Bis(4-pyridylmeth­yl) hexa­nedioate

Yang, J.-H.; Zhang, J.-M.; Chen, Y.-X.; Diao, J.-Z.; Peng, Z.

doi:10.1107/S1600536808014414

organic compounds

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Volume 64| Part 6| June 2008| Page o1100

doi:10.1107/S1600536808014414

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Bis(4-pyridylmethyl) hexanedioate

Jin-Hui Yang,^a Jian-Min Zhang,^a Yan-Xue Chen,^b ^* Jian-Zhi Diao ^a and Zheng Peng ^a

^aSchool of Materials Science and Engineering, Shijiazhuang Railway Institute, Shijiazhuang 050043, People's Republic of China, and ^bSchool of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, People's Republic of China
^*Correspondence e-mail: chenyanxue8010@yahoo.com.cn

(Received 8 May 2008; accepted 13 May 2008; online 17 May 2008)

The asymmetric unit of the title compound, C₁₈H₂₀N₂O₄, contains one half-molecule. The molecule lies on an inversion centre and is roughly planar, the chains between the two pyridine rings being only slightly twisted, with torsion angles ranging from 170.9 (1) to 177.2 (1)°. Weak C—H⋯O hydrogen bonds result in the formation of a three-dimensional network.

Related literature

For related literature, see: Banfi et al. (2002 ); Magden & Basel (1984 ).

Experimental

Crystal data

C₁₈H₂₀N₂O₄
M_r = 328.36
Monoclinic, P 2₁ /c
a = 9.1489 (18) Å
b = 10.164 (2) Å
c = 8.9206 (18) Å
β = 102.11 (3)°
V = 811.1 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 113 (2) K
0.12 × 0.10 × 0.08 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.979, T_max = 0.988
9823 measured reflections
1918 independent reflections
1288 reflections with I > 2σ(I)
R_int = 0.060

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.106
S = 0.98
1918 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6B⋯O2ⁱ	0.97	2.56	3.3333 (17)	137
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ) and ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808014414/dn2349sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808014414/dn2349Isup2.hkl

checkCIF report

Comment top

Hexanedioic acid dipyridin-4-ylmethyl ester is a very important intermediate in the synthesis of cephalosporins (Magden & Basel, 1984). Also, it can be used as a ligand designed for the self-assembly of coordination frameworks and architectures (Banfi et al., 2002);

The title compound is arranged around an inversion centre located in the middle of the C9-C9ⁱ bond [symmetry code:(i) 1-x, 1-y, 1-z ] (Fig. 1). The molecule is roughly planar, the chains between the two pyridyl rings being only slightly twisted with torsion angles ranging from 170.9 (1) to 177.2 (1)° .

Weak intermolecular C—H···O hydrogen bonds (Table 1) result in the formation of a three dimensionnal network

Related literature top

For related literature, see: Banfi et al. (2002); Magden & Basel (1984).

Experimental top

4-pyridinemethanol (9.82 g, 0.09 mol) and dimethyl adipate (5.22 g, 0.03 mol) were stirred with 200 ml n-octane at 343 k,then titaniun tetraisopropoxide (0.2 g) was added.The mixture was heated to 399 k, the methanol was distilled off. After stirring at this temperature for 4 h,the reaction finished. The solvent was evaporated under reduced pressure. The product was purified by chromatography on silica. Crystals of hexanedioic acid dipyridin-4-ylmethyl ester were obtained by slow evaporation of a solution of ethyl acetation at room temperature(m.p. 359 k).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. A view of the molecular structure of (I)with the atoms labelling scheme. Displacement ellopsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry code: (i) 1-x, 1-y, 1-z ]

Bis(4-pyridylmethyl) hexanedioate top

Crystal data top

C₁₈H₂₀N₂O₄	F(000) = 348
M_r = 328.36	D_x = 1.345 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2434 reflections
a = 9.1489 (18) Å	θ = 2.3–27.9°
b = 10.164 (2) Å	µ = 0.10 mm⁻¹
c = 8.9206 (18) Å	T = 113 K
β = 102.11 (3)°	Block, colorless
V = 811.1 (3) Å³	0.12 × 0.10 × 0.08 mm
Z = 2

Data collection top

Rigaku Saturn diffractometer	1918 independent reflections
Radiation source: rotating anode	1288 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.060
ω scans	θ_max = 27.9°, θ_min = 2.3°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −12→12
T_min = 0.979, T_max = 0.988	k = −13→13
9823 measured reflections	l = −11→11

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H-atom parameters constrained
S = 0.98	w = 1/[σ²(F_o²) + (0.0564P)²] where P = (F_o² + 2F_c²)/3
1918 reflections	(Δ/σ)_max < 0.001
109 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₈H₂₀N₂O₄	V = 811.1 (3) Å³
M_r = 328.36	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.1489 (18) Å	µ = 0.10 mm⁻¹
b = 10.164 (2) Å	T = 113 K
c = 8.9206 (18) Å	0.12 × 0.10 × 0.08 mm
β = 102.11 (3)°

Data collection top

Rigaku Saturn diffractometer	1918 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1288 reflections with I > 2σ(I)
T_min = 0.979, T_max = 0.988	R_int = 0.060
9823 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.107	H-atom parameters constrained
S = 0.98	Δρ_max = 0.34 e Å⁻³
1918 reflections	Δρ_min = −0.24 e Å⁻³
109 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.70599 (9)	0.51214 (8)	0.11415 (9)	0.0198 (2)
O2	0.64123 (11)	0.69241 (9)	0.22847 (10)	0.0307 (3)
N1	0.90646 (13)	0.38939 (10)	−0.35175 (12)	0.0234 (3)
C1	0.89598 (14)	0.58417 (13)	−0.20251 (14)	0.0219 (3)
H1	0.9218	0.6722	−0.1854	0.026*
C2	0.93751 (15)	0.51700 (13)	−0.32073 (15)	0.0226 (3)
H2	0.9901	0.5625	−0.3828	0.027*
C3	0.83041 (15)	0.32799 (13)	−0.25920 (15)	0.0250 (3)
H3	0.8082	0.2394	−0.2773	0.030*
C4	0.78264 (14)	0.38780 (13)	−0.13832 (14)	0.0221 (3)
H4	0.7297	0.3404	−0.0781	0.026*
C5	0.81535 (14)	0.51996 (12)	−0.10895 (13)	0.0184 (3)
C6	0.76640 (15)	0.59800 (12)	0.01395 (14)	0.0206 (3)
H6A	0.8509	0.6460	0.0727	0.025*
H6B	0.6910	0.6614	−0.0323	0.025*
C7	0.64740 (13)	0.57452 (13)	0.22139 (13)	0.0188 (3)
C8	0.59372 (14)	0.47965 (12)	0.32611 (14)	0.0200 (3)
H8A	0.6751	0.4212	0.3707	0.024*
H8B	0.5141	0.4264	0.2669	0.024*
C9	0.53658 (14)	0.54786 (11)	0.45402 (14)	0.0196 (3)
H9A	0.6193	0.5912	0.5219	0.023*
H9B	0.4647	0.6148	0.4102	0.023*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0269 (5)	0.0179 (5)	0.0184 (5)	0.0006 (4)	0.0133 (4)	0.0013 (4)
O2	0.0492 (7)	0.0193 (5)	0.0301 (6)	−0.0007 (4)	0.0230 (5)	−0.0018 (4)
N1	0.0283 (6)	0.0223 (6)	0.0218 (6)	0.0034 (5)	0.0102 (5)	−0.0005 (5)
C1	0.0242 (7)	0.0193 (7)	0.0236 (7)	0.0012 (5)	0.0081 (6)	0.0020 (6)
C2	0.0244 (7)	0.0263 (7)	0.0197 (7)	0.0016 (6)	0.0106 (6)	0.0040 (6)
C3	0.0288 (8)	0.0211 (7)	0.0263 (8)	−0.0004 (6)	0.0089 (6)	−0.0040 (6)
C4	0.0235 (7)	0.0249 (7)	0.0199 (7)	−0.0010 (5)	0.0093 (6)	0.0018 (6)
C5	0.0189 (6)	0.0216 (7)	0.0145 (6)	0.0016 (5)	0.0033 (5)	0.0012 (5)
C6	0.0283 (7)	0.0175 (7)	0.0191 (7)	−0.0018 (5)	0.0122 (6)	0.0023 (5)
C7	0.0199 (7)	0.0208 (7)	0.0168 (7)	0.0002 (5)	0.0062 (5)	−0.0028 (6)
C8	0.0240 (7)	0.0183 (6)	0.0202 (7)	−0.0005 (5)	0.0106 (5)	0.0010 (5)
C9	0.0220 (7)	0.0204 (7)	0.0187 (7)	−0.0001 (5)	0.0098 (6)	0.0005 (6)

Geometric parameters (Å, º) top

O1—C7	1.3489 (14)	C4—H4	0.9300
O1—C6	1.4398 (14)	C5—C6	1.4959 (17)
O2—C7	1.2019 (15)	C6—H6A	0.9700
N1—C3	1.3402 (16)	C6—H6B	0.9700
N1—C2	1.3441 (16)	C7—C8	1.4954 (17)
C1—C2	1.3751 (17)	C8—C9	1.5186 (17)
C1—C5	1.3874 (16)	C8—H8A	0.9700
C1—H1	0.9300	C8—H8B	0.9700
C2—H2	0.9300	C9—C9ⁱ	1.516 (2)
C3—C4	1.3860 (17)	C9—H9A	0.9700
C3—H3	0.9300	C9—H9B	0.9700
C4—C5	1.3891 (18)

C7—O1—C6	114.63 (10)	C5—C6—H6A	109.6
C3—N1—C2	115.92 (11)	O1—C6—H6B	109.6
C2—C1—C5	119.68 (12)	C5—C6—H6B	109.6
C2—C1—H1	120.2	H6A—C6—H6B	108.1
C5—C1—H1	120.2	O2—C7—O1	122.40 (11)
N1—C2—C1	123.82 (12)	O2—C7—C8	125.79 (11)
N1—C2—H2	118.1	O1—C7—C8	111.80 (11)
C1—C2—H2	118.1	C7—C8—C9	112.64 (10)
N1—C3—C4	124.35 (12)	C7—C8—H8A	109.1
N1—C3—H3	117.8	C9—C8—H8A	109.1
C4—C3—H3	117.8	C7—C8—H8B	109.1
C3—C4—C5	118.70 (11)	C9—C8—H8B	109.1
C3—C4—H4	120.6	H8A—C8—H8B	107.8
C5—C4—H4	120.6	C9ⁱ—C9—C8	111.98 (12)
C1—C5—C4	117.52 (11)	C9ⁱ—C9—H9A	109.2
C1—C5—C6	118.04 (11)	C8—C9—H9A	109.2
C4—C5—C6	124.42 (11)	C9ⁱ—C9—H9B	109.2
O1—C6—C5	110.27 (10)	C8—C9—H9B	109.2
O1—C6—H6A	109.6	H9A—C9—H9B	107.9

C1—C5—C6—O1	−170.85 (11)	O1—C7—C8—C9	176.27 (10)
C6—O1—C7—C8	−177.17 (10)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6B···O2ⁱⁱ	0.97	2.56	3.3333 (17)	137

Symmetry code: (ii) x, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₈H₂₀N₂O₄
M_r	328.36
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	113
a, b, c (Å)	9.1489 (18), 10.164 (2), 8.9206 (18)
β (°)	102.11 (3)
V (Å³)	811.1 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.979, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	9823, 1918, 1288
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.657

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.107, 0.98
No. of reflections	1918
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.24

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6B···O2ⁱ	0.97	2.56	3.3333 (17)	136.6

Symmetry code: (i) x, −y+3/2, z−1/2.

References

Banfi, S., Carlucci, L., Caruso, E., Ciani, G. & Proserpio, D. (2002). J. Chem. Soc. Dalton Trans. pp. 2714–2721. Web of Science CSD CrossRef Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Magden, A. & Basel, E. (1984). United States Patent US 4 461 898. Google Scholar
Rigaku (2005). CrystalClear. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1100

doi:10.1107/S1600536808014414

Open

access