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

Feng, Q.; Tang, Q.; Xu, H.; Yao, C.

doi:10.1107/S1600536809012835

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o1127

doi:10.1107/S1600536809012835

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

Qi Feng,^a Qiong Tang,^a Hao Xu ^a and Cheng Yao ^a ^*

^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 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₇H₁₉N₃O₂
M_r = 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 ) T_min = 0.975, T_max = 0.992
1743 measured reflections
1566 independent reflections
1249 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.86	2.30	3.113 (5)	158
C16—H16A⋯Cg2ⁱⁱ	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 ); cell refinement: CAD-4 Software; 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).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809012835/hk2661sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809012835/hk2661Isup2.hkl

checkCIF report

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.

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

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme.
	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

C₁₇H₁₉N₃O₂	F(000) = 316
M_r = 297.35	D_x = 1.259 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 25 reflections
a = 5.3080 (11) Å	θ = 9–13°
b = 6.3010 (13) Å	µ = 0.08 mm⁻¹
c = 23.459 (5) Å	T = 294 K
β = 91.01 (3)°	Needle, colorless
V = 784.5 (3) Å³	0.30 × 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 tube	R_int = 0.028
Graphite monochromator	θ_max = 25.3°, θ_min = 1.7°
ω/2θ scans	h = 0→6
Absorption correction: ψ scan (North et al., 1968)	k = 0→7
T_min = 0.975, T_max = 0.992	l = −28→28
1743 measured reflections	3 standard reflections every 120 min
1566 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.170	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.1P)² + 0.33P] where P = (F_o² + 2F_c²)/3
1566 reflections	(Δ/σ)_max < 0.001
199 parameters	Δρ_max = 0.16 e Å⁻³
1 restraint	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₇H₁₉N₃O₂	V = 784.5 (3) Å³
M_r = 297.35	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 5.3080 (11) Å	µ = 0.08 mm⁻¹
b = 6.3010 (13) Å	T = 294 K
c = 23.459 (5) Å	0.30 × 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)	R_int = 0.028
T_min = 0.975, T_max = 0.992	3 standard reflections every 120 min
1743 measured reflections	intensity decay: 1%
1566 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	1 restraint
wR(F²) = 0.170	H-atom parameters constrained
S = 1.00	Δρ_max = 0.16 e Å⁻³
1566 reflections	Δρ_min = −0.21 e Å⁻³
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

	x	y	z	U_iso*/U_eq
O1	0.5696 (5)	1.5114 (6)	0.37089 (14)	0.0589 (9)
O2	0.8570 (6)	1.3033 (6)	0.32757 (16)	0.0688 (10)
N1	0.4371 (6)	1.2553 (6)	0.31524 (16)	0.0524 (9)
H1A	0.2891	1.3001	0.3235	0.063*
N2	0.4651 (7)	1.0839 (6)	0.27985 (16)	0.0507 (9)
N3	0.1499 (6)	0.2707 (7)	0.06762 (16)	0.0545 (10)
C1	0.5928 (11)	1.7923 (13)	0.4341 (3)	0.099 (2)
H1B	0.5025	1.8791	0.4071	0.149*
H1C	0.6959	1.8808	0.4583	0.149*
H1D	0.4751	1.7155	0.4569	0.149*
C2	0.9263 (10)	1.7590 (10)	0.3637 (2)	0.0684 (14)
H2B	0.8254	1.8437	0.3381	0.103*
H2C	1.0257	1.6612	0.3423	0.103*
H2D	1.0356	1.8496	0.3859	0.103*
C3	0.9018 (11)	1.4977 (13)	0.4441 (2)	0.0815 (18)
H3A	1.0048	1.4006	0.4233	0.122*
H3B	0.7854	1.4195	0.4669	0.122*
H3C	1.0069	1.5841	0.4684	0.122*
C4	0.7575 (8)	1.6377 (9)	0.40286 (19)	0.0569 (12)
C5	0.6416 (8)	1.3524 (7)	0.3368 (2)	0.0506 (10)
C6	0.2709 (8)	1.0167 (8)	0.25407 (19)	0.0505 (10)
H6A	0.1184	1.0872	0.2581	0.061*
C7	0.2841 (8)	0.8282 (8)	0.21781 (17)	0.0476 (10)
C8	0.4830 (8)	0.6875 (9)	0.2220 (2)	0.0544 (12)
H8A	0.6092	0.7110	0.2493	0.065*
C9	0.4994 (8)	0.5144 (8)	0.18695 (19)	0.0532 (11)
H9A	0.6369	0.4236	0.1905	0.064*
C10	0.3124 (7)	0.4726 (7)	0.14596 (16)	0.0410 (9)
C11	0.1129 (8)	0.6120 (8)	0.1429 (2)	0.0567 (12)
H11A	−0.0145	0.5891	0.1159	0.068*
C12	0.0966 (8)	0.7830 (9)	0.17841 (19)	0.0566 (12)
H12A	−0.0441	0.8706	0.1759	0.068*
C13	0.3321 (7)	0.2892 (7)	0.10648 (16)	0.0412 (9)
C14	0.5270 (9)	0.1443 (8)	0.1101 (2)	0.0564 (12)
H14A	0.6522	0.1580	0.1381	0.068*
C15	0.5332 (9)	−0.0208 (9)	0.0717 (2)	0.0612 (13)
H15A	0.6635	−0.1194	0.0735	0.073*
C16	0.3498 (9)	−0.0394 (8)	0.0314 (2)	0.0566 (12)
H16A	0.3513	−0.1501	0.0052	0.068*
C17	0.1603 (9)	0.1099 (9)	0.0301 (2)	0.0590 (12)
H17A	0.0346	0.0991	0.0021	0.071*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0443 (15)	0.052 (2)	0.081 (2)	−0.0021 (15)	0.0055 (14)	−0.0195 (18)
O2	0.0480 (17)	0.057 (2)	0.102 (2)	0.0030 (18)	0.0129 (16)	−0.022 (2)
N1	0.0446 (18)	0.042 (2)	0.070 (2)	0.0005 (18)	0.0065 (15)	−0.015 (2)
N2	0.057 (2)	0.036 (2)	0.059 (2)	0.0007 (18)	0.0094 (16)	−0.0084 (18)
N3	0.0498 (19)	0.047 (2)	0.066 (2)	−0.001 (2)	−0.0026 (16)	−0.010 (2)
C1	0.070 (3)	0.100 (6)	0.129 (5)	−0.010 (4)	0.012 (3)	−0.068 (5)
C2	0.072 (3)	0.055 (3)	0.078 (3)	−0.008 (3)	−0.005 (2)	0.007 (3)
C3	0.081 (3)	0.096 (5)	0.066 (3)	−0.007 (4)	−0.020 (2)	0.018 (4)
C4	0.050 (2)	0.055 (3)	0.065 (3)	−0.004 (2)	0.003 (2)	−0.011 (3)
C5	0.049 (2)	0.035 (2)	0.067 (3)	0.003 (2)	0.0086 (19)	−0.008 (2)
C6	0.046 (2)	0.044 (2)	0.061 (2)	−0.001 (2)	0.0100 (18)	−0.006 (2)
C7	0.048 (2)	0.044 (2)	0.051 (2)	−0.003 (2)	0.0120 (17)	−0.001 (2)
C8	0.052 (2)	0.049 (3)	0.062 (3)	0.010 (2)	−0.0083 (19)	−0.011 (2)
C9	0.049 (2)	0.042 (2)	0.068 (3)	0.010 (2)	−0.0021 (19)	−0.004 (2)
C10	0.0413 (19)	0.041 (2)	0.0405 (18)	−0.0016 (19)	0.0030 (14)	0.0036 (18)
C11	0.046 (2)	0.050 (3)	0.074 (3)	0.003 (2)	−0.008 (2)	−0.010 (3)
C12	0.042 (2)	0.056 (3)	0.072 (3)	0.014 (2)	−0.0091 (19)	−0.010 (3)
C13	0.0380 (18)	0.040 (2)	0.0461 (19)	−0.004 (2)	0.0050 (15)	−0.0028 (19)
C14	0.059 (3)	0.046 (3)	0.064 (3)	0.009 (2)	0.003 (2)	−0.001 (2)
C15	0.061 (3)	0.049 (3)	0.073 (3)	0.011 (3)	0.009 (2)	−0.003 (3)
C16	0.062 (3)	0.046 (3)	0.062 (3)	−0.004 (2)	0.008 (2)	−0.013 (2)
C17	0.061 (3)	0.055 (3)	0.061 (3)	−0.008 (3)	−0.002 (2)	−0.013 (3)

Geometric parameters (Å, º) top

O1—C5	1.341 (5)	C6—C7	1.463 (6)
O1—C4	1.471 (5)	C6—H6A	0.9300
O2—C5	1.208 (5)	C7—C12	1.376 (6)
N1—C5	1.338 (6)	C7—C8	1.381 (6)
N1—N2	1.372 (5)	C8—C9	1.369 (7)
N1—H1A	0.8600	C8—H8A	0.9300
N2—C6	1.259 (6)	C9—C10	1.395 (6)
N3—C13	1.322 (5)	C9—H9A	0.9300
N3—C17	1.344 (6)	C10—C11	1.377 (6)
C1—C4	1.508 (8)	C10—C13	1.486 (6)
C1—H1B	0.9600	C11—C12	1.365 (7)
C1—H1C	0.9600	C11—H11A	0.9300
C1—H1D	0.9600	C12—H12A	0.9300
C2—C4	1.503 (7)	C13—C14	1.381 (6)
C2—H2B	0.9600	C14—C15	1.377 (7)
C2—H2C	0.9600	C14—H14A	0.9300
C2—H2D	0.9600	C15—C16	1.351 (7)
C3—C4	1.508 (8)	C15—H15A	0.9300
C3—H3A	0.9600	C16—C17	1.377 (7)
C3—H3B	0.9600	C16—H16A	0.9300
C3—H3C	0.9600	C17—H17A	0.9300

C5—O1—C4	120.6 (3)	C7—C6—H6A	119.8
C5—N1—N2	119.6 (3)	C12—C7—C8	117.2 (4)
C5—N1—H1A	120.2	C12—C7—C6	121.2 (4)
N2—N1—H1A	120.2	C8—C7—C6	121.6 (4)
C6—N2—N1	117.3 (4)	C9—C8—C7	121.7 (4)
C13—N3—C17	118.7 (4)	C9—C8—H8A	119.1
C4—C1—H1B	109.5	C7—C8—H8A	119.1
C4—C1—H1C	109.5	C8—C9—C10	120.8 (4)
H1B—C1—H1C	109.5	C8—C9—H9A	119.6
C4—C1—H1D	109.5	C10—C9—H9A	119.6
H1B—C1—H1D	109.5	C11—C10—C9	116.9 (4)
H1C—C1—H1D	109.5	C11—C10—C13	121.8 (4)
C4—C2—H2B	109.5	C9—C10—C13	121.3 (4)
C4—C2—H2C	109.5	C12—C11—C10	121.9 (4)
H2B—C2—H2C	109.5	C12—C11—H11A	119.0
C4—C2—H2D	109.5	C10—C11—H11A	119.0
H2B—C2—H2D	109.5	C11—C12—C7	121.4 (4)
H2C—C2—H2D	109.5	C11—C12—H12A	119.3
C4—C3—H3A	109.5	C7—C12—H12A	119.3
C4—C3—H3B	109.5	N3—C13—C14	121.5 (4)
H3A—C3—H3B	109.5	N3—C13—C10	116.1 (4)
C4—C3—H3C	109.5	C14—C13—C10	122.5 (3)
H3A—C3—H3C	109.5	C15—C14—C13	119.1 (4)
H3B—C3—H3C	109.5	C15—C14—H14A	120.5
O1—C4—C2	111.7 (4)	C13—C14—H14A	120.5
O1—C4—C3	110.1 (5)	C16—C15—C14	119.9 (5)
C2—C4—C3	112.8 (4)	C16—C15—H15A	120.1
O1—C4—C1	101.7 (4)	C14—C15—H15A	120.1
C2—C4—C1	109.0 (5)	C15—C16—C17	118.3 (5)
C3—C4—C1	111.0 (5)	C15—C16—H16A	120.9
O2—C5—N1	125.4 (4)	C17—C16—H16A	120.9
O2—C5—O1	125.4 (4)	N3—C17—C16	122.6 (4)
N1—C5—O1	109.2 (3)	N3—C17—H17A	118.7
N2—C6—C7	120.3 (4)	C16—C17—H17A	118.7
N2—C6—H6A	119.8

C5—N1—N2—C6	−170.0 (5)	C13—C10—C11—C12	−178.8 (4)
C5—O1—C4—C2	63.9 (6)	C10—C11—C12—C7	2.3 (7)
C5—O1—C4—C3	−62.3 (5)	C8—C7—C12—C11	−3.3 (7)
C5—O1—C4—C1	−180.0 (5)	C6—C7—C12—C11	177.3 (4)
N2—N1—C5—O2	0.7 (7)	C17—N3—C13—C14	−1.8 (6)
N2—N1—C5—O1	−178.7 (3)	C17—N3—C13—C10	178.8 (4)
C4—O1—C5—O2	−2.8 (7)	C11—C10—C13—N3	1.4 (6)
C4—O1—C5—N1	176.6 (4)	C9—C10—C13—N3	−176.9 (4)
N1—N2—C6—C7	−177.0 (4)	C11—C10—C13—C14	−178.0 (4)
N2—C6—C7—C12	−163.2 (5)	C9—C10—C13—C14	3.7 (6)
N2—C6—C7—C8	17.4 (7)	N3—C13—C14—C15	1.1 (7)
C12—C7—C8—C9	2.5 (7)	C10—C13—C14—C15	−179.6 (4)
C6—C7—C8—C9	−178.1 (4)	C13—C14—C15—C16	−0.2 (7)
C7—C8—C9—C10	−0.8 (7)	C14—C15—C16—C17	0.1 (7)
C8—C9—C10—C11	−0.3 (7)	C13—N3—C17—C16	1.7 (7)
C8—C9—C10—C13	178.0 (4)	C15—C16—C17—N3	−0.8 (7)
C9—C10—C11—C12	−0.4 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.86	2.30	3.113 (5)	158
C16—H16A···Cg2ⁱⁱ	0.93	2.80	3.588 (4)	144

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

Experimental details

Crystal data
Chemical formula	C₁₇H₁₉N₃O₂
M_r	297.35
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	294
a, b, c (Å)	5.3080 (11), 6.3010 (13), 23.459 (5)
β (°)	91.01 (3)
V (Å³)	784.5 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Nonius–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.975, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	1743, 1566, 1249
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.170, 1.00
No. of reflections	1566
No. of parameters	199
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.86	2.30	3.113 (5)	158
C16—H16A···Cg2ⁱⁱ	0.93	2.80	3.588 (4)	144

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

Acknowledgements

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

References

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