Quinolinium fumarate

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.

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


 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

---

S1. Comment

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.

S2. Experimental

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.

S3. Refinement

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

Computing details

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

	Fig. 1. The molecular unit of (I), showing displacement ellipsoids at the 50% probability level (XP; Sheldrick, 1993).
	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

Crystal data

C9H8N^+·C4H3O4^−	Dx = 1.456 Mg m^−3 Dm = no Mg m^−3 Dm measured by not measured
Mr = 245.23	Melting point: not measured K
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
a = 22.5838 (5) Å	Cell parameters from 9880 reflections
b = 3.7273 (1) Å	θ = 1.8–27.5°
c = 13.2912 (5) Å	µ = 0.11 mm^−1
V = 1118.81 (6) Å^3	T = 140 K
Z = 4	Block, colourless
F(000) = 512	0.23 × 0.23 × 0.16 mm

Data collection

Nonius KappaCCD diffractometer	2329 independent reflections
Radiation source: fine-focus sealed tube	2118 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
thin–slice ω and ϕ scans	θmax = 27.5°, θmin = 1.8°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −23→29
Tmin = 0.877, Tmax = 0.985	k = −4→3
9868 measured reflections	l = −17→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.085	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0494P)^2 + 0.0496P] where P = (Fo^2 + 2Fc^2)/3
2325 reflections	(Δ/σ)max = 0.001
163 parameters	Δρmax = 0.20 e Å^−3
1 restraint	Δρmin = −0.23 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.70065 (6)	0.3852 (3)	0.91328 (10)	0.0229 (3)
H02	0.6801	0.4547	0.8605	0.028*
O2	0.92188 (5)	0.7454 (3)	0.61425 (10)	0.0331 (3)
O4	1.14159 (4)	1.4168 (3)	0.75918 (9)	0.0311 (3)
O3	1.06865 (5)	1.2868 (3)	0.86560 (10)	0.0378 (3)
O1	0.99508 (5)	0.9657 (3)	0.51896 (9)	0.0319 (3)
H01	0.9738	0.8899	0.4717	0.038*
C7	0.76386 (7)	0.1615 (4)	1.08004 (12)	0.0259 (4)
H7	0.7852	0.0819	1.1375	0.031*
C6	0.79456 (6)	0.2974 (3)	0.99555 (12)	0.0228 (3)
C2	0.78992 (7)	0.5428 (4)	0.82504 (12)	0.0252 (3)
H2	0.7674	0.6179	0.7684	0.030*
C9	0.67253 (6)	0.2611 (4)	0.99297 (14)	0.0266 (3)
H9	0.6305	0.2499	0.9923	0.032*
C13	1.08959 (7)	1.3009 (4)	0.78005 (12)	0.0242 (3)
C1	0.76118 (6)	0.4082 (4)	0.91110 (11)	0.0214 (3)
C3	0.85029 (7)	0.5651 (4)	0.82326 (14)	0.0302 (4)
H3	0.8697	0.6538	0.7649	0.036*
C5	0.85695 (6)	0.3265 (4)	0.99134 (14)	0.0279 (3)
H5	0.8802	0.2543	1.0474	0.034*
C8	0.70331 (7)	0.1452 (4)	1.07873 (12)	0.0282 (4)
H8	0.6823	0.0561	1.1354	0.034*
C12	1.05486 (7)	1.1844 (4)	0.68978 (13)	0.0240 (3)
H12	1.0709	1.2313	0.6250	0.029*
C10	0.96883 (6)	0.8973 (4)	0.60642 (12)	0.0247 (3)
C11	1.00317 (7)	1.0202 (4)	0.69517 (13)	0.0255 (3)
H11	0.9869	0.9780	0.7600	0.031*
C4	0.88398 (7)	0.4575 (4)	0.90732 (14)	0.0312 (4)
H4	0.9259	0.4764	0.9054	0.037*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0249 (7)	0.0232 (6)	0.0207 (7)	0.0025 (5)	−0.0042 (5)	0.0000 (5)
O2	0.0252 (6)	0.0458 (7)	0.0283 (7)	−0.0099 (5)	0.0005 (5)	0.0003 (5)
O4	0.0261 (6)	0.0434 (7)	0.0239 (6)	−0.0082 (5)	−0.0008 (5)	−0.0017 (5)
O3	0.0381 (7)	0.0523 (8)	0.0230 (7)	−0.0140 (5)	0.0026 (6)	−0.0002 (5)
O1	0.0277 (6)	0.0455 (7)	0.0225 (6)	−0.0095 (5)	−0.0003 (5)	−0.0034 (5)
C7	0.0347 (9)	0.0218 (7)	0.0211 (9)	−0.0003 (6)	−0.0040 (6)	0.0013 (6)
C6	0.0289 (8)	0.0176 (6)	0.0218 (8)	0.0013 (5)	−0.0037 (7)	−0.0017 (6)
C2	0.0323 (8)	0.0240 (7)	0.0193 (8)	0.0006 (6)	−0.0020 (7)	0.0010 (6)
C9	0.0268 (7)	0.0266 (7)	0.0265 (8)	−0.0005 (6)	0.0019 (8)	−0.0012 (6)
C13	0.0273 (7)	0.0242 (7)	0.0212 (9)	−0.0019 (6)	−0.0012 (7)	0.0002 (6)
C1	0.0264 (8)	0.0167 (6)	0.0212 (8)	0.0008 (5)	−0.0005 (6)	−0.0033 (5)
C3	0.0335 (8)	0.0290 (8)	0.0281 (9)	−0.0019 (6)	0.0058 (7)	0.0022 (7)
C5	0.0277 (8)	0.0250 (7)	0.0311 (9)	−0.0008 (6)	−0.0089 (7)	0.0005 (7)
C8	0.0364 (9)	0.0271 (8)	0.0211 (9)	−0.0022 (6)	0.0035 (7)	0.0008 (6)
C12	0.0278 (8)	0.0238 (6)	0.0202 (8)	0.0007 (6)	0.0021 (6)	0.0007 (6)
C10	0.0232 (8)	0.0264 (7)	0.0245 (9)	0.0005 (6)	−0.0023 (7)	−0.0002 (6)
C11	0.0263 (8)	0.0303 (8)	0.0198 (8)	−0.0017 (6)	0.0023 (6)	0.0003 (7)
C4	0.0254 (8)	0.0296 (8)	0.0385 (10)	−0.0001 (6)	−0.0001 (7)	−0.0001 (7)

Geometric parameters (Å, º)

N1—C9	1.319 (2)	C2—H2	0.9500
N1—C1	1.3702 (19)	C9—C8	1.403 (2)
N1—H02	0.8800	C9—H9	0.9500
O2—C10	1.207 (2)	C13—C12	1.498 (2)
O4—C13	1.282 (2)	C3—C4	1.410 (3)
O3—C13	1.233 (2)	C3—H3	0.9500
O1—C10	1.330 (2)	C5—C4	1.363 (3)
O1—H01	0.8400	C5—H5	0.9500
C7—C8	1.369 (2)	C8—H8	0.9500
C7—C6	1.414 (2)	C12—C11	1.320 (2)
C7—H7	0.9500	C12—H12	0.9500
C6—C1	1.414 (2)	C10—C11	1.484 (2)
C6—C5	1.414 (2)	C11—H11	0.9500
C2—C3	1.366 (2)	C4—H4	0.9500
C2—C1	1.408 (2)
C9—N1—C1	121.29 (14)	C2—C3—C4	120.50 (15)
C9—N1—H02	119.4	C2—C3—H3	119.7
C1—N1—H02	119.4	C4—C3—H3	119.7
C10—O1—H01	109.5	C4—C5—C6	120.40 (16)
C8—C7—C6	119.72 (14)	C4—C5—H5	119.8
C8—C7—H7	120.1	C6—C5—H5	119.8
C6—C7—H7	120.1	C7—C8—C9	119.44 (14)
C7—C6—C1	118.29 (13)	C7—C8—H8	120.3
C7—C6—C5	123.20 (15)	C9—C8—H8	120.3
C1—C6—C5	118.51 (15)	C11—C12—C13	123.63 (15)
C3—C2—C1	119.72 (14)	C11—C12—H12	118.2
C3—C2—H2	120.1	C13—C12—H12	118.2
C1—C2—H2	120.1	O2—C10—O1	123.86 (15)
N1—C9—C8	121.46 (13)	O2—C10—C11	122.37 (15)
N1—C9—H9	119.3	O1—C10—C11	113.76 (12)
C8—C9—H9	119.3	C12—C11—C10	124.19 (16)
O3—C13—O4	124.44 (15)	C12—C11—H11	117.9
O3—C13—C12	121.72 (14)	C10—C11—H11	117.9
O4—C13—C12	113.84 (14)	C5—C4—C3	120.62 (15)
N1—C1—C2	119.96 (14)	C5—C4—H4	119.7
N1—C1—C6	119.80 (13)	C3—C4—H4	119.7
C2—C1—C6	120.24 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H02···O4^i	0.88	1.67	2.553 (2)	179
C9—H9···O3^i	0.95	2.79	3.348 (2)	119
O1—H01···O3^ii	0.84	1.83	2.667 (2)	177
C3—H3···O2	0.95	2.35	3.284 (2)	168

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