4,4′-Bipyridine–3-nitro­benzoic acid (1/2)

Zhu, Z.; Wang, F.-Q.; Zhao, Y.-N.

doi:10.1107/S1600536810003594

organic compounds

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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page o546

doi:10.1107/S1600536810003594

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4,4′-Bipyridine–3-nitrobenzoic acid (1/2)

Zhen Zhu,^a Feng-Qin Wang ^b ^* and Yong-Nan Zhao ^a

^aCollege of Materials and Engineering, Tianjin Polytechnic University, Tianjin 300160, People's Republic of China, and ^bCollege of Environment and Chemical Engineering & Tianjin Key Laboratory of Fiber Modification and Functional Fiber, Tianjin Polytechnic University, Tianjin 300160, People's Republic of China
^*Correspondence e-mail: wfengqin@yahoo.com.cn

(Received 12 January 2010; accepted 29 January 2010; online 6 February 2010)

The title compound, C₁₀H₈N₂·2C₇H₅NO₄,was obtained unintentionally as the harvested product of the hydrothermal reaction between Co(OAc)₂·4H₂O and 4,4′-bipyridine in the presence of 3-nitrophthalic acid. In the reaction, 3-nitrophthalic acid is transformed into 3-nitrobenzoic acid by an in situ decarboxylation reaction, in which the carboxylate group is not deprotonated and is uncoordinated. In the crystal, the uncoordinated 3-nitrobenzoic acid and free 4,4′-bipyridine molecules are linked alternately by O—H⋯N hydrogen bonds into chains, which are assembled by C—H⋯O hydrogen bonds into a three-dimensional supramolecular network.

Related literature

For the use of 3-nitrophthalic acid in the self-assembly of coordination compounds, see: Deng et al. (2007a ,b ); Huang et al. (2007 ); Song et al. (2007 ); Wang et al. (2009 ).

Experimental

Crystal data

C₁₀H₈N₂·2C₇H₅NO₄
M_r = 490.42
Monoclinic, C 2/c
a = 26.489 (7) Å
b = 6.7757 (14) Å
c = 13.291 (3) Å
β = 112.19 (3)°
V = 2208.8 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 113 K
0.20 × 0.12 × 0.10 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.978, T_max = 0.989
7177 measured reflections
1935 independent reflections
1646 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.103
S = 1.09
1935 reflections
166 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯N2ⁱ	0.85 (1)	1.76 (1)	2.608 (2)	175 (2)
C5—H5⋯O3ⁱⁱ	0.93	2.49	3.390 (2)	162
C9—H9⋯O4ⁱⁱⁱ	0.93	2.55	3.436 (2)	159
C12—H12⋯O1^iv	0.93	2.35	3.242 (2)	160
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x, y, -z+{\script{1\over 2}}]$ ; (iii) -x, -y+1, -z; (iv) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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 I, global. DOI: 10.1107/S1600536810003594/bg2325sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810003594/bg2325Isup2.hkl

checkCIF report

Comment top

3-nitrophthic acid acting as a multifunctional organic ligand has been widely used in the self-assembly of various coordination compounds (Deng et al., 2007a,b; Huang et al., 2007; Song et al., 2007, Wang et al., 2009). The title compound were obtained unintentionally as the harvested product of the hydrothermal reaction between Co(oAc)₂.4H₂O and 4,4'-bipyridine in the presence of 3-nitrophthic acid. In the title compound, 3-nitrophthlic acid is transformed into 3-nitrobenzoic acid by in situ decarboxylation reaction, in which the carboxylate group is not deprotoned and is uncoordinated. The molecular structure of the title compound is illustrated in Fig. 1. The bond distances and angles are normal within experimental error.

The crystal packing of the title compound is illustrated in Fig. 2. The uncoordinated 3-nitrobenzoic acid and free 4,4'-bipyridine molecules are linked alternately by hydrogen bonds (O—H···O) into one-dimensional chains. Furthermore, these one-dimensional chains are assembled by hydrogen bonds(C—H···O) into three-dimensional supramolecular network.

Related literature top

For the use of 3-nitrophthic acid in the self-assembly of coordination compounds, see: Deng et al. (2007a,b); Huang et al. (2007); Song et al. (2007); Wang et al. (2009).

Experimental top

A mixture of 3-nitrophthalic acid(0.020 g, 0.1 mmol), Co(oAc)₂.4H₂O(0.025 g, 0.1 mmol), 4,4'-bipyridine (0.019 g, 0.1 mmol), deionized water (8 ml) was sealed in a Teflon-lined stainless steel vessel (23 ml) and heated at 160 °C for 4 days under autogenous pressure and then cooled slowly to room temperature. The solution was filtered and after allowed to stand for a few weeks at room temperature, purple-red crystals were obtained.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); 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 molecular structure of the title compound, showing the atom-numbering scheme. Dispacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound along b axis. Hydrogen bonds are indicated by dashed lines.

4,4'-Bipyridine–3-nitrobenzoic acid (1/2) top

Crystal data top

C₁₀H₈N₂·2C₇H₅NO₄	F(000) = 1016
M_r = 490.42	D_x = 1.475 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2874 reflections
a = 26.489 (7) Å	θ = 3.1–27.4°
b = 6.7757 (14) Å	µ = 0.11 mm⁻¹
c = 13.291 (3) Å	T = 113 K
β = 112.19 (3)°	Plate, purple–red
V = 2208.8 (9) Å³	0.20 × 0.12 × 0.10 mm
Z = 4

Data collection top

Rigaku Saturn CCD area-detector diffractometer	1935 independent reflections
Radiation source: rotating anode	1646 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.029
Detector resolution: 7.31 pixels mm^-1	θ_max = 25.0°, θ_min = 3.1°
ω and ϕ scans	h = −31→31
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −7→8
T_min = 0.978, T_max = 0.989	l = −13→15
7177 measured reflections

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0674P)² + 0.0461P] where P = (F_o² + 2F_c²)/3
1935 reflections	(Δ/σ)_max < 0.001
166 parameters	Δρ_max = 0.18 e Å⁻³
1 restraint	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₀H₈N₂·2C₇H₅NO₄	V = 2208.8 (9) Å³
M_r = 490.42	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 26.489 (7) Å	µ = 0.11 mm⁻¹
b = 6.7757 (14) Å	T = 113 K
c = 13.291 (3) Å	0.20 × 0.12 × 0.10 mm
β = 112.19 (3)°

Data collection top

Rigaku Saturn CCD area-detector diffractometer	1935 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	1646 reflections with I > 2σ(I)
T_min = 0.978, T_max = 0.989	R_int = 0.029
7177 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	1 restraint
wR(F²) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.18 e Å⁻³
1935 reflections	Δρ_min = −0.24 e Å⁻³
166 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
O1	0.30213 (4)	0.58310 (15)	0.39895 (8)	0.0316 (3)
O2	0.26214 (4)	0.60692 (13)	0.21797 (8)	0.0238 (3)
H2	0.2955 (4)	0.608 (2)	0.2257 (14)	0.036*
O3	0.01600 (4)	0.66151 (15)	0.13387 (9)	0.0328 (3)
O4	0.06802 (4)	0.65732 (16)	0.04209 (8)	0.0363 (3)
N1	0.06088 (4)	0.64662 (15)	0.12810 (10)	0.0223 (3)
N2	0.13751 (4)	0.10542 (14)	0.27135 (9)	0.0189 (3)
C1	0.26146 (5)	0.59392 (18)	0.31583 (11)	0.0204 (3)
C2	0.20523 (5)	0.59219 (17)	0.31772 (11)	0.0189 (3)
C3	0.19834 (5)	0.56014 (18)	0.41546 (11)	0.0231 (3)
H3	0.2287	0.5420	0.4791	0.028*
C4	0.14675 (6)	0.55513 (18)	0.41864 (12)	0.0247 (3)
H4	0.1427	0.5334	0.4843	0.030*
C5	0.10097 (5)	0.58232 (18)	0.32441 (11)	0.0224 (3)
H5	0.0661	0.5781	0.3256	0.027*
C6	0.10882 (5)	0.61589 (17)	0.22863 (11)	0.0188 (3)
C7	0.15989 (5)	0.62214 (17)	0.22295 (11)	0.0181 (3)
H7	0.1637	0.6458	0.1573	0.022*
C8	0.09648 (5)	0.14365 (18)	0.17646 (11)	0.0200 (3)
H8	0.1049	0.1696	0.1158	0.024*
C9	0.04234 (5)	0.14626 (18)	0.16471 (11)	0.0193 (3)
H9	0.0152	0.1758	0.0978	0.023*
C10	0.02882 (5)	0.10427 (17)	0.25412 (11)	0.0175 (3)
C11	0.07148 (5)	0.06255 (18)	0.35231 (11)	0.0195 (3)
H11	0.0642	0.0326	0.4138	0.023*
C12	0.12465 (5)	0.06609 (17)	0.35760 (11)	0.0197 (3)
H12	0.1527	0.0400	0.4239	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0164 (5)	0.0538 (7)	0.0208 (6)	−0.0010 (4)	0.0028 (4)	0.0011 (4)
O2	0.0140 (5)	0.0381 (6)	0.0195 (5)	0.0001 (4)	0.0066 (4)	0.0023 (4)
O3	0.0145 (5)	0.0425 (6)	0.0437 (7)	0.0011 (4)	0.0134 (5)	−0.0002 (5)
O4	0.0229 (6)	0.0611 (7)	0.0243 (6)	0.0058 (5)	0.0083 (5)	0.0070 (5)
N1	0.0167 (6)	0.0213 (6)	0.0295 (7)	0.0001 (4)	0.0095 (5)	−0.0005 (5)
N2	0.0153 (6)	0.0180 (6)	0.0226 (6)	0.0008 (4)	0.0064 (5)	−0.0013 (4)
C1	0.0190 (7)	0.0219 (7)	0.0205 (7)	−0.0017 (5)	0.0075 (6)	−0.0003 (5)
C2	0.0185 (7)	0.0183 (6)	0.0203 (7)	−0.0013 (5)	0.0078 (6)	−0.0015 (5)
C3	0.0233 (7)	0.0260 (7)	0.0195 (7)	−0.0018 (5)	0.0076 (6)	0.0001 (5)
C4	0.0302 (8)	0.0256 (7)	0.0235 (8)	−0.0019 (6)	0.0161 (6)	0.0002 (6)
C5	0.0227 (8)	0.0179 (6)	0.0321 (8)	−0.0014 (5)	0.0167 (6)	−0.0026 (5)
C6	0.0169 (7)	0.0154 (6)	0.0233 (8)	−0.0005 (5)	0.0067 (6)	−0.0018 (5)
C7	0.0201 (7)	0.0166 (6)	0.0198 (7)	−0.0013 (5)	0.0100 (6)	−0.0018 (5)
C8	0.0189 (7)	0.0192 (7)	0.0233 (8)	−0.0017 (5)	0.0096 (6)	−0.0009 (5)
C9	0.0150 (7)	0.0197 (7)	0.0209 (7)	0.0005 (5)	0.0042 (6)	0.0006 (5)
C10	0.0153 (7)	0.0147 (6)	0.0220 (7)	−0.0007 (5)	0.0067 (6)	−0.0025 (5)
C11	0.0187 (7)	0.0200 (6)	0.0203 (7)	0.0009 (5)	0.0079 (6)	0.0001 (5)
C12	0.0150 (7)	0.0197 (7)	0.0211 (7)	0.0018 (5)	0.0030 (6)	−0.0009 (5)

Geometric parameters (Å, º) top

O1—C1	1.2197 (17)	C4—H4	0.9300
O2—C1	1.3106 (17)	C5—C6	1.3839 (19)
O2—H2	0.850 (9)	C5—H5	0.9300
O3—N1	1.2242 (14)	C6—C7	1.3838 (18)
O4—N1	1.2294 (14)	C7—H7	0.9300
N1—C6	1.4695 (18)	C8—C9	1.3827 (18)
N2—C12	1.3402 (18)	C8—H8	0.9300
N2—C8	1.3430 (18)	C9—C10	1.3938 (19)
C1—C2	1.4991 (19)	C9—H9	0.9300
C2—C7	1.388 (2)	C10—C11	1.3950 (19)
C2—C3	1.3954 (19)	C10—C10ⁱ	1.489 (2)
C3—C4	1.3835 (19)	C11—C12	1.3836 (18)
C3—H3	0.9300	C11—H11	0.9300
C4—C5	1.388 (2)	C12—H12	0.9300

C1—O2—H2	106.5 (12)	C7—C6—N1	118.22 (12)
O3—N1—O4	123.21 (12)	C5—C6—N1	118.77 (11)
O3—N1—C6	118.74 (12)	C6—C7—C2	118.33 (13)
O4—N1—C6	118.05 (10)	C6—C7—H7	120.8
C12—N2—C8	117.68 (11)	C2—C7—H7	120.8
O1—C1—O2	124.35 (13)	N2—C8—C9	123.06 (13)
O1—C1—C2	121.85 (13)	N2—C8—H8	118.5
O2—C1—C2	113.79 (12)	C9—C8—H8	118.5
C7—C2—C3	119.66 (13)	C8—C9—C10	119.38 (12)
C7—C2—C1	120.54 (12)	C8—C9—H9	120.3
C3—C2—C1	119.80 (12)	C10—C9—H9	120.3
C4—C3—C2	120.68 (13)	C9—C10—C11	117.44 (12)
C4—C3—H3	119.7	C9—C10—C10ⁱ	121.59 (14)
C2—C3—H3	119.7	C11—C10—C10ⁱ	120.97 (15)
C3—C4—C5	120.38 (13)	C12—C11—C10	119.56 (13)
C3—C4—H4	119.8	C12—C11—H11	120.2
C5—C4—H4	119.8	C10—C11—H11	120.2
C6—C5—C4	117.93 (12)	N2—C12—C11	122.87 (12)
C6—C5—H5	121.0	N2—C12—H12	118.6
C4—C5—H5	121.0	C11—C12—H12	118.6
C7—C6—C5	123.01 (13)

O1—C1—C2—C7	174.30 (12)	O4—N1—C6—C5	−173.13 (11)
O2—C1—C2—C7	−6.02 (16)	C5—C6—C7—C2	0.37 (18)
O1—C1—C2—C3	−5.73 (18)	N1—C6—C7—C2	−179.69 (10)
O2—C1—C2—C3	173.94 (10)	C3—C2—C7—C6	−1.03 (17)
C7—C2—C3—C4	0.92 (18)	C1—C2—C7—C6	178.94 (10)
C1—C2—C3—C4	−179.05 (11)	C12—N2—C8—C9	0.77 (17)
C2—C3—C4—C5	−0.11 (18)	N2—C8—C9—C10	−1.16 (18)
C3—C4—C5—C6	−0.54 (18)	C8—C9—C10—C11	0.43 (16)
C4—C5—C6—C7	0.42 (18)	C8—C9—C10—C10ⁱ	−179.76 (8)
C4—C5—C6—N1	−179.52 (10)	C9—C10—C11—C12	0.59 (17)
O3—N1—C6—C7	−172.63 (10)	C10ⁱ—C10—C11—C12	−179.22 (8)
O4—N1—C6—C7	6.93 (16)	C8—N2—C12—C11	0.33 (17)
O3—N1—C6—C5	7.31 (16)	C10—C11—C12—N2	−1.01 (18)

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
O2—H2···N2ⁱⁱ	0.85 (1)	1.76 (1)	2.608 (2)	175 (2)
C5—H5···O3ⁱ	0.93	2.49	3.390 (2)	162
C9—H9···O4ⁱⁱⁱ	0.93	2.55	3.436 (2)	159
C12—H12···O1^iv	0.93	2.35	3.242 (2)	160

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

Experimental details

Crystal data
Chemical formula	C₁₀H₈N₂·2C₇H₅NO₄
M_r	490.42
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	113
a, b, c (Å)	26.489 (7), 6.7757 (14), 13.291 (3)
β (°)	112.19 (3)
V (Å³)	2208.8 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.20 × 0.12 × 0.10

Data collection
Diffractometer	Rigaku Saturn CCD area-detector diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.978, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	7177, 1935, 1646
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.103, 1.09
No. of reflections	1935
No. of parameters	166
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.24

Computer programs: CrystalClear (Rigaku/MSC, 2005), 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
O2—H2···N2ⁱ	0.85 (1)	1.76 (1)	2.608 (2)	175 (2)
C5—H5···O3ⁱⁱ	0.930	2.490	3.390 (2)	162
C9—H9···O4ⁱⁱⁱ	0.930	2.550	3.436 (2)	159
C12—H12···O1^iv	0.930	2.350	3.242 (2)	160

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

Acknowledgements

We thank Tianjin Polytechnic University for financial support.

References

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