organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890
Volume 65| Part 5| May 2009| Page o1127

tert-Butyl N′-[4-(2-pyrid­yl)benzyl­­idene]hydrazine­carboxyl­ate

aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
*Correspondence e-mail: yaocheng@njut.edu.cn

(Received 2 April 2009; accepted 4 April 2009; online 25 April 2009)

In the mol­ecule of the title compound, C17H19N3O2, the aromatic rings are oriented at a dihedral angle of 3.68 (3)°. In the crystal structure, inter­molecular N—H⋯O hydrogen bonds link the mol­ecules into chains along the a axis. A weak C—H⋯π inter­action is also present.

Related literature

For a related structure, see: Sugi et al. (2002[Sugi, K., Matsui, K., Shintaku, T. & Itaya, N. (2002). US Patent No. 6 376 678.]). For bond-length data, see: Allen et al. (1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]).

[Scheme 1]

Experimental

Crystal data
  • C17H19N3O2

  • Mr = 297.35

  • Monoclinic, P 21

  • a = 5.3080 (11) Å

  • b = 6.3010 (13) Å

  • c = 23.459 (5) Å

  • β = 91.01 (3)°

  • V = 784.5 (3) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.08 mm−1

  • T = 294 K

  • 0.30 × 0.20 × 0.10 mm

Data collection
  • Enraf–Nonius–Nonius CAD-4 diffractometer

  • Absorption correction: ψ scan (North et al., 1968[North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351-359.]) Tmin = 0.975, Tmax = 0.992

  • 1743 measured reflections

  • 1566 independent reflections

  • 1249 reflections with I > 2σ(I)

  • Rint = 0.028

  • 3 standard reflections frequency: 120 min intensity decay: 1%

Refinement
  • R[F2 > 2σ(F2)] = 0.051

  • wR(F2) = 0.170

  • S = 1.00

  • 1566 reflections

  • 199 parameters

  • 1 restraint

  • H-atom parameters constrained

  • Δρmax = 0.16 e Å−3

  • Δρmin = −0.21 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1A⋯O2i 0.86 2.30 3.113 (5) 158
C16—H16ACg2ii 0.93 2.80 3.588 (4) 144
Symmetry codes: (i) x-1, y, z; (ii) [-x+1, y-{\script{1\over 2}}, -z]. Cg2 is the centroid of the N3/C13–C17 ring.

Data collection: CAD-4 Software (Enraf–Nonius, 1985[Enraf-Nonius (1985). CAD-4 Software. Enraf-Nonius, Delft, The Netherlands.]); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995[Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]).

Supporting information


Comment top

The title compound is an important intermediate in the syntheses of medicines. We report herein its crystal structure.

In the molecule of the title compound (Fig 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (C7-C12) and B (N3/C13-C17) are, of course, planar, and they are oriented at a dihedral angle of 3.68 (3)°. So, they are nearly coplanar.

In the crystal structure, intermolecular N-H···O hydrogen bonds (Table 1) link the molecules into chains along the a axis, in which they may be effective in the stabilization of the structure. There also exists a weak C—H···π interaction (Table 1).

Related literature top

For a related structure, see: Sugi et al. (2002). For bond-length data, see: Allen et al. (1987). Cg2 is the centroid of the N3/C13–C17 ring.

Experimental top

The title compound was prepared according to a literature method (Sugi et al., 2002). Crystals suitable for X-ray analysis were obtained by dissolving the title compound (1.5 g) in methanol (25 ml) and evaporating the solvent slowly at room temperature for about 5 d.

Refinement top

H atoms were positioned geometrically, with N-H = 0.86 Å (for NH) and C-H = 0.93 and 0.96 Å for aromatic and methyl H, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C,N), where x = 1.5 for methyl H and x = 1.2 for all other H atoms. The absolute structure could not be determined reliably, and 338 Friedel pairs were averaged before the last cycle of refinement.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme.
[Figure 2] Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.
tert-Butyl N'-[4-(2-pyridyl)benzylidene]hydrazinecarboxylate top
Crystal data top
C17H19N3O2F(000) = 316
Mr = 297.35Dx = 1.259 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 25 reflections
a = 5.3080 (11) Åθ = 9–13°
b = 6.3010 (13) ŵ = 0.08 mm1
c = 23.459 (5) ÅT = 294 K
β = 91.01 (3)°Needle, colorless
V = 784.5 (3) Å30.30 × 0.20 × 0.10 mm
Z = 2
Data collection top
Nonius–Nonius CAD-4
diffractometer
1249 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.028
Graphite monochromatorθmax = 25.3°, θmin = 1.7°
ω/2θ scansh = 06
Absorption correction: ψ scan
(North et al., 1968)
k = 07
Tmin = 0.975, Tmax = 0.992l = 2828
1743 measured reflections3 standard reflections every 120 min
1566 independent reflections intensity decay: 1%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.170H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.1P)2 + 0.33P]
where P = (Fo2 + 2Fc2)/3
1566 reflections(Δ/σ)max < 0.001
199 parametersΔρmax = 0.16 e Å3
1 restraintΔρmin = 0.21 e Å3
Crystal data top
C17H19N3O2V = 784.5 (3) Å3
Mr = 297.35Z = 2
Monoclinic, P21Mo Kα radiation
a = 5.3080 (11) ŵ = 0.08 mm1
b = 6.3010 (13) ÅT = 294 K
c = 23.459 (5) Å0.30 × 0.20 × 0.10 mm
β = 91.01 (3)°
Data collection top
Nonius–Nonius CAD-4
diffractometer
1249 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.028
Tmin = 0.975, Tmax = 0.9923 standard reflections every 120 min
1743 measured reflections intensity decay: 1%
1566 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0511 restraint
wR(F2) = 0.170H-atom parameters constrained
S = 1.00Δρmax = 0.16 e Å3
1566 reflectionsΔρmin = 0.21 e Å3
199 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
xyzUiso*/Ueq
O10.5696 (5)1.5114 (6)0.37089 (14)0.0589 (9)
O20.8570 (6)1.3033 (6)0.32757 (16)0.0688 (10)
N10.4371 (6)1.2553 (6)0.31524 (16)0.0524 (9)
H1A0.28911.30010.32350.063*
N20.4651 (7)1.0839 (6)0.27985 (16)0.0507 (9)
N30.1499 (6)0.2707 (7)0.06762 (16)0.0545 (10)
C10.5928 (11)1.7923 (13)0.4341 (3)0.099 (2)
H1B0.50251.87910.40710.149*
H1C0.69591.88080.45830.149*
H1D0.47511.71550.45690.149*
C20.9263 (10)1.7590 (10)0.3637 (2)0.0684 (14)
H2B0.82541.84370.33810.103*
H2C1.02571.66120.34230.103*
H2D1.03561.84960.38590.103*
C30.9018 (11)1.4977 (13)0.4441 (2)0.0815 (18)
H3A1.00481.40060.42330.122*
H3B0.78541.41950.46690.122*
H3C1.00691.58410.46840.122*
C40.7575 (8)1.6377 (9)0.40286 (19)0.0569 (12)
C50.6416 (8)1.3524 (7)0.3368 (2)0.0506 (10)
C60.2709 (8)1.0167 (8)0.25407 (19)0.0505 (10)
H6A0.11841.08720.25810.061*
C70.2841 (8)0.8282 (8)0.21781 (17)0.0476 (10)
C80.4830 (8)0.6875 (9)0.2220 (2)0.0544 (12)
H8A0.60920.71100.24930.065*
C90.4994 (8)0.5144 (8)0.18695 (19)0.0532 (11)
H9A0.63690.42360.19050.064*
C100.3124 (7)0.4726 (7)0.14596 (16)0.0410 (9)
C110.1129 (8)0.6120 (8)0.1429 (2)0.0567 (12)
H11A0.01450.58910.11590.068*
C120.0966 (8)0.7830 (9)0.17841 (19)0.0566 (12)
H12A0.04410.87060.17590.068*
C130.3321 (7)0.2892 (7)0.10648 (16)0.0412 (9)
C140.5270 (9)0.1443 (8)0.1101 (2)0.0564 (12)
H14A0.65220.15800.13810.068*
C150.5332 (9)0.0208 (9)0.0717 (2)0.0612 (13)
H15A0.66350.11940.07350.073*
C160.3498 (9)0.0394 (8)0.0314 (2)0.0566 (12)
H16A0.35130.15010.00520.068*
C170.1603 (9)0.1099 (9)0.0301 (2)0.0590 (12)
H17A0.03460.09910.00210.071*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0443 (15)0.052 (2)0.081 (2)0.0021 (15)0.0055 (14)0.0195 (18)
O20.0480 (17)0.057 (2)0.102 (2)0.0030 (18)0.0129 (16)0.022 (2)
N10.0446 (18)0.042 (2)0.070 (2)0.0005 (18)0.0065 (15)0.015 (2)
N20.057 (2)0.036 (2)0.059 (2)0.0007 (18)0.0094 (16)0.0084 (18)
N30.0498 (19)0.047 (2)0.066 (2)0.001 (2)0.0026 (16)0.010 (2)
C10.070 (3)0.100 (6)0.129 (5)0.010 (4)0.012 (3)0.068 (5)
C20.072 (3)0.055 (3)0.078 (3)0.008 (3)0.005 (2)0.007 (3)
C30.081 (3)0.096 (5)0.066 (3)0.007 (4)0.020 (2)0.018 (4)
C40.050 (2)0.055 (3)0.065 (3)0.004 (2)0.003 (2)0.011 (3)
C50.049 (2)0.035 (2)0.067 (3)0.003 (2)0.0086 (19)0.008 (2)
C60.046 (2)0.044 (2)0.061 (2)0.001 (2)0.0100 (18)0.006 (2)
C70.048 (2)0.044 (2)0.051 (2)0.003 (2)0.0120 (17)0.001 (2)
C80.052 (2)0.049 (3)0.062 (3)0.010 (2)0.0083 (19)0.011 (2)
C90.049 (2)0.042 (2)0.068 (3)0.010 (2)0.0021 (19)0.004 (2)
C100.0413 (19)0.041 (2)0.0405 (18)0.0016 (19)0.0030 (14)0.0036 (18)
C110.046 (2)0.050 (3)0.074 (3)0.003 (2)0.008 (2)0.010 (3)
C120.042 (2)0.056 (3)0.072 (3)0.014 (2)0.0091 (19)0.010 (3)
C130.0380 (18)0.040 (2)0.0461 (19)0.004 (2)0.0050 (15)0.0028 (19)
C140.059 (3)0.046 (3)0.064 (3)0.009 (2)0.003 (2)0.001 (2)
C150.061 (3)0.049 (3)0.073 (3)0.011 (3)0.009 (2)0.003 (3)
C160.062 (3)0.046 (3)0.062 (3)0.004 (2)0.008 (2)0.013 (2)
C170.061 (3)0.055 (3)0.061 (3)0.008 (3)0.002 (2)0.013 (3)
Geometric parameters (Å, º) top
O1—C51.341 (5)C6—C71.463 (6)
O1—C41.471 (5)C6—H6A0.9300
O2—C51.208 (5)C7—C121.376 (6)
N1—C51.338 (6)C7—C81.381 (6)
N1—N21.372 (5)C8—C91.369 (7)
N1—H1A0.8600C8—H8A0.9300
N2—C61.259 (6)C9—C101.395 (6)
N3—C131.322 (5)C9—H9A0.9300
N3—C171.344 (6)C10—C111.377 (6)
C1—C41.508 (8)C10—C131.486 (6)
C1—H1B0.9600C11—C121.365 (7)
C1—H1C0.9600C11—H11A0.9300
C1—H1D0.9600C12—H12A0.9300
C2—C41.503 (7)C13—C141.381 (6)
C2—H2B0.9600C14—C151.377 (7)
C2—H2C0.9600C14—H14A0.9300
C2—H2D0.9600C15—C161.351 (7)
C3—C41.508 (8)C15—H15A0.9300
C3—H3A0.9600C16—C171.377 (7)
C3—H3B0.9600C16—H16A0.9300
C3—H3C0.9600C17—H17A0.9300
C5—O1—C4120.6 (3)C7—C6—H6A119.8
C5—N1—N2119.6 (3)C12—C7—C8117.2 (4)
C5—N1—H1A120.2C12—C7—C6121.2 (4)
N2—N1—H1A120.2C8—C7—C6121.6 (4)
C6—N2—N1117.3 (4)C9—C8—C7121.7 (4)
C13—N3—C17118.7 (4)C9—C8—H8A119.1
C4—C1—H1B109.5C7—C8—H8A119.1
C4—C1—H1C109.5C8—C9—C10120.8 (4)
H1B—C1—H1C109.5C8—C9—H9A119.6
C4—C1—H1D109.5C10—C9—H9A119.6
H1B—C1—H1D109.5C11—C10—C9116.9 (4)
H1C—C1—H1D109.5C11—C10—C13121.8 (4)
C4—C2—H2B109.5C9—C10—C13121.3 (4)
C4—C2—H2C109.5C12—C11—C10121.9 (4)
H2B—C2—H2C109.5C12—C11—H11A119.0
C4—C2—H2D109.5C10—C11—H11A119.0
H2B—C2—H2D109.5C11—C12—C7121.4 (4)
H2C—C2—H2D109.5C11—C12—H12A119.3
C4—C3—H3A109.5C7—C12—H12A119.3
C4—C3—H3B109.5N3—C13—C14121.5 (4)
H3A—C3—H3B109.5N3—C13—C10116.1 (4)
C4—C3—H3C109.5C14—C13—C10122.5 (3)
H3A—C3—H3C109.5C15—C14—C13119.1 (4)
H3B—C3—H3C109.5C15—C14—H14A120.5
O1—C4—C2111.7 (4)C13—C14—H14A120.5
O1—C4—C3110.1 (5)C16—C15—C14119.9 (5)
C2—C4—C3112.8 (4)C16—C15—H15A120.1
O1—C4—C1101.7 (4)C14—C15—H15A120.1
C2—C4—C1109.0 (5)C15—C16—C17118.3 (5)
C3—C4—C1111.0 (5)C15—C16—H16A120.9
O2—C5—N1125.4 (4)C17—C16—H16A120.9
O2—C5—O1125.4 (4)N3—C17—C16122.6 (4)
N1—C5—O1109.2 (3)N3—C17—H17A118.7
N2—C6—C7120.3 (4)C16—C17—H17A118.7
N2—C6—H6A119.8
C5—N1—N2—C6170.0 (5)C13—C10—C11—C12178.8 (4)
C5—O1—C4—C263.9 (6)C10—C11—C12—C72.3 (7)
C5—O1—C4—C362.3 (5)C8—C7—C12—C113.3 (7)
C5—O1—C4—C1180.0 (5)C6—C7—C12—C11177.3 (4)
N2—N1—C5—O20.7 (7)C17—N3—C13—C141.8 (6)
N2—N1—C5—O1178.7 (3)C17—N3—C13—C10178.8 (4)
C4—O1—C5—O22.8 (7)C11—C10—C13—N31.4 (6)
C4—O1—C5—N1176.6 (4)C9—C10—C13—N3176.9 (4)
N1—N2—C6—C7177.0 (4)C11—C10—C13—C14178.0 (4)
N2—C6—C7—C12163.2 (5)C9—C10—C13—C143.7 (6)
N2—C6—C7—C817.4 (7)N3—C13—C14—C151.1 (7)
C12—C7—C8—C92.5 (7)C10—C13—C14—C15179.6 (4)
C6—C7—C8—C9178.1 (4)C13—C14—C15—C160.2 (7)
C7—C8—C9—C100.8 (7)C14—C15—C16—C170.1 (7)
C8—C9—C10—C110.3 (7)C13—N3—C17—C161.7 (7)
C8—C9—C10—C13178.0 (4)C15—C16—C17—N30.8 (7)
C9—C10—C11—C120.4 (7)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.862.303.113 (5)158
C16—H16A···Cg2ii0.932.803.588 (4)144
Symmetry codes: (i) x1, y, z; (ii) x+1, y1/2, z.

Experimental details

Crystal data
Chemical formulaC17H19N3O2
Mr297.35
Crystal system, space groupMonoclinic, P21
Temperature (K)294
a, b, c (Å)5.3080 (11), 6.3010 (13), 23.459 (5)
β (°) 91.01 (3)
V3)784.5 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.30 × 0.20 × 0.10
Data collection
DiffractometerNonius–Nonius CAD-4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.975, 0.992
No. of measured, independent and
observed [I > 2σ(I)] reflections
1743, 1566, 1249
Rint0.028
(sin θ/λ)max1)0.601
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.051, 0.170, 1.00
No. of reflections1566
No. of parameters199
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.16, 0.21

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.862.303.113 (5)158
C16—H16A···Cg2ii0.932.803.588 (4)144
Symmetry codes: (i) x1, y, z; (ii) x+1, y1/2, z.
 

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

References

First citationAllen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.  CrossRef Web of Science Google Scholar
First citationEnraf–Nonius (1985). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands.  Google Scholar
First citationHarms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.  Google Scholar
First citationNorth, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.  CrossRef IUCr Journals Web of Science Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSugi, K., Matsui, K., Shintaku, T. & Itaya, N. (2002). US Patent No. 6 376 678.  Google Scholar

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ISSN: 2056-9890
Volume 65| Part 5| May 2009| Page o1127
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