



Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989015000791/hb7348sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S2056989015000791/hb7348Isup2.hkl |
CCDC reference: 1043592
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean
(C-C) = 0.004 Å
- R factor = 0.038
- wR factor = 0.108
- Data-to-parameter ratio = 13.5
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT031_ALERT_4_C Refined Extinction Parameter within Range ...... 3.250 Sigma PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds ............... 0.0043 Ang. PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ... -0.668 Report PLAT915_ALERT_3_C Low Friedel Pair Coverage ...................... 63 %
Alert level G PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite 2 Note PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please Do ! PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms .............. 2 Report PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings Differ Please Check PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical ? Check PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd. # 2 Note C6 H7 N PLAT860_ALERT_3_G Number of Least-Squares Restraints ............. 3 Note PLAT899_ALERT_4_G SHELXL97 is Deprecated and Succeeded by SHELXL 2014 Note PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ... 2 Report PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 5 Note
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 4 ALERT level C = Check. Ensure it is not caused by an omission or oversight 10 ALERT level G = General information/check it is not something unexpected 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 5 ALERT type 3 Indicator that the structure quality may be low 4 ALERT type 4 Improvement, methodology, query or suggestion 2 ALERT type 5 Informative message, check
Aminopyridine and its derivatives play an important role in heterocyclic chemistry (Katritzky et al., 1996). Some pyridine derivatives possess nonlinear optical (NLO) properties (Tomaru et al., 1991) and possess antibacterial and antifungal activities (Akkurt et al., 2005). we herewith, report the synthesis and the crystal structure of (I) (Fig. 1).
The molecular structure of the title compound (I) is shown in (Fig. 1). It consists of two independent molecules in the assymetric unit. In the 4-aminobenzoic acid molecule, the carboxyl group is twisted at an angle of 4.32 (18)° with respect to the aromatic ring. In the 4-methylpyridine molecule, the pyridine ring (C8—C12/N2) is almost planar [maximum deviation 0.002 (3) Å]. The dihedral angle between the benzene ring (C1—C6) and pyridine ring (C8—C12/N2) is 57.11 (14)°.
In the crystal structure, 4-aminobenzoate and 4-methylpyridine molecules are linked by weak intermolecular O—H···N hydrogen bonds and forms infinite one-dimensional chain along [0 0 1]. The adjacent 4-aminobenzoate molecules are connected by weak intermolecular N—H···O hydrogen bonds, forming R22(12) ring motif in a two-dimensional network in the (010) plane (Table 2 & Fig. 2).
Several similar structures containing methylpyridinium and nitrobenzoate molecules have been reported earlier: i.e., 2-Amino-5-methylpyridinium 2-aminobenzoate (Thanigaimani et al., 2012); 2-Amino-5-chloropyridinium 4-aminobenzoate (Kannan et al., 2012); 2-Amino-4-methylpyridinium 2-nitrobenzoate (Muralidharan et al., 2013); 4-Methylpyridinium 2-carboxy-4,5-dichlorobenzoate monohydrate [Smith & Wermuth, (2010)]; 2-Amino-4-methylpyridinium 2-hydroxybenzoate [Hemamalini & Fun (2010)].
Equimolar quantity of 4-methylpyridine and 4-aminobenzoic acid were dissolved in methanol-water mixed solvent and colourless blocks of the title adduct were grown by slow evaporation of the solvents.
Crystal data, data collection and structure refinement details are summarized in Table 1. The hydrogen atoms attached to C atoms and N atom were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic) or 0.96 Å (methyl) and N—H = 0.86 Å with Uiso(H) = 1.2 Ueq(C or N) or 1.5 Ueq(C) The hydroxyl H atom was located in a difference Fourier map, and refined with Uiso(H) = 1.2 Ueq(O) and distance restraint O—H = 0.82 Å.
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2015).
![]() | Fig. 1. The molecular structure of (I), with 30% probability displacement ellipsoids for non-H atoms. |
C6H7N·C7H7NO2 | F(000) = 244 |
Mr = 230.26 | Dx = 1.232 Mg m−3 |
Monoclinic, Pc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P -2yc | Cell parameters from 2749 reflections |
a = 7.5970 (7) Å | θ = 3.4–21.8° |
b = 11.6665 (12) Å | µ = 0.09 mm−1 |
c = 7.6754 (8) Å | T = 295 K |
β = 114.200 (3)° | Block, colourless |
V = 620.49 (11) Å3 | 0.28 × 0.24 × 0.20 mm |
Z = 2 |
Bruker Kappa APEXII CCD diffractometer | 2144 independent reflections |
Radiation source: fine-focus sealed tube | 1458 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ω and ϕ scan | θmax = 26.7°, θmin = 3.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→8 |
Tmin = 0.977, Tmax = 0.983 | k = −14→14 |
10064 measured reflections | l = −9→9 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.038 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.108 | w = 1/[σ2(Fo2) + (0.0554P)2 + 0.0229P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
2144 reflections | Δρmax = 0.12 e Å−3 |
159 parameters | Δρmin = −0.13 e Å−3 |
3 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.013 (4) |
C6H7N·C7H7NO2 | V = 620.49 (11) Å3 |
Mr = 230.26 | Z = 2 |
Monoclinic, Pc | Mo Kα radiation |
a = 7.5970 (7) Å | µ = 0.09 mm−1 |
b = 11.6665 (12) Å | T = 295 K |
c = 7.6754 (8) Å | 0.28 × 0.24 × 0.20 mm |
β = 114.200 (3)° |
Bruker Kappa APEXII CCD diffractometer | 2144 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1458 reflections with I > 2σ(I) |
Tmin = 0.977, Tmax = 0.983 | Rint = 0.030 |
10064 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 3 restraints |
wR(F2) = 0.108 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.12 e Å−3 |
2144 reflections | Δρmin = −0.13 e Å−3 |
159 parameters |
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 > 2sigma(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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.3693 (4) | 0.1034 (2) | 0.7149 (4) | 0.0567 (6) | |
C2 | 0.4434 (4) | 0.2029 (2) | 0.6722 (4) | 0.0591 (7) | |
H2 | 0.3671 | 0.2471 | 0.5675 | 0.071* | |
C3 | 0.6273 (4) | 0.2362 (2) | 0.7829 (3) | 0.0558 (6) | |
H3 | 0.6737 | 0.3037 | 0.7529 | 0.067* | |
C4 | 0.7475 (4) | 0.1730 (2) | 0.9383 (4) | 0.0508 (6) | |
C5 | 0.6737 (4) | 0.0738 (2) | 0.9798 (4) | 0.0594 (7) | |
H5 | 0.7516 | 0.0294 | 1.0835 | 0.071* | |
C6 | 0.4892 (4) | 0.0392 (2) | 0.8724 (4) | 0.0629 (7) | |
H6 | 0.4429 | −0.0278 | 0.9043 | 0.076* | |
C7 | 0.9416 (4) | 0.2104 (2) | 1.0596 (4) | 0.0587 (7) | |
C8 | 0.4371 (5) | 0.4546 (2) | 1.3188 (5) | 0.0729 (8) | |
H8 | 0.3567 | 0.5148 | 1.3183 | 0.087* | |
C9 | 0.6306 (4) | 0.4655 (2) | 1.4263 (4) | 0.0693 (8) | |
H9 | 0.6791 | 0.5319 | 1.4967 | 0.083* | |
C10 | 0.7534 (4) | 0.3784 (2) | 1.4304 (4) | 0.0639 (7) | |
C11 | 0.6716 (4) | 0.2836 (2) | 1.3242 (4) | 0.0718 (8) | |
H11 | 0.7487 | 0.2220 | 1.3229 | 0.086* | |
C12 | 0.4767 (5) | 0.2790 (3) | 1.2196 (4) | 0.0766 (9) | |
H12 | 0.4249 | 0.2135 | 1.1479 | 0.092* | |
C13 | 0.9658 (5) | 0.3866 (3) | 1.5468 (6) | 0.0954 (11) | |
H13A | 1.0310 | 0.3941 | 1.4635 | 0.143* | |
H13B | 1.0099 | 0.3186 | 1.6229 | 0.143* | |
H13C | 0.9930 | 0.4524 | 1.6289 | 0.143* | |
N1 | 0.1840 (4) | 0.0710 (2) | 0.6087 (4) | 0.0827 (8) | |
H1A | 0.1113 | 0.1124 | 0.5137 | 0.099* | |
H1B | 0.1395 | 0.0092 | 0.6364 | 0.099* | |
N2 | 0.3582 (3) | 0.3627 (2) | 1.2152 (4) | 0.0722 (6) | |
O1 | 0.9921 (3) | 0.30989 (17) | 1.0123 (3) | 0.0808 (6) | |
H1 | 1.109 (2) | 0.324 (3) | 1.076 (5) | 0.121* | |
O2 | 1.0516 (3) | 0.15755 (17) | 1.1996 (3) | 0.0778 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0545 (16) | 0.0584 (15) | 0.0526 (15) | −0.0071 (14) | 0.0173 (13) | −0.0070 (14) |
C2 | 0.0599 (17) | 0.0581 (15) | 0.0489 (15) | 0.0009 (12) | 0.0118 (13) | 0.0088 (12) |
C3 | 0.0582 (16) | 0.0536 (13) | 0.0509 (15) | −0.0050 (13) | 0.0175 (13) | 0.0058 (12) |
C4 | 0.0529 (14) | 0.0490 (12) | 0.0442 (13) | 0.0040 (12) | 0.0135 (12) | 0.0026 (12) |
C5 | 0.0671 (18) | 0.0516 (14) | 0.0484 (16) | 0.0021 (13) | 0.0124 (14) | 0.0046 (12) |
C6 | 0.077 (2) | 0.0518 (14) | 0.0590 (17) | −0.0076 (14) | 0.0273 (15) | 0.0048 (13) |
C7 | 0.0563 (17) | 0.0532 (13) | 0.0583 (17) | 0.0045 (13) | 0.0150 (14) | 0.0003 (14) |
C8 | 0.0630 (18) | 0.0626 (16) | 0.081 (2) | 0.0031 (15) | 0.0172 (16) | 0.0007 (16) |
C9 | 0.068 (2) | 0.0617 (17) | 0.0665 (19) | −0.0085 (14) | 0.0150 (16) | −0.0042 (13) |
C10 | 0.0579 (18) | 0.0740 (17) | 0.0585 (17) | −0.0045 (16) | 0.0225 (14) | 0.0063 (15) |
C11 | 0.0680 (19) | 0.0723 (18) | 0.078 (2) | 0.0015 (15) | 0.0325 (18) | −0.0048 (16) |
C12 | 0.077 (2) | 0.0747 (19) | 0.074 (2) | −0.0158 (17) | 0.0260 (17) | −0.0171 (16) |
C13 | 0.0604 (19) | 0.105 (2) | 0.104 (3) | −0.0070 (17) | 0.0163 (18) | 0.002 (2) |
N1 | 0.0655 (16) | 0.0852 (18) | 0.0809 (18) | −0.0163 (13) | 0.0132 (14) | 0.0063 (15) |
N2 | 0.0567 (14) | 0.0719 (15) | 0.0766 (16) | −0.0059 (13) | 0.0157 (12) | −0.0023 (13) |
O1 | 0.0588 (11) | 0.0691 (12) | 0.0883 (16) | −0.0105 (10) | 0.0035 (11) | 0.0130 (11) |
O2 | 0.0678 (13) | 0.0726 (12) | 0.0665 (12) | 0.0068 (10) | 0.0006 (10) | 0.0090 (10) |
C1—N1 | 1.359 (4) | C8—H8 | 0.9300 |
C1—C2 | 1.387 (3) | C9—C10 | 1.371 (4) |
C1—C6 | 1.397 (4) | C9—H9 | 0.9300 |
C2—C3 | 1.361 (4) | C10—C11 | 1.363 (4) |
C2—H2 | 0.9300 | C10—C13 | 1.493 (5) |
C3—C4 | 1.380 (3) | C11—C12 | 1.366 (4) |
C3—H3 | 0.9300 | C11—H11 | 0.9300 |
C4—C5 | 1.379 (3) | C12—N2 | 1.319 (4) |
C4—C7 | 1.452 (3) | C12—H12 | 0.9300 |
C5—C6 | 1.364 (4) | C13—H13A | 0.9600 |
C5—H5 | 0.9300 | C13—H13B | 0.9600 |
C6—H6 | 0.9300 | C13—H13C | 0.9600 |
C7—O2 | 1.224 (3) | N1—H1A | 0.8600 |
C7—O1 | 1.319 (3) | N1—H1B | 0.8600 |
C8—N2 | 1.323 (3) | O1—H1 | 0.836 (10) |
C8—C9 | 1.365 (4) | ||
N1—C1—C2 | 120.8 (2) | C8—C9—C10 | 119.9 (3) |
N1—C1—C6 | 121.2 (2) | C8—C9—H9 | 120.0 |
C2—C1—C6 | 118.0 (2) | C10—C9—H9 | 120.0 |
C3—C2—C1 | 120.2 (2) | C11—C10—C9 | 116.6 (3) |
C3—C2—H2 | 119.9 | C11—C10—C13 | 121.7 (3) |
C1—C2—H2 | 119.9 | C9—C10—C13 | 121.7 (3) |
C2—C3—C4 | 122.2 (2) | C10—C11—C12 | 120.2 (3) |
C2—C3—H3 | 118.9 | C10—C11—H11 | 119.9 |
C4—C3—H3 | 118.9 | C12—C11—H11 | 119.9 |
C5—C4—C3 | 117.4 (2) | N2—C12—C11 | 123.4 (3) |
C5—C4—C7 | 120.4 (2) | N2—C12—H12 | 118.3 |
C3—C4—C7 | 122.1 (2) | C11—C12—H12 | 118.3 |
C6—C5—C4 | 121.5 (2) | C10—C13—H13A | 109.5 |
C6—C5—H5 | 119.2 | C10—C13—H13B | 109.5 |
C4—C5—H5 | 119.2 | H13A—C13—H13B | 109.5 |
C5—C6—C1 | 120.6 (2) | C10—C13—H13C | 109.5 |
C5—C6—H6 | 119.7 | H13A—C13—H13C | 109.5 |
C1—C6—H6 | 119.7 | H13B—C13—H13C | 109.5 |
O2—C7—O1 | 120.9 (3) | C1—N1—H1A | 120.0 |
O2—C7—C4 | 124.1 (2) | C1—N1—H1B | 120.0 |
O1—C7—C4 | 115.0 (2) | H1A—N1—H1B | 120.0 |
N2—C8—C9 | 123.3 (3) | C12—N2—C8 | 116.6 (3) |
N2—C8—H8 | 118.4 | C7—O1—H1 | 112 (3) |
C9—C8—H8 | 118.4 | ||
N1—C1—C2—C3 | 178.1 (3) | C3—C4—C7—O2 | 179.2 (3) |
C6—C1—C2—C3 | −0.5 (4) | C5—C4—C7—O1 | −176.1 (2) |
C1—C2—C3—C4 | 0.9 (4) | C3—C4—C7—O1 | 1.3 (3) |
C2—C3—C4—C5 | −0.5 (4) | N2—C8—C9—C10 | 0.0 (5) |
C2—C3—C4—C7 | −178.1 (2) | C8—C9—C10—C11 | −0.2 (4) |
C3—C4—C5—C6 | −0.2 (4) | C8—C9—C10—C13 | −179.7 (3) |
C7—C4—C5—C6 | 177.4 (2) | C9—C10—C11—C12 | 0.4 (4) |
C4—C5—C6—C1 | 0.5 (4) | C13—C10—C11—C12 | 179.9 (3) |
N1—C1—C6—C5 | −178.8 (3) | C10—C11—C12—N2 | −0.4 (5) |
C2—C1—C6—C5 | −0.2 (4) | C11—C12—N2—C8 | 0.1 (5) |
C5—C4—C7—O2 | 1.7 (4) | C9—C8—N2—C12 | 0.1 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N2i | 0.84 (1) | 1.81 (1) | 2.644 (3) | 177 (4) |
N1—H1A···O2ii | 0.86 | 2.32 | 3.049 (3) | 142 |
N1—H1B···O2iii | 0.86 | 2.17 | 3.031 (3) | 174 |
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z−1; (iii) x−1, −y, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N2i | 0.836 (10) | 1.809 (11) | 2.644 (3) | 177 (4) |
N1—H1A···O2ii | 0.86 | 2.32 | 3.049 (3) | 142 |
N1—H1B···O2iii | 0.86 | 2.17 | 3.031 (3) | 174 |
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z−1; (iii) x−1, −y, z−1/2. |