In the crystal of the title molecular salt, ion pairs are linked by C—H⋯Br and N—H⋯Br hydrogen bonds, which are connected into helical chains extending along the c-axis direction by weak, electrostatic S⋯Br− interactions.
Keywords: crystal structure, dihydronaphthalene, thiazole, hydrazinium salt, hydrogen bond
Abstract
In the title molecular salt, C26H24N3S+·Br−, the dihedral angles between the thiazole ring and its attached phenyl and benzoyl rings are 54.81 (7) and 85.51 (7)°, respectively. In the crystal, ion pairs are linked by C—H⋯Br and N—H⋯Br hydrogen bonds and are connected into helical chains extending along the c-axis direction by weak, electrostatic S⋯Br− interactions. A Hirshfeld surface analysis was performed, which showed the dominant role of H⋯H contacts (51.3%).
Chemical context
Thiazoles are a class of heterocyclic compounds found in many biologically active drugs such as sulfathiazol (antimicrobial drug), ritonavir (antiretroviral drug), abafungin (antifungal drug) and tiazofurin (antineoplastic drug) (Siddiqui et al., 2009 ▸). Other compounds containing the thiazole or thiazolyl moiety show numerous biological activities such as antimicrobial and antifungal (Vasu et al., 2013 ▸), anti-inflammatory (Singh et al., 2008 ▸), anticancer (Luzina et al., 2009 ▸), antihypertensive (Turan-Zitouni et al., 2000 ▸), anti-HIV (Rawal et al., 2008 ▸), anticonvulsant (Satoh et al., 2009 ▸) and antidiabetic properties (Iino et al., 2009 ▸). As with many biologically active molecules, the molecular conformation adopted may have a significant effect on the activity which prompted an examination of the crystal structure of the title salt, C26H24N3S·Br, I (Fig. 1 ▸).
Figure 1.
The title molecule showing 50% probability ellipsoids.
Structural commentary
As expected, the C11/C12/C13/N3/S1 thiazole ring in I is almost planar (r.m.s. deviation = 0.0056 Å) and the mean planes of the C14–C19 and C21–C26 benzene rings are inclined to this plane by 54.81 (7) and 85.51 (7)°, respectively. The dihedral angle between the mean planes of the thiazole and C2–C7 rings is 13.1 (1)°. A puckering analysis of the C1/C2/C7–C10 ring yielded the parameters Q = 0.499 (3) Å, θ = 58.6 (3)° and φ = 225.6 (3)°, indicating a half-chair conformation.
Supramolecular features
In the crystal, the S1⋯Br1 distance of 3.5017 (7) Å is some 0.15 Å less than the sum of the van der Waals radii and likely represents an electrostatic interaction between the two atoms since S1 is near to the cationic charge. Over 200 structures having S⋯Br− contacts of this length or shorter are present in the Cambridge Structural Database, two examples being reported by Auffinger et al. (2004 ▸) and Thompson & Richardson (1977 ▸). This interaction, together with the N2—H2⋯Br1, C10—H10B⋯Br1, C20—H20B⋯Br1 and C26—H26⋯Br1 hydrogen bonds (Table 1 ▸) form helical chains extending along the c-axis direction (Fig. 2 ▸). It may be noted that the same bromide ion Br1(x, 1 − y, z − 
) accepts all the identified contacts. These [001] chains pack in the other two dimensions with normal van der Waals contacts (Fig. 3 ▸), in agreement with the results of the Hirshfeld surface analysis (vide infra).
Table 1. Hydrogen-bond geometry (Å, °).
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| N2—H2⋯Br1i | 0.91 | 2.63 | 3.4633 (18) | 152 |
| C10—H10B⋯Br1i | 0.99 | 2.88 | 3.837 (2) | 164 |
| C20—H20B⋯Br1i | 0.99 | 2.84 | 3.7560 (19) | 155 |
| C26—H26⋯Br1i | 0.95 | 2.90 | 3.730 (2) | 146 |
Symmetry code: (i) x, -y+1, z-{\script{1\over 2}}.
Figure 2.
Detail of a supramolecular chain viewed along the a-axis direction with C—H⋯Br and N—H⋯Br hydrogen bonds depicted by brown dashed lines. The short Br⋯S contact is depicted by a yellow dashed line.
Figure 3.
Packing seen along the c-axis direction giving an end view of the chains. Intermolecular interactions are depicted as in Fig. 2 ▸.
Database survey
A search of the Cambridge Structural Database (CSD, updated to Dec. 31, 2020; Groom, et al., 2016 ▸) using the fragment A yielded 30 hits of which 11 were considered similar to I. Among these, (Z)-1-[(2E)-3,4-diphenyl-2,3-dihydro-1,3-thiazol-2-ylidene]-2-[1-(4-hydroxyphenyl)ethylidene]hydrazinium bromide unknown solvate (CSD refcode BOCROC; Mague, et al., 2014 ▸) and (E)-2-[(2-nitrophenyl)methylidene]-1-[(2Z)-4-phenyl-2,3-dihydro-1,3-thiazol-2-ylidene]hydrazinium bromide (NUCLOO; Hassan et al., 2016 ▸) are the closest analogues and another similar compound is 2-{1-[(3,4-diphenyl-1,3-thiazol-2(3H)-ylidene)hydrazinylidene]ethyl}pyridinium bromide monohydrate (QOCGIA; Akkurt et al., 2014 ▸). Key bond distances and angles for I and these three compounds are listed in supplementary Table 1. In the thiazole ring there is little variation except for the N—C distance c in NUCLOO, which is marginally shorter than in the others, possibly due to the nitrogen atom being unsubstituted. The most noticeable differences occur in the N—C and C=N distances d and e where the difference between the two is largest in QOCGIA where the absence of the positive charge on the nitrogen atom bound to the thiazole ring leads to a greater localization of the π-electron density in the C=N bond.
Hirshfeld surface analysis
The Hirshfeld surface for I was calculated using Crystal Explorer17 (Turner et al., 2017 ▸) following the procedures described by Tan et al. (2019). Fig. 4 ▸ a presents the Hirshfeld surface plotted over d norm with a second cation closest to the bromide ion also present, clearly showing the N—H⋯Br and C—H⋯Br interactions as well as the S1⋯Br1 short contact (dashed lines). The surface plotted over shape (Fig. 4 ▸ b) and curvature indices (Fig. 4 ▸ c) do not show much flat surface or evidence for π-stacking interactions, in agreement with the results given in Section 3. Fig. 5 ▸ presents fingerprint plots for all intermolecular interactions (a) and resolved into all H⋯H contacts (b, 51.3%), H⋯C/C⋯H contacts (c, 21.9%), Br⋯H/H⋯Br contacts (d, 14.1%) and S⋯H/H⋯S contacts (d, 3.3%). The N⋯H/H⋯N contacts contribute only 1.3%.
Figure 4.
The Hirshfeld surface plotted over (a) d norm and (b) shape and (c) curvature indices.
Figure 5.
Fingerprint plots showing all (a) interactions and resolved into (b) H⋯H, (c) H⋯C/C⋯H, (d) Br⋯H/H⋯Br and (e) S⋯H/H⋯S contacts.
Synthesis and crystallization
The title compound was prepared according to our previously reported method (Mohamed et al., 2013 ▸). Mono-crystals of I suitable for X-ray diffraction were obtained by recrystallization of the crude product from ethanol solution.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. H atoms attached to carbon were placed in calculated positions (C—H = 0.95–0.99 Å) while that attached to nitrogen was placed in a location derived from a difference map and its coordinates adjusted to give N—H = 0.91 Å. All were included as riding contributions with isotropic displacement parameters 1.2–1.5 times those of the attached atoms.
Table 2. Experimental details.
| Crystal data | |
| Chemical formula | C26H24N3S+·Br− |
| M r | 490.45 |
| Crystal system, space group | Monoclinic, C c |
| Temperature (K) | 150 |
| a, b, c (Å) | 14.5474 (7), 17.8777 (8), 9.0803 (4) |
| β (°) | 108.773 (2) |
| V (Å3) | 2235.92 (18) |
| Z | 4 |
| Radiation type | Mo Kα |
| μ (mm−1) | 1.95 |
| Crystal size (mm) | 0.22 × 0.12 × 0.06 |
| Data collection | |
| Diffractometer | Bruker D8 QUEST PHOTON 3 diffractometer |
| Absorption correction | Numerical (SADABS; Krause et al., 2015 ▸) |
| T min, T max | 0.69, 0.89 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 48057, 6797, 6460 |
| R int | 0.026 |
| (sin θ/λ)max (Å−1) | 0.715 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.023, 0.052, 1.03 |
| No. of reflections | 6797 |
| No. of parameters | 280 |
| No. of restraints | 2 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.56, −0.22 |
| Absolute structure | Parsons et al. (2013 ▸) |
| Absolute structure parameter | 0.0130 (18) |
Supplementary Material
Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989021002863/hb7963sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989021002863/hb7963Isup2.hkl
Geometrical data for title compound and related phases. DOI: 10.1107/S2056989021002863/hb7963sup3.pdf
Supporting information file. DOI: 10.1107/S2056989021002863/hb7963Isup5.cml
CCDC reference: 2071135
Additional supporting information: crystallographic information; 3D view; checkCIF report
supplementary crystallographic information
Crystal data
| C26H24N3S+·Br− | F(000) = 1008 |
| Mr = 490.45 | Dx = 1.457 Mg m−3 |
| Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
| a = 14.5474 (7) Å | Cell parameters from 9847 reflections |
| b = 17.8777 (8) Å | θ = 2.6–30.5° |
| c = 9.0803 (4) Å | µ = 1.95 mm−1 |
| β = 108.773 (2)° | T = 150 K |
| V = 2235.92 (18) Å3 | Column, colourless |
| Z = 4 | 0.22 × 0.12 × 0.06 mm |
Data collection
| Bruker D8 QUEST PHOTON 3 diffractometer | 6797 independent reflections |
| Radiation source: fine-focus sealed tube | 6460 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.026 |
| Detector resolution: 7.3910 pixels mm-1 | θmax = 30.6°, θmin = 2.6° |
| φ and ω scans | h = −20→20 |
| Absorption correction: numerical (SADABS; Krause et al., 2015) | k = −25→25 |
| Tmin = 0.69, Tmax = 0.89 | l = −12→12 |
| 48057 measured reflections |
Refinement
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: mixed |
| R[F2 > 2σ(F2)] = 0.023 | H-atom parameters constrained |
| wR(F2) = 0.052 | w = 1/[σ2(Fo2) + (0.0262P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.03 | (Δ/σ)max < 0.001 |
| 6797 reflections | Δρmax = 0.56 e Å−3 |
| 280 parameters | Δρmin = −0.22 e Å−3 |
| 2 restraints | Absolute structure: Parsons et al. (2013) |
| Primary atom site location: dual | Absolute structure parameter: 0.0130 (18) |
Special details
| 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. |
| Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 - 0.99 Å) while that attached to nitrogen was placed in a location derived from a difference map and its coordinates adjusted to give N—H = 0.91 %A. All were included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached atoms. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| Br1 | 0.44542 (2) | 0.28839 (2) | 0.58421 (2) | 0.02486 (6) | |
| S1 | 0.49752 (4) | 0.46885 (3) | 0.48367 (6) | 0.02090 (10) | |
| N1 | 0.62223 (12) | 0.54541 (10) | 0.3655 (2) | 0.0209 (3) | |
| N2 | 0.55946 (13) | 0.59721 (10) | 0.3976 (2) | 0.0224 (4) | |
| H2 | 0.543925 | 0.639353 | 0.338574 | 0.027* | |
| N3 | 0.42532 (11) | 0.59882 (9) | 0.49354 (19) | 0.0175 (3) | |
| C1 | 0.68896 (14) | 0.57005 (11) | 0.3140 (2) | 0.0200 (4) | |
| C2 | 0.74987 (14) | 0.51162 (12) | 0.2755 (2) | 0.0204 (4) | |
| C3 | 0.72405 (16) | 0.43611 (12) | 0.2725 (3) | 0.0253 (4) | |
| H3 | 0.668268 | 0.422211 | 0.298899 | 0.030* | |
| C4 | 0.77838 (18) | 0.38168 (12) | 0.2319 (3) | 0.0292 (5) | |
| H4 | 0.760010 | 0.330612 | 0.230188 | 0.035* | |
| C5 | 0.86007 (17) | 0.40157 (14) | 0.1934 (3) | 0.0307 (5) | |
| H5 | 0.897430 | 0.364250 | 0.164362 | 0.037* | |
| C6 | 0.88672 (17) | 0.47585 (13) | 0.1977 (3) | 0.0307 (5) | |
| H6 | 0.943027 | 0.489020 | 0.172126 | 0.037* | |
| C7 | 0.83287 (15) | 0.53211 (12) | 0.2386 (3) | 0.0247 (4) | |
| C8 | 0.86140 (18) | 0.61314 (13) | 0.2398 (4) | 0.0377 (6) | |
| H8A | 0.900626 | 0.620413 | 0.169772 | 0.045* | |
| H8B | 0.901484 | 0.627820 | 0.346198 | 0.045* | |
| C9 | 0.77120 (19) | 0.66194 (13) | 0.1863 (3) | 0.0335 (5) | |
| H9A | 0.732936 | 0.648836 | 0.077981 | 0.040* | |
| H9B | 0.790648 | 0.715091 | 0.188104 | 0.040* | |
| C10 | 0.70864 (16) | 0.65141 (12) | 0.2911 (3) | 0.0251 (4) | |
| H10A | 0.741830 | 0.674405 | 0.393677 | 0.030* | |
| H10B | 0.646075 | 0.677709 | 0.244715 | 0.030* | |
| C11 | 0.49537 (14) | 0.56397 (11) | 0.4544 (2) | 0.0181 (4) | |
| C12 | 0.39810 (15) | 0.47730 (11) | 0.5475 (2) | 0.0212 (4) | |
| H12 | 0.368071 | 0.436044 | 0.579688 | 0.025* | |
| C13 | 0.36779 (14) | 0.54826 (10) | 0.5468 (2) | 0.0174 (4) | |
| C14 | 0.28248 (14) | 0.57165 (11) | 0.5907 (2) | 0.0181 (4) | |
| C15 | 0.19406 (15) | 0.53523 (12) | 0.5184 (2) | 0.0248 (4) | |
| H15 | 0.189962 | 0.497890 | 0.442080 | 0.030* | |
| C16 | 0.11274 (16) | 0.55376 (13) | 0.5583 (3) | 0.0313 (5) | |
| H16 | 0.052661 | 0.529488 | 0.508398 | 0.038* | |
| C17 | 0.11875 (17) | 0.60770 (13) | 0.6709 (3) | 0.0307 (5) | |
| H17 | 0.062685 | 0.620568 | 0.697431 | 0.037* | |
| C18 | 0.20603 (17) | 0.64264 (12) | 0.7444 (3) | 0.0273 (5) | |
| H18 | 0.210020 | 0.678992 | 0.822524 | 0.033* | |
| C19 | 0.28772 (16) | 0.62514 (11) | 0.7051 (3) | 0.0214 (4) | |
| H19 | 0.347538 | 0.649539 | 0.756080 | 0.026* | |
| C20 | 0.40757 (14) | 0.68028 (11) | 0.4697 (2) | 0.0189 (4) | |
| H20A | 0.348715 | 0.693577 | 0.496169 | 0.023* | |
| H20B | 0.394775 | 0.692002 | 0.358296 | 0.023* | |
| C21 | 0.49177 (14) | 0.72801 (11) | 0.5665 (2) | 0.0188 (4) | |
| C22 | 0.52950 (17) | 0.72086 (12) | 0.7273 (3) | 0.0261 (4) | |
| H22 | 0.505130 | 0.683350 | 0.778964 | 0.031* | |
| C23 | 0.60270 (18) | 0.76845 (15) | 0.8124 (3) | 0.0329 (5) | |
| H23 | 0.627952 | 0.763814 | 0.922321 | 0.039* | |
| C24 | 0.63909 (17) | 0.82285 (15) | 0.7369 (3) | 0.0345 (5) | |
| H24 | 0.689705 | 0.855074 | 0.795090 | 0.041* | |
| C25 | 0.60187 (18) | 0.82998 (14) | 0.5785 (3) | 0.0371 (6) | |
| H25 | 0.626501 | 0.867479 | 0.527208 | 0.044* | |
| C26 | 0.52811 (19) | 0.78259 (12) | 0.4922 (3) | 0.0287 (5) | |
| H26 | 0.502782 | 0.787744 | 0.382335 | 0.034* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.03693 (11) | 0.01870 (9) | 0.02011 (9) | 0.00145 (9) | 0.01078 (7) | 0.00129 (8) |
| S1 | 0.0231 (2) | 0.0190 (2) | 0.0225 (2) | 0.00341 (19) | 0.01004 (18) | −0.00098 (19) |
| N1 | 0.0207 (8) | 0.0209 (8) | 0.0239 (8) | 0.0026 (7) | 0.0109 (7) | −0.0022 (7) |
| N2 | 0.0229 (8) | 0.0213 (9) | 0.0274 (9) | 0.0018 (7) | 0.0144 (7) | −0.0006 (7) |
| N3 | 0.0185 (8) | 0.0170 (7) | 0.0193 (8) | −0.0005 (6) | 0.0091 (6) | −0.0005 (6) |
| C1 | 0.0196 (9) | 0.0208 (9) | 0.0195 (9) | 0.0018 (8) | 0.0061 (7) | −0.0012 (7) |
| C2 | 0.0201 (9) | 0.0220 (10) | 0.0201 (9) | 0.0036 (8) | 0.0077 (8) | −0.0008 (8) |
| C3 | 0.0248 (10) | 0.0241 (10) | 0.0297 (11) | 0.0029 (8) | 0.0123 (9) | 0.0023 (8) |
| C4 | 0.0337 (12) | 0.0202 (10) | 0.0356 (12) | 0.0037 (9) | 0.0139 (10) | −0.0005 (9) |
| C5 | 0.0297 (12) | 0.0287 (11) | 0.0356 (12) | 0.0090 (9) | 0.0130 (10) | −0.0043 (9) |
| C6 | 0.0247 (11) | 0.0332 (12) | 0.0400 (13) | 0.0041 (9) | 0.0182 (10) | −0.0003 (10) |
| C7 | 0.0222 (10) | 0.0250 (10) | 0.0297 (11) | 0.0013 (8) | 0.0122 (9) | −0.0002 (9) |
| C8 | 0.0313 (13) | 0.0271 (12) | 0.0657 (18) | −0.0026 (9) | 0.0310 (13) | −0.0010 (12) |
| C9 | 0.0422 (13) | 0.0214 (10) | 0.0471 (15) | −0.0008 (10) | 0.0288 (12) | 0.0040 (10) |
| C10 | 0.0252 (11) | 0.0198 (10) | 0.0342 (12) | 0.0015 (8) | 0.0149 (9) | −0.0004 (9) |
| C11 | 0.0194 (9) | 0.0179 (9) | 0.0169 (9) | 0.0003 (7) | 0.0058 (7) | −0.0019 (7) |
| C12 | 0.0217 (9) | 0.0209 (9) | 0.0234 (10) | −0.0016 (8) | 0.0105 (8) | −0.0014 (8) |
| C13 | 0.0187 (9) | 0.0180 (9) | 0.0165 (8) | −0.0007 (7) | 0.0069 (7) | 0.0012 (7) |
| C14 | 0.0187 (9) | 0.0174 (9) | 0.0199 (9) | 0.0005 (7) | 0.0086 (7) | 0.0039 (7) |
| C15 | 0.0245 (10) | 0.0258 (11) | 0.0250 (10) | −0.0049 (8) | 0.0094 (8) | −0.0002 (8) |
| C16 | 0.0195 (10) | 0.0370 (13) | 0.0385 (13) | −0.0060 (9) | 0.0109 (9) | 0.0022 (10) |
| C17 | 0.0252 (11) | 0.0296 (12) | 0.0441 (13) | 0.0042 (9) | 0.0205 (10) | 0.0047 (10) |
| C18 | 0.0336 (12) | 0.0206 (10) | 0.0350 (12) | 0.0037 (9) | 0.0213 (10) | 0.0013 (9) |
| C19 | 0.0229 (10) | 0.0180 (9) | 0.0255 (10) | −0.0007 (8) | 0.0110 (8) | 0.0014 (8) |
| C20 | 0.0209 (9) | 0.0167 (9) | 0.0209 (9) | 0.0008 (7) | 0.0092 (8) | 0.0008 (7) |
| C21 | 0.0203 (10) | 0.0177 (9) | 0.0203 (9) | 0.0013 (7) | 0.0094 (8) | −0.0022 (7) |
| C22 | 0.0273 (11) | 0.0310 (11) | 0.0213 (10) | 0.0025 (8) | 0.0096 (9) | 0.0025 (8) |
| C23 | 0.0305 (12) | 0.0409 (13) | 0.0233 (11) | 0.0029 (10) | 0.0031 (9) | −0.0048 (10) |
| C24 | 0.0307 (12) | 0.0338 (13) | 0.0373 (13) | −0.0052 (10) | 0.0088 (10) | −0.0148 (10) |
| C25 | 0.0446 (15) | 0.0309 (13) | 0.0370 (13) | −0.0187 (11) | 0.0151 (11) | −0.0066 (10) |
| C26 | 0.0398 (13) | 0.0245 (11) | 0.0225 (11) | −0.0089 (9) | 0.0110 (10) | −0.0032 (8) |
Geometric parameters (Å, º)
| S1—C11 | 1.720 (2) | C10—H10B | 0.9900 |
| S1—C12 | 1.729 (2) | C12—C13 | 1.342 (3) |
| N1—C1 | 1.283 (3) | C12—H12 | 0.9500 |
| N1—N2 | 1.396 (2) | C13—C14 | 1.480 (3) |
| N2—C11 | 1.341 (3) | C14—C19 | 1.396 (3) |
| N2—H2 | 0.9100 | C14—C15 | 1.402 (3) |
| N3—C11 | 1.337 (2) | C15—C16 | 1.384 (3) |
| N3—C13 | 1.419 (2) | C15—H15 | 0.9500 |
| N3—C20 | 1.483 (2) | C16—C17 | 1.388 (3) |
| C1—C2 | 1.483 (3) | C16—H16 | 0.9500 |
| C1—C10 | 1.510 (3) | C17—C18 | 1.379 (3) |
| C2—C3 | 1.399 (3) | C17—H17 | 0.9500 |
| C2—C7 | 1.402 (3) | C18—C19 | 1.382 (3) |
| C3—C4 | 1.377 (3) | C18—H18 | 0.9500 |
| C3—H3 | 0.9500 | C19—H19 | 0.9500 |
| C4—C5 | 1.388 (3) | C20—C21 | 1.519 (3) |
| C4—H4 | 0.9500 | C20—H20A | 0.9900 |
| C5—C6 | 1.381 (3) | C20—H20B | 0.9900 |
| C5—H5 | 0.9500 | C21—C26 | 1.384 (3) |
| C6—C7 | 1.397 (3) | C21—C22 | 1.391 (3) |
| C6—H6 | 0.9500 | C22—C23 | 1.387 (3) |
| C7—C8 | 1.506 (3) | C22—H22 | 0.9500 |
| C8—C9 | 1.519 (4) | C23—C24 | 1.389 (4) |
| C8—H8A | 0.9900 | C23—H23 | 0.9500 |
| C8—H8B | 0.9900 | C24—C25 | 1.370 (4) |
| C9—C10 | 1.525 (3) | C24—H24 | 0.9500 |
| C9—H9A | 0.9900 | C25—C26 | 1.394 (3) |
| C9—H9B | 0.9900 | C25—H25 | 0.9500 |
| C10—H10A | 0.9900 | C26—H26 | 0.9500 |
| C11—S1—C12 | 89.42 (10) | N2—C11—S1 | 121.16 (15) |
| C1—N1—N2 | 118.09 (17) | C13—C12—S1 | 112.95 (15) |
| C11—N2—N1 | 111.65 (17) | C13—C12—H12 | 123.5 |
| C11—N2—H2 | 121.5 | S1—C12—H12 | 123.5 |
| N1—N2—H2 | 118.8 | C12—C13—N3 | 112.01 (17) |
| C11—N3—C13 | 112.19 (16) | C12—C13—C14 | 124.63 (17) |
| C11—N3—C20 | 122.06 (16) | N3—C13—C14 | 123.33 (16) |
| C13—N3—C20 | 125.56 (15) | C19—C14—C15 | 119.26 (19) |
| N1—C1—C2 | 115.06 (19) | C19—C14—C13 | 122.95 (18) |
| N1—C1—C10 | 125.46 (19) | C15—C14—C13 | 117.71 (18) |
| C2—C1—C10 | 119.48 (18) | C16—C15—C14 | 119.9 (2) |
| C3—C2—C7 | 119.61 (19) | C16—C15—H15 | 120.0 |
| C3—C2—C1 | 120.48 (18) | C14—C15—H15 | 120.0 |
| C7—C2—C1 | 119.89 (19) | C15—C16—C17 | 120.2 (2) |
| C4—C3—C2 | 120.9 (2) | C15—C16—H16 | 119.9 |
| C4—C3—H3 | 119.6 | C17—C16—H16 | 119.9 |
| C2—C3—H3 | 119.6 | C18—C17—C16 | 120.1 (2) |
| C3—C4—C5 | 119.9 (2) | C18—C17—H17 | 120.0 |
| C3—C4—H4 | 120.1 | C16—C17—H17 | 120.0 |
| C5—C4—H4 | 120.1 | C17—C18—C19 | 120.4 (2) |
| C6—C5—C4 | 119.7 (2) | C17—C18—H18 | 119.8 |
| C6—C5—H5 | 120.2 | C19—C18—H18 | 119.8 |
| C4—C5—H5 | 120.2 | C18—C19—C14 | 120.1 (2) |
| C5—C6—C7 | 121.6 (2) | C18—C19—H19 | 119.9 |
| C5—C6—H6 | 119.2 | C14—C19—H19 | 119.9 |
| C7—C6—H6 | 119.2 | N3—C20—C21 | 113.39 (16) |
| C6—C7—C2 | 118.4 (2) | N3—C20—H20A | 108.9 |
| C6—C7—C8 | 121.2 (2) | C21—C20—H20A | 108.9 |
| C2—C7—C8 | 120.42 (19) | N3—C20—H20B | 108.9 |
| C7—C8—C9 | 110.03 (19) | C21—C20—H20B | 108.9 |
| C7—C8—H8A | 109.7 | H20A—C20—H20B | 107.7 |
| C9—C8—H8A | 109.7 | C26—C21—C22 | 119.5 (2) |
| C7—C8—H8B | 109.7 | C26—C21—C20 | 118.49 (19) |
| C9—C8—H8B | 109.7 | C22—C21—C20 | 121.89 (19) |
| H8A—C8—H8B | 108.2 | C23—C22—C21 | 120.1 (2) |
| C8—C9—C10 | 110.9 (2) | C23—C22—H22 | 120.0 |
| C8—C9—H9A | 109.5 | C21—C22—H22 | 120.0 |
| C10—C9—H9A | 109.5 | C22—C23—C24 | 120.1 (2) |
| C8—C9—H9B | 109.5 | C22—C23—H23 | 120.0 |
| C10—C9—H9B | 109.5 | C24—C23—H23 | 120.0 |
| H9A—C9—H9B | 108.0 | C25—C24—C23 | 119.9 (2) |
| C1—C10—C9 | 112.50 (18) | C25—C24—H24 | 120.1 |
| C1—C10—H10A | 109.1 | C23—C24—H24 | 120.1 |
| C9—C10—H10A | 109.1 | C24—C25—C26 | 120.4 (2) |
| C1—C10—H10B | 109.1 | C24—C25—H25 | 119.8 |
| C9—C10—H10B | 109.1 | C26—C25—H25 | 119.8 |
| H10A—C10—H10B | 107.8 | C21—C26—C25 | 120.0 (2) |
| N3—C11—N2 | 125.43 (18) | C21—C26—H26 | 120.0 |
| N3—C11—S1 | 113.41 (14) | C25—C26—H26 | 120.0 |
| C1—N1—N2—C11 | −178.27 (18) | C11—S1—C12—C13 | −0.65 (16) |
| N2—N1—C1—C2 | −177.26 (17) | S1—C12—C13—N3 | 0.0 (2) |
| N2—N1—C1—C10 | 2.7 (3) | S1—C12—C13—C14 | 177.93 (15) |
| N1—C1—C2—C3 | 10.0 (3) | C11—N3—C13—C12 | 0.9 (2) |
| C10—C1—C2—C3 | −170.0 (2) | C20—N3—C13—C12 | 176.04 (18) |
| N1—C1—C2—C7 | −171.39 (19) | C11—N3—C13—C14 | −177.07 (18) |
| C10—C1—C2—C7 | 8.6 (3) | C20—N3—C13—C14 | −1.9 (3) |
| C7—C2—C3—C4 | −0.8 (3) | C12—C13—C14—C19 | 125.0 (2) |
| C1—C2—C3—C4 | 177.8 (2) | N3—C13—C14—C19 | −57.4 (3) |
| C2—C3—C4—C5 | 0.1 (3) | C12—C13—C14—C15 | −51.8 (3) |
| C3—C4—C5—C6 | 0.6 (4) | N3—C13—C14—C15 | 125.9 (2) |
| C4—C5—C6—C7 | −0.6 (4) | C19—C14—C15—C16 | 1.5 (3) |
| C5—C6—C7—C2 | −0.2 (4) | C13—C14—C15—C16 | 178.37 (19) |
| C5—C6—C7—C8 | −178.8 (2) | C14—C15—C16—C17 | −0.7 (3) |
| C3—C2—C7—C6 | 0.8 (3) | C15—C16—C17—C18 | −0.5 (4) |
| C1—C2—C7—C6 | −177.8 (2) | C16—C17—C18—C19 | 0.9 (4) |
| C3—C2—C7—C8 | 179.5 (2) | C17—C18—C19—C14 | −0.2 (3) |
| C1—C2—C7—C8 | 0.8 (3) | C15—C14—C19—C18 | −1.1 (3) |
| C6—C7—C8—C9 | 144.2 (2) | C13—C14—C19—C18 | −177.76 (19) |
| C2—C7—C8—C9 | −34.4 (3) | C11—N3—C20—C21 | −64.4 (2) |
| C7—C8—C9—C10 | 58.8 (3) | C13—N3—C20—C21 | 120.94 (19) |
| N1—C1—C10—C9 | −163.3 (2) | N3—C20—C21—C26 | 128.1 (2) |
| C2—C1—C10—C9 | 16.7 (3) | N3—C20—C21—C22 | −55.2 (2) |
| C8—C9—C10—C1 | −50.3 (3) | C26—C21—C22—C23 | 0.3 (3) |
| C13—N3—C11—N2 | 178.69 (19) | C20—C21—C22—C23 | −176.3 (2) |
| C20—N3—C11—N2 | 3.3 (3) | C21—C22—C23—C24 | −0.6 (4) |
| C13—N3—C11—S1 | −1.4 (2) | C22—C23—C24—C25 | 0.7 (4) |
| C20—N3—C11—S1 | −176.74 (14) | C23—C24—C25—C26 | −0.5 (4) |
| N1—N2—C11—N3 | −178.87 (18) | C22—C21—C26—C25 | −0.1 (4) |
| N1—N2—C11—S1 | 1.2 (2) | C20—C21—C26—C25 | 176.6 (2) |
| C12—S1—C11—N3 | 1.18 (15) | C24—C25—C26—C21 | 0.2 (4) |
| C12—S1—C11—N2 | −178.90 (18) |
Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2···Br1i | 0.91 | 2.63 | 3.4633 (18) | 152 |
| C10—H10B···Br1i | 0.99 | 2.88 | 3.837 (2) | 164 |
| C20—H20B···Br1i | 0.99 | 2.84 | 3.7560 (19) | 155 |
| C26—H26···Br1i | 0.95 | 2.90 | 3.730 (2) | 146 |
Symmetry code: (i) x, −y+1, z−1/2.
Comparison of pertinent bond lengths and angles (Å, °)
| Metric* | I | BOCROC | NUCLOO | QOCGIA |
| a | 1.720 (2) | 1.711 (4) | 1.7182 (15) | 1.740 (2) |
| b | 1.729 (2) | 1.740 (4) | 1.7373 (15) | 1.735 (3) |
| c | 1.419 (2) | 1.417 (5) | 1.3974 (19) | 1.414 (4) |
| d | 1.337 (2) | 1.341 (4) | 1.3314 (19) | 1.373 (4) |
| e | 1.341 (3) | 1.329 (5) | 1.328 (2) | 1.309 (3) |
| f | 1.396 (2) | 1.395 (4) | 1.3806 (17) | 1.381 (3) |
| g | 1.283 (3) | 1.275 (5) | 1.280 (2) | 1.293 (4) |
| h | 121.16 (15) | 123.0 (3) | 124.94 (11) | 126.51 (19) |
| i | 125.43 (18) | 123.8 (3) | 122.85 (13) | 122.3 (2) |
| j | 111.65 (17) | 114.9 (3) | 117.49 (12) | 109.4 (2) |
| k | 118.09 (17) | 115.5 (3) | 114.40 (13) | 116.0 (2) |
*Key is A in Scheme 2.
Funding Statement
This work was funded by Tulane University grant .
References
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989021002863/hb7963sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989021002863/hb7963Isup2.hkl
Geometrical data for title compound and related phases. DOI: 10.1107/S2056989021002863/hb7963sup3.pdf
Supporting information file. DOI: 10.1107/S2056989021002863/hb7963Isup5.cml
CCDC reference: 2071135
Additional supporting information: crystallographic information; 3D view; checkCIF report