Crystal structure of 3-meth-oxy-2-[5-(naphthalen-1-yl)-4,5-di-hydro-1H-pyrazol-3-yl]phenol.

In the title compound, C20H18N2O2, the central pyrazoline ring has an envelope conformation with the atom substituted by the naphthalene ring as the flap. It bridges a benzene ring and a naphthalene ring system which are almost normal to one another, making a dihedral angle of 82.03 (6) °. There is an intra-molecular O-H⋯N hydrogen bond forming an S(6) ring motif. In the crystal, mol-ecules are linked by pairs of N-H⋯π inter-actions, forming inversion dimers. There are also C-H⋯π inter-actions present and the dimers are linked via C-H⋯O hydrogen bonds, forming ribbons propagating along the a-axis direction.

Related literature

For the biological properties and synthesis of pyrazoline derivatives, see: Viveka et al. (2015 ▸); Neudorfer et al. (2014 ▸); Hwang et al. (2013 ▸); Congiu et al. (2010 ▸). For the N—H⋯π inter­action, see: Naveen et al. (2015 ▸). For related structures, see: Zhu et al. (2013 ▸); Patel et al. (2013 ▸).

Experimental

Crystal data

C20H18N2O2

M = 318.36

Triclinic,

a = 7.7280 (12) Å

b = 8.6933 (14) Å

c = 12.721 (2) Å

α = 78.507 (4)°

β = 73.781 (4)°

γ = 76.148 (4)°

V = 788.7 (2) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 147 K

0.23 × 0.14 × 0.10 mm

Data collection

Bruker Kappa APEX-DUO CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2012 ▸) T min = 0.980, T max = 0.991

6731 measured reflections

3605 independent reflections

2963 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.119

S = 1.06

3605 reflections

226 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.28 e Å−3

Δρmin = −0.26 e Å−3

Data collection: APEX2 (Bruker, 2012 ▸); cell refinement: SAINT (Bruker, 2012 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: PLATON (Spek, 2009 ▸); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▸) and PLATON.

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015018472/su5207sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015018472/su5207Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015018472/su5207Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015018472/su5207fig1.tif

The mol­ecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level. The intra­molecular O-H⋯N hydrogen bond is shown as a dashed line (see Table 1).

Click here for additional data file.

. DOI: 10.1107/S2056989015018472/su5207fig2.tif

Part of the crystal structure of the title compound, showing the intra­molecular O—H⋯N hydrogen bond and the inter­molecular N—H⋯π inter­actions, as dashed lines (see Table 1). H atoms not involved in these inter­actions have been omitted for clarity.

CCDC reference: 1429221

Additional supporting information: crystallographic information; 3D view; checkCIF report

C20H18N2O2	Z = 2
Mr = 318.36	F(000) = 336
Triclinic, P1	Dx = 1.341 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7280 (12) Å	Cell parameters from 2949 reflections
b = 8.6933 (14) Å	θ = 2.4–27.5°
c = 12.721 (2) Å	µ = 0.09 mm−1
α = 78.507 (4)°	T = 147 K
β = 73.781 (4)°	Needle, yellow
γ = 76.148 (4)°	0.23 × 0.14 × 0.10 mm
V = 788.7 (2) Å3

Bruker Kappa APEX-DUO CCD diffractometer	3605 independent reflections
Radiation source: fine-focus sealed tube	2963 reflections with I > 2σ(I)
Bruker Triumph monochromator	Rint = 0.027
φ and ω scans	θmax = 27.5°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −10→9
Tmin = 0.980, Tmax = 0.991	k = −11→10
6731 measured reflections	l = −16→16

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0564P)2 + 0.190P] where P = (Fo2 + 2Fc2)/3
3605 reflections	(Δ/σ)max < 0.001
226 parameters	Δρmax = 0.28 e Å−3
0 restraints	Δρmin = −0.26 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
O1	0.59916 (15)	0.28958 (14)	0.48006 (8)	0.0359 (3)
O2	0.28750 (13)	0.15225 (12)	0.24649 (8)	0.0271 (2)
N1	0.58945 (14)	0.25517 (12)	0.16583 (8)	0.0194 (2)
N2	0.75708 (14)	0.27317 (13)	0.09019 (9)	0.0201 (2)
C1	0.60118 (16)	0.26040 (14)	0.26482 (10)	0.0185 (3)
C2	0.78599 (16)	0.29279 (15)	0.26322 (10)	0.0206 (3)
H2A	0.8680	0.1942	0.2881	0.025*
H2B	0.7727	0.3756	0.3098	0.025*
C3	0.85658 (16)	0.35262 (14)	0.13973 (10)	0.0187 (3)
H3A	0.9918	0.3116	0.1156	0.022*
C4	0.81502 (15)	0.53454 (14)	0.11606 (10)	0.0173 (2)
C5	0.67014 (16)	0.61697 (15)	0.07244 (11)	0.0207 (3)
H5A	0.5946	0.5589	0.0550	0.025*
C6	0.63041 (17)	0.78560 (15)	0.05276 (11)	0.0236 (3)
H6A	0.5291	0.8395	0.0224	0.028*
C7	0.73662 (17)	0.87181 (15)	0.07702 (11)	0.0223 (3)
H7A	0.7090	0.9854	0.0635	0.027*
C8	0.88810 (16)	0.79261 (14)	0.12231 (10)	0.0182 (3)
C9	1.00239 (17)	0.88065 (15)	0.14546 (10)	0.0219 (3)
H9A	0.9754	0.9943	0.1319	0.026*
C10	1.15088 (17)	0.80452 (16)	0.18700 (11)	0.0246 (3)
H10A	1.2267	0.8649	0.2018	0.029*
C11	1.19088 (17)	0.63583 (16)	0.20777 (11)	0.0239 (3)
H11A	1.2940	0.5830	0.2367	0.029*
C12	1.08277 (16)	0.54708 (15)	0.18673 (10)	0.0207 (3)
H12A	1.1113	0.4336	0.2020	0.025*
C13	0.92878 (15)	0.62248 (14)	0.14245 (9)	0.0171 (2)
C14	0.45128 (16)	0.22550 (15)	0.36055 (10)	0.0206 (3)
C15	0.45112 (18)	0.23952 (16)	0.46981 (11)	0.0260 (3)
C16	0.3089 (2)	0.20441 (19)	0.55885 (12)	0.0347 (3)
H16A	0.3110	0.2143	0.6315	0.042*
C17	0.1636 (2)	0.1547 (2)	0.54096 (13)	0.0389 (4)
H17A	0.0656	0.1311	0.6021	0.047*
C18	0.1581 (2)	0.13886 (19)	0.43663 (12)	0.0340 (3)
H18A	0.0571	0.1046	0.4260	0.041*
C19	0.30079 (17)	0.17304 (16)	0.34678 (11)	0.0234 (3)
C20	0.6108 (2)	0.3009 (2)	0.58802 (13)	0.0419 (4)
H20A	0.7229	0.3389	0.5827	0.063*
H20B	0.6140	0.1953	0.6332	0.063*
H20C	0.5034	0.3764	0.6224	0.063*
H2O	0.383 (3)	0.178 (2)	0.1972 (18)	0.050 (5)*
H2N	0.739 (2)	0.318 (2)	0.0247 (15)	0.032 (4)*

	U11	U22	U33	U12	U13	U23
O1	0.0432 (6)	0.0524 (7)	0.0186 (5)	−0.0193 (5)	−0.0083 (4)	−0.0069 (5)
O2	0.0268 (5)	0.0338 (6)	0.0235 (5)	−0.0144 (4)	−0.0055 (4)	−0.0010 (4)
N1	0.0224 (5)	0.0184 (5)	0.0177 (5)	−0.0075 (4)	−0.0019 (4)	−0.0034 (4)
N2	0.0237 (5)	0.0202 (5)	0.0167 (5)	−0.0086 (4)	−0.0009 (4)	−0.0042 (4)
C1	0.0216 (6)	0.0148 (6)	0.0192 (6)	−0.0041 (4)	−0.0047 (5)	−0.0027 (5)
C2	0.0218 (6)	0.0197 (6)	0.0210 (6)	−0.0053 (4)	−0.0059 (5)	−0.0022 (5)
C3	0.0186 (5)	0.0167 (6)	0.0209 (6)	−0.0045 (4)	−0.0033 (4)	−0.0036 (5)
C4	0.0175 (5)	0.0171 (6)	0.0160 (6)	−0.0046 (4)	−0.0003 (4)	−0.0033 (4)
C5	0.0190 (6)	0.0210 (6)	0.0236 (6)	−0.0063 (5)	−0.0049 (5)	−0.0045 (5)
C6	0.0209 (6)	0.0222 (6)	0.0265 (7)	−0.0004 (5)	−0.0079 (5)	−0.0021 (5)
C7	0.0235 (6)	0.0165 (6)	0.0250 (7)	−0.0019 (5)	−0.0044 (5)	−0.0033 (5)
C8	0.0196 (6)	0.0183 (6)	0.0155 (6)	−0.0042 (4)	−0.0003 (4)	−0.0046 (5)
C9	0.0260 (6)	0.0206 (6)	0.0194 (6)	−0.0074 (5)	−0.0010 (5)	−0.0066 (5)
C10	0.0267 (6)	0.0306 (7)	0.0213 (6)	−0.0126 (5)	−0.0041 (5)	−0.0089 (5)
C11	0.0209 (6)	0.0321 (7)	0.0202 (6)	−0.0041 (5)	−0.0073 (5)	−0.0055 (5)
C12	0.0213 (6)	0.0208 (6)	0.0194 (6)	−0.0035 (5)	−0.0046 (5)	−0.0029 (5)
C13	0.0177 (5)	0.0185 (6)	0.0142 (6)	−0.0039 (4)	−0.0013 (4)	−0.0032 (4)
C14	0.0242 (6)	0.0177 (6)	0.0181 (6)	−0.0033 (5)	−0.0034 (5)	−0.0013 (5)
C15	0.0306 (7)	0.0260 (7)	0.0207 (7)	−0.0052 (5)	−0.0061 (5)	−0.0024 (5)
C16	0.0419 (8)	0.0403 (9)	0.0171 (7)	−0.0072 (6)	−0.0017 (6)	−0.0017 (6)
C17	0.0331 (8)	0.0492 (10)	0.0256 (8)	−0.0127 (7)	0.0054 (6)	0.0028 (7)
C18	0.0271 (7)	0.0419 (9)	0.0301 (8)	−0.0130 (6)	−0.0030 (6)	0.0036 (6)
C19	0.0243 (6)	0.0220 (6)	0.0217 (7)	−0.0047 (5)	−0.0049 (5)	0.0013 (5)
C20	0.0533 (10)	0.0545 (11)	0.0247 (8)	−0.0106 (8)	−0.0159 (7)	−0.0118 (7)

O1—C15	1.3637 (16)	C8—C9	1.4183 (16)
O1—C20	1.4253 (17)	C8—C13	1.4223 (17)
O2—C19	1.3582 (16)	C9—C10	1.3675 (18)
O2—H2O	0.87 (2)	C9—H9A	0.9500
N1—C1	1.2980 (16)	C10—C11	1.4108 (19)
N1—N2	1.4032 (14)	C10—H10A	0.9500
N2—C3	1.4710 (15)	C11—C12	1.3714 (17)
N2—H2N	0.880 (18)	C11—H11A	0.9500
C1—C14	1.4662 (17)	C12—C13	1.4201 (16)
C1—C2	1.5145 (16)	C12—H12A	0.9500
C2—C3	1.5387 (17)	C14—C19	1.4109 (18)
C2—H2A	0.9900	C14—C15	1.4189 (18)
C2—H2B	0.9900	C15—C16	1.383 (2)
C3—C4	1.5218 (16)	C16—C17	1.383 (2)
C3—H3A	1.0000	C16—H16A	0.9500
C4—C5	1.3709 (17)	C17—C18	1.375 (2)
C4—C13	1.4349 (16)	C17—H17A	0.9500
C5—C6	1.4097 (18)	C18—C19	1.3885 (19)
C5—H5A	0.9500	C18—H18A	0.9500
C6—C7	1.3634 (18)	C20—H20A	0.9800
C6—H6A	0.9500	C20—H20B	0.9800
C7—C8	1.4174 (17)	C20—H20C	0.9800
C7—H7A	0.9500
C15—O1—C20	118.42 (12)	C8—C9—H9A	119.5
C19—O2—H2O	108.3 (13)	C9—C10—C11	119.64 (11)
C1—N1—N2	109.49 (10)	C9—C10—H10A	120.2
N1—N2—C3	108.34 (9)	C11—C10—H10A	120.2
N1—N2—H2N	110.6 (11)	C12—C11—C10	120.83 (11)
C3—N2—H2N	116.6 (11)	C12—C11—H11A	119.6
N1—C1—C14	120.08 (11)	C10—C11—H11A	119.6
N1—C1—C2	111.19 (10)	C11—C12—C13	120.89 (12)
C14—C1—C2	128.58 (11)	C11—C12—H12A	119.6
C1—C2—C3	101.19 (9)	C13—C12—H12A	119.6
C1—C2—H2A	111.5	C12—C13—C8	118.13 (11)
C3—C2—H2A	111.5	C12—C13—C4	122.86 (11)
C1—C2—H2B	111.5	C8—C13—C4	119.00 (10)
C3—C2—H2B	111.5	C19—C14—C15	117.14 (11)
H2A—C2—H2B	109.3	C19—C14—C1	120.32 (11)
N2—C3—C4	114.54 (10)	C15—C14—C1	122.53 (11)
N2—C3—C2	100.63 (9)	O1—C15—C16	123.05 (12)
C4—C3—C2	111.44 (10)	O1—C15—C14	115.53 (11)
N2—C3—H3A	110.0	C16—C15—C14	121.42 (13)
C4—C3—H3A	110.0	C15—C16—C17	119.26 (13)
C2—C3—H3A	110.0	C15—C16—H16A	120.4
C5—C4—C13	119.03 (11)	C17—C16—H16A	120.4
C5—C4—C3	122.04 (10)	C18—C17—C16	121.39 (13)
C13—C4—C3	118.91 (10)	C18—C17—H17A	119.3
C4—C5—C6	121.70 (11)	C16—C17—H17A	119.3
C4—C5—H5A	119.1	C17—C18—C19	119.76 (14)
C6—C5—H5A	119.1	C17—C18—H18A	120.1
C7—C6—C5	120.35 (11)	C19—C18—H18A	120.1
C7—C6—H6A	119.8	O2—C19—C18	116.51 (12)
C5—C6—H6A	119.8	O2—C19—C14	122.46 (11)
C6—C7—C8	120.27 (12)	C18—C19—C14	121.03 (12)
C6—C7—H7A	119.9	O1—C20—H20A	109.5
C8—C7—H7A	119.9	O1—C20—H20B	109.5
C7—C8—C9	120.87 (11)	H20A—C20—H20B	109.5
C7—C8—C13	119.64 (11)	O1—C20—H20C	109.5
C9—C8—C13	119.47 (11)	H20A—C20—H20C	109.5
C10—C9—C8	121.02 (12)	H20B—C20—H20C	109.5
C10—C9—H9A	119.5
C1—N1—N2—C3	−22.01 (13)	C9—C8—C13—C12	0.77 (17)
N2—N1—C1—C14	−172.78 (10)	C7—C8—C13—C4	0.13 (17)
N2—N1—C1—C2	3.08 (13)	C9—C8—C13—C4	−178.41 (10)
N1—C1—C2—C3	15.56 (13)	C5—C4—C13—C12	−179.29 (11)
C14—C1—C2—C3	−169.03 (11)	C3—C4—C13—C12	2.02 (17)
N1—N2—C3—C4	−89.55 (12)	C5—C4—C13—C8	−0.16 (17)
N1—N2—C3—C2	30.09 (12)	C3—C4—C13—C8	−178.84 (10)
C1—C2—C3—N2	−26.20 (11)	N1—C1—C14—C19	5.35 (18)
C1—C2—C3—C4	95.64 (10)	C2—C1—C14—C19	−169.70 (11)
N2—C3—C4—C5	12.88 (16)	N1—C1—C14—C15	−175.78 (11)
C2—C3—C4—C5	−100.52 (13)	C2—C1—C14—C15	9.2 (2)
N2—C3—C4—C13	−168.47 (10)	C20—O1—C15—C16	2.2 (2)
C2—C3—C4—C13	78.13 (13)	C20—O1—C15—C14	−177.87 (13)
C13—C4—C5—C6	0.10 (18)	C19—C14—C15—O1	179.62 (11)
C3—C4—C5—C6	178.75 (11)	C1—C14—C15—O1	0.72 (18)
C4—C5—C6—C7	0.0 (2)	C19—C14—C15—C16	−0.46 (19)
C5—C6—C7—C8	0.00 (19)	C1—C14—C15—C16	−179.36 (13)
C6—C7—C8—C9	178.47 (11)	O1—C15—C16—C17	179.83 (13)
C6—C7—C8—C13	−0.06 (18)	C14—C15—C16—C17	−0.1 (2)
C7—C8—C9—C10	−178.63 (12)	C15—C16—C17—C18	0.3 (2)
C13—C8—C9—C10	−0.10 (18)	C16—C17—C18—C19	0.0 (2)
C8—C9—C10—C11	−0.32 (19)	C17—C18—C19—O2	178.98 (13)
C9—C10—C11—C12	0.06 (19)	C17—C18—C19—C14	−0.6 (2)
C10—C11—C12—C13	0.63 (19)	C15—C14—C19—O2	−178.77 (11)
C11—C12—C13—C8	−1.03 (18)	C1—C14—C19—O2	0.16 (19)
C11—C12—C13—C4	178.11 (11)	C15—C14—C19—C18	0.80 (19)
C7—C8—C13—C12	179.31 (11)	C1—C14—C19—C18	179.73 (12)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···N1	0.87 (2)	1.79 (2)	2.5681 (14)	148.0 (19)
N2—H2N···Cg3i	0.88 (2)	2.56 (2)	3.1811 (13)	128.1 (14)
C3—H3A···Cg2i	1.00	2.80	3.5306 (15)	130
C12—H12A···O2ii	0.95	2.54	3.4488 (17)	161

Table 1

Hydrogen-bond geometry (, )

Cg2 and Cg3 are the centroids of rings C4C8/C13 and C8C13, respectively.

DHA	DH	HA	D A	DHA
O2H2ON1	0.87(2)	1.79(2)	2.5681(14)	148.0(19)
N2H2N Cg3i	0.88(2)	2.56(2)	3.1811(13)	128.1(14)
C3H3A Cg2i	1.00	2.80	3.5306(15)	130
C12H12AO2ii	0.95	2.54	3.4488(17)	161

Symmetry codes: (i) ; (ii) .