A monoclinic modification of propane-1,3-diyl bis­­(pyridine-3-carboxyl­ate)

In the title compound, C₁₅H₁₄N₂O₄, (I), the mol­ecule lies on a twofold rotation axis which passes through the central C atom of the aliphatic chain, giving one half-mol­ecule per asymmetric unit. The structure is a monoclinic polymorph of the triclinic structure previously reported [Brito, Vallejos, Bolte & López-Rodríguez (2010). Acta Cryst. E66, o792], (II). The most obvious difference between them is the O/C/C/C—O/C/C/C torsion angle [58.2 (7)° in (I) and 173.4 (3)/70.2 (3)° in (II) for GG and TG conformations, respectively]. Another important difference is observed in the dihedral angle between the planes of the aromatic rings [86.49 (7)° for (I) and 76.4 (3)° for (II)]. The crystal structure features a weak π–π inter­action [centroid–centroid distance = 4.1397 (10)Å]; this latter kind of inter­action is not evident in the triclinic polymorph.

Related literature

For conformation definitions, see: Carlucci et al. (2002). For the structure of the triclinic polymorph, see: Brito et al. (2010a). For the synthesis and structural characterization of coordination polymers, see: Brito et al. (2010b).

Experimental

Crystal data

• C₁₅H₁₄N₂O₄

• M_r = 286.28

• Monoclinic, C 2/c

• a = 24.414 (3) Å

• b = 4.8328 (4) Å

• c = 11.5667 (14) Å

• β = 100.671 (10)°

• V = 1341.1 (3) ų

• Z = 4

• Mo Kα radiation

• μ = 0.11 mm⁻¹

• T = 173 K

• 0.35 × 0.33 × 0.13 mm

Data collection

• Stoe IPDS II two-circle diffractometer

• 3193 measured reflections

• 1249 independent reflections

• 939 reflections with I > 2σ(I)

• R_int = 0.037

Refinement

• R[F² > 2σ(F²)] = 0.033

• wR(F²) = 0.081

• S = 0.92

• 1249 reflections

• 97 parameters

• H-atom parameters constrained

• Δρ_max = 0.17 e Å⁻³

• Δρ_min = −0.14 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 in SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

S1. Comment

This paper forms part of our continuing study of the synthesis and structural characterization of coordination polymers (Brito et al., 2010b). We are particularly interested in the utility of the title compound of as a flexible ligand, and its binding modes, for the fabrication of different coordination polymers topologies. We report here the structure of a new polymorph of propane-1,3-diyl bis(pyridine-3-carboxylate) isolated during attempts to synthetize coordination polymers with silver trifluoromethanesulfonate of the ligand (Fig. 1, Table 1). In the title compound, (I) the molecule lies on a twofold rotation axis which passes through the central C atom of the aliphatic chain, giving one half-molecule per asymmetric unit. The structure is a monoclinic polymorph of the triclinic structure previously reported [Brito et al. (2010a). Acta Cryst. E66, o792], (II). There is excellent agreement between the geometric parameters of (I) and (II). The propanedyl group can adopt four possible conformations: trans-trans (TT), trans-gauche (TG), gauche-gauche (GG) and gauche-gauche' (GG') (Carlucci et al., 2002).The most obvious difference between them is the O/C/C/C—O/C/C/C torsion angle [58.2 (7)° in (I) and 173.4 (3)/70.2 (3)° in (II) for GG and TG conformations, respectively]. Another difference between them is the angle between the planes of aromatic rings [86.49 (7)° for (I) and 76.4 (3)° for triclinic modification]. The crystal structure of the title compound has one intramolecular C—O··· H and one weak π–π interaction (4.1397 (10)Å Cg1— Cg1(i), symmetry code (i) =3/2 - x, 1/2 - y 1 - z; Cg1= N13/C12/C11/C16/C15/C14), whereas this last kind of interaction is not evident in the triclinic polymorph.The triclinic modification is less compact, as noted from the lower density (1.395 Mg m^-3 compared with 1.418 Mg m^-3 for the monoclinic form).

Related literature

For conformation definitions, see: Carlucci et al. (2002). For the structure of the polymorph, see: Brito et al. (2010a). For the synthesis and structural characterization of coordination polymers, see: Brito et al. (2010b).

S2. Experimental

All reactions were carried out under an atmosphere of purified nitrogen. Solvents were dried and distilled prior to use. 5,5'-dinitro-2,2'-dithiodipyridine and silver trifluoromethanesulfonate were purchased from Aldrich. The title compound was obtained as colourless block crystals, in an attempt to prepare coordination polymers with silver trifluoromethanesulfonate and the ligand (II). The compound (I) was obtained by a mixture of (II) (1 mmol, 27.3 mg) and silver trifluoromethanesulfonate (1 mmol, 25.6 mg) in CH₃CN (5 ml). The title compound was filtered off and washed with CH₃CN. FT–IR (KBr pellet, cm^-1): ν (w, C—H) 3086, ν(s, N=O of NO₂ asymmetric) 1581, ν (v.s. of NO₂ symmetric) 1352, ν(w, C—H disubstitution 1,4) 1962, ν(s, C—H disubstitution 1,4) 852, ν (w, C—N) 1101, ν(s, C=C) 1603, ν (w, C—H) 1010, (s, C=N) 1510, ν (w, C—S) 740, ν(w S—S) 552.

S3. Refinement

All H atoms could be located by difference Fourier synthesis but were ultimately placed in calculated positions using a riding model with C— H = 0.95 - 1.00 Å and with fixed individual displacement parameters [U_iso(H) = 1.2 U_eq(C)].

Computing details

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 in SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

Fig. 1. The structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are plotted at the 50% probability level. [symmetry code: A = 1 - x,y,1/2 - z]

propane-1,3-diyl bis(pyridine-3-carboxylate)

Crystal data

C15H14N2O4	F(000) = 600
Mr = 286.28	Dx = 1.418 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2928 reflections
a = 24.414 (3) Å	θ = 3.4–25.9°
b = 4.8328 (4) Å	µ = 0.11 mm^−1
c = 11.5667 (14) Å	T = 173 K
β = 100.671 (10)°	Block, colourless
V = 1341.1 (3) Å^3	0.35 × 0.33 × 0.13 mm
Z = 4

Data collection

Stoe IPDS II two-circle diffractometer	939 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.037
Graphite monochromator	θmax = 25.6°, θmin = 3.4°
ω scans	h = −29→29
3193 measured reflections	k = −5→5
1249 independent reflections	l = −14→13

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.033	H-atom parameters constrained
wR(F^2) = 0.081	w = 1/[σ^2(Fo^2) + (0.0497P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.92	(Δ/σ)max = 0.001
1249 reflections	Δρmax = 0.17 e Å^−3
97 parameters	Δρmin = −0.14 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0099 (13)

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
O1	0.57094 (4)	0.5968 (2)	0.53846 (8)	0.0343 (3)
C1	0.58554 (6)	0.5710 (3)	0.44442 (11)	0.0250 (3)
O2	0.56326 (4)	0.7135 (2)	0.34794 (7)	0.0273 (3)
C3	0.51676 (6)	0.8926 (3)	0.36128 (11)	0.0272 (3)
H3A	0.5280	1.0184	0.4291	0.033*
H3B	0.4849	0.7795	0.3759	0.033*
C4	0.5000	1.0583 (4)	0.2500	0.0266 (5)
H4A	0.4679	1.1804	0.2599	0.032*
C11	0.62930 (6)	0.3744 (3)	0.42290 (11)	0.0254 (3)
C12	0.65354 (6)	0.2013 (3)	0.51425 (12)	0.0299 (4)
H12	0.6415	0.2180	0.5875	0.036*
N13	0.69262 (5)	0.0130 (3)	0.50556 (10)	0.0342 (3)
C14	0.70870 (6)	−0.0051 (3)	0.40112 (12)	0.0324 (4)
H14	0.7368	−0.1360	0.3930	0.039*
C15	0.68699 (6)	0.1548 (3)	0.30476 (12)	0.0317 (4)
H15	0.6998	0.1327	0.2325	0.038*
C16	0.64628 (6)	0.3481 (3)	0.31495 (11)	0.0290 (3)
H16	0.6303	0.4601	0.2499	0.035*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0395 (6)	0.0414 (6)	0.0238 (5)	0.0043 (5)	0.0102 (4)	0.0026 (4)
C1	0.0281 (8)	0.0259 (7)	0.0199 (6)	−0.0060 (6)	0.0013 (6)	0.0007 (5)
O2	0.0313 (6)	0.0290 (5)	0.0220 (5)	0.0045 (4)	0.0062 (4)	0.0017 (4)
C3	0.0274 (8)	0.0293 (8)	0.0260 (7)	0.0015 (6)	0.0080 (6)	−0.0020 (6)
C4	0.0259 (11)	0.0260 (11)	0.0281 (9)	0.000	0.0057 (8)	0.000
C11	0.0268 (7)	0.0248 (7)	0.0238 (6)	−0.0053 (6)	0.0030 (6)	−0.0014 (5)
C12	0.0355 (9)	0.0308 (8)	0.0232 (6)	−0.0007 (7)	0.0049 (6)	−0.0009 (6)
N13	0.0378 (8)	0.0339 (7)	0.0303 (6)	0.0037 (6)	0.0045 (5)	0.0008 (5)
C14	0.0306 (9)	0.0315 (8)	0.0354 (8)	0.0008 (6)	0.0067 (6)	−0.0042 (6)
C15	0.0335 (8)	0.0346 (8)	0.0282 (7)	−0.0043 (7)	0.0091 (6)	−0.0037 (6)
C16	0.0321 (8)	0.0312 (8)	0.0231 (7)	−0.0052 (6)	0.0037 (6)	0.0009 (6)

Geometric parameters (Å, º)

O1—C1	1.2122 (14)	C11—C16	1.3925 (16)
C1—O2	1.3381 (16)	C12—N13	1.3355 (19)
C1—C11	1.4849 (19)	C12—H12	0.9500
O2—C3	1.4585 (16)	N13—C14	1.3405 (17)
C3—C4	1.5069 (17)	C14—C15	1.379 (2)
C3—H3A	0.9900	C14—H14	0.9500
C3—H3B	0.9900	C15—C16	1.385 (2)
C4—C3^i	1.5069 (17)	C15—H15	0.9500
C4—H4A	1.0042	C16—H16	0.9500
C11—C12	1.391 (2)
O1—C1—O2	123.62 (13)	C16—C11—C1	123.47 (12)
O1—C1—C11	123.82 (12)	N13—C12—C11	124.20 (12)
O2—C1—C11	112.54 (10)	N13—C12—H12	117.9
C1—O2—C3	114.92 (9)	C11—C12—H12	117.9
O2—C3—C4	108.59 (9)	C12—N13—C14	116.40 (13)
O2—C3—H3A	110.0	N13—C14—C15	123.98 (14)
C4—C3—H3A	110.0	N13—C14—H14	118.0
O2—C3—H3B	110.0	C15—C14—H14	118.0
C4—C3—H3B	110.0	C14—C15—C16	118.94 (12)
H3A—C3—H3B	108.4	C14—C15—H15	120.5
C3^i—C4—C3	115.77 (17)	C16—C15—H15	120.5
C3^i—C4—H4A	108.4	C15—C16—C11	118.38 (13)
C3—C4—H4A	108.0	C15—C16—H16	120.8
C12—C11—C16	118.09 (13)	C11—C16—H16	120.8
C12—C11—C1	118.41 (11)
O1—C1—O2—C3	−3.94 (19)	C16—C11—C12—N13	0.8 (2)
C11—C1—O2—C3	174.99 (11)	C1—C11—C12—N13	178.94 (14)
C1—O2—C3—C4	174.58 (12)	C11—C12—N13—C14	0.1 (2)
O2—C3—C4—C3^i	58.11 (8)	C12—N13—C14—C15	−0.7 (2)
O1—C1—C11—C12	2.7 (2)	N13—C14—C15—C16	0.4 (2)
O2—C1—C11—C12	−176.23 (13)	C14—C15—C16—C11	0.5 (2)
O1—C1—C11—C16	−179.25 (13)	C12—C11—C16—C15	−1.1 (2)
O2—C1—C11—C16	1.83 (19)	C1—C11—C16—C15	−179.13 (13)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O1	0.95	2.51	2.8298 (18)	100