1,3-Di-4-pyrid­ylpropane–2-hydroxy­benzene-1,4-dicarboxylic acid (1/2)

Qin, J.-H.; Hao, E.-J.; Wang, J.-G.

doi:10.1107/S1600536808037835

organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2398

doi:10.1107/S1600536808037835

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1,3-Di-4-pyridylpropane–2-hydroxybenzene-1,4-dicarboxylic acid (1/2)

Jian-Hua Qin,^a ^* Er-Jun Hao ^b and Jian-Ge Wang ^a

^aCollege of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, People's Republic of China, and ^bCollege of Chemistry and Environmental Science, Henan Normal University, Xinxiang, 453007, People's Republic of China
^*Correspondence e-mail: jh_q128105@126.com

(Received 3 September 2008; accepted 14 November 2008; online 20 November 2008)

In the title compound, C₁₃H₁₄N₂·2C₈H₆O₅, which crystallized in the monoclinic C2/c space group, the 1,3-bis(4-pyridyl)propane molecules and 2-hydroxy-1,4-benzenedicarboxylic acid molecules are alternately linked by O—H⋯N and O—H⋯O hydrogen bonds into herringbone/zigzag chains.

Related literature

For general background, see: Bowers et al. (2005 ); Mukherjee et al. (2004 ). For the substitution of bromine for hydroxyl, see: Chen & Tong (2007 ); Zhang (2005 ).

Experimental

Crystal data

C₁₃H₁₄N₂·2C₈H₆O₅
M_r = 562.52
Monoclinic, C 2/c
a = 22.939 (11) Å
b = 4.781 (2) Å
c = 24.163 (11) Å
β = 96.542 (6)°
V = 2633 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 291 (2) K
0.35 × 0.19 × 0.05 mm

Data collection

Bruker CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.963, T_max = 0.994
9178 measured reflections
2444 independent reflections
1335 reflections with I > 2σ(I)
R_int = 0.049

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.173
S = 1.03
2444 reflections
187 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O5ⁱ	0.82	1.82	2.631 (3)	172
O2—H2⋯N1	0.82	1.75	2.568 (3)	174
O1—H1⋯O3	0.82	1.79	2.516 (3)	147
Symmetry code: (i) -x+1, -y+4, -z+1.

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808037835/ww2129sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808037835/ww2129Isup2.hkl

checkCIF report

Comment top

The aromatic dicarboxylate are used extensively in the synthesis of coordination polymers (Mukherjee et al., 2004) and the generation of hydrogen-bonding arrays of organic co-crystals (Bowers et al., 2005). The 2-bromo-1,4-benzenedicarboxylic acid, possesses several interesting characteristics: (a) it has two carboxyl groups which may be completely or partially deprotonated, inducing rich coordination modes and allowing interesting structures with higher dimensions; (b) it can act not only as hydrogen-bond acceptor but also as hydrogen-bond donor, depending upon the number of deprotonated carboxyl groups. To propagate non-covalent interactions only along one direction, each unit must have two-point interactions with two adjacent neighbors. Dicarboxylic acids epitomize this model and exhibits a two-point contact per unit that can result in 1-D hydrogen bonding networks.

The crystal structure of the title compound comprises half of a 1,3-bis(4-pyridyl)propane (bpp) molecule and a 2-hydroxy-1,4-benzenedicarboxylic acid molecule per asymmetric unit (Fig. 1). One bpp molecule connects two adjacent 2-hydroxy-1,4-benzenedicarboxylic acid molecules via O—H···N hydrogen bonds, and complementary via O—H···O hydrogen bonds between adjacent dicarboxylic acid molecules, which extend into an one-dimensional herringbone/zigzag chain structure (Fig. 2). The dihedral angle between two pyridyl rings is 85.551 (11)°, and thus incorporation into supramolecular architecture imparts significant conformation change in the bpp molecule. The 1-D chain structure seems to suggest that the CH₂ chain in pyridyl bases is not an inert spacer but could have a conformational and structural role in controlling the supramolecular architecture.

Related literature top

For related literature, see: Bowers et al. (2005); Chen & Tong (2007); Mukherjee et al. (2004); Zhang (2005). It would be much more useful to readers if the "Related literature" section had some kind of simple sub-division, so that, instead of just "For related literature, see···" it said, for example, "For general background, see···. For related structures, see···; etc. Please revise this section as indicated.

Experimental top

1,3-Bis(4-pyridyl)propane (bpp) (0.5 mmol), 2-bromo-1,4-benzenedicarboxylic acid (1.0 mmol), and KOH (0.5 mmol) were added to water (12 ml) in a Teflon-lined stainless steel reactor. The mixture was heated at 435 K for 3 d, and then slowly cooled down to room temperature. Colorless crystals of the title compound were obtained. Elemental analysis – found: C, 61.81%; H, 4.56%; N, 4.92%; calc. for C₂₉H₂₆N₂ O₁₀: C, 61.86%; H, 4.62%; N, 4.98%. Note the substitution of bromine for hydroxyl in the formation of title compound, which commonly happened under hydro(solvo)thermal conditions (Chen & Tong, 2007; Zhang, 2005).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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 top

	Fig. 1. A view of the title compound, showing 30% probability displacement ellipsoids. Symmetry code: (A) -x, y, 1/2 - z.
	Fig. 2. The unit-cell packing of the title compound, showing the hydrogen bonding interactions.

1,3-Di-4-pyridylpropane–2-hydroxybenzene-1,4-dicarboxylic acid (1/2) top

Crystal data top

C₁₃H₁₄N₂·2C₈H₆O₅	F(000) = 1176
M_r = 562.52	D_x = 1.419 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1102 reflections
a = 22.939 (11) Å	θ = 3.4–23.3°
b = 4.781 (2) Å	µ = 0.11 mm⁻¹
c = 24.163 (11) Å	T = 291 K
β = 96.542 (6)°	Block, colorless
V = 2633 (2) Å³	0.35 × 0.19 × 0.05 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2444 independent reflections
Radiation source: fine-focus sealed tube	1335 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
ω & ϕ scans	θ_max = 25.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −27→27
T_min = 0.963, T_max = 0.994	k = −5→5
9178 measured reflections	l = −29→28

Refinement top

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.173	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0772P)² + 1.353P] where P = (F_o² + 2F_c²)/3
2444 reflections	(Δ/σ)_max < 0.001
187 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₃H₁₄N₂·2C₈H₆O₅	V = 2633 (2) Å³
M_r = 562.52	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 22.939 (11) Å	µ = 0.11 mm⁻¹
b = 4.781 (2) Å	T = 291 K
c = 24.163 (11) Å	0.35 × 0.19 × 0.05 mm
β = 96.542 (6)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2444 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	1335 reflections with I > 2σ(I)
T_min = 0.963, T_max = 0.994	R_int = 0.049
9178 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.173	H-atom parameters constrained
S = 1.03	Δρ_max = 0.39 e Å⁻³
2444 reflections	Δρ_min = −0.18 e Å⁻³
187 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.38415 (11)	1.0471 (6)	0.32590 (9)	0.0857 (9)
H1	0.3557	0.9516	0.3141	0.129*
O2	0.24082 (9)	0.8169 (5)	0.40221 (9)	0.0642 (7)
H2	0.2203	0.6976	0.3852	0.096*
O3	0.29118 (9)	0.7716 (5)	0.32941 (9)	0.0695 (7)
O4	0.43663 (9)	1.8252 (5)	0.51792 (9)	0.0666 (7)
H4	0.4624	1.9400	0.5274	0.100*
O5	0.48854 (9)	1.7794 (5)	0.44642 (10)	0.0679 (7)
N1	0.17662 (11)	0.4242 (5)	0.35544 (11)	0.0516 (7)
C1	0.32537 (12)	1.0947 (6)	0.40090 (12)	0.0467 (7)
C2	0.37382 (13)	1.1721 (6)	0.37430 (13)	0.0539 (8)
C3	0.41262 (13)	1.3722 (6)	0.39812 (13)	0.0568 (8)
H3	0.4451	1.4215	0.3805	0.068*
C4	0.40338 (12)	1.4989 (6)	0.44770 (12)	0.0470 (7)
C5	0.35515 (13)	1.4263 (6)	0.47459 (13)	0.0535 (8)
H5	0.3486	1.5125	0.5078	0.064*
C6	0.31687 (13)	1.2222 (6)	0.45088 (13)	0.0551 (8)
H6	0.2849	1.1702	0.4690	0.066*
C7	0.28337 (13)	0.8782 (6)	0.37506 (14)	0.0527 (8)
C8	0.44604 (13)	1.7142 (6)	0.47143 (13)	0.0493 (8)
C9	0.18299 (12)	0.3070 (7)	0.30666 (13)	0.0534 (8)
H9	0.2147	0.3584	0.2881	0.064*
C10	0.14366 (12)	0.1103 (6)	0.28276 (12)	0.0516 (8)
H10	0.1493	0.0298	0.2488	0.062*
C11	0.09577 (12)	0.0334 (6)	0.30954 (12)	0.0449 (7)
C12	0.09152 (13)	0.1551 (7)	0.36110 (13)	0.0570 (8)
H12	0.0609	0.1056	0.3813	0.068*
C13	0.13223 (14)	0.3479 (7)	0.38230 (13)	0.0575 (8)
H13	0.1285	0.4277	0.4168	0.069*
C14	0.04828 (11)	−0.1557 (6)	0.28235 (12)	0.0499 (8)
H14A	0.0318	−0.2651	0.3106	0.060*
H14B	0.0648	−0.2837	0.2572	0.060*
C15	0.0000	0.0194 (8)	0.2500	0.0498 (11)
H15A	0.0176	0.1391	0.2241	0.060*	0.50
H15B	−0.0176	0.1391	0.2759	0.060*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.109 (2)	0.092 (2)	0.0608 (15)	−0.0379 (16)	0.0301 (15)	−0.0327 (13)
O2	0.0605 (14)	0.0580 (14)	0.0726 (15)	−0.0154 (11)	0.0015 (12)	−0.0059 (12)
O3	0.0756 (15)	0.0679 (16)	0.0653 (15)	−0.0160 (12)	0.0091 (12)	−0.0159 (12)
O4	0.0658 (14)	0.0597 (14)	0.0748 (16)	−0.0169 (12)	0.0102 (12)	−0.0179 (13)
O5	0.0593 (14)	0.0617 (15)	0.0858 (16)	−0.0161 (12)	0.0222 (12)	−0.0191 (12)
N1	0.0513 (15)	0.0481 (15)	0.0543 (16)	−0.0003 (12)	0.0012 (13)	0.0053 (13)
C1	0.0496 (18)	0.0359 (16)	0.0527 (18)	−0.0006 (13)	−0.0027 (14)	−0.0012 (14)
C2	0.0597 (19)	0.0483 (18)	0.0543 (19)	−0.0076 (16)	0.0086 (15)	−0.0058 (16)
C3	0.059 (2)	0.0497 (19)	0.063 (2)	−0.0116 (16)	0.0148 (16)	−0.0048 (16)
C4	0.0456 (17)	0.0362 (17)	0.0578 (19)	0.0010 (13)	−0.0004 (15)	0.0018 (15)
C5	0.0593 (19)	0.0459 (18)	0.0552 (19)	−0.0024 (16)	0.0061 (15)	−0.0058 (15)
C6	0.0499 (18)	0.0527 (19)	0.063 (2)	−0.0059 (16)	0.0087 (15)	0.0009 (17)
C7	0.0475 (18)	0.0449 (18)	0.065 (2)	−0.0004 (14)	0.0028 (16)	0.0041 (17)
C8	0.0513 (18)	0.0350 (16)	0.061 (2)	0.0017 (14)	0.0033 (16)	−0.0043 (15)
C9	0.0450 (17)	0.055 (2)	0.061 (2)	−0.0051 (15)	0.0094 (15)	0.0089 (17)
C10	0.0518 (18)	0.0529 (19)	0.0509 (18)	0.0026 (15)	0.0093 (15)	0.0022 (15)
C11	0.0465 (17)	0.0364 (16)	0.0508 (17)	0.0044 (13)	0.0008 (14)	0.0045 (14)
C12	0.0504 (18)	0.064 (2)	0.059 (2)	−0.0045 (16)	0.0137 (15)	−0.0006 (17)
C13	0.062 (2)	0.058 (2)	0.0532 (19)	−0.0054 (17)	0.0070 (16)	−0.0081 (16)
C14	0.0467 (17)	0.0411 (17)	0.0607 (19)	−0.0015 (14)	0.0010 (14)	0.0004 (15)
C15	0.049 (2)	0.038 (2)	0.061 (3)	0.000	0.002 (2)	0.000

Geometric parameters (Å, º) top

O1—C2	1.358 (3)	C5—C6	1.391 (4)
O1—H1	0.8200	C5—H5	0.9300
O2—C7	1.271 (3)	C6—H6	0.9300
O2—H2	0.8200	C9—C10	1.383 (4)
O3—C7	1.246 (4)	C9—H9	0.9300
O4—C8	1.283 (3)	C10—C11	1.387 (4)
O4—H4	0.8200	C10—H10	0.9300
O5—C8	1.244 (3)	C11—C12	1.389 (4)
N1—C13	1.320 (4)	C11—C14	1.507 (4)
N1—C9	1.328 (4)	C12—C13	1.369 (4)
C1—C6	1.386 (4)	C12—H12	0.9300
C1—C2	1.396 (4)	C13—H13	0.9300
C1—C7	1.501 (4)	C14—C15	1.530 (3)
C2—C3	1.386 (4)	C14—H14A	0.9700
C3—C4	1.380 (4)	C14—H14B	0.9700
C3—H3	0.9300	C15—C14ⁱ	1.530 (3)
C4—C5	1.389 (4)	C15—H15A	0.9700
C4—C8	1.489 (4)	C15—H15B	0.9700

C2—O1—H1	109.5	N1—C9—C10	121.7 (3)
C7—O2—H2	109.5	N1—C9—H9	119.2
C8—O4—H4	109.5	C10—C9—H9	119.2
C13—N1—C9	119.3 (3)	C9—C10—C11	120.0 (3)
C6—C1—C2	118.9 (3)	C9—C10—H10	120.0
C6—C1—C7	121.2 (3)	C11—C10—H10	120.0
C2—C1—C7	119.9 (3)	C10—C11—C12	116.6 (3)
O1—C2—C3	119.6 (3)	C10—C11—C14	121.8 (3)
O1—C2—C1	120.4 (3)	C12—C11—C14	121.4 (3)
C3—C2—C1	119.9 (3)	C13—C12—C11	120.2 (3)
C4—C3—C2	120.6 (3)	C13—C12—H12	119.9
C4—C3—H3	119.7	C11—C12—H12	119.9
C2—C3—H3	119.7	N1—C13—C12	122.3 (3)
C3—C4—C5	120.4 (3)	N1—C13—H13	118.9
C3—C4—C8	118.6 (3)	C12—C13—H13	118.9
C5—C4—C8	121.0 (3)	C11—C14—C15	109.9 (2)
C4—C5—C6	118.8 (3)	C11—C14—H14A	109.7
C4—C5—H5	120.6	C15—C14—H14A	109.7
C6—C5—H5	120.6	C11—C14—H14B	109.7
C1—C6—C5	121.5 (3)	C15—C14—H14B	109.7
C1—C6—H6	119.3	H14A—C14—H14B	108.2
C5—C6—H6	119.3	C14—C15—C14ⁱ	113.7 (3)
O3—C7—O2	124.0 (3)	C14—C15—H15A	108.8
O3—C7—C1	120.0 (3)	C14ⁱ—C15—H15A	108.8
O2—C7—C1	116.0 (3)	C14—C15—H15B	108.8
O5—C8—O4	122.8 (3)	C14ⁱ—C15—H15B	108.8
O5—C8—C4	120.2 (3)	H15A—C15—H15B	107.7
O4—C8—C4	117.0 (3)

C6—C1—C2—O1	178.6 (3)	C2—C1—C7—O2	179.2 (3)
C7—C1—C2—O1	−1.8 (4)	C3—C4—C8—O5	0.9 (4)
C6—C1—C2—C3	0.4 (4)	C5—C4—C8—O5	−179.0 (3)
C7—C1—C2—C3	180.0 (3)	C3—C4—C8—O4	−179.1 (3)
O1—C2—C3—C4	−179.1 (3)	C5—C4—C8—O4	1.0 (4)
C1—C2—C3—C4	−0.8 (5)	C13—N1—C9—C10	1.2 (4)
C2—C3—C4—C5	0.3 (5)	N1—C9—C10—C11	0.7 (4)
C2—C3—C4—C8	−179.5 (3)	C9—C10—C11—C12	−2.3 (4)
C3—C4—C5—C6	0.6 (4)	C9—C10—C11—C14	173.2 (3)
C8—C4—C5—C6	−179.5 (3)	C10—C11—C12—C13	2.2 (4)
C2—C1—C6—C5	0.6 (5)	C14—C11—C12—C13	−173.4 (3)
C7—C1—C6—C5	−179.0 (3)	C9—N1—C13—C12	−1.4 (5)
C4—C5—C6—C1	−1.1 (4)	C11—C12—C13—N1	−0.3 (5)
C6—C1—C7—O3	178.2 (3)	C10—C11—C14—C15	−90.2 (3)
C2—C1—C7—O3	−1.4 (4)	C12—C11—C14—C15	85.1 (3)
C6—C1—C7—O2	−1.3 (4)	C11—C14—C15—C14ⁱ	176.1 (3)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O5ⁱⁱ	0.82	1.82	2.631 (3)	172
O2—H2···N1	0.82	1.75	2.568 (3)	174
O1—H1···O3	0.82	1.79	2.516 (3)	147

Symmetry code: (ii) −x+1, −y+4, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₄N₂·2C₈H₆O₅
M_r	562.52
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	291
a, b, c (Å)	22.939 (11), 4.781 (2), 24.163 (11)
β (°)	96.542 (6)
V (Å³)	2633 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.35 × 0.19 × 0.05

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.963, 0.994
No. of measured, independent and observed [I > 2σ(I)] reflections	9178, 2444, 1335
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.173, 1.03
No. of reflections	2444
No. of parameters	187
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.18

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O5ⁱ	0.82	1.82	2.631 (3)	171.6
O2—H2···N1	0.82	1.75	2.568 (3)	174.1
O1—H1···O3	0.82	1.79	2.516 (3)	147.3

Symmetry code: (i) −x+1, −y+4, −z+1.

Acknowledgements

The authors thank Luoyang Normal University for supporting this work.

References

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