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

Sandhu, B.; Draguta, S.; Fonari, M.S.; Antipin, M.; Timofeeva, T.V.

doi:10.1107/S1600536813013445

organic compounds

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ISSN: 2056-9890

Volume 69| Part 6| June 2013| Page o940

doi:10.1107/S1600536813013445

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

Bhupinder Sandhu,^a Sergiu Draguta,^a Marina S. Fonari,^b ^* Mikhail Antipin ^a and Tatiana V. Timofeeva ^a

^aDepartment of Chemistry & Biology, New Mexico Highlands University, 803 University Avenue, Las Vegas, NM 87701, USA, and ^bInstitute of Applied Physics Academy of Sciences of Moldova, Academy str. 5, MD-2028 Chisinau, Republic of Moldova
^*Correspondence e-mail: fonari.xray@gmail.com

(Received 22 March 2013; accepted 15 May 2013; online 22 May 2013)

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, molecules 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_r = 330.29
Triclinic, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.033
wR(F²) = 0.094
S = 1.06
5022 reflections
337 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 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
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)

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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813013445/gw2133sup1.cif

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

Supporting information file. DOI: 10.1107/S1600536813013445/gw2133Isup3.cml

checkCIF report

Comment top

The co-crystallization process is widely used to obtain new solid forms of active pharmaceutical ingredients (API) with enhanced physiochemical properties such as stability, dissolution rate, and solubility without altering their pharmacological behavior (Aakeroy et al. 2006; Desiraju, 2003). The pyridine-4-carboxaldehyde and fumaric acid are widely used in the biological and medicinal fields. Pyridine-4-carboxaldehyde is used as a starting material for the preparation of cytokine suppressive drugs to treat arthritis (Boehm et al. 1996). Fumaric acid is of interest since it is known to form supramolecular assemblies with N-aromatic bases (Batchelor et al.2000) and is generally regarded as safe (GRAS) in the list of pharmaceutically acceptable cocrystal formers. The asymmetric unit of the title compound contains three planar molecules of pyridine-4-carboxaldehyde, and one and a half molecules of fumaric acid. They comprise two crystallographically different H-bonded trimers (C₆H₅NO)_2.(C₄H₄O₄), one of which occupies general position, while another resides on an inversion center in the triclinic unit cell as shown in Fig. 1. In the fumaric acid molecules, the C₂₂—O₆, C₁₉—O₄, and C₂₃—O₈ bond distances of 1.220 (3) Å, 1.219 (2) Å, 1.215 (3) Å are much shorter than the C₂₂—O₇, C₁₉—O₅, and C₂₃—O₉ bond distances of 1.312 (3) Å, 1.318 (2) Å, and 1.317 (2) Å respectively, indicating the neutral carboxyl groups in the crystal structure (Liu et al. 2003). However, the carboxylic O—H-atoms are on their way to the pyridine nitrogen atoms as it follows from the increased O—H distances in comparison with the standard values (0.86 Å).

The dihedral angles between the planar pyridine rings and the mean planes of fumaric acid molecules are 19.2° and 22.2° in the first, and of 25.7° in the second formula units in the crystal structure.

In the trimer, the neutral entities are held together via two (COOH) H···N (pyridine) hydrogen-bonds forming a complementary ADA array. The slightly corrugated aggregates are packed in stacks as shown in Fig. 2. The crystal packing is further stabilized by the weak C—H···O intermolecular interactions with participation of carbonyl oxygen atoms.

Related literature top

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 molecular complexes 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 top

Pyridine-4-carboxaldehyde (19.3 µL, 0.20 mmol) was dissolved in 5 ml of ethanol. To this solution was added fumaric acid (0.012 g, 0.10 mmol) in 5 mL of ethanol. The resulting solution was heated until the both compounds were dissolved completely and allowed to stand for slow evaporation. White prisms were obtained after 3 days. mp 215–220°C.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (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 (C₆H₅NO)_2.(C₄H₄O₄) showing (50%) probablity displacement ellipsoids and the atoms numbering scheme.
	Fig. 2. Crystal packing showing intermolecular hydrogen bonding interactions, view along c axis.

Pyridine-4-carbaldehyde–fumaric acid (2/1) top

Crystal data top

2C₆H₅NO·C₄H₄O₄	Z = 3
M_r = 330.29	F(000) = 516
Triclinic, P1	D_x = 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

Data collection top

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

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)] = 0.033	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(F_o²) + (0.0502P)² + 0.2407P] where P = (F_o² + 2F_c²)/3
5022 reflections	(Δ/σ)_max = 0.001
337 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

2C₆H₅NO·C₄H₄O₄	γ = 80.064 (3)°
M_r = 330.29	V = 1155.6 (4) Å³
Triclinic, P1	Z = 3
a = 6.9388 (12) Å	Mo Kα radiation
b = 10.1962 (18) Å	µ = 0.11 mm⁻¹
c = 17.002 (3) Å	T = 100 K
α = 82.450 (3)°	0.04 × 0.03 × 0.02 mm
β = 78.615 (3)°

Data collection top

Bruker APEXII CCD diffractometer	5022 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	4351 reflections with I > 2σ(I)
T_min = 0.996, T_max = 0.998	R_int = 0.018
11918 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.30 e Å⁻³
5022 reflections	Δρ_min = −0.24 e Å⁻³
337 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	0.03877 (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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Symmetry code: (i) −x+1, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

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)

Experimental details

Crystal data
Chemical formula	2C₆H₅NO·C₄H₄O₄
M_r	330.29
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	6.9388 (12), 10.1962 (18), 17.002 (3)
α, β, γ (°)	82.450 (3), 78.615 (3), 80.064 (3)
V (Å³)	1155.6 (4)
Z	3
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.04 × 0.03 × 0.02

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.996, 0.998
No. of measured, independent and observed [I > 2σ(I)] reflections	11918, 5022, 4351
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.094, 1.06
No. of reflections	5022
No. of parameters	337
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.24

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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)

Acknowledgements

The authors are grateful for NSF support via DMR grant 0934212 (PREM) and CHE 0832622.)

References

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