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

Abstract

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,

• a = 7.4183 (9) Å

• b = 8.2829 (10) Å

• c = 15.375 (2) Å

• β = 93.273 (1)°

• V = 943.2 (2) ų

• 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[F ² > 2σ(F ²)] = 0.039

• wR(F ²) = 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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

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.

Experimental

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 %.

Refinement

H atoms were placed geometrically and treated as riding on their parent atoms with C—H = 0.93 Å (pyridine), 0.97 Å (methylene) or 0.96 Å (methyl), and with U_iso(H) = 1.2 or 1.5U_eq(C).

Figures

Fig. 1.

Molecular structure showing 30% probability displacement ellipsoids for non-H atoms.

Crystal data

C20H24N2O4	F(000) = 380
Mr = 356.41	Dx = 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

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

Refinement

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(Fo2) + (0.0497P)2 + 0.199P] where P = (Fo2 + 2Fc2)/3
1654 reflections	(Δ/σ)max < 0.001
119 parameters	Δρmax = 0.15 e Å−3
0 restraints	Δρmin = −0.13 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x+2, −y+1, −z.