N-(4-Fluoro-benz-yl)-3-nitro-pyridine-2,6-diamine.

In the title compound, C(12)H(11)FN(4)O(2), the pyridine ring is connected to a benzene ring by a -CH(2)-NH(2)- chain. The nitro group is twisted out of the pyridine ring plane [torsion angle O-N-C-C = 10.41 (10)°]. An intramolecular N-H⋯O hydrogen bond occurs. The fluoro-benzene ring is disordered over two positions [occupancy ratio = 0.59 (3):0.41 (3)]. Inter-molecular N-H⋯O and N-H⋯N hydrogen bonds stabilize the crystal structure.

Related literature

The title compound is an inter­mediate in the synthesis of analgesic drugs. For the analgesic properties of flupirtine (systematic name eth­yl{2-amino-6-[(4-fluoro­benz­yl)amino]­pyridin-3-yl}carbamate), see: Klawe & Maschke (2009 ▶). For synthetic procedures, see: Gerhard & Ilia (2010 ▶). For a related structure, see: Wang (2009 ▶).

Experimental

Crystal data

C12H11FN4O2

M = 262.25

Monoclinic,

a = 14.8187 (14) Å

b = 5.9972 (6) Å

c = 14.8840 (15) Å

β = 109.827 (1)°

V = 1244.3 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 298 K

0.38 × 0.15 × 0.11 mm

Data collection

Rigaku SCXmini CCD diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.960, T max = 0.988

5923 measured reflections

2184 independent reflections

1169 reflections with I > 2σ(I)

R int = 0.056

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.140

S = 1.03

2184 reflections

227 parameters

H-atom parameters constrained

Δρmax = 0.21 e Å−3

Δρmin = −0.22 e Å−3

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811018642/pv2411sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811018642/pv2411Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811018642/pv2411Isup3.cml

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

C12H11FN4O2	F(000) = 544
Mr = 262.25	Dx = 1.400 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1144 reflections
a = 14.8187 (14) Å	θ = 2.4–26.9°
b = 5.9972 (6) Å	µ = 0.11 mm−1
c = 14.8840 (15) Å	T = 298 K
β = 109.827 (1)°	Prism, yellow
V = 1244.3 (2) Å3	0.38 × 0.15 × 0.11 mm
Z = 4

Rigaku SCXmini CCD diffractometer	2184 independent reflections
Radiation source: fine-focus sealed tube	1169 reflections with I > 2σ(I)
graphite	Rint = 0.056
Detector resolution: 8.192 pixels mm-1	θmax = 25.0°, θmin = 2.4°
φ and ω scans	h = −14→17
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −5→7
Tmin = 0.960, Tmax = 0.988	l = −17→17
5923 measured reflections

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.140	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0585P)2] where P = (Fo2 + 2Fc2)/3
2184 reflections	(Δ/σ)max = 0.001
227 parameters	Δρmax = 0.21 e Å−3
0 restraints	Δρmin = −0.22 e Å−3

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
F1	0.6846 (16)	0.5113 (18)	0.0036 (13)	0.121 (4)	0.59 (3)
F1'	0.7330 (17)	0.538 (2)	0.050 (2)	0.105 (5)	0.41 (3)
N1	0.55771 (13)	0.2584 (4)	0.46588 (14)	0.0474 (6)
N2	0.49151 (15)	0.4615 (4)	0.33021 (15)	0.0608 (7)
H2	0.4453	0.3666	0.3173	0.073*
N3	0.61662 (15)	0.0425 (4)	0.59818 (14)	0.0597 (7)
H3A	0.5670	−0.0413	0.5754	0.072*
H3B	0.6593	0.0109	0.6523	0.072*
N4	0.78769 (16)	0.3201 (4)	0.66405 (17)	0.0611 (7)
O1	0.78379 (14)	0.1726 (4)	0.72145 (14)	0.0792 (7)
O2	0.86264 (15)	0.4308 (4)	0.68041 (15)	0.0852 (7)
C1	0.56363 (18)	0.4356 (5)	0.41323 (18)	0.0487 (7)
C2	0.6413 (2)	0.5883 (5)	0.4429 (2)	0.0604 (8)
H2A	0.6429	0.7126	0.4061	0.072*
C3	0.71288 (19)	0.5481 (5)	0.5260 (2)	0.0581 (8)
H3	0.7649	0.6448	0.5463	0.070*
C4	0.70977 (17)	0.3639 (4)	0.58174 (18)	0.0488 (7)
C5	0.62743 (17)	0.2205 (4)	0.54982 (17)	0.0454 (6)
C6	0.4844 (2)	0.6355 (5)	0.2601 (2)	0.0666 (8)
H6A	0.5020	0.7765	0.2934	0.080*
H6B	0.4180	0.6470	0.2188	0.080*
C7	0.5459 (2)	0.6006 (5)	0.1989 (2)	0.0611 (8)
C8	0.6128 (14)	0.425 (4)	0.2145 (16)	0.067 (4)	0.59 (3)
H8	0.6195	0.3224	0.2632	0.081*	0.59 (3)
C9	0.669 (3)	0.407 (6)	0.156 (3)	0.097 (7)	0.59 (3)
H9	0.7225	0.3149	0.1712	0.116*	0.59 (3)
C10	0.6390 (18)	0.540 (6)	0.071 (2)	0.087 (6)	0.59 (3)
C11	0.5858 (15)	0.726 (3)	0.0609 (13)	0.082 (4)	0.59 (3)
H11	0.5823	0.8329	0.0145	0.099*	0.59 (3)
C12	0.5373 (18)	0.747 (4)	0.1241 (16)	0.072 (4)	0.59 (3)
H12	0.4958	0.8669	0.1164	0.086*	0.59 (3)
C8'	0.581 (2)	0.398 (6)	0.186 (2)	0.081 (6)	0.41 (3)
H8'	0.5631	0.2733	0.2137	0.097*	0.41 (3)
C9'	0.641 (3)	0.369 (8)	0.134 (3)	0.086 (8)	0.41 (3)
H9'	0.6603	0.2268	0.1225	0.103*	0.41 (3)
C10'	0.673 (3)	0.559 (7)	0.098 (3)	0.078 (7)	0.41 (3)
C11'	0.626 (2)	0.753 (4)	0.099 (2)	0.082 (6)	0.41 (3)
H11'	0.6350	0.8719	0.0630	0.099*	0.41 (3)
C12'	0.566 (2)	0.782 (7)	0.152 (3)	0.080 (7)	0.41 (3)
H12'	0.5393	0.9213	0.1550	0.096*	0.41 (3)

	U11	U22	U33	U12	U13	U23
F1	0.158 (10)	0.109 (4)	0.135 (8)	0.014 (5)	0.100 (7)	0.009 (5)
F1'	0.124 (10)	0.090 (5)	0.141 (11)	0.018 (6)	0.097 (9)	0.018 (6)
N1	0.0386 (12)	0.0553 (15)	0.0437 (12)	−0.0061 (10)	0.0080 (10)	0.0023 (11)
N2	0.0504 (14)	0.0698 (17)	0.0557 (14)	−0.0039 (11)	0.0096 (12)	0.0163 (12)
N3	0.0514 (13)	0.0679 (17)	0.0481 (12)	−0.0160 (12)	0.0016 (11)	0.0080 (12)
N4	0.0469 (15)	0.0722 (18)	0.0548 (15)	−0.0129 (13)	0.0050 (13)	−0.0155 (14)
O1	0.0631 (13)	0.0991 (18)	0.0574 (12)	−0.0146 (12)	−0.0030 (10)	0.0125 (12)
O2	0.0537 (13)	0.0941 (18)	0.0881 (15)	−0.0231 (12)	−0.0015 (11)	−0.0111 (13)
C1	0.0441 (15)	0.0529 (18)	0.0504 (15)	−0.0001 (13)	0.0180 (13)	0.0025 (14)
C2	0.0638 (18)	0.0505 (19)	0.0666 (19)	−0.0090 (15)	0.0218 (16)	0.0059 (14)
C3	0.0485 (16)	0.0545 (19)	0.0687 (18)	−0.0170 (14)	0.0165 (15)	−0.0079 (16)
C4	0.0418 (15)	0.0527 (18)	0.0478 (15)	−0.0069 (12)	0.0100 (13)	−0.0068 (13)
C5	0.0399 (14)	0.0534 (18)	0.0417 (14)	−0.0054 (13)	0.0121 (12)	−0.0031 (13)
C6	0.0653 (19)	0.071 (2)	0.0636 (18)	0.0142 (16)	0.0224 (16)	0.0190 (16)
C7	0.0670 (19)	0.054 (2)	0.0666 (19)	0.0078 (16)	0.0278 (16)	0.0107 (16)
C8	0.078 (9)	0.056 (7)	0.074 (8)	0.010 (6)	0.034 (7)	0.010 (6)
C9	0.108 (15)	0.074 (14)	0.122 (15)	0.017 (10)	0.056 (12)	0.005 (9)
C10	0.101 (14)	0.081 (11)	0.102 (13)	0.014 (11)	0.063 (10)	0.009 (9)
C11	0.101 (10)	0.073 (7)	0.083 (8)	0.011 (7)	0.044 (7)	0.024 (6)
C12	0.082 (11)	0.064 (9)	0.079 (10)	0.015 (7)	0.039 (8)	0.019 (7)
C8'	0.101 (18)	0.060 (9)	0.090 (16)	−0.004 (11)	0.045 (12)	0.012 (10)
C9'	0.11 (2)	0.057 (12)	0.111 (19)	0.010 (13)	0.069 (16)	0.007 (13)
C10'	0.096 (18)	0.057 (10)	0.11 (2)	−0.003 (13)	0.066 (14)	0.010 (12)
C11'	0.098 (14)	0.067 (9)	0.098 (14)	−0.004 (9)	0.054 (11)	0.019 (10)
C12'	0.091 (17)	0.062 (10)	0.097 (19)	0.003 (11)	0.044 (13)	0.010 (11)

F1—C10	1.39 (3)	C6—H6B	0.9700
F1'—C10'	1.32 (4)	C7—C8'	1.36 (3)
N1—C1	1.341 (3)	C7—C12'	1.38 (4)
N1—C5	1.343 (3)	C7—C12	1.39 (3)
N2—C1	1.341 (3)	C7—C8	1.41 (2)
N2—C6	1.454 (3)	C8—C9	1.40 (4)
N2—H2	0.8600	C8—H8	0.9300
N3—C5	1.327 (3)	C9—C10	1.43 (5)
N3—H3A	0.8600	C9—H9	0.9300
N3—H3B	0.8600	C10—C11	1.35 (4)
N4—O1	1.245 (3)	C11—C12	1.37 (3)
N4—O2	1.245 (3)	C11—H11	0.9300
N4—C4	1.394 (3)	C12—H12	0.9300
C1—C2	1.419 (4)	C8'—C9'	1.38 (6)
C2—C3	1.350 (4)	C8'—H8'	0.9300
C2—H2A	0.9300	C9'—C10'	1.41 (7)
C3—C4	1.392 (4)	C9'—H9'	0.9300
C3—H3	0.9300	C10'—C11'	1.36 (5)
C4—C5	1.436 (3)	C11'—C12'	1.38 (4)
C6—C7	1.506 (4)	C11'—H11'	0.9300
C6—H6A	0.9700	C12'—H12'	0.9300
C1—N1—C5	119.7 (2)	C12—C7—C8	118.1 (15)
C1—N2—C6	125.8 (2)	C8'—C7—C6	123.0 (15)
C1—N2—H2	117.1	C12'—C7—C6	118.4 (18)
C6—N2—H2	117.1	C12—C7—C6	119.2 (12)
C5—N3—H3A	120.0	C8—C7—C6	122.6 (10)
C5—N3—H3B	120.0	C9—C8—C7	119 (2)
H3A—N3—H3B	120.0	C9—C8—H8	120.4
O1—N4—O2	119.4 (2)	C7—C8—H8	120.4
O1—N4—C4	121.3 (2)	C8—C9—C10	116 (3)
O2—N4—C4	119.3 (3)	C8—C9—H9	122.0
N2—C1—N1	116.1 (2)	C10—C9—H9	122.0
N2—C1—C2	121.4 (3)	C11—C10—F1	116 (2)
N1—C1—C2	122.5 (2)	C11—C10—C9	123 (3)
C3—C2—C1	118.1 (3)	F1—C10—C9	119 (3)
C3—C2—H2A	120.9	C10—C11—C12	115 (2)
C1—C2—H2A	120.9	C10—C11—H11	122.5
C2—C3—C4	120.9 (3)	C12—C11—H11	122.5
C2—C3—H3	119.6	C11—C12—C7	125 (2)
C4—C3—H3	119.6	C11—C12—H12	117.7
C3—C4—N4	119.2 (2)	C7—C12—H12	117.7
C3—C4—C5	118.3 (2)	C7—C8'—C9'	123 (3)
N4—C4—C5	122.4 (2)	C7—C8'—H8'	118.7
N3—C5—N1	116.4 (2)	C9'—C8'—H8'	118.7
N3—C5—C4	123.2 (2)	C8'—C9'—C10'	119 (4)
N1—C5—C4	120.4 (2)	C8'—C9'—H9'	120.7
N2—C6—C7	115.0 (2)	C10'—C9'—H9'	120.7
N2—C6—H6A	108.5	F1'—C10'—C11'	122 (3)
C7—C6—H6A	108.5	F1'—C10'—C9'	120 (4)
N2—C6—H6B	108.5	C11'—C10'—C9'	116 (4)
C7—C6—H6B	108.5	C10'—C11'—C12'	123 (3)
H6A—C6—H6B	107.5	C10'—C11'—H11'	118.3
C8'—C7—C12'	119 (2)	C12'—C11'—H11'	118.3
C8'—C7—C12	112.9 (17)	C7—C12'—C11'	119 (3)
C12'—C7—C12	21.8 (14)	C7—C12'—H12'	120.7
C8'—C7—C8	22.5 (12)	C11'—C12'—H12'	120.7
C12'—C7—C8	114.4 (19)
C6—N2—C1—N1	−177.6 (2)	C12—C7—C8—C9	1.3 (19)
C6—N2—C1—C2	2.4 (4)	C6—C7—C8—C9	−178.4 (13)
C5—N1—C1—N2	179.7 (2)	C7—C8—C9—C10	−14 (3)
C5—N1—C1—C2	−0.3 (4)	C8—C9—C10—C11	24 (3)
N2—C1—C2—C3	−178.1 (2)	C8—C9—C10—F1	−172.7 (18)
N1—C1—C2—C3	2.0 (4)	F1—C10—C11—C12	176.8 (13)
C1—C2—C3—C4	−0.9 (4)	C9—C10—C11—C12	−19 (3)
C2—C3—C4—N4	176.0 (2)	C10—C11—C12—C7	5(2)
C2—C3—C4—C5	−1.5 (4)	C8'—C7—C12—C11	−21 (2)
O1—N4—C4—C3	171.9 (3)	C12'—C7—C12—C11	89 (8)
O2—N4—C4—C3	−8.0 (4)	C8—C7—C12—C11	3.6 (19)
O1—N4—C4—C5	−10.7 (4)	C6—C7—C12—C11	−176.7 (11)
O2—N4—C4—C5	169.3 (2)	C12'—C7—C8'—C9'	5(3)
C1—N1—C5—N3	179.8 (2)	C12—C7—C8'—C9'	29 (3)
C1—N1—C5—C4	−2.3 (3)	C8—C7—C8'—C9'	−80 (6)
C3—C4—C5—N3	−179.0 (2)	C6—C7—C8'—C9'	−177 (2)
N4—C4—C5—N3	3.6 (4)	C7—C8'—C9'—C10'	5(4)
C3—C4—C5—N1	3.2 (4)	C8'—C9'—C10'—F1'	178 (3)
N4—C4—C5—N1	−174.2 (2)	C8'—C9'—C10'—C11'	−14 (5)
C1—N2—C6—C7	77.2 (3)	F1'—C10'—C11'—C12'	−177.8 (19)
N2—C6—C7—C8'	20.6 (16)	C9'—C10'—C11'—C12'	15 (4)
N2—C6—C7—C12'	−161.0 (15)	C8'—C7—C12'—C11'	−5(2)
N2—C6—C7—C12	174.1 (10)	C12—C7—C12'—C11'	−85 (8)
N2—C6—C7—C8	−6.3 (10)	C8—C7—C12'—C11'	20 (2)
C8'—C7—C8—C9	83 (6)	C6—C7—C12'—C11'	176.8 (13)
C12'—C7—C8—C9	−23 (2)	C10'—C11'—C12'—C7	−6(3)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···O1	0.86	2.03	2.651 (3)	129
N3—H3A···N1i	0.86	2.17	3.028 (3)	174
N2—H2···O1ii	0.86	2.35	3.060 (3)	141

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3B⋯O1	0.86	2.03	2.651 (3)	129
N3—H3A⋯N1i	0.86	2.17	3.028 (3)	174
N2—H2⋯O1ii	0.86	2.35	3.060 (3)	141

Symmetry codes: (i) ; (ii) .