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

In the title compound, C21H20N2O3, the planes of the benzene ring and the naphthalene ring system are inclined to one another by 70.95°, and by 4.99 (6) and 75.93 (5)°, respectively, to the mean plane of the pyrazoline ring. The latter has an envelope conformation with the methine (CH) C atom as the flap. There is an intra-molecular O-H⋯N hydrogen bond that forms an S(6) ring motif. In the crystal, mol-ecules are linked by C-H⋯O hydrogen bonds, forming chains along [100]. The chains are linked via C-H⋯N hydrogen bonds, forming sheets parallel to the ab plane. The sheets are linked by a series of N-H⋯π and C-H⋯π inter-actions forming a three-dimensional structure.

Related literature

For the synthesis and biological properties of pyrazoline derivatives, see: Bano et al. (2015 ▸); Viveka et al. (2015 ▸); Neudorfer et al. (2014 ▸); Hwang et al. (2013 ▸); Yong et al. (2013 ▸); Congiu et al. (2010 ▸). For N—H⋯π inter­actions in the crystal structure of 3-(thio­phen-2-yl)-5-p-tolyl-4,5-di­hydro-1H-pyrazole-1-carbo­thio­amide, see: Naveen et al. (2015 ▸). For related structures, see: Zhu et al. (2013 ▸); Patel et al. (2013 ▸).

Experimental

Crystal data

C21H20N2O3

M = 348.39

Triclinic,

a = 7.6248 (5) Å

b = 8.6044 (6) Å

c = 13.1757 (9) Å

α = 92.832 (4)°

β = 90.777 (3)°

γ = 99.099 (3)°

V = 852.30 (10) Å3

Z = 2

Cu Kα radiation

μ = 0.74 mm−1

T = 147 K

0.18 × 0.11 × 0.09 mm

Data collection

Bruker Kappa APEX DUO CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2012 ▸) T min = 0.698, T max = 0.753

21626 measured reflections

2906 independent reflections

2736 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.096

S = 1.04

2906 reflections

245 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.16 e Å−3

Δρmin = −0.22 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 ▸) and Mercury (Macrae et al., 2008 ▸); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▸) and PLATON.

Crystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989015016369/su5198sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015016369/su5198Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015016369/su5198Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015016369/su5198fig1.tif

The mol­ecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

Click here for additional data file.

c . DOI: 10.1107/S2056989015016369/su5198fig2.tif

A view along the c axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines (see Table 1).

Click here for additional data file.

. DOI: 10.1107/S2056989015016369/su5198fig3.tif

A view of the inversion dimers formed by a pair of N-H⋯π inter­actions (dashed lines; see Table 1), in the crystal structure of the title compound.

Click here for additional data file.

. DOI: 10.1107/S2056989015016369/su5198fig4.tif

Synthetic scheme for the preparation of the title pyrazoline compound.

CCDC reference: 1421849

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

C21H20N2O3	Z = 2
Mr = 348.39	F(000) = 368
Triclinic, P1	Dx = 1.358 Mg m−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54178 Å
a = 7.6248 (5) Å	Cell parameters from 48 reflections
b = 8.6044 (6) Å	θ = 6.7–26.4°
c = 13.1757 (9) Å	µ = 0.74 mm−1
α = 92.832 (4)°	T = 147 K
β = 90.777 (3)°	Needle, yellow
γ = 99.099 (3)°	0.18 × 0.11 × 0.09 mm
V = 852.30 (10) Å3

Bruker Kappa APEX DUO CCD diffractometer	2906 independent reflections
Radiation source: Bruker ImuS	2736 reflections with I > 2σ(I)
Multi-layer optics monochromator	Rint = 0.029
φ and ω scans	θmax = 66.4°, θmin = 3.4°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −9→8
Tmin = 0.698, Tmax = 0.753	k = −10→10
21626 measured reflections	l = −15→15

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0556P)2 + 0.2046P] where P = (Fo2 + 2Fc2)/3
2906 reflections	(Δ/σ)max = 0.002
245 parameters	Δρmax = 0.16 e Å−3
0 restraints	Δρmin = −0.22 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	0.76267 (11)	0.65287 (11)	0.56445 (6)	0.0345 (2)
O2	0.23406 (12)	0.84718 (12)	0.45432 (7)	0.0395 (2)
O3	0.33246 (11)	0.79173 (10)	0.79830 (6)	0.0274 (2)
N1	0.61828 (13)	0.70426 (11)	0.86156 (7)	0.0238 (2)
N2	0.75961 (13)	0.69468 (12)	0.92877 (7)	0.0257 (2)
C1	0.66848 (15)	0.68552 (12)	0.76873 (8)	0.0219 (2)
C2	0.85512 (15)	0.64594 (13)	0.76522 (8)	0.0239 (3)
H2A	0.9417	0.7366	0.7448	0.029*
H2B	0.8615	0.5538	0.7182	0.029*
C3	0.88660 (15)	0.60817 (13)	0.87658 (8)	0.0233 (3)
H3A	1.0104	0.6549	0.8989	0.028*
C4	0.85672 (15)	0.43149 (13)	0.89158 (8)	0.0223 (3)
C5	0.70235 (15)	0.35538 (14)	0.93005 (9)	0.0260 (3)
H5A	0.6109	0.4141	0.9480	0.031*
C6	0.67599 (16)	0.19168 (14)	0.94364 (9)	0.0294 (3)
H6A	0.5673	0.1419	0.9701	0.035*
C7	0.80537 (17)	0.10457 (14)	0.91907 (9)	0.0281 (3)
H7A	0.7871	−0.0052	0.9296	0.034*
C8	0.96708 (16)	0.17698 (13)	0.87785 (8)	0.0244 (3)
C9	1.10302 (17)	0.08870 (14)	0.85020 (9)	0.0290 (3)
H9A	1.0856	−0.0214	0.8596	0.035*
C10	1.25809 (17)	0.15898 (15)	0.81043 (9)	0.0313 (3)
H10A	1.3475	0.0980	0.7924	0.038*
C11	1.28539 (16)	0.32194 (15)	0.79617 (9)	0.0295 (3)
H11A	1.3938	0.3706	0.7687	0.035*
C12	1.15695 (15)	0.41116 (14)	0.82154 (8)	0.0252 (3)
H12A	1.1773	0.5209	0.8110	0.030*
C13	0.99403 (15)	0.34213 (13)	0.86326 (8)	0.0222 (3)
C14	0.55542 (15)	0.71703 (13)	0.68409 (8)	0.0229 (3)
C15	0.60542 (15)	0.70520 (14)	0.58125 (9)	0.0257 (3)
C16	0.50164 (16)	0.74640 (15)	0.50250 (9)	0.0290 (3)
H16A	0.5377	0.7370	0.4340	0.035*
C17	0.34405 (16)	0.80168 (15)	0.52538 (9)	0.0291 (3)
C18	0.28868 (15)	0.81417 (14)	0.62462 (9)	0.0284 (3)
H18A	0.1801	0.8508	0.6391	0.034*
C19	0.39277 (15)	0.77291 (13)	0.70265 (9)	0.0240 (3)
C20	0.82165 (18)	0.64268 (18)	0.46210 (9)	0.0379 (3)
H20A	0.9381	0.6080	0.4614	0.057*
H20B	0.8312	0.7464	0.4332	0.057*
H20C	0.7361	0.5666	0.4216	0.057*
C21	0.29040 (19)	0.85176 (19)	0.35185 (10)	0.0419 (3)
H21A	0.2038	0.8948	0.3103	0.063*
H21B	0.2996	0.7448	0.3256	0.063*
H21C	0.4066	0.9188	0.3490	0.063*
H3O	0.420 (2)	0.7700 (19)	0.8426 (14)	0.050 (5)*
H2N	0.719 (2)	0.6571 (18)	0.9879 (13)	0.039 (4)*

	U11	U22	U33	U12	U13	U23
O1	0.0324 (5)	0.0539 (6)	0.0208 (4)	0.0170 (4)	0.0019 (3)	0.0033 (4)
O2	0.0316 (5)	0.0590 (6)	0.0291 (5)	0.0082 (4)	−0.0082 (4)	0.0141 (4)
O3	0.0307 (5)	0.0307 (5)	0.0232 (4)	0.0109 (3)	0.0021 (3)	0.0039 (3)
N1	0.0302 (5)	0.0208 (5)	0.0212 (5)	0.0071 (4)	−0.0036 (4)	0.0012 (4)
N2	0.0334 (5)	0.0256 (5)	0.0198 (5)	0.0108 (4)	−0.0046 (4)	0.0010 (4)
C1	0.0275 (6)	0.0162 (5)	0.0217 (6)	0.0026 (4)	−0.0011 (4)	0.0017 (4)
C2	0.0274 (6)	0.0228 (6)	0.0222 (6)	0.0060 (4)	−0.0021 (4)	0.0036 (4)
C3	0.0275 (6)	0.0213 (6)	0.0217 (6)	0.0062 (4)	−0.0040 (4)	0.0010 (4)
C4	0.0278 (6)	0.0227 (6)	0.0165 (5)	0.0051 (4)	−0.0062 (4)	0.0008 (4)
C5	0.0286 (6)	0.0270 (6)	0.0229 (6)	0.0060 (5)	−0.0027 (4)	0.0009 (4)
C6	0.0317 (6)	0.0287 (6)	0.0260 (6)	−0.0014 (5)	−0.0011 (5)	0.0029 (5)
C7	0.0401 (7)	0.0193 (6)	0.0235 (6)	0.0007 (5)	−0.0065 (5)	0.0019 (4)
C8	0.0335 (6)	0.0221 (6)	0.0178 (5)	0.0057 (5)	−0.0082 (4)	−0.0008 (4)
C9	0.0417 (7)	0.0225 (6)	0.0240 (6)	0.0108 (5)	−0.0091 (5)	−0.0028 (5)
C10	0.0370 (7)	0.0342 (7)	0.0255 (6)	0.0166 (5)	−0.0051 (5)	−0.0041 (5)
C11	0.0299 (6)	0.0355 (7)	0.0236 (6)	0.0076 (5)	−0.0019 (5)	0.0001 (5)
C12	0.0302 (6)	0.0247 (6)	0.0209 (5)	0.0051 (5)	−0.0035 (4)	0.0022 (4)
C13	0.0288 (6)	0.0215 (6)	0.0164 (5)	0.0052 (4)	−0.0065 (4)	0.0003 (4)
C14	0.0261 (6)	0.0200 (6)	0.0222 (6)	0.0022 (4)	−0.0020 (4)	0.0030 (4)
C15	0.0255 (6)	0.0271 (6)	0.0244 (6)	0.0035 (5)	−0.0014 (4)	0.0020 (5)
C16	0.0298 (6)	0.0354 (7)	0.0207 (6)	0.0011 (5)	−0.0020 (5)	0.0039 (5)
C17	0.0264 (6)	0.0323 (7)	0.0274 (6)	−0.0008 (5)	−0.0069 (5)	0.0082 (5)
C18	0.0246 (6)	0.0305 (7)	0.0306 (6)	0.0047 (5)	−0.0019 (5)	0.0065 (5)
C19	0.0269 (6)	0.0205 (6)	0.0240 (6)	0.0017 (4)	0.0005 (4)	0.0037 (4)
C20	0.0376 (7)	0.0549 (9)	0.0234 (6)	0.0137 (6)	0.0056 (5)	0.0037 (6)
C21	0.0459 (8)	0.0534 (9)	0.0260 (7)	0.0051 (6)	−0.0112 (6)	0.0086 (6)

O1—C15	1.3629 (15)	C8—C9	1.4198 (17)
O1—C20	1.4304 (14)	C8—C13	1.4263 (16)
O2—C17	1.3609 (15)	C9—C10	1.3640 (19)
O2—C21	1.4229 (16)	C9—H9A	0.9500
O3—C19	1.3584 (14)	C10—C11	1.4070 (18)
O3—H3O	0.926 (18)	C10—H10A	0.9500
N1—C1	1.2965 (15)	C11—C12	1.3717 (17)
N1—N2	1.4005 (13)	C11—H11A	0.9500
N2—C3	1.4697 (15)	C12—C13	1.4197 (17)
N2—H2N	0.898 (17)	C12—H12A	0.9500
C1—C14	1.4622 (16)	C14—C15	1.4158 (16)
C1—C2	1.5155 (16)	C14—C19	1.4192 (17)
C2—C3	1.5423 (15)	C15—C16	1.3896 (17)
C2—H2A	0.9900	C16—C17	1.3919 (18)
C2—H2B	0.9900	C16—H16A	0.9500
C3—C4	1.5243 (15)	C17—C18	1.3838 (18)
C3—H3A	1.0000	C18—C19	1.3842 (17)
C4—C5	1.3698 (17)	C18—H18A	0.9500
C4—C13	1.4364 (16)	C20—H20A	0.9800
C5—C6	1.4116 (17)	C20—H20B	0.9800
C5—H5A	0.9500	C20—H20C	0.9800
C6—C7	1.3632 (18)	C21—H21A	0.9800
C6—H6A	0.9500	C21—H21B	0.9800
C7—C8	1.4185 (18)	C21—H21C	0.9800
C7—H7A	0.9500
C15—O1—C20	118.10 (9)	C9—C10—H10A	120.0
C17—O2—C21	118.23 (10)	C11—C10—H10A	120.0
C19—O3—H3O	107.0 (11)	C12—C11—C10	120.59 (11)
C1—N1—N2	109.61 (9)	C12—C11—H11A	119.7
N1—N2—C3	108.80 (8)	C10—C11—H11A	119.7
N1—N2—H2N	110.6 (10)	C11—C12—C13	121.07 (11)
C3—N2—H2N	116.0 (10)	C11—C12—H12A	119.5
N1—C1—C14	120.11 (10)	C13—C12—H12A	119.5
N1—C1—C2	111.37 (9)	C12—C13—C8	118.16 (10)
C14—C1—C2	128.25 (10)	C12—C13—C4	122.84 (10)
C1—C2—C3	101.50 (9)	C8—C13—C4	119.00 (10)
C1—C2—H2A	111.5	C15—C14—C19	116.38 (10)
C3—C2—H2A	111.5	C15—C14—C1	122.99 (10)
C1—C2—H2B	111.5	C19—C14—C1	120.48 (10)
C3—C2—H2B	111.5	O1—C15—C16	122.12 (11)
H2A—C2—H2B	109.3	O1—C15—C14	115.85 (10)
N2—C3—C4	114.59 (9)	C16—C15—C14	122.03 (11)
N2—C3—C2	100.95 (9)	C15—C16—C17	119.04 (11)
C4—C3—C2	112.32 (9)	C15—C16—H16A	120.5
N2—C3—H3A	109.6	C17—C16—H16A	120.5
C4—C3—H3A	109.6	O2—C17—C18	115.09 (11)
C2—C3—H3A	109.6	O2—C17—C16	123.79 (11)
C5—C4—C13	119.16 (10)	C18—C17—C16	121.12 (11)
C5—C4—C3	122.00 (10)	C17—C18—C19	119.50 (11)
C13—C4—C3	118.84 (10)	C17—C18—H18A	120.3
C4—C5—C6	121.56 (11)	C19—C18—H18A	120.3
C4—C5—H5A	119.2	O3—C19—C18	116.33 (10)
C6—C5—H5A	119.2	O3—C19—C14	121.73 (10)
C7—C6—C5	120.49 (11)	C18—C19—C14	121.93 (11)
C7—C6—H6A	119.8	O1—C20—H20A	109.5
C5—C6—H6A	119.8	O1—C20—H20B	109.5
C6—C7—C8	120.33 (11)	H20A—C20—H20B	109.5
C6—C7—H7A	119.8	O1—C20—H20C	109.5
C8—C7—H7A	119.8	H20A—C20—H20C	109.5
C7—C8—C9	121.52 (11)	H20B—C20—H20C	109.5
C7—C8—C13	119.45 (11)	O2—C21—H21A	109.5
C9—C8—C13	119.03 (11)	O2—C21—H21B	109.5
C10—C9—C8	121.24 (11)	H21A—C21—H21B	109.5
C10—C9—H9A	119.4	O2—C21—H21C	109.5
C8—C9—H9A	119.4	H21A—C21—H21C	109.5
C9—C10—C11	119.91 (11)	H21B—C21—H21C	109.5
C1—N1—N2—C3	−21.89 (12)	C9—C8—C13—C4	−179.78 (9)
N2—N1—C1—C14	−169.55 (9)	C5—C4—C13—C12	179.10 (10)
N2—N1—C1—C2	4.94 (12)	C3—C4—C13—C12	−0.14 (15)
N1—C1—C2—C3	12.50 (12)	C5—C4—C13—C8	−1.20 (15)
C14—C1—C2—C3	−173.56 (10)	C3—C4—C13—C8	179.56 (9)
N1—N2—C3—C4	−92.86 (11)	N1—C1—C14—C15	177.33 (10)
N1—N2—C3—C2	28.06 (11)	C2—C1—C14—C15	3.86 (18)
C1—C2—C3—N2	−23.31 (10)	N1—C1—C14—C19	1.95 (16)
C1—C2—C3—C4	99.21 (10)	C2—C1—C14—C19	−171.52 (10)
N2—C3—C4—C5	14.33 (15)	C20—O1—C15—C16	0.79 (17)
C2—C3—C4—C5	−100.10 (12)	C20—O1—C15—C14	−178.39 (11)
N2—C3—C4—C13	−166.45 (9)	C19—C14—C15—O1	179.38 (10)
C2—C3—C4—C13	79.12 (12)	C1—C14—C15—O1	3.83 (17)
C13—C4—C5—C6	0.78 (16)	C19—C14—C15—C16	0.20 (17)
C3—C4—C5—C6	180.00 (10)	C1—C14—C15—C16	−175.35 (10)
C4—C5—C6—C7	0.37 (17)	O1—C15—C16—C17	−178.84 (11)
C5—C6—C7—C8	−1.09 (17)	C14—C15—C16—C17	0.29 (18)
C6—C7—C8—C9	−179.07 (10)	C21—O2—C17—C18	174.16 (11)
C6—C7—C8—C13	0.64 (16)	C21—O2—C17—C16	−5.72 (18)
C7—C8—C9—C10	179.88 (10)	C15—C16—C17—O2	179.07 (11)
C13—C8—C9—C10	0.16 (16)	C15—C16—C17—C18	−0.81 (18)
C8—C9—C10—C11	0.00 (17)	O2—C17—C18—C19	−179.07 (10)
C9—C10—C11—C12	−0.28 (17)	C16—C17—C18—C19	0.82 (18)
C10—C11—C12—C13	0.38 (17)	C17—C18—C19—O3	178.46 (10)
C11—C12—C13—C8	−0.20 (16)	C17—C18—C19—C14	−0.30 (18)
C11—C12—C13—C4	179.50 (10)	C15—C14—C19—O3	−178.89 (10)
C7—C8—C13—C12	−179.78 (9)	C1—C14—C19—O3	−3.22 (16)
C9—C8—C13—C12	−0.07 (15)	C15—C14—C19—C18	−0.20 (17)
C7—C8—C13—C4	0.50 (15)	C1—C14—C19—C18	175.47 (10)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···N1	0.926 (18)	1.718 (18)	2.5578 (12)	149.3 (16)
C7—H7A···N2i	0.95	2.56	3.4976 (16)	171
C12—H12A···O3ii	0.95	2.46	3.3663 (15)	161
N2—H2N···Cg3iii	0.898 (17)	2.609 (17)	3.1906 (11)	123.2 (12)
C3—H3A···Cg2iii	1.00	2.84	3.5842 (12)	131
C20—H20C···Cg4iv	0.98	2.93	3.7892 (16)	146
C21—H21C···Cg4v	0.98	2.85	3.6296 (17)	137

Table 1

Hydrogen-bond geometry (, )

Cg2, Cg3 and Cg4 are the centroids of rings C4C8/C13, C8C13 and C14C19, respectively.

DHA	DH	HA	D A	DHA
O3H3ON1	0.926(18)	1.718(18)	2.5578(12)	149.3(16)
C7H7AN2i	0.95	2.56	3.4976(16)	171
C12H12AO3ii	0.95	2.46	3.3663(15)	161
N2H2N Cg3iii	0.898(17)	2.609(17)	3.1906(11)	123.2(12)
C3H3A Cg2iii	1.00	2.84	3.5842(12)	131
C20H20C Cg4iv	0.98	2.93	3.7892(16)	146
C21H21C Cg4v	0.98	2.85	3.6296(17)	137

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .