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

Abstract

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,

• a = 5.3080 (11) Å

• b = 6.3010 (13) Å

• c = 23.459 (5) Å

• β = 91.01 (3)°

• V = 784.5 (3) ų

• 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[F ² > 2σ(F ²)] = 0.051

• wR(F ²) = 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

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 ▶).

Supplementary Material

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

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) ; (ii) . Cg2 is the centroid of the N3/C13–C17 ring.

supplementary crystallographic information

Comment

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).

Experimental

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

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 U_iso(H) = xU_eq(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.

Figures

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.

Crystal data

C17H19N3O2	F(000) = 316
Mr = 297.35	Dx = 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

Nonius–Nonius CAD-4 diffractometer	1249 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.028
graphite	θmax = 25.3°, θmin = 1.7°
ω/2θ scans	h = 0→6
Absorption correction: ψ scan (North et al., 1968)	k = 0→7
Tmin = 0.975, Tmax = 0.992	l = −28→28
1743 measured reflections	3 standard reflections every 120 min
1566 independent reflections	intensity decay: 1%

Refinement

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(Fo2) + (0.1P)2 + 0.33P] where P = (Fo2 + 2Fc2)/3
1566 reflections	(Δ/σ)max < 0.001
199 parameters	Δρmax = 0.16 e Å−3
1 restraint	Δρmin = −0.21 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.