In the title zwitterion, C
15H
13NO
4, obtained from the condensation of 5-aminosalicylic acid and 4-methoxybenzaldehyde, the 4-hydoxyanilinic group of the 5-aminosalicylic acid moiety and the 4-methoxybenzaldehyde moiety are twisted with respect to one another, making a dihedral angle of 10.37 (7)°. The carboxylate group makes a dihedral angle of 5.7 (2)° with the parent 4-hydoxyanilinic group. An intramolecular O—H
O hydrogen bond forms an
S(6) ring motif. In the crystal, intermolecular C—H
O and N—H
O hydrogen bonds with
R21(7) ring motifs link the molecules into infinite chains extending along the
c axis. The occurence of slipped π–π stacking between symmetry-related aromatic rings reinforces the packing.
Supporting information
CCDC reference: 797760
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.003 Å
- R factor = 0.050
- wR factor = 0.143
- Data-to-parameter ratio = 12.7
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) ..... 1
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 7
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF .... 3
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
3 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
0 ALERT type 2 Indicator that the structure model may be wrong or deficient
3 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
Equimolar quantities of 5-aminosalicylic acid and 4-anisaldehyde were refluxed
in methanol for 30 min resulting in clear brown solution. The solution was
kept at room temperature which affoarded light brown prisms after 72 h.
All H atoms attached to C atoms and N atom were fixed geometrically and treated
as riding with C—H = 0.95 Å (methyl) or 0.93 Å (aromatic) and N—H =
0.86 Å with Uiso(H) = 1.2Ueq(Caromatic or N) or Uiso(H) =
1.5Ueq(Cmethyl). H atoms of the hydroxyl group was located in difference
Fourier maps and included in the subsequent refinement using restraints (O—H
=
0.85 (1) Å) with Uiso(H) = 1.5Ueq(O). In the last cycles of refinement
this hydrogen was treated as riding on its parent O atom.
Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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 PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).
2-Hydroxy-5-{[(
E)-4-methoxybenzylidene]azaniumyl}benzoate
top
Crystal data top
C15H13NO4 | F(000) = 568 |
Mr = 271.26 | Dx = 1.401 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1583 reflections |
a = 13.4369 (12) Å | θ = 2.9–25.3° |
b = 8.5619 (8) Å | µ = 0.10 mm−1 |
c = 12.6653 (11) Å | T = 296 K |
β = 118.004 (3)° | Prism, light brown |
V = 1286.5 (2) Å3 | 0.26 × 0.20 × 0.18 mm |
Z = 4 | |
Data collection top
Bruker Kappa APEXII CCD diffractometer | 2320 independent reflections |
Radiation source: fine-focus sealed tube | 1583 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
Detector resolution: 8.10 pixels mm-1 | θmax = 25.3°, θmin = 2.9° |
ω scans | h = −15→16 |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | k = −10→10 |
Tmin = 0.982, Tmax = 0.987 | l = −15→10 |
9561 measured reflections | |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.143 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0831P)2 + 0.1187P] where P = (Fo2 + 2Fc2)/3 |
2320 reflections | (Δ/σ)max < 0.001 |
182 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
Crystal data top
C15H13NO4 | V = 1286.5 (2) Å3 |
Mr = 271.26 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.4369 (12) Å | µ = 0.10 mm−1 |
b = 8.5619 (8) Å | T = 296 K |
c = 12.6653 (11) Å | 0.26 × 0.20 × 0.18 mm |
β = 118.004 (3)° | |
Data collection top
Bruker Kappa APEXII CCD diffractometer | 2320 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 1583 reflections with I > 2σ(I) |
Tmin = 0.982, Tmax = 0.987 | Rint = 0.031 |
9561 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.143 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.28 e Å−3 |
2320 reflections | Δρmin = −0.18 e Å−3 |
182 parameters | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds 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 | Uiso*/Ueq | |
O1 | −0.19046 (12) | 0.62390 (19) | 0.15961 (12) | 0.0667 (5) | |
O2 | −0.03306 (11) | 0.49725 (16) | 0.27753 (10) | 0.0510 (4) | |
O3 | −0.29868 (11) | 0.56256 (18) | −0.05677 (12) | 0.0613 (5) | |
H3 | −0.2728 | 0.6015 | 0.0176 | 0.092* | |
O4 | 0.50744 (13) | −0.1897 (2) | 0.09919 (15) | 0.0857 (6) | |
N1 | 0.04782 (11) | 0.17725 (17) | −0.01733 (13) | 0.0405 (4) | |
H1 | 0.0329 | 0.1255 | −0.0813 | 0.049* | |
C1 | −0.11320 (15) | 0.5260 (2) | 0.17761 (15) | 0.0406 (5) | |
C2 | −0.11993 (13) | 0.4447 (2) | 0.06936 (14) | 0.0353 (4) | |
C3 | −0.21322 (15) | 0.4691 (2) | −0.04323 (16) | 0.0437 (5) | |
C4 | −0.21754 (16) | 0.3965 (3) | −0.14312 (17) | 0.0548 (6) | |
H4 | −0.2793 | 0.4128 | −0.2178 | 0.066* | |
C5 | −0.13155 (15) | 0.3009 (2) | −0.13273 (16) | 0.0507 (5) | |
H5 | −0.1350 | 0.2530 | −0.2002 | 0.061* | |
C6 | −0.03929 (14) | 0.2756 (2) | −0.02139 (15) | 0.0382 (4) | |
C7 | −0.03399 (13) | 0.3462 (2) | 0.07921 (15) | 0.0371 (4) | |
H7 | 0.0273 | 0.3276 | 0.1537 | 0.044* | |
C8 | 0.14683 (14) | 0.1574 (2) | 0.07203 (16) | 0.0421 (5) | |
H8 | 0.1627 | 0.2105 | 0.1423 | 0.051* | |
C9 | 0.23438 (14) | 0.0614 (2) | 0.07311 (16) | 0.0413 (5) | |
C10 | 0.33683 (16) | 0.0561 (3) | 0.17828 (17) | 0.0548 (6) | |
H10 | 0.3447 | 0.1116 | 0.2449 | 0.066* | |
C11 | 0.42584 (16) | −0.0289 (3) | 0.18534 (18) | 0.0633 (7) | |
H11 | 0.4934 | −0.0315 | 0.2562 | 0.076* | |
C12 | 0.41467 (16) | −0.1115 (3) | 0.08600 (18) | 0.0547 (6) | |
C13 | 0.31336 (17) | −0.1093 (3) | −0.01877 (18) | 0.0541 (5) | |
H13 | 0.3056 | −0.1665 | −0.0846 | 0.065* | |
C14 | 0.22442 (16) | −0.0231 (2) | −0.02569 (17) | 0.0476 (5) | |
H14 | 0.1570 | −0.0209 | −0.0967 | 0.057* | |
C15 | 0.5007 (2) | −0.2741 (4) | −0.0010 (3) | 0.1025 (10) | |
H15A | 0.5716 | −0.3243 | 0.0206 | 0.154* | |
H15B | 0.4836 | −0.2032 | −0.0660 | 0.154* | |
H15C | 0.4424 | −0.3515 | −0.0250 | 0.154* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0623 (9) | 0.0904 (12) | 0.0448 (8) | 0.0283 (9) | 0.0230 (7) | −0.0037 (8) |
O2 | 0.0533 (8) | 0.0604 (9) | 0.0315 (7) | 0.0028 (7) | 0.0135 (6) | 0.0023 (6) |
O3 | 0.0447 (8) | 0.0827 (11) | 0.0461 (8) | 0.0220 (7) | 0.0127 (7) | −0.0035 (7) |
O4 | 0.0628 (10) | 0.1237 (15) | 0.0748 (11) | 0.0473 (10) | 0.0358 (9) | 0.0216 (11) |
N1 | 0.0403 (8) | 0.0448 (9) | 0.0360 (8) | 0.0020 (7) | 0.0176 (7) | −0.0029 (7) |
C1 | 0.0401 (10) | 0.0465 (11) | 0.0365 (10) | −0.0018 (9) | 0.0189 (9) | 0.0033 (8) |
C2 | 0.0337 (9) | 0.0390 (10) | 0.0332 (9) | −0.0022 (8) | 0.0157 (8) | 0.0026 (8) |
C3 | 0.0361 (9) | 0.0522 (12) | 0.0392 (10) | 0.0055 (9) | 0.0147 (8) | 0.0013 (9) |
C4 | 0.0436 (11) | 0.0728 (14) | 0.0321 (10) | 0.0118 (11) | 0.0046 (9) | −0.0036 (10) |
C5 | 0.0472 (11) | 0.0620 (13) | 0.0345 (10) | 0.0066 (10) | 0.0120 (9) | −0.0085 (9) |
C6 | 0.0360 (9) | 0.0402 (10) | 0.0388 (10) | 0.0019 (8) | 0.0177 (8) | 0.0009 (8) |
C7 | 0.0320 (9) | 0.0417 (10) | 0.0332 (9) | −0.0005 (8) | 0.0118 (8) | 0.0050 (8) |
C8 | 0.0408 (10) | 0.0478 (11) | 0.0362 (10) | −0.0014 (9) | 0.0168 (8) | −0.0032 (8) |
C9 | 0.0369 (10) | 0.0465 (11) | 0.0385 (10) | 0.0012 (8) | 0.0161 (8) | 0.0009 (8) |
C10 | 0.0445 (11) | 0.0755 (15) | 0.0372 (11) | 0.0052 (10) | 0.0131 (9) | −0.0055 (10) |
C11 | 0.0399 (11) | 0.0946 (18) | 0.0445 (12) | 0.0129 (11) | 0.0108 (10) | 0.0063 (12) |
C12 | 0.0457 (11) | 0.0698 (14) | 0.0526 (13) | 0.0199 (11) | 0.0264 (10) | 0.0174 (11) |
C13 | 0.0569 (12) | 0.0628 (13) | 0.0435 (11) | 0.0120 (11) | 0.0243 (10) | 0.0011 (10) |
C14 | 0.0393 (10) | 0.0557 (12) | 0.0399 (10) | 0.0071 (9) | 0.0120 (9) | −0.0008 (9) |
C15 | 0.103 (2) | 0.123 (2) | 0.107 (2) | 0.0604 (19) | 0.0700 (18) | 0.0201 (19) |
Geometric parameters (Å, º) top
O1—C1 | 1.269 (2) | C6—C7 | 1.381 (2) |
O2—C1 | 1.242 (2) | C7—H7 | 0.9300 |
O3—C3 | 1.343 (2) | C8—C9 | 1.430 (2) |
O3—H3 | 0.9015 | C8—H8 | 0.9300 |
O4—C12 | 1.354 (2) | C9—C10 | 1.396 (2) |
O4—C15 | 1.426 (3) | C9—C14 | 1.396 (3) |
N1—C8 | 1.291 (2) | C10—C11 | 1.367 (3) |
N1—C6 | 1.423 (2) | C10—H10 | 0.9300 |
N1—H1 | 0.8600 | C11—C12 | 1.389 (3) |
C1—C2 | 1.502 (2) | C11—H11 | 0.9300 |
C2—C7 | 1.388 (2) | C12—C13 | 1.385 (3) |
C2—C3 | 1.404 (2) | C13—C14 | 1.372 (3) |
C3—C4 | 1.386 (3) | C13—H13 | 0.9300 |
C4—C5 | 1.371 (3) | C14—H14 | 0.9300 |
C4—H4 | 0.9300 | C15—H15A | 0.9600 |
C5—C6 | 1.390 (2) | C15—H15B | 0.9600 |
C5—H5 | 0.9300 | C15—H15C | 0.9600 |
| | | |
C3—O3—H3 | 101.5 | N1—C8—H8 | 117.0 |
C12—O4—C15 | 118.07 (18) | C9—C8—H8 | 117.0 |
C8—N1—C6 | 126.96 (16) | C10—C9—C14 | 118.36 (17) |
C8—N1—H1 | 116.5 | C10—C9—C8 | 117.77 (17) |
C6—N1—H1 | 116.5 | C14—C9—C8 | 123.85 (16) |
O2—C1—O1 | 123.99 (17) | C11—C10—C9 | 121.33 (19) |
O2—C1—C2 | 119.34 (16) | C11—C10—H10 | 119.3 |
O1—C1—C2 | 116.65 (15) | C9—C10—H10 | 119.3 |
C7—C2—C3 | 119.37 (16) | C10—C11—C12 | 119.54 (18) |
C7—C2—C1 | 120.59 (15) | C10—C11—H11 | 120.2 |
C3—C2—C1 | 120.04 (15) | C12—C11—H11 | 120.2 |
O3—C3—C4 | 118.93 (16) | O4—C12—C13 | 124.0 (2) |
O3—C3—C2 | 121.38 (16) | O4—C12—C11 | 115.99 (18) |
C4—C3—C2 | 119.68 (16) | C13—C12—C11 | 120.05 (18) |
C5—C4—C3 | 120.52 (17) | C14—C13—C12 | 120.22 (19) |
C5—C4—H4 | 119.7 | C14—C13—H13 | 119.9 |
C3—C4—H4 | 119.7 | C12—C13—H13 | 119.9 |
C4—C5—C6 | 120.05 (17) | C13—C14—C9 | 120.49 (17) |
C4—C5—H5 | 120.0 | C13—C14—H14 | 119.8 |
C6—C5—H5 | 120.0 | C9—C14—H14 | 119.8 |
C7—C6—C5 | 120.18 (16) | O4—C15—H15A | 109.5 |
C7—C6—N1 | 122.70 (15) | O4—C15—H15B | 109.5 |
C5—C6—N1 | 117.12 (16) | H15A—C15—H15B | 109.5 |
C6—C7—C2 | 120.18 (15) | O4—C15—H15C | 109.5 |
C6—C7—H7 | 119.9 | H15A—C15—H15C | 109.5 |
C2—C7—H7 | 119.9 | H15B—C15—H15C | 109.5 |
N1—C8—C9 | 126.07 (17) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O1 | 0.90 | 1.62 | 2.4816 (19) | 159 |
N1—H1···O2i | 0.86 | 1.90 | 2.7408 (19) | 166 |
C8—H8···O1ii | 0.93 | 2.47 | 3.179 (2) | 133 |
C14—H14···O2i | 0.93 | 2.30 | 3.183 (2) | 159 |
C15—H15A···O3iii | 0.96 | 2.56 | 3.393 (3) | 145 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x, y−1/2, −z+1/2; (iii) x+1, y−1, z. |
Experimental details
Crystal data |
Chemical formula | C15H13NO4 |
Mr | 271.26 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 13.4369 (12), 8.5619 (8), 12.6653 (11) |
β (°) | 118.004 (3) |
V (Å3) | 1286.5 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.26 × 0.20 × 0.18 |
|
Data collection |
Diffractometer | Bruker Kappa APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
Tmin, Tmax | 0.982, 0.987 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9561, 2320, 1583 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.600 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.143, 1.02 |
No. of reflections | 2320 |
No. of parameters | 182 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.18 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O1 | 0.90 | 1.62 | 2.4816 (19) | 158.6 |
N1—H1···O2i | 0.86 | 1.90 | 2.7408 (19) | 166.4 |
C8—H8···O1ii | 0.93 | 2.47 | 3.179 (2) | 133.0 |
C14—H14···O2i | 0.93 | 2.30 | 3.183 (2) | 158.9 |
C15—H15A···O3iii | 0.96 | 2.56 | 3.393 (3) | 145.4 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x, y−1/2, −z+1/2; (iii) x+1, y−1, z. |
π–π stacking interactions (Å, °) topCg1 and Cg2 are the centroids of the C2–C7
and C9–C14 rings, respectively. |
Cg···Cg | centroid–centroid distance | mean interplanar distancea | slippage angleb |
Cg1···Cg1i | 3.7848 (13) | 3.428 (1) | 25.1 |
Cg1···Cg2ii | 3.8456 (13) | 3.567 (1) | 22.0 |
Symmetry codes: (i) -x, 1-y, -z, (ii) -x, -y, -z.
Notes: (a) distance from one plane to the
neighbouring centroid;
(b) angle subtended by
the intercentroid vector to the plane normal. For details, see: Janiak
(2000). |
The title compound (I) has been synthesized as a potential ligand which could be used with various metals.
The title compound (I) is a Zwitterion. In (I), the group A (C2—C7/N1/O3) of 5-aminosalicylic acid moiety and the 4-methoxybenzaldehyde moiety B (C8—C15/O4) are planar with r. m. s. deviations of 0.0076 and 0.0255 Å, respectively. The dihedral angle between A/B is 10.37 (7)°. The carboxylate group C (O1/C1/O2) is oriented at a dihedral angle of 5.73 (24)° with the parent group A (Fig. 1). The title molecule is closely related to p-[(p-methoxybenzylidene)amino]phenol (Bryan et al., 1978) and N-benzyl-N'-{6- [(4-carboxylatobenzyl)aminocarbonyl]-2-pyridylmethyl}guanidinium (Ashiq et al., 2010)
The values of the C═O bond [1.241 (2), 1.269 (3) Å] are in agreement with the value, 1.235 (3)–1.261 (3) Å, reported for the N-benzyl-N'-{6- [(4-carboxylatobenzyl)aminocarbonyl]-2-pyridylmethyl}guanidinium (Ashiq et al., 2010). In the title compound S(6) ring motifs (Bernstein et al., 1995), is formed due to intramolecular H-bondings of O—H···O type (Table 1, Fig. 2). There exist R21(7) ring motif due to intermolecular H-bondings of C—H···O and N—H···O types linking the molecules to form infinite one dimensional chains extending along the crystallographic c-axis.
The occurence of slippest π–π stacking (Janiak, 2000) between symmetry related aromatic rings play an important role in stabilizing the packing.