1-(3-Carboxyl­atophen­yl)-4,4′-bipyridin-1-ium dihydrate

Fan, M.; Yao, Z.; Li, C.; Fu, Z.

doi:10.1107/S1600536813024197

organic compounds

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Volume 69| Part 10| October 2013| Page o1503

doi:10.1107/S1600536813024197

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1-(3-Carboxylatophenyl)-4,4′-bipyridin-1-ium dihydrate

Mengchan Fan,^a Zhenguo Yao,^a Chen Li ^a and Zhiyong Fu ^a ^*

^aKey Lab for Fuel Cell Technology of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, People's Republic of China
^*Correspondence e-mail: zyfu@scut.edu.cn

(Received 16 August 2013; accepted 29 August 2013; online 4 September 2013)

In the crystal structure of the title compound, C₁₇H₁₂N₂O₂·2H₂O, the carboxylate group is linked via O—H⋯O hydrogen bonds to two water molecules. The crystal packing is best described as parallel layers (viewed along the a axis) of viologen and water molecules associated via O—H⋯O hydrogen bonds and π–π interactions, with a centroid–centroid separation of 3.8276 (9) Å.

Related literature

For background to the applications of viologen complexes, see: Strutt et al. (2012 ). For related structures, see: Coe et al. (1998 ); Leblanc et al. (2010 ); Xu et al. (2007 ).

Experimental

Crystal data

C₁₇H₁₂N₂O₂·2H₂O
M_r = 312.32
Triclinic, $[P \overline 1]$
a = 7.8700 (16) Å
b = 10.090 (2) Å
c = 10.250 (2) Å
α = 81.36 (3)°
β = 73.13 (3)°
γ = 74.64 (3)°
V = 748.7 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 K
0.13 × 0.12 × 0.12 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.971, T_max = 0.993
6136 measured reflections
2741 independent reflections
2120 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.172
S = 1.18
2741 reflections
221 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H3⋯O1	0.89 (3)	1.84 (2)	2.703 (2)	164 (1)
O3—H1⋯O2	0.91 (2)	1.94 (2)	2.843 (3)	174 (1)

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2013 (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/S1600536813024197/fj2640sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813024197/fj2640Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813024197/fj2640Isup3.cml

checkCIF report

Comment top

Viologen species are electron deficient compounds, which have been used as electron acceptor in the construction of charge transfer molecular systems and donor-acceptor-type photochromic materials (Strutt et al., 2012). Recently, many classes of photosensitive model systems have been explored with dimethyl-,diethyl-, dibetaine- and benzyl viologens as ligands (Coe et al. 1998; Leblanc et al., 2010; Xu et al., 2007). Here we report the synthesis and characterization of a new viologen compound. Single crystal data indicate that the asymmetric unit of the title compound contains a monosubstituted pyridylium molecule (1-(3-carboxyphenyl)-4,4,-bipyridinium), and two water molecule (Figure 1). The carboxyl group of viologen molecule is hydrogen bonded in a O···H—O manner with two adjacent water molecules (O1···O4 = 2.7034 Å, O1···O4 = 2.8427 Å). The pyridylium molecules are arranged in a parallel packing mode. And the phenyl rings among them interact with each other through π–π stacking [centroid-centroid separation = 3.8276 (9) Å]. These noncovalent forces link the adjcent units and generate a two dimensional supramolecular network (Figure 2).

Related literature top

For background to the applications of viologen complexes, see: Strutt et al. (2012). For related structures, see: Coe et al. (1998); Leblanc et al. (2010); Xu et al. (2007).

Experimental top

N-(3-carboxyphenyl)-4,4,-bipyridinium chloride (0.33 mmol,0.092 g) and CuI(0.66 mmol, 0.13 g) were added to a solution of triethylamine (0.5 mL) and ethanol (10 mL). The solution was refluxed for 24 h. To the mixture was added 20 mL dichloromethane, yellow crystals (0.048 g, 0.17 mmol) were obtained after one day.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. Layer structure of (I).

1-(3-Carboxylatophenyl)-4,4'-bipyridin-1-ium dihydrate top

Crystal data top

C₁₇H₁₂N₂O₂·2H₂O	Z = 2
M_r = 312.32	F(000) = 328
Triclinic, P1	D_x = 1.385 Mg m⁻³
a = 7.8700 (16) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.090 (2) Å	Cell parameters from 6136 reflections
c = 10.250 (2) Å	θ = 3.0–25.4°
α = 81.36 (3)°	µ = 0.10 mm⁻¹
β = 73.13 (3)°	T = 298 K
γ = 74.64 (3)°	Block, yellow
V = 748.7 (3) Å³	0.13 × 0.12 × 0.12 mm

Data collection top

Bruker SMART CCD diffractometer	2120 reflections with I > 2σ(I)
Radiation source: fine-focus tube	R_int = 0.014
ω scans	θ_max = 25.4°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→9
T_min = 0.971, T_max = 0.993	k = −12→12
6136 measured reflections	l = −12→12
2741 independent reflections

Refinement top

Refinement on F²	4 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.172	w = 1/[σ²(F_o²) + (0.1108P)² + 0.0207P] where P = (F_o² + 2F_c²)/3
S = 1.18	(Δ/σ)_max < 0.001
2741 reflections	Δρ_max = 0.26 e Å⁻³
221 parameters	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₇H₁₂N₂O₂·2H₂O	γ = 74.64 (3)°
M_r = 312.32	V = 748.7 (3) Å³
Triclinic, P1	Z = 2
a = 7.8700 (16) Å	Mo Kα radiation
b = 10.090 (2) Å	µ = 0.10 mm⁻¹
c = 10.250 (2) Å	T = 298 K
α = 81.36 (3)°	0.13 × 0.12 × 0.12 mm
β = 73.13 (3)°

Data collection top

Bruker SMART CCD diffractometer	2741 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2120 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.993	R_int = 0.014
6136 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	4 restraints
wR(F²) = 0.172	H atoms treated by a mixture of independent and constrained refinement
S = 1.18	Δρ_max = 0.26 e Å⁻³
2741 reflections	Δρ_min = −0.29 e Å⁻³
221 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	−0.30377 (18)	0.27817 (16)	0.65560 (13)	0.0580 (4)
O2	−0.32509 (18)	0.40158 (14)	0.82326 (13)	0.0604 (4)
O3	−0.2973 (2)	0.5061 (2)	1.05692 (18)	0.0752 (5)
H1	−0.297 (4)	0.472 (3)	0.980 (2)	0.113*
H2	−0.411 (3)	0.549 (3)	1.091 (3)	0.113*
O4	−0.2512 (2)	0.16627 (17)	0.41923 (14)	0.0644 (4)
H3	−0.255 (4)	0.213 (3)	0.487 (2)	0.087*
H4	−0.177 (4)	0.192 (3)	0.348 (2)	0.113 (11)*
N1	0.9650 (2)	−0.16420 (18)	−0.16937 (16)	0.0582 (5)
N2	0.35792 (18)	0.20963 (14)	0.37683 (13)	0.0390 (4)
C1	0.8954 (3)	−0.2281 (2)	−0.0513 (2)	0.0700 (7)
H1A	0.9321	−0.3238	−0.0414	0.084*
C2	0.7715 (3)	−0.1613 (2)	0.0583 (2)	0.0640 (6)
H2A	0.7263	−0.2118	0.1387	0.077*
C3	0.9079 (3)	−0.0286 (2)	−0.1783 (2)	0.0677 (6)
H3A	0.9535	0.0193	−0.2605	0.081*
C4	0.7868 (3)	0.0465 (2)	−0.0755 (2)	0.0635 (6)
H4A	0.7529	0.1421	−0.0888	0.076*
C5	0.7152 (2)	−0.01950 (17)	0.04765 (16)	0.0402 (4)
C6	0.5871 (2)	0.05920 (17)	0.16200 (16)	0.0392 (4)
C7	0.4871 (2)	−0.00366 (18)	0.27897 (17)	0.0442 (4)
H7A	0.4963	−0.0981	0.2854	0.053*
C8	0.3756 (2)	0.07283 (18)	0.38421 (17)	0.0440 (4)
H8A	0.3111	0.0294	0.4621	0.053*
C9	0.5631 (3)	0.20167 (19)	0.15781 (18)	0.0501 (5)
H9A	0.6250	0.2481	0.0809	0.060*
C10	0.4506 (3)	0.27350 (18)	0.26465 (18)	0.0484 (5)
H10A	0.4375	0.3683	0.2602	0.058*
C11	0.2450 (2)	0.28855 (17)	0.49151 (16)	0.0388 (4)
C12	0.3181 (2)	0.37361 (19)	0.54246 (18)	0.0469 (5)
H12A	0.4384	0.3802	0.5042	0.056*
C13	0.2094 (3)	0.4484 (2)	0.65104 (19)	0.0516 (5)
H13A	0.2568	0.5055	0.6871	0.062*
C14	0.0297 (3)	0.43901 (19)	0.70679 (18)	0.0469 (4)
H14A	−0.0429	0.4906	0.7795	0.056*
C15	0.0660 (2)	0.27777 (17)	0.54661 (16)	0.0393 (4)
H15A	0.0194	0.2200	0.5108	0.047*
C16	−0.0432 (2)	0.35330 (17)	0.65519 (15)	0.0388 (4)
C17	−0.2405 (2)	0.34373 (17)	0.71527 (16)	0.0413 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0458 (8)	0.0799 (10)	0.0496 (7)	−0.0242 (7)	0.0005 (6)	−0.0184 (7)
O2	0.0515 (8)	0.0625 (9)	0.0572 (8)	−0.0111 (7)	0.0101 (6)	−0.0272 (7)
O3	0.0608 (10)	0.0918 (13)	0.0733 (10)	−0.0222 (9)	−0.0073 (8)	−0.0201 (9)
O4	0.0642 (10)	0.0820 (11)	0.0501 (8)	−0.0358 (8)	0.0032 (7)	−0.0173 (7)
N1	0.0570 (10)	0.0578 (10)	0.0506 (9)	−0.0097 (8)	0.0010 (7)	−0.0132 (8)
N2	0.0331 (7)	0.0408 (8)	0.0408 (7)	−0.0077 (6)	−0.0065 (6)	−0.0044 (6)
C1	0.0842 (16)	0.0437 (11)	0.0632 (13)	−0.0089 (10)	0.0087 (11)	−0.0138 (10)
C2	0.0801 (15)	0.0448 (11)	0.0489 (11)	−0.0109 (10)	0.0079 (10)	−0.0045 (9)
C3	0.0795 (15)	0.0595 (13)	0.0436 (10)	−0.0115 (11)	0.0092 (10)	−0.0007 (9)
C4	0.0781 (14)	0.0440 (10)	0.0470 (11)	−0.0038 (9)	0.0059 (9)	−0.0017 (9)
C5	0.0384 (9)	0.0431 (9)	0.0388 (9)	−0.0099 (7)	−0.0086 (7)	−0.0042 (7)
C6	0.0371 (9)	0.0402 (9)	0.0388 (9)	−0.0085 (7)	−0.0085 (7)	−0.0023 (7)
C7	0.0495 (10)	0.0378 (9)	0.0420 (9)	−0.0125 (7)	−0.0041 (7)	−0.0041 (7)
C8	0.0431 (9)	0.0430 (9)	0.0417 (9)	−0.0132 (7)	−0.0028 (7)	−0.0013 (7)
C9	0.0538 (11)	0.0420 (10)	0.0438 (9)	−0.0116 (8)	0.0016 (8)	0.0008 (8)
C10	0.0528 (11)	0.0362 (9)	0.0472 (10)	−0.0093 (8)	−0.0011 (8)	−0.0024 (8)
C11	0.0347 (9)	0.0409 (9)	0.0379 (8)	−0.0050 (7)	−0.0074 (7)	−0.0054 (7)
C12	0.0367 (9)	0.0502 (10)	0.0546 (10)	−0.0110 (8)	−0.0101 (8)	−0.0090 (8)
C13	0.0538 (11)	0.0529 (11)	0.0551 (10)	−0.0166 (9)	−0.0162 (8)	−0.0145 (9)
C14	0.0494 (10)	0.0452 (10)	0.0434 (9)	−0.0077 (8)	−0.0076 (7)	−0.0109 (8)
C15	0.0375 (9)	0.0410 (9)	0.0396 (9)	−0.0085 (7)	−0.0087 (7)	−0.0076 (7)
C16	0.0389 (9)	0.0378 (8)	0.0361 (8)	−0.0048 (7)	−0.0077 (7)	−0.0036 (7)
C17	0.0420 (9)	0.0383 (9)	0.0379 (8)	−0.0058 (7)	−0.0035 (7)	−0.0061 (7)

Geometric parameters (Å, º) top

O1—C17	1.238 (2)	C8—H8A	0.9300
O2—C17	1.253 (2)	C9—C10	1.358 (3)
N1—C3	1.320 (3)	C9—H9A	0.9300
N1—C1	1.322 (3)	C10—H10A	0.9300
N2—C8	1.343 (2)	C11—C12	1.383 (3)
N2—C10	1.345 (2)	C11—C15	1.384 (2)
N2—C11	1.451 (2)	C12—C13	1.378 (3)
C1—C2	1.382 (3)	C12—H12A	0.9300
C1—H1A	0.9300	C13—C14	1.386 (3)
C2—C5	1.379 (3)	C13—H13A	0.9300
C2—H2A	0.9300	C14—C16	1.390 (3)
C3—C4	1.367 (3)	C14—H14A	0.9300
C3—H3A	0.9300	C15—C16	1.382 (2)
C4—C5	1.374 (3)	C15—H15A	0.9300
C4—H4A	0.9300	C16—C17	1.519 (2)
C5—C6	1.480 (2)	O4—H3	0.891 (17)
C6—C9	1.395 (2)	O4—H4	0.847 (17)
C6—C7	1.396 (2)	O3—H2	0.880 (18)
C7—C8	1.368 (2)	O3—H1	0.904 (18)
C7—H7A	0.9300

C3—N1—C1	115.64 (17)	C10—C9—H9A	119.6
C8—N2—C10	119.98 (15)	C6—C9—H9A	119.6
C8—N2—C11	120.41 (14)	N2—C10—C9	121.01 (16)
C10—N2—C11	119.57 (14)	N2—C10—H10A	119.5
N1—C1—C2	123.91 (19)	C9—C10—H10A	119.5
N1—C1—H1A	118.0	C12—C11—C15	121.54 (16)
C2—C1—H1A	118.0	C12—C11—N2	119.25 (15)
C5—C2—C1	119.65 (17)	C15—C11—N2	119.20 (15)
C5—C2—H2A	120.2	C13—C12—C11	118.75 (16)
C1—C2—H2A	120.2	C13—C12—H12A	120.6
N1—C3—C4	124.66 (18)	C11—C12—H12A	120.6
N1—C3—H3A	117.7	C12—C13—C14	120.29 (17)
C4—C3—H3A	117.7	C12—C13—H13A	119.9
C3—C4—C5	119.83 (18)	C14—C13—H13A	119.9
C3—C4—H4A	120.1	C13—C14—C16	120.73 (17)
C5—C4—H4A	120.1	C13—C14—H14A	119.6
C4—C5—C2	116.29 (17)	C16—C14—H14A	119.6
C4—C5—C6	121.07 (16)	C16—C15—C11	119.65 (16)
C2—C5—C6	122.63 (15)	C16—C15—H15A	120.2
C9—C6—C7	116.72 (16)	C11—C15—H15A	120.2
C9—C6—C5	120.71 (15)	C15—C16—C14	119.05 (16)
C7—C6—C5	122.56 (15)	C15—C16—C17	120.11 (15)
C8—C7—C6	120.38 (16)	C14—C16—C17	120.83 (16)
C8—C7—H7A	119.8	O1—C17—O2	125.33 (17)
C6—C7—H7A	119.8	O1—C17—C16	117.90 (15)
N2—C8—C7	121.04 (15)	O2—C17—C16	116.75 (16)
N2—C8—H8A	119.5	H3—O4—H4	108 (3)
C7—C8—H8A	119.5	H2—O3—H1	105 (3)
C10—C9—C6	120.85 (16)

C3—N1—C1—C2	−0.3 (4)	C11—N2—C10—C9	177.37 (16)
N1—C1—C2—C5	−0.5 (4)	C6—C9—C10—N2	−0.7 (3)
C1—N1—C3—C4	0.7 (4)	C8—N2—C11—C12	127.44 (17)
N1—C3—C4—C5	−0.2 (4)	C10—N2—C11—C12	−50.1 (2)
C3—C4—C5—C2	−0.6 (3)	C8—N2—C11—C15	−53.1 (2)
C3—C4—C5—C6	178.5 (2)	C10—N2—C11—C15	129.41 (17)
C1—C2—C5—C4	0.9 (3)	C15—C11—C12—C13	0.3 (3)
C1—C2—C5—C6	−178.2 (2)	N2—C11—C12—C13	179.77 (15)
C4—C5—C6—C9	−12.6 (3)	C11—C12—C13—C14	−0.6 (3)
C2—C5—C6—C9	166.49 (19)	C12—C13—C14—C16	0.6 (3)
C4—C5—C6—C7	168.32 (19)	C12—C11—C15—C16	−0.1 (2)
C2—C5—C6—C7	−12.6 (3)	N2—C11—C15—C16	−179.52 (13)
C9—C6—C7—C8	−1.6 (3)	C11—C15—C16—C14	0.1 (2)
C5—C6—C7—C8	177.51 (15)	C11—C15—C16—C17	179.20 (14)
C10—N2—C8—C7	0.0 (3)	C13—C14—C16—C15	−0.4 (3)
C11—N2—C8—C7	−177.48 (15)	C13—C14—C16—C17	−179.46 (15)
C6—C7—C8—N2	0.9 (3)	C15—C16—C17—O1	−7.1 (2)
C7—C6—C9—C10	1.5 (3)	C14—C16—C17—O1	171.97 (16)
C5—C6—C9—C10	−177.65 (16)	C15—C16—C17—O2	171.73 (14)
C8—N2—C10—C9	−0.1 (3)	C14—C16—C17—O2	−9.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H3···O1	0.89 (3)	1.84 (2)	2.703 (2)	164 (1)
O3—H1···O2	0.91 (2)	1.94 (2)	2.843 (3)	174 (1)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H3···O1	0.89 (3)	1.84 (2)	2.703 (2)	163.82 (3)
O3—H1···O2	0.91 (2)	1.94 (2)	2.843 (3)	173.69 (4)

Acknowledgements

The authors thank the Project on Integration of Industry, Education and Research of Guangdong Province (2012B091100430), the Fundamental Research Funds for the Central Universities (2012ZD0038), the National Undergraduate Research Program and the SRP program for financial support.

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