4-Carbamoylpyridinium perchlorate

Chen, L.-Z.

doi:10.1107/S1600536809039026

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2626

https://doi.org/10.1107/S1600536809039026

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4-Carbamoylpyridinium perchlorate

Li-Zhuang Chen ^a ^*

^aSchool of Material Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, People's Republic of China
^*Correspondence e-mail: clz1977@sina.com

(Received 14 August 2009; accepted 25 September 2009; online 3 October 2009)

In the cation of the title compound, C₆H₇N₂O⁺·ClO₄⁻, the amide group is oriented at a dihedral angle of 10.41 (17)° to the benzene ring. The crystal structure is stabilized by intermolecular N—H⋯O hydrogen bonding.

Related literature

For general background to structural features and physical properties of simple molecular–ionic crystals containing organic cations and acid radicals (1:1 molar ratio), see: Czupiński et al. (2002 ); Katrusiak & Szafrański (1999 , 2006 ). For the crystal structure of 4-carbamoylpyridinium dihydrogen phosphate, see: Gholivand et al. (2007 ) and for that of 3-(aminocarbonyl)pyridinium perchlorate, see: Athimoolam & Natarajan (2007 ).

Experimental

Crystal data

C₆H₇N₂O⁺·ClO₄⁻
M_r = 222.59
Monoclinic, P 2₁ /c
a = 10.935 (2) Å
b = 10.082 (2) Å
c = 8.2021 (16) Å
β = 99.37 (3)°
V = 892.2 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.43 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.22 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.87, T_max = 0.90
8863 measured reflections
2033 independent reflections
1421 reflections with I > 2σ(I)
R_int = 0.074

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.176
S = 1.04
2033 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3ⁱ	0.86	2.10	2.932 (4)	162
N2—H2A⋯O1ⁱⁱ	0.86	2.32	3.162 (4)	168
N2—H2B⋯O5ⁱⁱⁱ	0.86	2.17	3.004 (4)	164
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x, -y+1, -z; (iii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); 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: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809039026/xu2591sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809039026/xu2591Isup2.hkl

checkCIF report

Comment top

Recently much attention has been devoted to simple molecular–ionic crystals containing organic cations and acid radicals (1:1 molar ratio) due to the tunability of their special structural features and their interesting physical properties (Czupiński et al., 2002; Katrusiak & Szafrański, 1999; Katrusiak & Szafrański, 2006). The crystal structures of 4-carbamoylpyridinium dihydrogen phosphate (Gholivand et al., 2007) and 3-(aminocarbonyl)pyridinium perchlorate (Athimoolam & Natarajan, 2007) have been reported previously. In our laboratory, a compound containing 4-carbamoylpyridinium cation and ClO₄^- anion has been synthesized, its crystal structure is reported herein.

The asymmetric unit of the title compound (Fig. 1) consists of one 4-carbamoylpyridinium cation and one ClO₄^- anion. The crystal structure is stabilized by intermolecular N—H···O hydrogen bonds (Table 1).

Related literature top

For general background to structural features and physical properties of simple molecular–ionic crystals containing organic cations and acid radicals (1:1 molar ratio), see: Czupiński et al. (2002); Katrusiak & Szafrański (1999, 2006). For the crystal structure of 4-carbamoylpyridinium dihydrogen phosphate, see: Gholivand et al. (2007). For the crystal structure of 3-(aminocarbonyl)pyridinium perchlorate, see: Athimoolam & Natarajan (2007).

Experimental top

4-Carbamoylpyridine (2.44 g, 20 mmol) and 10% aqueous solution (15 ml) of HClO₄ were dissolved in 30 ml water. The solution was heated at 343 K for 0.5 h, forming a clear solution. The reaction mixture was cooled slowly to room temperature, block crystals of the title compound were formed.

Structure description top

For general background to structural features and physical properties of simple molecular–ionic crystals containing organic cations and acid radicals (1:1 molar ratio), see: Czupiński et al. (2002); Katrusiak & Szafrański (1999, 2006). For the crystal structure of 4-carbamoylpyridinium dihydrogen phosphate, see: Gholivand et al. (2007). For the crystal structure of 3-(aminocarbonyl)pyridinium perchlorate, see: Athimoolam & Natarajan (2007).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The asymmetric unit of the title compound with atom labels. Displacement ellipsoids were drawn at the 30% probability level.

4-Carbamoylpyridinium perchlorate top

Crystal data top

C₆H₇N₂O⁺·ClO₄⁻	F(000) = 456
M_r = 222.59	D_x = 1.657 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1421 reflections
a = 10.935 (2) Å	θ = 3.2–27.5°
b = 10.082 (2) Å	µ = 0.43 mm⁻¹
c = 8.2021 (16) Å	T = 293 K
β = 99.37 (3)°	Block, colorless
V = 892.2 (3) Å³	0.30 × 0.25 × 0.22 mm
Z = 4

Data collection top

Rigaku SCXmini diffractometer	2033 independent reflections
Radiation source: fine-focus sealed tube	1421 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.074
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
ω scans	h = −14→14
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −13→13
T_min = 0.87, T_max = 0.90	l = −10→10
8863 measured reflections

Refinement top

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.176	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0844P)² + 0.3072P] where P = (F_o² + 2F_c²)/3
2033 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

C₆H₇N₂O⁺·ClO₄⁻	V = 892.2 (3) Å³
M_r = 222.59	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.935 (2) Å	µ = 0.43 mm⁻¹
b = 10.082 (2) Å	T = 293 K
c = 8.2021 (16) Å	0.30 × 0.25 × 0.22 mm
β = 99.37 (3)°

Data collection top

Rigaku SCXmini diffractometer	2033 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1421 reflections with I > 2σ(I)
T_min = 0.87, T_max = 0.90	R_int = 0.074
8863 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.176	H-atom parameters constrained
S = 1.04	Δρ_max = 0.42 e Å⁻³
2033 reflections	Δρ_min = −0.42 e Å⁻³
127 parameters

Special details top

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
Cl1	0.35049 (7)	0.39747 (7)	0.09900 (9)	0.0473 (3)
O5	0.0368 (2)	0.8048 (2)	0.2309 (3)	0.0650 (7)
N2	−0.0251 (3)	0.5945 (3)	0.1873 (4)	0.0698 (10)
H2A	−0.0862	0.6169	0.1127	0.084*
H2B	−0.0128	0.5123	0.2130	0.084*
C6	0.0493 (3)	0.6856 (3)	0.2619 (4)	0.0463 (7)
C4	0.2469 (3)	0.7332 (3)	0.4470 (4)	0.0479 (8)
H4A	0.2386	0.8205	0.4104	0.057*
N1	0.3573 (2)	0.5717 (3)	0.6122 (3)	0.0541 (8)
H1A	0.4218	0.5492	0.6813	0.065*
C3	0.1569 (2)	0.6406 (3)	0.3883 (3)	0.0399 (7)
O4	0.4364 (2)	0.2906 (2)	0.1204 (3)	0.0707 (8)
O3	0.3944 (2)	0.4992 (2)	0.2176 (3)	0.0653 (7)
C2	0.1692 (3)	0.5117 (3)	0.4485 (4)	0.0457 (8)
H2C	0.1096	0.4479	0.4117	0.055*
C5	0.3479 (3)	0.6961 (4)	0.5590 (4)	0.0549 (9)
H5A	0.4094	0.7575	0.5973	0.066*
O2	0.3407 (3)	0.4505 (3)	−0.0636 (3)	0.0843 (9)
O1	0.2315 (2)	0.3517 (3)	0.1231 (4)	0.0759 (8)
C1	0.2713 (3)	0.4798 (3)	0.5636 (4)	0.0536 (9)
H1B	0.2803	0.3945	0.6072	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0405 (5)	0.0430 (5)	0.0519 (5)	0.0012 (3)	−0.0116 (3)	0.0000 (3)
O5	0.0581 (15)	0.0403 (14)	0.0867 (19)	0.0094 (11)	−0.0176 (12)	0.0095 (12)
N2	0.0575 (19)	0.0488 (18)	0.087 (2)	−0.0020 (13)	−0.0377 (17)	0.0116 (15)
C6	0.0397 (17)	0.0405 (18)	0.0548 (19)	0.0032 (13)	−0.0039 (13)	0.0050 (14)
C4	0.0466 (18)	0.0361 (16)	0.057 (2)	−0.0056 (13)	−0.0036 (14)	0.0033 (13)
N1	0.0460 (16)	0.0565 (18)	0.0509 (17)	0.0061 (12)	−0.0187 (13)	−0.0010 (12)
C3	0.0346 (16)	0.0371 (15)	0.0448 (17)	0.0021 (11)	−0.0030 (12)	−0.0012 (12)
O4	0.0550 (15)	0.0510 (15)	0.097 (2)	0.0147 (11)	−0.0145 (14)	−0.0040 (13)
O3	0.0595 (16)	0.0570 (15)	0.0721 (17)	−0.0015 (11)	−0.0110 (12)	−0.0208 (12)
C2	0.0469 (18)	0.0319 (15)	0.0520 (19)	−0.0018 (12)	−0.0109 (14)	−0.0034 (12)
C5	0.0438 (19)	0.055 (2)	0.060 (2)	−0.0120 (15)	−0.0079 (15)	−0.0007 (16)
O2	0.106 (2)	0.087 (2)	0.0518 (17)	−0.0028 (17)	−0.0107 (15)	0.0126 (14)
O1	0.0434 (15)	0.0839 (19)	0.096 (2)	−0.0120 (13)	−0.0021 (13)	−0.0088 (16)
C1	0.060 (2)	0.0381 (17)	0.055 (2)	0.0063 (15)	−0.0145 (16)	−0.0002 (14)

Geometric parameters (Å, º) top

Cl1—O4	1.421 (2)	C4—C3	1.385 (4)
Cl1—O2	1.424 (3)	C4—H4A	0.9300
Cl1—O1	1.425 (3)	N1—C5	1.327 (4)
Cl1—O3	1.441 (2)	N1—C1	1.334 (4)
O5—C6	1.231 (3)	N1—H1A	0.8600
N2—C6	1.310 (4)	C3—C2	1.389 (4)
N2—H2A	0.8600	C2—C1	1.377 (4)
N2—H2B	0.8600	C2—H2C	0.9300
C6—C3	1.507 (4)	C5—H5A	0.9300
C4—C5	1.369 (5)	C1—H1B	0.9300

O4—Cl1—O2	110.33 (19)	C5—N1—C1	123.0 (3)
O4—Cl1—O1	109.76 (17)	C5—N1—H1A	118.5
O2—Cl1—O1	108.68 (18)	C1—N1—H1A	118.5
O4—Cl1—O3	108.36 (15)	C4—C3—C2	119.0 (3)
O2—Cl1—O3	109.30 (18)	C4—C3—C6	117.9 (3)
O1—Cl1—O3	110.41 (17)	C2—C3—C6	123.1 (3)
C6—N2—H2A	120.0	C1—C2—C3	118.9 (3)
C6—N2—H2B	120.0	C1—C2—H2C	120.6
H2A—N2—H2B	120.0	C3—C2—H2C	120.6
O5—C6—N2	123.2 (3)	N1—C5—C4	119.3 (3)
O5—C6—C3	118.9 (3)	N1—C5—H5A	120.3
N2—C6—C3	117.8 (3)	C4—C5—H5A	120.3
C5—C4—C3	120.0 (3)	N1—C1—C2	119.7 (3)
C5—C4—H4A	120.0	N1—C1—H1B	120.1
C3—C4—H4A	120.0	C2—C1—H1B	120.1

C5—C4—C3—C2	1.9 (5)	C4—C3—C2—C1	−0.6 (5)
C5—C4—C3—C6	−178.4 (3)	C6—C3—C2—C1	179.7 (3)
O5—C6—C3—C4	−9.0 (5)	C1—N1—C5—C4	−1.0 (5)
N2—C6—C3—C4	169.5 (3)	C3—C4—C5—N1	−1.2 (5)
O5—C6—C3—C2	170.7 (3)	C5—N1—C1—C2	2.4 (5)
N2—C6—C3—C2	−10.9 (5)	C3—C2—C1—N1	−1.5 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3ⁱ	0.86	2.10	2.932 (4)	162
N2—H2A···O1ⁱⁱ	0.86	2.32	3.162 (4)	168
N2—H2B···O5ⁱⁱⁱ	0.86	2.17	3.004 (4)	164

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

Experimental details

Crystal data
Chemical formula	C₆H₇N₂O⁺·ClO₄⁻
M_r	222.59
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	10.935 (2), 10.082 (2), 8.2021 (16)
β (°)	99.37 (3)
V (Å³)	892.2 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.43
Crystal size (mm)	0.30 × 0.25 × 0.22

Data collection
Diffractometer	Rigaku SCXmini
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.87, 0.90
No. of measured, independent and observed [I > 2σ(I)] reflections	8863, 2033, 1421
R_int	0.074
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.176, 1.04
No. of reflections	2033
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.42

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3ⁱ	0.86	2.10	2.932 (4)	161.7
N2—H2A···O1ⁱⁱ	0.86	2.32	3.162 (4)	168.1
N2—H2B···O5ⁱⁱⁱ	0.86	2.17	3.004 (4)	164.2

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

Acknowledgements

This work was supported by a start-up grant from Jiangsu University of Science and Technology, China.

References

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