Dimethyl 4,4′-(pyridine-2,6-diyl)dibenzoate

Cui, Y.; Gao, Q.; Wang, H.-H.; Wang, L.; Xie, Y.-B.

doi:10.1107/S160053681004362X

organic compounds

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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o2975

https://doi.org/10.1107/S160053681004362X

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Dimethyl 4,4′-(pyridine-2,6-diyl)dibenzoate

Yue Cui,^a Qian Gao,^a Huan-Huan Wang,^a Lin Wang ^a and Ya-Bo Xie ^a ^*

^aCollege of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124, People's Republic of China
^*Correspondence e-mail: xieyabo@bjut.edu.cn

(Received 17 October 2010; accepted 26 October 2010; online 31 October 2010)

The title molecule, C₂₁H₁₇NO₄, reveals axial symmetry, with the pyridine N atom located on a crystallographic twofold axis. The molecule is dish-shaped, with dihedral angles between the benzene and pyridine rings of 24.643 (1) and 24.797 (1)°, respectively. The –COO plane and the benzene ring are almost coplanar [dihedral angle = 5.286 (1)°].

Related literature

For applications of the title compound, see: Boyle et al. (2010 ). For the synthesis, see: Li & Zhou (2009 ).

Experimental

Crystal data

C₂₁H₁₇NO₄
M_r = 347.36
Orthorhombic, C m c 2₁
a = 34.296 (10) Å
b = 7.401 (2) Å
c = 6.623 (2) Å
V = 1681.1 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.60 × 0.40 × 0.36 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.945, T_max = 0.966
7265 measured reflections
2264 independent reflections
2151 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.109
S = 1.05
2264 reflections
122 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; 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: https://doi.org/10.1107/S160053681004362X/kp2283sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681004362X/kp2283Isup2.hkl

checkCIF report

Comment top

Pyridine-type compounds and their derivatives have been extensively investigated because of their wide application for the synthesis of various complex compounds (Boyle et al., 2010). Herein, we report the crystal structure of the title compound (Fig. 1), dimethyl 4,4'-pyridine-2,6-diyldibenzoate.

The title compound, C₂₁H₁₇NO₄, was synthesised by the reaction of 2,6-dibromopyridine and 4-methoxycarbonylphenylboronic acid. The molecule reveals a crystallographic twofold axis with the N atom lying on a special position - the rotation twofold axis. The dihedral angles between the benzene ring and the pyridine ring are 24.643 (1)° and 24.797 (1)°, respectively. The –COO plane and the benzene ring are almost coplanar, and the dihedral angles are 5.363 (1)° and 4.794 (1)°, respectively.

Related literature top

For the application of the title compound, see: Boyle et al. (2010). For the synthesis of the title compound, see: Li & Zhou (2009).

Experimental top

The title compound was synthesised according to the reported procedure (Li & Zhou, 2009). Colourless single crystals suitable for X-ray diffraction were obtained by recrystallisation from a solvents mixture of ethyl acetate and hexane.

Structure description top

For the application of the title compound, see: Boyle et al. (2010). For the synthesis of the title compound, see: Li & Zhou (2009).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level, H atoms are shown as small circles of arbitrary radius. Symmetry code: A = -x, y, z.

Dimethyl 4,4'-(pyridine-2,6-diyl)dibenzoate top

Crystal data top

C₂₁H₁₇NO₄	F(000) = 728
M_r = 347.36	D_x = 1.372 Mg m⁻³
Orthorhombic, Cmc2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2c -2	Cell parameters from 4869 reflections
a = 34.296 (10) Å	θ = 2.4–30.5°
b = 7.401 (2) Å	µ = 0.10 mm⁻¹
c = 6.623 (2) Å	T = 296 K
V = 1681.1 (9) Å³	Block, colourless
Z = 4	0.60 × 0.40 × 0.36 mm

Data collection top

Bruker APEXII CCD diffractometer	2264 independent reflections
Radiation source: fine-focus sealed tube	2151 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
φ and ω scans	θ_max = 30.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −48→44
T_min = 0.945, T_max = 0.966	k = −10→10
7265 measured reflections	l = −9→7

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.069P)² + 0.231P] where P = (F_o² + 2F_c²)/3
2264 reflections	(Δ/σ)_max < 0.001
122 parameters	Δρ_max = 0.25 e Å⁻³
1 restraint	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₂₁H₁₇NO₄	V = 1681.1 (9) Å³
M_r = 347.36	Z = 4
Orthorhombic, Cmc2₁	Mo Kα radiation
a = 34.296 (10) Å	µ = 0.10 mm⁻¹
b = 7.401 (2) Å	T = 296 K
c = 6.623 (2) Å	0.60 × 0.40 × 0.36 mm

Data collection top

Bruker APEXII CCD diffractometer	2264 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	2151 reflections with I > 2σ(I)
T_min = 0.945, T_max = 0.966	R_int = 0.035
7265 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	1 restraint
wR(F²) = 0.109	H-atom parameters constrained
S = 1.05	Δρ_max = 0.25 e Å⁻³
2264 reflections	Δρ_min = −0.16 e Å⁻³
122 parameters

Special details top

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
O1	0.20583 (3)	0.17226 (19)	0.8336 (2)	0.0693 (4)
N1	0.0000	0.24751 (18)	0.5426 (2)	0.0316 (3)
C1	0.17708 (3)	0.24851 (18)	0.8930 (2)	0.0429 (3)
O2	0.17487 (3)	0.32976 (15)	1.0717 (2)	0.0535 (3)
C2	0.13992 (3)	0.25470 (16)	0.77804 (19)	0.0360 (3)
C3	0.13855 (4)	0.16771 (18)	0.5923 (2)	0.0424 (3)
H3	0.1609	0.1139	0.5408	0.051*
C4	0.10431 (4)	0.16036 (18)	0.4834 (2)	0.0416 (3)
H4	0.1038	0.1010	0.3597	0.050*
C5	0.07037 (3)	0.24139 (14)	0.55745 (17)	0.0323 (2)
C6	0.07197 (3)	0.33053 (14)	0.74267 (19)	0.0328 (2)
H6	0.0496	0.3854	0.7936	0.039*
C7	0.10641 (3)	0.33846 (14)	0.8520 (2)	0.0343 (2)
H7	0.1072	0.3996	0.9746	0.041*
C8	0.03362 (3)	0.23143 (15)	0.44012 (18)	0.0330 (3)
C9	0.03455 (4)	0.20276 (19)	0.2306 (2)	0.0405 (3)
H9	0.0583	0.1927	0.1634	0.049*
C10	0.0000	0.1898 (3)	0.1258 (3)	0.0439 (4)
H10	0.0000	0.1725	−0.0133	0.053*
C11	0.21015 (5)	0.3231 (3)	1.1922 (3)	0.0644 (5)
H11A	0.2192	0.2006	1.2007	0.097*
H11B	0.2048	0.3677	1.3254	0.097*
H11C	0.2299	0.3967	1.1303	0.097*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0334 (4)	0.0929 (10)	0.0817 (9)	0.0119 (5)	0.0066 (5)	−0.0199 (8)
N1	0.0386 (6)	0.0284 (6)	0.0279 (7)	0.000	0.000	−0.0001 (5)
C1	0.0309 (5)	0.0434 (7)	0.0545 (9)	−0.0021 (4)	0.0080 (5)	−0.0022 (5)
O2	0.0386 (4)	0.0624 (7)	0.0597 (7)	0.0080 (4)	−0.0070 (5)	−0.0122 (5)
C2	0.0305 (4)	0.0341 (6)	0.0435 (7)	−0.0025 (4)	0.0093 (4)	−0.0004 (4)
C3	0.0374 (5)	0.0446 (7)	0.0453 (8)	0.0031 (5)	0.0150 (5)	−0.0053 (5)
C4	0.0450 (6)	0.0423 (6)	0.0374 (7)	0.0019 (5)	0.0111 (5)	−0.0080 (5)
C5	0.0371 (5)	0.0294 (5)	0.0305 (6)	−0.0024 (4)	0.0065 (5)	0.0006 (4)
C6	0.0316 (5)	0.0340 (5)	0.0328 (6)	0.0008 (4)	0.0076 (4)	−0.0022 (4)
C7	0.0329 (5)	0.0356 (5)	0.0344 (6)	−0.0004 (4)	0.0060 (5)	−0.0053 (4)
C8	0.0419 (6)	0.0275 (5)	0.0298 (6)	−0.0016 (4)	0.0034 (4)	0.0001 (4)
C9	0.0513 (7)	0.0404 (6)	0.0297 (6)	−0.0019 (5)	0.0072 (5)	−0.0001 (5)
C10	0.0669 (12)	0.0405 (9)	0.0244 (8)	0.000	0.000	−0.0014 (7)
C11	0.0470 (7)	0.0742 (11)	0.0722 (13)	0.0074 (8)	−0.0192 (8)	−0.0093 (9)

Geometric parameters (Å, º) top

O1—C1	1.2025 (16)	C5—C8	1.4823 (15)
N1—C8ⁱ	1.3433 (13)	C6—C7	1.3866 (17)
N1—C8	1.3433 (13)	C6—H6	0.9300
C1—O2	1.3294 (19)	C7—H7	0.9300
C1—C2	1.4854 (17)	C8—C9	1.4041 (18)
O2—C11	1.4503 (18)	C9—C10	1.3768 (17)
C2—C3	1.3895 (19)	C9—H9	0.9300
C2—C7	1.3945 (14)	C10—C9ⁱ	1.3768 (17)
C3—C4	1.379 (2)	C10—H10	0.9300
C3—H3	0.9300	C11—H11A	0.9600
C4—C5	1.3981 (16)	C11—H11B	0.9600
C4—H4	0.9300	C11—H11C	0.9600
C5—C6	1.3940 (17)

C8ⁱ—N1—C8	118.29 (15)	C5—C6—H6	119.6
O1—C1—O2	123.39 (14)	C6—C7—C2	119.98 (11)
O1—C1—C2	123.39 (14)	C6—C7—H7	120.0
O2—C1—C2	113.18 (10)	C2—C7—H7	120.0
C1—O2—C11	115.28 (12)	N1—C8—C9	122.14 (12)
C3—C2—C7	119.28 (11)	N1—C8—C5	117.42 (11)
C3—C2—C1	117.95 (11)	C9—C8—C5	120.42 (11)
C7—C2—C1	122.73 (12)	C10—C9—C8	119.31 (13)
C4—C3—C2	120.65 (11)	C10—C9—H9	120.3
C4—C3—H3	119.7	C8—C9—H9	120.3
C2—C3—H3	119.7	C9ⁱ—C10—C9	118.78 (17)
C3—C4—C5	120.59 (12)	C9ⁱ—C10—H10	120.6
C3—C4—H4	119.7	C9—C10—H10	120.6
C5—C4—H4	119.7	O2—C11—H11A	109.5
C6—C5—C4	118.59 (11)	O2—C11—H11B	109.5
C6—C5—C8	121.23 (9)	H11A—C11—H11B	109.5
C4—C5—C8	120.18 (10)	O2—C11—H11C	109.5
C7—C6—C5	120.88 (10)	H11A—C11—H11C	109.5
C7—C6—H6	119.6	H11B—C11—H11C	109.5

O1—C1—O2—C11	0.9 (2)	C5—C6—C7—C2	−0.78 (16)
C2—C1—O2—C11	178.41 (13)	C3—C2—C7—C6	1.58 (17)
O1—C1—C2—C3	0.0 (2)	C1—C2—C7—C6	−176.21 (11)
O2—C1—C2—C3	−177.60 (12)	C8ⁱ—N1—C8—C9	1.5 (2)
O1—C1—C2—C7	177.77 (15)	C8ⁱ—N1—C8—C5	−177.32 (8)
O2—C1—C2—C7	0.22 (18)	C6—C5—C8—N1	−24.37 (16)
C7—C2—C3—C4	−1.41 (18)	C4—C5—C8—N1	155.51 (12)
C1—C2—C3—C4	176.48 (12)	C6—C5—C8—C9	156.81 (12)
C2—C3—C4—C5	0.4 (2)	C4—C5—C8—C9	−23.31 (16)
C3—C4—C5—C6	0.39 (18)	N1—C8—C9—C10	−0.29 (19)
C3—C4—C5—C8	−179.49 (11)	C5—C8—C9—C10	178.47 (14)
C4—C5—C6—C7	−0.21 (16)	C8—C9—C10—C9ⁱ	−0.9 (3)
C8—C5—C6—C7	179.67 (10)

Symmetry code: (i) −x, y, z.

Experimental details

Crystal data
Chemical formula	C₂₁H₁₇NO₄
M_r	347.36
Crystal system, space group	Orthorhombic, Cmc2₁
Temperature (K)	296
a, b, c (Å)	34.296 (10), 7.401 (2), 6.623 (2)
V (Å³)	1681.1 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.60 × 0.40 × 0.36

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.945, 0.966
No. of measured, independent and observed [I > 2σ(I)] reflections	7265, 2264, 2151
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.713

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.109, 1.05
No. of reflections	2264
No. of parameters	122
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.16

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant No. 21075114), the Science and Technology Development Project of Beijing Education Committee (grant No. KM200910005025) and the Special Environmental Protection Fund for Public Welfare (project No. 201009015).

References

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