5-Hydr­oxy-1-(3-hydr­oxy-2-naphtho­yl)-3,5-dimethyl-2-pyrazoline

Chen, Y.; Li, D.-C.; Zhu, Y.; Wang, D.-Q.

doi:10.1107/S1600536808023027

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1629

doi:10.1107/S1600536808023027

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5-Hydroxy-1-(3-hydroxy-2-naphthoyl)-3,5-dimethyl-2-pyrazoline

Yuting Chen,^a,^b Da-Cheng Li,^b ^* Yuehua Zhu ^c and Da-Qi Wang ^b

^aDepartment of Chemistry, Dezhou University, Dezhou 253023, People's Republic of China, ^bCollege of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059, People's Republic of China, and ^cSchool of Materials Science and Engineering, Liaocheng University, Liaocheng 252059, People's Republic of China
^*Correspondence e-mail: lidacheng@lcu.edu.cn

(Received 8 July 2008; accepted 22 July 2008; online 31 July 2008)

In the title molecule, C₁₆H₁₆N₂O₃, intramolecular O—H⋯O hydrogen bonds influence the molecular conformation. Intermolecular O—H⋯O hydrogen bonds [O⋯O = 2.922 (2) Å] link the molecules into centrosymmetric dimers. Weak intermolecular C—H⋯O interactions assemble these dimers into layers parallel to the bc plane.

Related literature

A highly puckered 60-membered metalladiazamacrocycle was reported by Moon et al. (2006 ), and two manganese metallacrowns with the ligand N-acyl-3-hydroxy-2-naphthalenecarbohydrazide were reported by Dou et al. (2006 ). The ligand 1-benzoyl-3,5-dimethyl-5-(1-benzoylhydrazido)pyrazoline was first synthesized by Mukhopadhyay & Pal (2004 ).

Experimental

Crystal data

C₁₆H₁₆N₂O₃
M_r = 284.31
Monoclinic, P 2₁ /c
a = 12.368 (6) Å
b = 7.428 (4) Å
c = 17.041 (9) Å
β = 109.331 (7)°
V = 1477.3 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 (2) K
0.64 × 0.57 × 0.39 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.945, T_max = 0.966
7363 measured reflections
2588 independent reflections
1627 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.130
S = 1.00
2588 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1	0.82	1.79	2.518 (2)	147
O3—H3⋯O1	0.82	2.36	2.888 (2)	122
O3—H3⋯O2ⁱ	0.82	2.27	2.922 (2)	137
C9—H9⋯O3ⁱⁱ	0.93	2.57	3.388 (3)	147
Symmetry codes: (i) -x, -y, -z; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808023027/cv2430sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808023027/cv2430Isup2.hkl

checkCIF report

Comment top

Aroylhydrazine ligands have gained an increasing attraction due to their interesting chemical activities (Moon et al., 2006). As an extension of our work on the structural characterization of aroylhydrazine derivatives, along with our work of successful assembly of two azametallacrowns using N-acyl-3-hydroxy-2-naphthalenecarbohydrazide (Dou et al., 2006), the title compound, (I), was synthesized and characterized.

Pyrazoline ring in (I) is nearly co-planar with the mean deviation of 0.0379 Å from its least-squares plane, and the distances of N1—N2, C13—N1 and C15—N2 are 1.403 (2), 1.498 (2) and 1.275 (2) Å, respectively, which are in agreement with those of the analogous compound (Mukhopadhyay & Pal, 2004). The dihedral angle between the pyrazoline ring and naphthalene ring is 28.2 (3)°.

There are intramolecular O2—H2···O1 and O3—H3···O1 hydrogen bonds (Table 1, Fig. 1), which influence the molecular conformation. The intermolecular O—H···O (Table 1) hydrogen bonds link molecules into centrosymmetric dimers, and the weak intermolecular C—H···O interactions (Table 1) assemble further these dimers into the layers parallel to bc-plane.

Related literature top

A highly puckered 60-membered metalladiazamacrocycle was reported by Moon et al. (2006), and two manganese metallacrowns with the ligand N-acyl-3-hydroxy-2-naphthalenecarbohydrazide were reported by Dou et al. (2006). The ligand 1-benzoyl-3,5-dimethyl-5-(1-benzoylhydrazido)pyrazoline was first synthesized by Mukhopadhyay & Pal (2004).

Experimental top

0.21 ml of acetylacetone (0.205 g, 2.05 mmol) were added into a methanol solution (15 ml) of 3-hydroxy-2-naphthoylhydrazine (0.404 g, 2 mmol). The mixture was refluxed for 3 h followed by evaporation to approximate 1/3 of the original volume on a rotary evaporator, then the solution was cooled to room temperature. After the solution was allowed to stand for 2 weeks, yellow block crystals suitable for X-ray structure determination was obtained. Yield: 0.400 g, 70.37%. m.p.: 565–567 K. Anal. for C₁₆H₁₆N₂O₃: Calc. C, 67.53; H, 5.63; N, 9.85; Found: C, 67.20; H, 5.49; N, 9.28%. The No. of CCDC: 693975.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound showing the atomic numbering and 30% probability displacement ellipsoids. Dashed lines denote hydrogen bonds.

5-Hydroxy-1-(3-hydroxy-2-naphthoyl)-3,5-dimethyl-2-pyrazoline top

Crystal data top

C₁₆H₁₆N₂O₃	F(000) = 600
M_r = 284.31	D_x = 1.278 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.368 (6) Å	Cell parameters from 2043 reflections
b = 7.428 (4) Å	θ = 2.5–23.0°
c = 17.041 (9) Å	µ = 0.09 mm⁻¹
β = 109.331 (7)°	T = 298 K
V = 1477.3 (13) Å³	Block, yellow
Z = 4	0.64 × 0.57 × 0.39 mm

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	2588 independent reflections
Radiation source: fine-focus sealed tube	1627 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→14
T_min = 0.945, T_max = 0.966	k = −8→8
7363 measured reflections	l = −20→19

Refinement top

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.130	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0553P)² + 0.3243P] where P = (F_o² + 2F_c²)/3
2588 reflections	(Δ/σ)_max < 0.001
190 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₆H₁₆N₂O₃	V = 1477.3 (13) Å³
M_r = 284.31	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.368 (6) Å	µ = 0.09 mm⁻¹
b = 7.428 (4) Å	T = 298 K
c = 17.041 (9) Å	0.64 × 0.57 × 0.39 mm
β = 109.331 (7)°

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	2588 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1627 reflections with I > 2σ(I)
T_min = 0.945, T_max = 0.966	R_int = 0.042
7363 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.130	H-atom parameters constrained
S = 1.00	Δρ_max = 0.15 e Å⁻³
2588 reflections	Δρ_min = −0.18 e Å⁻³
190 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
N1	−0.04413 (13)	0.2580 (2)	0.17142 (9)	0.0490 (5)
N2	−0.01893 (14)	0.2214 (2)	0.25642 (10)	0.0518 (5)
O1	−0.00569 (12)	0.2318 (2)	0.05376 (8)	0.0685 (5)
O2	0.18079 (13)	0.1067 (2)	0.04814 (9)	0.0751 (5)
H2	0.1117	0.1265	0.0322	0.113*
O3	−0.21475 (12)	0.1233 (2)	0.08086 (9)	0.0660 (5)
H3	−0.1868	0.1116	0.0437	0.099*
C1	0.03222 (17)	0.2371 (3)	0.13121 (12)	0.0492 (5)
C2	0.15776 (16)	0.2220 (3)	0.17539 (12)	0.0459 (5)
C3	0.22724 (19)	0.1534 (3)	0.12957 (13)	0.0547 (6)
C4	0.34226 (19)	0.1307 (3)	0.16761 (15)	0.0650 (6)
H4	0.3857	0.0837	0.1372	0.078*
C5	0.39654 (18)	0.1758 (3)	0.25100 (15)	0.0585 (6)
C6	0.5152 (2)	0.1459 (4)	0.29304 (19)	0.0809 (8)
H6	0.5599	0.0937	0.2648	0.097*
C7	0.5633 (2)	0.1923 (4)	0.3733 (2)	0.0918 (9)
H7	0.6409	0.1707	0.3998	0.110*
C8	0.4998 (2)	0.2720 (4)	0.41801 (17)	0.0803 (8)
H8	0.5351	0.3034	0.4735	0.096*
C9	0.38560 (18)	0.3038 (3)	0.38005 (14)	0.0639 (6)
H9	0.3434	0.3579	0.4097	0.077*
C10	0.33104 (16)	0.2550 (3)	0.29614 (13)	0.0510 (5)
C11	0.21191 (16)	0.2757 (3)	0.25610 (12)	0.0478 (5)
H11	0.1685	0.3277	0.2854	0.057*
C12	−0.19627 (19)	0.4480 (3)	0.07493 (14)	0.0704 (7)
H12A	−0.1643	0.5503	0.1092	0.106*
H12B	−0.2778	0.4624	0.0510	0.106*
H12C	−0.1634	0.4385	0.0314	0.106*
C13	−0.17009 (16)	0.2794 (3)	0.12726 (12)	0.0512 (5)
C14	−0.21392 (17)	0.2823 (3)	0.20069 (12)	0.0561 (6)
H14A	−0.2422	0.4008	0.2078	0.067*
H14B	−0.2750	0.1952	0.1932	0.067*
C15	−0.11177 (18)	0.2339 (3)	0.27323 (12)	0.0503 (5)
C16	−0.1148 (2)	0.2027 (4)	0.35844 (13)	0.0700 (7)
H16A	−0.0392	0.1736	0.3948	0.105*
H16B	−0.1658	0.1048	0.3576	0.105*
H16C	−0.1413	0.3096	0.3780	0.105*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0456 (9)	0.0637 (12)	0.0350 (9)	0.0036 (8)	0.0099 (7)	−0.0026 (8)
N2	0.0550 (10)	0.0632 (12)	0.0363 (9)	0.0032 (9)	0.0139 (8)	−0.0016 (8)
O1	0.0661 (10)	0.1004 (14)	0.0375 (9)	0.0037 (9)	0.0149 (7)	−0.0036 (8)
O2	0.0795 (11)	0.0951 (13)	0.0596 (10)	−0.0029 (10)	0.0349 (8)	−0.0186 (9)
O3	0.0613 (9)	0.0802 (12)	0.0583 (9)	−0.0128 (8)	0.0220 (7)	−0.0254 (8)
C1	0.0543 (12)	0.0527 (13)	0.0402 (12)	−0.0009 (10)	0.0149 (10)	−0.0026 (10)
C2	0.0477 (11)	0.0455 (12)	0.0458 (12)	−0.0003 (9)	0.0172 (9)	0.0000 (9)
C3	0.0618 (14)	0.0525 (14)	0.0552 (14)	−0.0047 (11)	0.0264 (11)	−0.0050 (11)
C4	0.0583 (14)	0.0659 (16)	0.0843 (18)	0.0027 (12)	0.0418 (13)	−0.0087 (13)
C5	0.0487 (12)	0.0512 (14)	0.0780 (16)	−0.0018 (10)	0.0241 (11)	0.0009 (12)
C6	0.0516 (15)	0.083 (2)	0.111 (2)	0.0078 (13)	0.0310 (15)	−0.0011 (17)
C7	0.0461 (14)	0.110 (2)	0.109 (2)	0.0047 (15)	0.0115 (16)	0.006 (2)
C8	0.0534 (15)	0.092 (2)	0.0789 (18)	−0.0047 (14)	0.0001 (13)	0.0033 (15)
C9	0.0519 (13)	0.0683 (16)	0.0643 (15)	−0.0033 (11)	0.0095 (11)	−0.0032 (12)
C10	0.0463 (12)	0.0437 (13)	0.0617 (14)	−0.0021 (9)	0.0159 (10)	0.0017 (10)
C11	0.0467 (11)	0.0460 (12)	0.0518 (12)	0.0014 (9)	0.0177 (9)	−0.0011 (10)
C12	0.0645 (14)	0.0791 (18)	0.0578 (14)	0.0139 (13)	0.0072 (11)	0.0067 (13)
C13	0.0442 (11)	0.0611 (14)	0.0422 (12)	0.0014 (10)	0.0059 (9)	−0.0105 (10)
C14	0.0513 (12)	0.0642 (15)	0.0525 (13)	0.0044 (10)	0.0169 (10)	−0.0115 (11)
C15	0.0556 (13)	0.0515 (13)	0.0450 (12)	0.0024 (10)	0.0184 (10)	−0.0088 (10)
C16	0.0845 (17)	0.0810 (18)	0.0526 (14)	0.0132 (14)	0.0337 (12)	−0.0003 (12)

Geometric parameters (Å, º) top

N1—C1	1.347 (3)	C7—C8	1.393 (4)
N1—N2	1.404 (2)	C7—H7	0.9300
N1—C13	1.497 (3)	C8—C9	1.366 (3)
N2—C15	1.276 (3)	C8—H8	0.9300
O1—C1	1.246 (2)	C9—C10	1.412 (3)
O2—C3	1.360 (2)	C9—H9	0.9300
O2—H2	0.8200	C10—C11	1.412 (3)
O3—C13	1.409 (2)	C11—H11	0.9300
O3—H3	0.8200	C12—C13	1.509 (3)
C1—O1	1.246 (2)	C12—H12A	0.9600
C1—C2	1.489 (3)	C12—H12B	0.9600
C2—C11	1.375 (3)	C12—H12C	0.9600
C2—C3	1.432 (3)	C13—C14	1.520 (3)
C3—C4	1.365 (3)	C14—C15	1.490 (3)
C4—C5	1.397 (3)	C14—H14A	0.9700
C4—H4	0.9300	C14—H14B	0.9700
C5—C10	1.416 (3)	C15—C16	1.483 (3)
C5—C6	1.421 (3)	C16—H16A	0.9600
C6—C7	1.344 (4)	C16—H16B	0.9600
C6—H6	0.9300	C16—H16C	0.9600

C1—N1—N2	123.32 (16)	C9—C10—C11	122.3 (2)
C1—N1—C13	122.99 (16)	C9—C10—C5	119.29 (19)
N2—N1—C13	112.21 (15)	C11—C10—C5	118.4 (2)
C15—N2—N1	107.99 (16)	C2—C11—C10	122.45 (19)
C3—O2—H2	109.5	C2—C11—H11	118.8
C13—O3—H3	109.5	C10—C11—H11	118.8
O1—C1—N1	117.46 (18)	C13—C12—H12A	109.5
O1—C1—C2	119.79 (18)	C13—C12—H12B	109.5
N1—C1—C2	122.75 (17)	H12A—C12—H12B	109.5
C11—C2—C3	117.85 (18)	C13—C12—H12C	109.5
C11—C2—C1	124.41 (18)	H12A—C12—H12C	109.5
C3—C2—C1	117.69 (18)	H12B—C12—H12C	109.5
O2—C3—C4	118.35 (19)	O3—C13—N1	110.11 (16)
O2—C3—C2	121.35 (19)	O3—C13—C12	112.56 (17)
C4—C3—C2	120.3 (2)	N1—C13—C12	111.68 (18)
C3—C4—C5	121.9 (2)	O3—C13—C14	107.04 (18)
C3—C4—H4	119.1	N1—C13—C14	100.54 (15)
C5—C4—H4	119.1	C12—C13—C14	114.20 (19)
C4—C5—C10	118.92 (19)	C15—C14—C13	104.14 (17)
C4—C5—C6	122.9 (2)	C15—C14—H14A	110.9
C10—C5—C6	118.1 (2)	C13—C14—H14A	110.9
C7—C6—C5	120.6 (2)	C15—C14—H14B	110.9
C7—C6—H6	119.7	C13—C14—H14B	110.9
C5—C6—H6	119.7	H14A—C14—H14B	108.9
C6—C7—C8	121.7 (2)	N2—C15—C16	121.66 (19)
C6—C7—H7	119.1	N2—C15—C14	114.22 (18)
C8—C7—H7	119.1	C16—C15—C14	124.1 (2)
C9—C8—C7	119.7 (3)	C15—C16—H16A	109.5
C9—C8—H8	120.1	C15—C16—H16B	109.5
C7—C8—H8	120.1	H16A—C16—H16B	109.5
C8—C9—C10	120.5 (2)	C15—C16—H16C	109.5
C8—C9—H9	119.7	H16A—C16—H16C	109.5
C10—C9—H9	119.7	H16B—C16—H16C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1	0.82	1.79	2.518 (2)	147
O3—H3···O1	0.82	2.36	2.888 (2)	122
O3—H3···O2ⁱ	0.82	2.27	2.922 (2)	137
C9—H9···O3ⁱⁱ	0.93	2.57	3.388 (3)	147

Symmetry codes: (i) −x, −y, −z; (ii) −x, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₆N₂O₃
M_r	284.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	12.368 (6), 7.428 (4), 17.041 (9)
β (°)	109.331 (7)
V (Å³)	1477.3 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.64 × 0.57 × 0.39

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.945, 0.966
No. of measured, independent and observed [I > 2σ(I)] reflections	7363, 2588, 1627
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.130, 1.00
No. of reflections	2588
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.18

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1	0.82	1.79	2.518 (2)	146.9
O3—H3···O1	0.82	2.36	2.888 (2)	122.4
O3—H3···O2ⁱ	0.82	2.27	2.922 (2)	136.5
C9—H9···O3ⁱⁱ	0.93	2.57	3.388 (3)	146.7

Symmetry codes: (i) −x, −y, −z; (ii) −x, y+1/2, −z+1/2.

Acknowledgements

The authors acknowledge the support of the National Natural Science Foundation of China (grant No. 20671048).

References

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