2-Hydroxy-N,N′-diisopropylpropane-1,3-diaminium dichloride

Hou, X.; Zhao, L.

doi:10.1107/S1600536810023585

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1766

doi:10.1107/S1600536810023585

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2-Hydroxy-N,N′-diisopropylpropane-1,3-diaminium dichloride

Xuehui Hou ^a ^* and Likui Zhao ^a

^aDepartment of Quality Detection and Management, Zhengzhou College of Animal Husbandry Engineering, Zhengzhou 450011, People's Republic of China
^*Correspondence e-mail: muzhi527@163.com

(Received 11 June 2010; accepted 17 June 2010; online 23 June 2010)

In the crystal structure of the title amino alcohol derivative, C₉H₂₄N₂O²⁺·2Cl⁻, the cations and anions are linked by intermolecular O—H⋯Cl and N—H⋯Cl hydrogen bonds into a three-dimensional network.

Related literature

For the applications of amino alcohols and their derivatives in organic synthesis, see: Ellison & Gandhi (2005 ); Li et al. (2004 ).

Experimental

Crystal data

C₉H₂₄N₂O²⁺·2Cl⁻
M_r = 247.20
Triclinic, $[P \overline 1]$
a = 6.240 (1) Å
b = 10.0081 (14) Å
c = 11.3519 (16) Å
α = 86.198 (1)°
β = 88.052 (2)°
γ = 83.308 (1)°
V = 702.31 (18) Å³
Z = 2
Mo Kα radiation
μ = 0.44 mm⁻¹
T = 298 K
0.50 × 0.45 × 0.44 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.810, T_max = 0.830
3684 measured reflections
2448 independent reflections
1999 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.096
S = 1.03
2448 reflections
131 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯Cl1ⁱ	0.82	2.33	3.1445 (15)	172
N2—H2B⋯Cl1ⁱ	0.90	2.24	3.1336 (15)	173
N2—H2A⋯Cl2ⁱⁱ	0.90	2.22	3.1130 (15)	172
N1—H1B⋯Cl2ⁱⁱⁱ	0.90	2.20	3.0920 (15)	174
N1—H1A⋯Cl1^iv	0.90	2.38	3.2119 (16)	154
Symmetry codes: (i) x, y, z-1; (ii) -x+1, -y+1, -z; (iii) x-1, y, z; (iv) -x, -y, -z+1.

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; 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/S1600536810023585/rz2467sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810023585/rz2467Isup2.hkl

checkCIF report

Comment top

Amino alcohols are important structural elements for the asymmetric catalysis of chiral ligands (Li et al., 2004) as well as of biologically active compounds (Ellison & Gandhi, 2005). In order to develop new applications for amino alcohols and their derivatives, structural modifications of these compounds have been extensively investigated. As a contribution in this filed, we report here the crystal structure of the title compound.

The molecular structure of the title compound is shown in Fig. 1. Bond lengths and angles in the cation are not unusual. In the crystal packing (Fig. 2), intermolecular O—H···Cl and N—H···Cl hydrogen bonds (Table 1) link molecules into a three-dimensional network.

Related literature top

For the applications of amino alcohols and their derivatives in organic synthesis, see: Ellison & Gandhi (2005); Li et al. (2004).

Experimental top

To a solution of isopropamide (24.0 g, 0.4 mol) in acetone (200 ml), epichlorohydrin (9.2 g, 0.1 mol) and K₂CO₃ (13.8 g, 0.1 mol) were added. The mixture was stirred at room temperature for 8 h, followed by filtration and purification by crystallization from ethyl acetate, giving title compound as colourless single crystals suitable for X-ray analysis.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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. The molecular structure of the compound, with atom labels and 50% probability displacement ellipsoids.
	Fig. 2. Crystal packing of the title compound. showing a three-dimensional structure linked by hydrogen bonds (dashed lines).

2-Hydroxy-N,N'-diisopropylpropane-1,3-diaminium dichloride top

Crystal data top

C₉H₂₄N₂O²⁺·2Cl⁻	Z = 2
M_r = 247.20	F(000) = 268
Triclinic, P1	D_x = 1.169 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.240 (1) Å	Cell parameters from 2066 reflections
b = 10.0081 (14) Å	θ = 2.6–27.6°
c = 11.3519 (16) Å	µ = 0.44 mm⁻¹
α = 86.198 (1)°	T = 298 K
β = 88.052 (2)°	Block, colourless
γ = 83.308 (1)°	0.50 × 0.45 × 0.44 mm
V = 702.31 (18) Å³

Data collection top

Siemens SMART CCD area-detector diffractometer	2448 independent reflections
Radiation source: fine-focus sealed tube	1999 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
phi and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→5
T_min = 0.810, T_max = 0.830	k = −11→11
3684 measured reflections	l = −13→10

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.048P)² + 0.1942P] where P = (F_o² + 2F_c²)/3
2448 reflections	(Δ/σ)_max < 0.001
131 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₉H₂₄N₂O²⁺·2Cl⁻	γ = 83.308 (1)°
M_r = 247.20	V = 702.31 (18) Å³
Triclinic, P1	Z = 2
a = 6.240 (1) Å	Mo Kα radiation
b = 10.0081 (14) Å	µ = 0.44 mm⁻¹
c = 11.3519 (16) Å	T = 298 K
α = 86.198 (1)°	0.50 × 0.45 × 0.44 mm
β = 88.052 (2)°

Data collection top

Siemens SMART CCD area-detector diffractometer	2448 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1999 reflections with I > 2σ(I)
T_min = 0.810, T_max = 0.830	R_int = 0.016
3684 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 1.03	Δρ_max = 0.25 e Å⁻³
2448 reflections	Δρ_min = −0.23 e Å⁻³
131 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	0.19859 (8)	0.04318 (5)	0.75891 (4)	0.04461 (17)
Cl2	0.73770 (9)	0.43851 (5)	0.17643 (6)	0.0585 (2)
N1	0.0878 (2)	0.20330 (14)	0.24284 (12)	0.0307 (3)
H1A	0.0376	0.1276	0.2223	0.037*
H1B	−0.0074	0.2733	0.2183	0.037*
N2	0.4576 (2)	0.26100 (14)	−0.14466 (12)	0.0302 (3)
H2A	0.3877	0.3447	−0.1542	0.036*
H2B	0.3742	0.2041	−0.1738	0.036*
O1	0.1777 (3)	0.09416 (15)	0.02964 (12)	0.0524 (4)
H1	0.1697	0.0850	−0.0413	0.079*
C1	0.2960 (3)	0.21572 (19)	0.17837 (16)	0.0345 (4)
H1C	0.4012	0.1409	0.2033	0.041*
H1D	0.3503	0.2987	0.1968	0.041*
C2	0.2656 (3)	0.21601 (17)	0.04656 (15)	0.0316 (4)
H2	0.1629	0.2932	0.0209	0.038*
C3	0.4813 (3)	0.22602 (19)	−0.01638 (16)	0.0355 (4)
H3A	0.5534	0.2942	0.0182	0.043*
H3B	0.5710	0.1405	−0.0051	0.043*
C4	0.0935 (3)	0.1991 (2)	0.37596 (16)	0.0394 (5)
H4	−0.0526	0.1880	0.4065	0.047*
C5	0.2409 (4)	0.0782 (2)	0.4228 (2)	0.0577 (6)
H5A	0.2060	−0.0012	0.3880	0.087*
H5B	0.2223	0.0675	0.5071	0.087*
H5C	0.3881	0.0913	0.4031	0.087*
C6	0.1505 (5)	0.3315 (2)	0.4160 (2)	0.0646 (7)
H6A	0.2959	0.3434	0.3908	0.097*
H6B	0.1385	0.3309	0.5006	0.097*
H6C	0.0534	0.4043	0.3821	0.097*
C7	0.6661 (3)	0.25586 (19)	−0.21644 (18)	0.0385 (4)
H7	0.7421	0.1646	−0.2069	0.046*
C8	0.8085 (3)	0.3540 (2)	−0.1736 (2)	0.0548 (6)
H8A	0.7330	0.4433	−0.1790	0.082*
H8B	0.9383	0.3518	−0.2216	0.082*
H8C	0.8445	0.3291	−0.0929	0.082*
C9	0.6110 (4)	0.2857 (3)	−0.34475 (19)	0.0578 (6)
H9A	0.5186	0.2223	−0.3678	0.087*
H9B	0.7412	0.2783	−0.3926	0.087*
H9C	0.5383	0.3754	−0.3554	0.087*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0475 (3)	0.0492 (3)	0.0417 (3)	−0.0200 (2)	0.0034 (2)	−0.0139 (2)
Cl2	0.0460 (3)	0.0349 (3)	0.0946 (5)	0.0039 (2)	−0.0206 (3)	−0.0090 (3)
N1	0.0315 (8)	0.0292 (8)	0.0316 (8)	−0.0018 (6)	−0.0026 (6)	−0.0046 (6)
N2	0.0298 (8)	0.0272 (7)	0.0345 (8)	−0.0060 (6)	−0.0002 (6)	−0.0043 (6)
O1	0.0714 (10)	0.0555 (9)	0.0375 (8)	−0.0341 (8)	0.0079 (7)	−0.0129 (7)
C1	0.0317 (10)	0.0387 (10)	0.0336 (10)	−0.0049 (8)	−0.0013 (8)	−0.0051 (8)
C2	0.0328 (10)	0.0309 (9)	0.0319 (10)	−0.0050 (7)	−0.0029 (8)	−0.0031 (7)
C3	0.0337 (10)	0.0371 (10)	0.0358 (10)	−0.0044 (8)	−0.0030 (8)	−0.0010 (8)
C4	0.0432 (11)	0.0474 (11)	0.0284 (10)	−0.0070 (9)	0.0023 (8)	−0.0065 (8)
C5	0.0689 (16)	0.0640 (15)	0.0370 (12)	0.0020 (12)	−0.0064 (11)	0.0072 (10)
C6	0.0913 (19)	0.0615 (15)	0.0450 (13)	−0.0129 (13)	−0.0062 (13)	−0.0226 (11)
C7	0.0317 (10)	0.0351 (10)	0.0479 (12)	−0.0020 (8)	0.0083 (8)	−0.0046 (9)
C8	0.0344 (11)	0.0639 (15)	0.0677 (15)	−0.0160 (10)	0.0017 (10)	0.0003 (12)
C9	0.0636 (15)	0.0685 (15)	0.0427 (13)	−0.0159 (12)	0.0136 (11)	−0.0068 (11)

Geometric parameters (Å, º) top

N1—C1	1.483 (2)	C4—C6	1.513 (3)
N1—C4	1.510 (2)	C4—H4	0.9800
N1—H1A	0.9000	C5—H5A	0.9600
N1—H1B	0.9000	C5—H5B	0.9600
N2—C3	1.483 (2)	C5—H5C	0.9600
N2—C7	1.509 (2)	C6—H6A	0.9600
N2—H2A	0.9000	C6—H6B	0.9600
N2—H2B	0.9000	C6—H6C	0.9600
O1—C2	1.421 (2)	C7—C9	1.510 (3)
O1—H1	0.8200	C7—C8	1.512 (3)
C1—C2	1.514 (2)	C7—H7	0.9800
C1—H1C	0.9700	C8—H8A	0.9600
C1—H1D	0.9700	C8—H8B	0.9600
C2—C3	1.513 (2)	C8—H8C	0.9600
C2—H2	0.9800	C9—H9A	0.9600
C3—H3A	0.9700	C9—H9B	0.9600
C3—H3B	0.9700	C9—H9C	0.9600
C4—C5	1.511 (3)

C1—N1—C4	116.24 (14)	N1—C4—H4	107.3
C1—N1—H1A	108.2	C5—C4—H4	107.3
C4—N1—H1A	108.2	C6—C4—H4	107.3
C1—N1—H1B	108.2	C4—C5—H5A	109.5
C4—N1—H1B	108.2	C4—C5—H5B	109.5
H1A—N1—H1B	107.4	H5A—C5—H5B	109.5
C3—N2—C7	115.27 (14)	C4—C5—H5C	109.5
C3—N2—H2A	108.5	H5A—C5—H5C	109.5
C7—N2—H2A	108.5	H5B—C5—H5C	109.5
C3—N2—H2B	108.5	C4—C6—H6A	109.5
C7—N2—H2B	108.5	C4—C6—H6B	109.5
H2A—N2—H2B	107.5	H6A—C6—H6B	109.5
C2—O1—H1	109.5	C4—C6—H6C	109.5
N1—C1—C2	110.12 (14)	H6A—C6—H6C	109.5
N1—C1—H1C	109.6	H6B—C6—H6C	109.5
C2—C1—H1C	109.6	N2—C7—C9	108.02 (16)
N1—C1—H1D	109.6	N2—C7—C8	110.37 (16)
C2—C1—H1D	109.6	C9—C7—C8	112.24 (18)
H1C—C1—H1D	108.1	N2—C7—H7	108.7
O1—C2—C3	113.58 (15)	C9—C7—H7	108.7
O1—C2—C1	105.22 (14)	C8—C7—H7	108.7
C3—C2—C1	108.81 (14)	C7—C8—H8A	109.5
O1—C2—H2	109.7	C7—C8—H8B	109.5
C3—C2—H2	109.7	H8A—C8—H8B	109.5
C1—C2—H2	109.7	C7—C8—H8C	109.5
N2—C3—C2	112.00 (14)	H8A—C8—H8C	109.5
N2—C3—H3A	109.2	H8B—C8—H8C	109.5
C2—C3—H3A	109.2	C7—C9—H9A	109.5
N2—C3—H3B	109.2	C7—C9—H9B	109.5
C2—C3—H3B	109.2	H9A—C9—H9B	109.5
H3A—C3—H3B	107.9	C7—C9—H9C	109.5
N1—C4—C5	110.60 (16)	H9A—C9—H9C	109.5
N1—C4—C6	110.44 (16)	H9B—C9—H9C	109.5
C5—C4—C6	113.51 (19)

C4—N1—C1—C2	178.96 (14)	C1—C2—C3—N2	−165.75 (14)
N1—C1—C2—O1	−56.87 (18)	C1—N1—C4—C5	−61.5 (2)
N1—C1—C2—C3	−178.91 (14)	C1—N1—C4—C6	65.0 (2)
C7—N2—C3—C2	−172.65 (14)	C3—N2—C7—C9	176.59 (16)
O1—C2—C3—N2	77.43 (19)	C3—N2—C7—C8	−60.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Cl1ⁱ	0.82	2.33	3.1445 (15)	172
N2—H2B···Cl1ⁱ	0.90	2.24	3.1336 (15)	173
N2—H2A···Cl2ⁱⁱ	0.90	2.22	3.1130 (15)	172
N1—H1B···Cl2ⁱⁱⁱ	0.90	2.20	3.0920 (15)	174
N1—H1A···Cl1^iv	0.90	2.38	3.2119 (16)	154

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

Experimental details

Crystal data
Chemical formula	C₉H₂₄N₂O²⁺·2Cl⁻
M_r	247.20
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	6.240 (1), 10.0081 (14), 11.3519 (16)
α, β, γ (°)	86.198 (1), 88.052 (2), 83.308 (1)
V (Å³)	702.31 (18)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.44
Crystal size (mm)	0.50 × 0.45 × 0.44

Data collection
Diffractometer	Siemens SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.810, 0.830
No. of measured, independent and observed [I > 2σ(I)] reflections	3684, 2448, 1999
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.096, 1.03
No. of reflections	2448
No. of parameters	131
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.23

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Cl1ⁱ	0.82	2.33	3.1445 (15)	171.5
N2—H2B···Cl1ⁱ	0.90	2.24	3.1336 (15)	173.2
N2—H2A···Cl2ⁱⁱ	0.90	2.22	3.1130 (15)	171.7
N1—H1B···Cl2ⁱⁱⁱ	0.90	2.20	3.0920 (15)	173.5
N1—H1A···Cl1^iv	0.90	2.38	3.2119 (16)	154.0

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

Acknowledgements

The authors gratefully acknowledge financial support from the National Natural Science Foundation of China (No. 20572103).

References

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