(1R,2R)-2-(Pyridin-4-yl­methyl­amino)­cyclo­hexa­naminium chloride

Cheng, L.; Zhang, L.-M.; Wang, J.-Q.

doi:10.1107/S1600536811005526

organic compounds

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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page o676

doi:10.1107/S1600536811005526

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(1R,2R)-2-(Pyridin-4-ylmethylamino)cyclohexanaminium chloride

Lin Cheng,^a ^* Li-Min Zhang ^a and Jian-Quan Wang ^a

^aDepartment of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: cep02chl@yahoo.com.cn

(Received 11 February 2011; accepted 15 February 2011; online 19 February 2011)

In the crystal structure of the title compound, C₁₂H₂₀N₃⁺·Cl⁻, the protonated (1R,2R)-(pyridin-4-ylmethyl)cyclohexane-1,2-diamine cations and chloride anions are linked via N—H⋯N and N—H⋯Cl hydrogen bonds into a three-dimensional network.

Related literature

For coordination polymers, see: He et al. (2010 ). For related structures, see: Gou et al. (2010 ).

Experimental

Crystal data

C₁₂H₂₀N₃⁺·Cl⁻
M_r = 241.76
Orthorhombic, P 2₁ 2₁ 2₁
a = 5.5256 (10) Å
b = 13.928 (2) Å
c = 16.685 (3) Å
V = 1284.1 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 291 K
0.25 × 0.20 × 0.18 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1995 ) T_min = 0.934, T_max = 0.952
5296 measured reflections
2516 independent reflections
2259 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.102
S = 1.06
2516 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.24 e Å⁻³
Absolute structure: Flack (1983 ), 1031 Friedel pairs
Flack parameter: −0.04 (8)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯N3ⁱ	0.89	2.13	2.926 (2)	148
N1—H1C⋯Cl1	0.89	2.32	3.201 (2)	172
N1—H1D⋯Cl1ⁱⁱ	0.89	2.28	3.1583 (19)	170
N2—H2C⋯Cl1ⁱⁱⁱ	0.89	2.72	3.5538 (19)	157
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y-{\script{3\over 2}}, -z-1]$ ; (ii) x-1, y, z; (iii) $[-x+1, y-{\script{1\over 2}}, -z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT-Plus (Bruker, 2000); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811005526/bt5470sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811005526/bt5470Isup2.hkl

checkCIF report

Comment top

Recent years have witnessed an explosion of great interest in chiral coordination polymers because of their potential utility in enantiomerically selective catalysis and separations, second-order nonlinearoptical (NLO) applications and magnetism (He et al. 2010). We tried to synthesize such polymers by use of chiral (1R,2R)-(pyridin-4-ylmethyl)cyclohexane-1,2-diamine ligand and zinc chloride. However, Zn(II) ions weren't ligated to the chiral ligands and the hydrochloride of the ligand has been obtained in the reaction conditions. Herein, we report the structure of this hydrochloride, 1.HCl [1 = (1R,2R)-(pyridin-4-ylmethyl)cyclohexane-1,2-diamine].

The asymmetric unit of the title compound contains a protonated (1R,2R)-(pyridin-4-ylmethyl)cyclohexane-1,2-diamine and a chloride ion. In the molecule, the distances of the C—N bonds of the pyridine ring are 1.331 (3) and 1.338 (3) Å, which are shorter than those of C—N bonds (1.452 (3), 1.478 (2) and 1.498 (2) Å) of cyclohexane-1,2-diamine. The protonated (1R,2R)-(pyridin-4-ylmethyl)cyclohexane-1,2-diamine cations and chloride anions are linked to each other, via N—H···N (N1···N3a 2.926 (2) Å, symmetry code: a, -1/2 + x, -3/2 - y, -1 - z) and N—H···Cl (N1···Cl1 3.201 (2) Å, N1···Cl1b 3.158 (2) Å, symmetry code: b, -1 + x, y, z) hydrogen bonds between the N atoms of aminium and the N atoms of adjacent pyridine rings, as well as the N atoms of aminium and chloride anions into a one-dimensional hydrogen bonding chain along the a axis (Fig.2), which are further constructed into a three-dimensional supramolecular network by interchain N—H···Cl hydrogen-bonds (N2···Cl1c 3.554 (2) Å, symmetry code: c, 1 - x, -1/2 + y, -1/2 - z) between secondary amines and chloride anions.

Related literature top

For coordination polymers, see: He et al. (2010). For related structures, see: Gou et al. (2010).

Experimental top

1R,2R)-(pyridin-4-ylmethyl)cyclohexane-1,2-diamine (0.021 g, 0.1 mmol) dissolved in water (5 ml) was added to a methanol solution (10 ml) ZnCl₂ (0.019 g, 0.1 mmol). The mixture solution was stirred for 2 h at room temperature and then filtered. The filtrate was allowed to evaporate slowly at room temperature. After 2 weeks, colorless block crystals were obtained in 33.1% yield (0.008 g).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT-Plus (Bruker, 2000); data reduction: SAINT-Plus (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. View of the asymmetric unit of the title compoundcompound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. View of the one-dimesional hydrogen bonding chain along the a axis.
	Fig. 3. View of the three-dimensional supramolecular network along the bc plane.

(1R,2R)-2-(Pyridin-4-ylmethylamino)cyclohexanaminium chloride top

Crystal data top

C₁₂H₂₀N₃⁺·Cl⁻	F(000) = 520
M_r = 241.76	D_x = 1.251 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 780 reflections
a = 5.5256 (10) Å	θ = 2.5–28.0°
b = 13.928 (2) Å	µ = 0.28 mm⁻¹
c = 16.685 (3) Å	T = 291 K
V = 1284.1 (4) Å³	Block, colorless
Z = 4	0.25 × 0.20 × 0.18 mm

Data collection top

Bruker SMART APEX CCD diffractometer	2516 independent reflections
Radiation source: fine-focus sealed tube	2259 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1995)	h = −6→6
T_min = 0.934, T_max = 0.952	k = −17→16
5296 measured reflections	l = −6→20

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)] = 0.041	H-atom parameters constrained
wR(F²) = 0.102	w = 1/[σ²(F_o²) + (0.0552P)² + 0.1405P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2516 reflections	Δρ_max = 0.26 e Å⁻³
145 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1031 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.04 (8)

Crystal data top

C₁₂H₂₀N₃⁺·Cl⁻	V = 1284.1 (4) Å³
M_r = 241.76	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 5.5256 (10) Å	µ = 0.28 mm⁻¹
b = 13.928 (2) Å	T = 291 K
c = 16.685 (3) Å	0.25 × 0.20 × 0.18 mm

Data collection top

Bruker SMART APEX CCD diffractometer	2516 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1995)	2259 reflections with I > 2σ(I)
T_min = 0.934, T_max = 0.952	R_int = 0.019
5296 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.102	Δρ_max = 0.26 e Å⁻³
S = 1.06	Δρ_min = −0.24 e Å⁻³
2516 reflections	Absolute structure: Flack (1983), 1031 Friedel pairs
145 parameters	Absolute structure parameter: −0.04 (8)
0 restraints

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	0.80278 (10)	−0.57398 (4)	−0.18879 (4)	0.05595 (19)
C1	0.2910 (4)	−0.76369 (13)	−0.19230 (10)	0.0334 (4)
H1A	0.1413	−0.7975	−0.2063	0.040*
C2	0.2862 (4)	−0.74096 (15)	−0.10296 (10)	0.0411 (5)
H2A	0.4249	−0.7015	−0.0894	0.049*
H2B	0.1410	−0.7048	−0.0905	0.049*
C3	0.2912 (5)	−0.83212 (16)	−0.05335 (12)	0.0500 (6)
H3A	0.2945	−0.8158	0.0032	0.060*
H3B	0.1459	−0.8692	−0.0636	0.060*
C4	0.5108 (5)	−0.89136 (16)	−0.07397 (12)	0.0489 (6)
H4A	0.5090	−0.9502	−0.0429	0.059*
H4B	0.6559	−0.8560	−0.0599	0.059*
C5	0.5163 (5)	−0.91576 (15)	−0.16282 (12)	0.0464 (5)
H5A	0.3803	−0.9571	−0.1754	0.056*
H5B	0.6636	−0.9509	−0.1746	0.056*
C6	0.5051 (4)	−0.82635 (13)	−0.21600 (10)	0.0341 (4)
H6A	0.6531	−0.7892	−0.2067	0.041*
C7	0.7097 (5)	−0.89100 (19)	−0.33387 (12)	0.0534 (6)
H7A	0.7163	−0.9575	−0.3168	0.064*
H7B	0.8493	−0.8583	−0.3116	0.064*
C8	0.7219 (4)	−0.88678 (13)	−0.42405 (11)	0.0371 (5)
C9	0.9147 (4)	−0.84386 (15)	−0.46266 (14)	0.0439 (5)
H9A	1.0437	−0.8198	−0.4330	0.053*
C10	0.9160 (5)	−0.83668 (16)	−0.54485 (14)	0.0476 (6)
H10A	1.0495	−0.8084	−0.5693	0.057*
C11	0.5538 (4)	−0.91212 (16)	−0.55406 (12)	0.0447 (5)
H11A	0.4288	−0.9367	−0.5852	0.054*
C12	0.5397 (4)	−0.92329 (16)	−0.47230 (12)	0.0432 (5)
H12A	0.4087	−0.9551	−0.4495	0.052*
N1	0.2983 (3)	−0.67078 (11)	−0.23746 (9)	0.0377 (4)
H1B	0.3011	−0.6827	−0.2899	0.057*
H1C	0.4305	−0.6382	−0.2237	0.057*
H1D	0.1676	−0.6362	−0.2256	0.057*
N2	0.4907 (3)	−0.84717 (12)	−0.30272 (9)	0.0380 (4)
H2C	0.3781	−0.8927	−0.3056	0.057*
N3	0.7369 (4)	−0.86795 (12)	−0.59140 (10)	0.0447 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0377 (3)	0.0491 (3)	0.0811 (4)	0.0058 (3)	−0.0025 (3)	0.0005 (3)
C1	0.0329 (9)	0.0365 (9)	0.0309 (9)	0.0019 (8)	0.0000 (9)	0.0007 (7)
C2	0.0437 (12)	0.0489 (11)	0.0308 (9)	0.0119 (11)	0.0016 (9)	−0.0052 (8)
C3	0.0536 (13)	0.0626 (14)	0.0340 (10)	0.0020 (13)	0.0029 (10)	0.0052 (10)
C4	0.0653 (16)	0.0475 (12)	0.0340 (10)	0.0102 (12)	−0.0032 (11)	0.0073 (9)
C5	0.0638 (15)	0.0375 (11)	0.0379 (10)	0.0082 (12)	−0.0023 (10)	−0.0008 (9)
C6	0.0363 (11)	0.0359 (10)	0.0301 (9)	0.0041 (9)	−0.0018 (8)	−0.0026 (7)
C7	0.0519 (13)	0.0710 (15)	0.0372 (10)	0.0208 (13)	0.0009 (10)	−0.0047 (10)
C8	0.0406 (12)	0.0354 (10)	0.0353 (9)	0.0088 (9)	0.0034 (9)	−0.0056 (8)
C9	0.0408 (12)	0.0395 (11)	0.0514 (12)	−0.0010 (10)	−0.0041 (10)	−0.0065 (10)
C10	0.0457 (13)	0.0437 (12)	0.0532 (13)	−0.0009 (10)	0.0117 (11)	0.0075 (10)
C11	0.0435 (12)	0.0491 (12)	0.0414 (11)	−0.0011 (11)	−0.0022 (9)	−0.0093 (10)
C12	0.0382 (11)	0.0475 (12)	0.0439 (11)	−0.0031 (11)	0.0072 (9)	−0.0033 (10)
N1	0.0384 (9)	0.0403 (9)	0.0344 (8)	0.0069 (8)	−0.0010 (7)	−0.0009 (7)
N2	0.0415 (10)	0.0421 (9)	0.0304 (8)	0.0065 (8)	0.0013 (8)	−0.0049 (7)
N3	0.0506 (12)	0.0458 (10)	0.0377 (8)	0.0048 (9)	0.0064 (8)	−0.0002 (7)

Geometric parameters (Å, º) top

C1—N1	1.498 (2)	C7—N2	1.452 (3)
C1—C6	1.523 (3)	C7—C8	1.507 (3)
C1—C2	1.524 (2)	C7—H7A	0.9700
C1—H1A	0.9800	C7—H7B	0.9700
C2—C3	1.516 (3)	C8—C9	1.381 (3)
C2—H2A	0.9700	C8—C12	1.386 (3)
C2—H2B	0.9700	C9—C10	1.375 (3)
C3—C4	1.507 (3)	C9—H9A	0.9300
C3—H3A	0.9700	C10—N3	1.331 (3)
C3—H3B	0.9700	C10—H10A	0.9300
C4—C5	1.521 (3)	C11—N3	1.338 (3)
C4—H4A	0.9700	C11—C12	1.375 (3)
C4—H4B	0.9700	C11—H11A	0.9300
C5—C6	1.530 (3)	C12—H12A	0.9300
C5—H5A	0.9700	N1—H1B	0.8900
C5—H5B	0.9700	N1—H1C	0.8900
C6—N2	1.478 (2)	N1—H1D	0.8900
C6—H6A	0.9800	N2—H2C	0.8899

N1—C1—C6	110.08 (15)	C1—C6—H6A	107.7
N1—C1—C2	108.24 (14)	C5—C6—H6A	107.7
C6—C1—C2	112.74 (16)	N2—C7—C8	112.22 (19)
N1—C1—H1A	108.6	N2—C7—H7A	109.2
C6—C1—H1A	108.6	C8—C7—H7A	109.2
C2—C1—H1A	108.6	N2—C7—H7B	109.2
C3—C2—C1	111.09 (16)	C8—C7—H7B	109.2
C3—C2—H2A	109.4	H7A—C7—H7B	107.9
C1—C2—H2A	109.4	C9—C8—C12	116.63 (18)
C3—C2—H2B	109.4	C9—C8—C7	121.1 (2)
C1—C2—H2B	109.4	C12—C8—C7	122.2 (2)
H2A—C2—H2B	108.0	C10—C9—C8	120.1 (2)
C4—C3—C2	110.41 (19)	C10—C9—H9A	120.0
C4—C3—H3A	109.6	C8—C9—H9A	120.0
C2—C3—H3A	109.6	N3—C10—C9	123.6 (2)
C4—C3—H3B	109.6	N3—C10—H10A	118.2
C2—C3—H3B	109.6	C9—C10—H10A	118.2
H3A—C3—H3B	108.1	N3—C11—C12	123.8 (2)
C3—C4—C5	111.15 (19)	N3—C11—H11A	118.1
C3—C4—H4A	109.4	C12—C11—H11A	118.1
C5—C4—H4A	109.4	C11—C12—C8	119.6 (2)
C3—C4—H4B	109.4	C11—C12—H12A	120.2
C5—C4—H4B	109.4	C8—C12—H12A	120.2
H4A—C4—H4B	108.0	C1—N1—H1B	109.5
C4—C5—C6	112.48 (16)	C1—N1—H1C	109.5
C4—C5—H5A	109.1	H1B—N1—H1C	109.5
C6—C5—H5A	109.1	C1—N1—H1D	109.5
C4—C5—H5B	109.1	H1B—N1—H1D	109.5
C6—C5—H5B	109.1	H1C—N1—H1D	109.5
H5A—C5—H5B	107.8	C7—N2—C6	112.84 (16)
N2—C6—C1	108.96 (15)	C7—N2—H2C	105.3
N2—C6—C5	114.22 (15)	C6—N2—H2C	103.3
C1—C6—C5	110.31 (16)	C10—N3—C11	116.16 (17)
N2—C6—H6A	107.7

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···N3ⁱ	0.89	2.13	2.926 (2)	148
N1—H1C···Cl1	0.89	2.32	3.201 (2)	172
N1—H1D···Cl1ⁱⁱ	0.89	2.28	3.1583 (19)	170
N2—H2C···Cl1ⁱⁱⁱ	0.89	2.72	3.5538 (19)	157

Symmetry codes: (i) x−1/2, −y−3/2, −z−1; (ii) x−1, y, z; (iii) −x+1, y−1/2, −z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₂₀N₃⁺·Cl⁻
M_r	241.76
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	291
a, b, c (Å)	5.5256 (10), 13.928 (2), 16.685 (3)
V (Å³)	1284.1 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.25 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1995)
T_min, T_max	0.934, 0.952
No. of measured, independent and observed [I > 2σ(I)] reflections	5296, 2516, 2259
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.102, 1.06
No. of reflections	2516
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.24
Absolute structure	Flack (1983), 1031 Friedel pairs
Absolute structure parameter	−0.04 (8)

Computer programs: SMART (Bruker, 2000), SAINT-Plus (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···N3ⁱ	0.89	2.13	2.926 (2)	148
N1—H1C···Cl1	0.89	2.32	3.201 (2)	172
N1—H1D···Cl1ⁱⁱ	0.89	2.28	3.1583 (19)	170
N2—H2C···Cl1ⁱⁱⁱ	0.89	2.72	3.5538 (19)	157

Symmetry codes: (i) x−1/2, −y−3/2, −z−1; (ii) x−1, y, z; (iii) −x+1, y−1/2, −z−1/2.

Acknowledgements

The authors thank the Program for Young Excellent Talents in Southeast University for financial support.

References

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