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ISSN: 2056-9890

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

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[Boyle, T. J., Ottley, L. M. & Raymond, R. (2010). J. Coord. Chem., 63, 545-557.]). For the synthesis, see: Li & Zhou (2009[Li, J. R. & Zhou, H. C. (2009). Angew. Chem. Int. Ed. A48, 1-5.]).

[Scheme 1]

Experimental

Crystal data
  • C21H17NO4

  • Mr = 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[Bruker (1998). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.945, Tmax = 0.966

  • 7265 measured reflections

  • 2264 independent reflections

  • 2151 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.25 e Å−3

  • Δρmin = −0.16 e Å−3

Data collection: SMART (Bruker, 1998[Bruker (1998). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 1998[Bruker (1998). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


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.

Refinement top

All H atoms were placed in calculated positions with C—H = 0.93–0.96 Å, and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmethyl).

Structure description 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.

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
[Figure 1] 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
C21H17NO4F(000) = 728
Mr = 347.36Dx = 1.372 Mg m3
Orthorhombic, Cmc21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2c -2Cell parameters from 4869 reflections
a = 34.296 (10) Åθ = 2.4–30.5°
b = 7.401 (2) ŵ = 0.10 mm1
c = 6.623 (2) ÅT = 296 K
V = 1681.1 (9) Å3Block, colourless
Z = 40.60 × 0.40 × 0.36 mm
Data collection top
Bruker APEXII CCD
diffractometer
2264 independent reflections
Radiation source: fine-focus sealed tube2151 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.035
φ and ω scansθmax = 30.5°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Bruker, 1998)
h = 4844
Tmin = 0.945, Tmax = 0.966k = 1010
7265 measured reflectionsl = 97
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.069P)2 + 0.231P]
where P = (Fo2 + 2Fc2)/3
2264 reflections(Δ/σ)max < 0.001
122 parametersΔρmax = 0.25 e Å3
1 restraintΔρmin = 0.16 e Å3
Crystal data top
C21H17NO4V = 1681.1 (9) Å3
Mr = 347.36Z = 4
Orthorhombic, Cmc21Mo Kα radiation
a = 34.296 (10) ŵ = 0.10 mm1
b = 7.401 (2) ÅT = 296 K
c = 6.623 (2) Å0.60 × 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)
Tmin = 0.945, Tmax = 0.966Rint = 0.035
7265 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0371 restraint
wR(F2) = 0.109H-atom parameters constrained
S = 1.05Δρmax = 0.25 e Å3
2264 reflectionsΔρmin = 0.16 e Å3
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
xyzUiso*/Ueq
O10.20583 (3)0.17226 (19)0.8336 (2)0.0693 (4)
N10.00000.24751 (18)0.5426 (2)0.0316 (3)
C10.17708 (3)0.24851 (18)0.8930 (2)0.0429 (3)
O20.17487 (3)0.32976 (15)1.0717 (2)0.0535 (3)
C20.13992 (3)0.25470 (16)0.77804 (19)0.0360 (3)
C30.13855 (4)0.16771 (18)0.5923 (2)0.0424 (3)
H30.16090.11390.54080.051*
C40.10431 (4)0.16036 (18)0.4834 (2)0.0416 (3)
H40.10380.10100.35970.050*
C50.07037 (3)0.24139 (14)0.55745 (17)0.0323 (2)
C60.07197 (3)0.33053 (14)0.74267 (19)0.0328 (2)
H60.04960.38540.79360.039*
C70.10641 (3)0.33846 (14)0.8520 (2)0.0343 (2)
H70.10720.39960.97460.041*
C80.03362 (3)0.23143 (15)0.44012 (18)0.0330 (3)
C90.03455 (4)0.20276 (19)0.2306 (2)0.0405 (3)
H90.05830.19270.16340.049*
C100.00000.1898 (3)0.1258 (3)0.0439 (4)
H100.00000.17250.01330.053*
C110.21015 (5)0.3231 (3)1.1922 (3)0.0644 (5)
H11A0.21920.20061.20070.097*
H11B0.20480.36771.32540.097*
H11C0.22990.39671.13030.097*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0334 (4)0.0929 (10)0.0817 (9)0.0119 (5)0.0066 (5)0.0199 (8)
N10.0386 (6)0.0284 (6)0.0279 (7)0.0000.0000.0001 (5)
C10.0309 (5)0.0434 (7)0.0545 (9)0.0021 (4)0.0080 (5)0.0022 (5)
O20.0386 (4)0.0624 (7)0.0597 (7)0.0080 (4)0.0070 (5)0.0122 (5)
C20.0305 (4)0.0341 (6)0.0435 (7)0.0025 (4)0.0093 (4)0.0004 (4)
C30.0374 (5)0.0446 (7)0.0453 (8)0.0031 (5)0.0150 (5)0.0053 (5)
C40.0450 (6)0.0423 (6)0.0374 (7)0.0019 (5)0.0111 (5)0.0080 (5)
C50.0371 (5)0.0294 (5)0.0305 (6)0.0024 (4)0.0065 (5)0.0006 (4)
C60.0316 (5)0.0340 (5)0.0328 (6)0.0008 (4)0.0076 (4)0.0022 (4)
C70.0329 (5)0.0356 (5)0.0344 (6)0.0004 (4)0.0060 (5)0.0053 (4)
C80.0419 (6)0.0275 (5)0.0298 (6)0.0016 (4)0.0034 (4)0.0001 (4)
C90.0513 (7)0.0404 (6)0.0297 (6)0.0019 (5)0.0072 (5)0.0001 (5)
C100.0669 (12)0.0405 (9)0.0244 (8)0.0000.0000.0014 (7)
C110.0470 (7)0.0742 (11)0.0722 (13)0.0074 (8)0.0192 (8)0.0093 (9)
Geometric parameters (Å, º) top
O1—C11.2025 (16)C5—C81.4823 (15)
N1—C8i1.3433 (13)C6—C71.3866 (17)
N1—C81.3433 (13)C6—H60.9300
C1—O21.3294 (19)C7—H70.9300
C1—C21.4854 (17)C8—C91.4041 (18)
O2—C111.4503 (18)C9—C101.3768 (17)
C2—C31.3895 (19)C9—H90.9300
C2—C71.3945 (14)C10—C9i1.3768 (17)
C3—C41.379 (2)C10—H100.9300
C3—H30.9300C11—H11A0.9600
C4—C51.3981 (16)C11—H11B0.9600
C4—H40.9300C11—H11C0.9600
C5—C61.3940 (17)
C8i—N1—C8118.29 (15)C5—C6—H6119.6
O1—C1—O2123.39 (14)C6—C7—C2119.98 (11)
O1—C1—C2123.39 (14)C6—C7—H7120.0
O2—C1—C2113.18 (10)C2—C7—H7120.0
C1—O2—C11115.28 (12)N1—C8—C9122.14 (12)
C3—C2—C7119.28 (11)N1—C8—C5117.42 (11)
C3—C2—C1117.95 (11)C9—C8—C5120.42 (11)
C7—C2—C1122.73 (12)C10—C9—C8119.31 (13)
C4—C3—C2120.65 (11)C10—C9—H9120.3
C4—C3—H3119.7C8—C9—H9120.3
C2—C3—H3119.7C9i—C10—C9118.78 (17)
C3—C4—C5120.59 (12)C9i—C10—H10120.6
C3—C4—H4119.7C9—C10—H10120.6
C5—C4—H4119.7O2—C11—H11A109.5
C6—C5—C4118.59 (11)O2—C11—H11B109.5
C6—C5—C8121.23 (9)H11A—C11—H11B109.5
C4—C5—C8120.18 (10)O2—C11—H11C109.5
C7—C6—C5120.88 (10)H11A—C11—H11C109.5
C7—C6—H6119.6H11B—C11—H11C109.5
O1—C1—O2—C110.9 (2)C5—C6—C7—C20.78 (16)
C2—C1—O2—C11178.41 (13)C3—C2—C7—C61.58 (17)
O1—C1—C2—C30.0 (2)C1—C2—C7—C6176.21 (11)
O2—C1—C2—C3177.60 (12)C8i—N1—C8—C91.5 (2)
O1—C1—C2—C7177.77 (15)C8i—N1—C8—C5177.32 (8)
O2—C1—C2—C70.22 (18)C6—C5—C8—N124.37 (16)
C7—C2—C3—C41.41 (18)C4—C5—C8—N1155.51 (12)
C1—C2—C3—C4176.48 (12)C6—C5—C8—C9156.81 (12)
C2—C3—C4—C50.4 (2)C4—C5—C8—C923.31 (16)
C3—C4—C5—C60.39 (18)N1—C8—C9—C100.29 (19)
C3—C4—C5—C8179.49 (11)C5—C8—C9—C10178.47 (14)
C4—C5—C6—C70.21 (16)C8—C9—C10—C9i0.9 (3)
C8—C5—C6—C7179.67 (10)
Symmetry code: (i) x, y, z.

Experimental details

Crystal data
Chemical formulaC21H17NO4
Mr347.36
Crystal system, space groupOrthorhombic, Cmc21
Temperature (K)296
a, b, c (Å)34.296 (10), 7.401 (2), 6.623 (2)
V3)1681.1 (9)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.60 × 0.40 × 0.36
Data collection
DiffractometerBruker APEXII CCD
Absorption correctionMulti-scan
(SADABS; Bruker, 1998)
Tmin, Tmax0.945, 0.966
No. of measured, independent and
observed [I > 2σ(I)] reflections
7265, 2264, 2151
Rint0.035
(sin θ/λ)max1)0.713
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.109, 1.05
No. of reflections2264
No. of parameters122
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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

First citationBoyle, T. J., Ottley, L. M. & Raymond, R. (2010). J. Coord. Chem., 63, 545–557.  Web of Science CSD CrossRef CAS Google Scholar
First citationBruker (1998). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationLi, J. R. & Zhou, H. C. (2009). Angew. Chem. Int. Ed. A48, 1–5.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890
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