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Acta Crystallogr Sect E Struct Rep Online. 2010 July 1; 66(Pt 7): o1850.
Published online 2010 June 26. doi:  10.1107/S1600536810024438
PMCID: PMC3007032

N-(1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)acetamide–naphthalene-2,3-diol (1/1)

Abstract

In the reaction of naphthalene-2,3-diol and 4-amino­anti­pyrine in the presence of acetic acid, the amine function is acetyl­ated and the resulting acetamide co-crystallizes with the diol in the title compound, C13H15N3O2·C10H8O2, with 1:1 molar stoichiometry. The two components are linked by two O–H(...)O=C hydrogen bonds. One of the hy­droxy groups inter­acts with the pyrazolone carbonyl O atom and the other hy­droxy group inter­acts with the amide O atom of another component, generating a chain motif. Adjacent chains are linked into a layer motif via N—H(...)O inter­actions involving only the heterocyclic acetamide component.

Related literature

For the crystal structure of 4-acetamido-2,3-dimethyl-1-phenyl-5-pyrazol-3-one, see: Kuznetsov et al. (1999 [triangle]). For co-crystals of naphthalene-2,3-diol, see: Fritchie & Johnston (1975 [triangle]); Herbert & Truter (1980 [triangle]); Kuo et al. (1974 [triangle]); Nakamatsu et al. (2003 [triangle]); Wang et al. (2008 [triangle]); Wells et al. (1974 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1850-scheme1.jpg

Experimental

Crystal data

  • C13H15N3O2·C10H8O2
  • M r = 405.44
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1850-efi1.jpg
  • a = 12.426 (1) Å
  • b = 14.304 (2) Å
  • c = 12.959 (1) Å
  • β = 117.845 (1)°
  • V = 2036.7 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 100 K
  • 0.25 × 0.25 × 0.10 mm

Data collection

  • Bruker SMART APEX diffractometer
  • 19263 measured reflections
  • 4683 independent reflections
  • 3189 reflections with I > 2σ(I)
  • R int = 0.061

Refinement

  • R[F 2 > 2σ(F 2)] = 0.052
  • wR(F 2) = 0.131
  • S = 1.02
  • 4683 reflections
  • 286 parameters
  • 27 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.31 e Å−3
  • Δρmin = −0.36 e Å−3

Data collection: APEX2 (Bruker, 2009 [triangle]); cell refinement: SAINT (Bruker, 2009 [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: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2010 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810024438/im2213sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810024438/im2213Isup2.hkl

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

Acknowledgments

We thank King Abdul Aziz University and the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

Naphthalene-2,3-diol forms co-crystals with a number of neutral organic compounds (Fritchie & Johnston, 1975; Herbert & Truter, 1980; Kuo et al., 1974; Nakamatsu et al., 2003; Wang et al., 2008; Wells et al., 1974). The attempt to co-crystallize it with the drug 4-aminoantipyrine was sussessful when the reaction was carried out in the presence of acetic acid, but the acetic acid converted the amino group to an acetamido group instead. In the co-crystal (Scheme I, Fig. 1), the acetamide and the diol are linked by two O–H···O═C hydrogen bonds. One of the hydroxy groups interacts with the pyrazolyl carbonyl O-atom and the other hydroxy group interacts with the amido O-atom of another component to generate a chain motif. Adjacent chains are linked into a layer motif via N–H···O interactions that involves the acetamide component only.

Experimental

Naphthalene-2,3-diol (0.35 g, 2.2 mol) and 4-aminoantipyrine (0.45 g, 2.2 mmol) were heated in methanol (15 ml) for 5 h; three drops of acetic acid were added. Crystals separated from the cool solution when it was set aside for a day.

Refinement

Carbon-bound H-atoms were placed in calculated positions [C–H 0.95 to 0.98 Å, U(H) = 1.2 to 1.5Ueq(C)] and were included in the refinement in the riding model approximation. The hydroxy and amino H-atoms were located in a difference Fourier map, and were refined with distance restraints of O–H 0.84±0.01Å and N–H 0.86±0.01 Å. Their temperature factors were freely refined.

The anisotropic temperature factors of C17 to C20 atoms of the naphthalene fused-ring were restrained to be nearly isotropic and with the restraints, the ellipsoids were somewhat elongated.

Figures

Fig. 1.
Thermal ellipsoid plot (Barbour, 2001) of the (C13H15N3O2)(C10H8O2) co-crystal at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

C13H15N3O2·C10H8O2F(000) = 856
Mr = 405.44Dx = 1.322 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2505 reflections
a = 12.426 (1) Åθ = 2.3–27.9°
b = 14.304 (2) ŵ = 0.09 mm1
c = 12.959 (1) ÅT = 100 K
β = 117.845 (1)°Prism, colorless
V = 2036.7 (4) Å30.25 × 0.25 × 0.10 mm
Z = 4

Data collection

Bruker SMART APEX diffractometer3189 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.061
graphiteθmax = 27.5°, θmin = 1.9°
ω scansh = −16→16
19263 measured reflectionsk = −18→18
4683 independent reflectionsl = −16→16

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.131H atoms treated by a mixture of independent and constrained refinement
S = 1.02w = 1/[σ2(Fo2) + (0.0544P)2 + 0.6929P] where P = (Fo2 + 2Fc2)/3
4683 reflections(Δ/σ)max = 0.001
286 parametersΔρmax = 0.31 e Å3
27 restraintsΔρmin = −0.35 e Å3

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

xyzUiso*/Ueq
O10.33173 (12)0.73209 (10)0.32885 (12)0.0290 (3)
O20.65387 (11)0.56345 (9)0.48381 (11)0.0232 (3)
O30.56600 (12)0.65279 (10)0.60626 (11)0.0253 (3)
O40.44923 (12)0.70985 (10)0.71521 (12)0.0279 (3)
N10.37471 (14)0.57790 (11)0.36783 (14)0.0224 (4)
N20.51486 (14)0.55398 (11)0.18066 (13)0.0233 (4)
N30.61709 (14)0.55929 (11)0.29124 (13)0.0219 (4)
C10.25557 (17)0.65611 (14)0.44515 (17)0.0255 (4)
H1A0.18790.70070.41230.038*
H1B0.31050.67280.52640.038*
H1C0.22370.59290.44220.038*
C20.32386 (16)0.65897 (14)0.37571 (16)0.0219 (4)
C30.58105 (17)0.56524 (12)0.37598 (16)0.0199 (4)
C40.45083 (17)0.57041 (13)0.31423 (16)0.0218 (4)
C50.41487 (17)0.56533 (13)0.19785 (16)0.0240 (4)
C60.29135 (19)0.57192 (16)0.09672 (18)0.0326 (5)
H6A0.23020.55910.12260.049*
H6B0.28350.52610.03740.049*
H6C0.27880.63500.06340.049*
C70.52538 (19)0.60264 (14)0.08616 (17)0.0284 (5)
H7A0.45400.58850.01160.043*
H7B0.59920.58170.08360.043*
H7C0.53000.67020.10020.043*
C80.73390 (18)0.53349 (14)0.30516 (17)0.0266 (4)
C90.7468 (2)0.45251 (15)0.25275 (18)0.0326 (5)
H90.67850.41350.20910.039*
C100.8600 (2)0.4293 (2)0.2648 (2)0.0501 (7)
H100.86960.37450.22850.060*
C110.9594 (2)0.4857 (2)0.3296 (3)0.0681 (10)
H111.03710.46980.33750.082*
C120.9456 (2)0.5654 (2)0.3830 (3)0.0676 (10)
H121.01440.60350.42840.081*
C130.8323 (2)0.59026 (18)0.3707 (2)0.0428 (6)
H130.82260.64520.40670.051*
C140.63471 (17)0.66192 (13)0.72372 (15)0.0202 (4)
C150.75639 (18)0.64515 (14)0.78429 (17)0.0266 (4)
H150.79870.62320.74400.032*
C160.82114 (19)0.65991 (16)0.90656 (18)0.0339 (5)
C170.9490 (2)0.6515 (2)0.9714 (2)0.0634 (9)
H170.99450.63160.93350.076*
C181.0082 (3)0.6715 (3)1.0883 (2)0.0872 (13)
H181.09440.66741.12990.105*
C190.9427 (2)0.6980 (3)1.1467 (2)0.0719 (10)
H190.98450.71041.22810.086*
C200.8197 (2)0.70618 (18)1.08762 (19)0.0406 (6)
H200.77610.72351.12850.049*
C210.75571 (18)0.68925 (14)0.96659 (17)0.0274 (4)
C220.62919 (17)0.70463 (13)0.90182 (16)0.0211 (4)
H220.58480.72350.94130.025*
C230.56923 (16)0.69285 (12)0.78342 (16)0.0198 (4)
H10.373 (2)0.5318 (11)0.4107 (17)0.036 (6)*
H30.608 (2)0.6281 (17)0.577 (2)0.054 (8)*
H40.419 (2)0.7345 (19)0.755 (2)0.067 (9)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0304 (8)0.0313 (8)0.0338 (8)0.0020 (6)0.0222 (7)0.0056 (6)
O20.0239 (7)0.0308 (7)0.0178 (7)−0.0018 (6)0.0121 (6)−0.0039 (5)
O30.0269 (7)0.0340 (8)0.0172 (7)0.0026 (6)0.0121 (6)−0.0035 (6)
O40.0215 (7)0.0423 (9)0.0207 (7)0.0040 (6)0.0106 (6)−0.0036 (6)
N10.0230 (8)0.0287 (9)0.0210 (9)−0.0039 (7)0.0147 (7)0.0004 (7)
N20.0266 (9)0.0303 (9)0.0165 (8)−0.0067 (7)0.0131 (7)−0.0030 (7)
N30.0238 (8)0.0281 (9)0.0175 (8)−0.0064 (7)0.0127 (7)−0.0067 (7)
C10.0186 (9)0.0374 (11)0.0224 (10)0.0005 (8)0.0111 (8)0.0010 (8)
C20.0169 (9)0.0310 (10)0.0170 (9)−0.0037 (8)0.0073 (8)−0.0025 (8)
C30.0263 (10)0.0194 (9)0.0196 (10)−0.0040 (7)0.0155 (8)−0.0036 (7)
C40.0246 (10)0.0240 (10)0.0214 (10)−0.0042 (8)0.0147 (8)−0.0025 (8)
C50.0273 (10)0.0275 (10)0.0203 (10)−0.0063 (8)0.0137 (8)−0.0024 (8)
C60.0285 (11)0.0463 (13)0.0221 (11)−0.0047 (10)0.0110 (9)−0.0027 (9)
C70.0387 (12)0.0323 (11)0.0211 (10)−0.0084 (9)0.0198 (10)−0.0035 (8)
C80.0275 (10)0.0352 (11)0.0251 (11)−0.0061 (8)0.0191 (9)−0.0079 (8)
C90.0346 (12)0.0400 (12)0.0291 (12)−0.0036 (10)0.0198 (10)−0.0093 (9)
C100.0452 (15)0.0678 (18)0.0458 (15)0.0041 (13)0.0284 (13)−0.0223 (13)
C110.0308 (14)0.117 (3)0.0654 (19)−0.0044 (15)0.0300 (14)−0.0417 (18)
C120.0341 (14)0.110 (3)0.071 (2)−0.0277 (15)0.0349 (14)−0.0542 (19)
C130.0349 (13)0.0565 (15)0.0477 (15)−0.0169 (11)0.0282 (12)−0.0290 (12)
C140.0257 (10)0.0207 (9)0.0159 (9)−0.0005 (8)0.0111 (8)−0.0022 (7)
C150.0262 (10)0.0348 (11)0.0247 (11)0.0040 (8)0.0169 (9)−0.0030 (8)
C160.0252 (11)0.0538 (14)0.0230 (11)0.0065 (10)0.0115 (9)−0.0049 (10)
C170.0274 (13)0.125 (3)0.0358 (14)0.0178 (14)0.0129 (11)−0.0205 (15)
C180.0297 (15)0.180 (4)0.0390 (16)0.0292 (19)0.0051 (13)−0.025 (2)
C190.0341 (14)0.142 (3)0.0275 (14)0.0191 (16)0.0041 (11)−0.0231 (16)
C200.0315 (12)0.0672 (17)0.0221 (11)0.0076 (11)0.0117 (10)−0.0076 (11)
C210.0251 (10)0.0361 (11)0.0215 (10)0.0012 (9)0.0115 (9)−0.0030 (8)
C220.0259 (10)0.0235 (9)0.0186 (9)−0.0005 (8)0.0145 (8)−0.0003 (7)
C230.0201 (9)0.0205 (9)0.0197 (10)0.0000 (7)0.0101 (8)−0.0004 (7)

Geometric parameters (Å, °)

O1—C21.236 (2)C8—C91.389 (3)
O2—C31.261 (2)C9—C101.381 (3)
O3—C141.360 (2)C9—H90.9500
O3—H30.85 (3)C10—C111.383 (4)
O4—C231.354 (2)C10—H100.9500
O4—H40.85 (3)C11—C121.385 (4)
N1—C21.347 (2)C11—H110.9500
N1—C41.415 (2)C12—C131.388 (3)
N1—H10.868 (10)C12—H120.9500
N2—C51.371 (2)C13—H130.9500
N2—N31.404 (2)C14—C151.361 (3)
N2—C71.466 (2)C14—C231.430 (2)
N3—C31.369 (2)C15—C161.418 (3)
N3—C81.425 (2)C15—H150.9500
C1—C21.498 (2)C16—C171.413 (3)
C1—H1A0.9800C16—C211.426 (3)
C1—H1B0.9800C17—C181.369 (4)
C1—H1C0.9800C17—H170.9500
C3—C41.433 (3)C18—C191.398 (4)
C4—C51.360 (3)C18—H180.9500
C5—C61.484 (3)C19—C201.358 (3)
C6—H6A0.9800C19—H190.9500
C6—H6B0.9800C20—C211.409 (3)
C6—H6C0.9800C20—H200.9500
C7—H7A0.9800C21—C221.411 (3)
C7—H7B0.9800C22—C231.367 (3)
C7—H7C0.9800C22—H220.9500
C8—C131.380 (3)
C14—O3—H3109.9 (18)C10—C9—H9120.4
C23—O4—H4110.2 (19)C8—C9—H9120.4
C2—N1—C4123.16 (16)C9—C10—C11120.1 (2)
C2—N1—H1117.1 (15)C9—C10—H10119.9
C4—N1—H1118.4 (15)C11—C10—H10119.9
C5—N2—N3106.52 (14)C10—C11—C12120.0 (2)
C5—N2—C7121.38 (17)C10—C11—H11120.0
N3—N2—C7115.82 (15)C12—C11—H11120.0
C3—N3—N2110.07 (14)C11—C12—C13120.6 (2)
C3—N3—C8127.60 (16)C11—C12—H12119.7
N2—N3—C8119.84 (14)C13—C12—H12119.7
C2—C1—H1A109.5C8—C13—C12118.7 (2)
C2—C1—H1B109.5C8—C13—H13120.7
H1A—C1—H1B109.5C12—C13—H13120.7
C2—C1—H1C109.5O3—C14—C15125.21 (16)
H1A—C1—H1C109.5O3—C14—C23114.64 (16)
H1B—C1—H1C109.5C15—C14—C23120.15 (17)
O1—C2—N1122.93 (17)C14—C15—C16121.07 (17)
O1—C2—C1121.01 (17)C14—C15—H15119.5
N1—C2—C1116.05 (17)C16—C15—H15119.5
O2—C3—N3123.60 (17)C17—C16—C15123.06 (19)
O2—C3—C4131.17 (16)C17—C16—C21117.99 (19)
N3—C3—C4105.21 (15)C15—C16—C21118.87 (18)
C5—C4—N1126.85 (17)C18—C17—C16121.0 (2)
C5—C4—C3108.47 (16)C18—C17—H17119.5
N1—C4—C3124.68 (16)C16—C17—H17119.5
C4—C5—N2109.47 (17)C17—C18—C19120.5 (2)
C4—C5—C6130.11 (18)C17—C18—H18119.8
N2—C5—C6120.40 (17)C19—C18—H18119.8
C5—C6—H6A109.5C20—C19—C18120.3 (2)
C5—C6—H6B109.5C20—C19—H19119.8
H6A—C6—H6B109.5C18—C19—H19119.8
C5—C6—H6C109.5C19—C20—C21120.9 (2)
H6A—C6—H6C109.5C19—C20—H20119.5
H6B—C6—H6C109.5C21—C20—H20119.5
N2—C7—H7A109.5C20—C21—C22121.83 (18)
N2—C7—H7B109.5C20—C21—C16119.28 (19)
H7A—C7—H7B109.5C22—C21—C16118.82 (18)
N2—C7—H7C109.5C23—C22—C21121.33 (17)
H7A—C7—H7C109.5C23—C22—H22119.3
H7B—C7—H7C109.5C21—C22—H22119.3
C13—C8—C9121.35 (19)O4—C23—C22124.57 (16)
C13—C8—N3118.83 (18)O4—C23—C14115.71 (16)
C9—C8—N3119.81 (18)C22—C23—C14119.71 (17)
C10—C9—C8119.3 (2)
C5—N2—N3—C35.4 (2)C8—C9—C10—C110.8 (4)
C7—N2—N3—C3143.68 (16)C9—C10—C11—C120.3 (5)
C5—N2—N3—C8168.77 (16)C10—C11—C12—C13−1.0 (5)
C7—N2—N3—C8−52.9 (2)C9—C8—C13—C120.5 (4)
C4—N1—C2—O15.8 (3)N3—C8—C13—C12−179.3 (2)
C4—N1—C2—C1−174.38 (16)C11—C12—C13—C80.6 (5)
N2—N3—C3—O2174.23 (16)O3—C14—C15—C16177.70 (19)
C8—N3—C3—O212.4 (3)C23—C14—C15—C16−1.5 (3)
N2—N3—C3—C4−4.09 (19)C14—C15—C16—C17−174.2 (2)
C8—N3—C3—C4−165.87 (17)C14—C15—C16—C212.5 (3)
C2—N1—C4—C5−79.6 (3)C15—C16—C17—C18176.3 (3)
C2—N1—C4—C3101.6 (2)C21—C16—C17—C18−0.4 (5)
O2—C3—C4—C5−176.82 (19)C16—C17—C18—C192.0 (6)
N3—C3—C4—C51.3 (2)C17—C18—C19—C20−1.5 (6)
O2—C3—C4—N12.2 (3)C18—C19—C20—C21−0.7 (5)
N3—C3—C4—N1−179.66 (17)C19—C20—C21—C22−174.8 (3)
N1—C4—C5—N2−176.99 (17)C19—C20—C21—C162.3 (4)
C3—C4—C5—N22.0 (2)C17—C16—C21—C20−1.7 (3)
N1—C4—C5—C64.2 (3)C15—C16—C21—C20−178.5 (2)
C3—C4—C5—C6−176.78 (19)C17—C16—C21—C22175.4 (2)
N3—N2—C5—C4−4.4 (2)C15—C16—C21—C22−1.4 (3)
C7—N2—C5—C4−139.91 (18)C20—C21—C22—C23176.4 (2)
N3—N2—C5—C6174.48 (17)C16—C21—C22—C23−0.7 (3)
C7—N2—C5—C639.0 (3)C21—C22—C23—O4−177.26 (18)
C3—N3—C8—C13−64.6 (3)C21—C22—C23—C141.7 (3)
N2—N3—C8—C13135.2 (2)O3—C14—C23—O4−0.8 (2)
C3—N3—C8—C9115.5 (2)C15—C14—C23—O4178.42 (17)
N2—N3—C8—C9−44.7 (3)O3—C14—C23—C22−179.90 (16)
C13—C8—C9—C10−1.2 (3)C15—C14—C23—C22−0.6 (3)
N3—C8—C9—C10178.6 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O2i0.87 (1)2.07 (1)2.924 (2)169 (2)
O3—H3···O20.85 (3)1.81 (3)2.639 (2)163 (3)
O4—H4···O1ii0.85 (3)1.81 (3)2.646 (2)168 (3)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+3/2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IM2213).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
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