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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): o1629.
Published online 2008 July 31. doi:  10.1107/S1600536808023027
PMCID: PMC2962119

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

Abstract

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 [triangle]), and two manganese metallacrowns with the ligand N-acyl-3-hydr­oxy-2-naphthalene­carbohydrazide were reported by Dou et al. (2006 [triangle]). The ligand 1-benzoyl-3,5-dimethyl-5-(1-benzoyl­hydrazido)pyrazoline was first synthesized by Mukhopadhyay & Pal (2004 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o1629-scheme1.jpg

Experimental

Crystal data

  • C16H16N2O3
  • M r = 284.31
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1629-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.044
  • wR(F 2) = 0.130
  • S = 1.00
  • 2588 reflections
  • 190 parameters
  • H-atom parameters constrained
  • Δρmax = 0.15 e Å−3
  • Δρmin = −0.18 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

All H atoms were placed in geometrically idealized positions (C—H 0.93–0.96 Å, O—H 0.82 Å) and treated as riding on their parent atoms, with Uiso(H)= 1.2–1.5Ueq of the parent atom.

Figures

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

Crystal data

C16H16N2O3F000 = 600
Mr = 284.31Dx = 1.278 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
a = 12.368 (6) ÅCell parameters from 2043 reflections
b = 7.428 (4) Åθ = 2.5–23.0º
c = 17.041 (9) ŵ = 0.09 mm1
β = 109.331 (7)ºT = 298 (2) K
V = 1477.3 (13) Å3Block, yellow
Z = 40.64 × 0.57 × 0.39 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer2588 independent reflections
Radiation source: fine-focus sealed tube1627 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.042
T = 298(2) Kθmax = 25.0º
[var phi] and ω scansθmin = 2.6º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −12→14
Tmin = 0.945, Tmax = 0.966k = −8→8
7363 measured reflectionsl = −20→19

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.130  w = 1/[σ2(Fo2) + (0.0553P)2 + 0.3243P] where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
2588 reflectionsΔρmax = 0.15 e Å3
190 parametersΔρmin = −0.18 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

xyzUiso*/Ueq
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)
O20.18079 (13)0.1067 (2)0.04814 (9)0.0751 (5)
H20.11170.12650.03220.113*
O3−0.21475 (12)0.1233 (2)0.08086 (9)0.0660 (5)
H3−0.18680.11160.04370.099*
C10.03222 (17)0.2371 (3)0.13121 (12)0.0492 (5)
C20.15776 (16)0.2220 (3)0.17539 (12)0.0459 (5)
C30.22724 (19)0.1534 (3)0.12957 (13)0.0547 (6)
C40.34226 (19)0.1307 (3)0.16761 (15)0.0650 (6)
H40.38570.08370.13720.078*
C50.39654 (18)0.1758 (3)0.25100 (15)0.0585 (6)
C60.5152 (2)0.1459 (4)0.29304 (19)0.0809 (8)
H60.55990.09370.26480.097*
C70.5633 (2)0.1923 (4)0.3733 (2)0.0918 (9)
H70.64090.17070.39980.110*
C80.4998 (2)0.2720 (4)0.41801 (17)0.0803 (8)
H80.53510.30340.47350.096*
C90.38560 (18)0.3038 (3)0.38005 (14)0.0639 (6)
H90.34340.35790.40970.077*
C100.33104 (16)0.2550 (3)0.29614 (13)0.0510 (5)
C110.21191 (16)0.2757 (3)0.25610 (12)0.0478 (5)
H110.16850.32770.28540.057*
C12−0.19627 (19)0.4480 (3)0.07493 (14)0.0704 (7)
H12A−0.16430.55030.10920.106*
H12B−0.27780.46240.05100.106*
H12C−0.16340.43850.03140.106*
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−0.24220.40080.20780.067*
H14B−0.27500.19520.19320.067*
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−0.03920.17360.39480.105*
H16B−0.16580.10480.35760.105*
H16C−0.14130.30960.37800.105*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0456 (9)0.0637 (12)0.0350 (9)0.0036 (8)0.0099 (7)−0.0026 (8)
N20.0550 (10)0.0632 (12)0.0363 (9)0.0032 (9)0.0139 (8)−0.0016 (8)
O10.0661 (10)0.1004 (14)0.0375 (9)0.0037 (9)0.0149 (7)−0.0036 (8)
O20.0795 (11)0.0951 (13)0.0596 (10)−0.0029 (10)0.0349 (8)−0.0186 (9)
O30.0613 (9)0.0802 (12)0.0583 (9)−0.0128 (8)0.0220 (7)−0.0254 (8)
C10.0543 (12)0.0527 (13)0.0402 (12)−0.0009 (10)0.0149 (10)−0.0026 (10)
C20.0477 (11)0.0455 (12)0.0458 (12)−0.0003 (9)0.0172 (9)0.0000 (9)
C30.0618 (14)0.0525 (14)0.0552 (14)−0.0047 (11)0.0264 (11)−0.0050 (11)
C40.0583 (14)0.0659 (16)0.0843 (18)0.0027 (12)0.0418 (13)−0.0087 (13)
C50.0487 (12)0.0512 (14)0.0780 (16)−0.0018 (10)0.0241 (11)0.0009 (12)
C60.0516 (15)0.083 (2)0.111 (2)0.0078 (13)0.0310 (15)−0.0011 (17)
C70.0461 (14)0.110 (2)0.109 (2)0.0047 (15)0.0115 (16)0.006 (2)
C80.0534 (15)0.092 (2)0.0789 (18)−0.0047 (14)0.0001 (13)0.0033 (15)
C90.0519 (13)0.0683 (16)0.0643 (15)−0.0033 (11)0.0095 (11)−0.0032 (12)
C100.0463 (12)0.0437 (13)0.0617 (14)−0.0021 (9)0.0159 (10)0.0017 (10)
C110.0467 (11)0.0460 (12)0.0518 (12)0.0014 (9)0.0177 (9)−0.0011 (10)
C120.0645 (14)0.0791 (18)0.0578 (14)0.0139 (13)0.0072 (11)0.0067 (13)
C130.0442 (11)0.0611 (14)0.0422 (12)0.0014 (10)0.0059 (9)−0.0105 (10)
C140.0513 (12)0.0642 (15)0.0525 (13)0.0044 (10)0.0169 (10)−0.0115 (11)
C150.0556 (13)0.0515 (13)0.0450 (12)0.0024 (10)0.0184 (10)−0.0088 (10)
C160.0845 (17)0.0810 (18)0.0526 (14)0.0132 (14)0.0337 (12)−0.0003 (12)

Geometric parameters (Å, °)

N1—C11.347 (3)C7—C81.393 (4)
N1—N21.404 (2)C7—H70.9300
N1—C131.497 (3)C8—C91.366 (3)
N2—C151.276 (3)C8—H80.9300
O1—C11.246 (2)C9—C101.412 (3)
O2—C31.360 (2)C9—H90.9300
O2—H20.8200C10—C111.412 (3)
O3—C131.409 (2)C11—H110.9300
O3—H30.8200C12—C131.509 (3)
C1—O11.246 (2)C12—H12A0.9600
C1—C21.489 (3)C12—H12B0.9600
C2—C111.375 (3)C12—H12C0.9600
C2—C31.432 (3)C13—C141.520 (3)
C3—C41.365 (3)C14—C151.490 (3)
C4—C51.397 (3)C14—H14A0.9700
C4—H40.9300C14—H14B0.9700
C5—C101.416 (3)C15—C161.483 (3)
C5—C61.421 (3)C16—H16A0.9600
C6—C71.344 (4)C16—H16B0.9600
C6—H60.9300C16—H16C0.9600
C1—N1—N2123.32 (16)C9—C10—C11122.3 (2)
C1—N1—C13122.99 (16)C9—C10—C5119.29 (19)
N2—N1—C13112.21 (15)C11—C10—C5118.4 (2)
C15—N2—N1107.99 (16)C2—C11—C10122.45 (19)
C3—O2—H2109.5C2—C11—H11118.8
C13—O3—H3109.5C10—C11—H11118.8
O1—C1—N1117.46 (18)C13—C12—H12A109.5
O1—C1—C2119.79 (18)C13—C12—H12B109.5
N1—C1—C2122.75 (17)H12A—C12—H12B109.5
C11—C2—C3117.85 (18)C13—C12—H12C109.5
C11—C2—C1124.41 (18)H12A—C12—H12C109.5
C3—C2—C1117.69 (18)H12B—C12—H12C109.5
O2—C3—C4118.35 (19)O3—C13—N1110.11 (16)
O2—C3—C2121.35 (19)O3—C13—C12112.56 (17)
C4—C3—C2120.3 (2)N1—C13—C12111.68 (18)
C3—C4—C5121.9 (2)O3—C13—C14107.04 (18)
C3—C4—H4119.1N1—C13—C14100.54 (15)
C5—C4—H4119.1C12—C13—C14114.20 (19)
C4—C5—C10118.92 (19)C15—C14—C13104.14 (17)
C4—C5—C6122.9 (2)C15—C14—H14A110.9
C10—C5—C6118.1 (2)C13—C14—H14A110.9
C7—C6—C5120.6 (2)C15—C14—H14B110.9
C7—C6—H6119.7C13—C14—H14B110.9
C5—C6—H6119.7H14A—C14—H14B108.9
C6—C7—C8121.7 (2)N2—C15—C16121.66 (19)
C6—C7—H7119.1N2—C15—C14114.22 (18)
C8—C7—H7119.1C16—C15—C14124.1 (2)
C9—C8—C7119.7 (3)C15—C16—H16A109.5
C9—C8—H8120.1C15—C16—H16B109.5
C7—C8—H8120.1H16A—C16—H16B109.5
C8—C9—C10120.5 (2)C15—C16—H16C109.5
C8—C9—H9119.7H16A—C16—H16C109.5
C10—C9—H9119.7H16B—C16—H16C109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2···O10.821.792.518 (2)147
O3—H3···O10.822.362.888 (2)122
O3—H3···O2i0.822.272.922 (2)137
C9—H9···O3ii0.932.573.388 (3)147

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV2430).

References

  • Dou, J. M., Liu, M. L., Li, D. C. & Wang, D. Q. (2006). Eur. J. Inorg. Chem.23, 4866–4871.
  • Moon, D., Lee, K., John, R. P., Kim, G. H., Sun, B. J. & Lah, M. S. (2006). Inorg. Chem.45, 7991–7993. [PubMed]
  • Mukhopadhyay, A. & Pal, S. (2004). Polyhedron, 23, 1997–2004.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Siemens (1996). SMART and SAINT Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

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