organic compounds
H-pyrazol-4-yl}methanone
of (3,5-dibromo-2-hydroxyphenyl){1-[(naphthalen-1-yl)carbonyl]-1aSchool of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, Shizuoka 422-8526 , Japan
*Correspondence e-mail: ishi206@u-shizuoka-ken.ac.jp
In the title compound, C21H12Br2N2O3, a 1,4-diaroyl pyrazole derivative, the dihedral angles between the naphthalene ring system and the pyrazole ring, the pyrazole and benzene rings, and the naphthalene ring system and benzene ring are 50.0 (2), 51.1 (2) and 1.34 (16)°, respectively. The phenolic proton forms an intramolecular O—H⋯O hydrogen bond with the adjacent carbonyl O atom. In the crystal, molecules are linked by C—H⋯O hydrogen bonds, forming inversion dimers. The dimers are linked by C—H⋯Br hydrogen bonds, forming double stranded chains along [01-1]. The chains are linked by π–π interactions between the pyrazole rings and between the naphthalene and benzene rings [centroid–centroid distances = 3.592 (4) and 3.632 (4) Å, respectively].
Keywords: crystal structure; diaroyl pyrazole; cyclization; stacking interaction; C—H⋯O hydrogen bonding.
CCDC reference: 1019490
1. Related literature
For the biological activity of related compounds, see: Khan et al. (2009); Tu et al. (2013). For related structures, see: Ishikawa (2014); Ishikawa & Watanabe (2014a,b,c,d).
2. Experimental
2.1. Crystal data
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2.3. Refinement
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Data collection: WinAFC (Rigaku, 1999); cell WinAFC; data reduction: WinAFC; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2010); software used to prepare material for publication: CrystalStructure.
Supporting information
CCDC reference: 1019490
10.1107/S1600536814018601/tk5338sup1.cif
contains datablocks General, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814018601/tk5338Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814018601/tk5338Isup3.cml
Schiff base derivatives of 3-formylchromones have attracted much attention due to their biological functions such as enzyme inhibition (Khan et al. 2009; Tu et al. 2013). We have recently reported the crystal structures of such compounds (Ishikawa & Watanabe, 2014a,b,c,d), which were prepared from condensation reaction of 3-formylchromones with arylhydrazides.
The reaction of 6,8-dibromo-3-formylchromone (Ishikawa, 2014) with 1-naphthoylhydrazide in ethanol gave white solids, and orange crystals were obtained from an acetonitrile/ethanol solution of the white solids (Fig. 1). The crystallographic analysis revealed that the structure of the orange crystals is a 1,4-diaroyl pyrazole, as shown in Fig. 2, which should be thermodynamically more stable than that of the white solids. The dihedral angles between the naphthalene and pyrazole rings, the pyrazole and benzene rings and the naphthalene and benzene rings are 50.0 (2), 51.1 (2) and 1.34 (16)°, respectively. The phenolic proton forms an intramolecular O—H···O hydrogen bond with the adjacent carbonyl O2 atom. In the crystal, the molecules are linked through stacking interactions between the pyrazole rings and the naphthalene and benzene rings [centroid–centroid distances = 3.553 (4) and 3.632 (4) Å, respectively, i: –x + 2, –y, –z + 1], and are further connected through intermolecular C–H···O hydrogen bonds, as shown in Fig. 3. A significant short contact around the bromine atoms is not observed.
The driving force of the intramolecular
(Fig. 1) should be a resonance energy gain, resulting from the extension of the across the entire molecule. The intramolecular is not observed for the chromone derivatives with electron-donating substituents (Ishikawa & Watanabe, 2014a,b,c,d), and thus the activation energy for the chromone derivative with the electron-withdrawing substituents should be lower than that for ones with electron-donating substituents.Preparation of the white precursor, (E)-N'-((6,8-dibromo-4-oxo-4H-chromen-3-yl)methylene)-1-naphthohydrazide, is as follows: 1-naphthohydrazide (1.1 mmol) and 6,8-dibromo-3-formylchromone (1.1 mmol) were dissolved in 50 ml of ethanol, and the mixture was refluxed with Dean-Stark apparatus for 15 min with stirring. After cooling, the white precipitates were collected, washed with n-hexane and dried in vacuo (yield 25%). 1H NMR (400 MHz, DMSO-d6): δ = 7.60–7.64 (m, 4H), 7.77 (d, 1H, J = 6.8 Hz), 8.02–8.05 (m, 1H), 8.11 (d, 1H, J = 8.3 Hz), 8.17 (d, 1H, J = 2.4 Hz), 8.21–8.23 (m, 1H), 8.45 (d, 1H, J = 1.9 Hz), 8.47 (s, 1H), 12.16 (s, 1H). DART-MS (negative mode) calcd for [C21H12Br2N2O3]: 499.919, found 498.920. The orange crystals suitable for X-ray diffraction were obtained by slow evaporation of an acetonitrile/ethanol solution of the white precursor at room temperature.
The O- and C(sp2)-bound hydrogen atoms were placed in their geometric positions [O—H = 0.84 Å and C—H 0.95 Å, Uiso(H) = 1.2Ueq(O,C)], and refined using a riding model. Three reflections, i.e. (4 6 7), (4 6 3) and (4 6 5) were omitted owing to poor agreement. The maximum and minimum residual electron density peaks of 2.15 and 2.52 eÅ-3, respectively, were located 0.88 and 1.05 Å from the Br1 and Br2 atoms, respectively.
Data collection: WinAFC (Rigaku, 1999); cell
WinAFC (Rigaku, 1999); data reduction: WinAFC (Rigaku, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2010); software used to prepare material for publication: CrystalStructure (Rigaku, 2010).C21H12Br2N2O3 | Z = 2 |
Mr = 500.15 | F(000) = 492.00 |
Triclinic, P1 | Dx = 1.871 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71069 Å |
a = 7.390 (5) Å | Cell parameters from 25 reflections |
b = 8.919 (4) Å | θ = 15.1–17.5° |
c = 14.955 (9) Å | µ = 4.61 mm−1 |
α = 74.61 (4)° | T = 100 K |
β = 76.71 (5)° | Plate, orange |
γ = 71.03 (4)° | 0.40 × 0.18 × 0.08 mm |
V = 887.5 (9) Å3 |
Rigaku AFC7R diffractometer | Rint = 0.062 |
ω–2θ scans | θmax = 27.5° |
Absorption correction: ψ scan (North et al., 1968) | h = −5→9 |
Tmin = 0.448, Tmax = 0.692 | k = −10→11 |
5003 measured reflections | l = −18→19 |
4088 independent reflections | 3 standard reflections every 150 reflections |
3359 reflections with F2 > 2.0σ(F2) | intensity decay: −0.6% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.064 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.204 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.1444P)2 + 3.2256P] where P = (Fo2 + 2Fc2)/3 |
4088 reflections | (Δ/σ)max < 0.001 |
254 parameters | Δρmax = 2.15 e Å−3 |
0 restraints | Δρmin = −2.52 e Å−3 |
Primary atom site location: structure-invariant direct methods |
C21H12Br2N2O3 | γ = 71.03 (4)° |
Mr = 500.15 | V = 887.5 (9) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.390 (5) Å | Mo Kα radiation |
b = 8.919 (4) Å | µ = 4.61 mm−1 |
c = 14.955 (9) Å | T = 100 K |
α = 74.61 (4)° | 0.40 × 0.18 × 0.08 mm |
β = 76.71 (5)° |
Rigaku AFC7R diffractometer | 3359 reflections with F2 > 2.0σ(F2) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.062 |
Tmin = 0.448, Tmax = 0.692 | 3 standard reflections every 150 reflections |
5003 measured reflections | intensity decay: −0.6% |
4088 independent reflections |
R[F2 > 2σ(F2)] = 0.064 | 0 restraints |
wR(F2) = 0.204 | H-atom parameters constrained |
S = 1.07 | Δρmax = 2.15 e Å−3 |
4088 reflections | Δρmin = −2.52 e Å−3 |
254 parameters |
Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.50138 (8) | −0.13169 (6) | 0.83532 (4) | 0.0176 (2) | |
Br2 | 0.31452 (8) | 0.48290 (7) | 0.92499 (4) | 0.0201 (2) | |
O1 | 0.4963 (6) | 0.5714 (5) | 0.7244 (4) | 0.0187 (9) | |
O2 | 0.7063 (7) | 0.5130 (5) | 0.5684 (3) | 0.0202 (9) | |
O3 | 0.6724 (7) | −0.0505 (6) | 0.4014 (4) | 0.0240 (10) | |
N1 | 0.9928 (7) | 0.1676 (6) | 0.3998 (4) | 0.0160 (10) | |
N2 | 0.8285 (7) | 0.1192 (6) | 0.4157 (4) | 0.0139 (9) | |
C1 | 0.5910 (8) | 0.3094 (6) | 0.6818 (4) | 0.0127 (10) | |
C2 | 0.5037 (8) | 0.4138 (7) | 0.7463 (5) | 0.0145 (11) | |
C3 | 0.4201 (8) | 0.3493 (7) | 0.8375 (4) | 0.0139 (11) | |
C4 | 0.4218 (8) | 0.1885 (7) | 0.8626 (4) | 0.0146 (11) | |
C5 | 0.5058 (8) | 0.0873 (7) | 0.7989 (5) | 0.0142 (11) | |
C6 | 0.5922 (8) | 0.1444 (7) | 0.7097 (4) | 0.0132 (10) | |
C7 | 0.6900 (8) | 0.3729 (7) | 0.5888 (4) | 0.0139 (10) | |
C8 | 0.7757 (8) | 0.2698 (7) | 0.5188 (4) | 0.0134 (10) | |
C9 | 0.6977 (8) | 0.1766 (7) | 0.4881 (4) | 0.0147 (11) | |
C10 | 0.9595 (8) | 0.2605 (7) | 0.4605 (5) | 0.0160 (11) | |
C11 | 0.7991 (8) | 0.0156 (7) | 0.3655 (4) | 0.0152 (11) | |
C12 | 0.9184 (8) | 0.0025 (7) | 0.2726 (4) | 0.0132 (10) | |
C13 | 0.9601 (8) | 0.1394 (7) | 0.2138 (5) | 0.0157 (11) | |
C14 | 1.0545 (8) | 0.1378 (7) | 0.1201 (5) | 0.0165 (11) | |
C15 | 1.1092 (8) | −0.0030 (7) | 0.0873 (4) | 0.0135 (10) | |
C16 | 1.1317 (8) | −0.2919 (8) | 0.1108 (5) | 0.0186 (12) | |
C17 | 1.0949 (9) | −0.4298 (7) | 0.1657 (5) | 0.0187 (12) | |
C18 | 0.9958 (9) | −0.4307 (7) | 0.2580 (5) | 0.0202 (12) | |
C19 | 0.9346 (8) | −0.2926 (7) | 0.2944 (5) | 0.0161 (11) | |
C20 | 1.0704 (8) | −0.1464 (7) | 0.1456 (4) | 0.0130 (10) | |
C21 | 0.9702 (8) | −0.1460 (7) | 0.2399 (4) | 0.0135 (10) | |
H1 | 0.3650 | 0.1466 | 0.9241 | 0.0175* | |
H2 | 0.6521 | 0.0733 | 0.6672 | 0.0158* | |
H3 | 0.5769 | 0.5890 | 0.6760 | 0.0225* | |
H4 | 0.5756 | 0.1558 | 0.5125 | 0.0176* | |
H5 | 1.0474 | 0.3148 | 0.4649 | 0.0192* | |
H6 | 0.9250 | 0.2364 | 0.2367 | 0.0189* | |
H7 | 1.0797 | 0.2336 | 0.0801 | 0.0198* | |
H8 | 1.1739 | −0.0043 | 0.0247 | 0.0162* | |
H9 | 1.1988 | −0.2924 | 0.0485 | 0.0223* | |
H10 | 1.1363 | −0.5261 | 0.1418 | 0.0224* | |
H11 | 0.9707 | −0.5279 | 0.2958 | 0.0243* | |
H12 | 0.8676 | −0.2959 | 0.3570 | 0.0193* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0169 (4) | 0.0074 (3) | 0.0300 (4) | −0.0043 (2) | −0.0080 (3) | −0.0017 (3) |
Br2 | 0.0234 (4) | 0.0131 (4) | 0.0230 (4) | −0.0001 (3) | −0.0030 (3) | −0.0092 (3) |
O1 | 0.022 (2) | 0.0063 (18) | 0.031 (3) | −0.0053 (15) | −0.0045 (17) | −0.0060 (16) |
O2 | 0.025 (3) | 0.0088 (19) | 0.027 (3) | −0.0068 (16) | −0.0039 (18) | −0.0027 (17) |
O3 | 0.020 (2) | 0.030 (3) | 0.029 (3) | −0.0151 (19) | 0.0060 (18) | −0.016 (2) |
N1 | 0.013 (3) | 0.016 (3) | 0.022 (3) | −0.0056 (18) | −0.0070 (18) | −0.0047 (19) |
N2 | 0.012 (2) | 0.013 (3) | 0.019 (3) | −0.0031 (17) | −0.0018 (18) | −0.0072 (18) |
C1 | 0.010 (3) | 0.007 (3) | 0.023 (3) | 0.0008 (18) | −0.007 (2) | −0.006 (2) |
C2 | 0.013 (3) | 0.007 (3) | 0.028 (3) | −0.0048 (19) | −0.008 (2) | −0.004 (2) |
C3 | 0.010 (3) | 0.011 (3) | 0.023 (3) | 0.0010 (19) | −0.004 (2) | −0.010 (2) |
C4 | 0.010 (3) | 0.012 (3) | 0.022 (3) | −0.000 (2) | −0.003 (2) | −0.008 (2) |
C5 | 0.013 (3) | 0.006 (3) | 0.025 (3) | 0.0006 (18) | −0.011 (2) | −0.002 (2) |
C6 | 0.012 (3) | 0.007 (3) | 0.021 (3) | −0.0001 (18) | −0.007 (2) | −0.004 (2) |
C7 | 0.013 (3) | 0.010 (3) | 0.018 (3) | −0.0016 (19) | −0.004 (2) | −0.004 (2) |
C8 | 0.015 (3) | 0.010 (3) | 0.016 (3) | −0.0046 (19) | −0.004 (2) | −0.002 (2) |
C9 | 0.017 (3) | 0.010 (3) | 0.019 (3) | −0.005 (2) | −0.004 (2) | −0.005 (2) |
C10 | 0.017 (3) | 0.009 (3) | 0.023 (3) | −0.007 (2) | −0.006 (3) | 0.000 (2) |
C11 | 0.014 (3) | 0.015 (3) | 0.019 (3) | −0.003 (2) | −0.002 (2) | −0.009 (2) |
C12 | 0.009 (3) | 0.015 (3) | 0.019 (3) | −0.0044 (19) | −0.0037 (19) | −0.005 (2) |
C13 | 0.012 (3) | 0.008 (3) | 0.032 (4) | −0.0010 (19) | −0.012 (3) | −0.006 (3) |
C14 | 0.016 (3) | 0.011 (3) | 0.023 (3) | −0.003 (2) | −0.009 (3) | −0.001 (2) |
C15 | 0.010 (3) | 0.015 (3) | 0.017 (3) | −0.007 (2) | −0.0023 (19) | −0.002 (2) |
C16 | 0.014 (3) | 0.017 (3) | 0.025 (3) | 0.003 (2) | −0.005 (3) | −0.014 (3) |
C17 | 0.019 (3) | 0.009 (3) | 0.031 (4) | 0.001 (2) | −0.012 (3) | −0.008 (3) |
C18 | 0.025 (3) | 0.011 (3) | 0.030 (4) | −0.008 (3) | −0.014 (3) | 0.001 (3) |
C19 | 0.017 (3) | 0.013 (3) | 0.020 (3) | −0.005 (2) | −0.008 (2) | −0.001 (2) |
C20 | 0.011 (3) | 0.011 (3) | 0.018 (3) | −0.0032 (19) | −0.004 (2) | −0.004 (2) |
C21 | 0.012 (3) | 0.011 (3) | 0.021 (3) | −0.0029 (19) | −0.008 (2) | −0.005 (2) |
Br1—C5 | 1.893 (6) | C13—C14 | 1.417 (9) |
Br2—C3 | 1.870 (7) | C14—C15 | 1.373 (9) |
O1—C2 | 1.341 (7) | C15—C20 | 1.417 (8) |
O2—C7 | 1.243 (8) | C16—C17 | 1.356 (9) |
O3—C11 | 1.213 (8) | C16—C20 | 1.425 (10) |
N1—N2 | 1.368 (8) | C17—C18 | 1.404 (9) |
N1—C10 | 1.317 (9) | C18—C19 | 1.378 (10) |
N2—C9 | 1.364 (7) | C19—C21 | 1.416 (8) |
N2—C11 | 1.427 (10) | C20—C21 | 1.434 (8) |
C1—C2 | 1.419 (9) | O1—H3 | 0.840 |
C1—C6 | 1.417 (8) | C4—H1 | 0.950 |
C1—C7 | 1.475 (8) | C6—H2 | 0.950 |
C2—C3 | 1.415 (8) | C9—H4 | 0.950 |
C3—C4 | 1.379 (8) | C10—H5 | 0.950 |
C4—C5 | 1.389 (9) | C13—H6 | 0.950 |
C5—C6 | 1.380 (8) | C14—H7 | 0.950 |
C7—C8 | 1.473 (9) | C15—H8 | 0.950 |
C8—C9 | 1.367 (11) | C16—H9 | 0.950 |
C8—C10 | 1.426 (8) | C17—H10 | 0.950 |
C11—C12 | 1.476 (8) | C18—H11 | 0.950 |
C12—C13 | 1.382 (8) | C19—H12 | 0.950 |
C12—C21 | 1.438 (9) | ||
Br2···O1 | 3.001 (5) | H11···H12 | 2.3146 |
O1···O2 | 2.565 (7) | Br1···H7iii | 3.3724 |
O1···C7 | 2.867 (8) | Br1···H8viii | 3.4550 |
O2···C2 | 2.807 (7) | Br1···H10ix | 3.3397 |
O2···C9 | 3.538 (9) | Br2···H6v | 3.3350 |
O2···C10 | 2.996 (8) | Br2···H7viii | 3.3550 |
O3···N1 | 3.512 (9) | Br2···H7v | 3.1777 |
O3···C9 | 2.751 (10) | Br2···H9x | 2.8779 |
O3···C13 | 3.512 (8) | Br2···H9iii | 3.5074 |
O3···C19 | 2.944 (8) | Br2···H10x | 3.1965 |
O3···C21 | 2.972 (7) | Br2···H10ii | 3.5687 |
N1···C12 | 2.930 (10) | O1···H6v | 3.0327 |
N1···C13 | 2.928 (10) | O1···H10iii | 3.5909 |
N2···C13 | 2.926 (8) | O2···H4v | 3.1289 |
C1···C4 | 2.795 (8) | O2···H5vi | 2.6299 |
C1···C9 | 3.252 (9) | O2···H11iii | 3.5241 |
C2···C5 | 2.803 (8) | O2···H12iv | 3.3240 |
C3···C6 | 2.800 (9) | O2···H12iii | 3.3782 |
C6···C8 | 2.958 (8) | O3···H2ii | 2.8993 |
C6···C9 | 3.181 (9) | O3···H4ii | 2.3008 |
C8···C11 | 3.570 (10) | O3···H5iii | 3.1732 |
C10···C11 | 3.507 (11) | N1···H2iii | 2.9620 |
C11···C19 | 2.994 (9) | N1···H11iv | 2.7216 |
C12···C15 | 2.810 (8) | N2···H3v | 3.5425 |
C13···C20 | 2.802 (9) | N2···H11iv | 3.5371 |
C14···C21 | 2.848 (8) | C2···H11ii | 3.4752 |
C16···C19 | 2.797 (9) | C3···H9iii | 3.4520 |
C17···C21 | 2.827 (10) | C3···H11ii | 3.5806 |
C18···C20 | 2.789 (9) | C4···H8viii | 3.1593 |
Br1···O1i | 3.492 (6) | C4···H8iii | 3.4809 |
Br1···C12ii | 3.542 (7) | C6···H12ii | 3.4958 |
Br1···C14iii | 3.477 (7) | C7···H12iii | 3.3582 |
O1···Br1iv | 3.492 (6) | C8···H11iv | 3.5695 |
O1···N2v | 3.564 (7) | C9···H3v | 3.3636 |
O1···C17iii | 3.481 (9) | C10···H11iv | 2.6785 |
O1···C18iii | 3.598 (8) | C10···H12iii | 3.3923 |
O2···C9v | 3.440 (7) | C11···H4ii | 3.5045 |
O2···C10vi | 3.558 (9) | C11···H5iii | 3.4029 |
O2···C18iii | 3.563 (10) | C12···H2iii | 3.3072 |
O2···C19iii | 3.476 (8) | C13···H2iii | 3.4633 |
O3···O3ii | 3.530 (7) | C13···H10iv | 3.4537 |
O3···C6ii | 3.253 (10) | C13···H11iv | 3.5269 |
O3···C9ii | 3.227 (8) | C14···H1xi | 3.2807 |
O3···C10iii | 3.520 (8) | C14···H9vii | 3.2254 |
N1···N2iii | 3.411 (7) | C14···H10iv | 3.3528 |
N1···C9iii | 3.455 (7) | C15···H1xi | 3.0172 |
N2···O1v | 3.564 (7) | C15···H8vii | 2.9417 |
N2···N1iii | 3.411 (7) | C15···H9vii | 3.4108 |
N2···C10iii | 3.451 (7) | C16···H1ii | 3.5849 |
C1···C19iii | 3.556 (9) | C16···H7vii | 3.4040 |
C1···C21iii | 3.432 (8) | C16···H8vii | 3.4014 |
C2···C16iii | 3.539 (10) | C17···H3iii | 3.4810 |
C2···C17iii | 3.566 (11) | C17···H6i | 3.4220 |
C3···C16iii | 3.421 (9) | C18···H3iii | 3.2763 |
C3···C18ii | 3.468 (10) | C18···H5i | 3.3353 |
C4···C15iii | 3.481 (8) | C18···H6i | 3.2839 |
C5···C14iii | 3.513 (8) | C19···H5iii | 3.5826 |
C5···C15iii | 3.422 (9) | C20···H8vii | 3.2058 |
C5···C19ii | 3.570 (9) | H1···C14viii | 3.2807 |
C5···C21ii | 3.544 (9) | H1···C15viii | 3.0172 |
C6···O3ii | 3.253 (10) | H1···C16ii | 3.5849 |
C6···C12iii | 3.470 (8) | H1···H1xii | 3.3932 |
C6···C21iii | 3.491 (10) | H1···H7viii | 2.8501 |
C7···C19iii | 3.395 (10) | H1···H8viii | 2.2922 |
C9···O2v | 3.440 (7) | H1···H8iii | 3.4174 |
C9···O3ii | 3.227 (8) | H2···O3ii | 2.8993 |
C9···N1iii | 3.455 (7) | H2···N1iii | 2.9620 |
C10···O2vi | 3.558 (9) | H2···C12iii | 3.3072 |
C10···O3iii | 3.520 (8) | H2···C13iii | 3.4633 |
C10···N2iii | 3.451 (7) | H3···N2v | 3.5425 |
C10···C11iii | 3.448 (8) | H3···C9v | 3.3636 |
C10···C18iv | 3.537 (8) | H3···C17iii | 3.4810 |
C11···C10iii | 3.448 (8) | H3···C18iii | 3.2763 |
C12···Br1ii | 3.542 (7) | H3···H4v | 3.2835 |
C12···C6iii | 3.470 (8) | H3···H5vi | 3.2838 |
C14···Br1iii | 3.477 (7) | H3···H11iii | 3.3159 |
C14···C5iii | 3.513 (8) | H4···O2v | 3.1289 |
C15···C4iii | 3.481 (8) | H4···O3ii | 2.3008 |
C15···C5iii | 3.422 (9) | H4···C11ii | 3.5045 |
C15···C15vii | 3.352 (10) | H4···H3v | 3.2835 |
C16···C2iii | 3.539 (10) | H4···H4ii | 3.4472 |
C16···C3iii | 3.421 (9) | H4···H12ii | 3.4341 |
C17···O1iii | 3.481 (9) | H5···O2vi | 2.6299 |
C17···C2iii | 3.566 (11) | H5···O3iii | 3.1732 |
C18···O1iii | 3.598 (8) | H5···C11iii | 3.4029 |
C18···O2iii | 3.563 (10) | H5···C18iv | 3.3353 |
C18···C3ii | 3.468 (10) | H5···C19iii | 3.5826 |
C18···C10i | 3.537 (8) | H5···H3vi | 3.2838 |
C19···O2iii | 3.476 (8) | H5···H5vi | 3.5363 |
C19···C1iii | 3.556 (9) | H5···H11iv | 2.6349 |
C19···C5ii | 3.570 (9) | H5···H12iv | 3.3818 |
C19···C7iii | 3.395 (10) | H5···H12iii | 2.8249 |
C21···C1iii | 3.432 (8) | H6···Br2v | 3.3350 |
C21···C5ii | 3.544 (9) | H6···O1v | 3.0327 |
C21···C6iii | 3.491 (10) | H6···C17iv | 3.4220 |
Br1···H1 | 2.9064 | H6···C18iv | 3.2839 |
Br1···H2 | 2.9157 | H6···H10iv | 2.9117 |
Br2···H1 | 2.9029 | H6···H11iv | 2.6271 |
O2···H3 | 1.8478 | H7···Br1iii | 3.3724 |
O2···H5 | 2.9382 | H7···Br2xi | 3.3550 |
O3···H4 | 2.6228 | H7···Br2v | 3.1777 |
O3···H12 | 2.3649 | H7···C16vii | 3.4040 |
N1···H4 | 3.1758 | H7···H1xi | 2.8501 |
N1···H6 | 2.4781 | H7···H9vii | 2.9645 |
N2···H5 | 3.0438 | H7···H10iv | 2.7262 |
N2···H6 | 2.6233 | H8···Br1xi | 3.4550 |
C1···H3 | 2.4414 | H8···C4xi | 3.1593 |
C1···H4 | 3.2200 | H8···C4iii | 3.4809 |
C2···H1 | 3.2819 | H8···C15vii | 2.9417 |
C2···H2 | 3.3118 | H8···C16vii | 3.4014 |
C3···H3 | 3.0549 | H8···C20vii | 3.2058 |
C4···H2 | 3.2658 | H8···H1xi | 2.2922 |
C6···H1 | 3.2617 | H8···H1iii | 3.4174 |
C6···H4 | 2.9521 | H8···H8vii | 2.8061 |
C7···H2 | 2.6957 | H8···H9vii | 3.3014 |
C7···H3 | 2.4287 | H9···Br2xiii | 2.8779 |
C7···H4 | 2.9062 | H9···Br2iii | 3.5074 |
C7···H5 | 2.8364 | H9···C3iii | 3.4520 |
C8···H2 | 2.6214 | H9···C14vii | 3.2254 |
C9···H2 | 2.5715 | H9···C15vii | 3.4108 |
C9···H5 | 3.1225 | H9···H7vii | 2.9645 |
C10···H4 | 3.1375 | H9···H8vii | 3.3014 |
C10···H6 | 3.4812 | H10···Br1ix | 3.3397 |
C11···H4 | 2.7515 | H10···Br2xiii | 3.1965 |
C11···H6 | 2.6092 | H10···Br2ii | 3.5687 |
C11···H12 | 2.6897 | H10···O1iii | 3.5909 |
C12···H7 | 3.2902 | H10···C13i | 3.4537 |
C12···H12 | 2.7322 | H10···C14i | 3.3528 |
C13···H8 | 3.2701 | H10···H6i | 2.9117 |
C15···H6 | 3.2629 | H10···H7i | 2.7262 |
C15···H9 | 2.6357 | H11···O2iii | 3.5241 |
C16···H8 | 2.6301 | H11···N1i | 2.7216 |
C16···H11 | 3.2439 | H11···N2i | 3.5371 |
C17···H12 | 3.2752 | H11···C2ii | 3.4752 |
C18···H9 | 3.2522 | H11···C3ii | 3.5806 |
C19···H10 | 3.2731 | H11···C8i | 3.5695 |
C20···H7 | 3.2871 | H11···C10i | 2.6785 |
C20···H10 | 3.2758 | H11···C13i | 3.5269 |
C20···H12 | 3.3011 | H11···H3iii | 3.3159 |
C21···H6 | 3.3053 | H11···H5i | 2.6349 |
C21···H8 | 3.3269 | H11···H6i | 2.6271 |
C21···H9 | 3.3286 | H12···O2i | 3.3240 |
C21···H11 | 3.2836 | H12···O2iii | 3.3782 |
H2···H4 | 2.3745 | H12···C6ii | 3.4958 |
H6···H7 | 2.3618 | H12···C7iii | 3.3582 |
H7···H8 | 2.3192 | H12···C10iii | 3.3923 |
H8···H9 | 2.4494 | H12···H4ii | 3.4341 |
H9···H10 | 2.3002 | H12···H5i | 3.3818 |
H10···H11 | 2.3456 | H12···H5iii | 2.8249 |
N2—N1—C10 | 104.6 (5) | C14—C15—C20 | 121.0 (5) |
N1—N2—C9 | 111.9 (6) | C17—C16—C20 | 120.6 (6) |
N1—N2—C11 | 124.5 (5) | C16—C17—C18 | 120.2 (6) |
C9—N2—C11 | 123.5 (6) | C17—C18—C19 | 121.0 (6) |
C2—C1—C6 | 119.7 (5) | C18—C19—C21 | 120.8 (6) |
C2—C1—C7 | 118.9 (5) | C15—C20—C16 | 120.0 (5) |
C6—C1—C7 | 121.2 (5) | C15—C20—C21 | 120.3 (6) |
O1—C2—C1 | 122.9 (5) | C16—C20—C21 | 119.7 (5) |
O1—C2—C3 | 118.5 (6) | C12—C21—C19 | 125.0 (5) |
C1—C2—C3 | 118.6 (5) | C12—C21—C20 | 117.3 (5) |
Br2—C3—C2 | 119.1 (5) | C19—C21—C20 | 117.7 (6) |
Br2—C3—C4 | 120.3 (5) | C2—O1—H3 | 109.471 |
C2—C3—C4 | 120.5 (6) | C3—C4—H1 | 119.719 |
C3—C4—C5 | 120.6 (5) | C5—C4—H1 | 119.718 |
Br1—C5—C4 | 119.3 (4) | C1—C6—H2 | 120.184 |
Br1—C5—C6 | 119.8 (5) | C5—C6—H2 | 120.182 |
C4—C5—C6 | 120.9 (6) | N2—C9—H4 | 126.528 |
C1—C6—C5 | 119.6 (6) | C8—C9—H4 | 126.542 |
O2—C7—C1 | 121.0 (6) | N1—C10—H5 | 124.031 |
O2—C7—C8 | 118.7 (5) | C8—C10—H5 | 124.022 |
C1—C7—C8 | 120.4 (5) | C12—C13—H6 | 119.423 |
C7—C8—C9 | 130.1 (5) | C14—C13—H6 | 119.416 |
C7—C8—C10 | 125.1 (7) | C13—C14—H7 | 120.217 |
C9—C8—C10 | 104.6 (6) | C15—C14—H7 | 120.214 |
N2—C9—C8 | 106.9 (6) | C14—C15—H8 | 119.513 |
N1—C10—C8 | 111.9 (6) | C20—C15—H8 | 119.515 |
O3—C11—N2 | 117.1 (6) | C17—C16—H9 | 119.699 |
O3—C11—C12 | 125.0 (7) | C20—C16—H9 | 119.707 |
N2—C11—C12 | 117.8 (6) | C16—C17—H10 | 119.889 |
C11—C12—C13 | 119.0 (6) | C18—C17—H10 | 119.880 |
C11—C12—C21 | 120.0 (5) | C17—C18—H11 | 119.506 |
C13—C12—C21 | 120.6 (5) | C19—C18—H11 | 119.498 |
C12—C13—C14 | 121.2 (6) | C18—C19—H12 | 119.584 |
C13—C14—C15 | 119.6 (6) | C21—C19—H12 | 119.586 |
H3—O1—C2—C1 | −17.0 | C9—C8—C10—H5 | 179.2 |
H3—O1—C2—C3 | 163.3 | C10—C8—C9—N2 | −0.7 (5) |
N2—N1—C10—C8 | 1.9 (6) | C10—C8—C9—H4 | 179.3 |
N2—N1—C10—H5 | −178.1 | O3—C11—C12—C13 | 139.0 (6) |
C10—N1—N2—C9 | −2.4 (5) | O3—C11—C12—C21 | −33.7 (8) |
C10—N1—N2—C11 | −179.9 (4) | N2—C11—C12—C13 | −38.1 (7) |
N1—N2—C9—C8 | 1.9 (6) | N2—C11—C12—C21 | 149.2 (5) |
N1—N2—C9—H4 | −178.1 | C11—C12—C13—C14 | −172.6 (5) |
N1—N2—C11—O3 | 161.6 (5) | C11—C12—C13—H6 | 7.4 |
N1—N2—C11—C12 | −21.1 (7) | C11—C12—C21—C19 | −7.7 (9) |
C9—N2—C11—O3 | −15.7 (7) | C11—C12—C21—C20 | 174.2 (5) |
C9—N2—C11—C12 | 161.7 (4) | C13—C12—C21—C19 | 179.8 (5) |
C11—N2—C9—C8 | 179.5 (4) | C13—C12—C21—C20 | 1.7 (8) |
C11—N2—C9—H4 | −0.5 | C21—C12—C13—C14 | 0.1 (9) |
C2—C1—C6—C5 | 1.0 (9) | C21—C12—C13—H6 | −179.9 |
C2—C1—C6—H2 | −179.0 | C12—C13—C14—C15 | −1.4 (9) |
C6—C1—C2—O1 | −179.6 (5) | C12—C13—C14—H7 | 178.6 |
C6—C1—C2—C3 | 0.1 (9) | H6—C13—C14—C15 | 178.6 |
C2—C1—C7—O2 | 3.7 (9) | H6—C13—C14—H7 | −1.4 |
C2—C1—C7—C8 | −177.7 (5) | C13—C14—C15—C20 | 0.8 (9) |
C7—C1—C2—O1 | 4.4 (9) | C13—C14—C15—H8 | −179.2 |
C7—C1—C2—C3 | −175.9 (5) | H7—C14—C15—C20 | −179.2 |
C6—C1—C7—O2 | −172.3 (5) | H7—C14—C15—H8 | 0.8 |
C6—C1—C7—C8 | 6.4 (9) | C14—C15—C20—C16 | −178.9 (5) |
C7—C1—C6—C5 | 176.9 (5) | C14—C15—C20—C21 | 1.0 (9) |
C7—C1—C6—H2 | −3.1 | H8—C15—C20—C16 | 1.1 |
O1—C2—C3—Br2 | −3.0 (8) | H8—C15—C20—C21 | −179.0 |
O1—C2—C3—C4 | 179.0 (5) | C17—C16—C20—C15 | −179.8 (6) |
C1—C2—C3—Br2 | 177.3 (5) | C17—C16—C20—C21 | 0.4 (9) |
C1—C2—C3—C4 | −0.7 (9) | C20—C16—C17—C18 | −0.0 (10) |
Br2—C3—C4—C5 | −177.8 (4) | C20—C16—C17—H10 | 180.0 |
Br2—C3—C4—H1 | 2.2 | H9—C16—C17—C18 | 180.0 |
C2—C3—C4—C5 | 0.1 (9) | H9—C16—C17—H10 | −0.0 |
C2—C3—C4—H1 | −179.9 | H9—C16—C20—C15 | 0.2 |
C3—C4—C5—Br1 | −178.9 (5) | H9—C16—C20—C21 | −179.6 |
C3—C4—C5—C6 | 1.1 (9) | C16—C17—C18—C19 | −0.1 (10) |
H1—C4—C5—Br1 | 1.1 | C16—C17—C18—H11 | 179.9 |
H1—C4—C5—C6 | −178.9 | H10—C17—C18—C19 | 179.9 |
Br1—C5—C6—C1 | 178.4 (4) | H10—C17—C18—H11 | −0.1 |
Br1—C5—C6—H2 | −1.6 | C17—C18—C19—C21 | −0.1 (10) |
C4—C5—C6—C1 | −1.6 (9) | C17—C18—C19—H12 | 179.9 |
C4—C5—C6—H2 | 178.4 | H11—C18—C19—C21 | 179.9 |
O2—C7—C8—C9 | −132.1 (6) | H11—C18—C19—H12 | −0.1 |
O2—C7—C8—C10 | 41.0 (8) | C18—C19—C21—C12 | −177.6 (6) |
C1—C7—C8—C9 | 49.2 (8) | C18—C19—C21—C20 | 0.5 (9) |
C1—C7—C8—C10 | −137.7 (5) | H12—C19—C21—C12 | 2.4 |
C7—C8—C9—N2 | 173.5 (5) | H12—C19—C21—C20 | −179.5 |
C7—C8—C9—H4 | −6.5 | C15—C20—C21—C12 | −2.2 (8) |
C7—C8—C10—N1 | −175.3 (5) | C15—C20—C21—C19 | 179.6 (5) |
C7—C8—C10—H5 | 4.7 | C16—C20—C21—C12 | 177.6 (5) |
C9—C8—C10—N1 | −0.8 (6) | C16—C20—C21—C19 | −0.6 (8) |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y, −z+1; (iii) −x+2, −y, −z+1; (iv) x, y+1, z; (v) −x+1, −y+1, −z+1; (vi) −x+2, −y+1, −z+1; (vii) −x+2, −y, −z; (viii) x−1, y, z+1; (ix) −x+2, −y−1, −z+1; (x) x−1, y+1, z+1; (xi) x+1, y, z−1; (xii) −x+1, −y, −z+2; (xiii) x+1, y−1, z−1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H3···O2 | 0.84 | 1.85 | 2.565 (7) | 142 |
C9—H4···O3ii | 0.95 | 2.30 | 3.227 (8) | 165 |
C16—H9···Br2xiii | 0.95 | 2.88 | 3.613 (7) | 135 |
Symmetry codes: (ii) −x+1, −y, −z+1; (xiii) x+1, y−1, z−1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H3···O2 | 0.84 | 1.848 | 2.565 (7) | 142 |
C9—H4···O3i | 0.95 | 2.301 | 3.227 (8) | 165 |
C16—H9···Br2ii | 0.95 | 2.88 | 3.613 (7) | 135 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x+1, y−1, z−1. |
Acknowledgements
We acknowledge the University of Shizuoka for instrumental support and Professor Kei Manabe (University of Shizuoka) for helpful discussions.
References
Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. CrossRef Web of Science IUCr Journals Google Scholar
Ishikawa, Y. (2014). Acta Cryst. E70, o439. CSD CrossRef IUCr Journals Google Scholar
Ishikawa, Y. & Watanabe, K. (2014a). Acta Cryst. E70, o472. CSD CrossRef IUCr Journals Google Scholar
Ishikawa, Y. & Watanabe, K. (2014b). Acta Cryst. E70, o565. CSD CrossRef IUCr Journals Google Scholar
Ishikawa, Y. & Watanabe, K. (2014c). Acta Cryst. E70, o784. CrossRef IUCr Journals Google Scholar
Ishikawa, Y. & Watanabe, K. (2014d). Acta Cryst. E70, o832. CSD CrossRef IUCr Journals Google Scholar
Khan, K. M., Ambreen, N., Hussain, S., Perveen, S. & Choudhary, M. I. (2009). Bioorg. Med. Chem. 17, 2983–2988. Web of Science CrossRef PubMed CAS Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Rigaku (1999). WinAFC. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2010). CrystalStructure. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tu, Q. D., Li, D., Sun, Y., Han, X. Y., Yi, F., Sha, Y., Ren, Y. L., Ding, M. W., Feng, L. L. & Wan, J. (2013). Bioorg. Med. Chem. 21, 2826–2831. Web of Science CrossRef CAS PubMed Google Scholar
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