Diisopropyl­ammonium nitrite

Wang, Y.-C.; Jie, X.

doi:10.1107/S1600536812008574

organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o986

doi:10.1107/S1600536812008574

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Diisopropylammonium nitrite

Ying-Chun Wang ^a ^* and Xu Jie ^a

^aCollege of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: wangyc33@yahoo.com.cn

(Received 25 February 2012; accepted 26 February 2012; online 7 March 2012)

In the title molecular salt, C₆H₁₆N⁺·NO₂⁻, the cation forms two N—H⋯O hydrogen bonds to nearby nitrite anions which link the ionic units into chains propagating along the b-axis direction.

Related literature

For a related structure, see: Xu (2012 ). For background to molecular ferroelectric compounds, see: Fu et al. (2011 ).

Experimental

Crystal data

C₆H₁₆N⁺·NO₂⁻
M_r = 148.21
Monoclinic, P 2₁ /n
a = 8.2314 (16) Å
b = 7.7466 (15) Å
c = 14.583 (3) Å
β = 94.16 (3)°
V = 927.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 298 K
0.10 × 0.03 × 0.03 mm

Data collection

Rigaku Mercury2 CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.910, T_max = 1.000
9189 measured reflections
2127 independent reflections
1130 reflections with I > 2σ(I)
R_int = 0.075

Refinement

R[F² > 2σ(F²)] = 0.084
wR(F²) = 0.285
S = 1.07
2127 reflections
95 parameters
15 restraints
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1E⋯O1	0.90	1.90	2.800 (3)	174
N1—H1D⋯O1ⁱ	0.90	2.00	2.869 (3)	161
Symmetry code: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812008574/hb6657sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812008574/hb6657Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812008574/hb6657Isup3.cml

checkCIF report

Comment top

Simple organic salts containig amino cations have attracted an attention as materials which display ferroelectric-paraelectric phase transitions (Fu et al., 2011). As part of our ongonig studies in this area, (Xu, 2012), various amines have been studied and a series of new materials with this organic molecules have been elaborated. Herein we present the crystal structure of the title compound, di-isopropylammonium nitrite.

The asymmetric unit of the title compound contains one di-isopropylammonium cation and one NO₂^- anion (Fig. 1). The amino N atom was protonated. The O-N-O bond angle of NO₂- anion is 116.4 (4)°. And the other geometric parameters of the title compound are in the normal range.

In the crystal structure, all the ammonium H atoms are involved in intermolecular N—H···O H-bonding interactions with both the O atoms of the NO₂^- anion (with N···O distances of 2.800 (3)Å and 2.869 (3)Å, respectively). These hydrogen bonds link the ionic units into a one-dimentional chain along the b-axis (Table 1 and Fig.2).

Related literature top

For a related structure, see: Xu (2012). For background to molecular ferroelectric compounds, see: Fu et al. (2011).

Experimental top

A mixture of di-isopropylamine (0.8 mmol), HCl (0.8 mmol) and NaNO₂ (0.8 mmol) were dissolved in EtOH/distilled water (1:1 v/v) solvent. The solution was slowly evaporated in air affording colourless block-shaped crystals of the title compound.

Structure description top

For a related structure, see: Xu (2012). For background to molecular ferroelectric compounds, see: Fu et al. (2011).

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the title compound with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound showing the one-dimensionnal hydrogen bondings chain along the b axis (dashed line). H atoms not involved in hydrogen bonding (dashed line) have been omitted for clarity.

Diisopropylammonium nitrite top

Crystal data top

C₆H₁₆N⁺·NO₂⁻	F(000) = 328
M_r = 148.21	D_x = 1.061 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2127 reflections
a = 8.2314 (16) Å	θ = 3.6–27.5°
b = 7.7466 (15) Å	µ = 0.08 mm⁻¹
c = 14.583 (3) Å	T = 298 K
β = 94.16 (3)°	Block, colourless
V = 927.5 (3) Å³	0.10 × 0.03 × 0.03 mm
Z = 4

Data collection top

Rigaku Mercury2 CCD diffractometer	2127 independent reflections
Radiation source: fine-focus sealed tube	1130 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.075
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.6°
CCD profile fitting scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −10→10
T_min = 0.910, T_max = 1.000	l = −18→18
9189 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)] = 0.084	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.285	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.1379P)² + 0.0979P] where P = (F_o² + 2F_c²)/3
2127 reflections	(Δ/σ)_max < 0.001
95 parameters	Δρ_max = 0.50 e Å⁻³
15 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₆H₁₆N⁺·NO₂⁻	V = 927.5 (3) Å³
M_r = 148.21	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.2314 (16) Å	µ = 0.08 mm⁻¹
b = 7.7466 (15) Å	T = 298 K
c = 14.583 (3) Å	0.10 × 0.03 × 0.03 mm
β = 94.16 (3)°

Data collection top

Rigaku Mercury2 CCD diffractometer	2127 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1130 reflections with I > 2σ(I)
T_min = 0.910, T_max = 1.000	R_int = 0.075
9189 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.084	15 restraints
wR(F²) = 0.285	H-atom parameters constrained
S = 1.07	Δρ_max = 0.50 e Å⁻³
2127 reflections	Δρ_min = −0.32 e Å⁻³
95 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
N1	0.6713 (3)	0.1958 (3)	0.35567 (15)	0.0543 (7)
H1D	0.6950	0.0825	0.3543	0.065*
H1E	0.6890	0.2393	0.3000	0.065*
C2	0.4930 (4)	0.2132 (4)	0.3690 (2)	0.0624 (9)
H2A	0.4733	0.1702	0.4304	0.075*
O1	0.7263 (3)	0.3533 (3)	0.18791 (17)	0.0931 (9)
C5	0.7889 (4)	0.2792 (4)	0.4247 (2)	0.0686 (9)
H5A	0.7676	0.4037	0.4255	0.082*
N2	0.7438 (4)	0.2425 (4)	0.1320 (2)	0.0925 (9)
O2	0.8050 (4)	0.2847 (5)	0.0648 (2)	0.1177 (10)
C6	0.7724 (5)	0.2066 (6)	0.5196 (2)	0.0918 (12)
H6A	0.6642	0.2277	0.5376	0.138*
H6B	0.8500	0.2614	0.5626	0.138*
H6C	0.7925	0.0846	0.5192	0.138*
C3	0.3999 (4)	0.1012 (6)	0.2986 (3)	0.0909 (12)
H3A	0.4409	−0.0148	0.3032	0.136*
H3B	0.4133	0.1453	0.2381	0.136*
H3C	0.2865	0.1017	0.3099	0.136*
C4	0.9579 (5)	0.2488 (7)	0.3938 (3)	0.1037 (14)
H4A	0.9700	0.3099	0.3374	0.156*
H4B	0.9736	0.1275	0.3841	0.156*
H4C	1.0374	0.2895	0.4402	0.156*
C1	0.4425 (5)	0.3998 (5)	0.3631 (3)	0.0941 (13)
H1A	0.5025	0.4643	0.4104	0.141*
H1B	0.3280	0.4089	0.3710	0.141*
H1C	0.4646	0.4452	0.3040	0.141*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0532 (15)	0.0552 (13)	0.0547 (13)	0.0026 (10)	0.0053 (10)	0.0051 (10)
C2	0.0558 (19)	0.0711 (19)	0.0611 (17)	0.0005 (14)	0.0101 (14)	0.0032 (14)
O1	0.1178 (19)	0.0879 (17)	0.0762 (14)	0.0013 (13)	0.0258 (13)	0.0032 (11)
C5	0.063 (2)	0.0582 (17)	0.082 (2)	−0.0024 (14)	−0.0121 (16)	0.0038 (15)
N2	0.116 (2)	0.0955 (18)	0.0689 (15)	0.0076 (14)	0.0293 (14)	−0.0001 (13)
O2	0.145 (2)	0.126 (2)	0.0854 (16)	0.0130 (16)	0.0308 (15)	0.0006 (14)
C6	0.102 (3)	0.110 (3)	0.061 (2)	0.003 (2)	−0.0109 (18)	−0.005 (2)
C3	0.061 (2)	0.114 (3)	0.097 (3)	−0.0143 (19)	0.0022 (19)	−0.014 (2)
C4	0.056 (2)	0.142 (4)	0.111 (3)	−0.011 (2)	−0.003 (2)	0.025 (3)
C1	0.068 (2)	0.089 (3)	0.125 (3)	0.0240 (19)	0.006 (2)	0.003 (2)

Geometric parameters (Å, º) top

N1—C5	1.492 (4)	C6—H6A	0.9600
N1—C2	1.500 (4)	C6—H6B	0.9600
N1—H1D	0.9000	C6—H6C	0.9600
N1—H1E	0.9000	C3—H3A	0.9600
C2—C1	1.505 (5)	C3—H3B	0.9600
C2—C3	1.509 (5)	C3—H3C	0.9600
C2—H2A	0.9800	C4—H4A	0.9600
O1—N2	1.200 (4)	C4—H4B	0.9600
C5—C6	1.510 (5)	C4—H4C	0.9600
C5—C4	1.512 (5)	C1—H1A	0.9600
C5—H5A	0.9800	C1—H1B	0.9600
N2—O2	1.181 (4)	C1—H1C	0.9600

C5—N1—C2	117.8 (2)	C5—C6—H6C	109.5
C5—N1—H1D	107.9	H6A—C6—H6C	109.5
C2—N1—H1D	107.9	H6B—C6—H6C	109.5
C5—N1—H1E	107.9	C2—C3—H3A	109.5
C2—N1—H1E	107.9	C2—C3—H3B	109.5
H1D—N1—H1E	107.2	H3A—C3—H3B	109.5
N1—C2—C1	110.4 (3)	C2—C3—H3C	109.5
N1—C2—C3	108.2 (2)	H3A—C3—H3C	109.5
C1—C2—C3	112.9 (3)	H3B—C3—H3C	109.5
N1—C2—H2A	108.4	C5—C4—H4A	109.5
C1—C2—H2A	108.4	C5—C4—H4B	109.5
C3—C2—H2A	108.4	H4A—C4—H4B	109.5
N1—C5—C6	111.1 (3)	C5—C4—H4C	109.5
N1—C5—C4	107.3 (3)	H4A—C4—H4C	109.5
C6—C5—C4	111.2 (3)	H4B—C4—H4C	109.5
N1—C5—H5A	109.1	C2—C1—H1A	109.5
C6—C5—H5A	109.1	C2—C1—H1B	109.5
C4—C5—H5A	109.1	H1A—C1—H1B	109.5
O2—N2—O1	116.4 (4)	C2—C1—H1C	109.5
C5—C6—H6A	109.5	H1A—C1—H1C	109.5
C5—C6—H6B	109.5	H1B—C1—H1C	109.5
H6A—C6—H6B	109.5

C5—N1—C2—C1	63.0 (3)	C2—N1—C5—C6	60.4 (3)
C5—N1—C2—C3	−173.0 (3)	C2—N1—C5—C4	−177.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1E···O1	0.90	1.90	2.800 (3)	174
N1—H1D···O1ⁱ	0.90	2.00	2.869 (3)	161

Symmetry code: (i) −x+3/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₆H₁₆N⁺·NO₂⁻
M_r	148.21
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	8.2314 (16), 7.7466 (15), 14.583 (3)
β (°)	94.16 (3)
V (Å³)	927.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.10 × 0.03 × 0.03

Data collection
Diffractometer	Rigaku Mercury2 CCD
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.910, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	9189, 2127, 1130
R_int	0.075
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.084, 0.285, 1.07
No. of reflections	2127
No. of parameters	95
No. of restraints	15
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.32

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1E···O1	0.90	1.90	2.800 (3)	174
N1—H1D···O1ⁱ	0.90	2.00	2.869 (3)	161

Symmetry code: (i) −x+3/2, y−1/2, −z+1/2.

Acknowledgements

This work was supported by the Doctoral Foundation of Southeast University, China.

References

Fu, D.-W., Zhang, W., Cai, H.-L., Zhang, Y., Ge, J.-Z., Xiong, R.-G., Huang, S. P. D. & Nakamura, T. (2011). Angew. Chem. Int. Ed. 50, 11947–11951. Web of Science CSD CrossRef CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xu, J. (2012). Acta Cryst. E68, o894. CSD CrossRef IUCr Journals Google Scholar