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Acta Crystallogr Sect E Struct Rep Online. 2009 May 1; 65(Pt 5): o1111–o1112.
Published online 2009 April 25. doi:  10.1107/S1600536809014561
PMCID: PMC2977788

(E)-2-{(2-Hydroxy­naphthalen-1-yl)methyl­ene}hydrazinecarboxamide

Abstract

In the title mol­ecule, C12H11N3O2, the dihedral angle between the mean planes of the naphthalene and carboxamide groups is 28.9 (8)°. The hydrazine N atoms are twisted slightly out of the plane of the carboxamide group [C—C—N—N torsion angle = −175.06 (13)°]. The crystal packing is influenced by N—H(...)O hydrogen bonding which includes a bifurcated hydrogen bond between the amide N atom and nearby carboxyl and hydroxyl O atoms. A second bifurcated hydrogen bond occurs between the hydroxyl O atom and nearby amide (inter­molecular) and hydrazine (intra­molecular) N atoms. As a result, mol­ecules are linked into a co-operative hydrogen-bonded network of infinite one-dimensional O—H(...)O—H(...)O—H chains along the (101) plane of the unit cell in a zigzag pattern, the dihedral angle between the mean planes of the naphthalene groups of adjacent mol­ecules in the chain being 86.9 (2)°. A MOPAC PM3 calculation provides support to these observations.

Related literature

For related semicarbazones, see: Noblia et al. (2005 [triangle]). For the bioactivity of semicarbazones, see: Beraldo & Gambino (2004 [triangle]). For their applications in polymers, see: Khuhawar et al. (2004 [triangle]) and in sensors, see: Oter et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1111-scheme1.jpg

Experimental

Crystal data

  • C12H11N3O2
  • M r = 229.24
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1111-efi1.jpg
  • a = 16.0886 (4) Å
  • b = 4.72900 (10) Å
  • c = 15.6452 (4) Å
  • β = 114.647 (3)°
  • V = 1081.89 (5) Å3
  • Z = 4
  • Cu Kα radiation
  • μ = 0.82 mm−1
  • T = 200 K
  • 0.57 × 0.22 × 0.12 mm

Data collection

  • Oxford Diffraction Gemini R diffractometer
  • Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 [triangle]) T min = 0.819, T max = 0.907
  • 7383 measured reflections
  • 2135 independent reflections
  • 1724 reflections with I > 2σ(I)
  • R int = 0.031

Refinement

  • R[F 2 > 2σ(F 2)] = 0.047
  • wR(F 2) = 0.124
  • S = 1.03
  • 2135 reflections
  • 155 parameters
  • H-atom parameters constrained
  • Δρmax = 0.30 e Å−3
  • Δρmin = −0.26 e Å−3

Data collection: CrysAlisPro (Oxford Diffraction, 2007 [triangle]); cell refinement: CrysAlisPro; data reduction: CrysAlis RED (Oxford Diffraction, 2007 [triangle]); 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 and WebMOPro (Schmidt & Polik, 2007 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809014561/rk2136sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809014561/rk2136Isup2.hkl

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

Acknowledgments

Support to YMH and OO was provided by DOE–CETBR grant No. DE–FG02–03ER63580 and NSF–RISE Award No. HRD–0627276. RJB acknowledges the NSF MRI program (grant No. CHE–0619278) for funds to purchase an X–ray diffractometer.

supplementary crystallographic information

Comment

The title compound, C12H11N3O2, is a tridentate semicarbazone ligand and forms complexes with a variety of metals. It coordinates with vanadium which forms complexes with potential antitumor activity (Noblia et al., 2005). Semicarbazones show significant bioactivities including antiprotozoa and anticonvulsant types (Beraldo & Gambino, 2004), and additionally some derivatives have been used as selective fiber optic sensors for copper(II) (Oter et al., 2007) or incorported into polymers (Khuhawar et al., 2004).

The title molecule, C12H11N3O2, consists of a 2–hydroxynaphthalen–1–yl group and a hydrazinecarboxamide group bonded to a methylene carbon atom with the dihedral angle between the mean planes of the naphthalene and carboxamide groups measuring 28.9 (8)° (Fig. 1). The hydrazine nitrogen atoms are twisted slightly out of the plane of the carboxamide group [torsion angles C1–C11–N1–N2 = -175.06 (13)°]. The hydroxyl group is in the plane of the napthalene group [torsion angle = 179.62 (15)°]. Crystal packing is influenced by extensive strong intermolecular N—H···O hydrogen bonding which includes a bifurcated hydrogen bond between the amide nitrogen atom, N1, and a nearby carboxyl oxygen atom (O2) and hydroxyl oxygen atom (O1) (see Fig. 2, Table 1). A second bifurcated hydrogen bond occurs between the hydroxyl oxygen atom (O1) and nearby amide (N3) (intermolecular) and hydrazine (N1) (intramolecular) nitrogen atoms. As a result the molecules are linked into a cooperative hydrogen bond network of infinite one–dimensionsl O—H···O—H···O—H chains along the (1 0 1) plane of the unit cell in a zigzag pattern with the dihedral angle between the mean planes of the naphthalene groups of consecutive molecules in the chain measuring 86.9 (2)° (Fig. 3).

After a MOPAC PM3 calculation [Parameterized Model 3 approximation together with the Hartree–Fock closed–shell (restricted) wavefunction was used and minimizations were teminnated at an r.m.s. gradient of less than 0.01 kJ mol-1 Å-1] of the molecule in the asymmetric unit with WebMO Pro (Schmidt & Polik, 2007), the mean planes between the naphthalene and carboxamide groups changes from 28.9 (8)° to 14.8 (1)°, producing a significantly less twisted, more planar, molecule than that observed in the crystalline environment. It is apparent that the extensive hydrogen bonding scheme described significantly influences the crystal packing in the unit cell highlighted by a network of infinite one–dimensionsl O—H···O—H···O—H chains.

Experimental

The title compound (I) was synthesized by adding a solution of 2–hydroxy–1–naphthaldehyde (1.72 g, 10 mmol) dissolved in 5 ml of ethanol to a solution of 1.15 g (10.4 mmol) of semicarbazide hydrochloride in 10 ml of water. The mixture was stirred at room temperature. A green precipitate formed. The mixture was stirred for 30 minutes then diluted with 50 ml of water, filtered and dried. Recrystallization from ethanol and slow evaporation of the solvent gave a light yellowish–green solid 1.55 g (68%). m.p. with decomposition > 503 K. 1H NMR (DMSO–d6, 400 MHz) δ (p.p.m.): 11.24 (br. s, 1H), 10.25 (br. s, 1H), 8.87 (s, 1H), 8.38 (d, J = 8.5 Hz, 1H), 7.85 (m, 2H), 7.55 (dt, J = 7.75, 1.4 Hz, 1 H), 7.37(t, J = 7.5 Hz, 1H), 7.17(d, J = 8.85, Hz, 1 H), 6.30 (br s, 2H); 13C NMR (DMSO–d6, 100 MHz) δ (p.p.m.): 156.07, 155.83, 139.86, 131.40, 131.31, 128.67, 127.94, 127.47, 123.26, 121.99, 118.44, 109.79.

Refinement

The atoms H3A, H3B and H10 were obtained from a difference fourier map. The remaining H atoms were placed in their calculated positions and then refined using the riding model with C—H = 0.95 Å, and with Uiso(H) = 1.18–1.21 Ueq(C,N,O).

Figures

Fig. 1.
The molecular structure of C12H11N3O2, showing the atom numbering scheme. Displacement ellipsoids are drawn at 50% probability level. H atoms are presented as a small cyrcles of arbitrary radius.
Fig. 2.
The molecular packing for C12H11N3O2 viewed down the c axis showing the cooperative hydrogen bond network of infinite one–dimensional O—H···O—H···O—H chains in a zigzag pattern. ...
Fig. 3.
The molecular packing for C12H11N3O2 viewed down the b axis showing the cooperative hydrogen bond network of infinite one–dimensional O—H···O—H···O—H chains along the (1 0 ...

Crystal data

C12H11N3O2F(000) = 480
Mr = 229.24Dx = 1.407 Mg m3
Monoclinic, P21/cCu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybcCell parameters from 4156 reflections
a = 16.0886 (4) Åθ = 5.2–73.5°
b = 4.7290 (1) ŵ = 0.82 mm1
c = 15.6452 (4) ÅT = 200 K
β = 114.647 (3)°Needle, pale yellow
V = 1081.89 (5) Å30.57 × 0.22 × 0.12 mm
Z = 4

Data collection

Oxford Diffraction Gemini R diffractometer2135 independent reflections
Radiation source: Fine–focus sealed tube1724 reflections with I > 2σ(I)
GraphiteRint = 0.031
Detector resolution: 10.5081 pixels mm-1θmax = 73.5°, θmin = 5.7°
[var phi] and ω scansh = −18→20
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)k = −4→5
Tmin = 0.819, Tmax = 0.907l = −19→19
7383 measured reflections

Refinement

Refinement on F2Primary atom site location: Direct
Least-squares matrix: FullSecondary atom site location: Difmap
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: Geom
wR(F2) = 0.124H-atom parameters constrained
S = 1.03w = 1/[σ2(Fo2) + (0.0706P)2 + 0.3033P] where P = (Fo2 + 2Fc2)/3
2135 reflections(Δ/σ)max < 0.001
155 parametersΔρmax = 0.30 e Å3
0 restraintsΔρmin = −0.26 e Å3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
O10.31323 (8)0.7964 (3)0.22177 (8)0.0437 (3)
H1O0.34980.67740.25790.052*
O20.56353 (8)−0.0031 (2)0.42849 (8)0.0369 (3)
N10.38963 (8)0.4986 (3)0.37070 (9)0.0317 (3)
N20.44479 (9)0.2745 (3)0.41411 (9)0.0332 (3)
H2A0.43220.16780.45330.040*
N30.54082 (10)0.4022 (3)0.34432 (10)0.0391 (4)
H3A0.58810.37060.33120.047*
H3B0.50760.55570.32310.047*
C10.26235 (9)0.7936 (3)0.34640 (10)0.0280 (3)
C20.25746 (10)0.8928 (4)0.26045 (10)0.0325 (4)
C30.19255 (11)1.0963 (4)0.20808 (11)0.0391 (4)
H3C0.19021.15860.14940.047*
C40.13328 (11)1.2044 (4)0.24071 (12)0.0386 (4)
H4A0.08961.34130.20440.046*
C50.13540 (10)1.1162 (3)0.32839 (11)0.0325 (4)
C60.07427 (11)1.2315 (4)0.36314 (12)0.0408 (4)
H6A0.03121.37070.32740.049*
C70.07638 (12)1.1455 (4)0.44726 (13)0.0438 (4)
H7A0.03451.22250.46940.053*
C80.14048 (12)0.9437 (4)0.50068 (12)0.0414 (4)
H8A0.14190.88490.55930.050*
C90.20126 (10)0.8293 (4)0.46977 (11)0.0348 (4)
H9A0.24470.69420.50770.042*
C100.20044 (9)0.9091 (3)0.38214 (10)0.0287 (3)
C110.32667 (10)0.5704 (3)0.39663 (10)0.0291 (3)
H11A0.32200.47820.44840.035*
C120.51931 (10)0.2162 (3)0.39678 (10)0.0303 (3)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0468 (7)0.0513 (8)0.0418 (6)0.0135 (6)0.0272 (5)0.0132 (5)
O20.0394 (6)0.0298 (6)0.0446 (6)0.0091 (5)0.0208 (5)0.0026 (5)
N10.0305 (6)0.0290 (7)0.0354 (6)0.0038 (5)0.0135 (5)0.0024 (5)
N20.0337 (7)0.0283 (7)0.0408 (7)0.0063 (5)0.0187 (6)0.0074 (5)
N30.0418 (7)0.0330 (8)0.0523 (8)0.0081 (6)0.0293 (6)0.0057 (6)
C10.0251 (7)0.0271 (8)0.0302 (7)−0.0010 (6)0.0098 (6)0.0006 (6)
C20.0321 (8)0.0330 (9)0.0334 (7)0.0003 (6)0.0145 (6)0.0011 (6)
C30.0410 (9)0.0404 (10)0.0333 (8)0.0023 (7)0.0129 (7)0.0090 (7)
C40.0319 (8)0.0347 (9)0.0408 (8)0.0056 (7)0.0068 (6)0.0065 (7)
C50.0252 (7)0.0282 (8)0.0400 (8)−0.0020 (6)0.0095 (6)−0.0039 (6)
C60.0293 (8)0.0355 (9)0.0531 (10)0.0042 (7)0.0127 (7)−0.0048 (7)
C70.0355 (8)0.0447 (10)0.0569 (10)−0.0011 (7)0.0249 (8)−0.0148 (8)
C80.0410 (9)0.0459 (10)0.0426 (9)−0.0037 (8)0.0226 (7)−0.0081 (8)
C90.0332 (8)0.0363 (9)0.0352 (8)0.0024 (6)0.0146 (6)−0.0016 (6)
C100.0247 (7)0.0263 (8)0.0333 (7)−0.0036 (6)0.0103 (6)−0.0045 (6)
C110.0293 (7)0.0279 (8)0.0296 (7)−0.0002 (6)0.0119 (6)0.0002 (6)
C120.0305 (7)0.0289 (8)0.0310 (7)0.0008 (6)0.0125 (6)−0.0044 (6)

Geometric parameters (Å, °)

O1—C21.3534 (19)C3—H3C0.9500
O1—H1O0.8400C4—C51.421 (2)
O2—C121.2386 (18)C4—H4A0.9500
N1—C111.284 (2)C5—C61.416 (2)
N1—N21.3674 (18)C5—C101.424 (2)
N2—C121.3630 (19)C6—C71.364 (3)
N2—H2A0.8800C6—H6A0.9500
N3—C121.343 (2)C7—C81.398 (3)
N3—H3A0.8800C7—H7A0.9500
N3—H3B0.8800C8—C91.370 (2)
C1—C21.395 (2)C8—H8A0.9500
C1—C101.438 (2)C9—C101.417 (2)
C1—C111.457 (2)C9—H9A0.9500
C2—C31.405 (2)C11—H11A0.9500
C3—C41.355 (2)
C2—O1—H1O109.5C4—C5—C10119.23 (14)
C11—N1—N2118.82 (13)C7—C6—C5120.90 (16)
C12—N2—N1120.02 (13)C7—C6—H6A119.6
C12—N2—H2A120.0C5—C6—H6A119.6
N1—N2—H2A120.0C6—C7—C8119.71 (16)
C12—N3—H3A120.0C6—C7—H7A120.1
C12—N3—H3B120.0C8—C7—H7A120.1
H3A—N3—H3B120.0C9—C8—C7121.05 (16)
C2—C1—C10118.52 (13)C9—C8—H8A119.5
C2—C1—C11120.34 (14)C7—C8—H8A119.5
C10—C1—C11121.10 (13)C8—C9—C10121.09 (15)
O1—C2—C1122.44 (14)C8—C9—H9A119.5
O1—C2—C3116.10 (14)C10—C9—H9A119.5
C1—C2—C3121.45 (14)C9—C10—C5117.57 (14)
C4—C3—C2120.48 (15)C9—C10—C1123.14 (14)
C4—C3—H3C119.8C5—C10—C1119.29 (14)
C2—C3—H3C119.8N1—C11—C1119.82 (13)
C3—C4—C5121.03 (15)N1—C11—H11A120.1
C3—C4—H4A119.5C1—C11—H11A120.1
C5—C4—H4A119.5O2—C12—N3122.81 (14)
C6—C5—C4121.10 (15)O2—C12—N2119.71 (14)
C6—C5—C10119.67 (15)N3—C12—N2117.48 (14)
C11—N1—N2—C12−171.55 (13)C8—C9—C10—C51.2 (2)
C10—C1—C2—O1179.81 (14)C8—C9—C10—C1−179.55 (15)
C11—C1—C2—O1−2.4 (2)C6—C5—C10—C9−0.6 (2)
C10—C1—C2—C3−1.4 (2)C4—C5—C10—C9179.18 (14)
C11—C1—C2—C3176.35 (15)C6—C5—C10—C1−179.86 (14)
O1—C2—C3—C4179.62 (15)C4—C5—C10—C1−0.1 (2)
C1—C2—C3—C40.8 (3)C2—C1—C10—C9−178.19 (14)
C2—C3—C4—C50.2 (3)C11—C1—C10—C94.1 (2)
C3—C4—C5—C6179.19 (15)C2—C1—C10—C51.1 (2)
C3—C4—C5—C10−0.5 (2)C11—C1—C10—C5−176.66 (13)
C4—C5—C6—C7179.81 (15)N2—N1—C11—C1−175.06 (13)
C10—C5—C6—C7−0.5 (2)C2—C1—C11—N112.1 (2)
C5—C6—C7—C80.9 (3)C10—C1—C11—N1−170.23 (13)
C6—C7—C8—C9−0.3 (3)N1—N2—C12—O2−172.55 (13)
C7—C8—C9—C10−0.8 (3)N1—N2—C12—N36.8 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1O···N10.841.822.5562 (17)146
N2—H2A···O2i0.881.982.8290 (17)161
N3—H3A···O1ii0.882.102.9762 (18)171
N3—H3B···O2iii0.882.583.0618 (18)116

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RK2136).

References

  • Beraldo, H. & Gambino, D. (2004). Mini Rev. Med. Chem., 4, 31–39. [PubMed]
  • Khuhawar, M. Y., Mughal, M. A. & Channar, A. H. (2004). Eur. Polym. J.40, 805–809.
  • Noblia, P., Vieites, M., Parajon–Costa, B. S., Baran, E. J., Cerecetto, H., Draper, P., Gonzalez, M., Piro, O. E., Castellano, E. E., Azqueta, A., Lopez de Cerain, A., Monge–Vega, A. & Gambino, D. (2005). J. Inorg. Biochem.99, 443–451. [PubMed]
  • Oter, O., Ertekin, K., Kirilmis, C. & Koca, M. (2007). Anal. Chim. Acta, 584, 308–314. [PubMed]
  • Oxford Diffraction (2007). CrysAlisPro and CrysAlis RED Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.
  • Schmidt, J. R. & Polik, W. F. (2007). WebMO Pro WebMO, LLC, Holland, MI, USA. Available from http://www.webmo.net.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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