Methyl N-(3-cyano-picolino-yl)-l-tryptophanate.

In the title compound, C19H16N4O3, the stereocenter has an l configuration; l-tryptophan methyl ester hydro-chloride being used as a starting material. The indole ring system and the pyridine ring are inclined to one another by 13.55 (14)°. In the crystal, adjacent mol-ecules are linked via N-H⋯O hydrogen bonds, forming chains propagating along the c-axis direction.

Related literature

Cyano-substituted compounds, like the title compound, are useful as inter­mediates in the synthesis of N-hy­droxy­benzamidines, see: Peterlin-Mašič & Kikelj (2001 ▶). For the synthesis of the title compound, see: Devillers et al. (2002 ▶). For the biological activity of 1,2,4-oxa­diazole derivatives, see: Kundu et al. (2012 ▶); Sakamoto et al. (2007 ▶); Tyrkov & Sukhenko (2004 ▶).

Experimental

Crystal data

C19H16N4O3

M = 348.36

Monoclinic,

a = 7.473 (2) Å

b = 11.977 (4) Å

c = 9.661 (3) Å

β = 91.01 (2)°

V = 864.6 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 293 K

0.34 × 0.29 × 0.21 mm

Data collection

Agilent Xcalibur Sapphire3 diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.753, T max = 1.000

9857 measured reflections

4832 independent reflections

2596 reflections with I > 2σ(I)

R int = 0.047

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.133

S = 0.93

4832 reflections

236 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.20 e Å−3

Δρmin = −0.14 e Å−3

Absolute structure: Flack parameter determined using 855 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons et al., 2013 ▶)

Absolute structure parameter: −0.001 (3)

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S160053681303153X/su2666sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681303153X/su2666Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S160053681303153X/su2666Isup3.cdx

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S160053681303153X/su2666Isup4.cml

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

C19H16N4O3	F(000) = 364
Mr = 348.36	Dx = 1.338 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: P 2yb	Cell parameters from 1601 reflections
a = 7.473 (2) Å	θ = 3.2–32.1°
b = 11.977 (4) Å	µ = 0.09 mm−1
c = 9.661 (3) Å	T = 293 K
β = 91.01 (2)°	Block, colourless
V = 864.6 (4) Å3	0.34 × 0.29 × 0.21 mm
Z = 2

Agilent Xcalibur Sapphire3 diffractometer	4832 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2596 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
Detector resolution: 16.1827 pixels mm-1	θmax = 30.0°, θmin = 3.2°
ω scans	h = −10→10
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −16→16
Tmin = 0.753, Tmax = 1.000	l = −13→13
9857 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.051	H-atom parameters constrained
wR(F2) = 0.133	w = 1/[σ2(Fo2) + (0.0481P)2] where P = (Fo2 + 2Fc2)/3
S = 0.93	(Δ/σ)max = 0.002
4832 reflections	Δρmax = 0.20 e Å−3
236 parameters	Δρmin = −0.14 e Å−3
1 restraint	Absolute structure: Flack parameter determined using 855 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
64 constraints	Absolute structure parameter: −0.001 (3)
Primary atom site location: structure-invariant direct methods

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.

	x	y	z	Uiso*/Ueq
O1	0.3366 (4)	0.9180 (2)	0.4295 (2)	0.0820 (8)
O2	−0.0128 (4)	1.0476 (3)	0.1272 (4)	0.0933 (9)
O3	0.1275 (3)	1.2086 (2)	0.1722 (3)	0.0744 (8)
N1	0.2235 (4)	0.7036 (2)	0.1931 (3)	0.0593 (7)
N2	0.4469 (6)	0.7467 (3)	0.6623 (4)	0.0918 (12)
N3	0.2808 (4)	0.9245 (2)	0.2012 (3)	0.0588 (7)
H3	0.2553	0.8865	0.1280	0.071*
N4	0.3014 (4)	0.9839 (3)	−0.2741 (3)	0.0649 (8)
H4	0.2870	0.9343	−0.3376	0.078*
C1	0.2040 (5)	0.5917 (3)	0.1847 (4)	0.0733 (11)
H1	0.1587	0.5615	0.1026	0.088*
C2	0.2477 (5)	0.5201 (3)	0.2913 (5)	0.0779 (12)
H2	0.2344	0.4434	0.2802	0.094*
C3	0.3103 (5)	0.5626 (4)	0.4126 (4)	0.0710 (10)
H3A	0.3404	0.5156	0.4860	0.085*
C4	0.3291 (4)	0.6783 (3)	0.4258 (3)	0.0565 (9)
C5	0.3958 (5)	0.7217 (3)	0.5548 (4)	0.0692 (10)
C6	0.2835 (4)	0.7458 (3)	0.3133 (3)	0.0540 (8)
C7	0.3022 (5)	0.8708 (3)	0.3205 (3)	0.0544 (8)
C8	0.2987 (4)	1.0447 (3)	0.1894 (3)	0.0534 (8)
H8	0.3446	1.0731	0.2783	0.064*
C9	0.1191 (5)	1.0983 (3)	0.1613 (3)	0.0576 (9)
C10	−0.0323 (6)	1.2707 (4)	0.1397 (6)	0.0924 (15)
H10A	−0.0786	1.2479	0.0508	0.139*
H10B	−0.0049	1.3490	0.1377	0.139*
H10C	−0.1201	1.2567	0.2089	0.139*
C11	0.4336 (5)	1.0773 (3)	0.0766 (3)	0.0611 (9)
H11A	0.4658	1.1551	0.0895	0.073*
H11B	0.5414	1.0333	0.0906	0.073*
C12	0.3694 (4)	1.0617 (3)	−0.0696 (3)	0.0555 (8)
C13	0.3676 (5)	0.9647 (3)	−0.1435 (3)	0.0628 (9)
H13	0.4058	0.8957	−0.1100	0.075*
C14	0.2617 (5)	1.0954 (3)	−0.2872 (3)	0.0558 (9)
C15	0.3002 (4)	1.1473 (3)	−0.1602 (3)	0.0521 (8)
C16	0.2762 (5)	1.2624 (3)	−0.1484 (4)	0.0651 (10)
H16	0.3016	1.2987	−0.0653	0.078*
C17	0.2146 (6)	1.3211 (3)	−0.2616 (5)	0.0776 (12)
H17	0.1990	1.3979	−0.2546	0.093*
C18	0.1748 (5)	1.2681 (4)	−0.3863 (5)	0.0800 (12)
H18	0.1324	1.3099	−0.4610	0.096*
C19	0.1972 (5)	1.1552 (4)	−0.4010 (3)	0.0680 (10)
H19	0.1701	1.1197	−0.4843	0.082*

	U11	U22	U33	U12	U13	U23
O1	0.138 (2)	0.0690 (16)	0.0390 (13)	0.0108 (16)	−0.0117 (14)	−0.0018 (12)
O2	0.0744 (18)	0.0795 (19)	0.125 (3)	−0.0159 (16)	−0.0208 (17)	0.0269 (18)
O3	0.0749 (18)	0.0649 (16)	0.0831 (18)	0.0101 (13)	−0.0101 (13)	−0.0138 (13)
N1	0.0617 (18)	0.0628 (18)	0.0533 (18)	0.0036 (14)	−0.0028 (14)	−0.0073 (14)
N2	0.136 (3)	0.090 (2)	0.0489 (19)	0.045 (2)	−0.0133 (19)	0.0005 (18)
N3	0.0815 (19)	0.0571 (17)	0.0374 (15)	−0.0026 (15)	−0.0072 (13)	−0.0031 (12)
N4	0.088 (2)	0.0628 (18)	0.0445 (17)	−0.0164 (16)	0.0091 (14)	−0.0101 (14)
C1	0.074 (3)	0.071 (3)	0.074 (3)	−0.003 (2)	−0.008 (2)	−0.014 (2)
C2	0.075 (3)	0.060 (2)	0.099 (4)	−0.0003 (19)	−0.003 (2)	0.002 (2)
C3	0.072 (2)	0.067 (2)	0.074 (3)	0.010 (2)	−0.004 (2)	0.012 (2)
C4	0.0557 (19)	0.063 (2)	0.051 (2)	0.0115 (15)	0.0030 (15)	0.0044 (16)
C5	0.087 (3)	0.066 (2)	0.054 (2)	0.026 (2)	0.0042 (19)	0.0076 (19)
C6	0.0508 (19)	0.064 (2)	0.0478 (19)	0.0073 (16)	0.0032 (14)	−0.0031 (16)
C7	0.063 (2)	0.064 (2)	0.0362 (18)	0.0110 (16)	−0.0013 (15)	0.0013 (15)
C8	0.069 (2)	0.0526 (19)	0.0380 (16)	−0.0012 (16)	−0.0088 (14)	−0.0014 (15)
C9	0.061 (2)	0.065 (2)	0.0465 (18)	−0.0050 (17)	0.0004 (15)	0.0072 (16)
C10	0.079 (3)	0.084 (3)	0.114 (4)	0.028 (2)	−0.002 (2)	−0.002 (3)
C11	0.064 (2)	0.066 (2)	0.0531 (19)	−0.0022 (18)	−0.0010 (15)	0.0000 (17)
C12	0.0613 (19)	0.0580 (19)	0.0474 (17)	−0.0095 (17)	0.0079 (14)	−0.0039 (16)
C13	0.079 (2)	0.058 (2)	0.051 (2)	−0.0090 (18)	0.0086 (17)	−0.0012 (17)
C14	0.060 (2)	0.061 (2)	0.0473 (18)	−0.0087 (16)	0.0130 (15)	0.0006 (16)
C15	0.0559 (18)	0.0554 (19)	0.0454 (17)	−0.0082 (16)	0.0117 (14)	−0.0022 (16)
C16	0.073 (2)	0.061 (2)	0.062 (2)	−0.0071 (18)	0.0122 (18)	−0.0032 (19)
C17	0.080 (3)	0.067 (2)	0.087 (3)	0.003 (2)	0.021 (2)	0.005 (2)
C18	0.080 (3)	0.092 (3)	0.069 (3)	0.009 (2)	0.015 (2)	0.018 (2)
C19	0.071 (2)	0.088 (3)	0.0456 (19)	−0.007 (2)	0.0086 (16)	0.0029 (19)

O1—C7	1.219 (4)	C8—H8	0.9800
O2—C9	1.199 (4)	C8—C9	1.507 (5)
O3—C9	1.327 (4)	C8—C11	1.547 (4)
O3—C10	1.437 (5)	C10—H10A	0.9600
N1—C1	1.351 (5)	C10—H10B	0.9600
N1—C6	1.337 (4)	C10—H10C	0.9600
N2—C5	1.141 (5)	C11—H11A	0.9700
N3—H3	0.8600	C11—H11B	0.9700
N3—C7	1.327 (4)	C11—C12	1.495 (5)
N3—C8	1.451 (4)	C12—C13	1.364 (5)
N4—H4	0.8600	C12—C15	1.438 (5)
N4—C13	1.366 (4)	C13—H13	0.9300
N4—C14	1.374 (5)	C14—C15	1.401 (4)
C1—H1	0.9300	C14—C19	1.391 (5)
C1—C2	1.375 (6)	C15—C16	1.394 (5)
C2—H2	0.9300	C16—H16	0.9300
C2—C3	1.354 (6)	C16—C17	1.372 (6)
C3—H3A	0.9300	C17—H17	0.9300
C3—C4	1.399 (6)	C17—C18	1.389 (6)
C4—C5	1.431 (5)	C18—H18	0.9300
C4—C6	1.392 (5)	C18—C19	1.370 (6)
C6—C7	1.505 (5)	C19—H19	0.9300
C9—O3—C10	117.4 (3)	O3—C10—H10A	109.5
C6—N1—C1	117.5 (3)	O3—C10—H10B	109.5
C7—N3—H3	118.7	O3—C10—H10C	109.5
C7—N3—C8	122.7 (3)	H10A—C10—H10B	109.5
C8—N3—H3	118.7	H10A—C10—H10C	109.5
C13—N4—H4	125.6	H10B—C10—H10C	109.5
C13—N4—C14	108.9 (3)	C8—C11—H11A	108.4
C14—N4—H4	125.6	C8—C11—H11B	108.4
N1—C1—H1	118.3	H11A—C11—H11B	107.4
N1—C1—C2	123.4 (4)	C12—C11—C8	115.6 (3)
C2—C1—H1	118.3	C12—C11—H11A	108.4
C1—C2—H2	120.4	C12—C11—H11B	108.4
C3—C2—C1	119.2 (4)	C13—C12—C11	126.9 (3)
C3—C2—H2	120.4	C13—C12—C15	106.8 (3)
C2—C3—H3A	120.5	C15—C12—C11	126.3 (3)
C2—C3—C4	119.0 (4)	N4—C13—H13	125.1
C4—C3—H3A	120.5	C12—C13—N4	109.9 (3)
C3—C4—C5	118.1 (3)	C12—C13—H13	125.1
C6—C4—C3	118.7 (3)	N4—C14—C15	108.0 (3)
C6—C4—C5	123.1 (3)	N4—C14—C19	130.1 (3)
N2—C5—C4	173.8 (4)	C19—C14—C15	121.8 (3)
N1—C6—C4	122.2 (3)	C14—C15—C12	106.4 (3)
N1—C6—C7	116.5 (3)	C16—C15—C12	134.5 (3)
C4—C6—C7	121.3 (3)	C16—C15—C14	119.0 (3)
O1—C7—N3	123.1 (3)	C15—C16—H16	120.5
O1—C7—C6	121.3 (3)	C17—C16—C15	118.9 (4)
N3—C7—C6	115.6 (3)	C17—C16—H16	120.5
N3—C8—H8	107.9	C16—C17—H17	119.3
N3—C8—C9	110.7 (3)	C16—C17—C18	121.3 (4)
N3—C8—C11	111.6 (3)	C18—C17—H17	119.3
C9—C8—H8	107.9	C17—C18—H18	119.5
C9—C8—C11	110.8 (3)	C19—C18—C17	121.1 (4)
C11—C8—H8	107.9	C19—C18—H18	119.5
O2—C9—O3	124.3 (3)	C14—C19—H19	121.1
O2—C9—C8	124.0 (3)	C18—C19—C14	117.8 (4)
O3—C9—C8	111.6 (3)	C18—C19—H19	121.1
N1—C1—C2—C3	1.4 (6)	C8—C11—C12—C13	−81.6 (4)
N1—C6—C7—O1	171.7 (3)	C8—C11—C12—C15	99.6 (4)
N1—C6—C7—N3	−8.9 (4)	C9—C8—C11—C12	−50.2 (4)
N3—C8—C9—O2	−13.3 (5)	C10—O3—C9—O2	−0.6 (6)
N3—C8—C9—O3	169.9 (3)	C10—O3—C9—C8	176.3 (3)
N3—C8—C11—C12	73.6 (4)	C11—C8—C9—O2	111.1 (4)
N4—C14—C15—C12	1.3 (3)	C11—C8—C9—O3	−65.8 (4)
N4—C14—C15—C16	178.0 (3)	C11—C12—C13—N4	−179.2 (3)
N4—C14—C19—C18	−177.9 (3)	C11—C12—C15—C14	178.4 (3)
C1—N1—C6—C4	1.5 (5)	C11—C12—C15—C16	2.4 (6)
C1—N1—C6—C7	−179.4 (3)	C12—C15—C16—C17	176.0 (3)
C1—C2—C3—C4	−0.1 (6)	C13—N4—C14—C15	−1.4 (4)
C2—C3—C4—C5	−179.9 (3)	C13—N4—C14—C19	177.7 (3)
C2—C3—C4—C6	−0.3 (5)	C13—C12—C15—C14	−0.7 (3)
C3—C4—C6—N1	−0.4 (5)	C13—C12—C15—C16	−176.6 (4)
C3—C4—C6—C7	−179.4 (3)	C14—N4—C13—C12	1.0 (4)
C4—C6—C7—O1	−9.2 (5)	C14—C15—C16—C17	0.4 (5)
C4—C6—C7—N3	170.1 (3)	C15—C12—C13—N4	−0.2 (4)
C5—C4—C6—N1	179.2 (3)	C15—C14—C19—C18	1.2 (5)
C5—C4—C6—C7	0.1 (5)	C15—C16—C17—C18	0.4 (6)
C6—N1—C1—C2	−2.0 (6)	C16—C17—C18—C19	−0.5 (6)
C7—N3—C8—C9	−109.7 (4)	C17—C18—C19—C14	−0.3 (5)
C7—N3—C8—C11	126.5 (3)	C19—C14—C15—C12	−178.0 (3)
C8—N3—C7—O1	0.8 (6)	C19—C14—C15—C16	−1.2 (5)
C8—N3—C7—C6	−178.5 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···O1i	0.86	2.29	2.987 (3)	138

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4⋯O1i	0.86	2.29	2.987 (3)	138

Symmetry code: (i) .