2-Amino-N-(2-chloro­pyridin-3­yl)benzamide

Riad, N.M.; Zlotos, D.P.; Holzgrabe, U.

doi:10.1107/S241431461701536X

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 10| October 2017| x171536

https://doi.org/10.1107/S241431461701536X

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2-Amino-N-(2-chloropyridin-3yl)benzamide

Noura M. Riad,^a Darius P. Zlotos ^a ^* and Ulrike Holzgrabe ^b

^aThe German University in Cairo, Department of Pharmaceutical Chemistry, New Cairo City, 11835 Cairo, Egypt, and ^bInstitute of Pharmacy and Food Chemistry, Wuerzburg University, 97074 Wuerzburg, Germany
^*Correspondence e-mail: darius.zlotos@guc.edu.eg

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 18 October 2017; accepted 23 October 2017; online 27 October 2017)

The title compound, C₁₂H₁₀ClN₃O, is a condensation product of 3-amino-2-chloropyridine and ethyl 2-aminobenzoate in which the aromatic rings are almost coplanar [dihedral angle = 2.28 (9)°] and an intramolecular N—H⋯O hydrogen bond occurs. In the crystal, N—H⋯O and N—H⋯N hydrogen bonds link the molecules into (100) sheets.

Keywords: crystal structure; benzamide; hydrogen bonding.

CCDC reference: 1024196

Structure description

The title compound results from our research on subtype-selective ligands for muscarinic receptors (Mohr et al., 2004 , 2010 ). It was isolated in 23% yield as a ring-opened side product in a condensation reaction between 3-amino-2-chloropyridine and ethyl 2-aminobenzoate (Holzgrabe & Heller, 2003 ; Riad et al., 2015 ).

The molecular structure is shown in Fig. 1. As expected, the central amide group adopts an almost planar orientation (O=C—N—H torsion angle = 174°). The C12—C7—C6=O1 torsion angle is 145.9 (2)° and an intramolecular N—H⋯O hydrogen bond (Table 1) closes an S(6) ring. The aromatic rings are essentially coplanar [dihedral angle = 2.28 (9)°].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O1	0.86	2.10	2.7734 (19)	135
N2—H2⋯O1ⁱ	0.88	2.07	2.882 (2)	152
N3—H3B⋯N1ⁱⁱ	0.86	2.42	3.087 (2)	134
Symmetry codes: (i) x, y-1, z; (ii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Figure 1
The molecular structure, with displacement ellipsoids drawn at the 50% probability level.

In the crystal, molecules are linked by N—H⋯O and N—H⋯N hydrogen bonds to generate (100) sheets (Table 1, Fig. 2).

Figure 2
A view along the c axis of the packing. Hydrogen bonds (see Table 1

) are shown as dashed lines.

Synthesis and crystallization

The title compound was synthesized according to our previously reported procedure (Riad et al., 2017 ). Colourless blocks were obtained by recrystallization from a solvent mixture of methanol and toluene.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₂H₁₀ClN₃O
M_r	247.68
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	11.0965 (9), 4.7669 (4), 20.6624 (17)
β (°)	97.556 (3)
V (Å³)	1083.47 (15)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.34
Crystal size (mm)	0.57 × 0.39 × 0.21

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2013 )
T_min, T_max	0.862, 0.957
No. of measured, independent and observed [I > 2σ(I)] reflections	11807, 2283, 1963
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.633

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.091, 1.07
No. of reflections	2283
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.44
Computer programs: APEX2 and SAINT (Bruker, 2013), olex2.solve (Bourhis et al., 2015 ), SHELXL (Sheldrick, 2008 ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1024196

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S241431461701536X/hb4177sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431461701536X/hb4177Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S241431461701536X/hb4177Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: olex2.solve (Bourhis et al., 2015); program(s) used to refine structure: SHELXL (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

2-Amino-N-(2-chloropyridin-3yl)benzamide top

Crystal data top

C₁₂H₁₀ClN₃O	F(000) = 512
M_r = 247.68	D_x = 1.518 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.0965 (9) Å	Cell parameters from 2859 reflections
b = 4.7669 (4) Å	θ = 2.5–26.6°
c = 20.6624 (17) Å	µ = 0.34 mm⁻¹
β = 97.556 (3)°	T = 100 K
V = 1083.47 (15) Å³	Block, colourless
Z = 4	0.57 × 0.39 × 0.21 mm

Data collection top

Bruker APEXII CCD diffractometer	1963 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.044
Absorption correction: multi-scan (SADABS; Bruker, 2013)	θ_max = 26.8°, θ_min = 1.9°
T_min = 0.862, T_max = 0.957	h = −13→14
11807 measured reflections	k = −6→5
2283 independent reflections	l = −25→26

Refinement top

Refinement on F²	Primary atom site location: iterative
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.091	w = 1/[σ²(F_o²) + (0.0341P)² + 0.9297P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
2283 reflections	Δρ_max = 0.35 e Å⁻³
155 parameters	Δρ_min = −0.44 e Å⁻³
0 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.81489 (4)	0.23796 (9)	0.39806 (2)	0.01471 (13)
O1	0.70743 (12)	0.9552 (3)	0.22843 (6)	0.0161 (3)
N3	0.70224 (13)	0.8909 (3)	0.09469 (7)	0.0137 (3)
H3A	0.7063	1.0033	0.1275	0.016*
H3B	0.7206	0.9803	0.0611	0.016*
N2	0.71512 (13)	0.5248 (3)	0.27552 (7)	0.0113 (3)
H2	0.7345	0.3474	0.2712	0.014*
N1	0.65077 (14)	0.5388 (3)	0.44509 (7)	0.0139 (3)
C8	0.78996 (15)	0.6915 (4)	0.11373 (9)	0.0112 (4)
C9	0.85353 (16)	0.5653 (4)	0.06707 (9)	0.0141 (4)
H9	0.8375	0.6234	0.0228	0.017*
C6	0.74137 (15)	0.7094 (4)	0.22874 (8)	0.0109 (4)
C2	0.65890 (15)	0.6017 (4)	0.33025 (8)	0.0099 (3)
C7	0.81176 (15)	0.5917 (4)	0.17868 (8)	0.0110 (4)
C5	0.56237 (17)	0.7324 (4)	0.44136 (9)	0.0159 (4)
H5	0.5291	0.7798	0.4800	0.019*
C11	0.96468 (16)	0.2701 (4)	0.14867 (9)	0.0146 (4)
H11	1.0256	0.1328	0.1606	0.018*
C12	0.90038 (15)	0.3850 (4)	0.19498 (9)	0.0126 (4)
H12	0.9166	0.3225	0.2389	0.015*
C3	0.56528 (15)	0.7972 (4)	0.32742 (9)	0.0131 (4)
H3	0.5346	0.8827	0.2871	0.016*
C4	0.51739 (16)	0.8661 (4)	0.38375 (9)	0.0147 (4)
H4	0.4548	1.0026	0.3830	0.018*
C1	0.69709 (15)	0.4811 (4)	0.39114 (9)	0.0113 (4)
C10	0.93868 (16)	0.3588 (4)	0.08413 (9)	0.0153 (4)
H10	0.9801	0.2760	0.0515	0.018*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0156 (2)	0.0151 (2)	0.0135 (2)	0.00489 (17)	0.00259 (16)	0.00396 (16)
O1	0.0258 (7)	0.0090 (6)	0.0148 (7)	0.0026 (5)	0.0075 (5)	0.0002 (5)
N3	0.0171 (8)	0.0138 (8)	0.0102 (8)	0.0010 (6)	0.0021 (6)	0.0025 (6)
N2	0.0156 (7)	0.0084 (7)	0.0105 (7)	0.0015 (6)	0.0042 (6)	−0.0009 (6)
N1	0.0171 (8)	0.0144 (8)	0.0111 (8)	−0.0010 (6)	0.0046 (6)	−0.0012 (6)
C8	0.0105 (8)	0.0097 (8)	0.0133 (9)	−0.0038 (7)	0.0017 (7)	−0.0004 (7)
C9	0.0159 (9)	0.0169 (9)	0.0101 (9)	−0.0045 (7)	0.0035 (7)	−0.0009 (7)
C6	0.0117 (8)	0.0101 (8)	0.0102 (8)	−0.0015 (7)	−0.0011 (7)	−0.0015 (6)
C2	0.0121 (8)	0.0082 (8)	0.0096 (8)	−0.0022 (7)	0.0025 (6)	−0.0017 (6)
C7	0.0124 (8)	0.0087 (8)	0.0121 (9)	−0.0029 (7)	0.0027 (7)	−0.0016 (7)
C5	0.0181 (9)	0.0170 (9)	0.0142 (9)	−0.0006 (8)	0.0078 (7)	−0.0040 (7)
C11	0.0123 (8)	0.0140 (9)	0.0179 (10)	−0.0005 (7)	0.0034 (7)	−0.0005 (7)
C12	0.0124 (8)	0.0124 (8)	0.0127 (9)	−0.0018 (7)	0.0012 (7)	−0.0001 (7)
C3	0.0121 (8)	0.0133 (9)	0.0135 (9)	−0.0017 (7)	0.0002 (7)	0.0005 (7)
C4	0.0116 (8)	0.0128 (9)	0.0203 (10)	0.0007 (7)	0.0041 (7)	−0.0022 (7)
C1	0.0115 (8)	0.0097 (8)	0.0125 (9)	−0.0006 (7)	0.0005 (7)	−0.0010 (7)
C10	0.0145 (9)	0.0170 (9)	0.0159 (10)	−0.0033 (7)	0.0070 (7)	−0.0042 (7)

Geometric parameters (Å, º) top

Cl1—C1	1.7387 (17)	C6—C7	1.486 (2)
O1—C6	1.230 (2)	C2—C3	1.391 (2)
N3—H3A	0.8605	C2—C1	1.398 (2)
N3—H3B	0.8612	C7—C12	1.402 (2)
N3—C8	1.380 (2)	C5—H5	0.9500
N2—H2	0.8800	C5—C4	1.384 (3)
N2—C6	1.367 (2)	C11—H11	0.9500
N2—C2	1.410 (2)	C11—C12	1.380 (3)
N1—C5	1.342 (2)	C11—C10	1.393 (3)
N1—C1	1.316 (2)	C12—H12	0.9500
C8—C9	1.403 (2)	C3—H3	0.9500
C8—C7	1.414 (2)	C3—C4	1.381 (3)
C9—H9	0.9500	C4—H4	0.9500
C9—C10	1.378 (3)	C10—H10	0.9500

H3A—N3—H3B	109.4	N1—C5—H5	118.5
C8—N3—H3A	104.0	N1—C5—C4	122.98 (17)
C8—N3—H3B	109.8	C4—C5—H5	118.5
C6—N2—H2	118.0	C12—C11—H11	120.6
C6—N2—C2	123.91 (15)	C12—C11—C10	118.85 (17)
C2—N2—H2	118.0	C10—C11—H11	120.6
C1—N1—C5	117.33 (15)	C7—C12—H12	119.2
N3—C8—C9	119.93 (16)	C11—C12—C7	121.53 (17)
N3—C8—C7	121.89 (16)	C11—C12—H12	119.2
C9—C8—C7	117.98 (16)	C2—C3—H3	120.3
C8—C9—H9	119.3	C4—C3—C2	119.46 (16)
C10—C9—C8	121.36 (17)	C4—C3—H3	120.3
C10—C9—H9	119.3	C5—C4—H4	120.7
O1—C6—N2	121.56 (16)	C3—C4—C5	118.68 (17)
O1—C6—C7	122.99 (16)	C3—C4—H4	120.7
N2—C6—C7	115.44 (15)	N1—C1—Cl1	116.28 (13)
C3—C2—N2	123.17 (15)	N1—C1—C2	124.78 (16)
C3—C2—C1	116.73 (16)	C2—C1—Cl1	118.94 (13)
C1—C2—N2	120.10 (15)	C9—C10—C11	120.71 (17)
C8—C7—C6	119.58 (15)	C9—C10—H10	119.6
C12—C7—C8	119.44 (16)	C11—C10—H10	119.6
C12—C7—C6	120.98 (15)

O1—C6—C7—C8	−33.5 (2)	C6—N2—C2—C3	39.1 (2)
O1—C6—C7—C12	145.85 (17)	C6—N2—C2—C1	−140.53 (17)
N3—C8—C9—C10	−177.76 (16)	C6—C7—C12—C11	178.71 (16)
N3—C8—C7—C6	−1.9 (2)	C2—N2—C6—O1	−6.5 (3)
N3—C8—C7—C12	178.73 (15)	C2—N2—C6—C7	174.11 (14)
N2—C6—C7—C8	145.84 (16)	C2—C3—C4—C5	−1.6 (3)
N2—C6—C7—C12	−34.8 (2)	C7—C8—C9—C10	−2.8 (3)
N2—C2—C3—C4	−178.27 (16)	C5—N1—C1—Cl1	177.95 (13)
N2—C2—C1—Cl1	0.4 (2)	C5—N1—C1—C2	−1.6 (3)
N2—C2—C1—N1	179.89 (16)	C12—C11—C10—C9	2.4 (3)
N1—C5—C4—C3	0.2 (3)	C3—C2—C1—Cl1	−179.30 (13)
C8—C9—C10—C11	−0.4 (3)	C3—C2—C1—N1	0.2 (3)
C8—C7—C12—C11	−1.9 (3)	C1—N1—C5—C4	1.4 (3)
C9—C8—C7—C6	−176.72 (15)	C1—C2—C3—C4	1.4 (2)
C9—C8—C7—C12	3.9 (2)	C10—C11—C12—C7	−1.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1	0.86	2.10	2.7734 (19)	135
N2—H2···O1ⁱ	0.88	2.07	2.882 (2)	152
N3—H3B···N1ⁱⁱ	0.86	2.42	3.087 (2)	134

Symmetry codes: (i) x, y−1, z; (ii) x, −y+3/2, z−1/2.

Acknowledgements

The authors thank Andreas Lorbach and Todd B. Marder (Institute of Inorganic Chemistry, Wuerzburg University) for the data collection and structure solution.

Funding information

We appreciate the financial support provided to NMR by the Deutscher Akademischer Austauschdienst (DAAD).

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