Diisopropyl­ammonium thio­cyanate

Xu, J.

doi:10.1107/S1600536812007349

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o894

doi:10.1107/S1600536812007349

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Diisopropylammonium thiocyanate

Jie Xu ^a ^*

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

(Received 13 February 2012; accepted 18 February 2012; online 29 February 2012)

In the title molecular salt, C₆H₁₆N⁺·NCS⁻, the cation possesses approximate local twofold rotation symmetry. One of its NH atoms forms a hydrogen bond to a thiocyanate N atom and the other to a thiocyanate S atom. This results in [001] chains of alternating cations and anions.

Related literature

For background to molecular ferroelectrics, see: Fu et al. (2011 ).

Experimental

Crystal data

C₆H₁₆N⁺·NCS⁻
M_r = 160.28
Orthorhombic, P b c a
a = 11.785 (2) Å
b = 12.716 (3) Å
c = 13.288 (3) Å
V = 1991.3 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 298 K
0.20 × 0.05 × 0.05 mm

Data collection

Rigaku Mercury2 CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.90, T_max = 1.00
19260 measured reflections
2286 independent reflections
1864 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.107
S = 1.12
2286 reflections
96 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2D⋯N1ⁱ	0.90	1.99	2.888 (2)	172
N2—H2E⋯S1	0.90	2.47	3.3490 (14)	166
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812007349/hb6639sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812007349/hb6639Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812007349/hb6639Isup3.cml

checkCIF report

Comment top

Simple organic salts containig amino cations have attracted attention as materials that display ferroelectric-paraelectric phase transitions (Fu et al., 2011). As part of our ongonig studies in this area, we now present the crystal structure of the title compound, di-isopropylammonium thiocyanate.

The asymmetric unit of the title compound contains one di-isopropylammonium cation and one SCN^- anion (Fig. 1). The amine N2 atom was protonated. The SCN^- anion is almost linear with the bond angle of 179.80 (2)°. The 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···N and N—H···S H-bonding interactions with the N and S atoms of the SCN^- anion (with N···N and N···S distances of 2.888 (2)Å to 3.349 (2)Å, respectively). These hydrogen bonds link the ionic units into a one-dimentional chain along the c-axis (Table 1 and Fig.2).

Related literature top

For background to molecular ferroelectrics, see: Fu et al. (2011).

Experimental top

A mixture of di-isopropylamine (0.8 mmol), HCl (0.8 mmol) and KSCN (0.8 mmol) were dissolved in EtOH/distilled water (1:1 v/v) solvent. The solution was slowly evaporated in air affording colourless blocks.

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 c axis (dashed line). H atoms not involved in hydrogen bonding (dashed line) have been omitted for clarity.

Diisopropylammonium thiocyanate top

Crystal data top

C₆H₁₆N⁺·NCS⁻	F(000) = 704
M_r = 160.28	D_x = 1.069 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2286 reflections
a = 11.785 (2) Å	θ = 3.1–27.5°
b = 12.716 (3) Å	µ = 0.27 mm⁻¹
c = 13.288 (3) Å	T = 298 K
V = 1991.3 (7) Å³	Block, colourless
Z = 8	0.20 × 0.05 × 0.05 mm

Data collection top

Rigaku Mercury2 CCD diffractometer	2286 independent reflections
Radiation source: fine-focus sealed tube	1864 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
CCD profile fitting scans	h = −15→15
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −16→16
T_min = 0.90, T_max = 1.00	l = −17→17
19260 measured reflections

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)] = 0.045	H-atom parameters constrained
wR(F²) = 0.107	w = 1/[σ²(F_o²) + (0.0402P)² + 0.4971P] where P = (F_o² + 2F_c²)/3
S = 1.12	(Δ/σ)_max < 0.001
2286 reflections	Δρ_max = 0.18 e Å⁻³
96 parameters	Δρ_min = −0.15 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.044 (3)

Crystal data top

C₆H₁₆N⁺·NCS⁻	V = 1991.3 (7) Å³
M_r = 160.28	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 11.785 (2) Å	µ = 0.27 mm⁻¹
b = 12.716 (3) Å	T = 298 K
c = 13.288 (3) Å	0.20 × 0.05 × 0.05 mm

Data collection top

Rigaku Mercury2 CCD diffractometer	2286 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1864 reflections with I > 2σ(I)
T_min = 0.90, T_max = 1.00	R_int = 0.051
19260 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.107	H-atom parameters constrained
S = 1.12	Δρ_max = 0.18 e Å⁻³
2286 reflections	Δρ_min = −0.15 e Å⁻³
96 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
N2	0.42899 (11)	0.17785 (9)	0.36893 (10)	0.0400 (3)
H2D	0.3915	0.2112	0.3193	0.048*
H2E	0.3769	0.1567	0.4141	0.048*
C3	0.48334 (15)	0.08132 (13)	0.32473 (13)	0.0476 (4)
H3A	0.5226	0.0434	0.3787	0.057*
C5	0.57312 (16)	0.20499 (14)	0.50250 (15)	0.0551 (5)
H5A	0.6217	0.1522	0.4741	0.083*
H5B	0.5224	0.1729	0.5500	0.083*
H5C	0.6184	0.2571	0.5361	0.083*
C6	0.50507 (15)	0.25665 (13)	0.41958 (13)	0.0471 (4)
H6A	0.5578	0.2850	0.3694	0.056*
C7	0.4316 (2)	0.34550 (15)	0.45802 (16)	0.0666 (6)
H7A	0.3883	0.3743	0.4033	0.100*
H7B	0.4788	0.3994	0.4864	0.100*
H7C	0.3809	0.3193	0.5087	0.100*
C4	0.3906 (2)	0.01151 (17)	0.28384 (17)	0.0727 (6)
H4A	0.4231	−0.0530	0.2598	0.109*
H4B	0.3527	0.0467	0.2294	0.109*
H4C	0.3369	−0.0036	0.3363	0.109*
C2	0.5690 (2)	0.1114 (2)	0.24603 (18)	0.0774 (7)
H2A	0.6292	0.1508	0.2768	0.116*
H2B	0.5330	0.1536	0.1954	0.116*
H2C	0.5996	0.0490	0.2157	0.116*
S1	0.26970 (4)	0.06903 (3)	0.54981 (3)	0.04839 (18)
N1	0.32617 (17)	0.20204 (15)	0.70857 (14)	0.0754 (6)
C1	0.30276 (14)	0.14704 (14)	0.64316 (13)	0.0459 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N2	0.0425 (7)	0.0407 (7)	0.0369 (7)	0.0020 (6)	−0.0008 (6)	0.0052 (6)
C3	0.0555 (10)	0.0441 (9)	0.0432 (9)	0.0098 (8)	−0.0096 (8)	−0.0048 (7)
C5	0.0523 (10)	0.0544 (11)	0.0586 (11)	−0.0096 (8)	−0.0106 (9)	−0.0078 (9)
C6	0.0553 (10)	0.0370 (8)	0.0489 (9)	−0.0081 (7)	0.0062 (8)	0.0020 (7)
C7	0.0863 (15)	0.0420 (10)	0.0714 (14)	0.0048 (10)	0.0026 (11)	−0.0043 (9)
C4	0.0806 (15)	0.0675 (13)	0.0700 (14)	−0.0024 (11)	−0.0161 (11)	−0.0230 (11)
C2	0.0745 (15)	0.0887 (16)	0.0690 (14)	0.0145 (12)	0.0166 (11)	−0.0150 (13)
S1	0.0527 (3)	0.0463 (3)	0.0462 (3)	−0.00456 (19)	0.00129 (19)	−0.00236 (19)
N1	0.0879 (14)	0.0808 (12)	0.0576 (11)	−0.0223 (11)	−0.0029 (9)	−0.0157 (9)
C1	0.0422 (9)	0.0503 (10)	0.0451 (9)	−0.0037 (7)	0.0023 (7)	0.0037 (8)

Geometric parameters (Å, º) top

N2—C6	1.504 (2)	C6—H6A	0.9800
N2—C3	1.504 (2)	C7—H7A	0.9600
N2—H2D	0.9000	C7—H7B	0.9600
N2—H2E	0.9000	C7—H7C	0.9600
C3—C2	1.503 (3)	C4—H4A	0.9600
C3—C4	1.509 (3)	C4—H4B	0.9600
C3—H3A	0.9800	C4—H4C	0.9600
C5—C6	1.513 (2)	C2—H2A	0.9600
C5—H5A	0.9600	C2—H2B	0.9600
C5—H5B	0.9600	C2—H2C	0.9600
C5—H5C	0.9600	S1—C1	1.6354 (19)
C6—C7	1.512 (3)	N1—C1	1.149 (2)

C6—N2—C3	117.69 (13)	C7—C6—H6A	108.6
C6—N2—H2D	107.9	C5—C6—H6A	108.6
C3—N2—H2D	107.9	C6—C7—H7A	109.5
C6—N2—H2E	107.9	C6—C7—H7B	109.5
C3—N2—H2E	107.9	H7A—C7—H7B	109.5
H2D—N2—H2E	107.2	C6—C7—H7C	109.5
C2—C3—N2	110.49 (15)	H7A—C7—H7C	109.5
C2—C3—C4	112.70 (17)	H7B—C7—H7C	109.5
N2—C3—C4	108.19 (15)	C3—C4—H4A	109.5
C2—C3—H3A	108.5	C3—C4—H4B	109.5
N2—C3—H3A	108.5	H4A—C4—H4B	109.5
C4—C3—H3A	108.5	C3—C4—H4C	109.5
C6—C5—H5A	109.5	H4A—C4—H4C	109.5
C6—C5—H5B	109.5	H4B—C4—H4C	109.5
H5A—C5—H5B	109.5	C3—C2—H2A	109.5
C6—C5—H5C	109.5	C3—C2—H2B	109.5
H5A—C5—H5C	109.5	H2A—C2—H2B	109.5
H5B—C5—H5C	109.5	C3—C2—H2C	109.5
N2—C6—C7	107.91 (15)	H2A—C2—H2C	109.5
N2—C6—C5	110.65 (13)	H2B—C2—H2C	109.5
C7—C6—C5	112.46 (16)	N1—C1—S1	179.8 (2)
N2—C6—H6A	108.6

C6—N2—C3—C2	−59.45 (19)	C3—N2—C6—C7	−179.73 (14)
C6—N2—C3—C4	176.74 (15)	C3—N2—C6—C5	−56.31 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2D···N1ⁱ	0.90	1.99	2.888 (2)	172
N2—H2E···S1	0.90	2.47	3.3490 (14)	166

Symmetry code: (i) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₆H₁₆N⁺·NCS⁻
M_r	160.28
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	11.785 (2), 12.716 (3), 13.288 (3)
V (Å³)	1991.3 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
Crystal size (mm)	0.20 × 0.05 × 0.05

Data collection
Diffractometer	Rigaku Mercury2 CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.90, 1.00
No. of measured, independent and observed [I > 2σ(I)] reflections	19260, 2286, 1864
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.107, 1.12
No. of reflections	2286
No. of parameters	96
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.15

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
N2—H2D···N1ⁱ	0.90	1.99	2.888 (2)	172
N2—H2E···S1	0.90	2.47	3.3490 (14)	166

Symmetry code: (i) x, −y+1/2, z−1/2.

Acknowledgements

This work was supported by the Excellent Doctoral Dissertation Fund of Southeast University, China.

References

Fu, D.-W., Zhang, W., Cai, H.-L., Ge, J.-Z., Zhang, Y. & Xiong, R.-G. (2011). Adv. Mater. 23, 5658–5662. Web of Science CSD CrossRef CAS PubMed 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