Methyl 6-amino-5-cyano-4-(4-fluoro­phen­yl)-2-methyl­pyridine-3-carboxyl­ate

In the mol­ecule of the title compound, C₁₅H₁₂FN₃O₂, the benzene and pyridine rings are oriented at a dihedral angle of 54.91 (2)°. In the crystal structure, there are inter­molecular N—H...N hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.065
• wR factor = 0.168
• Data-to-parameter ratio = 12.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         42 Perc.
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.03 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.95 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         O1
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          6
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C2     -   C6     ...       1.42 Ang.
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C15

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Pyridine and its derivatives belong to a special class of compounds not only because of their interesting chemical and physical properties but also due to their immense utility in pharmaceutical industry (Temple et al., 1992). They have been used for enrichment of cereals (Badgett & Woodward, 1947). Some polyfunctional pyridines are used as nonlinear optical (Wang et al., 2000) and electrical materials (Kanbara et al., 1992). We have reported the synthesis of polyfunctional pyridine derivatives (Tu et al., 2006), previously, and report herein the crystal structure of the title compound, (I).

In the molecule of (I) (Fig. 1), the bond lengths and angles are within normal ranges (Allen et al., 1987). Rings A (N1/C1—C5) and B (C7—C12) are, of course, planar and they are oriented at a dihedral angle of 54.91 (2)°.

In the crystal structure, intermolecular N—H···N hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they seem to be effective in the stabilization of the structure.

Related literature

For related literature, see: Temple et al. (1992); Badgett & Woodward (1947); Wang et al. (2000); Kanbara et al. (1992); Tu et al. (2006). For bond- length data, see: Allen et al. (1987).

S2. Experimental

The title compound, (I), was prepared by the reaction of 4-fluorobenzaldehyde (124 mg, 1 mmol), methyl 3-aminobut-2-enoate (115 mg, 1 mmol) with malononitrile (66 mg, 1 mmol) in the solvent of ethylene glycol (1.0 ml) and acetic acid (0.5 ml) at 393 K under microwave irradiation (maximum power 200 W, initial power 100 W) for 6 min (yield; 254 mg, 89%, m.p. 552–554 K). Single crystals suitable for X-ray analysis were obtained from an ethanol solution (95%) by slow evaporation.

S3. Refinement

H1 and H2 (for NH₂) were located in difference syntheses and refined isotropically [N—H = 0.90 (4) and 0.86 (5) Å, U_iso(H) = 0.038 (14) and 0.076 (19) Ų]. The remaining H atoms were positioned geometrically, with 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), where x = 1.2 for aromatic H, and x = 1.5 for methyl H atoms.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL (Bruker, 1999).

Figures

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A packing diagram for (I). Hydrogen bonds are shown as dashed lines.

Methyl 6-amino-5-cyano-4-(4-fluorophenyl)-2-methylpyridine-3-carboxylate

Crystal data

C15H12FN3O2	Z = 2
Mr = 285.28	F(000) = 296
Triclinic, P1	Dx = 1.364 Mg m^−3
Hall symbol: -P 1	Melting point = 552–554 K
a = 6.549 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.658 (5) Å	Cell parameters from 542 reflections
c = 14.093 (10) Å	θ = 2.7–26.9°
α = 81.691 (11)°	µ = 0.10 mm^−1
β = 86.585 (11)°	T = 298 K
γ = 84.035 (10)°	Block, colourless
V = 694.8 (9) Å^3	0.38 × 0.10 × 0.07 mm

Data collection

Bruker CCD area-detector diffractometer	2398 independent reflections
Radiation source: fine-focus sealed tube	997 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
φ and ω scans	θmax = 25.0°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
Tmin = 0.962, Tmax = 0.993	k = −9→8
3578 measured reflections	l = −16→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.168	H atoms treated by a mixture of independent and constrained refinement
S = 0.94	w = 1/[σ^2(Fo^2) + (0.0642P)^2] where P = (Fo^2 + 2Fc^2)/3
2398 reflections	(Δ/σ)max < 0.001
198 parameters	Δρmax = 0.24 e Å^−3
0 restraints	Δρmin = −0.24 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
F1	1.1400 (5)	0.1422 (4)	0.9432 (2)	0.0852 (10)
N1	0.1942 (5)	0.5590 (4)	0.5771 (2)	0.0390 (9)
N2	0.2333 (7)	0.3171 (6)	0.4985 (3)	0.0469 (11)
N3	0.6296 (6)	0.0259 (5)	0.5904 (3)	0.0619 (13)
O1	0.6503 (6)	0.7125 (4)	0.7811 (2)	0.0593 (10)
O2	0.3267 (6)	0.7444 (5)	0.8390 (3)	0.0949 (15)
C1	0.2971 (7)	0.4024 (5)	0.5659 (3)	0.0358 (11)
C2	0.4638 (6)	0.3306 (5)	0.6242 (3)	0.0335 (11)
C3	0.5164 (6)	0.4202 (5)	0.6964 (3)	0.0367 (11)
C4	0.4060 (7)	0.5823 (5)	0.7077 (3)	0.0392 (11)
C5	0.2473 (7)	0.6473 (5)	0.6459 (3)	0.0402 (11)
C6	0.5614 (7)	0.1619 (6)	0.6082 (3)	0.0418 (12)
C7	0.6811 (7)	0.3398 (5)	0.7621 (3)	0.0368 (11)
C8	0.8750 (7)	0.2907 (5)	0.7254 (3)	0.0447 (12)
H8	0.9023	0.3030	0.6594	0.054*
C9	1.0292 (7)	0.2229 (6)	0.7878 (4)	0.0514 (13)
H9	1.1606	0.1886	0.7640	0.062*
C10	0.9864 (8)	0.2072 (6)	0.8830 (4)	0.0541 (14)
C11	0.7951 (8)	0.2497 (6)	0.9221 (3)	0.0553 (14)
H11	0.7691	0.2336	0.9882	0.066*
C12	0.6422 (7)	0.3169 (5)	0.8607 (3)	0.0486 (13)
H12	0.5107	0.3475	0.8855	0.058*
C13	0.4532 (9)	0.6880 (6)	0.7833 (4)	0.0539 (14)
C14	0.7148 (9)	0.7976 (8)	0.8582 (4)	0.100 (2)
H14A	0.8596	0.8092	0.8500	0.150*
H14B	0.6865	0.7271	0.9186	0.150*
H14C	0.6412	0.9130	0.8568	0.150*
C15	0.1249 (7)	0.8237 (6)	0.6492 (3)	0.0619 (15)
H15A	0.0245	0.8421	0.6009	0.093*
H15B	0.2153	0.9163	0.6375	0.093*
H15C	0.0567	0.8255	0.7113	0.093*
H1	0.113 (6)	0.365 (5)	0.474 (3)	0.038 (14)*
H2	0.286 (7)	0.216 (6)	0.484 (3)	0.076 (19)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F1	0.076 (2)	0.102 (2)	0.077 (2)	0.0023 (18)	−0.0401 (19)	−0.0036 (18)
N1	0.043 (2)	0.033 (2)	0.043 (2)	0.0013 (18)	−0.0063 (18)	−0.0147 (17)
N2	0.049 (3)	0.045 (3)	0.050 (3)	0.010 (2)	−0.020 (2)	−0.018 (2)
N3	0.073 (3)	0.050 (3)	0.064 (3)	0.016 (2)	−0.023 (2)	−0.021 (2)
O1	0.072 (3)	0.061 (2)	0.054 (2)	−0.0208 (19)	−0.0109 (19)	−0.0222 (17)
O2	0.080 (3)	0.132 (4)	0.085 (3)	0.011 (3)	−0.001 (2)	−0.072 (3)
C1	0.044 (3)	0.033 (3)	0.032 (3)	−0.002 (2)	0.000 (2)	−0.009 (2)
C2	0.038 (3)	0.026 (2)	0.037 (3)	−0.001 (2)	−0.003 (2)	−0.009 (2)
C3	0.043 (3)	0.037 (3)	0.030 (3)	−0.006 (2)	0.002 (2)	−0.003 (2)
C4	0.044 (3)	0.040 (3)	0.037 (3)	−0.003 (2)	−0.006 (2)	−0.013 (2)
C5	0.042 (3)	0.041 (3)	0.040 (3)	−0.004 (2)	0.003 (2)	−0.014 (2)
C6	0.045 (3)	0.042 (3)	0.041 (3)	0.001 (2)	−0.010 (2)	−0.013 (2)
C7	0.039 (3)	0.038 (3)	0.033 (3)	−0.003 (2)	−0.001 (2)	−0.007 (2)
C8	0.043 (3)	0.055 (3)	0.038 (3)	−0.008 (2)	−0.001 (3)	−0.010 (2)
C9	0.037 (3)	0.057 (3)	0.061 (4)	0.002 (3)	−0.005 (3)	−0.014 (3)
C10	0.051 (4)	0.061 (3)	0.051 (4)	−0.004 (3)	−0.024 (3)	−0.006 (3)
C11	0.069 (4)	0.061 (3)	0.035 (3)	−0.006 (3)	−0.006 (3)	−0.002 (2)
C12	0.053 (3)	0.050 (3)	0.042 (3)	0.002 (2)	−0.005 (3)	−0.009 (2)
C13	0.056 (4)	0.056 (3)	0.051 (3)	0.005 (3)	−0.011 (3)	−0.016 (3)
C14	0.130 (6)	0.112 (5)	0.082 (4)	−0.056 (4)	−0.019 (4)	−0.051 (4)
C15	0.062 (4)	0.048 (3)	0.079 (4)	0.017 (3)	−0.016 (3)	−0.032 (3)

Geometric parameters (Å, º)

F1—C10	1.362 (5)	C5—C15	1.503 (5)
N1—C1	1.339 (5)	C7—C8	1.378 (5)
N1—C5	1.341 (5)	C7—C12	1.386 (6)
N2—C1	1.336 (5)	C8—C9	1.388 (5)
N2—H1	0.90 (4)	C8—H8	0.9300
N2—H2	0.86 (5)	C9—C10	1.346 (6)
N3—C6	1.146 (5)	C9—H9	0.9300
O1—C13	1.321 (6)	C10—C11	1.365 (6)
O1—C14	1.449 (5)	C11—C12	1.372 (6)
O2—C13	1.197 (5)	C11—H11	0.9300
C1—C2	1.422 (5)	C12—H12	0.9300
C2—C3	1.385 (5)	C14—H14A	0.9600
C2—C6	1.423 (6)	C14—H14B	0.9600
C3—C4	1.395 (5)	C14—H14C	0.9600
C3—C7	1.488 (5)	C15—H15A	0.9600
C4—C5	1.400 (5)	C15—H15B	0.9600
C4—C13	1.493 (6)	C15—H15C	0.9600
C1—N1—C5	119.1 (4)	C10—C9—C8	119.2 (5)
C1—N2—H1	114 (2)	C10—C9—H9	120.4
C1—N2—H2	126 (3)	C8—C9—H9	120.4
H1—N2—H2	119 (4)	C9—C10—F1	118.5 (5)
C13—O1—C14	116.0 (4)	C9—C10—C11	123.0 (5)
N2—C1—N1	116.7 (4)	F1—C10—C11	118.5 (5)
N2—C1—C2	122.2 (4)	C10—C11—C12	117.9 (5)
N1—C1—C2	121.1 (4)	C10—C11—H11	121.1
C3—C2—C1	119.8 (4)	C12—C11—H11	121.1
C3—C2—C6	123.1 (4)	C11—C12—C7	120.9 (5)
C1—C2—C6	117.1 (4)	C11—C12—H12	119.5
C2—C3—C4	118.3 (4)	C7—C12—H12	119.5
C2—C3—C7	120.0 (4)	O2—C13—O1	124.2 (5)
C4—C3—C7	121.7 (4)	O2—C13—C4	123.8 (5)
C3—C4—C5	118.8 (4)	O1—C13—C4	112.0 (5)
C3—C4—C13	121.8 (4)	O1—C14—H14A	109.5
C5—C4—C13	119.4 (4)	O1—C14—H14B	109.5
N1—C5—C4	122.8 (4)	H14A—C14—H14B	109.5
N1—C5—C15	114.0 (4)	O1—C14—H14C	109.5
C4—C5—C15	123.1 (4)	H14A—C14—H14C	109.5
N3—C6—C2	175.0 (5)	H14B—C14—H14C	109.5
C8—C7—C12	119.4 (4)	C5—C15—H15A	109.5
C8—C7—C3	120.2 (4)	C5—C15—H15B	109.5
C12—C7—C3	120.4 (4)	H15A—C15—H15B	109.5
C7—C8—C9	119.5 (4)	C5—C15—H15C	109.5
C7—C8—H8	120.2	H15A—C15—H15C	109.5
C9—C8—H8	120.2	H15B—C15—H15C	109.5
C5—N1—C1—N2	177.7 (4)	C2—C3—C7—C8	56.5 (6)
C5—N1—C1—C2	−1.3 (6)	C4—C3—C7—C8	−126.1 (4)
N2—C1—C2—C3	−176.5 (4)	C2—C3—C7—C12	−124.9 (5)
N1—C1—C2—C3	2.5 (6)	C4—C3—C7—C12	52.5 (6)
N2—C1—C2—C6	−0.1 (6)	C12—C7—C8—C9	−1.4 (6)
N1—C1—C2—C6	178.9 (4)	C3—C7—C8—C9	177.3 (4)
C1—C2—C3—C4	−1.7 (6)	C7—C8—C9—C10	−0.3 (7)
C6—C2—C3—C4	−177.9 (4)	C8—C9—C10—F1	−179.3 (4)
C1—C2—C3—C7	175.8 (4)	C8—C9—C10—C11	2.2 (7)
C6—C2—C3—C7	−0.4 (6)	C9—C10—C11—C12	−2.2 (7)
C2—C3—C4—C5	0.0 (6)	F1—C10—C11—C12	179.3 (4)
C7—C3—C4—C5	−177.4 (4)	C10—C11—C12—C7	0.4 (7)
C2—C3—C4—C13	−179.7 (4)	C8—C7—C12—C11	1.4 (7)
C7—C3—C4—C13	2.8 (7)	C3—C7—C12—C11	−177.3 (4)
C1—N1—C5—C4	−0.5 (6)	C14—O1—C13—O2	6.5 (7)
C1—N1—C5—C15	178.2 (4)	C14—O1—C13—C4	−173.8 (4)
C3—C4—C5—N1	1.1 (6)	C3—C4—C13—O2	−128.8 (5)
C13—C4—C5—N1	−179.1 (4)	C5—C4—C13—O2	51.4 (7)
C3—C4—C5—C15	−177.4 (4)	C3—C4—C13—O1	51.5 (6)
C13—C4—C5—C15	2.4 (7)	C5—C4—C13—O1	−128.3 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···N1^i	0.90 (4)	2.17 (4)	3.063 (6)	171 (3)
N2—H2···N3^ii	0.86 (5)	2.26 (5)	3.099 (6)	164 (4)

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