2-Amino-pyridinium 1-phenyl-cyclo-propane-1-carboxyl-ate.

In the title salt, C(5)H(7)N(2) (+)·C(10)H(9)O(2) (-), 2-amino-pyridine and 1-phenyl-cyclo-propane-1-carb-oxy-lic acid crystallize together, forming a 2-amino-pyridinium-carboxyl-ate supra-molecular heterosynthon involving two N-H⋯O hydrogen bonds, which in turn dimerizes to form a four-component supra-molecular unit also sustained by N-H⋯O hydrogen bonding. A C-H⋯π inter-action between a pyridine C-H group and the centroid of the phenyl ring of the anion further stabilizes the four-component supra-molecular unit. The overall crystal packing also features C-H⋯O inter-actions.

Related literature

For structural studies of 2-amino­pyridine, see: Chao et al. (1975 ▶). For recent mol­ecular co-crystals and salts of 2-amino­pyridine, see: Sivaramkumar et al. (2010 ▶); Chitra et al. (2008 ▶); Quah et al. (2008 ▶); Xie (2007 ▶); Li et al. (2006 ▶, 2007 ▶); Yang & Qu (2006 ▶); Bis & Zaworotko (2005 ▶). For the use of 2-amino­pyridine in the synthesis of pharmaceuticals, see: O’Neil (2006 ▶). For our previous work on screening for molecular co-crystals and salts, see: He et al. (2009 ▶).

Experimental

Crystal data

C5H7N2 +·C10H9O2 −

M = 256.30

Triclinic,

a = 8.6147 (17) Å

b = 9.0555 (18) Å

c = 9.2346 (18) Å

α = 75.56 (3)°

β = 87.72 (3)°

γ = 72.79 (3)°

V = 666.0 (2) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 110 K

0.33 × 0.33 × 0.22 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer

Absorption correction: multi-scan (Blessing, 1995 ▶) T min = 0.972, T max = 0.981

9557 measured reflections

3271 independent reflections

3103 reflections with I > 2σ(I)

R int = 0.017

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.145

S = 1.12

3271 reflections

184 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.31 e Å−3

Δρmin = −0.24 e Å−3

Data collection: CrystalClear (Rigaku, 2008 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810049093/ng5075sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810049093/ng5075Isup2.hkl

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

C5H7N2+·C10H9O2−	Z = 2
Mr = 256.30	F(000) = 272
Triclinic, P1	Dx = 1.278 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.6147 (17) Å	Cell parameters from 1840 reflections
b = 9.0555 (18) Å	θ = 2.3–30.9°
c = 9.2346 (18) Å	µ = 0.09 mm−1
α = 75.56 (3)°	T = 110 K
β = 87.72 (3)°	Block, colorless
γ = 72.79 (3)°	0.33 × 0.33 × 0.22 mm
V = 666.0 (2) Å3

Rigaku Saturn CCD area-detector diffractometer	3271 independent reflections
Radiation source: fine-focus sealed tube	3103 reflections with I > 2σ(I)
graphite	Rint = 0.017
ω scans	θmax = 28.3°, θmin = 2.3°
Absorption correction: multi-scan (Blessing, 1995)	h = −11→11
Tmin = 0.972, Tmax = 0.981	k = −11→11
9557 measured reflections	l = −12→12

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.145	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ2(Fo2) + (0.0812P)2 + 0.1565P] where P = (Fo2 + 2Fc2)/3
3271 reflections	(Δ/σ)max < 0.001
184 parameters	Δρmax = 0.31 e Å−3
0 restraints	Δρmin = −0.24 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.

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.

	x	y	z	Uiso*/Ueq
O1	0.24208 (10)	0.61579 (11)	0.84154 (10)	0.0282 (2)
N1	0.14380 (12)	0.42572 (12)	0.71820 (11)	0.0242 (2)
O2	0.43518 (12)	0.64375 (12)	0.67744 (10)	0.0338 (2)
N2	0.35609 (13)	0.42026 (15)	0.55735 (13)	0.0309 (3)
C1	0.22273 (14)	0.37913 (14)	0.60017 (13)	0.0238 (2)
C6	0.41282 (13)	0.76759 (14)	0.87938 (13)	0.0234 (2)
C3	0.02113 (16)	0.25068 (15)	0.57653 (14)	0.0290 (3)
H3	−0.0231	0.1918	0.5263	0.035*
C9	0.36026 (13)	0.66849 (14)	0.79228 (13)	0.0235 (2)
C11	0.71088 (14)	0.73844 (14)	0.88508 (13)	0.0246 (2)
H11	0.7259	0.6408	0.9589	0.029*
C10	0.55559 (14)	0.82560 (14)	0.82490 (12)	0.0230 (2)
C12	0.84456 (14)	0.79240 (15)	0.83861 (13)	0.0268 (3)
H12	0.9499	0.7318	0.8806	0.032*
C2	0.15868 (15)	0.28868 (14)	0.52668 (13)	0.0257 (3)
H2	0.2114	0.2548	0.4432	0.031*
C5	0.00793 (15)	0.38539 (15)	0.76921 (13)	0.0269 (3)
H5	−0.0431	0.4190	0.8534	0.032*
C14	0.67030 (17)	1.02220 (15)	0.66824 (15)	0.0319 (3)
H14	0.6560	1.1190	0.5934	0.038*
C15	0.53697 (15)	0.96742 (15)	0.71553 (14)	0.0292 (3)
H15	0.4320	1.0277	0.6725	0.035*
C4	−0.05647 (16)	0.29794 (16)	0.70228 (14)	0.0304 (3)
H4	−0.1509	0.2694	0.7390	0.036*
C7	0.39043 (16)	0.72252 (17)	1.04712 (14)	0.0321 (3)
H7A	0.3474	0.6310	1.0878	0.038*
H7B	0.4712	0.7340	1.1135	0.038*
C13	0.82364 (15)	0.93486 (15)	0.73082 (14)	0.0288 (3)
H13	0.9145	0.9725	0.6999	0.035*
C8	0.27730 (15)	0.87131 (17)	0.95326 (15)	0.0332 (3)
H8A	0.2883	0.9746	0.9617	0.040*
H8B	0.1645	0.8716	0.9359	0.040*
H6	0.407 (2)	0.393 (2)	0.475 (2)	0.038 (4)*
H9	0.389 (2)	0.492 (2)	0.600 (2)	0.041 (5)*
H1	0.185 (2)	0.496 (2)	0.762 (2)	0.044 (5)*

	U11	U22	U33	U12	U13	U23
O1	0.0256 (4)	0.0351 (5)	0.0315 (5)	−0.0151 (3)	0.0083 (3)	−0.0157 (4)
N1	0.0263 (5)	0.0268 (5)	0.0226 (5)	−0.0103 (4)	0.0047 (4)	−0.0094 (4)
O2	0.0381 (5)	0.0433 (5)	0.0329 (5)	−0.0232 (4)	0.0150 (4)	−0.0210 (4)
N2	0.0292 (5)	0.0413 (6)	0.0326 (6)	−0.0188 (5)	0.0110 (4)	−0.0193 (5)
C1	0.0240 (5)	0.0242 (5)	0.0238 (5)	−0.0080 (4)	0.0027 (4)	−0.0063 (4)
C6	0.0212 (5)	0.0272 (6)	0.0249 (5)	−0.0082 (4)	0.0047 (4)	−0.0113 (4)
C3	0.0351 (6)	0.0295 (6)	0.0286 (6)	−0.0172 (5)	0.0054 (5)	−0.0097 (5)
C9	0.0213 (5)	0.0257 (5)	0.0256 (5)	−0.0078 (4)	0.0033 (4)	−0.0093 (4)
C11	0.0257 (6)	0.0256 (5)	0.0247 (5)	−0.0100 (4)	0.0033 (4)	−0.0078 (4)
C10	0.0238 (5)	0.0249 (5)	0.0244 (5)	−0.0094 (4)	0.0043 (4)	−0.0113 (4)
C12	0.0242 (5)	0.0316 (6)	0.0292 (6)	−0.0113 (4)	0.0030 (4)	−0.0123 (5)
C2	0.0302 (6)	0.0265 (6)	0.0234 (5)	−0.0111 (4)	0.0047 (4)	−0.0092 (4)
C5	0.0292 (6)	0.0286 (6)	0.0245 (5)	−0.0105 (5)	0.0073 (4)	−0.0082 (4)
C14	0.0403 (7)	0.0248 (6)	0.0318 (6)	−0.0137 (5)	0.0059 (5)	−0.0051 (5)
C15	0.0287 (6)	0.0260 (6)	0.0321 (6)	−0.0074 (5)	0.0009 (5)	−0.0065 (5)
C4	0.0323 (6)	0.0324 (6)	0.0314 (6)	−0.0169 (5)	0.0089 (5)	−0.0090 (5)
C7	0.0325 (6)	0.0468 (8)	0.0260 (6)	−0.0199 (6)	0.0090 (5)	−0.0167 (5)
C13	0.0326 (6)	0.0318 (6)	0.0308 (6)	−0.0182 (5)	0.0092 (5)	−0.0144 (5)
C8	0.0276 (6)	0.0372 (7)	0.0429 (7)	−0.0110 (5)	0.0115 (5)	−0.0242 (6)

O1—C9	1.2702 (14)	C11—H11	0.9500
N1—C1	1.3524 (15)	C10—C15	1.3927 (17)
N1—C5	1.3597 (15)	C12—C13	1.3870 (18)
N1—H1	0.983 (19)	C12—H12	0.9500
O2—C9	1.2530 (15)	C2—H2	0.9500
N2—C1	1.3261 (15)	C5—C4	1.3595 (18)
N2—H6	0.913 (18)	C5—H5	0.9500
N2—H9	0.949 (19)	C14—C13	1.385 (2)
C1—C2	1.4178 (17)	C14—C15	1.3947 (17)
C6—C10	1.4977 (15)	C14—H14	0.9500
C6—C9	1.5122 (16)	C15—H15	0.9500
C6—C7	1.5201 (17)	C4—H4	0.9500
C6—C8	1.5224 (17)	C7—C8	1.491 (2)
C3—C2	1.3614 (16)	C7—H7A	0.9900
C3—C4	1.4125 (18)	C7—H7B	0.9900
C3—H3	0.9500	C13—H13	0.9500
C11—C10	1.3918 (17)	C8—H8A	0.9900
C11—C12	1.3922 (16)	C8—H8B	0.9900
C1—N1—C5	121.81 (10)	C3—C2—C1	119.58 (11)
C1—N1—H1	117.1 (11)	C3—C2—H2	120.2
C5—N1—H1	121.0 (11)	C1—C2—H2	120.2
C1—N2—H6	118.9 (11)	C4—C5—N1	121.41 (11)
C1—N2—H9	120.8 (11)	C4—C5—H5	119.3
H6—N2—H9	119.5 (15)	N1—C5—H5	119.3
N2—C1—N1	118.89 (11)	C13—C14—C15	119.75 (12)
N2—C1—C2	122.65 (11)	C13—C14—H14	120.1
N1—C1—C2	118.46 (11)	C15—C14—H14	120.1
C10—C6—C9	117.44 (9)	C10—C15—C14	120.94 (12)
C10—C6—C7	118.19 (10)	C10—C15—H15	119.5
C9—C6—C7	115.04 (10)	C14—C15—H15	119.5
C10—C6—C8	118.76 (10)	C5—C4—C3	118.07 (11)
C9—C6—C8	115.60 (10)	C5—C4—H4	121.0
C7—C6—C8	58.71 (9)	C3—C4—H4	121.0
C2—C3—C4	120.64 (11)	C8—C7—C6	60.72 (9)
C2—C3—H3	119.7	C8—C7—H7A	117.7
C4—C3—H3	119.7	C6—C7—H7A	117.7
O2—C9—O1	124.47 (11)	C8—C7—H7B	117.7
O2—C9—C6	118.39 (10)	C6—C7—H7B	117.7
O1—C9—C6	117.13 (10)	H7A—C7—H7B	114.8
C10—C11—C12	120.92 (11)	C14—C13—C12	120.03 (11)
C10—C11—H11	119.5	C14—C13—H13	120.0
C12—C11—H11	119.5	C12—C13—H13	120.0
C11—C10—C15	118.48 (11)	C7—C8—C6	60.57 (8)
C11—C10—C6	120.06 (10)	C7—C8—H8A	117.7
C15—C10—C6	121.46 (11)	C6—C8—H8A	117.7
C13—C12—C11	119.87 (11)	C7—C8—H8B	117.7
C13—C12—H12	120.1	C6—C8—H8B	117.7
C11—C12—H12	120.1	H8A—C8—H8B	114.8

Cg1 is the centroid of the C10–C15 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.983 (19)	1.64 (2)	2.6255 (15)	176.2 (17)
N2—H6···O2i	0.913 (18)	1.938 (18)	2.8230 (16)	162.6 (16)
N2—H9···O2	0.949 (19)	1.844 (19)	2.7903 (15)	175.2 (16)
C11—H11···O1ii	0.95	2.53	3.479 (2)	178
C12—H12···O1iii	0.95	2.47	3.3212 (18)	149
C2—H2···Cg1i	0.95	2.62	3.5464 (15)	166

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C10–C15 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.983 (19)	1.64 (2)	2.6255 (15)	176.2 (17)
N2—H6⋯O2i	0.913 (18)	1.938 (18)	2.8230 (16)	162.6 (16)
N2—H9⋯O2	0.949 (19)	1.844 (19)	2.7903 (15)	175.2 (16)
C11—H11⋯O1ii	0.95	2.53	3.479 (2)	178
C12—H12⋯O1iii	0.95	2.47	3.3212 (18)	149
C2—H2⋯Cg1i	0.95	2.62	3.5464 (15)	166

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