4-Amino­pyridinium azide 4-amino­pyridine solvate

Qian, H.-F.; Huang, W.

doi:10.1107/S1600536810044843

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3086

https://doi.org/10.1107/S1600536810044843

Open

access

4-Aminopyridinium azide 4-aminopyridine solvate

Hui-Fen Qian ^a ^* and Wei Huang ^b ^*

^aCollege of Sciences, Nanjing University of Technology, Nanjing 210009, People's Republic of China, and ^bState Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, People's Republic of China
^*Correspondence e-mail: whuang@nju.edu.cn,

(Received 29 October 2010; accepted 2 November 2010; online 6 November 2010)

In the title compound, C₅H₇N₂⁺·N₃⁻·C₅H₆N₂, all N atoms of the azide anion are situated on a twofold rotational axis, so the 4-aminopyridinium cation and 4-aminopyridine molecule, being related by symmetry, occupy one position in the asymmetric unit. Intermolecular N—H⋯N hydrogen bonds generate a three-dimensional hydrogen-bonding network which consolidates the crystal packing.

Related literature

For a related compound, see: Teulon et al. (1985 ).

Experimental

Crystal data

C₅H₇N₂⁺·N₃⁻·C₅H₆N₂
M_r = 231.27
Monoclinic, C 2/c
a = 7.507 (3) Å
b = 12.247 (5) Å
c = 13.634 (5) Å
β = 99.278 (5)°
V = 1237.0 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 291 K
0.14 × 0.11 × 0.10 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.988, T_max = 0.992
3027 measured reflections
1096 independent reflections
852 reflections with I > 2σ(I)
R_int = 0.072

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.105
S = 1.08
1096 reflections
80 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.11 e Å⁻³
Δρ_min = −0.11 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N5ⁱ	0.86	2.15	3.008 (2)	174
N1—H1B⋯N3ⁱⁱ	0.86	2.14	2.9942 (18)	172
N2—H2A⋯N2ⁱⁱⁱ	0.86	1.84	2.689 (3)	169
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) -x+1, -y, -z+1; (iii) $[-x, y, -z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810044843/cv2787sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810044843/cv2787Isup2.hkl

checkCIF report

Comment top

The crystal structure of 4-aminopyridine hemiperchlorate, has been previously reported (Teulon et al., 1985). In this paper, we report the X-ray single-crystal structure of 4-aminopyridinium azide 4-aminopyridine (I).

The molecular structure of (I) is illustrated in Fig. 1. All N atoms of the azide anions are situated on a twofold rotational axis, so 4-aminopyridinium cation and 4-aminopyridine molecule being related by symmetry occupy one position in the asymmetric unit. Intermolecular N—H···N hydrogen bonds (Table 1) generate a three-dimensional hydrogen-bonding network which consolidate the crystal packing.

Related literature top

For a related compound, see: Teulon et al. (1985).

Experimental top

The title compound (I) was prepared by the treatment of 4-aminopyridine (0.5 mmol, 0.041 g) and excess sodium azide (NaN₃) in 20 ml methanol with a few drops of acetate acid (HOAc). Colourless single crystals suitable for X-ray diffraction measurement were grown from its methanol solution after five days' slow evaporation at room temperature in air. Anal. Calcd. for C₁₀H₁₃N₇: C, 51.94; H, 5.66; N, 42.40%. Found: C, 51.85; H, 5.81; N, 42.29%. FT–IR (KBr pellets, cm^-1): 3447 (vs), 2057 (s), 1645 (s), 1463 (m), 1202 (w), 1202 (w), 840 (w), and 590 (w).

Structure description top

For a related compound, see: Teulon et al. (1985).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

4-Aminopyridinium azide 4-aminopyridine solvate top

Crystal data top

C₅H₇N₂⁺·N₃⁻·C₅H₆N₂	F(000) = 488
M_r = 231.27	D_x = 1.242 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1359 reflections
a = 7.507 (3) Å	θ = 3.0–25.4°
b = 12.247 (5) Å	µ = 0.08 mm⁻¹
c = 13.634 (5) Å	T = 291 K
β = 99.278 (5)°	Block, colourless
V = 1237.0 (8) Å³	0.14 × 0.11 × 0.10 mm
Z = 4

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	1096 independent reflections
Radiation source: fine-focus sealed tube	852 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.072
φ and ω scans	θ_max = 25.0°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −8→8
T_min = 0.988, T_max = 0.992	k = −12→14
3027 measured reflections	l = −16→15

Refinement top

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)] = 0.036	H-atom parameters constrained
wR(F²) = 0.105	w = 1/[σ²(F_o²) + (0.0493P)² + 0.0478P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
1096 reflections	Δρ_max = 0.11 e Å⁻³
80 parameters	Δρ_min = −0.11 e Å⁻³
1 restraint	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.042 (5)

Crystal data top

C₅H₇N₂⁺·N₃⁻·C₅H₆N₂	V = 1237.0 (8) Å³
M_r = 231.27	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 7.507 (3) Å	µ = 0.08 mm⁻¹
b = 12.247 (5) Å	T = 291 K
c = 13.634 (5) Å	0.14 × 0.11 × 0.10 mm
β = 99.278 (5)°

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	1096 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	852 reflections with I > 2σ(I)
T_min = 0.988, T_max = 0.992	R_int = 0.072
3027 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	1 restraint
wR(F²) = 0.105	H-atom parameters constrained
S = 1.08	Δρ_max = 0.11 e Å⁻³
1096 reflections	Δρ_min = −0.11 e Å⁻³
80 parameters

Special details top

Experimental. The structure was solved by direct methods (Bruker, 2000) and successive difference Fourier syntheses.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.1721 (2)	0.05406 (12)	−0.09812 (12)	0.0879 (5)
H1	0.2321	0.0033	−0.1316	0.106*
C2	0.22248 (18)	0.06466 (10)	0.00146 (11)	0.0780 (4)
H2	0.3145	0.0214	0.0350	0.094*
C3	0.13523 (16)	0.14103 (10)	0.05345 (9)	0.0699 (4)
C4	−0.00162 (18)	0.20282 (11)	−0.00180 (11)	0.0791 (4)
H4	−0.0635	0.2547	0.0294	0.095*
C5	−0.0439 (2)	0.18672 (13)	−0.10131 (12)	0.0932 (5)
H5	−0.1355	0.2286	−0.1371	0.112*
N1	0.18164 (16)	0.15416 (9)	0.15211 (9)	0.0858 (4)
H1A	0.1265	0.2016	0.1828	0.103*
H1B	0.2665	0.1151	0.1846	0.103*
N2	0.04055 (19)	0.11306 (11)	−0.15027 (9)	0.0948 (4)
H2A	0.0108	0.1042	−0.2134	0.114*	0.50
N3	0.5000	−0.02503 (17)	0.7500	0.1009 (6)
N4	0.5000	0.07152 (17)	0.7500	0.0760 (5)
N5	0.5000	0.16656 (17)	0.7500	0.1062 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0948 (10)	0.0867 (9)	0.0891 (8)	−0.0181 (8)	0.0353 (8)	−0.0118 (8)
C2	0.0744 (8)	0.0752 (8)	0.0879 (8)	−0.0108 (6)	0.0231 (6)	−0.0057 (6)
C3	0.0681 (7)	0.0682 (7)	0.0762 (9)	−0.0163 (6)	0.0206 (6)	−0.0037 (6)
C4	0.0765 (8)	0.0799 (8)	0.0834 (9)	−0.0071 (6)	0.0205 (7)	−0.0009 (7)
C5	0.0938 (10)	0.1000 (11)	0.0854 (11)	−0.0100 (8)	0.0132 (8)	0.0090 (8)
N1	0.0900 (8)	0.0873 (8)	0.0803 (8)	0.0016 (5)	0.0144 (6)	−0.0086 (6)
N2	0.1105 (10)	0.1050 (9)	0.0714 (8)	−0.0251 (7)	0.0223 (7)	−0.0032 (7)
N3	0.0964 (13)	0.0868 (12)	0.1185 (15)	0.000	0.0141 (10)	0.000
N4	0.0626 (9)	0.0993 (13)	0.0671 (9)	0.000	0.0139 (6)	0.000
N5	0.1123 (14)	0.0918 (14)	0.1242 (16)	0.000	0.0488 (12)	0.000

Geometric parameters (Å, º) top

C1—N2	1.333 (2)	C4—H4	0.9300
C1—C2	1.356 (2)	C5—N2	1.341 (2)
C1—H1	0.9300	C5—H5	0.9300
C2—C3	1.3985 (18)	N1—H1A	0.8600
C2—H2	0.9300	N1—H1B	0.8600
C3—N1	1.3437 (17)	N2—H2A	0.8600
C3—C4	1.395 (2)	N3—N4	1.182 (3)
C4—C5	1.357 (2)	N4—N5	1.164 (2)

N2—C1—C2	123.06 (14)	C3—C4—H4	120.2
N2—C1—H1	118.5	N2—C5—C4	122.83 (15)
C2—C1—H1	118.5	N2—C5—H5	118.6
C1—C2—C3	119.58 (14)	C4—C5—H5	118.6
C1—C2—H2	120.2	C3—N1—H1A	120.0
C3—C2—H2	120.2	C3—N1—H1B	120.0
N1—C3—C4	121.68 (12)	H1A—N1—H1B	120.0
N1—C3—C2	121.36 (13)	C1—N2—C5	117.93 (13)
C4—C3—C2	116.97 (13)	C1—N2—H2A	121.0
C5—C4—C3	119.63 (14)	C5—N2—H2A	121.0
C5—C4—H4	120.2	N5—N4—N3	180.000 (1)

N2—C1—C2—C3	−0.5 (2)	C2—C3—C4—C5	0.10 (18)
C1—C2—C3—N1	−179.81 (11)	C3—C4—C5—N2	0.0 (2)
C1—C2—C3—C4	0.11 (17)	C2—C1—N2—C5	0.6 (2)
N1—C3—C4—C5	−179.98 (11)	C4—C5—N2—C1	−0.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N5ⁱ	0.86	2.15	3.008 (2)	174
N1—H1B···N3ⁱⁱ	0.86	2.14	2.9942 (18)	172
N2—H2A···N2ⁱⁱⁱ	0.86	1.84	2.689 (3)	169

Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x+1, −y, −z+1; (iii) −x, y, −z−1/2.

Experimental details

Crystal data
Chemical formula	C₅H₇N₂⁺·N₃⁻·C₅H₆N₂
M_r	231.27
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	291
a, b, c (Å)	7.507 (3), 12.247 (5), 13.634 (5)
β (°)	99.278 (5)
V (Å³)	1237.0 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.14 × 0.11 × 0.10

Data collection
Diffractometer	Bruker SMART 1K CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.988, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	3027, 1096, 852
R_int	0.072
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.105, 1.08
No. of reflections	1096
No. of parameters	80
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.11, −0.11

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N5ⁱ	0.86	2.15	3.008 (2)	173.8
N1—H1B···N3ⁱⁱ	0.86	2.14	2.9942 (18)	171.9
N2—H2A···N2ⁱⁱⁱ	0.86	1.84	2.689 (3)	168.9

Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x+1, −y, −z+1; (iii) −x, y, −z−1/2.

Acknowledgements

WH acknowledges the National Natural Science Foundation of China (grant No. 20871065) and the Jiangsu Province Department of Science and Technology (grant No. BK2009226) for financial support.

References

Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Teulon, P., Delaplane, R. G., Olovsson, I. & Rozière, J. (1985). Acta Cryst. C41, 479–483. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar