Propane-1,3-diyl bis-(pyridine-4-carboxyl-ate).

The title compound. C(15)H(14)N(2)O(4), (I), has a gauche-gauche (O/C/C/C-O/C/C/C or GG) conformation and is a positional isomer of propane-1,3-diyl bis-(pyridine-3-carboxyl-ate), (II). The mol-ecule of (I) lies on a twofold rotation axis, which passes through the central C atom of the aliphatic chain, giving one half-mol-ecule per asymmetric unit. There is excellent agreement of the geometric parameters of (I) and (II). The most obvious differences between them are the O/C/C/C-O/C/C/C torsion angles [56.6 (2)° in (I) and 174.0 (3)/70.2 (3)° in (II) for GG and TG conformations, respectively] and the dihedral angle between the planes of the aromatic rings [80.3 (10)° in (I) and 76.5 (3)° in (II)]. The crystal structure is stabilized by weak C-H⋯ N and C-H⋯ O hydrogen bonding.

Related literature

The title compound can be used as a nucleophilic tecton in self-assembly reactions with metal centres of varying lability. For conformation definitions see: Carlucci et al. (2002 ▶). For related structures, see: Brito et al. (2010 ▶); Chatterjee et al. (2004 ▶).

Experimental

Crystal data

C15H14N2O4

M = 286.28

Monoclinic,

a = 23.022 (4) Å

b = 4.9336 (5) Å

c = 11.9604 (18) Å

β = 98.118 (13)°

V = 1344.9 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 173 K

0.18 × 0.15 × 0.09 mm

Data collection

Stoe IPDS II two-circle diffractometer

4231 measured reflections

1251 independent reflections

799 reflections with I > 2σ(I)

R int = 0.070

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.094

S = 0.87

1251 reflections

96 parameters

H-atom parameters constrained

Δρmax = 0.16 e Å−3

Δρmin = −0.21 e Å−3

Data collection: X-AREA (Stoe & Cie, 2001 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810011700/fl2297sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810011700/fl2297Isup2.hkl

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

C15H14N2O4	F(000) = 600
Mr = 286.28	Dx = 1.414 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2383 reflections
a = 23.022 (4) Å	θ = 3.5–25.9°
b = 4.9336 (5) Å	µ = 0.10 mm−1
c = 11.9604 (18) Å	T = 173 K
β = 98.118 (13)°	Plate, colourless
V = 1344.9 (3) Å3	0.18 × 0.15 × 0.09 mm
Z = 4

Stoe IPDS II two-circle diffractometer	799 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.070
graphite	θmax = 25.6°, θmin = 3.4°
ω scans	h = −22→28
4231 measured reflections	k = −5→5
1251 independent reflections	l = −14→14

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094	H-atom parameters constrained
S = 0.87	w = 1/[σ2(Fo2) + (0.0427P)2] where P = (Fo2 + 2Fc2)/3
1251 reflections	(Δ/σ)max < 0.001
96 parameters	Δρmax = 0.16 e Å−3
0 restraints	Δρmin = −0.21 e Å−3

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.

	x	y	z	Uiso*/Ueq
O1	0.43077 (7)	0.6064 (3)	0.47123 (12)	0.0356 (4)
C1	0.41465 (9)	0.5769 (4)	0.56249 (16)	0.0270 (5)
O2	0.43693 (6)	0.7138 (3)	0.65570 (11)	0.0300 (4)
C3	0.48573 (9)	0.8943 (4)	0.64276 (16)	0.0287 (5)
H3A	0.4748	1.0166	0.5775	0.034*
H3B	0.5204	0.7871	0.6291	0.034*
C4	0.5000	1.0584 (6)	0.7500	0.0292 (7)
H4	0.4661	1.1769	0.7579	0.035*
C11	0.36822 (9)	0.3801 (4)	0.58462 (16)	0.0276 (5)
C12	0.34752 (9)	0.1948 (4)	0.50109 (17)	0.0299 (5)
H12	0.3621	0.1949	0.4307	0.036*
C13	0.30531 (10)	0.0107 (4)	0.52223 (17)	0.0323 (5)
H13	0.2921	−0.1177	0.4651	0.039*
N14	0.28183 (8)	0.0018 (4)	0.61815 (14)	0.0337 (5)
C15	0.30185 (10)	0.1843 (5)	0.69753 (18)	0.0360 (5)
H15	0.2857	0.1832	0.7663	0.043*
C16	0.34464 (10)	0.3735 (4)	0.68496 (17)	0.0326 (5)
H16	0.3577	0.4971	0.7441	0.039*

	U11	U22	U33	U12	U13	U23
O1	0.0412 (9)	0.0404 (9)	0.0264 (7)	−0.0035 (8)	0.0090 (6)	−0.0045 (7)
C1	0.0279 (11)	0.0268 (11)	0.0257 (10)	0.0040 (9)	0.0018 (8)	−0.0001 (8)
O2	0.0321 (8)	0.0326 (8)	0.0247 (7)	−0.0054 (7)	0.0021 (6)	−0.0008 (6)
C3	0.0268 (11)	0.0321 (11)	0.0274 (10)	−0.0021 (9)	0.0045 (8)	0.0024 (9)
C4	0.0307 (16)	0.0280 (16)	0.0286 (14)	0.000	0.0034 (12)	0.000
C11	0.0281 (11)	0.0283 (11)	0.0256 (9)	0.0053 (9)	0.0010 (8)	0.0019 (8)
C12	0.0352 (12)	0.0314 (11)	0.0227 (9)	0.0009 (10)	0.0033 (8)	0.0007 (8)
C13	0.0338 (12)	0.0309 (11)	0.0308 (10)	−0.0012 (10)	−0.0001 (9)	−0.0029 (9)
N14	0.0343 (11)	0.0326 (10)	0.0338 (10)	−0.0010 (9)	0.0029 (8)	0.0013 (8)
C15	0.0396 (13)	0.0401 (13)	0.0294 (11)	−0.0008 (11)	0.0085 (9)	−0.0004 (10)
C16	0.0364 (13)	0.0333 (12)	0.0280 (10)	−0.0018 (10)	0.0042 (9)	−0.0050 (9)

O1—C1	1.210 (2)	C11—C12	1.388 (3)
C1—O2	1.342 (2)	C12—C13	1.379 (3)
C1—C11	1.495 (3)	C12—H12	0.9500
O2—C3	1.459 (2)	C13—N14	1.336 (3)
C3—C4	1.513 (2)	C13—H13	0.9500
C3—H3A	0.9900	N14—C15	1.342 (3)
C3—H3B	0.9900	C15—C16	1.381 (3)
C4—C3i	1.513 (2)	C15—H15	0.9500
C4—H4	0.9900	C16—H16	0.9500
C11—C16	1.386 (3)
O1—C1—O2	124.0 (2)	C12—C11—C1	118.80 (18)
O1—C1—C11	123.76 (18)	C13—C12—C11	118.75 (19)
O2—C1—C11	112.26 (17)	C13—C12—H12	120.6
C1—O2—C3	115.39 (15)	C11—C12—H12	120.6
O2—C3—C4	108.35 (15)	N14—C13—C12	124.04 (19)
O2—C3—H3A	110.0	N14—C13—H13	118.0
C4—C3—H3A	110.0	C12—C13—H13	118.0
O2—C3—H3B	110.0	C13—N14—C15	116.44 (19)
C4—C3—H3B	110.0	N14—C15—C16	123.7 (2)
H3A—C3—H3B	108.4	N14—C15—H15	118.1
C3i—C4—C3	115.3 (2)	C16—C15—H15	118.1
C3i—C4—H4	108.3	C15—C16—C11	118.88 (19)
C3—C4—H4	108.5	C15—C16—H16	120.6
C16—C11—C12	118.1 (2)	C11—C16—H16	120.6
C16—C11—C1	123.08 (18)
O1—C1—O2—C3	−3.7 (3)	C16—C11—C12—C13	−1.0 (3)
C11—C1—O2—C3	175.34 (17)	C1—C11—C12—C13	179.05 (19)
C1—O2—C3—C4	172.61 (16)	C11—C12—C13—N14	1.4 (3)
O2—C3—C4—C3i	56.56 (11)	C12—C13—N14—C15	−0.7 (3)
O1—C1—C11—C16	−171.1 (2)	C13—N14—C15—C16	−0.5 (3)
O2—C1—C11—C16	9.9 (3)	N14—C15—C16—C11	0.8 (3)
O1—C1—C11—C12	8.9 (3)	C12—C11—C16—C15	0.0 (3)
O2—C1—C11—C12	−170.21 (18)	C1—C11—C16—C15	179.9 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···N14ii	0.95	2.65	3.505 (3)	151
C15—H15···N14iii	0.95	2.72	3.496 (3)	139
C3—H3A···O1iv	0.99	2.98	3.516 (3)	115
C3—H3B···O1v	0.99	2.62	3.521 (3)	152

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13⋯N14i	0.95	2.65	3.505 (3)	151
C15—H15⋯N14ii	0.95	2.72	3.496 (3)	139
C3—H3A⋯O1iii	0.99	2.98	3.516 (3)	115
C3—H3B⋯O1iv	0.99	2.62	3.521 (3)	152

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .