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In the title complex, C9H8N+·C4H3O4, fumarate anions are linked by O—H...O hydrogen bonds, forming infinite supramolecular chains along the c axis. Quinolinium cations are attached to the anionic chains via N—H...O and C—H...O interactions. The crystal structure determination confirms the protonation of the quinoline N atom and deprotonation of one of the carboxyl­ic acid groups of fumaric acid.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803004446/bt6244sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803004446/bt6244Isup2.hkl
Contains datablock I

CCDC reference: 209910

Key indicators

  • Single-crystal X-ray study
  • T = 140 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.034
  • wR factor = 0.085
  • Data-to-parameter ratio = 14.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
ABSTM_02 Alert C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90 Tmin and Tmax reported: 0.877 0.985 Tmin' and Tmax expected: 0.975 0.983 RR' = 0.898 Please check that your absorption correction is appropriate. General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 27.46 From the CIF: _reflns_number_total 2329 Count of symmetry unique reflns 1332 Completeness (_total/calc) 174.85% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 997 Fraction of Friedel pairs measured 0.748 Are heavy atom types Z>Si present no ALERT: MoKa measured Friedel data cannot be used to determine absolute structure in a light-atom study EXCEPT under VERY special conditions. It is preferred that Friedel data is merged in such cases.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

Fumaric acid is an organic dicarboxylic acid which crystallizes in two polymorphic forms: one in the monoclinic space group P21/c (Brown, 1966) and the other in the triclinic space group P1 (Bednowitz & Post, 1966). In both crystal structures, acid molecules are linked by carboxylic acid R22(8) hydrogen-bond pairs, forming one-dimensional supramolecular tapes. Fumaric acid is of interest since it is known to form supramolecular assemblies with N-aromatic complexes (Batchelor et al., 2000). As part of our analysis of supramolecular architectures, the structure of the title complex, (I), was determined at 140 K.

(I) consists of a 1:1 complex of fumarate anions and quinolinium cations. The asymmetric unit and atomic numbering scheme are shown in Fig. 1. Zigzag supramolecular acid chains are formed along the c axis via O1—H01···O3 hydrogen bonds (Table 2). In addition, quinolinium cations are linked to the acid chains (Fig. 2) by N1—H02···O4 hydrogen bonds and C9—H9···O3 interactions. Proton transfer is observed between the carboxylic acid group and the quinoline N atom (Table 1). Quinolinium cations form infinite stacks along the b axis with the distance between adjacent molecules within a stack being ca 3.5 Å.

Experimental top

Fumaric acid and quinoline were obtained from Aldrich without further purification. 46 mg of the acid and 52 mg of the base were mixed and dissolved in 9 ml of ethyl acetate and 10 drops of methanol mixture. Crystals of (I) were obtained by slow evaporation at room temperature.

Refinement top

All H atoms bonded to C atoms were placed geometrically and refined using a riding model, with the Uiso values for each H atom taken as 1.2 Ueq of the carrier atom. Atoms H01 and H02 were located from difference Fourier maps and refined using a riding model.

Computing details top

Data collection: COLLECT (Nonius B.V. 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Sheldrick, 1993); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular unit of (I), showing displacement ellipsoids at the 50% probability level (XP; Sheldrick, 1993).
[Figure 2] Fig. 2. Projection onto (010), showing the zigzag supramolecular tapes formed by O—H···O hydrogen bonds and proton transfer between the carboxylic acid and the aromatic N atom (CAMERON; Watkin et al., 1996).
Quinolinium Fumarate top
Crystal data top
C9H8N+·C4H3O4Dx = 1.456 Mg m3
Dm = no Mg m3
Dm measured by not measured
Mr = 245.23Melting point: not measured K
Orthorhombic, Pca21Mo Kα radiation, λ = 0.71073 Å
a = 22.5838 (5) ÅCell parameters from 9880 reflections
b = 3.7273 (1) Åθ = 1.8–27.5°
c = 13.2912 (5) ŵ = 0.11 mm1
V = 1118.81 (6) Å3T = 140 K
Z = 4Block, colourless
F(000) = 5120.23 × 0.23 × 0.16 mm
Data collection top
Nonius KappaCCD
diffractometer
2329 independent reflections
Radiation source: fine-focus sealed tube2118 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.050
thin–slice ω and ϕ scansθmax = 27.5°, θmin = 1.8°
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
h = 2329
Tmin = 0.877, Tmax = 0.985k = 43
9868 measured reflectionsl = 1714
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.085H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0494P)2 + 0.0496P]
where P = (Fo2 + 2Fc2)/3
2325 reflections(Δ/σ)max = 0.001
163 parametersΔρmax = 0.20 e Å3
1 restraintΔρmin = 0.23 e Å3
Crystal data top
C9H8N+·C4H3O4V = 1118.81 (6) Å3
Mr = 245.23Z = 4
Orthorhombic, Pca21Mo Kα radiation
a = 22.5838 (5) ŵ = 0.11 mm1
b = 3.7273 (1) ÅT = 140 K
c = 13.2912 (5) Å0.23 × 0.23 × 0.16 mm
Data collection top
Nonius KappaCCD
diffractometer
2329 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
2118 reflections with I > 2σ(I)
Tmin = 0.877, Tmax = 0.985Rint = 0.050
9868 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0341 restraint
wR(F2) = 0.085H-atom parameters constrained
S = 1.08Δρmax = 0.20 e Å3
2325 reflectionsΔρmin = 0.23 e Å3
163 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
xyzUiso*/Ueq
N10.70065 (6)0.3852 (3)0.91328 (10)0.0229 (3)
H020.68010.45470.86050.028*
O20.92188 (5)0.7454 (3)0.61425 (10)0.0331 (3)
O41.14159 (4)1.4168 (3)0.75918 (9)0.0311 (3)
O31.06865 (5)1.2868 (3)0.86560 (10)0.0378 (3)
O10.99508 (5)0.9657 (3)0.51896 (9)0.0319 (3)
H010.97380.88990.47170.038*
C70.76386 (7)0.1615 (4)1.08004 (12)0.0259 (4)
H70.78520.08191.13750.031*
C60.79456 (6)0.2974 (3)0.99555 (12)0.0228 (3)
C20.78992 (7)0.5428 (4)0.82504 (12)0.0252 (3)
H20.76740.61790.76840.030*
C90.67253 (6)0.2611 (4)0.99297 (14)0.0266 (3)
H90.63050.24990.99230.032*
C131.08959 (7)1.3009 (4)0.78005 (12)0.0242 (3)
C10.76118 (6)0.4082 (4)0.91110 (11)0.0214 (3)
C30.85029 (7)0.5651 (4)0.82326 (14)0.0302 (4)
H30.86970.65380.76490.036*
C50.85695 (6)0.3265 (4)0.99134 (14)0.0279 (3)
H50.88020.25431.04740.034*
C80.70331 (7)0.1452 (4)1.07873 (12)0.0282 (4)
H80.68230.05611.13540.034*
C121.05486 (7)1.1844 (4)0.68978 (13)0.0240 (3)
H121.07091.23130.62500.029*
C100.96883 (6)0.8973 (4)0.60642 (12)0.0247 (3)
C111.00317 (7)1.0202 (4)0.69517 (13)0.0255 (3)
H110.98690.97800.76000.031*
C40.88398 (7)0.4575 (4)0.90732 (14)0.0312 (4)
H40.92590.47640.90540.037*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0249 (7)0.0232 (6)0.0207 (7)0.0025 (5)0.0042 (5)0.0000 (5)
O20.0252 (6)0.0458 (7)0.0283 (7)0.0099 (5)0.0005 (5)0.0003 (5)
O40.0261 (6)0.0434 (7)0.0239 (6)0.0082 (5)0.0008 (5)0.0017 (5)
O30.0381 (7)0.0523 (8)0.0230 (7)0.0140 (5)0.0026 (6)0.0002 (5)
O10.0277 (6)0.0455 (7)0.0225 (6)0.0095 (5)0.0003 (5)0.0034 (5)
C70.0347 (9)0.0218 (7)0.0211 (9)0.0003 (6)0.0040 (6)0.0013 (6)
C60.0289 (8)0.0176 (6)0.0218 (8)0.0013 (5)0.0037 (7)0.0017 (6)
C20.0323 (8)0.0240 (7)0.0193 (8)0.0006 (6)0.0020 (7)0.0010 (6)
C90.0268 (7)0.0266 (7)0.0265 (8)0.0005 (6)0.0019 (8)0.0012 (6)
C130.0273 (7)0.0242 (7)0.0212 (9)0.0019 (6)0.0012 (7)0.0002 (6)
C10.0264 (8)0.0167 (6)0.0212 (8)0.0008 (5)0.0005 (6)0.0033 (5)
C30.0335 (8)0.0290 (8)0.0281 (9)0.0019 (6)0.0058 (7)0.0022 (7)
C50.0277 (8)0.0250 (7)0.0311 (9)0.0008 (6)0.0089 (7)0.0005 (7)
C80.0364 (9)0.0271 (8)0.0211 (9)0.0022 (6)0.0035 (7)0.0008 (6)
C120.0278 (8)0.0238 (6)0.0202 (8)0.0007 (6)0.0021 (6)0.0007 (6)
C100.0232 (8)0.0264 (7)0.0245 (9)0.0005 (6)0.0023 (7)0.0002 (6)
C110.0263 (8)0.0303 (8)0.0198 (8)0.0017 (6)0.0023 (6)0.0003 (7)
C40.0254 (8)0.0296 (8)0.0385 (10)0.0001 (6)0.0001 (7)0.0001 (7)
Geometric parameters (Å, º) top
N1—C91.319 (2)C2—H20.9500
N1—C11.3702 (19)C9—C81.403 (2)
N1—H020.8800C9—H90.9500
O2—C101.207 (2)C13—C121.498 (2)
O4—C131.282 (2)C3—C41.410 (3)
O3—C131.233 (2)C3—H30.9500
O1—C101.330 (2)C5—C41.363 (3)
O1—H010.8400C5—H50.9500
C7—C81.369 (2)C8—H80.9500
C7—C61.414 (2)C12—C111.320 (2)
C7—H70.9500C12—H120.9500
C6—C11.414 (2)C10—C111.484 (2)
C6—C51.414 (2)C11—H110.9500
C2—C31.366 (2)C4—H40.9500
C2—C11.408 (2)
C9—N1—C1121.29 (14)C2—C3—C4120.50 (15)
C9—N1—H02119.4C2—C3—H3119.7
C1—N1—H02119.4C4—C3—H3119.7
C10—O1—H01109.5C4—C5—C6120.40 (16)
C8—C7—C6119.72 (14)C4—C5—H5119.8
C8—C7—H7120.1C6—C5—H5119.8
C6—C7—H7120.1C7—C8—C9119.44 (14)
C7—C6—C1118.29 (13)C7—C8—H8120.3
C7—C6—C5123.20 (15)C9—C8—H8120.3
C1—C6—C5118.51 (15)C11—C12—C13123.63 (15)
C3—C2—C1119.72 (14)C11—C12—H12118.2
C3—C2—H2120.1C13—C12—H12118.2
C1—C2—H2120.1O2—C10—O1123.86 (15)
N1—C9—C8121.46 (13)O2—C10—C11122.37 (15)
N1—C9—H9119.3O1—C10—C11113.76 (12)
C8—C9—H9119.3C12—C11—C10124.19 (16)
O3—C13—O4124.44 (15)C12—C11—H11117.9
O3—C13—C12121.72 (14)C10—C11—H11117.9
O4—C13—C12113.84 (14)C5—C4—C3120.62 (15)
N1—C1—C2119.96 (14)C5—C4—H4119.7
N1—C1—C6119.80 (13)C3—C4—H4119.7
C2—C1—C6120.24 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H02···O4i0.881.672.553 (2)179
C9—H9···O3i0.952.793.348 (2)119
O1—H01···O3ii0.841.832.667 (2)177
C3—H3···O20.952.353.284 (2)168
Symmetry codes: (i) x1/2, y+2, z; (ii) x+2, y+2, z1/2.

Experimental details

Crystal data
Chemical formulaC9H8N+·C4H3O4
Mr245.23
Crystal system, space groupOrthorhombic, Pca21
Temperature (K)140
a, b, c (Å)22.5838 (5), 3.7273 (1), 13.2912 (5)
V3)1118.81 (6)
Z4
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.23 × 0.23 × 0.16
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SORTAV; Blessing, 1995)
Tmin, Tmax0.877, 0.985
No. of measured, independent and
observed [I > 2σ(I)] reflections
9868, 2329, 2118
Rint0.050
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.085, 1.08
No. of reflections2325
No. of parameters163
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.20, 0.23

Computer programs: COLLECT (Nonius B.V. 1998), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP (Sheldrick, 1993), SHELXL97.

Selected bond lengths (Å) top
O2—C101.207 (2)O3—C131.233 (2)
O4—C131.282 (2)O1—C101.330 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H02···O4i0.881.672.553 (2)179
C9—H9···O3i0.952.793.348 (2)119
O1—H01···O3ii0.841.832.667 (2)177
C3—H3···O20.952.353.284 (2)168
Symmetry codes: (i) x1/2, y+2, z; (ii) x+2, y+2, z1/2.
 

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