Crystal structure of (3,5-dibromo-2-hy­droxyphenyl){1-[(naphthalen-1-yl)carbonyl]-1H-pyrazol-4-yl}methanone

Ishikawa, Y.; Motohashi, Y.

doi:10.1107/S1600536814018601

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 9| September 2014| Page o1033

doi:10.1107/S1600536814018601

Open

access

Crystal structure of (3,5-dibromo-2-hydroxyphenyl){1-[(naphthalen-1-yl)carbonyl]-1H-pyrazol-4-yl}methanone

Yoshinobu Ishikawa ^a ^* and Yuya Motohashi ^a

^aSchool of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, Shizuoka 422-8526 , Japan
^*Correspondence e-mail: ishi206@u-shizuoka-ken.ac.jp

Edited by E. R. T. Tiekink, University of Malaya, Malaysia (Received 14 August 2014; accepted 15 August 2014; online 20 August 2014)

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

C₂₁H₁₂Br₂N₂O₃
M_r = 500.15
Triclinic, $[P \overline 1]$
a = 7.390 (5) Å
b = 8.919 (4) Å
c = 14.955 (9) Å
α = 74.61 (4)°
β = 76.71 (5)°
γ = 71.03 (4)°
V = 887.5 (9) Å³
Z = 2
Mo Kα radiation
μ = 4.61 mm⁻¹
T = 100 K
0.40 × 0.18 × 0.08 mm

2.2. Data collection

Rigaku AFC7R diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.448, T_max = 0.692
5003 measured reflections
4088 independent reflections
3359 reflections with F² > 2.0σ(F²)
R_int = 0.062
3 standard reflections every 150 reflections intensity decay: −0.6%

2.3. Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.204
S = 1.07
4088 reflections
254 parameters
H-atom parameters constrained
Δρ_max = 2.15 e Å⁻³
Δρ_min = −2.52 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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⋯O3ⁱ	0.95	2.30	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.

Data collection: WinAFC (Rigaku, 1999 ); cell refinement: 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

Crystal structure: contains datablocks General, I. DOI: 10.1107/S1600536814018601/tk5338sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814018601/tk5338Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814018601/tk5338Isup3.cml

checkCIF report

Structural commentary top

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 cyclization (Fig. 1) should be a resonance energy gain, resulting from the extension of the conjugated system across the entire molecule. The intramolecular cyclization 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.

Synthesis and crystallization top

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.

Refinement top

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, U_iso(H) = 1.2U_eq(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.

Related literature top

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).

Computing details top

Data collection: WinAFC (Rigaku, 1999); cell refinement: 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).

Figures top

	Fig. 1. Reaction scheme for the title compound.
	Fig. 2. The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. Hydrogen atoms are shown as small spheres of arbitrary radius.
	Fig. 3. A crystal packing view of the title compound. Intramolecular O—H···O and intermolecular C–H···O hydrogen bonds are represented by dashed lines.

(3,5-Dibromo-2-hydroxyphenyl){1-[(naphthalen-1-yl)carbonyl]-1H-pyrazol-4-yl}methanone top

Crystal data top

C₂₁H₁₂Br₂N₂O₃	Z = 2
M_r = 500.15	F(000) = 492.00
Triclinic, P1	D_x = 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

Data collection top

Rigaku AFC7R diffractometer	R_int = 0.062
ω–2θ scans	θ_max = 27.5°
Absorption correction: ψ scan (North et al., 1968)	h = −5→9
T_min = 0.448, T_max = 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 top

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(F_o²) + (0.1444P)² + 3.2256P] where P = (F_o² + 2F_c²)/3
4088 reflections	(Δ/σ)_max < 0.001
254 parameters	Δρ_max = 2.15 e Å⁻³
0 restraints	Δρ_min = −2.52 e Å⁻³
Primary atom site location: structure-invariant direct methods

Crystal data top

C₂₁H₁₂Br₂N₂O₃	γ = 71.03 (4)°
M_r = 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)°

Data collection top

Rigaku AFC7R diffractometer	3359 reflections with F² > 2.0σ(F²)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.062
T_min = 0.448, T_max = 0.692	3 standard reflections every 150 reflections
5003 measured reflections	intensity decay: −0.6%
4088 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.204	H-atom parameters constrained
S = 1.07	Δρ_max = 2.15 e Å⁻³
4088 reflections	Δρ_min = −2.52 e Å⁻³
254 parameters

Special details top

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).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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···H8^viii	3.4550
O2···C2	2.807 (7)	Br1···H10^ix	3.3397
O2···C9	3.538 (9)	Br2···H6^v	3.3350
O2···C10	2.996 (8)	Br2···H7^viii	3.3550
O3···N1	3.512 (9)	Br2···H7^v	3.1777
O3···C9	2.751 (10)	Br2···H9^x	2.8779
O3···C13	3.512 (8)	Br2···H9ⁱⁱⁱ	3.5074
O3···C19	2.944 (8)	Br2···H10^x	3.1965
O3···C21	2.972 (7)	Br2···H10ⁱⁱ	3.5687
N1···C12	2.930 (10)	O1···H6^v	3.0327
N1···C13	2.928 (10)	O1···H10ⁱⁱⁱ	3.5909
N2···C13	2.926 (8)	O2···H4^v	3.1289
C1···C4	2.795 (8)	O2···H5^vi	2.6299
C1···C9	3.252 (9)	O2···H11ⁱⁱⁱ	3.5241
C2···C5	2.803 (8)	O2···H12^iv	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···H11^iv	2.7216
C12···C15	2.810 (8)	N2···H3^v	3.5425
C13···C20	2.802 (9)	N2···H11^iv	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···H8^viii	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···Br1^iv	3.492 (6)	C8···H11^iv	3.5695
O1···N2^v	3.564 (7)	C9···H3^v	3.3636
O1···C17ⁱⁱⁱ	3.481 (9)	C10···H11^iv	2.6785
O1···C18ⁱⁱⁱ	3.598 (8)	C10···H12ⁱⁱⁱ	3.3923
O2···C9^v	3.440 (7)	C11···H4ⁱⁱ	3.5045
O2···C10^vi	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···H10^iv	3.4537
O3···C6ⁱⁱ	3.253 (10)	C13···H11^iv	3.5269
O3···C9ⁱⁱ	3.227 (8)	C14···H1^xi	3.2807
O3···C10ⁱⁱⁱ	3.520 (8)	C14···H9^vii	3.2254
N1···N2ⁱⁱⁱ	3.411 (7)	C14···H10^iv	3.3528
N1···C9ⁱⁱⁱ	3.455 (7)	C15···H1^xi	3.0172
N2···O1^v	3.564 (7)	C15···H8^vii	2.9417
N2···N1ⁱⁱⁱ	3.411 (7)	C15···H9^vii	3.4108
N2···C10ⁱⁱⁱ	3.451 (7)	C16···H1ⁱⁱ	3.5849
C1···C19ⁱⁱⁱ	3.556 (9)	C16···H7^vii	3.4040
C1···C21ⁱⁱⁱ	3.432 (8)	C16···H8^vii	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···H8^vii	3.2058
C5···C19ⁱⁱ	3.570 (9)	H1···C14^viii	3.2807
C5···C21ⁱⁱ	3.544 (9)	H1···C15^viii	3.0172
C6···O3ⁱⁱ	3.253 (10)	H1···C16ⁱⁱ	3.5849
C6···C12ⁱⁱⁱ	3.470 (8)	H1···H1^xii	3.3932
C6···C21ⁱⁱⁱ	3.491 (10)	H1···H7^viii	2.8501
C7···C19ⁱⁱⁱ	3.395 (10)	H1···H8^viii	2.2922
C9···O2^v	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···O2^vi	3.558 (9)	H2···C12ⁱⁱⁱ	3.3072
C10···O3ⁱⁱⁱ	3.520 (8)	H2···C13ⁱⁱⁱ	3.4633
C10···N2ⁱⁱⁱ	3.451 (7)	H3···N2^v	3.5425
C10···C11ⁱⁱⁱ	3.448 (8)	H3···C9^v	3.3636
C10···C18^iv	3.537 (8)	H3···C17ⁱⁱⁱ	3.4810
C11···C10ⁱⁱⁱ	3.448 (8)	H3···C18ⁱⁱⁱ	3.2763
C12···Br1ⁱⁱ	3.542 (7)	H3···H4^v	3.2835
C12···C6ⁱⁱⁱ	3.470 (8)	H3···H5^vi	3.2838
C14···Br1ⁱⁱⁱ	3.477 (7)	H3···H11ⁱⁱⁱ	3.3159
C14···C5ⁱⁱⁱ	3.513 (8)	H4···O2^v	3.1289
C15···C4ⁱⁱⁱ	3.481 (8)	H4···O3ⁱⁱ	2.3008
C15···C5ⁱⁱⁱ	3.422 (9)	H4···C11ⁱⁱ	3.5045
C15···C15^vii	3.352 (10)	H4···H3^v	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···O2^vi	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···C18^iv	3.3353
C18···C3ⁱⁱ	3.468 (10)	H5···C19ⁱⁱⁱ	3.5826
C18···C10ⁱ	3.537 (8)	H5···H3^vi	3.2838
C19···O2ⁱⁱⁱ	3.476 (8)	H5···H5^vi	3.5363
C19···C1ⁱⁱⁱ	3.556 (9)	H5···H11^iv	2.6349
C19···C5ⁱⁱ	3.570 (9)	H5···H12^iv	3.3818
C19···C7ⁱⁱⁱ	3.395 (10)	H5···H12ⁱⁱⁱ	2.8249
C21···C1ⁱⁱⁱ	3.432 (8)	H6···Br2^v	3.3350
C21···C5ⁱⁱ	3.544 (9)	H6···O1^v	3.0327
C21···C6ⁱⁱⁱ	3.491 (10)	H6···C17^iv	3.4220
Br1···H1	2.9064	H6···C18^iv	3.2839
Br1···H2	2.9157	H6···H10^iv	2.9117
Br2···H1	2.9029	H6···H11^iv	2.6271
O2···H3	1.8478	H7···Br1ⁱⁱⁱ	3.3724
O2···H5	2.9382	H7···Br2^xi	3.3550
O3···H4	2.6228	H7···Br2^v	3.1777
O3···H12	2.3649	H7···C16^vii	3.4040
N1···H4	3.1758	H7···H1^xi	2.8501
N1···H6	2.4781	H7···H9^vii	2.9645
N2···H5	3.0438	H7···H10^iv	2.7262
N2···H6	2.6233	H8···Br1^xi	3.4550
C1···H3	2.4414	H8···C4^xi	3.1593
C1···H4	3.2200	H8···C4ⁱⁱⁱ	3.4809
C2···H1	3.2819	H8···C15^vii	2.9417
C2···H2	3.3118	H8···C16^vii	3.4014
C3···H3	3.0549	H8···C20^vii	3.2058
C4···H2	3.2658	H8···H1^xi	2.2922
C6···H1	3.2617	H8···H1ⁱⁱⁱ	3.4174
C6···H4	2.9521	H8···H8^vii	2.8061
C7···H2	2.6957	H8···H9^vii	3.3014
C7···H3	2.4287	H9···Br2^xiii	2.8779
C7···H4	2.9062	H9···Br2ⁱⁱⁱ	3.5074
C7···H5	2.8364	H9···C3ⁱⁱⁱ	3.4520
C8···H2	2.6214	H9···C14^vii	3.2254
C9···H2	2.5715	H9···C15^vii	3.4108
C9···H5	3.1225	H9···H7^vii	2.9645
C10···H4	3.1375	H9···H8^vii	3.3014
C10···H6	3.4812	H10···Br1^ix	3.3397
C11···H4	2.7515	H10···Br2^xiii	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.

Hydrogen-bond geometry (Å, º) top

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···Br2^xiii	0.95	2.88	3.613 (7)	135

Symmetry codes: (ii) −x+1, −y, −z+1; (xiii) x+1, y−1, z−1.

Hydrogen-bond geometry (Å, º) top

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

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 9| September 2014| Page o1033

doi:10.1107/S1600536814018601

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure of (3,5-di­bromo-2-hy­droxyphenyl){1-[(naphthalen-1-yl)carbonyl]-1H-pyrazol-4-yl}methanone

1. Related literature

2. Experimental

2.1. Crystal data

2.2. Data collection

2.3. Refinement

Supporting information

Acknowledgements

References

organic compounds

Crystal structure of (3,5-dibromo-2-hydroxyphenyl){1-[(naphthalen-1-yl)carbonyl]-1H-pyrazol-4-yl}methanone