research communications
Syntheses and crystal structures of benzyl N′-[(E)-2-hydroxybenzylidene]hydrazinecarboxylate and benzyl N′-[(E)-5-bromo-2-hydroxybenzylidene]hydrazinecarboxylate
aDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysuru-570 006, India, and bDepartment of Chemistry, University of Kentucky, Lexington, KY, 40506-0055, USA
*Correspondence e-mail: yathirajan@hotmail.com
Benzyl N′-[(E)-2-hydroxybenzylidene]hydrazinecarboxylate, C15H14N2O3 (I) and benzyl N′-[(E)-5-bromo-2-hydroxybenzylidene]hydrazinecarboxylate (II), C15H13BrN2O3, have been synthesized by the reaction of either 2-hydroxybenzaldehyde or 5-bromo-2-hydroxybenzaldehyde with benzyl carbazate, respectively. Both the compounds crystallize in the monoclinic with space groups Pn (Z′ = 1, I) and P21/c (Z′ = 2, II). Molecular conformations in each structure are similar, and both structures feature strong intramolecular O—H⋯N hydrogen bonds, which form S(6) ring motifs. There are also strong N—H⋯O and weak C—H⋯O hydrogen bonds in both structures, but their modes of packing within their respective crystals are markedly different. Some comparisons are made with the structures of a few related compounds.
1. Chemical context
Hydroxybenzylidene et al., 2017). Benzaldehydehydrazone derivatives have received considerable attention for several decades as a result of their pharmacological activity (Parashar et al., 1988) and photochromic properties (Hadjoudis et al., 1987). Benzaldehydehydrazone derivatives are also important intermediates in the synthesis of 1,3,4-oxadiazoles, which are versatile compounds with many useful properties (Borg et al., 1999). Synthesis and biological activities of new hydrazide derivatives (Özdemir et al., 2009) and biological activities of hydrazone derivatives (Rollas & Küçükgüzel, 2007) have been reported. In view of the importance of benzylidene and benzaldehydehydrazone derivatives in general, this paper reports the crystal structures of the title compounds, C15H14N2O3 (I), and C15H13BrN2O3 (II).
exhibit a wide spectrum of biological activities (Sersen2. Structural commentary
The molecular structures of benzyl N′-[(E)-2-hydroxybenzylidene]hydrazinecarboxylate (I) (Fig. 1) and benzyl N′-[(E)-5-bromo-2-hydroxybenzylidene]hydrazinecarboxylate (II) (Fig. 2) each consist of a central N′-methylidenemethoxycarboxyl core flanked by a benzyl group attached to the singly bonded oxygen and a 2-hydroxyphenyl (I) or 5-bromo-2-hydroxyphenyl (II) attached to the methylidene. There are no unusual bond lengths or angles in either structure. The molecules have strong intramolecular O—H⋯N hydrogen bonds (Tables 1 and 2), forming S(6) ring motifs (Etter et al., 1990). The of I contains a single molecule while that of II contains two (labelled A and B in Fig. 2). In each case, the [(hydroxyphenyl)methylidene]carbohydrazide moieties are essentially planar [r.m.s. deviations 0.0429 Å (I), 0.0905 Å (IIA), 0.0692 (IIB)]. These form dihedral angles of 79.92 (3)°, 79.74 (4)°, and 74.27 (4)° to the benzyl groups of I, IIA, and IIB, respectively. Indeed, the V-shaped conformations of IIA, and IIB are strikingly similar, with I only deviating to any appreciable degree at the benzyl group, as evidenced by an overlay of the three molecules (Fig. 3). The conformation of I differs from IIA and IIB primarily by the torsion angles about bonds O2—C9 and C9—C10 (Table 3).
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3. Supramolecular features
In addition to the strong O—H⋯N intramolecular hydrogen bonds in I and II, the structures both feature strong N—H⋯O and weaker C—H⋯O intermolecular hydrogen bonds. These interactions are summarized in Tables 1 and 2. The packing modes are, however, quite different.
In I, the V-shaped (Fig. 3) molecules stack into columns along [100] (Fig. 4). These columns interact with n-glide-related columns via the strong N2—H2N⋯O1i (symmetry codes as per Table 1) hydrogen bonds to give C(7) chains (Etter et al., 1990) and with different n-glide-related columns via the bifurcated C6—H6⋯O3ii and C7—H7⋯O3ii (Table 1) hydrogen bonds. In combination, these interactions produce layers that extend in the ac plane (Fig. 5), which in turn stack along [010].
In II, the independent molecules (A and B) make hydrogen bonds to 21-screw-related copies of themselves via strong (N2—H2N⋯O1) and weak (C3—H3⋯O2 and C6—H6⋯O3) hydrogen bonds (Table 2), forming R22(8) and R33(13) ring motifs (Etter et al., 1990), leading to adjacent pairs of ribbons that extend along [010] (Fig. 6). The 5-bromo-2-hydroxyphenyl and benzyl groups of IIA and IIB have notably different environments. For example, inversion-related (−x, −y, −z) pairs of IIA molecules have close contacts of 3.3379 (9) Å between their Br1A atoms and the centroid of the inversion-related C10A–C15A ring. There is no corresponding close contact for the IIB molecule (Fig. 7).
The differences in packing are also apparent in the atom–atom contact coverages, as quantified by CrystalExplorer (Spackman et al., 2021) fingerprint diagrams (Figs. 8 and 9).
4. Database survey
A search of the Cambridge Structure Database (CSD, v5.43 with updates as of June 2022; Groom et al., 2016) for a search fragment consisting of the structure of I, but with the two aromatic rings replaced by `any group' gave 340 hits. A fragment including the benzyl group attached to the equivalent of O2 in I/II gave 105 hits, while a fragment including a phenyl ring at C7 gave 37 hits. A fragment consisting of I but without the phenolic OH group gave just four hits: HIXQIQ (Dong & Wang, 2014), QAVFAY (Shen et al., 2022), GEZTUD (Chang et al., 2018) and PIVKUD (Zhang et al., 2019). In HIXQIQ, a 5-chloro-2-hydroxy-2-(methoxycarbonyl)-2,3-dihydro-1H-inden-1-ylidene) group is attached to the hydrazine. QAVFAY features a four-membered 1,2-diazete ring, with the phenyl group fluorinated at its 4-position. Structures GEZTUD and PIVKUD each feature pyrazole rings; the former having a 2,2,2-trifluoroethyl group attached to the pyrazole and a methyl at the 4-position of the phenyl ring, and the latter having a 3,4,5-trimethoxyphenyl attached to its pyrazole ring.
New E)-benzyl 2-[1-(pyridin-3-yl)ethylidene]hydrazine-1-carboxylate (JENFEQ), (E)-benzyl2-[1-(pyridin-4-yl)ethylidene]hydrazinecarboxylate (JENFIU) (Nithya et al., 2017) have also been reported. A selection of other structures similar to I and II deposited in the CSD are listed in Table 4.
derived from benzyl carbazate with alkyl and heteroaryl and crystal structures of benzyl 2-cyclopentylidenehydrazinecarboxylate (JENFAM, (
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5. Synthesis and crystallization
Preparation of I and II followed similar synthetic routes. Either 2-hydroxybenzaldehyde (1.2 g, 0.01 mol) (for I) or 5-bromo-2-hydroxybenzaldehyde (2.0 g, 0.01 mol) (for II) and benzyl carbazate (1.66 g, 0.01 mol) were dissolved in methanol (25 ml) and stirred for 3 h at room temperature. The resulting solids were filtered off and recrystallized from ethanol to give I and II with yields of 80% in both cases. The general reaction scheme is summarized in Fig. 10. Single crystals suitable for X-ray analysis for both I and II were obtained by slow evaporation of methanolic solutions at room temperature (m.p.: 400–402 K for I and 468–470 K for II).
6. Crystal handling, data collection, and refinement
Crystals of I and II were each secured on the tips of fine glass fibres held in copper mounting pins. The crystal of I was mounted from a shallow liquid-nitrogen dewar using tongs first developed for protein cryocrystallography (Parkin & Hope, 1998), while the crystal of II was mounted directly into a cold-nitrogen stream. Data for both samples (Cu Kα for I and Mo Kα for II) were collected with the crystals held at 90.0 (2) K. Determination of the for I was inconclusive via traditional full-matrix of Flack's parameter [x = −0.08 (18); Flack & Bernardinelli, 1999], but Hooft's Bayesian approach [y = 0.00 (8); Hooft et al. (2008), as calculated using PLATON (Spek, 2020)] and Parsons' quotient method [z = 0.04 (10); Parsons et al., 2013] give credence to the assignment. progress was checked using PLATON (Spek, 2020) and by an R-tensor (Parkin, 2000). Crystal data, data collection, and are summarized in Table 5. Carbon-bound hydrogen atoms were included using riding models, with C—H distances constrained to 0.95 Å for Csp2H and 0.99 Å for R2CH2. N—H and O—H hydrogen-atom coordinates were refined. Uiso(H) parameters were set to values of either 1.2Ueq (C—H, N—H) or 1.5Ueq (O—H) of the attached atom.
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Supporting information
https://doi.org/10.1107/S2056989022009100/yk2176sup1.cif
contains datablocks I, II, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022009100/yk2176Isup4.hkl
Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989022009100/yk2176IIsup5.hkl
For both structures, data collection: APEX3 (Bruker, 2016); cell
APEX3 (Bruker, 2016); data reduction: APEX3 (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2019/2 (Sheldrick, 2015b); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: CIFFIX (Parkin, 2013) and publCIF (Westrip, 2010).C15H14N2O3 | F(000) = 284 |
Mr = 270.28 | Dx = 1.351 Mg m−3 |
Monoclinic, Pn | Cu Kα radiation, λ = 1.54184 Å |
a = 4.5017 (12) Å | Cell parameters from 6841 reflections |
b = 14.047 (4) Å | θ = 3.1–74.4° |
c = 10.567 (3) Å | µ = 0.79 mm−1 |
β = 96.300 (15)° | T = 90 K |
V = 664.2 (3) Å3 | Plate, colourless |
Z = 2 | 0.41 × 0.23 × 0.02 mm |
Bruker D8 Venture dual source diffractometer | 2511 independent reflections |
Radiation source: microsource | 2425 reflections with I > 2σ(I) |
Detector resolution: 7.41 pixels mm-1 | Rint = 0.028 |
φ and ω scans | θmax = 74.6°, θmin = 3.2° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −5→5 |
Tmin = 0.589, Tmax = 0.958 | k = −17→16 |
7271 measured reflections | l = −13→12 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.024 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.063 | w = 1/[σ2(Fo2) + (0.0283P)2 + 0.0531P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
2511 reflections | Δρmax = 0.13 e Å−3 |
187 parameters | Δρmin = −0.13 e Å−3 |
2 restraints | Absolute structure: Flack x determined using 1054 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.04 (10) |
Experimental. The crystal was mounted using polyisobutene oil on the tip of a fine glass fibre, which was fastened in a copper mounting pin with electrical solder. It was flash-cooled in liquid nitrogen and mounted into the cold gas stream of a liquid-nitrogen based cryostat using specially designed tongs (Parkin & Hope, 1998). Diffraction data were collected with the crystal at 90K, which is standard practice in this laboratory for the majority of flash-cooled crystals. |
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 progress was checked using Platon (Spek, 2020) and by an R-tensor (Parkin, 2000). The final model was further checked with the IUCr utility checkCIF. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.7525 (3) | 0.44387 (9) | 0.34649 (11) | 0.0268 (3) | |
H1O | 0.631 (6) | 0.4786 (18) | 0.391 (3) | 0.040* | |
O2 | −0.0407 (3) | 0.67535 (9) | 0.56997 (11) | 0.0243 (3) | |
O3 | 0.2021 (3) | 0.64243 (9) | 0.39780 (11) | 0.0248 (3) | |
N1 | 0.4688 (3) | 0.49495 (10) | 0.53076 (13) | 0.0202 (3) | |
N2 | 0.2728 (3) | 0.55477 (11) | 0.58048 (13) | 0.0214 (3) | |
H2N | 0.242 (5) | 0.5508 (15) | 0.660 (2) | 0.026* | |
C1 | 0.7887 (3) | 0.36137 (13) | 0.54751 (15) | 0.0205 (3) | |
C2 | 0.8612 (4) | 0.37060 (12) | 0.42217 (16) | 0.0221 (4) | |
C3 | 1.0493 (4) | 0.30492 (14) | 0.37311 (16) | 0.0275 (4) | |
H3 | 1.101603 | 0.312160 | 0.288959 | 0.033* | |
C4 | 1.1602 (4) | 0.22882 (14) | 0.44739 (19) | 0.0300 (4) | |
H4 | 1.284895 | 0.183155 | 0.413092 | 0.036* | |
C5 | 1.0907 (4) | 0.21882 (14) | 0.57132 (18) | 0.0289 (4) | |
H5 | 1.168389 | 0.166681 | 0.621816 | 0.035* | |
C6 | 0.9082 (4) | 0.28486 (13) | 0.62116 (15) | 0.0244 (4) | |
H6 | 0.863234 | 0.278254 | 0.706480 | 0.029* | |
C7 | 0.5866 (4) | 0.42754 (12) | 0.60123 (15) | 0.0204 (3) | |
H7 | 0.542993 | 0.420844 | 0.686734 | 0.025* | |
C8 | 0.1509 (4) | 0.62582 (12) | 0.50506 (15) | 0.0196 (3) | |
C9 | −0.1607 (4) | 0.76046 (13) | 0.50546 (17) | 0.0251 (4) | |
H9A | −0.343944 | 0.780464 | 0.542188 | 0.030* | |
H9B | −0.215620 | 0.746317 | 0.414103 | 0.030* | |
C10 | 0.0630 (4) | 0.83981 (12) | 0.51860 (17) | 0.0231 (4) | |
C11 | 0.1698 (4) | 0.87256 (14) | 0.63955 (19) | 0.0311 (4) | |
H11 | 0.100670 | 0.844554 | 0.712731 | 0.037* | |
C12 | 0.3763 (5) | 0.94578 (15) | 0.6533 (2) | 0.0401 (5) | |
H12 | 0.448310 | 0.967698 | 0.736024 | 0.048* | |
C13 | 0.4787 (5) | 0.98720 (14) | 0.5483 (3) | 0.0418 (6) | |
H13 | 0.619778 | 1.037661 | 0.558367 | 0.050* | |
C14 | 0.3742 (5) | 0.95472 (15) | 0.4275 (2) | 0.0390 (5) | |
H14 | 0.444340 | 0.982844 | 0.354578 | 0.047* | |
C15 | 0.1674 (4) | 0.88122 (13) | 0.41314 (18) | 0.0285 (4) | |
H15 | 0.096956 | 0.859121 | 0.330295 | 0.034* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0369 (8) | 0.0313 (7) | 0.0138 (5) | 0.0058 (5) | 0.0090 (5) | 0.0020 (5) |
O2 | 0.0269 (6) | 0.0267 (6) | 0.0202 (6) | 0.0045 (5) | 0.0066 (5) | 0.0022 (5) |
O3 | 0.0317 (6) | 0.0292 (6) | 0.0137 (5) | 0.0005 (5) | 0.0040 (4) | 0.0007 (5) |
N1 | 0.0235 (7) | 0.0242 (7) | 0.0132 (6) | 0.0005 (5) | 0.0041 (5) | −0.0019 (5) |
N2 | 0.0259 (8) | 0.0276 (8) | 0.0117 (6) | 0.0044 (6) | 0.0064 (5) | −0.0001 (5) |
C1 | 0.0217 (8) | 0.0251 (8) | 0.0148 (7) | −0.0008 (6) | 0.0029 (6) | −0.0008 (6) |
C2 | 0.0246 (8) | 0.0262 (9) | 0.0154 (7) | −0.0010 (7) | 0.0025 (6) | −0.0011 (7) |
C3 | 0.0322 (10) | 0.0338 (10) | 0.0172 (8) | 0.0015 (7) | 0.0062 (7) | −0.0041 (7) |
C4 | 0.0304 (10) | 0.0316 (10) | 0.0285 (9) | 0.0069 (8) | 0.0053 (7) | −0.0079 (8) |
C5 | 0.0313 (9) | 0.0284 (9) | 0.0265 (9) | 0.0061 (7) | 0.0009 (7) | 0.0018 (7) |
C6 | 0.0268 (8) | 0.0290 (9) | 0.0174 (8) | 0.0020 (7) | 0.0024 (7) | 0.0011 (6) |
C7 | 0.0233 (8) | 0.0269 (8) | 0.0114 (7) | −0.0004 (6) | 0.0035 (6) | 0.0001 (6) |
C8 | 0.0212 (8) | 0.0231 (8) | 0.0144 (8) | −0.0021 (6) | 0.0019 (6) | −0.0019 (6) |
C9 | 0.0216 (8) | 0.0278 (9) | 0.0256 (8) | 0.0037 (7) | 0.0009 (7) | 0.0018 (7) |
C10 | 0.0194 (7) | 0.0252 (9) | 0.0243 (8) | 0.0063 (6) | 0.0009 (6) | −0.0018 (7) |
C11 | 0.0254 (9) | 0.0386 (11) | 0.0290 (9) | 0.0068 (8) | 0.0010 (7) | −0.0067 (8) |
C12 | 0.0287 (10) | 0.0389 (11) | 0.0503 (13) | 0.0061 (8) | −0.0067 (9) | −0.0187 (9) |
C13 | 0.0240 (9) | 0.0252 (10) | 0.0741 (16) | 0.0034 (8) | −0.0039 (10) | −0.0034 (10) |
C14 | 0.0279 (10) | 0.0339 (11) | 0.0552 (12) | 0.0039 (8) | 0.0042 (9) | 0.0155 (10) |
C15 | 0.0251 (9) | 0.031 (1) | 0.0290 (9) | 0.0055 (7) | 0.0012 (7) | 0.0053 (7) |
O1—C2 | 1.361 (2) | C5—H5 | 0.9500 |
O1—H1O | 0.90 (3) | C6—H6 | 0.9500 |
O2—C8 | 1.352 (2) | C7—H7 | 0.9500 |
O2—C9 | 1.451 (2) | C9—C10 | 1.498 (2) |
O3—C8 | 1.204 (2) | C9—H9A | 0.9900 |
N1—C7 | 1.283 (2) | C9—H9B | 0.9900 |
N1—N2 | 1.365 (2) | C10—C15 | 1.384 (3) |
N2—C8 | 1.355 (2) | C10—C11 | 1.393 (3) |
N2—H2N | 0.87 (2) | C11—C12 | 1.383 (3) |
C1—C6 | 1.399 (2) | C11—H11 | 0.9500 |
C1—C2 | 1.405 (2) | C12—C13 | 1.376 (4) |
C1—C7 | 1.459 (2) | C12—H12 | 0.9500 |
C2—C3 | 1.390 (3) | C13—C14 | 1.388 (4) |
C3—C4 | 1.386 (3) | C13—H13 | 0.9500 |
C3—H3 | 0.9500 | C14—C15 | 1.387 (3) |
C4—C5 | 1.387 (3) | C14—H14 | 0.9500 |
C4—H4 | 0.9500 | C15—H15 | 0.9500 |
C5—C6 | 1.381 (3) | ||
C2—O1—H1O | 107.5 (17) | O3—C8—O2 | 125.21 (16) |
C8—O2—C9 | 114.27 (13) | O3—C8—N2 | 126.12 (17) |
C7—N1—N2 | 118.33 (14) | O2—C8—N2 | 108.67 (14) |
C8—N2—N1 | 117.65 (14) | O2—C9—C10 | 110.94 (13) |
C8—N2—H2N | 121.3 (14) | O2—C9—H9A | 109.5 |
N1—N2—H2N | 120.8 (15) | C10—C9—H9A | 109.5 |
C6—C1—C2 | 118.71 (16) | O2—C9—H9B | 109.5 |
C6—C1—C7 | 119.42 (15) | C10—C9—H9B | 109.5 |
C2—C1—C7 | 121.85 (15) | H9A—C9—H9B | 108.0 |
O1—C2—C3 | 118.50 (16) | C15—C10—C11 | 119.09 (18) |
O1—C2—C1 | 121.20 (16) | C15—C10—C9 | 121.48 (16) |
C3—C2—C1 | 120.30 (16) | C11—C10—C9 | 119.43 (17) |
C4—C3—C2 | 119.79 (17) | C12—C11—C10 | 120.1 (2) |
C4—C3—H3 | 120.1 | C12—C11—H11 | 119.9 |
C2—C3—H3 | 120.1 | C10—C11—H11 | 119.9 |
C3—C4—C5 | 120.55 (17) | C13—C12—C11 | 120.7 (2) |
C3—C4—H4 | 119.7 | C13—C12—H12 | 119.7 |
C5—C4—H4 | 119.7 | C11—C12—H12 | 119.7 |
C6—C5—C4 | 119.83 (17) | C12—C13—C14 | 119.5 (2) |
C6—C5—H5 | 120.1 | C12—C13—H13 | 120.2 |
C4—C5—H5 | 120.1 | C14—C13—H13 | 120.2 |
C5—C6—C1 | 120.81 (16) | C15—C14—C13 | 120.0 (2) |
C5—C6—H6 | 119.6 | C15—C14—H14 | 120.0 |
C1—C6—H6 | 119.6 | C13—C14—H14 | 120.0 |
N1—C7—C1 | 118.70 (14) | C10—C15—C14 | 120.53 (19) |
N1—C7—H7 | 120.7 | C10—C15—H15 | 119.7 |
C1—C7—H7 | 120.7 | C14—C15—H15 | 119.7 |
C7—N1—N2—C8 | 179.79 (15) | C9—O2—C8—O3 | −7.2 (2) |
C6—C1—C2—O1 | −179.68 (16) | C9—O2—C8—N2 | 173.15 (13) |
C7—C1—C2—O1 | 2.1 (2) | N1—N2—C8—O3 | −1.1 (3) |
C6—C1—C2—C3 | −0.3 (2) | N1—N2—C8—O2 | 178.58 (13) |
C7—C1—C2—C3 | −178.51 (16) | C8—O2—C9—C10 | −78.01 (18) |
O1—C2—C3—C4 | −179.13 (17) | O2—C9—C10—C15 | 119.80 (18) |
C1—C2—C3—C4 | 1.4 (3) | O2—C9—C10—C11 | −59.9 (2) |
C2—C3—C4—C5 | −1.5 (3) | C15—C10—C11—C12 | 0.3 (3) |
C3—C4—C5—C6 | 0.3 (3) | C9—C10—C11—C12 | −179.98 (17) |
C4—C5—C6—C1 | 0.9 (3) | C10—C11—C12—C13 | 0.1 (3) |
C2—C1—C6—C5 | −0.9 (3) | C11—C12—C13—C14 | −0.3 (3) |
C7—C1—C6—C5 | 177.40 (16) | C12—C13—C14—C15 | 0.2 (3) |
N2—N1—C7—C1 | 178.01 (14) | C11—C10—C15—C14 | −0.4 (3) |
C6—C1—C7—N1 | −177.06 (15) | C9—C10—C15—C14 | 179.89 (17) |
C2—C1—C7—N1 | 1.2 (2) | C13—C14—C15—C10 | 0.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···N1 | 0.90 (3) | 1.73 (3) | 2.546 (2) | 148 (2) |
N2—H2N···O1i | 0.87 (2) | 1.97 (2) | 2.8225 (19) | 168 (2) |
C7—H7···O3ii | 0.95 | 2.43 | 3.271 (2) | 147 |
Symmetry codes: (i) x−1/2, −y+1, z+1/2; (ii) x+1/2, −y+1, z+1/2. |
C15H13BrN2O3 | F(000) = 1408 |
Mr = 349.18 | Dx = 1.654 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 27.904 (2) Å | Cell parameters from 9936 reflections |
b = 11.1207 (6) Å | θ = 2.3–27.5° |
c = 9.0648 (7) Å | µ = 2.94 mm−1 |
β = 94.485 (2)° | T = 90 K |
V = 2804.3 (3) Å3 | Plate, colourless |
Z = 8 | 0.24 × 0.22 × 0.05 mm |
Bruker D8 Venture dual source diffractometer | 6401 independent reflections |
Radiation source: microsource | 5004 reflections with I > 2σ(I) |
Detector resolution: 7.41 pixels mm-1 | Rint = 0.047 |
φ and ω scans | θmax = 27.5°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −36→36 |
Tmin = 0.598, Tmax = 0.862 | k = −13→14 |
36145 measured reflections | l = −11→11 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.028 | Hydrogen site location: mixed |
wR(F2) = 0.064 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.024P)2 + 0.4336P] where P = (Fo2 + 2Fc2)/3 |
6401 reflections | (Δ/σ)max = 0.001 |
391 parameters | Δρmax = 0.36 e Å−3 |
0 restraints | Δρmin = −0.39 e Å−3 |
Experimental. The crystal was mounted using polyisobutene oil on the tip of a fine glass fibre, which was fastened in a copper mounting pin with electrical solder. It was placed directly into the cold gas stream of a liquid-nitrogen based cryostat (Parkin & Hope, 1998). Diffraction data were collected with the crystal at 90K, which is standard practice in this laboratory for the majority of flash-cooled crystals. |
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 progress was checked using Platon (Spek, 2020) and by an R-tensor (Parkin, 2000). The final model was further checked with the IUCr utility checkCIF. |
x | y | z | Uiso*/Ueq | ||
Br1A | −0.15724 (2) | 0.00040 (2) | −0.27291 (2) | 0.01837 (6) | |
O1A | −0.03689 (5) | 0.32791 (12) | 0.13515 (17) | 0.0155 (3) | |
H1AO | −0.0212 (8) | 0.285 (2) | 0.195 (3) | 0.023* | |
O2A | 0.07623 (4) | 0.09899 (12) | 0.57652 (16) | 0.0147 (3) | |
O3A | 0.05320 (5) | 0.27304 (12) | 0.45841 (16) | 0.0164 (3) | |
N1A | 0.00001 (5) | 0.13879 (14) | 0.25999 (19) | 0.0131 (4) | |
N2A | 0.03016 (6) | 0.08825 (15) | 0.3687 (2) | 0.0144 (4) | |
H2AN | 0.0326 (8) | 0.011 (2) | 0.378 (3) | 0.022* | |
C1A | −0.05776 (6) | 0.12521 (17) | 0.0571 (2) | 0.0123 (4) | |
C2A | −0.06384 (6) | 0.25104 (17) | 0.0464 (2) | 0.0128 (4) | |
C3A | −0.09807 (7) | 0.29968 (17) | −0.0559 (2) | 0.0151 (4) | |
H3A | −0.102322 | 0.384378 | −0.061072 | 0.018* | |
C4A | −0.12600 (7) | 0.22594 (18) | −0.1503 (2) | 0.0161 (4) | |
H4A | −0.149393 | 0.259472 | −0.220254 | 0.019* | |
C5A | −0.11949 (6) | 0.10144 (17) | −0.1417 (2) | 0.0135 (4) | |
C6A | −0.08603 (7) | 0.05145 (17) | −0.0399 (2) | 0.0133 (4) | |
H6A | −0.082137 | −0.033375 | −0.035397 | 0.016* | |
C7A | −0.02400 (7) | 0.07044 (17) | 0.1679 (2) | 0.0135 (4) | |
H7A | −0.019897 | −0.014331 | 0.171790 | 0.016* | |
C8A | 0.05341 (7) | 0.16443 (17) | 0.4676 (2) | 0.0134 (4) | |
C9A | 0.11033 (7) | 0.16320 (18) | 0.6787 (2) | 0.0159 (4) | |
H9A1 | 0.108034 | 0.132746 | 0.780527 | 0.019* | |
H9A2 | 0.102462 | 0.250018 | 0.677625 | 0.019* | |
C10A | 0.16046 (7) | 0.14533 (18) | 0.6338 (2) | 0.0152 (4) | |
C11A | 0.18757 (7) | 0.04758 (18) | 0.6867 (3) | 0.0199 (5) | |
H11A | 0.175224 | −0.004677 | 0.757468 | 0.024* | |
C12A | 0.23246 (7) | 0.0256 (2) | 0.6372 (3) | 0.0244 (5) | |
H12A | 0.250802 | −0.041479 | 0.673897 | 0.029* | |
C13A | 0.25050 (7) | 0.1014 (2) | 0.5344 (3) | 0.0236 (5) | |
H13A | 0.280911 | 0.084987 | 0.498459 | 0.028* | |
C14A | 0.22449 (7) | 0.2012 (2) | 0.4832 (3) | 0.0234 (5) | |
H14A | 0.237391 | 0.254413 | 0.414556 | 0.028* | |
C15A | 0.17947 (7) | 0.22296 (18) | 0.5330 (2) | 0.0184 (5) | |
H15A | 0.161541 | 0.291233 | 0.498007 | 0.022* | |
Br1B | 0.33187 (2) | 0.24274 (2) | −0.24668 (2) | 0.01864 (6) | |
O1B | 0.46666 (5) | 0.56485 (12) | 0.12357 (18) | 0.0175 (3) | |
H1BO | 0.4824 (8) | 0.526 (2) | 0.183 (3) | 0.026* | |
O2B | 0.58093 (5) | 0.33767 (12) | 0.56327 (17) | 0.0200 (3) | |
O3B | 0.55787 (5) | 0.51149 (12) | 0.44468 (17) | 0.0213 (3) | |
N1B | 0.50017 (6) | 0.37664 (15) | 0.2571 (2) | 0.0163 (4) | |
N2B | 0.53006 (6) | 0.32678 (15) | 0.3664 (2) | 0.0177 (4) | |
H2BN | 0.5316 (8) | 0.248 (2) | 0.381 (3) | 0.027* | |
C1B | 0.44047 (7) | 0.36259 (17) | 0.0590 (2) | 0.0144 (4) | |
C2B | 0.43755 (7) | 0.48817 (17) | 0.0413 (2) | 0.0155 (4) | |
C3B | 0.40395 (7) | 0.53794 (18) | −0.0621 (2) | 0.0187 (5) | |
H3B | 0.402207 | 0.622759 | −0.073766 | 0.022* | |
C4B | 0.37308 (7) | 0.46506 (18) | −0.1480 (2) | 0.0186 (5) | |
H4B | 0.349893 | 0.499454 | −0.217909 | 0.022* | |
C5B | 0.37609 (7) | 0.34063 (18) | −0.1317 (2) | 0.0157 (4) | |
C6B | 0.40953 (7) | 0.28942 (18) | −0.0301 (2) | 0.0153 (4) | |
H6B | 0.411493 | 0.204431 | −0.020934 | 0.018* | |
C7B | 0.47346 (7) | 0.30758 (17) | 0.1725 (2) | 0.0159 (5) | |
H7B | 0.475081 | 0.222686 | 0.183473 | 0.019* | |
C8B | 0.55672 (7) | 0.40391 (18) | 0.4573 (2) | 0.0164 (4) | |
C9B | 0.61708 (7) | 0.40024 (19) | 0.6607 (3) | 0.0199 (5) | |
H9B1 | 0.616291 | 0.369612 | 0.762983 | 0.024* | |
H9B2 | 0.609811 | 0.487367 | 0.661257 | 0.024* | |
C10B | 0.66606 (7) | 0.38057 (18) | 0.6078 (2) | 0.0177 (5) | |
C11B | 0.69188 (7) | 0.27764 (19) | 0.6499 (3) | 0.0243 (5) | |
H11B | 0.678700 | 0.220613 | 0.713444 | 0.029* | |
C12B | 0.73692 (8) | 0.2581 (2) | 0.5992 (3) | 0.0314 (6) | |
H12B | 0.754349 | 0.187171 | 0.627110 | 0.038* | |
C13B | 0.75634 (8) | 0.3413 (2) | 0.5085 (3) | 0.0339 (6) | |
H13B | 0.787039 | 0.327312 | 0.473303 | 0.041* | |
C14B | 0.73134 (8) | 0.4452 (2) | 0.4685 (3) | 0.0302 (6) | |
H14B | 0.745077 | 0.503149 | 0.407352 | 0.036* | |
C15B | 0.68621 (7) | 0.4646 (2) | 0.5178 (2) | 0.0216 (5) | |
H15B | 0.668973 | 0.535692 | 0.489816 | 0.026* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1A | 0.02056 (10) | 0.01578 (11) | 0.01793 (13) | −0.00204 (8) | −0.00389 (8) | −0.00260 (9) |
O1A | 0.0167 (7) | 0.0096 (7) | 0.0194 (9) | −0.0001 (5) | −0.0033 (6) | 0.0007 (6) |
O2A | 0.0156 (7) | 0.0133 (7) | 0.0146 (9) | −0.0002 (5) | −0.0031 (6) | −0.0003 (6) |
O3A | 0.0195 (7) | 0.0107 (7) | 0.0193 (9) | −0.0015 (5) | 0.0025 (6) | −0.0002 (6) |
N1A | 0.0121 (8) | 0.0127 (8) | 0.0143 (11) | 0.0018 (6) | 0.0009 (7) | 0.0020 (7) |
N2A | 0.0173 (8) | 0.0093 (8) | 0.0159 (11) | 0.0011 (7) | −0.0025 (7) | 0.0005 (7) |
C1A | 0.0124 (9) | 0.0113 (9) | 0.0134 (12) | 0.0006 (7) | 0.0033 (8) | 0.0007 (8) |
C2A | 0.0120 (9) | 0.0116 (9) | 0.0153 (12) | −0.0028 (8) | 0.0051 (8) | −0.0014 (8) |
C3A | 0.0155 (10) | 0.0102 (9) | 0.0196 (13) | 0.0018 (8) | 0.0019 (9) | 0.0018 (8) |
C4A | 0.015 (1) | 0.0161 (10) | 0.0172 (13) | 0.0025 (8) | 0.0018 (8) | 0.0035 (9) |
C5A | 0.0113 (9) | 0.0159 (10) | 0.0132 (12) | −0.0019 (8) | −0.0002 (8) | −0.0021 (8) |
C6A | 0.0158 (10) | 0.0101 (9) | 0.0145 (12) | −0.0009 (8) | 0.0049 (8) | 0.0007 (8) |
C7A | 0.0145 (9) | 0.0100 (9) | 0.0164 (13) | 0.0005 (7) | 0.0042 (8) | 0.0005 (8) |
C8A | 0.0109 (9) | 0.0134 (10) | 0.0164 (12) | −0.0005 (7) | 0.0045 (8) | −0.0003 (8) |
C9A | 0.0176 (10) | 0.0171 (10) | 0.0125 (12) | −0.0022 (8) | −0.0018 (9) | −0.0042 (8) |
C10A | 0.0155 (10) | 0.0172 (10) | 0.0124 (12) | −0.0013 (8) | −0.0029 (8) | −0.0060 (8) |
C11A | 0.0235 (11) | 0.0167 (10) | 0.0185 (13) | −0.0030 (9) | −0.0049 (9) | 0.0007 (9) |
C12A | 0.0185 (11) | 0.0253 (12) | 0.0278 (15) | 0.0061 (9) | −0.0083 (9) | −0.0055 (10) |
C13A | 0.0137 (10) | 0.0311 (13) | 0.0257 (15) | −0.0020 (9) | 0.0000 (9) | −0.0118 (10) |
C14A | 0.0211 (11) | 0.0254 (12) | 0.0237 (14) | −0.0073 (9) | 0.0026 (10) | −0.0037 (10) |
C15A | 0.0214 (10) | 0.0154 (10) | 0.0176 (13) | −0.0007 (8) | −0.0029 (9) | −0.0026 (9) |
Br1B | 0.0178 (1) | 0.01828 (11) | 0.01947 (13) | −0.00271 (8) | −0.00094 (8) | −0.00299 (9) |
O1B | 0.0174 (7) | 0.0116 (7) | 0.0227 (10) | −0.0013 (6) | −0.0037 (6) | −0.0002 (6) |
O2B | 0.0174 (7) | 0.0154 (7) | 0.0259 (10) | −0.0012 (6) | −0.0070 (6) | −0.0003 (6) |
O3B | 0.0230 (7) | 0.0118 (7) | 0.0284 (10) | −0.0024 (6) | −0.0017 (7) | −0.0006 (6) |
N1B | 0.0153 (9) | 0.0139 (9) | 0.0193 (12) | 0.0015 (6) | −0.0009 (8) | 0.0029 (7) |
N2B | 0.0183 (9) | 0.0115 (8) | 0.0221 (12) | 0.0006 (7) | −0.0058 (8) | 0.0015 (8) |
C1B | 0.0126 (9) | 0.0146 (10) | 0.0162 (12) | 0.0002 (8) | 0.0031 (8) | 0.0001 (8) |
C2B | 0.0137 (9) | 0.0133 (10) | 0.0200 (13) | −0.0021 (8) | 0.0034 (8) | −0.0029 (9) |
C3B | 0.0197 (10) | 0.0124 (10) | 0.0243 (14) | 0.0013 (8) | 0.0028 (9) | 0.0013 (9) |
C4B | 0.0189 (10) | 0.0177 (10) | 0.0189 (13) | 0.0015 (8) | −0.0004 (9) | 0.0017 (9) |
C5B | 0.0125 (9) | 0.0172 (10) | 0.0176 (13) | −0.0023 (8) | 0.0037 (8) | −0.0034 (9) |
C6B | 0.0167 (10) | 0.0111 (10) | 0.0186 (13) | −0.0006 (8) | 0.0039 (9) | −0.0004 (8) |
C7B | 0.0152 (10) | 0.0102 (9) | 0.0222 (13) | 0.0003 (8) | 0.0009 (9) | 0.0003 (8) |
C8B | 0.0132 (10) | 0.0165 (10) | 0.0197 (13) | 0.0002 (8) | 0.0024 (8) | 0.0011 (9) |
C9B | 0.018 (1) | 0.0211 (11) | 0.0195 (13) | −0.0016 (8) | −0.0056 (9) | −0.0039 (9) |
C10B | 0.0174 (10) | 0.0190 (11) | 0.0160 (13) | −0.0011 (8) | −0.0033 (9) | −0.0051 (9) |
C11B | 0.0229 (11) | 0.0182 (11) | 0.0307 (15) | −0.0014 (9) | −0.0041 (10) | −0.002 (1) |
C12B | 0.0240 (12) | 0.0267 (13) | 0.0419 (17) | 0.0059 (10) | −0.0069 (11) | −0.0121 (12) |
C13B | 0.0198 (12) | 0.0505 (16) | 0.0320 (17) | −0.0009 (11) | 0.0052 (11) | −0.0142 (13) |
C14B | 0.0285 (12) | 0.0410 (15) | 0.0213 (15) | −0.0098 (11) | 0.0042 (10) | −0.0048 (11) |
C15B | 0.0255 (11) | 0.0225 (11) | 0.0160 (13) | −0.0015 (9) | −0.0032 (9) | −0.0018 (9) |
Br1A—C5A | 1.8949 (19) | Br1B—C5B | 1.896 (2) |
O1A—C2A | 1.360 (2) | O1B—C2B | 1.360 (2) |
O1A—H1AO | 0.82 (2) | O1B—H1BO | 0.80 (2) |
O2A—C8A | 1.346 (2) | O2B—C8B | 1.349 (2) |
O2A—C9A | 1.461 (2) | O2B—C9B | 1.464 (2) |
O3A—C8A | 1.211 (2) | O3B—C8B | 1.203 (2) |
N1A—C7A | 1.279 (2) | N1B—C7B | 1.282 (2) |
N1A—N2A | 1.365 (2) | N1B—N2B | 1.362 (2) |
N2A—C8A | 1.361 (3) | N2B—C8B | 1.369 (3) |
N2A—H2AN | 0.87 (2) | N2B—H2BN | 0.88 (2) |
C1A—C6A | 1.399 (3) | C1B—C6B | 1.397 (3) |
C1A—C2A | 1.412 (3) | C1B—C2B | 1.407 (3) |
C1A—C7A | 1.456 (3) | C1B—C7B | 1.460 (3) |
C2A—C3A | 1.388 (3) | C2B—C3B | 1.388 (3) |
C3A—C4A | 1.381 (3) | C3B—C4B | 1.378 (3) |
C3A—H3A | 0.9500 | C3B—H3B | 0.9500 |
C4A—C5A | 1.398 (3) | C4B—C5B | 1.394 (3) |
C4A—H4A | 0.9500 | C4B—H4B | 0.9500 |
C5A—C6A | 1.378 (3) | C5B—C6B | 1.381 (3) |
C6A—H6A | 0.9500 | C6B—H6B | 0.9500 |
C7A—H7A | 0.9500 | C7B—H7B | 0.9500 |
C9A—C10A | 1.500 (3) | C9B—C10B | 1.499 (3) |
C9A—H9A1 | 0.9900 | C9B—H9B1 | 0.9900 |
C9A—H9A2 | 0.9900 | C9B—H9B2 | 0.9900 |
C10A—C11A | 1.388 (3) | C10B—C15B | 1.388 (3) |
C10A—C15A | 1.392 (3) | C10B—C11B | 1.390 (3) |
C11A—C12A | 1.385 (3) | C11B—C12B | 1.389 (3) |
C11A—H11A | 0.9500 | C11B—H11B | 0.9500 |
C12A—C13A | 1.380 (3) | C12B—C13B | 1.377 (4) |
C12A—H12A | 0.9500 | C12B—H12B | 0.9500 |
C13A—C14A | 1.386 (3) | C13B—C14B | 1.384 (4) |
C13A—H13A | 0.9500 | C13B—H13B | 0.9500 |
C14A—C15A | 1.389 (3) | C14B—C15B | 1.385 (3) |
C14A—H14A | 0.9500 | C14B—H14B | 0.9500 |
C15A—H15A | 0.9500 | C15B—H15B | 0.9500 |
C2A—O1A—H1AO | 105.5 (16) | C2B—O1B—H1BO | 107.9 (17) |
C8A—O2A—C9A | 116.62 (15) | C8B—O2B—C9B | 116.93 (16) |
C7A—N1A—N2A | 119.20 (16) | C7B—N1B—N2B | 119.03 (17) |
C8A—N2A—N1A | 117.02 (16) | N1B—N2B—C8B | 117.14 (17) |
C8A—N2A—H2AN | 121.5 (15) | N1B—N2B—H2BN | 122.0 (15) |
N1A—N2A—H2AN | 121.3 (15) | C8B—N2B—H2BN | 120.8 (15) |
C6A—C1A—C2A | 118.64 (18) | C6B—C1B—C2B | 118.97 (18) |
C6A—C1A—C7A | 119.38 (17) | C6B—C1B—C7B | 119.38 (18) |
C2A—C1A—C7A | 121.97 (18) | C2B—C1B—C7B | 121.59 (18) |
O1A—C2A—C3A | 118.04 (17) | O1B—C2B—C3B | 117.61 (18) |
O1A—C2A—C1A | 121.65 (18) | O1B—C2B—C1B | 122.20 (18) |
C3A—C2A—C1A | 120.30 (18) | C3B—C2B—C1B | 120.18 (18) |
C4A—C3A—C2A | 120.53 (18) | C4B—C3B—C2B | 120.41 (19) |
C4A—C3A—H3A | 119.7 | C4B—C3B—H3B | 119.8 |
C2A—C3A—H3A | 119.7 | C2B—C3B—H3B | 119.8 |
C3A—C4A—C5A | 119.28 (18) | C3B—C4B—C5B | 119.61 (19) |
C3A—C4A—H4A | 120.4 | C3B—C4B—H4B | 120.2 |
C5A—C4A—H4A | 120.4 | C5B—C4B—H4B | 120.2 |
C6A—C5A—C4A | 121.02 (18) | C6B—C5B—C4B | 120.81 (18) |
C6A—C5A—Br1A | 119.71 (14) | C6B—C5B—Br1B | 120.43 (15) |
C4A—C5A—Br1A | 119.27 (15) | C4B—C5B—Br1B | 118.72 (15) |
C5A—C6A—C1A | 120.22 (18) | C5B—C6B—C1B | 120.00 (18) |
C5A—C6A—H6A | 119.9 | C5B—C6B—H6B | 120.0 |
C1A—C6A—H6A | 119.9 | C1B—C6B—H6B | 120.0 |
N1A—C7A—C1A | 118.65 (17) | N1B—C7B—C1B | 118.39 (18) |
N1A—C7A—H7A | 120.7 | N1B—C7B—H7B | 120.8 |
C1A—C7A—H7A | 120.7 | C1B—C7B—H7B | 120.8 |
O3A—C8A—O2A | 126.12 (19) | O3B—C8B—O2B | 126.55 (19) |
O3A—C8A—N2A | 125.18 (19) | O3B—C8B—N2B | 125.7 (2) |
O2A—C8A—N2A | 108.70 (16) | O2B—C8B—N2B | 107.76 (17) |
O2A—C9A—C10A | 109.76 (16) | O2B—C9B—C10B | 109.90 (17) |
O2A—C9A—H9A1 | 109.7 | O2B—C9B—H9B1 | 109.7 |
C10A—C9A—H9A1 | 109.7 | C10B—C9B—H9B1 | 109.7 |
O2A—C9A—H9A2 | 109.7 | O2B—C9B—H9B2 | 109.7 |
C10A—C9A—H9A2 | 109.7 | C10B—C9B—H9B2 | 109.7 |
H9A1—C9A—H9A2 | 108.2 | H9B1—C9B—H9B2 | 108.2 |
C11A—C10A—C15A | 119.15 (19) | C15B—C10B—C11B | 119.4 (2) |
C11A—C10A—C9A | 120.30 (19) | C15B—C10B—C9B | 120.74 (19) |
C15A—C10A—C9A | 120.48 (18) | C11B—C10B—C9B | 119.9 (2) |
C12A—C11A—C10A | 120.6 (2) | C12B—C11B—C10B | 120.1 (2) |
C12A—C11A—H11A | 119.7 | C12B—C11B—H11B | 119.9 |
C10A—C11A—H11A | 119.7 | C10B—C11B—H11B | 119.9 |
C13A—C12A—C11A | 119.9 (2) | C13B—C12B—C11B | 120.0 (2) |
C13A—C12A—H12A | 120.1 | C13B—C12B—H12B | 120.0 |
C11A—C12A—H12A | 120.1 | C11B—C12B—H12B | 120.0 |
C12A—C13A—C14A | 120.4 (2) | C12B—C13B—C14B | 120.3 (2) |
C12A—C13A—H13A | 119.8 | C12B—C13B—H13B | 119.9 |
C14A—C13A—H13A | 119.8 | C14B—C13B—H13B | 119.9 |
C13A—C14A—C15A | 119.6 (2) | C13B—C14B—C15B | 119.8 (2) |
C13A—C14A—H14A | 120.2 | C13B—C14B—H14B | 120.1 |
C15A—C14A—H14A | 120.2 | C15B—C14B—H14B | 120.1 |
C14A—C15A—C10A | 120.4 (2) | C14B—C15B—C10B | 120.4 (2) |
C14A—C15A—H15A | 119.8 | C14B—C15B—H15B | 119.8 |
C10A—C15A—H15A | 119.8 | C10B—C15B—H15B | 119.8 |
C7A—N1A—N2A—C8A | −177.37 (18) | C7B—N1B—N2B—C8B | −177.79 (18) |
C6A—C1A—C2A—O1A | −178.68 (17) | C6B—C1B—C2B—O1B | −179.66 (18) |
C7A—C1A—C2A—O1A | 3.0 (3) | C7B—C1B—C2B—O1B | 3.1 (3) |
C6A—C1A—C2A—C3A | 1.6 (3) | C6B—C1B—C2B—C3B | 0.8 (3) |
C7A—C1A—C2A—C3A | −176.79 (18) | C7B—C1B—C2B—C3B | −176.38 (19) |
O1A—C2A—C3A—C4A | 179.10 (18) | O1B—C2B—C3B—C4B | −179.38 (19) |
C1A—C2A—C3A—C4A | −1.2 (3) | C1B—C2B—C3B—C4B | 0.2 (3) |
C2A—C3A—C4A—C5A | 0.0 (3) | C2B—C3B—C4B—C5B | −0.7 (3) |
C3A—C4A—C5A—C6A | 0.6 (3) | C3B—C4B—C5B—C6B | 0.2 (3) |
C3A—C4A—C5A—Br1A | −179.20 (15) | C3B—C4B—C5B—Br1B | 178.02 (16) |
C4A—C5A—C6A—C1A | −0.2 (3) | C4B—C5B—C6B—C1B | 0.8 (3) |
Br1A—C5A—C6A—C1A | 179.65 (14) | Br1B—C5B—C6B—C1B | −176.99 (15) |
C2A—C1A—C6A—C5A | −0.9 (3) | C2B—C1B—C6B—C5B | −1.3 (3) |
C7A—C1A—C6A—C5A | 177.49 (18) | C7B—C1B—C6B—C5B | 175.98 (19) |
N2A—N1A—C7A—C1A | 177.06 (16) | N2B—N1B—C7B—C1B | 178.03 (17) |
C6A—C1A—C7A—N1A | −176.88 (18) | C6B—C1B—C7B—N1B | −177.23 (19) |
C2A—C1A—C7A—N1A | 1.5 (3) | C2B—C1B—C7B—N1B | 0.0 (3) |
C9A—O2A—C8A—O3A | −11.2 (3) | C9B—O2B—C8B—O3B | −8.9 (3) |
C9A—O2A—C8A—N2A | 169.09 (15) | C9B—O2B—C8B—N2B | 171.53 (16) |
N1A—N2A—C8A—O3A | −7.7 (3) | N1B—N2B—C8B—O3B | −4.0 (3) |
N1A—N2A—C8A—O2A | 171.98 (15) | N1B—N2B—C8B—O2B | 175.60 (16) |
C8A—O2A—C9A—C10A | −98.12 (19) | C8B—O2B—C9B—C10B | −98.0 (2) |
O2A—C9A—C10A—C11A | −88.3 (2) | O2B—C9B—C10B—C15B | 95.9 (2) |
O2A—C9A—C10A—C15A | 88.5 (2) | O2B—C9B—C10B—C11B | −84.5 (2) |
C15A—C10A—C11A—C12A | −1.6 (3) | C15B—C10B—C11B—C12B | −1.5 (3) |
C9A—C10A—C11A—C12A | 175.19 (19) | C9B—C10B—C11B—C12B | 178.9 (2) |
C10A—C11A—C12A—C13A | 0.0 (3) | C10B—C11B—C12B—C13B | 0.8 (4) |
C11A—C12A—C13A—C14A | 1.7 (3) | C11B—C12B—C13B—C14B | 0.6 (4) |
C12A—C13A—C14A—C15A | −1.8 (3) | C12B—C13B—C14B—C15B | −1.1 (4) |
C13A—C14A—C15A—C10A | 0.1 (3) | C13B—C14B—C15B—C10B | 0.4 (3) |
C11A—C10A—C15A—C14A | 1.6 (3) | C11B—C10B—C15B—C14B | 1.0 (3) |
C9A—C10A—C15A—C14A | −175.24 (19) | C9B—C10B—C15B—C14B | −179.5 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1AO···N1A | 0.82 (2) | 1.81 (2) | 2.565 (2) | 151 (2) |
N2A—H2AN···O1Ai | 0.87 (2) | 2.04 (2) | 2.902 (2) | 171 (2) |
C3A—H3A···O2Aii | 0.95 | 2.50 | 3.392 (2) | 156 |
C6A—H6A···O3Ai | 0.95 | 2.38 | 3.296 (2) | 161 |
O1B—H1BO···N1B | 0.80 (2) | 1.84 (2) | 2.558 (2) | 148 (2) |
N2B—H2BN···O1Biii | 0.88 (2) | 2.04 (2) | 2.915 (2) | 171 (2) |
C3B—H3B···O2Biv | 0.95 | 2.44 | 3.360 (2) | 164 |
C6B—H6B···O3Biii | 0.95 | 2.39 | 3.297 (2) | 159 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x, y+1/2, −z+1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) −x+1, y+1/2, −z+1/2. |
I | |||
C8—O2—C9—C10 | -78.01 (18) | O2—C9—C10—C11 | -59.9 (2) |
II | |||
C8A—O2A—C9A—C10A | -98.12 (19) | O2A—C9A—C10A—C11A | -88.3 (2) |
C8B—O2B—C9B—C10B | -98.0 (2) | O2B—C9B—C10B—C11B | -84.5 (2) |
The above torsion angles quantify the most substantive differences between the conformations of I, IIA and IIB. |
R and R' represent groups attached at the equivalent of C4 and R'' represents the group attached at the equivalent of O3. |
CSD refcode | R | R' | R'' | Reference |
HODLOC | 2-hydroxyphenyl | H | methyl | Sun & Cheng (2008) |
QOFLAZ | 2-hydroxyphenyl | H | ethyl | Gao (2008) |
KODVUV | 4-hydroxyphenyl | H | methyl | Cheng (2008a) |
XOGVEV | phenyl | methyl | methyl | Cheng (2008b) |
XOGXEX | 4-hydroxyphenyl | H | ethyl | Cheng (2008c) |
XOGXIB | 3-methoxy-4-hydroxyphenyl | H | methyl | Cheng (2008d) |
AZOTAL | 3-hydroxyphenyl | H | methyl | Li et al. (2011) |
AWUJAE | 3-hydroxyphenyl | H | ethyl | Hu et al. (2011) |
WEFRUX | 4-diethylamino-2-hydroxyphenyl | H | methyl | Lv et al. (2017) |
Acknowledgements
One of the authors (V) is grateful to the DST–PURSE Project, Vijnana Bhavana, UOM for providing research facilities.
Funding information
HSY thanks UGC for a BSR Faculty fellowship for three years. Funding for this research was provided by: NSF (MRI CHE1625732) and the University of Kentucky (Bruker D8 Venture diffractometer).
References
Borg, S., Vollinga, R. C., Labarre, M., Payza, K., Terenius, L. & Luthman, K. (1999). J. Med. Chem. 42, 4331–4342. Web of Science CrossRef PubMed CAS Google Scholar
Bruker (2016). APEX3. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chang, B.-B., Su, Y.-P., Huang, D.-F., Wang, K.-H., Zhang, W.-G., Shi, Y., Zhang, X.-H. & Hu, Y.-L. (2018). J. Org. Chem. 83, 4365–4374. CSD CrossRef CAS PubMed Google Scholar
Cheng, X.-W. (2008a). Acta Cryst. E64, o1302. CSD CrossRef IUCr Journals Google Scholar
Cheng, X.-W. (2008b). Acta Cryst. E64, o1384. CSD CrossRef IUCr Journals Google Scholar
Cheng, X.-W. (2008c). Acta Cryst. E64, o1396. CSD CrossRef IUCr Journals Google Scholar
Cheng, X.-W. (2008d). Acta Cryst. E64, o1397. CSD CrossRef IUCr Journals Google Scholar
Dong, K. & Wang, Y. (2014). Acta Cryst. E70, o527. CSD CrossRef IUCr Journals Google Scholar
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. CrossRef ICSD CAS Web of Science IUCr Journals Google Scholar
Flack, H. D. & Bernardinelli, G. (1999). Acta Cryst. A55, 908–915. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gao, B. (2008). Acta Cryst. E64, o1547. CSD CrossRef 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
Hadjoudis, E., Vittorakis, M. & Moustakali-Mavridis, J. (1987). Tetrahedron, 43, 1345–1360. CrossRef CAS Web of Science Google Scholar
Hooft, R. W. W., Straver, L. H. & Spek, A. L. (2008). J. Appl. Cryst. 41, 96–103. Web of Science CrossRef CAS IUCr Journals Google Scholar
Hu, X.-C., Zhang, J., Yang, D.-Y. & Lv, L.-P. (2011). Acta Cryst. E67, o1884. CSD CrossRef IUCr Journals Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Li, W.-W., Yu, T.-M., Lv, L.-P. & Hu, X.-C. (2011). Acta Cryst. E67, o2584. CSD CrossRef IUCr Journals Google Scholar
Lv, L.-P., Lv, W.-D., Rao, J.-F. & Chen, J.-Y. (2017). Z. Kristallogr. New Cryst. Struct. 232, 667–668. CSD CrossRef CAS Google Scholar
Macrae, C. F., Sovago, I., Cottrell, S. J., Galek, P. T. A., McCabe, P., Pidcock, E., Platings, M., Shields, G. P., Stevens, J. S., Towler, M. & Wood, P. A. (2020). J. Appl. Cryst. 53, 226–235. Web of Science CrossRef CAS IUCr Journals Google Scholar
Nithya, P., Simpson, J., Helena, S., Rajamanikandan, R. & Govindarajan, S. (2017). J. Therm. Anal. Calorim. 129, 1001–1019. Web of Science CSD CrossRef CAS Google Scholar
Özdemir, A., Turan-Zitouni, G., Kaplancikli, Z. A. & Tunali, Y. (2009). J. Enzyme Inhib. Med. Chem. 24, 825–831. PubMed Google Scholar
Parashar, R. K., Sharma, R. C., Kumar, A. & Mohan, G. (1988). Inorg. Chim. Acta, 151, 201–208. CrossRef CAS Web of Science Google Scholar
Parkin, S. (2000). Acta Cryst. A56, 157–162. Web of Science CrossRef CAS IUCr Journals Google Scholar
Parkin, S. (2013). CIFFIX. https://xray.uky.edu/Resources/scripts/ciffix Google Scholar
Parkin, S. & Hope, H. (1998). J. Appl. Cryst. 31, 945–953. Web of Science CrossRef CAS IUCr Journals Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Rollas, S. & Küçükgüzel, S. G. (2007). Molecules, 12, 1910–1939. Web of Science CrossRef PubMed CAS Google Scholar
Sersen, F., Gregan, F., Kotora, P., Kmetova, J., Filo, J., Loos, D. & Gregan, J. (2017). Molecules, 22, 894. CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals 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
Shen, L.-W., Wang, Z.-H., You, Y., Zhao, J.-Q., Zhou, M.-Q. & Yuan, W.-C. (2022). Org. Lett. 24, 1094–1099. CSD CrossRef CAS PubMed Google Scholar
Spackman, P. R., Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Jayatilaka, D. & Spackman, M. A. (2021). J. Appl. Cryst. 54, 1006–1011. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2020). Acta Cryst. E76, 1–11. Web of Science CrossRef IUCr Journals Google Scholar
Sun, R. & Cheng, X.-W. (2008). Acta Cryst. E64, o1563. CSD CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, Y.-L., Li, B.-Y., Yang, R., Xia, L.-Y., Fan, A.-L., Chu, Y.-C., Wang, L.-J., Wang, Z.-C., Jiang, A.-Q. & Zhu, H.-L. (2019). Eur. J. Med. Chem. 163, 896–910. CSD CrossRef CAS PubMed Google Scholar
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