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ISSN: 2056-9890

Diiso­propyl­ammonium nitrite

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[Xu, J. (2012). Acta Cryst. E68, o894.]). For background to mol­ecular ferroelectric compounds, see: Fu et al. (2011[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.]).

[Scheme 1]

Experimental

Crystal data
  • C6H16N+·NO2

  • Mr = 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[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.910, Tmax = 1.000

  • 9189 measured reflections

  • 2127 independent reflections

  • 1130 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.50 e Å−3

  • Δρmin = −0.32 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


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.

Refinement top

All H atoms attached to C atoms were fixed geometrically and treated as riding with C-H = 0.98 Å(C methine) and C-H = 0.96 Å(C methyl) with Uiso(H) = 1.2Ueq(C methine) and Uiso(H) = 1.5Ueq(C methyl). The positional parameters of the H atoms (N) were refined freely. And in the last stage of the refinement, they were constrained with N—H = 0.90Å, and Uiso(H)=1.2Ueq(N).

Structure description 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).

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
[Figure 1] Fig. 1. A view of the title compound with displacement ellipsoids drawn at the 30% probability level.
[Figure 2] 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+·NO2F(000) = 328
Mr = 148.21Dx = 1.061 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2127 reflections
a = 8.2314 (16) Åθ = 3.6–27.5°
b = 7.7466 (15) ŵ = 0.08 mm1
c = 14.583 (3) ÅT = 298 K
β = 94.16 (3)°Block, colourless
V = 927.5 (3) Å30.10 × 0.03 × 0.03 mm
Z = 4
Data collection top
Rigaku Mercury2 CCD
diffractometer
2127 independent reflections
Radiation source: fine-focus sealed tube1130 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.075
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.6°
CCD profile fitting scansh = 1010
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
k = 1010
Tmin = 0.910, Tmax = 1.000l = 1818
9189 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.084Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.285H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.1379P)2 + 0.0979P]
where P = (Fo2 + 2Fc2)/3
2127 reflections(Δ/σ)max < 0.001
95 parametersΔρmax = 0.50 e Å3
15 restraintsΔρmin = 0.32 e Å3
Crystal data top
C6H16N+·NO2V = 927.5 (3) Å3
Mr = 148.21Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.2314 (16) ŵ = 0.08 mm1
b = 7.7466 (15) ÅT = 298 K
c = 14.583 (3) Å0.10 × 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)
Tmin = 0.910, Tmax = 1.000Rint = 0.075
9189 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.08415 restraints
wR(F2) = 0.285H-atom parameters constrained
S = 1.07Δρmax = 0.50 e Å3
2127 reflectionsΔρmin = 0.32 e Å3
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
xyzUiso*/Ueq
N10.6713 (3)0.1958 (3)0.35567 (15)0.0543 (7)
H1D0.69500.08250.35430.065*
H1E0.68900.23930.30000.065*
C20.4930 (4)0.2132 (4)0.3690 (2)0.0624 (9)
H2A0.47330.17020.43040.075*
O10.7263 (3)0.3533 (3)0.18791 (17)0.0931 (9)
C50.7889 (4)0.2792 (4)0.4247 (2)0.0686 (9)
H5A0.76760.40370.42550.082*
N20.7438 (4)0.2425 (4)0.1320 (2)0.0925 (9)
O20.8050 (4)0.2847 (5)0.0648 (2)0.1177 (10)
C60.7724 (5)0.2066 (6)0.5196 (2)0.0918 (12)
H6A0.66420.22770.53760.138*
H6B0.85000.26140.56260.138*
H6C0.79250.08460.51920.138*
C30.3999 (4)0.1012 (6)0.2986 (3)0.0909 (12)
H3A0.44090.01480.30320.136*
H3B0.41330.14530.23810.136*
H3C0.28650.10170.30990.136*
C40.9579 (5)0.2488 (7)0.3938 (3)0.1037 (14)
H4A0.97000.30990.33740.156*
H4B0.97360.12750.38410.156*
H4C1.03740.28950.44020.156*
C10.4425 (5)0.3998 (5)0.3631 (3)0.0941 (13)
H1A0.50250.46430.41040.141*
H1B0.32800.40890.37100.141*
H1C0.46460.44520.30400.141*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0532 (15)0.0552 (13)0.0547 (13)0.0026 (10)0.0053 (10)0.0051 (10)
C20.0558 (19)0.0711 (19)0.0611 (17)0.0005 (14)0.0101 (14)0.0032 (14)
O10.1178 (19)0.0879 (17)0.0762 (14)0.0013 (13)0.0258 (13)0.0032 (11)
C50.063 (2)0.0582 (17)0.082 (2)0.0024 (14)0.0121 (16)0.0038 (15)
N20.116 (2)0.0955 (18)0.0689 (15)0.0076 (14)0.0293 (14)0.0001 (13)
O20.145 (2)0.126 (2)0.0854 (16)0.0130 (16)0.0308 (15)0.0006 (14)
C60.102 (3)0.110 (3)0.061 (2)0.003 (2)0.0109 (18)0.005 (2)
C30.061 (2)0.114 (3)0.097 (3)0.0143 (19)0.0022 (19)0.014 (2)
C40.056 (2)0.142 (4)0.111 (3)0.011 (2)0.003 (2)0.025 (3)
C10.068 (2)0.089 (3)0.125 (3)0.0240 (19)0.006 (2)0.003 (2)
Geometric parameters (Å, º) top
N1—C51.492 (4)C6—H6A0.9600
N1—C21.500 (4)C6—H6B0.9600
N1—H1D0.9000C6—H6C0.9600
N1—H1E0.9000C3—H3A0.9600
C2—C11.505 (5)C3—H3B0.9600
C2—C31.509 (5)C3—H3C0.9600
C2—H2A0.9800C4—H4A0.9600
O1—N21.200 (4)C4—H4B0.9600
C5—C61.510 (5)C4—H4C0.9600
C5—C41.512 (5)C1—H1A0.9600
C5—H5A0.9800C1—H1B0.9600
N2—O21.181 (4)C1—H1C0.9600
C5—N1—C2117.8 (2)C5—C6—H6C109.5
C5—N1—H1D107.9H6A—C6—H6C109.5
C2—N1—H1D107.9H6B—C6—H6C109.5
C5—N1—H1E107.9C2—C3—H3A109.5
C2—N1—H1E107.9C2—C3—H3B109.5
H1D—N1—H1E107.2H3A—C3—H3B109.5
N1—C2—C1110.4 (3)C2—C3—H3C109.5
N1—C2—C3108.2 (2)H3A—C3—H3C109.5
C1—C2—C3112.9 (3)H3B—C3—H3C109.5
N1—C2—H2A108.4C5—C4—H4A109.5
C1—C2—H2A108.4C5—C4—H4B109.5
C3—C2—H2A108.4H4A—C4—H4B109.5
N1—C5—C6111.1 (3)C5—C4—H4C109.5
N1—C5—C4107.3 (3)H4A—C4—H4C109.5
C6—C5—C4111.2 (3)H4B—C4—H4C109.5
N1—C5—H5A109.1C2—C1—H1A109.5
C6—C5—H5A109.1C2—C1—H1B109.5
C4—C5—H5A109.1H1A—C1—H1B109.5
O2—N2—O1116.4 (4)C2—C1—H1C109.5
C5—C6—H6A109.5H1A—C1—H1C109.5
C5—C6—H6B109.5H1B—C1—H1C109.5
H6A—C6—H6B109.5
C5—N1—C2—C163.0 (3)C2—N1—C5—C660.4 (3)
C5—N1—C2—C3173.0 (3)C2—N1—C5—C4177.8 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1E···O10.901.902.800 (3)174
N1—H1D···O1i0.902.002.869 (3)161
Symmetry code: (i) x+3/2, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC6H16N+·NO2
Mr148.21
Crystal system, space groupMonoclinic, P21/n
Temperature (K)298
a, b, c (Å)8.2314 (16), 7.7466 (15), 14.583 (3)
β (°) 94.16 (3)
V3)927.5 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.10 × 0.03 × 0.03
Data collection
DiffractometerRigaku Mercury2 CCD
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.910, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
9189, 2127, 1130
Rint0.075
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.084, 0.285, 1.07
No. of reflections2127
No. of parameters95
No. of restraints15
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N1—H1E···O10.901.902.800 (3)174
N1—H1D···O1i0.902.002.869 (3)161
Symmetry code: (i) x+3/2, y1/2, z+1/2.
 

Acknowledgements

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

References

First citationFu, 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
First citationRigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationXu, J. (2012). Acta Cryst. E68, o894.  CSD CrossRef IUCr Journals Google Scholar

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ISSN: 2056-9890
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