4-Amino-3-methyl-benzoic acid-1,2-bis-(4-pyrid-yl)ethane (1/1).

In the crystal structure of the title 1:1 adduct, C(12)H(12)N(2)·C(8)H(9)NO(2), the 4-amino-3-methyl-benzoic acid mol-ecules and 1,2-bis-(4-pyrid-yl)ethane mol-ecules are linked by inter-molecular O-H⋯N, N-H⋯O and N-H⋯N hydrogen bonds, forming a two-dimensional supra-molecular network parallel to (001). In the 1,2-bis-(4-pyrid-yl)ethane mol-ecule, the two pyridine rings are twisted to each other by a dihedral angle of 12.12 (8)°. The non-H atoms of the 4-amino-3-methyl-benzoic acid mol-ecule are almost coplanar, the maximum atomic deviation being 0.029 (1) Å. Weak C-H⋯π inter-actions are present in the crystal structure.

Related literature

For related structures, see: Bowes et al. (2003 ▶); Ferguson et al. (1999 ▶); Shen & Lush (2010 ▶). For hydrogen-bond motifs, see: Etter et al. (1990 ▶).

Experimental

Crystal data

C12H12N2·C8H9NO2

M = 335.40

Monoclinic,

a = 8.0695 (3) Å

b = 13.0677 (5) Å

c = 17.6138 (10) Å

β = 99.501 (5)°

V = 1831.89 (15) Å3

Z = 4

Mo Kα radiation

μ = 0.08 mm−1

T = 297 K

0.60 × 0.18 × 0.12 mm

Data collection

Oxford Diffraction Gemini-S CCD diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T min = 0.919, T max = 1.000

8821 measured reflections

4277 independent reflections

1870 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.082

S = 1.03

4277 reflections

232 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.15 e Å−3

Δρmin = −0.22 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811005381/xu5156sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811005381/xu5156Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C12H12N2·C8H9NO2	F(000) = 712
Mr = 335.40	Dx = 1.216 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2506 reflections
a = 8.0695 (3) Å	θ = 3.0–29.0°
b = 13.0677 (5) Å	µ = 0.08 mm−1
c = 17.6138 (10) Å	T = 297 K
β = 99.501 (5)°	Parallelepiped, colorless
V = 1831.89 (15) Å3	0.60 × 0.18 × 0.12 mm
Z = 4

Oxford Diffraction Gemini-S CCD diffractometer	4277 independent reflections
Radiation source: fine-focus sealed tube	1870 reflections with I > 2σ(I)
graphite	Rint = 0.025
ω scans	θmax = 29.1°, θmin = 3.0°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −10→10
Tmin = 0.919, Tmax = 1.000	k = −17→16
8821 measured reflections	l = −24→20

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.025P)2] where P = (Fo2 + 2Fc2)/3
4277 reflections	(Δ/σ)max < 0.001
232 parameters	Δρmax = 0.15 e Å−3
3 restraints	Δρmin = −0.22 e Å−3

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.

	x	y	z	Uiso*/Ueq
N2	0.63037 (17)	0.47008 (10)	0.62737 (9)	0.0552 (6)
N3	1.58754 (19)	0.08351 (11)	0.60868 (10)	0.0692 (7)
C9	0.7078 (2)	0.47692 (12)	0.56699 (11)	0.0553 (7)
C10	0.8385 (2)	0.41502 (12)	0.55562 (10)	0.0521 (7)
C11	0.8957 (2)	0.34059 (12)	0.60903 (11)	0.0482 (7)
C12	0.8172 (2)	0.33448 (13)	0.67191 (11)	0.0650 (8)
C13	0.6872 (2)	0.39953 (15)	0.67901 (11)	0.0683 (8)
C14	1.0359 (2)	0.26912 (12)	0.59857 (12)	0.0705 (8)
C15	1.2064 (2)	0.30811 (12)	0.62896 (11)	0.0660 (7)
C16	1.3425 (2)	0.23093 (12)	0.62204 (11)	0.0506 (7)
C17	1.4071 (2)	0.16866 (14)	0.68217 (11)	0.0639 (8)
C18	1.5274 (2)	0.09729 (14)	0.67281 (12)	0.0710 (8)
C19	1.5251 (2)	0.14425 (15)	0.55151 (12)	0.0808 (9)
C20	1.4039 (2)	0.21762 (13)	0.55528 (11)	0.0686 (8)
O1	0.34436 (14)	0.56570 (8)	0.63298 (7)	0.0542 (5)
O2	0.47629 (14)	0.71109 (8)	0.61635 (7)	0.0664 (5)
N1	−0.25914 (19)	0.86901 (13)	0.64324 (10)	0.0628 (7)
C1	0.34970 (19)	0.66628 (12)	0.62564 (9)	0.0399 (4)
C2	0.18870 (19)	0.71739 (11)	0.63001 (9)	0.0399 (4)
C3	0.04752 (18)	0.66405 (11)	0.64278 (9)	0.0427 (6)
C4	−0.09994 (19)	0.71458 (11)	0.64585 (9)	0.0451 (6)
C5	−0.11212 (19)	0.82069 (12)	0.63671 (9)	0.0421 (6)
C6	0.0301 (2)	0.87564 (11)	0.62414 (9)	0.0465 (6)
C7	0.17592 (19)	0.82300 (11)	0.62061 (9)	0.0461 (6)
C8	0.0217 (2)	0.99081 (11)	0.61582 (12)	0.0818 (9)
H9A	0.67140	0.52660	0.53020	0.0660*
H10A	0.88840	0.42320	0.51200	0.0620*
H12A	0.85190	0.28610	0.71000	0.0780*
H13A	0.63640	0.39370	0.72250	0.0820*
H14A	1.01960	0.20490	0.62390	0.0850*
H14B	1.02920	0.25500	0.54410	0.0850*
H15A	1.21180	0.32640	0.68270	0.0790*
H15B	1.22680	0.36960	0.60110	0.0790*
H17A	1.36980	0.17460	0.72920	0.0770*
H18A	1.56900	0.05610	0.71470	0.0850*
H19A	1.56560	0.13720	0.50530	0.0970*
H20A	1.36450	0.25770	0.51250	0.0820*
H1A	0.4380 (9)	0.5416 (12)	0.6323 (10)	0.082 (7)*
H1B	−0.3449 (12)	0.8295 (10)	0.6418 (10)	0.075 (7)*
H1C	−0.2717 (19)	0.9312 (4)	0.6273 (8)	0.055 (6)*
H3A	0.05290	0.59340	0.64930	0.0510*
H4A	−0.19370	0.67760	0.65420	0.0540*
H7A	0.26980	0.85930	0.61160	0.0550*
H8A	0.12810	1.01620	0.60650	0.1230*
H8B	−0.00420	1.02060	0.66230	0.1230*
H8C	−0.06420	1.00870	0.57340	0.1230*

	U11	U22	U33	U12	U13	U23
N2	0.0437 (9)	0.0556 (9)	0.0657 (11)	0.0178 (7)	0.0069 (9)	0.0008 (8)
N3	0.0678 (11)	0.0797 (11)	0.0613 (12)	0.0363 (9)	0.0146 (9)	0.0079 (10)
C9	0.0509 (12)	0.0498 (10)	0.0631 (14)	0.0097 (9)	0.0032 (10)	0.0069 (10)
C10	0.0460 (11)	0.0559 (11)	0.0560 (13)	0.0066 (9)	0.0135 (9)	−0.0026 (10)
C11	0.0385 (10)	0.0426 (11)	0.0617 (13)	0.0093 (8)	0.0030 (10)	−0.0118 (10)
C12	0.0609 (13)	0.0670 (12)	0.0668 (14)	0.0282 (10)	0.0097 (11)	0.0173 (11)
C13	0.0588 (13)	0.0887 (14)	0.0608 (14)	0.0230 (11)	0.0196 (10)	0.0105 (12)
C14	0.0474 (12)	0.0566 (11)	0.1053 (17)	0.0179 (10)	0.0062 (11)	−0.0171 (11)
C15	0.0442 (11)	0.0605 (11)	0.0922 (16)	0.0139 (10)	0.0082 (11)	−0.0143 (11)
C16	0.0388 (11)	0.0516 (11)	0.0611 (14)	0.0114 (9)	0.0077 (10)	−0.0091 (10)
C17	0.0597 (13)	0.0812 (13)	0.0535 (14)	0.0216 (11)	0.0173 (10)	−0.0002 (11)
C18	0.0713 (14)	0.0834 (15)	0.0572 (15)	0.0318 (11)	0.0071 (12)	0.0163 (11)
C19	0.0877 (16)	0.1022 (16)	0.0580 (15)	0.0442 (14)	0.0285 (12)	0.0109 (13)
C20	0.0699 (14)	0.0747 (13)	0.0617 (15)	0.0361 (11)	0.0127 (11)	0.0150 (11)
O1	0.0387 (8)	0.0491 (7)	0.0761 (9)	0.0153 (6)	0.0130 (7)	−0.0007 (6)
O2	0.0306 (7)	0.0689 (8)	0.1025 (10)	−0.0004 (6)	0.0192 (7)	0.0135 (7)
N1	0.0418 (10)	0.0476 (10)	0.1012 (14)	0.0112 (9)	0.0184 (10)	−0.0012 (10)
C1	0.0324 (7)	0.0430 (7)	0.0442 (7)	0.0040 (5)	0.0058 (5)	−0.0032 (6)
C2	0.0324 (7)	0.0430 (7)	0.0442 (7)	0.0040 (5)	0.0058 (5)	−0.0032 (6)
C3	0.0354 (10)	0.0332 (8)	0.0604 (12)	0.0031 (8)	0.0109 (8)	−0.0035 (8)
C4	0.0313 (10)	0.0403 (10)	0.0651 (13)	−0.0011 (8)	0.0123 (8)	−0.0038 (8)
C5	0.0316 (9)	0.0430 (10)	0.0519 (12)	0.0085 (8)	0.0072 (8)	−0.0072 (9)
C6	0.0411 (11)	0.0378 (9)	0.0606 (13)	0.0039 (9)	0.0088 (9)	−0.0002 (9)
C7	0.0354 (10)	0.0444 (10)	0.0594 (12)	−0.0042 (8)	0.0109 (9)	0.0003 (9)
C8	0.0647 (14)	0.0445 (11)	0.138 (2)	0.0047 (9)	0.0217 (13)	0.0091 (11)

O1—C1	1.3221 (19)	C13—H13A	0.9300
O2—C1	1.2118 (19)	C14—H14A	0.9700
O1—H1A	0.821 (9)	C14—H14B	0.9700
N2—C13	1.323 (2)	C15—H15B	0.9700
N2—C9	1.322 (2)	C15—H15A	0.9700
N3—C18	1.313 (3)	C17—H17A	0.9300
N3—C19	1.315 (3)	C18—H18A	0.9300
N1—C5	1.366 (2)	C19—H19A	0.9300
N1—H1C	0.860 (7)	C20—H20A	0.9300
N1—H1B	0.860 (11)	C1—C2	1.474 (2)
C9—C10	1.370 (2)	C2—C3	1.385 (2)
C10—C11	1.379 (2)	C2—C7	1.392 (2)
C11—C12	1.366 (3)	C3—C4	1.370 (2)
C11—C14	1.502 (2)	C4—C5	1.398 (2)
C12—C13	1.372 (2)	C5—C6	1.402 (2)
C14—C15	1.482 (2)	C6—C7	1.373 (2)
C15—C16	1.511 (2)	C6—C8	1.513 (2)
C16—C17	1.369 (3)	C3—H3A	0.9300
C16—C20	1.360 (3)	C4—H4A	0.9300
C17—C18	1.376 (2)	C7—H7A	0.9300
C19—C20	1.379 (2)	C8—H8A	0.9600
C9—H9A	0.9300	C8—H8B	0.9600
C10—H10A	0.9300	C8—H8C	0.9600
C12—H12A	0.9300
C1—O1—H1A	109.6 (10)	H15A—C15—H15B	108.00
C9—N2—C13	116.35 (14)	C14—C15—H15A	109.00
C18—N3—C19	115.24 (16)	C16—C17—H17A	120.00
H1B—N1—H1C	120.4 (14)	C18—C17—H17A	120.00
C5—N1—H1B	115.2 (8)	N3—C18—H18A	118.00
C5—N1—H1C	117.8 (10)	C17—C18—H18A	118.00
N2—C9—C10	123.71 (16)	C20—C19—H19A	118.00
C9—C10—C11	119.73 (16)	N3—C19—H19A	118.00
C10—C11—C12	116.53 (15)	C16—C20—H20A	120.00
C10—C11—C14	121.95 (16)	C19—C20—H20A	120.00
C12—C11—C14	121.52 (16)	O2—C1—C2	123.92 (14)
C11—C12—C13	120.11 (17)	O1—C1—O2	122.37 (14)
N2—C13—C12	123.55 (17)	O1—C1—C2	113.71 (13)
C11—C14—C15	114.53 (14)	C1—C2—C7	119.45 (14)
C14—C15—C16	112.66 (14)	C3—C2—C7	118.13 (14)
C15—C16—C17	121.57 (16)	C1—C2—C3	122.42 (13)
C15—C16—C20	121.90 (16)	C2—C3—C4	120.46 (14)
C17—C16—C20	116.51 (16)	C3—C4—C5	121.25 (14)
C16—C17—C18	119.77 (17)	N1—C5—C4	119.65 (15)
N3—C18—C17	124.36 (18)	N1—C5—C6	121.45 (15)
N3—C19—C20	124.59 (18)	C4—C5—C6	118.85 (14)
C16—C20—C19	119.53 (17)	C5—C6—C8	120.01 (14)
C10—C9—H9A	118.00	C7—C6—C8	121.27 (14)
N2—C9—H9A	118.00	C5—C6—C7	118.72 (14)
C9—C10—H10A	120.00	C2—C7—C6	122.58 (14)
C11—C10—H10A	120.00	C2—C3—H3A	120.00
C11—C12—H12A	120.00	C4—C3—H3A	120.00
C13—C12—H12A	120.00	C3—C4—H4A	119.00
C12—C13—H13A	118.00	C5—C4—H4A	119.00
N2—C13—H13A	118.00	C2—C7—H7A	119.00
C11—C14—H14A	109.00	C6—C7—H7A	119.00
C11—C14—H14B	109.00	C6—C8—H8A	109.00
H14A—C14—H14B	108.00	C6—C8—H8B	109.00
C15—C14—H14A	109.00	C6—C8—H8C	109.00
C15—C14—H14B	109.00	H8A—C8—H8B	109.00
C16—C15—H15A	109.00	H8A—C8—H8C	110.00
C14—C15—H15B	109.00	H8B—C8—H8C	110.00
C16—C15—H15B	109.00
C13—N2—C9—C10	0.9 (3)	C16—C17—C18—N3	0.0 (3)
C9—N2—C13—C12	−1.0 (3)	N3—C19—C20—C16	0.6 (3)
C19—N3—C18—C17	0.4 (3)	O1—C1—C2—C3	1.7 (2)
C18—N3—C19—C20	−0.7 (3)	O1—C1—C2—C7	−177.92 (14)
N2—C9—C10—C11	0.0 (3)	O2—C1—C2—C3	−178.20 (16)
C9—C10—C11—C12	−0.9 (2)	O2—C1—C2—C7	2.2 (2)
C9—C10—C11—C14	178.60 (16)	C1—C2—C3—C4	−179.52 (15)
C10—C11—C12—C13	0.8 (3)	C7—C2—C3—C4	0.1 (2)
C14—C11—C12—C13	−178.66 (16)	C1—C2—C7—C6	−179.85 (15)
C10—C11—C14—C15	87.8 (2)	C3—C2—C7—C6	0.5 (2)
C12—C11—C14—C15	−92.8 (2)	C2—C3—C4—C5	−0.4 (2)
C11—C12—C13—N2	0.1 (3)	C3—C4—C5—N1	−177.34 (16)
C11—C14—C15—C16	176.12 (16)	C3—C4—C5—C6	0.0 (2)
C14—C15—C16—C17	−96.3 (2)	N1—C5—C6—C7	177.88 (16)
C14—C15—C16—C20	81.9 (2)	N1—C5—C6—C8	−1.3 (2)
C15—C16—C17—C18	178.08 (16)	C4—C5—C6—C7	0.6 (2)
C20—C16—C17—C18	−0.1 (2)	C4—C5—C6—C8	−178.64 (15)
C15—C16—C20—C19	−178.34 (16)	C5—C6—C7—C2	−0.9 (2)
C17—C16—C20—C19	−0.1 (2)	C8—C6—C7—C2	178.32 (16)

Cg is the centroid of the C2–C7 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N2	0.821 (9)	1.826 (11)	2.6407 (18)	171.6 (15)
N1—H1B···O2i	0.860 (11)	2.113 (12)	2.951 (2)	164.5 (14)
N1—H1C···N3ii	0.860 (7)	2.288 (9)	3.084 (2)	153.8 (14)
C12—H12A···Cgiii	0.93	2.76	3.540 (2)	141

Table 1

Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C2–C7 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N2	0.821 (9)	1.826 (11)	2.6407 (18)	171.6 (15)
N1—H1B⋯O2i	0.860 (11)	2.113 (12)	2.951 (2)	164.5 (14)
N1—H1C⋯N3ii	0.860 (7)	2.288 (9)	3.084 (2)	153.8 (14)
C12—H12A⋯Cgiii	0.93	2.76	3.540 (2)	141

Symmetry codes: (i) ; (ii) ; (iii) .