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Both maleic and fumaric acid readily form adducts or complexes with other organic mol­ecules. The 1:1 adduct formed by quinolin-8-ol (oxine) with maleic and fumaric acid are salts, namely 8-hydroxy­quinolinium hydrogen maleate, C9H8NO+·C4H3O4-, (I), and 8-hydroxy­quinolinium hydrogen fumarate, C9H8NO+·C4H3O4-, (II). The cations and anions of both salts are linked by ionic N+-H...O- hydrogen bonds. The maleate salt crystallizes in the space group P212121, while the fumarate salt crystallizes in P\overline{1}. The maleic and fumaric acids in their complex forms exist as semimaleate and semifumarate ions (mono-ionized state), respectively. Classical N-H...O and O-H...O hydrogen bonds, together with short C-H...O contacts, generate an extensive hydrogen-bonding network. The crystal structures of the maleate and fumarate salts of oxine have been elucidated to study the importance of noncovalent inter­actions in the aggregation and inter­action patterns of biological mol­ecules. The structures of the salts of the Z and E isomers of butenedioic acid (maleic and fumaric acid, respectively) with quinolin-8-ol are com­pared.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108044132/su3028sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108044132/su3028Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108044132/su3028IIsup3.hkl
Contains datablock II

CCDC references: 724206; 724207

Comment top

Oxine (8-hydroxyquinoline, 8-HQ), a monoprotic bidentate chelating agent, and its derivatives, are widely used as analytical reagents and potential anti-amoebic agents (Bambury, 1979). The complexes and the heterocycle itself exhibit antiseptic, disinfectant and pesticide properties (Phillips, 1956). Its solution in alcohol [Ethanol?] is used as a liquid bandage. 8-HQ was also once of interest as an anticancer drug (Shen et al., 1999). In this paper, we present the maleic and fumaric acid complexes of 8-HQ, compounds (I) and (II), respectively.

Maleic acid, the Z isomer of butenedioic acid, has been used as a simple building block in supramolecular architectures in two and three dimensions (Bowes et al., 2003; Jin et al., 2003). The maleic acid anion can exist in the fully deprotonated form, or as hydrogen maleate with one of the carboxylic acid groups protonated (Lah & Leban, 2003). Several singly dissociated maleate salts are reported in the Cambridge Structural Database (Version?; Allen, 2002). Fumaric acid, the E isomer of butenedioic acid, is of interest since it is known to form supramolecular assemblies with N-aromatic compounds (Batchelor et al., 2000). It tends to form infinite chains arranged in a nearly coplanar manner via pairs of strong O—H···O hydrogen bonds. This organic dicarboxylic acid crystallizes in two polymorphic forms; one is monoclinic, space group P21/c (Brown, 1966) and the other triclinic, space group P1 (Bednowitz & Post, 1966). In both crystal structures the acid molecules are linked by carboxylic acid R22(8) (Bernstein et al., 1995) hydrogen-bond pairs, forming one-dimensional supramolecular tapes. An extensive network of hydrogen bonds is observed in the majority of the crystal structures of salts of fumaric acid (Shan et al., 2003; Alagar, Krishnakumar et al., 2003; Videnova-Adrabińska, 1996; Smith et al., 1997; Li et al., 2007; Büyükgüngör et al., 2004). The title compounds, (I) and (II), are the salts of oxine with the cis and trans pair of dicarboxylic acids, maleic and fumaric acids, the Z and E isomers of butenedioic acid, respectively. They have been studied to explore their hydrogen-bonding patterns.

The structures of compounds (I) and (II) are shown in Figs. 1 and 2, respectively. The asymmetric unit of (I) consists of a 1:1 complex of a semimaleate anion and the hydroxyquinolinium cation. Compound (II) consists of a 1:1 complex of a semifumarate anion and the hydroxyquinolinium cation. The 8-HQ molecules in both compounds are protonated at atom N1. Proton transfer observed between the 8-HQ N atom and the carboxylic acid groups of both (I) and (II) is confirmed by the increase in the internal angles at N1, which are 122.1 (3) and 122.71 (12)°, respectively, compared with 119° observed in neutral 8-HQ (Roychowdhury et al., 1978).

The C8—O8 bond lengths in the 8-HQ cation in (I) and (II) are 1.338 (4) and 1.3434 (17) Å, respectively. These distances are shorter than the bond lengths observed in the neutral 8-HQ molecule (1.39 Å). Furthermore, the exocyclic angles, C7—C8—O8 and C9—C8—O8, in the cation of (I) are 126.0 (3) and 116.0 (3)°, respectively, and those in the cation of (II) are 126.08 (12) and 115.76 (11)°, respectively. These angles are significantly different from those observed in neutral 8-HQ (118.2 and 120.3°). This difference in the bond lengths and angles may be attributed to the presence of weak intramolecular N—H···O hydrogen bonds. Similar hydrogen bonds have been observed to result in an enhancement of the internal angle at the N centre in the crystal structures of the 8-HQ complexes quoted above. The O1—C11 and O4—C14 bonds of the semimaleate anion are longer than O2—C11 and O3—C14, showing differences between the C—O and CO bond types of the carboxylic acid group (Borthwick, 1980). Similarly, the O1—C11 and O4—C14 bonds of the semifumarate anion are longer than the O2—C11 and O3—C14 bonds.

The 8-HQ cations in both (I) and (II) are essentially planar. The dihedral angles between the fused rings are 0.77 and 2.23°, respectively, and the total puckering amplitudes (Cremer & Pople, 1975) Q are 0.026 (4) and 0.059 Å, respectively. The semimaleate and semifumarate anions are almost planar. The angles between the planes of the half-semimaleate anion in (I) and those of the semifumarate anion in (II) (O1/O2/C11/C12 and O3/O4/C13/C14) are 1.58 and 14.83°, respectively. The semimaleate anion is planar with a cis conformation about the central CC bond [C11—C12—C13—C14 = -0.2 (8)°], while the semifumarate anion is planar with a trans conformation about the central CC bond [C11—C12—C13—C14 = 179.94 (14)°]. Both the cations and anions of (I) and (II) are individually planar, but with dihedral angles of 10.92 and 73.17°, respectively.

The crystal packings of compounds (I) and (II) are stabilized by an extensive network of hydrogen bonds, which are summarized in Tables 1 and 2. Parts of the crystal structures of (I) and (II), depicting the hydrogen-bonding interactions and the formation of hydrogen-bonded motifs, are shown in Figs. 3 and 4, respectively. In both compounds, a strong intermolecular N+—H···O- hydrogen bond exists between the deprotonated carboxylate group of the anion and the hydroxyquinolinium N atom of the cation. The presence of an intramolecular N—H···O hydrogen bond, represented by a graph-set motif of S(5), in the 8-HQ cations of (I) and (II) has been observed in most of the 8-hydroxyquinolinium and related cation compounds (Balasubramanian & Muthiah, 1996; Balasubramanian & Thomas Muthiah, 1996; Jebamony & Thomas Muthiah, 1998; Banerjee et al., 1984; Smith et al., 2004). This hydrogen bond was observed to result in an enhancement of the internal angle at the N centre. An intramolecular hydrogen bond between atoms O1 and O4 in the semimaleate ion of (I) is found to be asymmetric, as in the crystal structures of maleic acid itself (James & Williams, 1974) and several maleate salts of various amino acids (Alagar, Krishnakumar et al., 2001, Alagar et al., 2002; Alagar, Subha Nandhini et al., 2003; Rajagopal et al., 2001, 2002). However, in the crystal structures of the complexes of maleic acid with DL- and L-arginine (Ravishankar et al., 1998), L-hystidine and L-lysine (Pratap et al., 2000), and L-phenylalaninium (Alagar, Krishnakumar & Natarajan, 2001), this intramolecular hydrogen bond is symmetric and generates an S(7) motif. C—H···O intramolecular interactions generate an S(5) motif in the semifumarate anion in molecule (II).

Intermolecular hydrogen-bonding interactions between the semimaleate anions in (I) are not observed. The hydroxyquinolinium cation is connected to the anion by N1—H1···O2 and C2—H2···O1 interactions to form a ring motif described by a graph-set motif of R22(7). In (II), however, intermolecular hydrogen-bonding interactions between the semifumarate anions, as well with the cations, are observed. The anions are linked by chains propagating perpendicularly to the ac plane via O4—H4A···O2 hydrogen bonds and can be described by a graph-set motif of C(7). Hydroxyquinolinium cations form infinite stacks propogating perpendicularly to the ac plane, the distance between adjacent molecules within a stack being 7.44 Å. A pair of cations and a pair of anions are linked through O—H···O and N—H···O hydrogen bonds to form a ring motif, represented by a graph-set motif of R22(8). The cations and anions in (I) aggregate through hydrogen bonds to form an extensive three-dimensional network, while in (II), they aggregate through hydrogen bonds to form a two-dimensional network.

Experimental top

Equimolar quantities of maleic acid and hydroxyquinoline were dissolved in water. The solution was stirred well and set aside to crystallize. Yellow needle-like crystals of (I), suitable for X-ray diffraction analysis, were obtained from the resulting solution after a week of slow evaporation. Similarly, equimolar quantities of fumaric acid and hydroxyquinoline were dissolved in water. The solution was stirred well and set aside to crystallize. Yellow crystals of (II), suitable for X-ray diffraction analysis, were obtained from the resulting solution after a week of slow evaporation.

Refinement top

For compound (I), which crystallized in the space group P212121, the Friedel equivalents were merged prior to the final refinement cycles. The O- and N-bound H atoms were located in difference Fourier maps and held fixed, with O—H = 0.94 and 1.03 Å in (I), and 0.92 and 0.94 Å in (II), N—H = 1.00 Å in (I) and 0.89 Å in (II), with Uiso(H) = 1.5Ueq(O) and = 1.2Ueq(N). The C-bound H atoms in both compounds were included in calculated positions and treated as riding atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C).

Computing details top

For both compounds, data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. The structure of compound (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate intramolecular hydrogen bonds.
[Figure 2] Fig. 2. The structure of compound (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. The dashed line indicates the intramolecular hydrogen bond.
[Figure 3] Fig. 3. Part of the crystal structure of (I), showing the formation of R22(7), S(7) and S(5) hydrogen-bonded motifs. For the sake of clarity, only H atoms involved in hydrogen bonding are shown. Dashed lines represent hydrogen bonds.
[Figure 4] Fig. 4. Part of the crystal structure of (II), showing the formation of rings propagating perpendicularly to the ac plane. For the sake of clarity, only H atoms involved in hydrogen bonding are shown. Dashed lines represent hydrogen bonds.
(I) 8-hydroxyquinolinium hydrogen maleate top
Crystal data top
C9H8NO+·C4H3O4F(000) = 544
Mr = 261.23Dx = 1.431 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 2732 reflections
a = 5.3777 (3) Åθ = 2.2–28.0°
b = 10.0563 (7) ŵ = 0.11 mm1
c = 22.4243 (12) ÅT = 273 K
V = 1212.70 (13) Å3Needle, yellow
Z = 40.40 × 0.30 × 0.22 mm
Data collection top
Bruker Kappa APEXII CCD
diffractometer
1291 reflections with I > 2σ(I)
ω and ϕ scansRint = 0.034
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
θmax = 28.3°, θmin = 2.2°
Tmin = 0.957, Tmax = 0.976h = 76
7633 measured reflectionsk = 1312
1764 independent reflectionsl = 2929
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.053H-atom parameters constrained
wR(F2) = 0.134 w = 1/[σ2(Fo2) + (0.0458P)2 + 0.4725P]
where P = (Fo2 + 2Fc2)/3
S = 1.16(Δ/σ)max = 0.001
1764 reflectionsΔρmax = 0.22 e Å3
172 parametersΔρmin = 0.17 e Å3
0 restraintsAbsolute structure: Flack (1983), with 1220 Friedel pairs
Primary atom site location: structure-invariant direct methods
Crystal data top
C9H8NO+·C4H3O4V = 1212.70 (13) Å3
Mr = 261.23Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 5.3777 (3) ŵ = 0.11 mm1
b = 10.0563 (7) ÅT = 273 K
c = 22.4243 (12) Å0.40 × 0.30 × 0.22 mm
Data collection top
Bruker Kappa APEXII CCD
diffractometer
1764 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
1291 reflections with I > 2σ(I)
Tmin = 0.957, Tmax = 0.976Rint = 0.034
7633 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0530 restraints
wR(F2) = 0.134H-atom parameters constrained
S = 1.16Δρmax = 0.22 e Å3
1764 reflectionsΔρmin = 0.17 e Å3
172 parametersAbsolute structure: Flack (1983), with 1220 Friedel pairs
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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
O80.1406 (5)0.7132 (3)0.04032 (10)0.0613 (9)
N10.0137 (5)0.8064 (3)0.14740 (10)0.0408 (8)
C20.0545 (7)0.8592 (4)0.19918 (13)0.0478 (10)
C30.0614 (7)0.8221 (4)0.25131 (14)0.0532 (13)
C40.2450 (8)0.7301 (4)0.24976 (14)0.0553 (11)
C50.5065 (9)0.5766 (4)0.19072 (17)0.0677 (16)
C60.5679 (10)0.5267 (5)0.1361 (2)0.0770 (17)
C70.4471 (9)0.5711 (4)0.08471 (17)0.0660 (16)
C80.2641 (7)0.6632 (4)0.08703 (14)0.0482 (11)
C90.1984 (6)0.7149 (3)0.14337 (13)0.0391 (9)
C100.3206 (7)0.6727 (4)0.19540 (14)0.0471 (11)
O10.5130 (5)0.0021 (3)0.13620 (9)0.0591 (9)
O20.7217 (5)0.0866 (3)0.06111 (10)0.0544 (8)
O30.0739 (7)0.2729 (4)0.09560 (13)0.0988 (15)
O40.1655 (6)0.1483 (3)0.15096 (11)0.0825 (10)
C110.5548 (6)0.0126 (3)0.08121 (13)0.0417 (10)
C120.4091 (7)0.0649 (4)0.03729 (14)0.0475 (10)
C130.2236 (7)0.1488 (4)0.04502 (15)0.0519 (11)
C140.0958 (8)0.1947 (4)0.09934 (17)0.0613 (16)
H10.089600.833500.112500.0490*
H20.181800.921800.200200.0570*
H30.013800.860000.287400.0640*
H40.322300.704500.285000.0660*
H50.588300.546700.224700.0810*
H60.691500.462400.133000.0920*
H70.493700.536500.047900.0790*
H80.174000.666300.004800.0920*
H4A0.319200.089700.144300.1240*
H120.456100.052200.002200.0570*
H130.162700.185700.009900.0620*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O80.0722 (17)0.0810 (18)0.0308 (11)0.0188 (16)0.0033 (12)0.0103 (12)
N10.0403 (14)0.0505 (15)0.0315 (12)0.0005 (13)0.0018 (12)0.0010 (11)
C20.052 (2)0.0560 (19)0.0353 (15)0.0031 (18)0.0030 (17)0.0037 (14)
C30.063 (3)0.065 (2)0.0315 (15)0.003 (2)0.0020 (18)0.0034 (15)
C40.064 (2)0.068 (2)0.0340 (16)0.000 (2)0.0077 (18)0.0053 (16)
C50.071 (3)0.075 (3)0.057 (2)0.023 (2)0.010 (2)0.004 (2)
C60.072 (3)0.078 (3)0.081 (3)0.033 (3)0.002 (3)0.002 (2)
C70.067 (3)0.075 (3)0.056 (2)0.017 (2)0.007 (2)0.012 (2)
C80.049 (2)0.0542 (19)0.0415 (17)0.0018 (18)0.0020 (16)0.0055 (15)
C90.0385 (17)0.0428 (16)0.0359 (14)0.0044 (15)0.0009 (14)0.0017 (13)
C100.050 (2)0.0511 (19)0.0402 (16)0.0014 (17)0.0018 (17)0.0033 (15)
O10.0590 (16)0.0847 (18)0.0335 (12)0.0186 (16)0.0016 (12)0.0026 (11)
O20.0524 (15)0.0720 (17)0.0387 (11)0.0144 (14)0.0067 (12)0.0075 (11)
O30.111 (3)0.114 (3)0.0713 (19)0.065 (3)0.013 (2)0.0079 (19)
O40.099 (2)0.108 (2)0.0404 (13)0.048 (2)0.0127 (16)0.0053 (15)
C110.0359 (17)0.0513 (18)0.0380 (17)0.0017 (16)0.0018 (14)0.0027 (14)
C120.0443 (19)0.065 (2)0.0332 (15)0.0027 (18)0.0001 (16)0.0001 (15)
C130.055 (2)0.060 (2)0.0406 (17)0.0075 (19)0.0049 (18)0.0051 (16)
C140.061 (3)0.070 (3)0.053 (2)0.019 (2)0.005 (2)0.0026 (19)
Geometric parameters (Å, º) top
O8—C81.338 (4)C6—C71.396 (6)
O8—H80.9400C7—C81.352 (6)
O1—C111.258 (4)C8—C91.411 (4)
O2—C111.250 (4)C9—C101.405 (5)
O3—C141.208 (6)C2—H20.9300
O4—C141.303 (5)C3—H30.9300
O4—H4A1.0300C4—H40.9300
N1—C91.357 (4)C5—H50.9300
N1—C21.328 (4)C6—H60.9300
N1—H11.0000C7—H70.9300
C2—C31.376 (5)C11—C121.480 (5)
C3—C41.354 (6)C12—C131.318 (5)
C4—C101.409 (5)C13—C141.473 (5)
C5—C101.394 (6)C12—H120.9300
C5—C61.364 (6)C13—H130.9300
O1···C9i3.315 (4)C11···N1ii3.407 (4)
O1···C2ii3.058 (5)C12···O3iii3.398 (5)
O2···C2ii3.366 (4)C3···H5xii2.9900
O2···N1ii2.714 (4)C11···H2ii3.0900
O2···C8iii3.418 (4)C11···H8iii2.5500
O2···O8ii3.057 (4)C11···H1ii2.5600
O2···O8iii2.643 (3)C12···H8iii2.8900
O3···C6iv3.324 (6)C12···H13iii3.0400
O3···C12v3.398 (5)C13···H7v3.0600
O4···C2i3.320 (5)C14···H3vi3.0900
O4···C3vi3.057 (5)H1···O1vii2.7500
O4···C4vi3.241 (5)H1···O2vii1.7300
O8···N12.666 (3)H1···C11vii2.5600
O8···O2vii3.057 (4)H1···O82.3700
O8···O2v2.643 (3)H2···O1vii2.3100
O1···H1ii2.7500H2···C11vii3.0900
O1···H2ii2.3100H3···O4x2.7200
O1···H4viii2.8700H3···C14x3.0900
O2···H8iii1.7000H3···O3x2.7800
O2···H1ii1.7300H3···H6xii2.6000
O2···H7iii2.8900H4···O1xii2.8700
O3···H13v2.7900H4···H52.5300
O3···H6iv2.4300H5···H42.5300
O3···H3vi2.7800H5···C3viii2.9900
O3···H12v2.7400H6···H3viii2.6000
O4···H3vi2.7200H6···O3xi2.4300
O8···H12.3700H7···H82.3700
N1···O2vii2.714 (4)H7···C13iii3.0600
N1···O82.666 (3)H7···O2v2.8900
N1···C11vii3.407 (4)H8···H72.3700
C2···O1vii3.058 (5)H8···O2v1.7000
C2···O2vii3.366 (4)H8···C12v2.8900
C2···O4ix3.320 (5)H8···H12v2.4900
C3···O4x3.057 (5)H8···C11v2.5500
C4···O4x3.241 (5)H12···O3iii2.7400
C6···O3xi3.324 (6)H12···H8iii2.4900
C8···O2v3.418 (4)H13···O3iii2.7900
C9···O1ix3.315 (4)H13···C12v3.0400
C8—O8—H8112.00C2—C3—H3120.00
C14—O4—H4A108.00C4—C3—H3120.00
C2—N1—C9122.1 (3)C3—C4—H4120.00
C9—N1—H1123.00C10—C4—H4120.00
C2—N1—H1115.00C6—C5—H5120.00
N1—C2—C3120.6 (3)C10—C5—H5120.00
C2—C3—C4119.6 (3)C7—C6—H6120.00
C3—C4—C10120.9 (3)C5—C6—H6120.00
C6—C5—C10119.7 (4)C6—C7—H7119.00
C5—C6—C7120.7 (5)C8—C7—H7119.00
C6—C7—C8121.7 (4)O1—C11—O2122.1 (3)
O8—C8—C9116.0 (3)O2—C11—C12117.0 (3)
O8—C8—C7126.0 (3)O1—C11—C12120.9 (3)
C7—C8—C9118.0 (3)C11—C12—C13130.6 (3)
C8—C9—C10121.0 (3)C12—C13—C14131.5 (3)
N1—C9—C8119.5 (3)O4—C14—C13119.2 (4)
N1—C9—C10119.5 (3)O3—C14—O4120.8 (4)
C4—C10—C9117.4 (3)O3—C14—C13120.0 (4)
C4—C10—C5123.8 (3)C11—C12—H12115.00
C5—C10—C9118.8 (3)C13—C12—H12115.00
C3—C2—H2120.00C12—C13—H13114.00
N1—C2—H2120.00C14—C13—H13114.00
C9—N1—C2—C30.1 (5)O8—C8—C9—N12.1 (5)
C2—N1—C9—C8179.5 (3)O8—C8—C9—C10178.1 (3)
C2—N1—C9—C100.8 (5)C7—C8—C9—N1179.3 (3)
N1—C2—C3—C40.6 (6)C7—C8—C9—C100.5 (5)
C2—C3—C4—C100.6 (6)N1—C9—C10—C40.8 (5)
C3—C4—C10—C5179.3 (4)N1—C9—C10—C5178.7 (3)
C3—C4—C10—C90.1 (6)C8—C9—C10—C4179.5 (3)
C10—C5—C6—C70.2 (7)C8—C9—C10—C51.1 (5)
C6—C5—C10—C4179.9 (4)O1—C11—C12—C131.6 (6)
C6—C5—C10—C90.7 (6)O2—C11—C12—C13179.4 (4)
C5—C6—C7—C80.8 (7)C11—C12—C13—C140.2 (8)
C6—C7—C8—O8178.9 (4)C12—C13—C14—O3179.5 (5)
C6—C7—C8—C90.5 (6)C12—C13—C14—O40.6 (7)
Symmetry codes: (i) x, y1, z; (ii) x+1, y1, z; (iii) x+1/2, y+1/2, z; (iv) x1, y, z; (v) x1/2, y+1/2, z; (vi) x, y1/2, z+1/2; (vii) x1, y+1, z; (viii) x+1, y1/2, z+1/2; (ix) x, y+1, z; (x) x, y+1/2, z+1/2; (xi) x+1, y, z; (xii) x+1, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2vii1.001.732.714 (4)167
N1—H1···O81.002.372.666 (3)96
O4—H4A···O11.031.402.427 (4)174
O8—H8···O2v0.941.702.643 (3)177
C2—H2···O1vii0.932.313.058 (5)137
C6—H6···O3xi0.932.433.324 (6)160
Symmetry codes: (v) x1/2, y+1/2, z; (vii) x1, y+1, z; (xi) x+1, y, z.
(II) 8-hydroxyquinolinium hydrogen fumarate top
Crystal data top
C9H8NO+·C4H3O4Z = 2
Mr = 261.23F(000) = 272
Triclinic, P1Dx = 1.451 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.3282 (3) ÅCell parameters from 6825 reflections
b = 7.4363 (3) Åθ = 2.8–33.0°
c = 11.5680 (5) ŵ = 0.11 mm1
α = 79.349 (2)°T = 273 K
β = 74.994 (2)°Block, yellow
γ = 89.337 (2)°0.30 × 0.20 × 0.16 mm
V = 597.97 (4) Å3
Data collection top
Bruker Kappa APEXII CCD
diffractometer
3049 reflections with I > 2σ(I)
ω and ϕ scansRint = 0.025
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
θmax = 33.3°, θmin = 2.8°
Tmin = 0.967, Tmax = 0.982h = 1011
15682 measured reflectionsk = 1111
4437 independent reflectionsl = 1717
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)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.152H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0668P)2 + 0.170P]
where P = (Fo2 + 2Fc2)/3
4437 reflections(Δ/σ)max < 0.001
172 parametersΔρmax = 0.45 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
C9H8NO+·C4H3O4γ = 89.337 (2)°
Mr = 261.23V = 597.97 (4) Å3
Triclinic, P1Z = 2
a = 7.3282 (3) ÅMo Kα radiation
b = 7.4363 (3) ŵ = 0.11 mm1
c = 11.5680 (5) ÅT = 273 K
α = 79.349 (2)°0.30 × 0.20 × 0.16 mm
β = 74.994 (2)°
Data collection top
Bruker Kappa APEXII CCD
diffractometer
4437 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
3049 reflections with I > 2σ(I)
Tmin = 0.967, Tmax = 0.982Rint = 0.025
15682 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.152H-atom parameters constrained
S = 1.07Δρmax = 0.45 e Å3
4437 reflectionsΔρmin = 0.24 e Å3
172 parameters
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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
O80.35340 (14)0.84094 (17)0.53120 (9)0.0439 (3)
N10.25392 (15)0.85725 (15)0.32353 (9)0.0314 (3)
C20.2160 (2)0.86895 (19)0.21670 (12)0.0368 (4)
C30.0373 (2)0.8185 (2)0.21063 (13)0.0423 (4)
C40.0991 (2)0.7580 (2)0.31579 (14)0.0399 (4)
C50.1962 (2)0.6898 (2)0.54225 (14)0.0412 (4)
C60.1473 (2)0.6891 (2)0.64845 (13)0.0423 (4)
C70.0359 (2)0.7400 (2)0.64921 (12)0.0371 (4)
C80.17279 (18)0.79266 (17)0.54205 (11)0.0311 (3)
C90.12277 (17)0.79750 (16)0.43155 (10)0.0280 (3)
C100.06041 (18)0.74554 (17)0.43036 (12)0.0322 (3)
O10.58773 (14)0.06213 (12)0.27497 (8)0.0348 (3)
O20.66839 (18)0.07780 (12)0.07461 (9)0.0461 (3)
O30.8069 (3)0.74935 (16)0.07584 (12)0.0793 (5)
O40.65185 (16)0.73101 (12)0.11737 (8)0.0390 (3)
C110.63628 (18)0.14898 (15)0.16694 (11)0.0290 (3)
C120.65203 (18)0.35315 (15)0.14914 (11)0.0302 (3)
C130.7118 (2)0.45877 (17)0.04200 (12)0.0390 (4)
C140.7287 (2)0.66130 (17)0.02162 (12)0.0361 (4)
H10.365100.903900.324500.0380*
H20.309300.911200.145300.0440*
H30.010900.825800.135500.0510*
H40.219000.724600.312000.0480*
H50.318000.653800.543800.0490*
H60.237900.653900.722200.0510*
H70.064900.738200.723100.0450*
H80.368900.869300.602100.0660*
H4A0.659600.859200.099200.0590*
H120.617700.407600.217500.0360*
H130.746000.403100.025800.0470*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O80.0366 (5)0.0657 (7)0.0315 (5)0.0089 (4)0.0105 (4)0.0115 (4)
N10.0337 (5)0.0318 (5)0.0290 (5)0.0024 (4)0.0094 (4)0.0044 (4)
C20.0434 (7)0.0379 (7)0.0288 (6)0.0004 (5)0.0107 (5)0.0035 (5)
C30.0482 (8)0.0484 (8)0.0356 (7)0.0015 (6)0.0209 (6)0.0070 (6)
C40.0377 (7)0.0431 (7)0.0442 (7)0.0015 (5)0.0196 (6)0.0093 (6)
C50.0302 (6)0.0486 (8)0.0436 (7)0.0007 (5)0.0070 (5)0.0093 (6)
C60.0359 (7)0.0512 (8)0.0340 (6)0.0013 (6)0.0003 (5)0.0060 (6)
C70.0398 (7)0.0440 (7)0.0275 (6)0.0014 (5)0.0079 (5)0.0078 (5)
C80.0337 (6)0.0322 (6)0.0291 (5)0.0011 (4)0.0098 (4)0.0078 (4)
C90.0314 (5)0.0255 (5)0.0279 (5)0.0017 (4)0.0085 (4)0.0060 (4)
C100.0319 (6)0.0312 (6)0.0355 (6)0.0027 (4)0.0117 (5)0.0077 (5)
O10.0468 (5)0.0293 (4)0.0273 (4)0.0067 (4)0.0099 (4)0.0020 (3)
O20.0856 (8)0.0225 (4)0.0293 (5)0.0018 (5)0.0117 (5)0.0068 (3)
O30.1402 (14)0.0302 (5)0.0404 (6)0.0044 (7)0.0205 (7)0.0007 (5)
O40.0610 (6)0.0217 (4)0.0323 (5)0.0022 (4)0.0079 (4)0.0060 (3)
C110.0392 (6)0.0210 (5)0.0272 (5)0.0015 (4)0.0096 (4)0.0039 (4)
C120.0409 (6)0.0213 (5)0.0297 (5)0.0002 (4)0.0094 (5)0.0075 (4)
C130.0639 (9)0.0221 (5)0.0298 (6)0.0016 (5)0.0084 (6)0.0071 (4)
C140.0535 (8)0.0222 (5)0.0300 (6)0.0001 (5)0.0068 (5)0.0040 (4)
Geometric parameters (Å, º) top
O8—C81.3434 (17)C6—C71.402 (2)
O8—H80.9200C7—C81.3719 (19)
O1—C111.2578 (15)C8—C91.4124 (17)
O2—C111.2459 (15)C9—C101.4054 (19)
O3—C141.1956 (19)C2—H20.9300
O4—C141.3020 (16)C3—H30.9300
O4—H4A0.9400C4—H40.9300
N1—C91.3658 (15)C5—H50.9300
N1—C21.3227 (17)C6—H60.9300
N1—H10.8900C7—H70.9300
C2—C31.389 (2)C11—C121.4957 (16)
C3—C41.364 (2)C12—C131.3084 (18)
C4—C101.412 (2)C13—C141.4823 (18)
C5—C61.365 (2)C12—H120.9300
C5—C101.408 (2)C13—H130.9300
O1···C8i3.3969 (16)C6···O3xii3.234 (2)
O1···O8ii3.1729 (14)C7···O3xii3.2019 (19)
O1···N1ii2.7711 (15)C8···C10xiii3.5744 (18)
O1···C2ii3.3672 (18)C8···O1i3.3969 (16)
O1···C4iii3.2636 (18)C10···C8xiii3.5744 (18)
O1···O8i2.6151 (14)C11···C2ii3.597 (2)
O2···C2iv3.2042 (17)C11···N1ii3.4494 (17)
O2···C3iv3.3980 (18)C11···O4ii3.2587 (15)
O2···C14ii3.2701 (16)C13···C13iv3.501 (2)
O2···O4ii2.5327 (13)C14···O2viii3.2701 (16)
O3···C7v3.2019 (19)C3···H13iv3.0500
O3···C3vi3.372 (2)C11···H1ii2.7500
O3···C6v3.234 (2)C11···H7i3.0000
O3···C2vi3.0267 (19)C11···H2ii3.0800
O4···C23.3217 (19)C11···H4Aii2.4200
O4···C4vii3.3148 (19)C11···H8i2.6400
O4···O2viii2.5327 (13)C12···H8i3.0100
O4···C3vii3.3832 (19)C12···H6xiv3.0100
O4···C11viii3.2587 (15)C12···H7i2.8500
O8···O8ix3.0687 (17)C14···H3vii3.0900
O8···O1i2.6151 (14)H1···O1viii1.9200
O8···O1viii3.1729 (14)H1···C11viii2.7500
O8···N12.6673 (14)H1···O82.3300
O1···H4iii2.8900H2···O2viii2.7800
O1···H4Aii2.6900H2···C11viii3.0800
O1···H1ii1.9200H2···H4A2.5200
O1···H8i1.7000H2···O2iv2.4900
O2···H3iv2.9000H2···O3vi2.7000
O2···H2iv2.4900H2···O42.8000
O2···H2ii2.7800H3···O4x2.8000
O2···H132.4900H3···C14x3.0900
O2···H4Aii1.6000H3···O2iv2.9000
O3···H7v2.6000H4···O4x2.6500
O3···H2vi2.7000H4···O1xi2.8900
O3···H6v2.6600H4···H52.5400
O4···H122.4500H4A···H22.5200
O4···H22.8000H4A···C11viii2.4200
O4···H3vii2.8000H4A···O2viii1.6000
O4···H4vii2.6500H4A···O1viii2.6900
O8···H5vii2.7900H5···O8x2.7900
O8···H8ix2.9000H5···H42.5400
O8···H12.3300H6···C12xiv3.0100
N1···C11viii3.4494 (17)H6···O3xii2.6600
N1···O1viii2.7711 (15)H7···H82.4100
N1···O82.6673 (14)H7···O3xii2.6000
C2···O43.3217 (19)H7···C11i3.0000
C2···O3vi3.0267 (19)H7···C12i2.8500
C2···C11viii3.597 (2)H8···H72.4100
C2···O2iv3.2042 (17)H8···O1i1.7000
C2···O1viii3.3672 (18)H8···O8ix2.9000
C3···O3vi3.372 (2)H8···C11i2.6400
C3···O4x3.3832 (19)H8···C12i3.0100
C3···O2iv3.3980 (18)H12···O42.4500
C4···O1xi3.2636 (18)H13···O22.4900
C4···O4x3.3148 (19)H13···C3iv3.0500
C8—O8—H8112.00C4—C3—H3120.00
C14—O4—H4A111.00C2—C3—H3120.00
C2—N1—C9122.71 (12)C3—C4—H4120.00
C9—N1—H1119.00C10—C4—H4120.00
C2—N1—H1118.00C10—C5—H5120.00
N1—C2—C3120.29 (13)C6—C5—H5120.00
C2—C3—C4119.43 (13)C5—C6—H6119.00
C3—C4—C10120.78 (14)C7—C6—H6119.00
C6—C5—C10119.36 (14)C8—C7—H7120.00
C5—C6—C7121.69 (13)C6—C7—H7120.00
C6—C7—C8120.63 (13)O1—C11—O2124.89 (11)
O8—C8—C7126.08 (12)O2—C11—C12118.08 (11)
C7—C8—C9118.16 (12)O1—C11—C12117.01 (10)
O8—C8—C9115.76 (11)C11—C12—C13123.11 (11)
C8—C9—C10121.38 (11)C12—C13—C14124.28 (12)
N1—C9—C10119.22 (11)O3—C14—C13121.29 (13)
N1—C9—C8119.39 (12)O4—C14—C13114.37 (11)
C4—C10—C5123.64 (13)O3—C14—O4124.34 (13)
C4—C10—C9117.58 (12)C11—C12—H12118.00
C5—C10—C9118.74 (12)C13—C12—H12118.00
N1—C2—H2120.00C12—C13—H13118.00
C3—C2—H2120.00C14—C13—H13118.00
C9—N1—C2—C30.4 (2)O8—C8—C9—N12.98 (18)
C2—N1—C9—C8178.60 (13)O8—C8—C9—C10178.31 (12)
C2—N1—C9—C100.14 (19)C7—C8—C9—N1177.09 (12)
N1—C2—C3—C40.5 (2)C7—C8—C9—C101.63 (19)
C2—C3—C4—C100.2 (2)N1—C9—C10—C40.08 (19)
C3—C4—C10—C5177.92 (14)N1—C9—C10—C5177.97 (12)
C3—C4—C10—C90.0 (2)C8—C9—C10—C4178.80 (12)
C10—C5—C6—C71.0 (2)C8—C9—C10—C50.75 (19)
C6—C5—C10—C4177.38 (14)O1—C11—C12—C13175.86 (14)
C6—C5—C10—C90.6 (2)O2—C11—C12—C135.5 (2)
C5—C6—C7—C80.0 (2)C11—C12—C13—C14179.94 (14)
C6—C7—C8—O8178.69 (14)C12—C13—C14—O3170.10 (18)
C6—C7—C8—C91.2 (2)C12—C13—C14—O410.1 (2)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y1, z; (iii) x+1, y1, z; (iv) x+1, y+1, z; (v) x+1, y, z1; (vi) x+1, y+2, z; (vii) x+1, y, z; (viii) x, y+1, z; (ix) x+1, y+2, z+1; (x) x1, y, z; (xi) x1, y+1, z; (xii) x1, y, z+1; (xiii) x, y+2, z+1; (xiv) x, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1viii0.891.922.7711 (15)159
N1—H1···O80.892.332.6673 (14)102
O4—H4A···O2viii0.941.602.5327 (13)177
O8—H8···O1i0.921.702.6151 (14)175
C2—H2···O2iv0.932.493.2042 (17)133
C12—H12···O40.932.452.7657 (15)100
C13—H13···O20.932.492.7988 (16)100
Symmetry codes: (i) x+1, y+1, z+1; (iv) x+1, y+1, z; (viii) x, y+1, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaC9H8NO+·C4H3O4C9H8NO+·C4H3O4
Mr261.23261.23
Crystal system, space groupOrthorhombic, P212121Triclinic, P1
Temperature (K)273273
a, b, c (Å)5.3777 (3), 10.0563 (7), 22.4243 (12)7.3282 (3), 7.4363 (3), 11.5680 (5)
α, β, γ (°)90, 90, 9079.349 (2), 74.994 (2), 89.337 (2)
V3)1212.70 (13)597.97 (4)
Z42
Radiation typeMo KαMo Kα
µ (mm1)0.110.11
Crystal size (mm)0.40 × 0.30 × 0.220.30 × 0.20 × 0.16
Data collection
DiffractometerBruker Kappa APEXII CCD
diffractometer
Bruker Kappa APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1999)
Multi-scan
(SADABS; Bruker, 1999)
Tmin, Tmax0.957, 0.9760.967, 0.982
No. of measured, independent and
observed [I > 2σ(I)] reflections
7633, 1764, 1291 15682, 4437, 3049
Rint0.0340.025
(sin θ/λ)max1)0.6680.772
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.053, 0.134, 1.16 0.047, 0.152, 1.07
No. of reflections17644437
No. of parameters172172
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.22, 0.170.45, 0.24
Absolute structureFlack (1983), with 1220 Friedel pairs?

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2i1.00001.73002.714 (4)167.00
N1—H1···O81.00002.37002.666 (3)96.08
O4—H4A···O11.03001.40002.427 (4)174.00
O8—H8···O2ii0.94001.70002.643 (3)177.00
C2—H2···O1i0.93002.31003.058 (5)137.00
C6—H6···O3iii0.93002.43003.324 (6)160.00
Symmetry codes: (i) x1, y+1, z; (ii) x1/2, y+1/2, z; (iii) x+1, y, z.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.89001.92002.7711 (15)159.00
N1—H1···O80.89002.33002.6673 (14)102.00
O4—H4A···O2i0.94001.60002.5327 (13)177.00
O8—H8···O1ii0.92001.70002.6151 (14)175.00
C2—H2···O2iii0.93002.49003.2042 (17)133.00
C12—H12···O40.93002.45002.7657 (15)100.00
C13—H13···O20.93002.49002.7988 (16)100.00
Symmetry codes: (i) x, y+1, z; (ii) x+1, y+1, z+1; (iii) x+1, y+1, z.
 

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