—C8—H8A | 109.5 | N19—C18—C17 | 113.38 (13) |
C7—C8—H8B | 109.5 | C21—C18—C17 | 125.40 (14) |
H8A—C8—H8B | 109.5 | C22—C21—C26 | 118.56 (15) |
C7—C8—H8C | 109.5 | C22—C21—C18 | 119.78 (15) |
H8A—C8—H8C | 109.5 | C26—C21—C18 | 121.66 (15) |
H8B—C8—H8C | 109.5 | C23—C22—C21 | 120.35 (18) |
C7—C9—H9A | 109.5 | C23—C22—H22 | 119.8 |
C7—C9—H9B | 109.5 | C21—C22—H22 | 119.8 |
H9A—C9—H9B | 109.5 | C24—C23—C22 | 120.60 (19) |
C7—C9—H9C | 109.5 | C24—C23—H23 | 119.7 |
H9A—C9—H9C | 109.5 | C22—C23—H23 | 119.7 |
H9B—C9—H9C | 109.5 | C23—C24—C25 | 119.85 (17) |
C7—C10—H10A | 109.5 | C23—C24—H24 | 120.1 |
C7—C10—H10B | 109.5 | C25—C24—H24 | 120.1 |
H10A—C10—H10B | 109.5 | C24—C25—C26 | 120.03 (18) |
C7—C10—H10C | 109.5 | C24—C25—H25 | 120.0 |
H10A—C10—H10C | 109.5 | C26—C25—H25 | 120.0 |
H10B—C10—H10C | 109.5 | C25—C26—C21 | 120.60 (18) |
C13—C11—C14 | 106.92 (15) | C25—C26—H26 | 119.7 |
C13—C11—C12 | 106.76 (15) | C21—C26—H26 | 119.7 |
C14—C11—C12 | 110.53 (15) | O29—C27—N28 | 124.31 (15) |
C13—C11—C3 | 111.83 (13) | O29—C27—N20 | 119.69 (15) |
C14—C11—C3 | 110.74 (14) | N28—C27—N20 | 116.00 (15) |
C18—N19—N20—C27 | 168.45 (14) | C27—N20—C16—C5 | 74.87 (19) |
C18—N19—N20—C16 | −6.82 (17) | N19—N20—C16—C5 | −110.05 (14) |
C6—C1—C2—O15 | −179.18 (15) | C27—N20—C16—C17 | −162.42 (14) |
C7—C1—C2—O15 | 0.0 (2) | N19—N20—C16—C17 | 12.66 (16) |
C6—C1—C2—C3 | 0.6 (2) | C6—C5—C16—N20 | −104.30 (16) |
C7—C1—C2—C3 | 179.85 (14) | C4—C5—C16—N20 | 74.21 (18) |
O15—C2—C3—C4 | −179.49 (14) | C6—C5—C16—C17 | 142.19 (14) |
C1—C2—C3—C4 | 0.7 (2) | C4—C5—C16—C17 | −39.3 (2) |
O15—C2—C3—C11 | 1.3 (2) | N20—C16—C17—C18 | −12.66 (14) |
C1—C2—C3—C11 | −178.56 (15) | C5—C16—C17—C18 | 107.30 (14) |
C2—C3—C4—C5 | −1.4 (2) | N20—N19—C18—C21 | 179.27 (12) |
C11—C3—C4—C5 | 177.80 (14) | N20—N19—C18—C17 | −2.84 (17) |
C3—C4—C5—C6 | 0.8 (2) | C16—C17—C18—N19 | 10.54 (16) |
C3—C4—C5—C16 | −177.68 (14) | C16—C17—C18—C21 | −171.67 (13) |
C4—C5—C6—C1 | 0.6 (2) | N19—C18—C21—C22 | 168.31 (14) |
C16—C5—C6—C1 | 179.16 (14) | C17—C18—C21—C22 | −9.3 (2) |
C2—C1—C6—C5 | −1.3 (2) | N19—C18—C21—C26 | −10.7 (2) |
C7—C1—C6—C5 | 179.48 (14) | C17—C18—C21—C26 | 171.63 (14) |
C6—C1—C7—C9 | −2.4 (2) | C26—C21—C22—C23 | 1.2 (2) |
C2—C1—C7—C9 | 178.43 (16) | C18—C21—C22—C23 | −177.89 (15) |
C6—C1—C7—C8 | −120.56 (17) | C21—C22—C23—C24 | −0.5 (3) |
C2—C1—C7—C8 | 60.3 (2) | C22—C23—C24—C25 | −0.2 (3) |
C6—C1—C7—C10 | 116.12 (17) | C23—C24—C25—C26 | 0.3 (3) |
C2—C1—C7—C10 | −63.0 (2) | C24—C25—C26—C21 | 0.3 (3) |
C4—C3—C11—C13 | 0.8 (2) | C22—C21—C26—C25 | −1.1 (2) |
C2—C3—C11—C13 | 180.00 (15) | C18—C21—C26—C25 | 177.97 (14) |
C4—C3—C11—C14 | 119.93 (17) | N19—N20—C27—O29 | −176.12 (14) |
C2—C3—C11—C14 | −60.9 (2) | C16—N20—C27—O29 | −1.4 (2) |
C4—C3—C11—C12 | −117.62 (17) | N19—N20—C27—N28 | 4.0 (2) |
C2—C3—C11—C12 | 61.6 (2) | C16—N20—C27—N28 | 178.67 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N28—H28B···N19 | 0.91 (2) | 2.30 (2) | 2.678 (3) | 105 (2) |
N28—H28A···O29i | 0.88 (2) | 2.03 (2) | 2.912 (3) | 174 (2) |
Symmetry code: (i) −x+2, −y+1, −z+1. |
References
Ansari, A., Ali, A., Asif, M. & Shamsuzzaman, S. (2017). New J. Chem. 41, 16–41. Web of Science CrossRef CAS Google Scholar
Asgarova, A. R., Allahverdiyev, M. A., Khalilov, A. N., Gurbanov, A. V. & Brito, I. (2011a). Acta Cryst. E67, o2024. Web of Science CSD CrossRef IUCr Journals Google Scholar
Asgarova, A. R., Khalilov, A. N., Brito, I., Maharramov, A. M., Shikhaliyev, N. G., Cisterna, J., Cárdenas, A., Gurbanov, A. V., Zubkov, F. I. & Mahmudov, K. T. (2019). Acta Cryst. C75, 342–347. Web of Science CSD CrossRef IUCr Journals Google Scholar
Asgarova, A. R., Maharramov, A. M., Khalilov, A. N., Gurbanov, A. V. & Ng, S. W. (2011b). Acta Cryst. E67, o852. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bruker (2003). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Hathwar, V. R., Sist, M., Jørgensen, M. R. V., Mamakhel, A. H., Wang, X., Hoffmann, C. M., Sugimoto, K., Overgaard, J. & Iversen, B. B. (2015). IUCrJ, 2, 563–574. Web of Science CSD CrossRef CAS PubMed IUCr Journals Google Scholar
Iimura, Y., Sakurai, T., Ohno, Y., Asahi, K.-I. & Isono, K. (1983). Acta Cryst. C39, 778–780. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Jayatilaka, D., Grimwood, D. J., Lee, A., Lemay, A., Russel, A. J., Taylor, C., Wolff, S. K., Cassam-Chenai, P. & Whitton, A. (2005). TONTO – A System for Computational Chemistry. Available at: https://hirshfeldsurface.net/ Google Scholar
Karrouchi, K., Radi, S., Ramli, Y., Taoufik, J., Mabkhot, Y. N., Al-aizari, F. A. & Ansar, M. (2018). Molecules, 23, 134–219. Web of Science CrossRef Google Scholar
Khalilov, A. N., Asgarova, A. R., Gurbanov, A. V., Maharramov, A. M., Nagiyev, F. N. & Brito, I. (2018a). Z. Kristallogr. New Cryst. Struct. 233, 1019–1020. Web of Science CSD CrossRef CAS Google Scholar
Khalilov, A. N., Asgarova, A. R., Gurbanov, A. V., Nagiyev, F. N. & Brito, I. (2018b). Z. Kristallogr. New Cryst. Struct. 233, 947–948. Web of Science CSD CrossRef CAS Google Scholar
Li, X., Wang, Z.-G., Chen, H.-H. & Liu, S.-G. (2014). Acta Cryst. C70, 1050–1053. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ma, Z., Gurbanov, A. V., Sutradhar, M., Kopylovich, M. N., Mahmudov, K. T., Maharramov, A. M., Guseinov, F. I., Zubkov, F. I. & Pombeiro, A. J. L. (2017). J. Mol. Catal. A Chem. 428, 17–23. CAS Google Scholar
Maharramov, A. M., Aliyeva, R. A., Aliyev, I. A., Pashaev, F. G., Gasanov, A. G., Azimova, S. I., Askerov, R. K., Kurbanov, A. V. & Mahmudov, K. T. (2010). Dyes Pigments, 85, 1–6. Web of Science CSD CrossRef CAS Google Scholar
Mahmoudi, G., Afkhami, F. A., Castiñeiras, A., García-Santos, I., Gurbanov, A., Zubkov, F. I., Mitoraj, M. P., Kukułka, M., Sagan, F., Szczepanik, D. W., Konyaeva, I. A. & Safin, D. A. (2018a). Inorg. Chem. 57, 4395–4408. Web of Science CSD CrossRef CAS PubMed Google Scholar
Mahmoudi, G., Bauzá, A., Gurbanov, A. V., Zubkov, F. I., Maniukiewicz, W., Rodríguez-Diéguez, A., López-Torres, E. & Frontera, A. (2016). CrystEngComm, 18, 9056–9066. Web of Science CSD CrossRef CAS Google Scholar
Mahmoudi, G., Gurbanov, A. V., Rodríguez-Hermida, S., Carballo, R., Amini, M., Bacchi, A., Mitoraj, M. P., Sagan, F., Kukułka, M. & Safin, D. A. (2017a). Inorg. Chem. 56, 9698–9709. Web of Science CSD CrossRef CAS PubMed Google Scholar
Mahmoudi, G., Seth, S. K., Bauzá, A., Zubkov, F. I., Gurbanov, A. V., White, J., Stilinović, V., Doert, Th. & Frontera, A. (2018b). CrystEngComm, 20, 2812–2821. Web of Science CSD CrossRef CAS Google Scholar
Mahmoudi, G., Zangrando, E., Mitoraj, M. P., Gurbanov, A. V., Zubkov, F. I., Moosavifar, M., Konyaeva, I. A., Kirillov, A. M. & Safin, D. A. (2018c). New J. Chem. 42, 4959–4971. Web of Science CSD CrossRef CAS Google Scholar
Mahmoudi, G., Zaręba, J. K., Gurbanov, A. V., Bauzá, A., Zubkov, F. I., Kubicki, M., Stilinović, V., Kinzhybalo, V. & Frontera, A. (2017b). Eur. J. Inorg. Chem. pp. 4763–4772. Web of Science CSD CrossRef Google Scholar
Mahmudov, K. T., Gurbanov, A. V., Guseinov, F. I. & Guedes da Silva, M. F. C. (2019). Coord. Chem. Rev. 387, 32–46. Web of Science CrossRef CAS Google Scholar
Mahmudov, K. T., Kopylovich, M. N., Maharramov, A. M., Kurbanova, M. M., Gurbanov, A. V. & Pombeiro, A. J. L. (2014). Coord. Chem. Rev. 265, 1–37. Web of Science CrossRef CAS Google Scholar
Mamedov, I. G., Bayramov, M. R., Mamedova, Y. V. & Maharramov, A. M. (2013). Magn. Reson. Chem. 51, 234–239. Web of Science CrossRef CAS PubMed Google Scholar
Mamedov, I. G., Bayramov, M. R., Mamedova, Y. V. & Maharramov, A. M. (2015). Magn. Reson. Chem. 53, 147–153. Web of Science CrossRef CAS PubMed Google Scholar
Mamedov, I. G., Mamedova, Y. V., Khrustalev, V. N., Bayramov, M. R. & Maharramov, A. M. (2017). Indian J. Chem. 56B, 192–196. CAS Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Shikhaliyev, N. Q., Ahmadova, N. E., Gurbanov, A. V., Maharramov, A. M., Mammadova, G. Z., Nenajdenko, V. G., Zubkov, F. I., Mahmudov, K. T. & Pombeiro, A. J. L. (2018). Dyes Pigments, 150, 377–381. Web of Science CSD CrossRef CAS Google Scholar
Spackman, M. A. & McKinnon, J. J. (2002). CrystEngComm, 4, 378–392. Web of Science CrossRef CAS Google Scholar
Spackman, M. A., McKinnon, J. J. & Jayatilaka, D. (2008). CrystEngComm, 10, 377–388. CAS Google Scholar
Spackman, M. & Jayatilaka, D. (2009). CrystEngComm, 11, 19–32. Web of Science CrossRef CAS Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). CrystalExplorer17. University of Western Australia. https://hirshfeldsurface.net Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.