4,4'-Bipyridine-3-nitro-benzoic acid (1/2).

The title compound, C(10)H(8)N(2)·2C(7)H(5)NO(4),was obtained unintentionally as the harvested product of the hydro-thermal reaction between Co(OAc)(2)·4H(2)O and 4,4'-bipyridine in the presence of 3-nitro-phthalic acid. In the reaction, 3-nitro-phthalic acid is transformed into 3-nitro-benzoic acid by an in situ deca-rboxylation reaction, in which the carboxyl-ate group is not deprotonated and is uncoordinated. In the crystal, the uncoordinated 3-nitro-benzoic acid and free 4,4'-bipyridine mol-ecules are linked alternately by O-H⋯N hydrogen bonds into chains, which are assembled by C-H⋯O hydrogen bonds into a three-dimensional supra-molecular 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 = 490.42

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.103

S = 1.09

1935 reflections

166 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.18 e Å−3

Δρmin = −0.24 e Å−3

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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810003594/bg2325sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C10H8N2·2C7H5NO4	F(000) = 1016
Mr = 490.42	Dx = 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

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

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(Fo2) + (0.0674P)2 + 0.0461P] where P = (Fo2 + 2Fc2)/3
1935 reflections	(Δ/σ)max < 0.001
166 parameters	Δρmax = 0.18 e Å−3
1 restraint	Δρmin = −0.24 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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···O1iv	0.93	2.35	3.242 (2)	160

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⋯O1iv	0.93	2.35	3.242 (2)	160

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .