Dibutyl 2,2′-bipyridine-4,4′-dicarboxyl­ate

Li, Q.; Zhang, R.; Shi, Y.

doi:10.1107/S1600536809003997

organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page o478

doi:10.1107/S1600536809003997

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Dibutyl 2,2′-bipyridine-4,4′-dicarboxylate

Qianli Li,^a Rufen Zhang ^b ^* and Yang Shi ^b

^aCollege of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China, and ^bDepartment of Chemistry, Liaocheng University, Liaocheng 252059, People's Republic of China
^*Correspondence e-mail: macl@lcu.edu.cn

(Received 3 January 2009; accepted 3 February 2009; online 6 February 2009)

In the title compound, C₂₀H₂₄N₂O₄, the molecule lies on a centre of symmetry and is approximately planar (r.m.s. deviation= 0.013 Å for 26 non-H atoms). The carboxylate group is inclined slightly to the neighbouring pyridine ring, forming a dihedral angle of 4.37 (2)°. The molecules form stacks with an interplanar separation of 3.547 (1) Å.

Related literature

For related structures, see: Stocco et al. (1996 ); Tynan et al. (2003 ); Fujihara et al. (2004 ).

Experimental

Crystal data

C₂₀H₂₄N₂O₄
M_r = 356.41
Monoclinic, P 2₁ /c
a = 7.4183 (9) Å
b = 8.2829 (10) Å
c = 15.375 (2) Å
β = 93.273 (1)°
V = 943.2 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 (2) K
0.40 × 0.30 × 0.15 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.966, T_max = 0.987
4552 measured reflections
1654 independent reflections
1135 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.115
S = 1.03
1654 reflections
119 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); 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: 10.1107/S1600536809003997/bi2343sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809003997/bi2343Isup2.hkl

checkCIF report

Comment top

The crystal structure of 2,2'-bipyridine-4,4'-dicarboxylic acid (H₂dcbp) has been reported by Tynan et al. (2003), and a polymeric structure contaning trimethyltin has been reported by Stocco et al. (1996). Herein, we have reacted H₂dcbp with tri-n-butyltin chloride. Unexpectedly, we obtained the centrosymmetric title compound only. The C2—N1—C6 bond angle of 117.47 (15)° is similar to those for the free pyridine (Fujihara et al., 2004). The dihedral angle between the pyridine ring and the carboxylate group [C1,O1,O2] is 4.37 (2)°. The bond lengths of C1—O1 and C7—O1 are 1.332 (2) and 1.458 (2) Å, respectively.

Related literature top

For related structures, see: Stocco et al. (1996); Tynan et al. (2003); Fujihara et al., (2004).

Experimental top

The reaction was carried out under a nitrogen atmosphere. 2,2'-Bipyridine-4,4'-dicarboxylic acid (1 mmol) and sodium ethoxide (2 mmol) were added to a stirred solution of benzene (30 ml) in a Schlenk flask and stirred for 0.5 h. Tri-n-butyltin chloride (2 mmol) was then added and the reaction mixture was stirred for 12 h at 353 K. The resulting clear solution was evaporated under vacuum. The product was crystallized from dichloromethane to yield colourless blocks (yield 83%. m.p. 435 K). Elemental analysis calculated: C, 67.10; H, 6.79; N, 7.86 %; found: C, 66.92; H, 6.95; N, 7.59 %.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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. Molecular structure showing 30% probability displacement ellipsoids for non-H atoms.

Dibutyl 2,2'-bipyridine-4,4'-dicarboxylate top

Crystal data top

C₂₀H₂₄N₂O₄	F(000) = 380
M_r = 356.41	D_x = 1.255 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1638 reflections
a = 7.4183 (9) Å	θ = 2.7–26.7°
b = 8.2829 (10) Å	µ = 0.09 mm⁻¹
c = 15.375 (2) Å	T = 298 K
β = 93.273 (1)°	Block, colorless
V = 943.2 (2) Å³	0.40 × 0.30 × 0.15 mm
Z = 2

Data collection top

Bruker SMART CCD diffractometer	1654 independent reflections
Radiation source: fine-focus sealed tube	1135 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −8→8
T_min = 0.966, T_max = 0.987	k = −9→8
4552 measured reflections	l = −18→18

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0497P)² + 0.199P] where P = (F_o² + 2F_c²)/3
1654 reflections	(Δ/σ)_max < 0.001
119 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.13 e Å⁻³

Crystal data top

C₂₀H₂₄N₂O₄	V = 943.2 (2) Å³
M_r = 356.41	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.4183 (9) Å	µ = 0.09 mm⁻¹
b = 8.2829 (10) Å	T = 298 K
c = 15.375 (2) Å	0.40 × 0.30 × 0.15 mm
β = 93.273 (1)°

Data collection top

Bruker SMART CCD diffractometer	1654 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1135 reflections with I > 2σ(I)
T_min = 0.966, T_max = 0.987	R_int = 0.021
4552 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 1.03	Δρ_max = 0.15 e Å⁻³
1654 reflections	Δρ_min = −0.13 e Å⁻³
119 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
N1	0.8610 (2)	0.42720 (18)	−0.09153 (9)	0.0544 (4)
O1	0.38773 (17)	0.20544 (16)	0.09033 (7)	0.0619 (4)
O2	0.57083 (19)	0.32666 (19)	0.19126 (8)	0.0755 (5)
C1	0.5333 (2)	0.2904 (2)	0.11660 (11)	0.0539 (5)
C2	0.9120 (2)	0.45867 (19)	−0.00815 (10)	0.0451 (4)
C3	0.8062 (2)	0.4163 (2)	0.06010 (10)	0.0481 (4)
H3	0.8437	0.4419	0.1172	0.058*
C4	0.6451 (2)	0.3358 (2)	0.04254 (10)	0.0469 (4)
C5	0.5929 (2)	0.3018 (2)	−0.04371 (11)	0.0540 (5)
H5	0.4857	0.2474	−0.0581	0.065*
C6	0.7040 (3)	0.3510 (2)	−0.10735 (11)	0.0588 (5)
H6	0.6674	0.3297	−0.1651	0.071*
C7	0.2671 (3)	0.1586 (3)	0.15756 (12)	0.0706 (6)
H7A	0.2245	0.2538	0.1869	0.085*
H7B	0.3307	0.0905	0.2005	0.085*
C8	0.1112 (2)	0.0691 (2)	0.11506 (11)	0.0567 (5)
H8A	0.1554	−0.0272	0.0873	0.068*
H8B	0.0530	0.1364	0.0701	0.068*
C9	−0.0258 (3)	0.0211 (3)	0.17920 (13)	0.0760 (6)
H9A	−0.0695	0.1177	0.2067	0.091*
H9B	0.0335	−0.0451	0.2244	0.091*
C10	−0.1854 (3)	−0.0711 (3)	0.13862 (14)	0.0768 (6)
H10A	−0.2392	−0.0103	0.0907	0.115*
H10B	−0.2729	−0.0876	0.1814	0.115*
H10C	−0.1455	−0.1737	0.1180	0.115*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0561 (9)	0.0655 (10)	0.0412 (8)	−0.0060 (8)	−0.0003 (7)	−0.0020 (7)
O1	0.0569 (8)	0.0808 (9)	0.0486 (7)	−0.0149 (7)	0.0077 (6)	0.0001 (6)
O2	0.0741 (10)	0.1073 (12)	0.0448 (7)	−0.0210 (8)	0.0004 (7)	−0.0002 (7)
C1	0.0511 (11)	0.0601 (12)	0.0500 (11)	−0.0004 (9)	−0.0006 (9)	0.0040 (9)
C2	0.0488 (9)	0.0461 (10)	0.0402 (9)	0.0038 (8)	−0.0008 (7)	0.0024 (7)
C3	0.0500 (10)	0.0538 (11)	0.0396 (9)	0.0026 (8)	−0.0048 (8)	0.0012 (8)
C4	0.0467 (10)	0.0489 (10)	0.0449 (9)	0.0053 (8)	0.0012 (7)	0.0029 (8)
C5	0.0516 (11)	0.0598 (11)	0.0499 (10)	−0.0042 (9)	−0.0028 (8)	−0.0042 (9)
C6	0.0627 (12)	0.0733 (13)	0.0396 (9)	−0.0066 (10)	−0.0036 (9)	−0.0054 (9)
C7	0.0682 (13)	0.0945 (16)	0.0497 (11)	−0.0170 (11)	0.0091 (10)	0.0039 (11)
C8	0.0573 (11)	0.0626 (12)	0.0506 (10)	−0.0001 (9)	0.0064 (9)	0.0042 (9)
C9	0.0731 (14)	0.1050 (17)	0.0507 (11)	−0.0187 (13)	0.0097 (10)	0.0063 (11)
C10	0.0684 (14)	0.0923 (16)	0.0705 (13)	−0.0141 (12)	0.0096 (11)	0.0132 (12)

Geometric parameters (Å, º) top

N1—C6	1.335 (2)	C6—H6	0.930
N1—C2	1.341 (2)	C7—C8	1.493 (3)
O1—C1	1.332 (2)	C7—H7A	0.970
O1—C7	1.458 (2)	C7—H7B	0.970
O2—C1	1.204 (2)	C8—C9	1.509 (3)
C1—C4	1.495 (2)	C8—H8A	0.970
C2—C3	1.391 (2)	C8—H8B	0.970
C2—C2ⁱ	1.483 (3)	C9—C10	1.513 (3)
C3—C4	1.381 (2)	C9—H9A	0.970
C3—H3	0.930	C9—H9B	0.970
C4—C5	1.389 (2)	C10—H10A	0.960
C5—C6	1.377 (2)	C10—H10B	0.960
C5—H5	0.930	C10—H10C	0.960

C6—N1—C2	117.47 (15)	C8—C7—H7A	110.0
C1—O1—C7	116.43 (14)	O1—C7—H7B	110.0
O2—C1—O1	124.07 (17)	C8—C7—H7B	110.0
O2—C1—C4	123.74 (17)	H7A—C7—H7B	108.4
O1—C1—C4	112.18 (15)	C7—C8—C9	112.24 (16)
N1—C2—C3	122.14 (15)	C7—C8—H8A	109.2
N1—C2—C2ⁱ	116.64 (18)	C9—C8—H8A	109.2
C3—C2—C2ⁱ	121.23 (17)	C7—C8—H8B	109.2
C4—C3—C2	119.56 (15)	C9—C8—H8B	109.2
C4—C3—H3	120.2	H8A—C8—H8B	107.9
C2—C3—H3	120.2	C8—C9—C10	113.81 (17)
C3—C4—C5	118.40 (16)	C8—C9—H9A	108.8
C3—C4—C1	118.96 (15)	C10—C9—H9A	108.8
C5—C4—C1	122.64 (16)	C8—C9—H9B	108.8
C6—C5—C4	118.21 (17)	C10—C9—H9B	108.8
C6—C5—H5	120.9	H9A—C9—H9B	107.7
C4—C5—H5	120.9	C9—C10—H10A	109.5
N1—C6—C5	124.20 (16)	C9—C10—H10B	109.5
N1—C6—H6	117.9	H10A—C10—H10B	109.5
C5—C6—H6	117.9	C9—C10—H10C	109.5
O1—C7—C8	108.26 (15)	H10A—C10—H10C	109.5
O1—C7—H7A	110.0	H10B—C10—H10C	109.5

C7—O1—C1—O2	1.5 (3)	O2—C1—C4—C5	−175.64 (18)
C7—O1—C1—C4	−178.51 (15)	O1—C1—C4—C5	4.4 (2)
C6—N1—C2—C3	−0.8 (3)	C3—C4—C5—C6	−0.4 (3)
C6—N1—C2—C2ⁱ	179.14 (18)	C1—C4—C5—C6	178.98 (16)
N1—C2—C3—C4	1.5 (3)	C2—N1—C6—C5	−0.6 (3)
C2ⁱ—C2—C3—C4	−178.40 (18)	C4—C5—C6—N1	1.2 (3)
C2—C3—C4—C5	−0.9 (2)	C1—O1—C7—C8	178.49 (16)
C2—C3—C4—C1	179.76 (15)	O1—C7—C8—C9	−177.70 (17)
O2—C1—C4—C3	3.7 (3)	C7—C8—C9—C10	−179.62 (19)
O1—C1—C4—C3	−176.26 (15)

Symmetry code: (i) −x+2, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₂₀H₂₄N₂O₄
M_r	356.41
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	7.4183 (9), 8.2829 (10), 15.375 (2)
β (°)	93.273 (1)
V (Å³)	943.2 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.40 × 0.30 × 0.15

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.966, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	4552, 1654, 1135
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.115, 1.03
No. of reflections	1654
No. of parameters	119
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.13

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors thank the National Natural Science Foundation of China (20741008) for financial support.

References

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