Pyridine-4-carbaldehyde-fumaric acid (2/1).

In the title co-crystal, 2C6H5NO·C4H4O4, two crystallographically different hydrogen-bonded trimers are formed, one in which the components occupy general positions, and one generated by an inversion centre. This results in the uncommon situation of Z = 3 for a triclinic crystal. In the formula units, mol-ecules are linked by O-H⋯N hydrogen bonds.

Related literature

For background to the synthetic procedure, see: Aakeroy et al. (2006 ▶); Desiraju (2003 ▶). For the use of pyridine-4-carboxaldehyde in cytokine suppressive drugs, see: Boehm et al. (1996 ▶). For adducts of neutral pyridine derivatives and neutral fumaric acid, see: Bowes et al. (2003 ▶); Aakeroy et al. (2002 ▶, 2006 ▶, 2007 ▶); Batchelor et al. (2000 ▶). For a related structure, see: Liu et al. (2003 ▶).

Experimental

Crystal data

2C6H5NO·C4H4O4

M = 330.29

Triclinic,

a = 6.9388 (12) Å

b = 10.1962 (18) Å

c = 17.002 (3) Å

α = 82.450 (3)°

β = 78.615 (3)°

γ = 80.064 (3)°

V = 1155.6 (4) Å3

Z = 3

Mo Kα radiation

μ = 0.11 mm−1

T = 100 K

0.04 × 0.03 × 0.02 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T min = 0.996, T max = 0.998

11918 measured reflections

5022 independent reflections

4351 reflections with I > 2σ(I)

R int = 0.018

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.094

S = 1.06

5022 reflections

337 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.30 e Å−3

Δρmin = −0.24 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813013445/gw2133sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813013445/gw2133Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813013445/gw2133Isup3.cml

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

2C6H5NO·C4H4O4	Z = 3
Mr = 330.29	F(000) = 516
Triclinic, P1	Dx = 1.424 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9388 (12) Å	Cell parameters from 15620 reflections
b = 10.1962 (18) Å	θ = 2.5–30.8°
c = 17.002 (3) Å	µ = 0.11 mm−1
α = 82.450 (3)°	T = 100 K
β = 78.615 (3)°	Prism, white
γ = 80.064 (3)°	0.04 × 0.03 × 0.02 mm
V = 1155.6 (4) Å3

Bruker APEXII CCD diffractometer	5022 independent reflections
Radiation source: fine-focus sealed tube	4351 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
φ and ω scans	θmax = 27.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −8→8
Tmin = 0.996, Tmax = 0.998	k = −13→13
11918 measured reflections	l = −21→21

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0502P)2 + 0.2407P] where P = (Fo2 + 2Fc2)/3
5022 reflections	(Δ/σ)max = 0.001
337 parameters	Δρmax = 0.30 e Å−3
0 restraints	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	0.03877 (12)	0.13984 (9)	0.93015 (5)	0.02957 (19)
O3	0.32546 (12)	0.76849 (8)	0.60910 (4)	0.02667 (18)
O2	0.31931 (13)	0.49716 (8)	−0.26052 (5)	0.02852 (19)
O8	0.41401 (12)	0.85465 (8)	0.13133 (4)	0.02579 (18)
O9	0.53088 (12)	1.02613 (8)	0.16686 (4)	0.02420 (18)
H9A	0.497 (3)	0.9765 (19)	0.2235 (11)	0.069 (6)*
O6	0.09363 (12)	0.27889 (8)	0.18081 (4)	0.02574 (18)
O7	0.22987 (12)	0.45738 (8)	0.19320 (4)	0.02386 (18)
O5	0.10344 (12)	0.24097 (8)	0.47468 (4)	0.02441 (18)
H5	0.104 (3)	0.222 (2)	0.5358 (12)	0.076 (6)*
O4	0.24013 (12)	0.41873 (8)	0.48845 (4)	0.02556 (18)
N1	0.08206 (13)	0.17896 (9)	0.62885 (5)	0.02060 (19)
N3	0.44019 (13)	0.91008 (9)	0.31230 (5)	0.02018 (19)
N2	0.24664 (13)	0.50591 (9)	0.03924 (5)	0.02043 (19)
C4	0.07788 (15)	0.27059 (11)	0.67926 (7)	0.0227 (2)
H4	0.0919	0.3598	0.6573	0.027*
C3	0.05391 (15)	0.24005 (11)	0.76207 (6)	0.0217 (2)
H3	0.0500	0.3072	0.7964	0.026*
C2	0.03570 (15)	0.10889 (10)	0.79403 (6)	0.0192 (2)
C6	0.03953 (15)	0.01376 (10)	0.74200 (6)	0.0204 (2)
H6	0.0265	−0.0763	0.7622	0.024*
C5	0.06278 (15)	0.05330 (11)	0.65996 (6)	0.0208 (2)
H5A	0.0652	−0.0115	0.6243	0.025*
C1	0.01669 (15)	0.06833 (11)	0.88228 (6)	0.0231 (2)
H1	−0.0145	−0.0185	0.9020	0.028*
C16	0.40393 (15)	0.97924 (10)	0.37691 (6)	0.0214 (2)
H16	0.4064	1.0730	0.3689	0.026*
C15	0.36315 (15)	0.91885 (10)	0.45471 (6)	0.0207 (2)
H15	0.3347	0.9706	0.4993	0.025*
C14	0.36431 (14)	0.78107 (10)	0.46684 (6)	0.0184 (2)
C18	0.40079 (15)	0.70913 (10)	0.40001 (6)	0.0206 (2)
H18	0.4011	0.6151	0.4064	0.025*
C17	0.43668 (15)	0.77782 (11)	0.32371 (6)	0.0216 (2)
H17	0.4596	0.7293	0.2779	0.026*
C13	0.33112 (15)	0.71201 (11)	0.55014 (6)	0.0211 (2)
H13	0.3138	0.6205	0.5572	0.025*
C11	0.23959 (15)	0.40809 (11)	−0.00530 (6)	0.0219 (2)
H11	0.2156	0.3230	0.0213	0.026*
C12	0.26613 (15)	0.42703 (10)	−0.08878 (6)	0.0206 (2)
H12	0.2629	0.3558	−0.1191	0.025*
C8	0.29763 (14)	0.55274 (10)	−0.12722 (6)	0.0188 (2)
C9	0.30255 (15)	0.65446 (10)	−0.08099 (6)	0.0203 (2)
H9	0.3224	0.7413	−0.1059	0.024*
C10	0.27795 (15)	0.62679 (10)	0.00226 (6)	0.0205 (2)
H10	0.2835	0.6957	0.0340	0.025*
C7	0.32694 (15)	0.57964 (11)	−0.21668 (6)	0.0214 (2)
H7A	0.3529	0.6659	−0.2405	0.026*
C23	0.48373 (15)	0.95840 (10)	0.11436 (6)	0.0198 (2)
C24	0.52458 (16)	1.02301 (11)	0.03024 (6)	0.0228 (2)
H24	0.5885	1.1003	0.0201	0.027*
C22	0.15105 (15)	0.34887 (10)	0.22167 (6)	0.0192 (2)
C21	0.13369 (15)	0.31551 (10)	0.31054 (6)	0.0202 (2)
H21	0.0709	0.2407	0.3347	0.024*
C20	0.20063 (15)	0.38402 (10)	0.35802 (6)	0.0200 (2)
H20	0.2633	0.4590	0.3340	0.024*
C19	0.18294 (15)	0.35002 (10)	0.44683 (6)	0.0193 (2)
H7	0.231 (3)	0.471 (2)	0.1308 (12)	0.077 (6)*

	U11	U22	U33	U12	U13	U23
O1	0.0306 (4)	0.0372 (5)	0.0216 (4)	−0.0025 (3)	−0.0053 (3)	−0.0080 (3)
O3	0.0327 (4)	0.0302 (4)	0.0173 (4)	−0.0076 (3)	−0.0034 (3)	−0.0010 (3)
O2	0.0369 (5)	0.0287 (4)	0.0214 (4)	−0.0058 (3)	−0.0054 (3)	−0.0065 (3)
O8	0.0331 (4)	0.0260 (4)	0.0196 (4)	−0.0131 (3)	−0.0037 (3)	0.0027 (3)
O9	0.0328 (4)	0.0262 (4)	0.0154 (4)	−0.0109 (3)	−0.0047 (3)	0.0004 (3)
O6	0.0345 (4)	0.0251 (4)	0.0205 (4)	−0.0114 (3)	−0.0067 (3)	−0.0005 (3)
O7	0.0316 (4)	0.0245 (4)	0.0168 (4)	−0.0131 (3)	−0.0033 (3)	0.0033 (3)
O5	0.0333 (4)	0.0244 (4)	0.0171 (4)	−0.0126 (3)	−0.0042 (3)	0.0029 (3)
O4	0.0322 (4)	0.0261 (4)	0.0211 (4)	−0.0108 (3)	−0.0063 (3)	−0.0016 (3)
N1	0.0189 (4)	0.0237 (5)	0.0186 (4)	−0.0052 (3)	−0.0027 (3)	0.0017 (3)
N3	0.0197 (4)	0.0228 (4)	0.0178 (4)	−0.0044 (3)	−0.0031 (3)	−0.0001 (3)
N2	0.0187 (4)	0.0232 (5)	0.0188 (4)	−0.0047 (3)	−0.0024 (3)	0.0009 (3)
C4	0.0221 (5)	0.0190 (5)	0.0273 (5)	−0.0056 (4)	−0.0058 (4)	0.0024 (4)
C3	0.0231 (5)	0.0199 (5)	0.0237 (5)	−0.0049 (4)	−0.0055 (4)	−0.0036 (4)
C2	0.0161 (5)	0.0222 (5)	0.0191 (5)	−0.0041 (4)	−0.0022 (4)	−0.0017 (4)
C6	0.0209 (5)	0.0185 (5)	0.0214 (5)	−0.0056 (4)	−0.0022 (4)	0.0002 (4)
C5	0.0216 (5)	0.0220 (5)	0.0191 (5)	−0.0052 (4)	−0.0019 (4)	−0.0035 (4)
C1	0.0215 (5)	0.0268 (5)	0.0196 (5)	−0.0030 (4)	−0.0021 (4)	−0.0006 (4)
C16	0.0233 (5)	0.0190 (5)	0.0222 (5)	−0.0054 (4)	−0.0039 (4)	−0.0011 (4)
C15	0.0217 (5)	0.0215 (5)	0.0198 (5)	−0.0052 (4)	−0.0031 (4)	−0.0041 (4)
C14	0.0161 (5)	0.0222 (5)	0.0175 (5)	−0.0056 (4)	−0.0029 (4)	−0.0006 (4)
C18	0.0218 (5)	0.0194 (5)	0.0214 (5)	−0.0047 (4)	−0.0040 (4)	−0.0030 (4)
C17	0.0219 (5)	0.0241 (5)	0.0197 (5)	−0.0041 (4)	−0.0033 (4)	−0.0050 (4)
C13	0.0205 (5)	0.0226 (5)	0.0202 (5)	−0.0060 (4)	−0.0033 (4)	0.0005 (4)
C11	0.0210 (5)	0.0201 (5)	0.0252 (5)	−0.0062 (4)	−0.0054 (4)	0.0023 (4)
C12	0.0214 (5)	0.0194 (5)	0.0227 (5)	−0.0052 (4)	−0.0058 (4)	−0.0022 (4)
C8	0.0161 (5)	0.0221 (5)	0.0182 (5)	−0.0032 (4)	−0.0032 (4)	−0.0017 (4)
C9	0.0216 (5)	0.0184 (5)	0.0208 (5)	−0.0048 (4)	−0.0035 (4)	−0.0002 (4)
C10	0.0213 (5)	0.0209 (5)	0.0192 (5)	−0.0038 (4)	−0.0027 (4)	−0.0028 (4)
C7	0.0226 (5)	0.0226 (5)	0.0188 (5)	−0.0040 (4)	−0.0038 (4)	−0.0008 (4)
C23	0.0186 (5)	0.0229 (5)	0.0174 (5)	−0.0036 (4)	−0.0029 (4)	−0.0002 (4)
C24	0.0281 (5)	0.0230 (5)	0.0185 (5)	−0.0109 (4)	−0.0035 (4)	0.0022 (4)
C22	0.0185 (5)	0.0200 (5)	0.0179 (5)	−0.0036 (4)	−0.0019 (4)	0.0008 (4)
C21	0.0211 (5)	0.0207 (5)	0.0180 (5)	−0.0060 (4)	−0.0019 (4)	0.0024 (4)
C20	0.0210 (5)	0.0194 (5)	0.0188 (5)	−0.0058 (4)	−0.0018 (4)	0.0022 (4)
C19	0.0183 (5)	0.0200 (5)	0.0188 (5)	−0.0039 (4)	−0.0022 (4)	0.0006 (4)

O1—C1	1.2089 (14)	C16—C15	1.3810 (14)
O3—C13	1.2109 (13)	C16—H16	0.9500
O2—C7	1.2089 (13)	C15—C14	1.3917 (15)
O8—C23	1.2155 (13)	C15—H15	0.9500
O9—C23	1.3175 (13)	C14—C18	1.3909 (14)
O9—H9A	1.030 (19)	C14—C13	1.4898 (14)
O6—C22	1.2199 (13)	C18—C17	1.3890 (14)
O7—C22	1.3119 (12)	C18—H18	0.9500
O7—H7	1.050 (19)	C17—H17	0.9500
O5—C19	1.3171 (12)	C13—H13	0.9500
O5—H5	1.03 (2)	C11—C12	1.3866 (15)
O4—C19	1.2191 (13)	C11—H11	0.9500
N1—C5	1.3388 (14)	C12—C8	1.3921 (14)
N1—C4	1.3415 (14)	C12—H12	0.9500
N3—C17	1.3408 (14)	C8—C9	1.3897 (14)
N3—C16	1.3418 (13)	C8—C7	1.4892 (14)
N2—C10	1.3403 (14)	C9—C10	1.3888 (14)
N2—C11	1.3419 (14)	C9—H9	0.9500
C4—C3	1.3846 (15)	C10—H10	0.9500
C4—H4	0.9500	C7—H7A	0.9500
C3—C2	1.3928 (14)	C23—C24	1.4888 (14)
C3—H3	0.9500	C24—C24i	1.309 (2)
C2—C6	1.3896 (14)	C24—H24	0.9500
C2—C1	1.4890 (14)	C22—C21	1.4900 (14)
C6—C5	1.3856 (14)	C21—C20	1.3280 (15)
C6—H6	0.9500	C21—H21	0.9500
C5—H5A	0.9500	C20—C19	1.4897 (14)
C1—H1	0.9500	C20—H20	0.9500
C23—O9—H9A	108.3 (10)	O3—C13—C14	122.26 (10)
C22—O7—H7	107.3 (11)	O3—C13—H13	118.9
C19—O5—H5	109.4 (11)	C14—C13—H13	118.9
C5—N1—C4	118.60 (9)	N2—C11—C12	122.25 (9)
C17—N3—C16	118.84 (9)	N2—C11—H11	118.9
C10—N2—C11	119.23 (9)	C12—C11—H11	118.9
N1—C4—C3	122.46 (10)	C11—C12—C8	118.55 (9)
N1—C4—H4	118.8	C11—C12—H12	120.7
C3—C4—H4	118.8	C8—C12—H12	120.7
C4—C3—C2	118.67 (10)	C9—C8—C12	119.17 (9)
C4—C3—H3	120.7	C9—C8—C7	119.64 (9)
C2—C3—H3	120.7	C12—C8—C7	121.19 (9)
C6—C2—C3	119.03 (9)	C10—C9—C8	118.76 (9)
C6—C2—C1	119.58 (9)	C10—C9—H9	120.6
C3—C2—C1	121.37 (9)	C8—C9—H9	120.6
C5—C6—C2	118.45 (9)	N2—C10—C9	122.02 (9)
C5—C6—H6	120.8	N2—C10—H10	119.0
C2—C6—H6	120.8	C9—C10—H10	119.0
N1—C5—C6	122.79 (9)	O2—C7—C8	123.27 (10)
N1—C5—H5A	118.6	O2—C7—H7A	118.4
C6—C5—H5A	118.6	C8—C7—H7A	118.4
O1—C1—C2	123.58 (10)	O8—C23—O9	124.76 (9)
O1—C1—H1	118.2	O8—C23—C24	122.67 (9)
C2—C1—H1	118.2	O9—C23—C24	112.57 (9)
N3—C16—C15	122.25 (10)	C24i—C24—C23	122.28 (12)
N3—C16—H16	118.9	C24i—C24—H24	118.9
C15—C16—H16	118.9	C23—C24—H24	118.9
C16—C15—C14	119.04 (9)	O6—C22—O7	124.52 (9)
C16—C15—H15	120.5	O6—C22—C21	120.91 (9)
C14—C15—H15	120.5	O7—C22—C21	114.57 (9)
C15—C14—C18	118.86 (9)	C20—C21—C22	123.99 (9)
C15—C14—C13	120.32 (9)	C20—C21—H21	118.0
C18—C14—C13	120.81 (9)	C22—C21—H21	118.0
C17—C18—C14	118.51 (10)	C21—C20—C19	123.71 (9)
C17—C18—H18	120.7	C21—C20—H20	118.1
C14—C18—H18	120.7	C19—C20—H20	118.1
N3—C17—C18	122.46 (9)	O4—C19—O5	124.32 (9)
N3—C17—H17	118.8	O4—C19—C20	121.40 (9)
C18—C17—H17	118.8	O5—C19—C20	114.27 (9)

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9A···N3	1.030 (19)	1.576 (19)	2.6047 (12)	176.1 (17)
O5—H5···N1	1.03 (2)	1.57 (2)	2.5952 (12)	172.0 (18)
O7—H7···N2	1.050 (19)	1.54 (2)	2.5826 (12)	172.9 (18)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9—H9A⋯N3	1.030 (19)	1.576 (19)	2.6047 (12)	176.1 (17)
O5—H5⋯N1	1.03 (2)	1.57 (2)	2.5952 (12)	172.0 (18)
O7—H7⋯N2	1.050 (19)	1.54 (2)	2.5826 (12)	172.9 (18)