6-Amino-2-(pivaloyl-amino)-pyridinium benzoate.

In the crystal structure of the title salt, C10H16N3O(+)·C7H5O2 (-), the cations and anions are linked to each other via N-H⋯O hydrogen bonds, forming infinite chains running along [010]. The crystal structure also features C-H⋯O and π-π stacking inter-actions, which assemble the chains into supra-molecular layers parallel to (100). The π-π stacking inter-actions are observed between the pyridine rings of inversion-related cations with a centroid-centroid distance of 3.867 (2) Å.

Related literature

For co-crystallization of pharmaceuticals, see: Vishweshwar et al. (2006 ▶); Lemmerer (2012 ▶). For the crystal structures of related compounds, see: Ośmiałowski et al. (2010b ▶); Aakeröy et al. (2006 ▶, 2010 ▶). For the role of steric effects in hydrogen-bonded compounds, see Ośmiałowski et al. (2012a ▶,b ▶, 2010a ▶,b ▶). For the synthesis of 2-pivaloyl­amino-6-amino­pyridine, see: Ośmiałowski et al. (2010a ▶).

Experimental

Crystal data

C10H16N3O+·C7H5O2 −

M = 315.37

Monoclinic,

a = 15.1438 (4) Å

b = 5.7099 (2) Å

c = 18.7388 (6) Å

β = 91.967 (2)°

V = 1619.38 (9) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 123 K

0.13 × 0.10 × 0.08 mm

Data collection

Bruker–Nonius KappaCCD diffractometer with APEXII detector

Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T min = 0.988, T max = 0.993

10993 measured reflections

3724 independent reflections

2054 reflections with I > 2σ(I)

R int = 0.094

Refinement

R[F 2 > 2σ(F 2)] = 0.066

wR(F 2) = 0.141

S = 1.00

3724 reflections

220 parameters

4 restraints

H-atom parameters constrained

Δρmax = 0.24 e Å−3

Δρmin = −0.28 e Å−3

Data collection: COLLECT (Bruker, 2008 ▶); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ▶); data reduction: DENZO-SMN; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL2013 and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813023787/fy2103sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813023787/fy2103Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813023787/fy2103Isup3.cml

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

C10H16N3O+·C7H5O2−	F(000) = 672
Mr = 315.37	Dx = 1.293 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.1438 (4) Å	Cell parameters from 4257 reflections
b = 5.7099 (2) Å	θ = 0.4–28.3°
c = 18.7388 (6) Å	µ = 0.09 mm−1
β = 91.967 (2)°	T = 123 K
V = 1619.38 (9) Å3	Block, colourless
Z = 4	0.13 × 0.10 × 0.08 mm

Bruker–Nonius KappaCCD diffractometer with APEXII detector	3724 independent reflections
Radiation source: fine-focus sealed tube	2054 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.094
Detector resolution: 9 pixels mm-1	θmax = 27.5°, θmin = 2.5°
φ and ω scans	h = −19→18
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	k = −7→7
Tmin = 0.988, Tmax = 0.993	l = −24→20
10993 measured reflections

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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.141	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0496P)2] where P = (Fo2 + 2Fc2)/3
3724 reflections	(Δ/σ)max < 0.001
220 parameters	Δρmax = 0.24 e Å−3
4 restraints	Δρmin = −0.28 e Å−3

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.

	x	y	z	Uiso*/Ueq
O8	0.69413 (12)	0.1535 (3)	0.54656 (10)	0.0370 (5)
N1	0.57982 (12)	0.6015 (4)	0.39112 (11)	0.0205 (5)
H1	0.6221 (14)	0.710 (4)	0.3842 (13)	0.025*
N6	0.48943 (14)	0.7758 (4)	0.30603 (12)	0.0278 (5)
H6A	0.5311 (15)	0.882 (4)	0.2960 (14)	0.033*
H6B	0.4404 (14)	0.774 (4)	0.2764 (13)	0.033*
N7	0.68521 (13)	0.4637 (4)	0.47095 (11)	0.0231 (5)
H7	0.7141 (15)	0.580 (4)	0.4546 (13)	0.028*
C2	0.60154 (15)	0.4307 (4)	0.43895 (13)	0.0223 (6)
C3	0.54405 (15)	0.2505 (4)	0.45137 (14)	0.0249 (6)
H3	0.5582	0.1307	0.4850	0.030*
C4	0.46378 (16)	0.2513 (4)	0.41222 (14)	0.0261 (6)
H4	0.4225	0.1295	0.4200	0.031*
C5	0.44278 (15)	0.4204 (4)	0.36334 (13)	0.0227 (6)
H5	0.3881	0.4149	0.3369	0.027*
C6	0.50276 (15)	0.6023 (4)	0.35252 (13)	0.0209 (6)
C8	0.72715 (16)	0.3289 (4)	0.52242 (14)	0.0234 (6)
C9	0.81731 (15)	0.4228 (4)	0.54969 (13)	0.0219 (6)
C10	0.79992 (16)	0.5515 (5)	0.61949 (14)	0.0293 (6)
H10A	0.7718	0.4443	0.6526	0.044*
H10B	0.7608	0.6852	0.6096	0.044*
H10C	0.8560	0.6072	0.6409	0.044*
C11	0.87823 (17)	0.2125 (4)	0.56515 (16)	0.0326 (7)
H11A	0.8896	0.1308	0.5204	0.049*
H11B	0.8497	0.1049	0.5980	0.049*
H11C	0.9342	0.2675	0.5869	0.049*
C12	0.86140 (15)	0.5877 (5)	0.49737 (14)	0.0263 (6)
H12A	0.8723	0.5037	0.4529	0.040*
H12B	0.9176	0.6436	0.5185	0.040*
H12C	0.8225	0.7216	0.4871	0.040*
O13A	0.71169 (10)	−0.1201 (3)	0.37777 (10)	0.0287 (5)
O13B	0.64016 (11)	0.0950 (3)	0.29481 (10)	0.0289 (5)
C13	0.70775 (15)	0.0432 (4)	0.33191 (13)	0.0215 (6)
C14	0.79105 (15)	0.1829 (4)	0.32285 (13)	0.0203 (6)
C15	0.87128 (15)	0.0994 (4)	0.35068 (13)	0.0220 (6)
H15	0.8731	−0.0436	0.3766	0.026*
C16	0.94848 (16)	0.2232 (4)	0.34092 (14)	0.0255 (6)
H16	1.0031	0.1649	0.3600	0.031*
C17	0.94615 (16)	0.4311 (4)	0.30351 (14)	0.0271 (6)
H17	0.9992	0.5155	0.2966	0.033*
C18	0.86638 (16)	0.5174 (5)	0.27596 (14)	0.0279 (6)
H18	0.8647	0.6621	0.2509	0.033*
C19	0.78894 (16)	0.3920 (4)	0.28499 (13)	0.0245 (6)
H19	0.7345	0.4494	0.2652	0.029*

	U11	U22	U33	U12	U13	U23
O8	0.0319 (11)	0.0331 (11)	0.0450 (13)	−0.0155 (8)	−0.0117 (9)	0.0167 (10)
N1	0.0153 (11)	0.0213 (11)	0.0248 (12)	−0.0069 (8)	0.0000 (8)	0.0002 (9)
N6	0.0206 (12)	0.0284 (13)	0.0339 (14)	−0.0070 (9)	−0.0076 (10)	0.0059 (11)
N7	0.0175 (11)	0.0242 (12)	0.0275 (13)	−0.0068 (9)	−0.0028 (9)	0.0046 (10)
C2	0.0197 (13)	0.0264 (14)	0.0208 (14)	−0.0036 (10)	0.0006 (10)	−0.0012 (11)
C3	0.0208 (13)	0.0273 (15)	0.0266 (15)	−0.0069 (10)	0.0002 (11)	0.0067 (11)
C4	0.0202 (14)	0.0284 (14)	0.0297 (16)	−0.0106 (11)	0.0016 (11)	−0.0020 (12)
C5	0.0166 (12)	0.0281 (14)	0.0234 (14)	−0.0049 (10)	−0.0005 (10)	−0.0004 (11)
C6	0.0165 (12)	0.0254 (14)	0.0210 (14)	−0.0004 (10)	0.0029 (10)	−0.0029 (11)
C8	0.0235 (13)	0.0221 (14)	0.0246 (15)	−0.0043 (11)	−0.0006 (11)	0.0012 (11)
C9	0.0172 (12)	0.0227 (13)	0.0255 (14)	−0.0018 (10)	−0.0039 (10)	−0.0019 (11)
C10	0.0215 (13)	0.0354 (16)	0.0309 (15)	−0.0046 (11)	−0.0012 (11)	−0.0032 (13)
C11	0.0264 (15)	0.0257 (16)	0.0449 (19)	0.0005 (11)	−0.0076 (12)	0.0017 (13)
C12	0.0171 (13)	0.0323 (15)	0.0295 (15)	−0.0046 (11)	−0.0007 (10)	−0.0001 (12)
O13A	0.0198 (9)	0.0276 (10)	0.0384 (12)	−0.0058 (7)	−0.0032 (8)	0.0102 (9)
O13B	0.0199 (9)	0.0326 (11)	0.0335 (11)	−0.0030 (7)	−0.0069 (8)	0.0078 (9)
C13	0.0201 (13)	0.0225 (14)	0.0220 (14)	−0.0029 (10)	0.0016 (10)	−0.0010 (12)
C14	0.0186 (13)	0.0227 (14)	0.0197 (14)	−0.0027 (10)	0.0022 (10)	−0.0021 (11)
C15	0.0214 (13)	0.0219 (13)	0.0227 (14)	−0.0017 (10)	0.0019 (10)	0.0010 (11)
C16	0.0192 (13)	0.0288 (15)	0.0287 (15)	−0.0016 (10)	0.0012 (10)	−0.0017 (12)
C17	0.0251 (14)	0.0302 (15)	0.0264 (15)	−0.0118 (11)	0.0062 (11)	−0.0010 (12)
C18	0.0329 (15)	0.0231 (14)	0.0278 (15)	−0.0058 (11)	0.0025 (12)	0.0051 (12)
C19	0.0264 (14)	0.0230 (14)	0.0242 (14)	−0.0012 (11)	−0.0008 (11)	0.0010 (12)

O8—C8	1.214 (3)	C10—H10B	0.9800
N1—C6	1.352 (3)	C10—H10C	0.9800
N1—C2	1.358 (3)	C11—H11A	0.9800
N1—H1	0.905 (16)	C11—H11B	0.9800
N6—C6	1.330 (3)	C11—H11C	0.9800
N6—H6A	0.899 (17)	C12—H12A	0.9800
N6—H6B	0.913 (16)	C12—H12B	0.9800
N7—C8	1.373 (3)	C12—H12C	0.9800
N7—C2	1.396 (3)	O13A—C13	1.268 (3)
N7—H7	0.859 (17)	O13B—C13	1.253 (3)
C2—C3	1.373 (3)	C13—C14	1.507 (3)
C3—C4	1.398 (3)	C14—C19	1.389 (3)
C3—H3	0.9500	C14—C15	1.390 (3)
C4—C5	1.361 (3)	C15—C16	1.384 (3)
C4—H4	0.9500	C15—H15	0.9500
C5—C6	1.400 (3)	C16—C17	1.379 (4)
C5—H5	0.9500	C16—H16	0.9500
C8—C9	1.538 (3)	C17—C18	1.388 (4)
C9—C12	1.529 (3)	C17—H17	0.9500
C9—C10	1.531 (3)	C18—C19	1.389 (3)
C9—C11	1.536 (3)	C18—H18	0.9500
C10—H10A	0.9800	C19—H19	0.9500
C6—N1—C2	122.7 (2)	C9—C10—H10C	109.5
C6—N1—H1	121.5 (16)	H10A—C10—H10C	109.5
C2—N1—H1	115.6 (16)	H10B—C10—H10C	109.5
C6—N6—H6A	123.2 (17)	C9—C11—H11A	109.5
C6—N6—H6B	119.4 (17)	C9—C11—H11B	109.5
H6A—N6—H6B	116 (2)	H11A—C11—H11B	109.5
C8—N7—C2	128.1 (2)	C9—C11—H11C	109.5
C8—N7—H7	117.2 (17)	H11A—C11—H11C	109.5
C2—N7—H7	114.7 (17)	H11B—C11—H11C	109.5
N1—C2—C3	120.7 (2)	C9—C12—H12A	109.5
N1—C2—N7	112.5 (2)	C9—C12—H12B	109.5
C3—C2—N7	126.9 (2)	H12A—C12—H12B	109.5
C2—C3—C4	117.0 (2)	C9—C12—H12C	109.5
C2—C3—H3	121.5	H12A—C12—H12C	109.5
C4—C3—H3	121.5	H12B—C12—H12C	109.5
C5—C4—C3	122.3 (2)	O13B—C13—O13A	124.6 (2)
C5—C4—H4	118.9	O13B—C13—C14	118.9 (2)
C3—C4—H4	118.9	O13A—C13—C14	116.5 (2)
C4—C5—C6	119.1 (2)	C19—C14—C15	119.4 (2)
C4—C5—H5	120.4	C19—C14—C13	120.5 (2)
C6—C5—H5	120.4	C15—C14—C13	120.0 (2)
N6—C6—N1	117.5 (2)	C16—C15—C14	120.4 (2)
N6—C6—C5	124.3 (2)	C16—C15—H15	119.8
N1—C6—C5	118.2 (2)	C14—C15—H15	119.8
O8—C8—N7	122.5 (2)	C17—C16—C15	120.0 (2)
O8—C8—C9	122.4 (2)	C17—C16—H16	120.0
N7—C8—C9	115.0 (2)	C15—C16—H16	120.0
C12—C9—C10	110.1 (2)	C16—C17—C18	120.1 (2)
C12—C9—C11	109.3 (2)	C16—C17—H17	119.9
C10—C9—C11	109.5 (2)	C18—C17—H17	119.9
C12—C9—C8	113.8 (2)	C17—C18—C19	120.0 (2)
C10—C9—C8	105.9 (2)	C17—C18—H18	120.0
C11—C9—C8	108.1 (2)	C19—C18—H18	120.0
C9—C10—H10A	109.5	C14—C19—C18	120.0 (2)
C9—C10—H10B	109.5	C14—C19—H19	120.0
H10A—C10—H10B	109.5	C18—C19—H19	120.0
C6—N1—C2—C3	−1.4 (4)	O8—C8—C9—C10	−79.0 (3)
C6—N1—C2—N7	178.4 (2)	N7—C8—C9—C10	98.3 (3)
C8—N7—C2—N1	178.5 (2)	O8—C8—C9—C11	38.3 (3)
C8—N7—C2—C3	−1.8 (4)	N7—C8—C9—C11	−144.3 (2)
N1—C2—C3—C4	0.7 (4)	O13B—C13—C14—C19	12.4 (4)
N7—C2—C3—C4	−179.1 (2)	O13A—C13—C14—C19	−167.2 (2)
C2—C3—C4—C5	0.6 (4)	O13B—C13—C14—C15	−165.7 (2)
C3—C4—C5—C6	−1.1 (4)	O13A—C13—C14—C15	14.7 (3)
C2—N1—C6—N6	−178.5 (2)	C19—C14—C15—C16	0.1 (4)
C2—N1—C6—C5	0.8 (4)	C13—C14—C15—C16	178.2 (2)
C4—C5—C6—N6	179.6 (3)	C14—C15—C16—C17	0.1 (4)
C4—C5—C6—N1	0.4 (4)	C15—C16—C17—C18	0.4 (4)
C2—N7—C8—O8	1.0 (4)	C16—C17—C18—C19	−1.1 (4)
C2—N7—C8—C9	−176.4 (2)	C15—C14—C19—C18	−0.8 (4)
O8—C8—C9—C12	159.9 (2)	C13—C14—C19—C18	−178.9 (2)
N7—C8—C9—C12	−22.8 (3)	C17—C18—C19—C14	1.3 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O13Ai	0.91 (2)	1.67 (2)	2.571 (2)	170 (2)
N6—H6A···O13Bi	0.90 (2)	2.05 (2)	2.934 (3)	167 (2)
N6—H6B···O13Bii	0.91 (2)	2.05 (2)	2.869 (3)	149 (2)
N7—H7···O13Ai	0.86 (2)	2.24 (2)	2.984 (3)	146 (2)
C4—H4···O8iii	0.95	2.49	3.433 (3)	172

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O13A i	0.91 (2)	1.67 (2)	2.571 (2)	170 (2)
N6—H6A⋯O13B i	0.90 (2)	2.05 (2)	2.934 (3)	167 (2)
N6—H6B⋯O13B ii	0.91 (2)	2.05 (2)	2.869 (3)	149 (2)
N7—H7⋯O13A i	0.86 (2)	2.24 (2)	2.984 (3)	146 (2)
C4—H4⋯O8iii	0.95	2.49	3.433 (3)	172

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