



Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810011700/fl2297sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536810011700/fl2297Isup2.hkl |
CCDC reference: 777932
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean
(C-C) = 0.003 Å
- R factor = 0.043
- wR factor = 0.094
- Data-to-parameter ratio = 13.0
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT480_ALERT_4_B Long H...A H-Bond Reported H3A .. O1 .. 2.98 Ang.
Alert level C PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) ..... 1 PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 3 PLAT480_ALERT_4_C Long H...A H-Bond Reported H13 .. N14 .. 2.65 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H15 .. N14 .. 2.72 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H3B .. O1 .. 2.62 Ang. PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 3
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 5 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Isonicotinic acid (15 g, 0.122 mol) was stirred in SOCl2 (40 ml) in the presence of DMF (0.6 ml) at 60°C for 12 h. Excess thionyl chloride was removed in vacuo. Dried 1,3-Propanediol (4.9 ml, 0.061 mol) was added. After the evolution of hydrogen chloride ended, the mixture was heated at 110°C for 2 h. The mixture was then dissolved in water, and NH4OH was added. After filtration, recrystallization in ethyl acetate gave colorless crystals suitable for X-ray analysis. Yield 8.23 g(24%). Analysis calculated for C15H14N2O4:C: 62.9, H: 4.89, N: 9.68; found: C: 62.45, H: 4.85, N: 9.85. IR (KBr, cm-1):(C=O) 1727 s, (C=C) 1596 s, (Ar C—C, C=N) 1408 s, (C—O) 1278 m.
H atoms were placed in idealized positions and treated as riding atoms with C—H distances in the range 0.95-0.99 Å and Uiso(H) = 1.2Ueq(C).
The propanediyl group can adopt four possible conformations: trans-trans (TT), trans-gauche (TG), gauche-gauche (GG), and gauche-gauche' (GG') (Carlucci et al., 2002). The title compound C15H14N2O4, (I) has a gauche-gauche (GG) conformation and is a positional isomer of the previously reported propane-1,3-diyl bis(pyridine-3-carboxylate), (II), (Brito et al., 2010). Similar compounds have also been reported by Chatterjee et al. (2004).
The molecules of the title compound lie on a twofold rotation axis passing through the central carbon atom of the aliphatic chain such that one half of the title compound forms the asymmetric unit (Fig. 1). Both compounds shows excellent agreement of their geometric parameters. The most obvious differences between them are in the torsion angles O/C/C/C—O/C/C/C[56.6 (2)° in (I) and 174.0 (3);70.2 (3)° in (II), GG and TG conformation, respectively] and the angle between the planes of aromatics rings [80.3 (10)° (I) and 76.5 (3)° (II)]. The crystal structure is stabilized by weak C—H··· N and C—H··· O hydrogen bonding (Table 1, Fig. 2). The title compound can be used as a nucleophilic tecton in self-assembly reactions with metal centres of varying lability.
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).
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); 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 (Sheldrick, 2008).
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 monochromator | 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 |
C15H14N2O4 | V = 1344.9 (3) Å3 |
Mr = 286.28 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 23.022 (4) Å | µ = 0.10 mm−1 |
b = 4.9336 (5) Å | T = 173 K |
c = 11.9604 (18) Å | 0.18 × 0.15 × 0.09 mm |
β = 98.118 (13)° |
Stoe IPDS II two-circle diffractometer | 799 reflections with I > 2σ(I) |
4231 measured reflections | Rint = 0.070 |
1251 independent reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 0.87 | Δρmax = 0.16 e Å−3 |
1251 reflections | Δρmin = −0.21 e Å−3 |
96 parameters |
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) |
Symmetry code: (i) −x+1, y, −z+3/2. |
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 |
Symmetry codes: (ii) −x+1/2, −y−1/2, −z+1; (iii) −x+1/2, y+1/2, −z+3/2; (iv) −x+1, −y+2, −z+1; (v) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C15H14N2O4 |
Mr | 286.28 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 173 |
a, b, c (Å) | 23.022 (4), 4.9336 (5), 11.9604 (18) |
β (°) | 98.118 (13) |
V (Å3) | 1344.9 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.18 × 0.15 × 0.09 |
Data collection | |
Diffractometer | Stoe IPDS II two-circle |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4231, 1251, 799 |
Rint | 0.070 |
(sin θ/λ)max (Å−1) | 0.608 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.094, 0.87 |
No. of reflections | 1251 |
No. of parameters | 96 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.16, −0.21 |
Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13···N14i | 0.95 | 2.65 | 3.505 (3) | 150.6 |
C15—H15···N14ii | 0.95 | 2.72 | 3.496 (3) | 139.3 |
C3—H3A···O1iii | 0.99 | 2.98 | 3.516 (3) | 115.1 |
C3—H3B···O1iv | 0.99 | 2.62 | 3.521 (3) | 151.7 |
Symmetry codes: (i) −x+1/2, −y−1/2, −z+1; (ii) −x+1/2, y+1/2, −z+3/2; (iii) −x+1, −y+2, −z+1; (iv) −x+1, −y+1, −z+1. |
The propanediyl group can adopt four possible conformations: trans-trans (TT), trans-gauche (TG), gauche-gauche (GG), and gauche-gauche' (GG') (Carlucci et al., 2002). The title compound C15H14N2O4, (I) has a gauche-gauche (GG) conformation and is a positional isomer of the previously reported propane-1,3-diyl bis(pyridine-3-carboxylate), (II), (Brito et al., 2010). Similar compounds have also been reported by Chatterjee et al. (2004).
The molecules of the title compound lie on a twofold rotation axis passing through the central carbon atom of the aliphatic chain such that one half of the title compound forms the asymmetric unit (Fig. 1). Both compounds shows excellent agreement of their geometric parameters. The most obvious differences between them are in the torsion angles O/C/C/C—O/C/C/C[56.6 (2)° in (I) and 174.0 (3);70.2 (3)° in (II), GG and TG conformation, respectively] and the angle between the planes of aromatics rings [80.3 (10)° (I) and 76.5 (3)° (II)]. The crystal structure is stabilized by weak C—H··· N and C—H··· O hydrogen bonding (Table 1, Fig. 2). The title compound can be used as a nucleophilic tecton in self-assembly reactions with metal centres of varying lability.