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Acta Crystallogr Sect E Struct Rep Online. 2012 September 1; 68(Pt 9): o2675–o2676.
Published online 2012 August 11. doi:  10.1107/S1600536812034599
PMCID: PMC3435698

2-Cyclo­pentyl­idenehydrazine­carboxamide

Abstract

The asymmetric unit of the title compound, C6H11N3O, consists of two independent mol­ecules in which the cyclo­pentane rings adopt envelope conformations with CH2 grouping as the flap and the semicarbazone groups are essentially planar, with maximums deviation of 0.0311 (12) and 0.0285 (12) Å. In the crystal, N—H(...)O, N—H(...)N and C—H(...)O hydrogen bonds link the mol­ecules to form sheets lying parallel to the ab plane.

Related literature  

For background to the biological activity of semicarbazones, see: Dogan et al. (1999 [triangle]); Pandeya & Dimmock (1993 [triangle]); Pandeya et al. (1998 [triangle]); Yogeeswari et al. (2004 [triangle]); Sriram et al. (2004 [triangle]); Fun et al. (2011 [triangle]). For related structures, see: Fun et al. (2009a [triangle],b [triangle]). For further synthetic details, see: Furniss et al. (1978 [triangle]). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-68-o2675-scheme1.jpg

Experimental  

Crystal data  

  • C6H11N3O
  • M r = 141.18
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-68-o2675-efi1.jpg
  • a = 8.9507 (1) Å
  • b = 10.7929 (2) Å
  • c = 15.0204 (2) Å
  • β = 95.126 (1)°
  • V = 1445.23 (4) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 100 K
  • 0.40 × 0.20 × 0.05 mm

Data collection  

  • Bruker SMART APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2009 [triangle]) T min = 0.964, T max = 0.995
  • 14322 measured reflections
  • 4231 independent reflections
  • 3120 reflections with I > 2σ(I)
  • R int = 0.040

Refinement  

  • R[F 2 > 2σ(F 2)] = 0.049
  • wR(F 2) = 0.114
  • S = 1.00
  • 4231 reflections
  • 205 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.28 e Å−3
  • Δρmin = −0.30 e Å−3

Data collection: APEX2 (Bruker, 2009 [triangle]); cell refinement: SAINT (Bruker, 2009 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812034599/hb6915sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812034599/hb6915Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812034599/hb6915Isup3.cml

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

Acknowledgments

HKF and WSL thank Universiti Sains Malaysia (USM) for the Research University Grant (1001/PFIZIK/811160). WSL also thanks the Malaysian Government and USM for the post of Research Officer under the Research University Grant (1001/PFIZIK/811160). AMI is thankful to the Board of Research in Nuclear Sciences, Government of India for the Young Scientist award. AMI also thanks the Vision Group on Science & Technology, Government of Karnataka, India for the Best Research Paper award.

supplementary crystallographic information

Comment

Various semicarbazones, have been known to possess biological activities against many of the most common species of bacteria (Dogan et al., 1999). Semicarbazones are of much interest due to their wide spectrum of antibacterial activities (Pandeya & Dimmock, 1993). Recently some workers reviewed the bioactivity of semicarbazones and they have exhibited anticonvulsant (Pandeya et al., 1998; Yogeeswari et al., 2004) and antitubercular (Sriram et al., 2004) properties. Our previous report highlights the synthesis and crystal structures of the semicarbozones (Fun et al., 2011). In continuation of our studies in this area, we now report the synthesis and structure of the title compound.

The asymmetric unit of the title compound, Fig. 1, consists of two crystallographically independent molecules. The cyclopentane (C1–C5) rings adopt an envelope conformation. The semicarbazone groups (O1/N1–N3/C6) are essentially planar with maximum deviation of 0.0311 (12) Å at atom N2A and 0.0285 (12) Å at atom N2B. Bond lengths and angles are comparable with the related structures (Fun et al. 2009a,b).

In the crystal, Fig. 2, N2A—H1N2···O1B, N3A—H1N3···N1B, N3A—H2N3···O1A, N2B—H2N2···O1A, N3B—H3N3···O1B, N3B—H4N3···N1A and C1A—H1AB···O1B hydrogen bonds (Table 1), link the molecules to form planes parallel to the ab plane.

Experimental

Semicarbazide hydrochloride (0.66 g, 0.0059 mol) and freshly recrystallized sodium acetate (0.58 g, 0.007 mol) were dissolved in water (10 ml) following a literature procedure (Furniss et al., 1978). The reaction mixture was stirred at room temperature for 10 minutes. To this, cyclopentanone (0.5 g, 0.0059 mol) was added and shaken well. A little alcohol was added to dissolve the turbidity. It was shaken for 10 more minutes and allowed to stand. The semicarbazone crystallized on standing for 6 h. The separated crystals were filtered, washed with cold water and recrystallized from ethanol as colourless plates. M.p. 495–498 K.

Refinement

N– bound H atoms were located from the difference Fourier map and were refined freely [N–H = 0.858 (18) to 0.926 (19) Å]. The remaining H atoms were located geometrically and were refined using a riding model with Uiso(H) = 1.2 Ueq(C) [C–H = 0.99 Å]. In the final refinement, one outliner was omitted, 6 11 8.

Figures

Fig. 1.
The molecular structure of the title compound, showing 50% probability displacement ellipsoids.
Fig. 2.
The crystal packing of the title compound, viewed along the a axis. H atoms not involved in the intermolecular interactions (dashed lines) have been omitted for clarity.

Crystal data

C6H11N3OF(000) = 608
Mr = 141.18Dx = 1.298 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3109 reflections
a = 8.9507 (1) Åθ = 2.7–29.3°
b = 10.7929 (2) ŵ = 0.09 mm1
c = 15.0204 (2) ÅT = 100 K
β = 95.126 (1)°Plate, colourless
V = 1445.23 (4) Å30.40 × 0.20 × 0.05 mm
Z = 8

Data collection

Bruker SMART APEXII CCD diffractometer4231 independent reflections
Radiation source: fine-focus sealed tube3120 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.040
[var phi] and ω scansθmax = 30.1°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)h = −12→12
Tmin = 0.964, Tmax = 0.995k = −12→15
14322 measured reflectionsl = −18→21

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)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114H atoms treated by a mixture of independent and constrained refinement
S = 1.00w = 1/[σ2(Fo2) + (0.0422P)2 + 0.6439P] where P = (Fo2 + 2Fc2)/3
4231 reflections(Δ/σ)max < 0.001
205 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = −0.30 e Å3

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.
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
O1B0.14864 (10)0.11961 (9)0.00969 (7)0.0163 (2)
N1B−0.03324 (12)0.35060 (10)0.12404 (8)0.0142 (2)
N2B0.07174 (12)0.29357 (11)0.07505 (8)0.0148 (2)
N3B−0.07584 (13)0.11717 (12)0.06934 (9)0.0180 (3)
C1B−0.11403 (15)0.53548 (13)0.19876 (10)0.0179 (3)
H1BA−0.08920.51960.26330.021*
H1BB−0.22000.51250.18240.021*
C2B−0.08570 (15)0.67107 (13)0.17588 (10)0.0196 (3)
H2BA−0.10790.72640.22560.024*
H2BB−0.14790.69640.12110.024*
C3B0.08159 (15)0.67431 (13)0.16132 (10)0.0187 (3)
H3BA0.14360.68150.21900.022*
H3BB0.10430.74500.12270.022*
C4B0.11103 (14)0.55001 (12)0.11528 (9)0.0154 (3)
H4BA0.10360.55970.04950.018*
H4BB0.21170.51750.13570.018*
C5B−0.01062 (14)0.46502 (12)0.14338 (9)0.0140 (3)
C6B0.05040 (14)0.17321 (12)0.04950 (9)0.0132 (3)
O1A0.35640 (10)0.37841 (9)0.00812 (7)0.0169 (2)
N1A0.57800 (12)0.13301 (11)0.09989 (8)0.0145 (2)
N2A0.45488 (12)0.19836 (11)0.06156 (8)0.0153 (3)
N3A0.60763 (13)0.36934 (12)0.04762 (9)0.0194 (3)
C1A0.67282 (15)−0.05543 (13)0.17484 (10)0.0173 (3)
H1AA0.7522−0.00470.20720.021*
H1AB0.7184−0.10930.13130.021*
C2A0.58742 (15)−0.13169 (14)0.23954 (10)0.0202 (3)
H2AA0.5718−0.08370.29410.024*
H2AB0.6417−0.20910.25690.024*
C3A0.43811 (16)−0.15927 (14)0.18545 (10)0.0208 (3)
H3AA0.3591−0.17880.22540.025*
H3AB0.4482−0.22990.14440.025*
C4A0.40070 (15)−0.03906 (13)0.13277 (10)0.0176 (3)
H4AA0.3551−0.05770.07180.021*
H4AB0.33070.01330.16370.021*
C5A0.55099 (14)0.02476 (12)0.12953 (9)0.0137 (3)
C6A0.47038 (14)0.31899 (12)0.03773 (9)0.0138 (3)
H1N20.3656 (19)0.1655 (16)0.0516 (12)0.028 (5)*
H1N30.682 (2)0.3267 (17)0.0710 (12)0.030 (5)*
H2N30.6182 (19)0.4510 (18)0.0303 (12)0.028 (5)*
H2N20.1582 (19)0.3309 (16)0.0600 (12)0.027 (5)*
H3N3−0.0968 (19)0.0420 (18)0.0474 (12)0.028 (5)*
H4N3−0.1441 (19)0.1587 (16)0.0927 (12)0.026 (5)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O1B0.0139 (4)0.0136 (5)0.0217 (5)0.0001 (3)0.0040 (4)−0.0029 (4)
N1B0.0147 (5)0.0156 (6)0.0128 (5)0.0013 (4)0.0032 (4)−0.0006 (4)
N2B0.0128 (5)0.0126 (6)0.0197 (6)−0.0009 (4)0.0059 (4)−0.0018 (5)
N3B0.0165 (5)0.0131 (6)0.0255 (7)−0.0022 (5)0.0082 (5)−0.0039 (5)
C1B0.0174 (6)0.0177 (7)0.0189 (7)−0.0005 (5)0.0038 (5)−0.0045 (6)
C2B0.0204 (6)0.0168 (7)0.0214 (7)0.0043 (5)0.0000 (5)−0.0050 (6)
C3B0.0205 (6)0.0138 (7)0.0216 (7)−0.0006 (5)−0.0001 (6)−0.0026 (6)
C4B0.0153 (6)0.0150 (6)0.0158 (7)0.0005 (5)0.0015 (5)−0.0005 (5)
C5B0.0141 (6)0.0143 (6)0.0136 (6)0.0001 (5)0.0002 (5)0.0007 (5)
C6B0.0138 (6)0.0127 (6)0.0128 (6)0.0006 (5)−0.0006 (5)0.0009 (5)
O1A0.0136 (4)0.0144 (5)0.0226 (5)0.0005 (4)0.0006 (4)0.0020 (4)
N1A0.0127 (5)0.0149 (6)0.0161 (6)0.0025 (4)0.0026 (4)0.0001 (5)
N2A0.0113 (5)0.0129 (6)0.0216 (6)−0.0004 (4)0.0007 (4)0.0031 (5)
N3A0.0132 (5)0.0153 (6)0.0293 (7)−0.0007 (4)0.0001 (5)0.0057 (5)
C1A0.0156 (6)0.0190 (7)0.0175 (7)0.0021 (5)0.0034 (5)0.0042 (6)
C2A0.0193 (7)0.0233 (8)0.0181 (7)−0.0014 (6)0.0032 (5)0.0063 (6)
C3A0.0213 (7)0.0185 (7)0.0225 (7)−0.0054 (5)0.0013 (6)0.0064 (6)
C4A0.0159 (6)0.0174 (7)0.0195 (7)−0.0022 (5)0.0019 (5)0.0022 (6)
C5A0.0149 (6)0.0149 (7)0.0118 (6)0.0005 (5)0.0036 (5)−0.0012 (5)
C6A0.0145 (6)0.0143 (7)0.0131 (6)0.0001 (5)0.0039 (5)−0.0019 (5)

Geometric parameters (Å, º)

O1B—C6B1.2488 (16)O1A—C6A1.2526 (15)
N1B—C5B1.2806 (17)N1A—C5A1.2811 (18)
N1B—N2B1.3882 (16)N1A—N2A1.3892 (14)
N2B—C6B1.3631 (17)N2A—C6A1.3605 (17)
N2B—H2N20.919 (17)N2A—H1N20.875 (17)
N3B—C6B1.3385 (17)N3A—C6A1.3394 (17)
N3B—H3N30.889 (19)N3A—H1N30.860 (18)
N3B—H4N30.858 (18)N3A—H2N30.926 (19)
C1B—C5B1.5049 (19)C1A—C5A1.5062 (17)
C1B—C2B1.530 (2)C1A—C2A1.529 (2)
C1B—H1BA0.9900C1A—H1AA0.9900
C1B—H1BB0.9900C1A—H1AB0.9900
C2B—C3B1.533 (2)C2A—C3A1.5300 (18)
C2B—H2BA0.9900C2A—H2AA0.9900
C2B—H2BB0.9900C2A—H2AB0.9900
C3B—C4B1.5427 (19)C3A—C4A1.541 (2)
C3B—H3BA0.9900C3A—H3AA0.9900
C3B—H3BB0.9900C3A—H3AB0.9900
C4B—C5B1.5124 (19)C4A—C5A1.5159 (18)
C4B—H4BA0.9900C4A—H4AA0.9900
C4B—H4BB0.9900C4A—H4AB0.9900
C5B—N1B—N2B116.56 (11)C5A—N1A—N2A116.09 (11)
C6B—N2B—N1B119.17 (11)C6A—N2A—N1A119.94 (11)
C6B—N2B—H2N2116.7 (11)C6A—N2A—H1N2117.2 (12)
N1B—N2B—H2N2124.1 (11)N1A—N2A—H1N2122.9 (12)
C6B—N3B—H3N3118.9 (12)C6A—N3A—H1N3119.9 (12)
C6B—N3B—H4N3120.1 (12)C6A—N3A—H2N3118.1 (10)
H3N3—N3B—H4N3119.6 (16)H1N3—N3A—H2N3121.9 (16)
C5B—C1B—C2B103.70 (12)C5A—C1A—C2A102.33 (11)
C5B—C1B—H1BA111.0C5A—C1A—H1AA111.3
C2B—C1B—H1BA111.0C2A—C1A—H1AA111.3
C5B—C1B—H1BB111.0C5A—C1A—H1AB111.3
C2B—C1B—H1BB111.0C2A—C1A—H1AB111.3
H1BA—C1B—H1BB109.0H1AA—C1A—H1AB109.2
C1B—C2B—C3B103.74 (11)C1A—C2A—C3A103.28 (11)
C1B—C2B—H2BA111.0C1A—C2A—H2AA111.1
C3B—C2B—H2BA111.0C3A—C2A—H2AA111.1
C1B—C2B—H2BB111.0C1A—C2A—H2AB111.1
C3B—C2B—H2BB111.0C3A—C2A—H2AB111.1
H2BA—C2B—H2BB109.0H2AA—C2A—H2AB109.1
C2B—C3B—C4B104.61 (11)C2A—C3A—C4A104.38 (11)
C2B—C3B—H3BA110.8C2A—C3A—H3AA110.9
C4B—C3B—H3BA110.8C4A—C3A—H3AA110.9
C2B—C3B—H3BB110.8C2A—C3A—H3AB110.9
C4B—C3B—H3BB110.8C4A—C3A—H3AB110.9
H3BA—C3B—H3BB108.9H3AA—C3A—H3AB108.9
C5B—C4B—C3B104.26 (11)C5A—C4A—C3A104.26 (10)
C5B—C4B—H4BA110.9C5A—C4A—H4AA110.9
C3B—C4B—H4BA110.9C3A—C4A—H4AA110.9
C5B—C4B—H4BB110.9C5A—C4A—H4AB110.9
C3B—C4B—H4BB110.9C3A—C4A—H4AB110.9
H4BA—C4B—H4BB108.9H4AA—C4A—H4AB108.9
N1B—C5B—C1B121.34 (12)N1A—C5A—C1A121.98 (11)
N1B—C5B—C4B128.67 (13)N1A—C5A—C4A128.40 (12)
C1B—C5B—C4B109.97 (11)C1A—C5A—C4A109.46 (11)
O1B—C6B—N3B122.81 (12)O1A—C6A—N3A122.79 (13)
O1B—C6B—N2B119.30 (12)O1A—C6A—N2A118.98 (11)
N3B—C6B—N2B117.89 (12)N3A—C6A—N2A118.24 (12)
C5B—N1B—N2B—C6B−177.45 (11)C5A—N1A—N2A—C6A172.46 (13)
C5B—C1B—C2B—C3B−34.21 (13)C5A—C1A—C2A—C3A38.89 (14)
C1B—C2B—C3B—C4B36.78 (14)C1A—C2A—C3A—C4A−38.43 (15)
C2B—C3B—C4B—C5B−24.62 (14)C2A—C3A—C4A—C5A22.39 (15)
N2B—N1B—C5B—C1B−177.98 (11)N2A—N1A—C5A—C1A−178.43 (12)
N2B—N1B—C5B—C4B4.09 (19)N2A—N1A—C5A—C4A−3.6 (2)
C2B—C1B—C5B—N1B−158.97 (12)C2A—C1A—C5A—N1A150.21 (13)
C2B—C1B—C5B—C4B19.31 (13)C2A—C1A—C5A—C4A−25.50 (15)
C3B—C4B—C5B—N1B−178.62 (13)C3A—C4A—C5A—N1A−173.30 (14)
C3B—C4B—C5B—C1B3.26 (13)C3A—C4A—C5A—C1A2.06 (15)
N1B—N2B—C6B—O1B−176.11 (11)N1A—N2A—C6A—O1A−175.88 (12)
N1B—N2B—C6B—N3B3.25 (18)N1A—N2A—C6A—N3A3.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···AD—HH···AD···AD—H···A
N2A—H1N2···O1B0.875 (17)2.048 (17)2.9088 (14)167.7 (17)
N3A—H1N3···N1Bi0.858 (18)2.614 (18)3.3214 (16)140.5 (16)
N3A—H2N3···O1Aii0.926 (19)1.949 (19)2.8749 (16)178.7 (15)
N2B—H2N2···O1A0.919 (17)2.065 (17)2.9663 (14)166.6 (16)
N3B—H3N3···O1Biii0.889 (19)1.980 (19)2.8682 (16)175.9 (18)
N3B—H4N3···N1Aiv0.858 (17)2.515 (17)3.1771 (16)134.7 (15)
C1A—H1AB···O1Bv0.992.523.3923 (18)146

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB6915).

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