Methyl 4-[(5-chloro­pyrimidin-2-yl)carbamo­yl]benzoate

Lu, C.-H.; Wu, C.-J.; Yeh, C.-W.; Chen, J.-D.

doi:10.1107/S1600536811025268

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o1872

doi:10.1107/S1600536811025268

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Methyl 4-[(5-chloropyrimidin-2-yl)carbamoyl]benzoate

Chun-Hsiang Lu,^a Chia-Jun Wu,^a Chun-Wei Yeh ^a and Jhy-Der Chen ^a ^*

^aDepartment of Chemistry, Chung-Yuan Christian University, Chung-Li, Taiwan
^*Correspondence e-mail: jdchen@cycu.edu.tw

(Received 24 June 2011; accepted 27 June 2011; online 2 July 2011)

Molecules of the title compound, C₁₃H₁₀ClN₃O₃, form centrosymmetric dimers via intermolecular N—H⋯N hydrogen bonds generating an R₂²(8) motif. The dimers are further connected through an O⋯Cl—C halogen bond [O⋯Cl = 3.233 (1) Å and O⋯Cl—C = 167.33 (1)°] into a chain along [110]. The secondary amide group adopts a cis conformation. Weak C—H⋯N hydrogen bonds among the methyl benzoate and pyrimidyl rings are also observed in the crystal structure.

Related literature

For silver complexes of the title compound, see: Wu et al. (2011 ). For the conformation of the amide group in similar compounds, see: Forbes et al. (2001 ); Oertli et al. (1992 ).

Experimental

Crystal data

C₁₃H₁₀ClN₃O₃
M_r = 291.69
Triclinic, $[P \overline 1]$
a = 5.9068 (8) Å
b = 7.3378 (9) Å
c = 15.816 (4) Å
α = 78.259 (14)°
β = 82.030 (13)°
γ = 67.986 (10)°
V = 620.78 (19) Å³
Z = 2
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 295 K
0.5 × 0.4 × 0.3 mm

Data collection

Siemens P4 diffractometer
Absorption correction: ψ scan (XSCANS; Siemens, 1995 ) T_min = 0.888, T_max = 0.918
2811 measured reflections
2140 independent reflections
1715 reflections with I > 2σ(I)
R_int = 0.026
3 standard reflections every 97 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.098
S = 1.02
2140 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3B⋯N2ⁱ	0.86	2.10	2.959 (2)	176
C13—H13C⋯N1ⁱⁱ	0.96	2.57	3.339 (2)	138
Symmetry codes: (i) -x+1, -y+2, -z; (ii) -x+1, -y+1, -z+1.

Data collection: XSCANS (Siemens, 1995); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811025268/gk2391sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811025268/gk2391Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811025268/gk2391Isup3.cml

checkCIF report

Comment top

The silver(I) complex containg methyl 4-(5-chloropyrimidin-2-ylcarbamoyl)benzoate ligand has been reported, which shows a two-dimensional network (Wu et al., 2011). Within this project the crystal structure of the title compound was determined (Fig. 1). In its crystal structure intermolecular N—H···N hydrogen bonds are found (Table 1) and the molecules are also interlinked through C—Cl···O interactions [3.233 (1) Å and 167.33 (1)°]. Weak C—H···N hydrogen bonds among the methyl benzoate and pyrimidyl rings are also observed in the solid state (Fig. 2). In the crystal structure the amide group of the title compound adopts the cis conformation, which is in marked contrast to the trans conformation found in the Ag complex (Wu et al., 2011).

Related literature top

For silver complexes of the title compound, see: Wu et al. (2011). For the conformation of the amide group in similar compounds, see: Forbes et al. (2001); Oertli et al. (1992).

Experimental top

The title compound was prepared according to a published procedure (Wu et al., 2011). Block crystals suitable for X-ray crystallography were obtained by slow evaporation of the solvent from a solution of the title compound in methanol.

Computing details top

Data collection: XSCANS (Siemens, 1995); cell refinement: XSCANS (Siemens, 1995); data reduction: SHELXTL (Sheldrick, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Crystal structure of the title compound wiFig. 1. Crystal structure of the title compound with atom labeling and displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. Partial packing diagram showing C—H···N and N—H···N hydrogen bonds and C—Cl···O interactions among the molecules, with atom labeling and displacement ellipsoids drawn at the 30% probability level. Symmetric code: (i) 1 - x, 2 - y, -z; (ii) 1 - x, 1 - y, 1 - z; (iii) 1 + x, 1 + y, z.

Methyl 4-[(5-chloropyrimidin-2-yl)carbamoyl]benzoate top

Crystal data top

C₁₃H₁₀ClN₃O₃	Z = 2
M_r = 291.69	F(000) = 300
Triclinic, P1	D_x = 1.560 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.9068 (8) Å	Cell parameters from 28 reflections
b = 7.3378 (9) Å	θ = 4.7–13.3°
c = 15.816 (4) Å	µ = 0.32 mm⁻¹
α = 78.259 (14)°	T = 295 K
β = 82.030 (13)°	Block, colourless
γ = 67.986 (10)°	0.5 × 0.4 × 0.3 mm
V = 620.78 (19) Å³

Data collection top

Siemens P4 diffractometer	1715 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.026
Graphite monochromator	θ_max = 25.0°, θ_min = 2.6°
ω scans	h = −1→7
Absorption correction: ψ scan (XSCANS; Siemens, 1995)	k = −8→8
T_min = 0.888, T_max = 0.918	l = −18→18
2811 measured reflections	3 standard reflections every 97 reflections
2140 independent reflections	intensity decay: none

Refinement top

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0507P)² + 0.1938P] where P = (F_o² + 2F_c²)/3
2140 reflections	(Δ/σ)_max < 0.001
182 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₃H₁₀ClN₃O₃	γ = 67.986 (10)°
M_r = 291.69	V = 620.78 (19) Å³
Triclinic, P1	Z = 2
a = 5.9068 (8) Å	Mo Kα radiation
b = 7.3378 (9) Å	µ = 0.32 mm⁻¹
c = 15.816 (4) Å	T = 295 K
α = 78.259 (14)°	0.5 × 0.4 × 0.3 mm
β = 82.030 (13)°

Data collection top

Siemens P4 diffractometer	1715 reflections with I > 2σ(I)
Absorption correction: ψ scan (XSCANS; Siemens, 1995)	R_int = 0.026
T_min = 0.888, T_max = 0.918	3 standard reflections every 97 reflections
2811 measured reflections	intensity decay: none
2140 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.02	Δρ_max = 0.17 e Å⁻³
2140 reflections	Δρ_min = −0.21 e Å⁻³
182 parameters

Special details top

Experimental. 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.

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 (Å²) top

	x	y	z	U_iso*/U_eq
Cl	0.10131 (12)	0.38338 (9)	0.11742 (4)	0.0550 (2)
C1	0.3775 (4)	0.5274 (3)	0.18741 (12)	0.0397 (5)
H1A	0.3782	0.4287	0.2349	0.048*
C2	0.2528 (4)	0.5446 (3)	0.11729 (12)	0.0367 (5)
C3	0.2556 (4)	0.6923 (3)	0.04841 (13)	0.0431 (5)
H3A	0.1746	0.7055	−0.0001	0.052*
C4	0.4859 (4)	0.7890 (3)	0.12062 (11)	0.0325 (4)
C5	0.7163 (4)	0.9541 (3)	0.18183 (12)	0.0347 (4)
C6	0.6516 (4)	0.8916 (3)	0.27530 (11)	0.0318 (4)
C7	0.8388 (4)	0.8014 (3)	0.33151 (12)	0.0359 (5)
H7A	1.0007	0.7763	0.3104	0.043*
C8	0.7837 (4)	0.7492 (3)	0.41870 (12)	0.0363 (5)
H8A	0.9091	0.6881	0.4562	0.044*
C9	0.5424 (4)	0.7875 (3)	0.45062 (11)	0.0311 (4)
C10	0.3554 (4)	0.8838 (3)	0.39472 (12)	0.0347 (4)
H10A	0.1930	0.9141	0.4162	0.042*
C11	0.4102 (4)	0.9345 (3)	0.30739 (12)	0.0354 (5)
H11A	0.2848	0.9976	0.2701	0.043*
C12	0.4893 (4)	0.7203 (3)	0.54431 (12)	0.0331 (4)
C13	0.1836 (4)	0.6842 (3)	0.65241 (12)	0.0411 (5)
H13A	0.0194	0.6854	0.6568	0.062*
H13B	0.1925	0.7730	0.6878	0.062*
H13C	0.2932	0.5516	0.6718	0.062*
N1	0.4973 (3)	0.6482 (3)	0.18929 (10)	0.0408 (4)
N2	0.3709 (3)	0.8174 (3)	0.04906 (10)	0.0393 (4)
N3	0.6073 (3)	0.9194 (2)	0.11818 (10)	0.0378 (4)
H3B	0.6161	0.9910	0.0684	0.045*
O1	0.8550 (3)	1.0460 (3)	0.16089 (9)	0.0527 (4)
O2	0.6419 (3)	0.6464 (3)	0.59689 (9)	0.0512 (4)
O3	0.2527 (3)	0.7486 (2)	0.56330 (8)	0.0406 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.0698 (4)	0.0616 (4)	0.0504 (3)	−0.0436 (3)	−0.0186 (3)	0.0026 (3)
C1	0.0561 (14)	0.0391 (11)	0.0274 (10)	−0.0232 (10)	−0.0099 (9)	0.0038 (8)
C2	0.0417 (12)	0.0423 (11)	0.0315 (10)	−0.0212 (10)	−0.0039 (9)	−0.0052 (8)
C3	0.0539 (13)	0.0585 (13)	0.0267 (10)	−0.0312 (11)	−0.0121 (9)	−0.0006 (9)
C4	0.0379 (11)	0.0393 (10)	0.0220 (9)	−0.0168 (9)	−0.0034 (8)	−0.0017 (7)
C5	0.0418 (11)	0.0381 (11)	0.0285 (10)	−0.0203 (9)	−0.0041 (8)	−0.0023 (8)
C6	0.0418 (11)	0.0350 (10)	0.0255 (9)	−0.0210 (9)	−0.0059 (8)	−0.0036 (8)
C7	0.0319 (11)	0.0478 (12)	0.0332 (10)	−0.0200 (9)	−0.0044 (8)	−0.0057 (8)
C8	0.0382 (11)	0.0443 (12)	0.0299 (10)	−0.0183 (9)	−0.0122 (8)	−0.0003 (8)
C9	0.0369 (11)	0.0347 (10)	0.0264 (9)	−0.0172 (9)	−0.0080 (8)	−0.0031 (7)
C10	0.0333 (11)	0.0424 (11)	0.0292 (10)	−0.0150 (9)	−0.0048 (8)	−0.0028 (8)
C11	0.0375 (12)	0.0425 (11)	0.0265 (10)	−0.0149 (9)	−0.0104 (8)	0.0007 (8)
C12	0.0392 (12)	0.0347 (10)	0.0287 (10)	−0.0165 (9)	−0.0085 (9)	−0.0024 (8)
C13	0.0477 (13)	0.0498 (12)	0.0272 (10)	−0.0225 (10)	−0.0024 (9)	0.0007 (9)
N1	0.0575 (11)	0.0432 (10)	0.0283 (9)	−0.0268 (9)	−0.0143 (8)	0.0047 (7)
N2	0.0504 (11)	0.0522 (11)	0.0224 (8)	−0.0285 (9)	−0.0084 (7)	0.0016 (7)
N3	0.0519 (11)	0.0469 (10)	0.0217 (8)	−0.0287 (9)	−0.0091 (7)	0.0045 (7)
O1	0.0702 (11)	0.0736 (11)	0.0343 (8)	−0.0522 (10)	−0.0029 (7)	−0.0013 (7)
O2	0.0452 (9)	0.0793 (11)	0.0298 (8)	−0.0269 (8)	−0.0155 (7)	0.0074 (7)
O3	0.0394 (8)	0.0553 (9)	0.0254 (7)	−0.0196 (7)	−0.0060 (6)	0.0043 (6)

Geometric parameters (Å, º) top

Cl—C2	1.730 (2)	C7—H7A	0.9300
C1—N1	1.332 (3)	C8—C9	1.387 (3)
C1—C2	1.374 (3)	C8—H8A	0.9300
C1—H1A	0.9300	C9—C10	1.390 (3)
C2—C3	1.375 (3)	C9—C12	1.492 (3)
C3—N2	1.334 (3)	C10—C11	1.382 (3)
C3—H3A	0.9300	C10—H10A	0.9300
C4—N1	1.328 (2)	C11—H11A	0.9300
C4—N2	1.341 (2)	C12—O2	1.206 (2)
C4—N3	1.387 (2)	C12—O3	1.334 (2)
C5—O1	1.217 (2)	C13—O3	1.446 (2)
C5—N3	1.378 (3)	C13—H13A	0.9600
C5—C6	1.497 (3)	C13—H13B	0.9600
C6—C11	1.385 (3)	C13—H13C	0.9600
C6—C7	1.391 (3)	N3—H3B	0.8600
C7—C8	1.381 (3)

N1—C1—C2	121.82 (17)	C8—C9—C10	119.59 (17)
N1—C1—H1A	119.1	C8—C9—C12	119.08 (17)
C2—C1—H1A	119.1	C10—C9—C12	121.31 (17)
C1—C2—C3	117.43 (19)	C11—C10—C9	120.16 (18)
C1—C2—Cl	120.22 (15)	C11—C10—H10A	119.9
C3—C2—Cl	122.34 (16)	C9—C10—H10A	119.9
N2—C3—C2	122.04 (18)	C10—C11—C6	120.13 (18)
N2—C3—H3A	119.0	C10—C11—H11A	119.9
C2—C3—H3A	119.0	C6—C11—H11A	119.9
N1—C4—N2	126.16 (18)	O2—C12—O3	123.57 (18)
N1—C4—N3	119.57 (16)	O2—C12—C9	124.38 (19)
N2—C4—N3	114.23 (16)	O3—C12—C9	112.05 (16)
O1—C5—N3	118.93 (17)	O3—C13—H13A	109.5
O1—C5—C6	120.70 (17)	O3—C13—H13B	109.5
N3—C5—C6	120.25 (17)	H13A—C13—H13B	109.5
C11—C6—C7	119.85 (17)	O3—C13—H13C	109.5
C11—C6—C5	121.36 (17)	H13A—C13—H13C	109.5
C7—C6—C5	118.62 (18)	H13B—C13—H13C	109.5
C8—C7—C6	119.92 (19)	C4—N1—C1	116.57 (16)
C8—C7—H7A	120.0	C3—N2—C4	115.95 (16)
C6—C7—H7A	120.0	C5—N3—C4	131.10 (16)
C7—C8—C9	120.30 (18)	C5—N3—H3B	114.4
C7—C8—H8A	119.9	C4—N3—H3B	114.4
C9—C8—H8A	119.9	C12—O3—C13	116.21 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···N2ⁱ	0.86	2.10	2.959 (2)	176
C13—H13C···N1ⁱⁱ	0.96	2.57	3.339 (2)	138

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₀ClN₃O₃
M_r	291.69
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	5.9068 (8), 7.3378 (9), 15.816 (4)
α, β, γ (°)	78.259 (14), 82.030 (13), 67.986 (10)
V (Å³)	620.78 (19)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.5 × 0.4 × 0.3

Data collection
Diffractometer	Siemens P4 diffractometer
Absorption correction	ψ scan (XSCANS; Siemens, 1995)
T_min, T_max	0.888, 0.918
No. of measured, independent and observed [I > 2σ(I)] reflections	2811, 2140, 1715
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.098, 1.02
No. of reflections	2140
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.21

Computer programs: XSCANS (Siemens, 1995), SHELXTL (Sheldrick, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···N2ⁱ	0.86	2.10	2.959 (2)	176
C13—H13C···N1ⁱⁱ	0.96	2.57	3.339 (2)	138

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

Acknowledgements

We are grateful to the National Science Council of the Republic of China for support.

References

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