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Both title compounds are derivatives of salicylic acid. 5-Formyl­salicylic acid (systematic name: 5-formyl-2-hy­droxy­benzoic acid), C8H6O4, possesses three good hydrogen-bond donors and/or acceptors coplanar with their attached benzene ring and abides very well by Etter's hydrogen-bond rules. Inter­molecular O-H...O and some weak C-H...O hydrogen bonds link the mol­ecules into a planar sheet. Reaction of this acid and o-phenylene­diamine in refluxing ethanol produced in high yield the new zwitterionic compound 5-(benzimidazolium-2-yl)salicylate [systematic name: 5-(1H-benzimidazol-3-ium-2-yl)-2-hy­droxy­benzoate], C14H10N2O3. Each imidazolium N-H group and its adjacent salicyl C-H group chelate one carboxyl­ate O atom via hydrogen bonds, forming seven-membered rings. As a result of steric hindrance, the planes of the molecules within these pairs of hydrogen-bonded molecules are inclined to one another by ~74°. There are also [pi]-[pi] stacking interactions between the parallel planes of the imidazole ring and the benzene ring of the salicyl component of the adjacent molecule on one side and the benzimidazolium component of the molecule on the other side.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110044926/sk3389sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110044926/sk3389Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110044926/sk3389IIsup3.hkl
Contains datablock II

CCDC references: 810018; 810019

Comment top

Salicylic acid is a plant hormone and widely used in organic synthesis (Hayat & Ahmad, 2007). This acid and many of its derivatives have medical applications, such as in anti-inflammatory treatments, easing aches and pains and reducing fevers. Formylation leads to separation of 3- and 5-formylsalicylic acids (Duff & Bills, 1932, 1934). The formyl group can then be used to react with various amines, which normally afford Schiff bases. The reaction of 5-formylsalicylic acid has received much less attention than that of 3-formylsalicylic acid. The crystal structure of 5-formylsalicylic acid, (I), has not been reported previously, although a cocrystal containing deprotonated (I), 2-aminopyridinium 5-formylsalicylate, has been published (Li et al., 2006).

A unique type of salicylic acid derivative, benzimidazolylsalicylic acids, was designed to combine both chemotherapeutic benzimidazole and salicylic acid moieties. These compounds have antimicrobial, cytotoxic and anthelmintic potential and were synthesized by interaction of 5,6-dimethyl- or 6-nitrobenzimidazoles with diazotized 5-aminosalicylic acid in the presence of cupric chloride (Dahiya & Pathak, 2007). The reported multi-step reaction is somewhat complicated. We found that when (I) is reacted with o-phenyldiamine in refluxing ethanol, the zwitterionic form of a benzimidazolylsalicylic acid, 5-(benzimidazolium-2-yl)salicylate, (II), could be obtained immediately in high yield. The imidazole ring in the new compound, (II), was formed through a one-step condensation between the formyl group of (I) and o-phenyldiamine, much more convenient than the method mentioned above (Dahiya & Pathak, 2007). Such an imidazole ring-enclosure approach involving aldehydes and aromatic orthodiamines has occasionally been utilized (Bindra & Elix, 1969; da Silva et al., 2010). However, in the case of 3-formylsalicylic acid, its reaction with o-phenyldiamine yielded a salen-type double Schiff base instead of an imidazolyl compound (Cheng & Liu, 2000; Lalehzari et al., 2008).

It is also notable that when (I) and o-phenyldiamine were mixed in refluxing syrupy phosphoric acid, which has a much higher boiling point than ethanol, it was the carboxyl not the aldehyde group of (I) that participated in the formation of imidazolyl ring closure, with the product being 2-(2-hydroxyphenyl)benzimidazole (Tong et al., 2005).

In (I), the parent phenyl ring and the three attached O-containing functional groups are almost exactly coplanar (Fig. 1). The interaction of the molecules can be analysed using the graph-set theory regarding the hydrogen-bond patterns of organic compounds, developed by Etter (1990). Some hydrogen-bond rules have been proposed, including one that all good H-atom donors and acceptors are used in hydrogen bonding, whereas less acidic H atoms may be used in hydrogen bonding when there are extra H-atom acceptors available after all the more acidic H atoms have found an acceptor. These rules apply very well in the case of (I). The hydroxyl, carboxyl and formyl groups are all good H-atom donors and/or acceptors. The hydroxyl and carboxyl groups, as H-atom donors, form both intra- and intermolecular O—H···O hydrogen bonds (Fig. 2, Table 1) and their hydrogen-bond patterns can be encoded as S(6) and R22(4), respectively (Etter, 1990). The resulting dimers are connected through intermolecular hydrogen bonding between the carboxyl donor and the formyl acceptor, leading to the formation of an infinite two-dimensional planar network parallel with the (102) plane. Some of the less acidic C—H groups also participate in intermolecular C—H···O hydrogen bonds, which are quite weak as the corresponding H···O distances are fairly long (Table 1), but which still agree with the description of C—H···O bonds (Steiner, 2003). Thus, a series of hydrogen-bond patterns is formed, including R33(9), R22(11), R32(7) and R22(10) (Fig. 2). Through these conventional and unconventional hydrogen bonds, one molecule of (I) is connected to six adjacent molecules in the same plane. These planar sheets are separated evenly by 3.406 Å, as there is a weak interaction between adjacent parallel phenyl rings (centroid-to-centroid distance 3.776 Å).

Compound (II) is the zwitterionic form of 5-(benzimidazol-2-yl)salicylic acid, in which the carboxyl group is deprotonated and an imidazole N atom is protonated, as shown in Fig. 3. The carboxylate and hydroxyl groups are coplanar with their attached phenyl ring, whereas the benzimidazolium moiety is slightly twisted from the salicyl moiety by 7.35°. Graph-set analysis is also applicable for the hydrogen bonding in (II). As shown in Fig. 4 and Table 2, the hydroxyl and carboxylate groups form an intramolecular S(6) hydrogen-bond pattern, similar to (I). Intermolecular N—H···O hydrogen bonds connect each molecule to four neighbouring molecules and form a two-dimensional network parallel to the (001) plane. Non-classical C—H···O hydrogen bonds also play an important role in the crystal packing. It is quite interesting that each of the two carboxylate O atoms is chelated by an N—H group and an adjacent salicyl C—H group, forming a seven-membered R21(7) ring. Due to steric requirements, these chelate cycles mean that each pair of hydrogen-bonded molecules is not coplanar but staggered, by an angle of ~74°. The three molecules on the same side of their connected molecule (Fig. 4) are aligned almost parallel and staggered. They are stabilized by two kinds of ππ stacking interactions between the imidazole ring and the benzene ring of either the salicyl or the benzoimidazolium moiety, as evident from the centroid-to-centroid distances: Cg(C1/C6/C7/N1/N2)···Cg(C8–C13)i = 3.5742 (8) Å, Cg(C1/C6/C7/N1/N2)···Cg(C1–C6)ii = 3.6978 (8) Å [symmetry codes: (i) -x + 1/2, y - 1/2, z; (ii) -x + 1/2, y + 1/2, z].

Experimental top

Compound (I) was prepared according to well established procedures (Duff & Bills, 1932, 1934). Single crystals were obtained by vapour diffusion of diethyl ether into an ethanol solution. Analysis, calculated for C8H6O4: C 57.84, H 3.64%; found: C 57.72, H 3.75%.

Compound (II) was synthesized as follows. A solution of o-phenyldiamine (1.08 g, 0.01 mol) in ethanol (20 ml) was added to a solution of (I) (1.66 g, 0.01 mol) in ethanol (20 ml). The mixture was refluxed for 6 h. The flaxen solid product was filtered, washed and recrystallized from ethanol (yield 2.14 g, 84%). Single crystals were obtained by vapour diffusion of diethyl ether into an ethanol solution. Analysis, calculated for C14H10N2O3: C 66.14, H 3.96, N 11.02%; found: C 65.97, H 3.94, N 11.14%.

Refinement top

H atoms attached to C or N atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93 Å and N—H = 0.86 Å, and Uiso(H) = 1.2Ueq(C or N). H atoms bound to O atoms were determined from difference Fourier maps and treated in the riding-model approximation, with O—H = 0.82 Å and Uiso(H) = 1.5Ueq(O). [Please check added X—H distances]

Computing details top

For both compounds, data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: APEX2 (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecule of (I), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. A planar sheet of molecules of (I) connected via O—H···O and C—H···O hydrogen bonds (dashed lines; red and green, respectively, in the electronic version of the journal). The hydrogen-bond patterns are shown by graph-set analysis.
[Figure 3] Fig. 3. The zwitterionic molecule of (II), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability and H atoms are shown as small spheres of arbitrary radii.
[Figure 4] Fig. 4. Interactions between the molecules of (II), including O—H···O, N—H···O (dashed lines; red in the electronic version of the journal) and C—H···O (dashed lines; green in the electronic version of the journal) hydrogen bonds, and ππ stacking interactions (stacking pairs of rings are highlighted with the same shading). [Symmetry codes: (i) -x + 1, y - 1/2, -z + 1/2; (ii) x - 1/2, y, -z + 1/2.]
(I) 5-Formyl-2-hydroxybenzoic acid top
Crystal data top
C8H6O4F(000) = 344
Mr = 166.13Dx = 1.539 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3041 reflections
a = 3.7762 (3) Åθ = 3.0–26.0°
b = 16.3219 (11) ŵ = 0.13 mm1
c = 11.6334 (8) ÅT = 298 K
β = 91.525 (5)°Block, colourless
V = 716.77 (9) Å30.50 × 0.30 × 0.20 mm
Z = 4
Data collection top
Bruker APEXII CCD area-detector
diffractometer
1708 independent reflections
Radiation source: fine-focus sealed tube1202 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.043
ϕ and ω scansθmax = 28.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
h = 43
Tmin = 0.956, Tmax = 0.975k = 2121
9607 measured reflectionsl = 1415
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)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.123H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0646P)2 + 0.0917P]
where P = (Fo2 + 2Fc2)/3
1699 reflections(Δ/σ)max < 0.001
111 parametersΔρmax = 0.22 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C8H6O4V = 716.77 (9) Å3
Mr = 166.13Z = 4
Monoclinic, P21/cMo Kα radiation
a = 3.7762 (3) ŵ = 0.13 mm1
b = 16.3219 (11) ÅT = 298 K
c = 11.6334 (8) Å0.50 × 0.30 × 0.20 mm
β = 91.525 (5)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
1708 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
1202 reflections with I > 2σ(I)
Tmin = 0.956, Tmax = 0.975Rint = 0.043
9607 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.123H-atom parameters constrained
S = 1.03Δρmax = 0.22 e Å3
1699 reflectionsΔρmin = 0.18 e Å3
111 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
C10.7100 (4)0.69404 (8)0.09974 (11)0.0363 (3)
C20.5386 (4)0.70240 (9)0.00863 (11)0.0396 (4)
C30.4729 (4)0.78064 (9)0.05358 (12)0.0426 (4)
H3A0.36250.78610.12560.051*
C40.5691 (4)0.84907 (9)0.00710 (12)0.0414 (4)
H40.52340.90070.02380.050*
C50.7371 (4)0.84197 (8)0.11620 (11)0.0380 (3)
C60.8046 (4)0.76454 (8)0.16036 (11)0.0370 (3)
H60.91580.75960.23230.044*
C70.7911 (4)0.61173 (9)0.14672 (12)0.0419 (4)
C80.8511 (4)0.91348 (9)0.18176 (12)0.0442 (4)
H80.96480.90490.25260.053*
O10.4342 (3)0.63807 (7)0.07275 (9)0.0547 (3)
H10.47420.59560.03710.082*
O20.6998 (3)0.54837 (6)0.09905 (10)0.0589 (4)
O30.9731 (3)0.61438 (6)0.24459 (9)0.0563 (4)
H31.01520.56760.26670.085*
O40.8078 (4)0.98366 (6)0.15020 (10)0.0641 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0407 (8)0.0318 (7)0.0363 (7)0.0006 (5)0.0050 (6)0.0005 (5)
C20.0442 (8)0.0383 (8)0.0359 (7)0.0032 (6)0.0051 (6)0.0056 (5)
C30.0491 (9)0.0445 (8)0.0336 (7)0.0003 (7)0.0123 (6)0.0013 (6)
C40.0481 (9)0.0355 (7)0.0401 (7)0.0019 (6)0.0085 (6)0.0057 (6)
C50.0427 (8)0.0324 (7)0.0386 (7)0.0006 (6)0.0064 (6)0.0006 (5)
C60.0430 (8)0.0352 (7)0.0324 (6)0.0001 (6)0.0085 (5)0.0012 (5)
C70.0517 (9)0.0338 (7)0.0397 (7)0.0015 (6)0.0054 (6)0.0006 (6)
C80.0538 (9)0.0369 (8)0.0413 (8)0.0007 (7)0.0120 (6)0.0002 (6)
O10.0784 (8)0.0405 (6)0.0441 (6)0.0048 (5)0.0198 (5)0.0069 (4)
O20.0845 (9)0.0331 (6)0.0581 (7)0.0037 (5)0.0174 (6)0.0054 (5)
O30.0860 (9)0.0317 (5)0.0499 (6)0.0037 (5)0.0255 (6)0.0030 (4)
O40.0975 (10)0.0308 (6)0.0622 (7)0.0027 (6)0.0305 (6)0.0020 (5)
Geometric parameters (Å, º) top
C1—C61.3913 (18)C5—C61.3854 (18)
C1—C21.408 (2)C5—C81.4532 (19)
C1—C71.4795 (19)C6—H60.9300
C2—O11.3411 (16)C7—O21.2187 (16)
C2—C31.400 (2)C7—O31.3149 (17)
C3—C41.365 (2)C8—O41.2126 (17)
C3—H3A0.9300C8—H80.9300
C4—C51.4086 (18)O1—H10.8200
C4—H40.9300O3—H30.8200
C6—C1—C2118.64 (12)C6—C5—C8119.29 (12)
C6—C1—C7121.06 (12)C4—C5—C8121.80 (12)
C2—C1—C7120.29 (12)C5—C6—C1121.62 (12)
O1—C2—C3117.39 (12)C5—C6—H6119.2
O1—C2—C1122.90 (13)C1—C6—H6119.2
C3—C2—C1119.71 (12)O2—C7—O3123.84 (14)
C4—C3—C2120.74 (12)O2—C7—C1123.31 (14)
C4—C3—H3A119.6O3—C7—C1112.85 (12)
C2—C3—H3A119.6O4—C8—C5124.34 (13)
C3—C4—C5120.39 (13)O4—C8—H8117.8
C3—C4—H4119.8C5—C8—H8117.8
C5—C4—H4119.8C2—O1—H1109.5
C6—C5—C4118.89 (12)C7—O3—H3109.5
C6—C1—C2—O1179.28 (13)C8—C5—C6—C1178.20 (13)
C7—C1—C2—O11.6 (2)C2—C1—C6—C50.6 (2)
C6—C1—C2—C31.1 (2)C7—C1—C6—C5178.56 (12)
C7—C1—C2—C3178.11 (13)C6—C1—C7—O2176.71 (14)
O1—C2—C3—C4179.49 (13)C2—C1—C7—O24.1 (2)
C1—C2—C3—C40.8 (2)C6—C1—C7—O33.7 (2)
C2—C3—C4—C50.1 (2)C2—C1—C7—O3175.47 (13)
C3—C4—C5—C60.3 (2)C6—C5—C8—O4179.28 (14)
C3—C4—C5—C8178.39 (14)C4—C5—C8—O41.2 (2)
C4—C5—C6—C10.1 (2)
Hydrogen-bond geometry (Å, º) top
Table 1
D—H···AD—HH···AD···AD—H···A
O3—H3···O4i0.821.802.5848 (15)161
O1—H1···O2ii0.822.543.0988 (16)127
O1—H1···O20.821.942.6528 (15)145
C3—H3A···O3iii0.932.633.4315 (18)144
C4—H4···O4iv0.932.683.5641 (18)158
C8—H8···O1v0.932.753.6576 (18)165
Symmetry codes: (i) x+2, y1/2, z+1/2; (ii) x+1, y+1, z; (iii) x1, y+3/2, z1/2; (iv) x+1, y+2, z; (v) x+1, y+3/2, z+1/2.
(II) 5-(1H-benzimidazol-3-ium-2-yl)-2-hydroxybenzoate top
Crystal data top
C14H10N2O3F(000) = 1056
Mr = 254.24Dx = 1.366 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 5133 reflections
a = 16.2033 (4) Åθ = 2.5–23.9°
b = 8.1005 (2) ŵ = 0.10 mm1
c = 18.8425 (5) ÅT = 298 K
V = 2473.17 (11) Å3Block, yellow
Z = 80.35 × 0.30 × 0.20 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
2949 independent reflections
Radiation source: fine-focus sealed tube2007 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.040
ϕ and ω scansθmax = 27.9°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
h = 2120
Tmin = 0.966, Tmax = 0.981k = 1010
23379 measured reflectionsl = 2424
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)] = 0.041H-atom parameters constrained
wR(F2) = 0.104 w = 1/[σ2(Fo2) + (0.0442P)2 + 0.3316P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
2949 reflectionsΔρmax = 0.20 e Å3
174 parametersΔρmin = 0.18 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0029 (5)
Crystal data top
C14H10N2O3V = 2473.17 (11) Å3
Mr = 254.24Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 16.2033 (4) ŵ = 0.10 mm1
b = 8.1005 (2) ÅT = 298 K
c = 18.8425 (5) Å0.35 × 0.30 × 0.20 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
2949 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
2007 reflections with I > 2σ(I)
Tmin = 0.966, Tmax = 0.981Rint = 0.040
23379 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.104H-atom parameters constrained
S = 1.05Δρmax = 0.20 e Å3
2949 reflectionsΔρmin = 0.18 e Å3
174 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
C10.16371 (8)0.04754 (17)0.37266 (7)0.0406 (3)
C20.09132 (9)0.0041 (2)0.40526 (9)0.0551 (4)
H20.03970.03010.38950.066*
C30.10025 (11)0.1088 (2)0.46222 (9)0.0662 (5)
H30.05330.14730.48520.079*
C40.17749 (11)0.1589 (2)0.48654 (9)0.0611 (5)
H40.18060.22820.52580.073*
C50.24948 (10)0.10858 (19)0.45404 (8)0.0496 (4)
H50.30100.14190.47040.060*
C60.24087 (8)0.00562 (17)0.39575 (7)0.0389 (3)
C70.25852 (7)0.15783 (16)0.30215 (7)0.0349 (3)
C80.29604 (7)0.25517 (16)0.24632 (7)0.0346 (3)
C90.24716 (8)0.33425 (16)0.19499 (7)0.0395 (3)
H90.19020.32080.19600.047*
C100.28206 (8)0.43070 (18)0.14350 (7)0.0430 (3)
H100.24870.48190.10990.052*
C110.36763 (8)0.45280 (17)0.14105 (7)0.0417 (3)
C120.41780 (7)0.37310 (16)0.19125 (7)0.0368 (3)
C130.38124 (7)0.27549 (16)0.24272 (7)0.0366 (3)
H130.41450.22210.27580.044*
C140.50975 (8)0.39180 (18)0.19040 (8)0.0428 (3)
N10.29802 (6)0.06433 (13)0.35000 (6)0.0384 (3)
H1A0.35060.05000.35200.046*
N20.17745 (6)0.14915 (13)0.31489 (6)0.0391 (3)
H2A0.13980.19900.29090.047*
O10.39888 (6)0.54939 (16)0.08991 (6)0.0643 (3)
H10.44930.55170.09330.096*
O20.55103 (5)0.31939 (14)0.23678 (6)0.0561 (3)
O30.54029 (6)0.48116 (14)0.14132 (5)0.0560 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0358 (7)0.0418 (8)0.0442 (8)0.0015 (6)0.0056 (6)0.0070 (7)
C20.0384 (8)0.0653 (10)0.0617 (10)0.0027 (7)0.0125 (7)0.0009 (9)
C30.0618 (11)0.0726 (12)0.0642 (11)0.0120 (9)0.0239 (9)0.0002 (10)
C40.0767 (12)0.0578 (10)0.0488 (9)0.0037 (8)0.0126 (8)0.0031 (8)
C50.0577 (9)0.0487 (9)0.0424 (8)0.0045 (7)0.0006 (7)0.0057 (7)
C60.0375 (7)0.0389 (7)0.0402 (8)0.0009 (6)0.0036 (6)0.0096 (6)
C70.0261 (6)0.0366 (7)0.0421 (7)0.0009 (5)0.0004 (5)0.0084 (6)
C80.0268 (6)0.0349 (7)0.0422 (7)0.0012 (5)0.0005 (5)0.0067 (6)
C90.0243 (6)0.0463 (8)0.0480 (8)0.0005 (5)0.0020 (5)0.0063 (7)
C100.0309 (7)0.0522 (9)0.0458 (8)0.0027 (6)0.0059 (6)0.0006 (7)
C110.0344 (7)0.0480 (8)0.0427 (8)0.0020 (6)0.0014 (6)0.0008 (7)
C120.0257 (6)0.0422 (8)0.0423 (7)0.0001 (5)0.0007 (5)0.0058 (6)
C130.0274 (6)0.0396 (7)0.0428 (8)0.0039 (5)0.0013 (5)0.0047 (6)
C140.0275 (7)0.0525 (9)0.0483 (8)0.0018 (6)0.0031 (6)0.0089 (7)
N10.0274 (5)0.0433 (7)0.0444 (7)0.0026 (5)0.0001 (5)0.0054 (5)
N20.0254 (6)0.0452 (7)0.0468 (7)0.0015 (5)0.0012 (4)0.0025 (6)
O10.0412 (6)0.0887 (9)0.0629 (7)0.0101 (6)0.0014 (5)0.0266 (6)
O20.0262 (5)0.0793 (8)0.0627 (7)0.0067 (5)0.0011 (4)0.0058 (6)
O30.0314 (5)0.0771 (8)0.0596 (7)0.0121 (5)0.0033 (4)0.0062 (6)
Geometric parameters (Å, º) top
C1—N21.3827 (17)C8—C91.4045 (18)
C1—C21.3888 (19)C9—C101.3681 (19)
C1—C61.3920 (19)C9—H90.9300
C2—C31.375 (2)C10—C111.3987 (18)
C2—H20.9300C10—H100.9300
C3—C41.393 (2)C11—O11.3405 (16)
C3—H30.9300C11—C121.4045 (19)
C4—C51.379 (2)C12—C131.3844 (18)
C4—H40.9300C12—C141.4977 (17)
C5—C61.386 (2)C13—H130.9300
C5—H50.9300C14—O21.2469 (17)
C6—N11.3861 (17)C14—O31.2745 (17)
C7—N21.3373 (15)N1—H1A0.8600
C7—N11.3402 (16)N2—H2A0.8600
C7—C81.4485 (18)O1—H10.8200
C8—C131.3919 (17)
N2—C1—C2131.57 (13)C10—C9—H9119.5
N2—C1—C6106.59 (11)C8—C9—H9119.5
C2—C1—C6121.82 (14)C9—C10—C11120.41 (13)
C3—C2—C1116.24 (14)C9—C10—H10119.8
C3—C2—H2121.9C11—C10—H10119.8
C1—C2—H2121.9O1—C11—C10118.22 (12)
C2—C3—C4122.05 (15)O1—C11—C12122.26 (12)
C2—C3—H3119.0C10—C11—C12119.52 (12)
C4—C3—H3119.0C13—C12—C11119.12 (12)
C5—C4—C3121.86 (16)C13—C12—C14119.40 (12)
C5—C4—H4119.1C11—C12—C14121.48 (12)
C3—C4—H4119.1C12—C13—C8121.74 (12)
C4—C5—C6116.39 (15)C12—C13—H13119.1
C4—C5—H5121.8C8—C13—H13119.1
C6—C5—H5121.8O2—C14—O3124.57 (12)
N1—C6—C5132.17 (13)O2—C14—C12118.59 (13)
N1—C6—C1106.22 (12)O3—C14—C12116.84 (13)
C5—C6—C1121.61 (13)C7—N1—C6109.29 (11)
N2—C7—N1108.58 (11)C7—N1—H1A125.4
N2—C7—C8124.84 (12)C6—N1—H1A125.4
N1—C7—C8126.58 (11)C7—N2—C1109.31 (11)
C13—C8—C9118.15 (12)C7—N2—H2A125.3
C13—C8—C7121.06 (12)C1—N2—H2A125.3
C9—C8—C7120.78 (11)C11—O1—H1109.5
C10—C9—C8121.05 (12)
N2—C1—C2—C3179.26 (14)O1—C11—C12—C13179.83 (13)
C6—C1—C2—C30.9 (2)C10—C11—C12—C130.7 (2)
C1—C2—C3—C40.7 (3)O1—C11—C12—C140.0 (2)
C2—C3—C4—C51.2 (3)C10—C11—C12—C14179.47 (12)
C3—C4—C5—C60.1 (2)C11—C12—C13—C80.44 (19)
C4—C5—C6—N1178.22 (14)C14—C12—C13—C8179.39 (12)
C4—C5—C6—C11.7 (2)C9—C8—C13—C121.28 (19)
N2—C1—C6—N10.96 (14)C7—C8—C13—C12177.57 (11)
C2—C1—C6—N1177.74 (13)C13—C12—C14—O20.56 (19)
N2—C1—C6—C5179.07 (12)C11—C12—C14—O2179.27 (13)
C2—C1—C6—C52.2 (2)C13—C12—C14—O3179.05 (12)
N2—C7—C8—C13171.03 (12)C11—C12—C14—O31.11 (19)
N1—C7—C8—C137.9 (2)N2—C7—N1—C60.74 (14)
N2—C7—C8—C97.78 (19)C8—C7—N1—C6178.31 (12)
N1—C7—C8—C9173.32 (12)C5—C6—N1—C7178.98 (14)
C13—C8—C9—C100.99 (19)C1—C6—N1—C71.06 (14)
C7—C8—C9—C10177.86 (12)N1—C7—N2—C10.11 (14)
C8—C9—C10—C110.1 (2)C8—C7—N2—C1178.96 (11)
C9—C10—C11—O1179.52 (13)C2—C1—N2—C7177.98 (15)
C9—C10—C11—C121.0 (2)C6—C1—N2—C70.54 (14)
Hydrogen-bond geometry (Å, º) top
Table 2
D—H···AD—HH···AD···AD—H···A
N1—H1A···O3i0.861.862.7102 (13)170
N2—H2A···O2ii0.861.812.6544 (14)165
O1—H1···O30.821.822.5482 (14)147
C9—H9···O2ii0.932.583.4303 (16)151
C13—H13···O3i0.932.603.4749 (17)156
Symmetry codes: (i) x+1, y1/2, z+1/2; (ii) x1/2, y, z+1/2.

Experimental details

(I)(II)
Crystal data
Chemical formulaC8H6O4C14H10N2O3
Mr166.13254.24
Crystal system, space groupMonoclinic, P21/cOrthorhombic, Pbca
Temperature (K)298298
a, b, c (Å)3.7762 (3), 16.3219 (11), 11.6334 (8)16.2033 (4), 8.1005 (2), 18.8425 (5)
α, β, γ (°)90, 91.525 (5), 9090, 90, 90
V3)716.77 (9)2473.17 (11)
Z48
Radiation typeMo KαMo Kα
µ (mm1)0.130.10
Crystal size (mm)0.50 × 0.30 × 0.200.35 × 0.30 × 0.20
Data collection
DiffractometerBruker APEXII CCD area-detector
diffractometer
Bruker APEXII CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2002)
Multi-scan
(SADABS; Bruker, 2002)
Tmin, Tmax0.956, 0.9750.966, 0.981
No. of measured, independent and
observed [I > 2σ(I)] reflections
9607, 1708, 1202 23379, 2949, 2007
Rint0.0430.040
(sin θ/λ)max1)0.6600.658
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.123, 1.03 0.041, 0.104, 1.05
No. of reflections16992949
No. of parameters111174
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.22, 0.180.20, 0.18

Computer programs: APEX2 (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) for (I) top
Table 1
D—H···AD—HH···AD···AD—H···A
O3—H3···O4i0.821.802.5848 (15)161
O1—H1···O2ii0.822.543.0988 (16)127
O1—H1···O20.821.942.6528 (15)145
C3—H3A···O3iii0.932.633.4315 (18)144
C4—H4···O4iv0.932.683.5641 (18)158
C8—H8···O1v0.932.753.6576 (18)165
Symmetry codes: (i) x+2, y1/2, z+1/2; (ii) x+1, y+1, z; (iii) x1, y+3/2, z1/2; (iv) x+1, y+2, z; (v) x+1, y+3/2, z+1/2.
Hydrogen-bond geometry (Å, º) for (II) top
Table 2
D—H···AD—HH···AD···AD—H···A
N1—H1A···O3i0.861.862.7102 (13)170
N2—H2A···O2ii0.861.812.6544 (14)165
O1—H1···O30.821.822.5482 (14)147
C9—H9···O2ii0.932.583.4303 (16)151
C13—H13···O3i0.932.603.4749 (17)156
Symmetry codes: (i) x+1, y1/2, z+1/2; (ii) x1/2, y, z+1/2.
 

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