Terephthalic acid–1,3-di-4-pyrid­ylpropane (1/1)

The title compound, C₁₃H₁₄N₂·C₈H₆O₄, was obtained by the hydro­thermal reaction of CuCl with 1,2,4,5-benzene­tetra­carboxylic acid and 1,3-bis­(4-pyrid­yl)propane. The 1,3-bis­(4-pyrid­yl)propane mol­ecule lies on a crystallographic twofold axis, and terephthalic acid is on an inversion centre. In the crystal structure, strong inter­molecular O—H...N hydrogen bonds between the components lead to the formation of zigzag chains extending along [10]. The chains are linked through inter­molecular C—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.043
• wR factor = 0.120
• Data-to-parameter ratio = 12.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT355_ALERT_3_C Long    O-H Bond (0.82A)   O1     -   H1     ...       1.06 Ang.
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.14 Ratio
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              C8 H6 O4

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   3 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
   1 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion

---

S1. Comment

The construction of inorganic coordination polymeric complexes has developed rapidly in recent years, owing to their interesting molecular topologies and crystal-packing motifs (Hagrman et al., 1999; Yaghi et al., 1998) along with potential applications as functional materials (Evans et al., 1999; Fujita et al., 1994). 1,2,4,5-Benzenetetracarboxylic acid (H₄btec) attracted our attention for the process of constructing coordination polymers. During the process, hydrothermal decarboxylation reaction was observed and the H₄btc ligand was in situ converted into terephthalic acid by loss of two carboxyl groups. We report here the synthesis and crystal structure of the title compound, (I).

The asymmetric unit contains one half-molecule each of terephthalic acid and 1,3-bis(4-pyridyl)propane; the 1,3-bis(4-pyridyl)propane molecule lies on a crystallographic twofold axis, and terephthalic acid is on an inversion centre (Fig. 1). In the crystal structure, O—H···N hydrogen bonds between carboxylic acid groups and N atoms of the pyridine rings link the molecules into zigzag chains along [101] (Table 2). Intermolecular C—H···O hydrogen bonds link the chains into a three-dimensional network (Fig. 2).

S2. Experimental

CuCl (0.10 g, 1 mmol), H₄btec (0.127 g, 0.5 mmol) and KOH (0.06 g, 1 mmol) were mixed in water (15 ml) and heated at 433 K for 3 d in a sealed 25 ml Teflon-lined stainless steel vessel under autogenous pressure. Cooling to room temperature at 5 K h⁻¹ produced yellow block crystals, which were collected, washed with water and dried in air.

S3. Refinement

H atoms were located in a difference Fourier map and both positional and isotropic displacement parameters were refined. The C—H range is 0.946 (16)–1.002 (16) Å and the O—H distance is 1.06 (2) Å.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Siemens, 1994); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The asymmetric unit of (I). Displacement ellipsoids are drawn at the 40% probability level. Unlabelled atoms in the terephthalic acid and 1,3-bis(4-pyridyl)propane molecules are related to labelled atoms in the same molecule by (1/2 − x, −1/2 − y, −z) and (−x, y, 1/2 − z), respectively.
	Fig. 2. The crystal packing of (I), showing the three-dimensional hydrogen-bonded (dashed lines) network.

(I)

Crystal data

C13H14N2·C8H6O4	F(000) = 768
Mr = 364.38	Dx = 1.340 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1874 reflections
a = 23.270 (2) Å	θ = 3.5–27.5°
b = 4.7000 (2) Å	µ = 0.09 mm^−1
c = 18.9600 (19) Å	T = 293 K
β = 119.440 (3)°	Prism, yellow
V = 1805.9 (3) Å^3	0.40 × 0.30 × 0.20 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	2063 independent reflections
Radiation source: fine-focus sealed tube	1811 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
ϕ and ω scans	θmax = 27.5°, θmin = 3.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −30→30
Tmin = 0.967, Tmax = 0.981	k = −5→6
6545 measured reflections	l = −13→24

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.120	All H-atom parameters refined
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0672P)^2 + 0.7554P] where P = (Fo^2 + 2Fc^2)/3
2063 reflections	(Δ/σ)max = 0.001
163 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.19 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	0.14122 (5)	0.6456 (2)	0.13847 (6)	0.0258 (3)
O1	0.20846 (4)	0.2893 (2)	0.10471 (5)	0.0295 (3)
O2	0.11567 (4)	0.1926 (2)	−0.01050 (6)	0.0324 (3)
C1	0.18213 (6)	−0.2281 (3)	−0.04976 (7)	0.0251 (3)
H1A	0.1345 (7)	−0.210 (3)	−0.0835 (9)	0.029 (4)*
C2	0.17427 (6)	0.1535 (3)	0.03589 (7)	0.0243 (3)
C3	0.28218 (6)	−0.0783 (3)	0.06842 (7)	0.0246 (3)
H3A	0.3051 (7)	0.044 (3)	0.1159 (9)	0.025 (3)*
C4	0.21406 (6)	−0.0561 (3)	0.01844 (7)	0.0227 (3)
C5	0.17126 (6)	0.7636 (3)	0.21225 (8)	0.0281 (3)
H5A	0.2164 (8)	0.712 (3)	0.2476 (9)	0.032 (4)*
C6	0.07776 (6)	0.7090 (3)	0.08891 (8)	0.0279 (3)
H6A	0.0588 (7)	0.616 (4)	0.0362 (10)	0.033 (4)*
C7	0.03551 (6)	1.1984 (3)	0.21572 (9)	0.0286 (3)
H7B	0.0658 (8)	1.336 (3)	0.2573 (10)	0.033 (4)*
H7A	0.0025 (8)	1.312 (4)	0.1700 (10)	0.036 (4)*
C8	0.04234 (6)	0.8894 (3)	0.11116 (8)	0.0286 (3)
H8A	−0.0030 (8)	0.920 (3)	0.0748 (10)	0.034 (4)*
C9	0.13928 (6)	0.9469 (3)	0.23881 (8)	0.0272 (3)
H9A	0.1633 (7)	1.028 (3)	0.2920 (10)	0.032 (4)*
C10	0.0000	1.0178 (4)	0.2500	0.0279 (4)
H10A	0.0332 (7)	0.892 (3)	0.2938 (10)	0.033 (4)*
C11	0.07317 (6)	1.0124 (3)	0.18769 (8)	0.0243 (3)
H1	0.1773 (10)	0.431 (5)	0.1136 (14)	0.075 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0249 (5)	0.0298 (6)	0.0254 (5)	−0.0007 (4)	0.0145 (4)	−0.0016 (4)
O1	0.0268 (5)	0.0357 (5)	0.0238 (5)	0.0044 (4)	0.0106 (4)	−0.0041 (4)
O2	0.0208 (4)	0.0395 (6)	0.0344 (5)	0.0009 (4)	0.0116 (4)	−0.0046 (4)
C1	0.0207 (5)	0.0304 (7)	0.0220 (6)	0.0003 (5)	0.0088 (5)	0.0014 (5)
C2	0.0245 (6)	0.0263 (6)	0.0235 (6)	−0.0009 (5)	0.0130 (5)	0.0022 (5)
C3	0.0245 (6)	0.0269 (6)	0.0206 (6)	−0.0010 (5)	0.0097 (5)	−0.0004 (5)
C4	0.0235 (6)	0.0245 (6)	0.0218 (6)	−0.0007 (5)	0.0124 (5)	0.0023 (5)
C5	0.0222 (6)	0.0355 (7)	0.0246 (6)	0.0013 (5)	0.0101 (5)	−0.0016 (5)
C6	0.0254 (6)	0.0343 (7)	0.0231 (6)	−0.0043 (5)	0.0113 (5)	−0.0036 (5)
C7	0.0300 (6)	0.0264 (7)	0.0367 (7)	0.0009 (5)	0.0220 (6)	0.0018 (5)
C8	0.0213 (6)	0.0356 (7)	0.0281 (6)	0.0000 (5)	0.0114 (5)	0.0024 (5)
C9	0.0264 (6)	0.0322 (7)	0.0220 (6)	−0.0024 (5)	0.0112 (5)	−0.0037 (5)
C10	0.0301 (9)	0.0250 (9)	0.0370 (10)	0.000	0.0230 (8)	0.000
C11	0.0262 (6)	0.0233 (6)	0.0289 (6)	−0.0008 (4)	0.0179 (5)	0.0029 (5)

Geometric parameters (Å, º)

N1—C6	1.3373 (16)	C5—H5A	0.959 (16)
N1—C5	1.3385 (16)	C6—C8	1.3850 (19)
O1—C2	1.3123 (15)	C6—H6A	0.975 (17)
O1—H1	1.06 (2)	C7—C11	1.5075 (17)
O2—C2	1.2197 (15)	C7—C10	1.5341 (16)
C1—C4	1.3903 (17)	C7—H7B	0.994 (16)
C1—C3^i	1.3896 (18)	C7—H7A	0.987 (17)
C1—H1A	0.974 (15)	C8—C11	1.3897 (18)
C2—C4	1.4963 (17)	C8—H8A	0.946 (16)
C3—C1^i	1.3896 (18)	C9—C11	1.3909 (17)
C3—C4	1.3947 (17)	C9—H9A	0.959 (16)
C3—H3A	0.975 (15)	C10—C7^ii	1.5341 (16)
C5—C9	1.3849 (18)	C10—H10A	1.002 (16)
C6—N1—C5	118.11 (11)	C8—C6—H6A	123.3 (9)
C2—O1—H1	109.6 (12)	C11—C7—C10	110.85 (11)
C4—C1—C3^i	120.29 (11)	C11—C7—H7B	110.4 (9)
C4—C1—H1A	118.3 (9)	C10—C7—H7B	110.0 (9)
C3^i—C1—H1A	121.4 (9)	C11—C7—H7A	109.9 (9)
O2—C2—O1	124.08 (12)	C10—C7—H7A	108.9 (9)
O2—C2—C4	122.25 (11)	H7B—C7—H7A	106.7 (14)
O1—C2—C4	113.67 (10)	C6—C8—C11	119.58 (11)
C1^i—C3—C4	119.86 (12)	C6—C8—H8A	119.2 (10)
C1^i—C3—H3A	119.7 (8)	C11—C8—H8A	121.1 (10)
C4—C3—H3A	120.5 (8)	C5—C9—C11	119.49 (12)
C1—C4—C3	119.85 (11)	C5—C9—H9A	119.2 (9)
C1—C4—C2	118.87 (11)	C11—C9—H9A	121.3 (9)
C3—C4—C2	121.28 (11)	C7—C10—C7^ii	112.82 (15)
N1—C5—C9	122.67 (11)	C7—C10—H10A	108.7 (8)
N1—C5—H5A	117.1 (9)	C7^ii—C10—H10A	109.4 (9)
C9—C5—H5A	120.2 (9)	C8—C11—C9	117.52 (12)
N1—C6—C8	122.63 (12)	C8—C11—C7	121.20 (11)
N1—C6—H6A	114.0 (9)	C9—C11—C7	121.21 (12)
C3^i—C1—C4—C3	−0.1 (2)	N1—C6—C8—C11	0.3 (2)
C3^i—C1—C4—C2	178.92 (11)	N1—C5—C9—C11	0.3 (2)
C1^i—C3—C4—C1	0.1 (2)	C11—C7—C10—C7^ii	176.37 (12)
C1^i—C3—C4—C2	−178.90 (11)	C6—C8—C11—C9	0.10 (19)
O2—C2—C4—C1	−5.18 (18)	C6—C8—C11—C7	−176.98 (12)
O1—C2—C4—C1	175.20 (11)	C5—C9—C11—C8	−0.36 (19)
O2—C2—C4—C3	173.86 (12)	C5—C9—C11—C7	176.72 (12)
O1—C2—C4—C3	−5.77 (16)	C10—C7—C11—C8	84.15 (14)
C6—N1—C5—C9	0.0 (2)	C10—C7—C11—C9	−92.82 (13)
C5—N1—C6—C8	−0.3 (2)

Symmetry codes: (i) −x+1/2, −y−1/2, −z; (ii) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	1.06 (2)	1.53 (2)	2.5782 (14)	171 (2)
C5—H5A···O1^iii	0.96 (2)	2.49 (2)	3.2162 (16)	132 (1)
C8—H8A···O2^iv	0.95 (2)	2.35 (2)	3.2268 (19)	155 (1)

Symmetry codes: (iii) −x+1/2, y+1/2, −z+1/2; (iv) −x, −y+1, −z.