3-[4-(3-Amino­prop­yl)piperazin-1-yl]propan-1-aminium chloride

Vaqueiro, P.

doi:10.1107/S1600536806020988

organic compounds

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ISSN: 2056-9890

Volume 62| Part 7| July 2006| Pages o2632-o2633

https://doi.org/10.1107/S1600536806020988

3-[4-(3-Aminopropyl)piperazin-1-yl]propan-1-aminium chloride

Paz Vaqueiro ^a ^*

^aDepartment of Chemistry, Heriot–Watt University, Edinburgh EH14 4AS, Scotland
^*Correspondence e-mail: chepv@hw.ac.uk

(Received 31 May 2006; accepted 1 June 2006; online 9 June 2006)

The title compound, C₁₀H₂₅N₄⁺·Cl⁻, contains monoprotonated amine cations and chloride anions. The cations form chains along the [101] direction via N—H⋯N bonds, while N—H⋯Cl hydrogen bonds link the anions and cations into a three-dimensional structure.

Comment

In solvothermal synthesis, organic amines are generally used as structure-directing agents, and it is known that sometimes salts of the amines appear as unwanted side products. However, recent work on the solvothermal synthesis of phosphates (Rao et al., 2000 ) and sulfates (Behera et al., 2004 ) suggests that these amine salts might play a role in the formation of open-framework phases. It has also been found that the use of amine salts as sources of structure-directing agents may result in the formation of new open-framework structures.

In the title compound, C₁₀H₂₅N₄⁺·Cl⁻, (I), which was the unexpected product of a solvothermal reaction, the amine 1,4-bis(3-aminopropyl)piperazine (bapp) crystallizes as a monoprotonated cation, H⁺bapp, accompanied by a charge-balancing chloride anion (Fig. 1). As well as electrostatic forces, the anions and cations in (I) interact by means of hydrogen bonds (Table 1). The H⁺bapp cations are connected by strong N—H⋯N hydrogen bonds, forming infinite chains that run along the [101] direction. The chains are cross-linked by N—H⋯Cl bonds arising from the terminal –NH₂ and –NH₃⁺ groups to form layers parallel to the ac plane (Fig. 2). Further N—H⋯Cl hydrogen bonds link the layers into a three-dimensional structure (Fig. 3).

Figure 1
View of (I)

, showing 50% probability displacement ellipsoids (arbitrary spheres for the H atoms).

Figure 2
View of a layer parallel to the (010) plane, showing the network of hydrogen bonds (dashed lines). Hydrogen atoms not participating in hydrogen bonding have been omitted for clarity.

Figure 3
View of the packing in (I)

. Drawing conventions as in Fig. 2

Experimental

A mixture of CuCl (2 mmol), Te (1 mmol) and 1,4-bis(3-aminopropyl)piperazine (4.2 ml) was loaded into a 23 ml Teflon-lined steel autoclave, heated for 13 days at 473 K and then cooled to room temperature over a period of 12 h. The product, consisting of hygroscopic colourless needles of (I) and a black powder, was filtered and washed with methanol and acetone.

Crystal data

C₁₀H₂₅N₄⁺·Cl⁻
M_r = 236.79
Monoclinic, P 2₁ /c
a = 10.9035 (9) Å
b = 15.9679 (13) Å
c = 7.8750 (6) Å
β = 96.693 (4)°
V = 1361.74 (19) Å³
Z = 4
D_x = 1.155 Mg m⁻³
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 293 K
Needle, colourless
0.50 × 0.10 × 0.10 mm

Data collection

Bruker–Nonius APEX2 CCD area-detector diffractometer
ω/2θ scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.811, T_max = 0.974
18638 measured reflections
3967 independent reflections
2257 reflections with I > 3.00σ(I)
R_int = 0.023
θ_max = 30.1°

Refinement

Refinement on F
R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.033
S = 1.11
2257 reflections
211 parameters
Only H-atom coordinates refined
W = [1 − (δF/6σF)²]²/[0.491T₀(x) + 0.340T₁(x) + 0.263T₂(x)] where T_i are Chebychev polynomials and x = F/F_max (Watkin, 1994 ; Prince, 1982 )
(Δ/σ)_max < 0.001
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H23⋯N5ⁱ	0.93 (2)	1.83 (2)	2.7574 (18)	175 (2)
N2—H21⋯Cl1ⁱ	0.91 (2)	2.27 (2)	3.1761 (12)	176 (2)
N2—H22⋯Cl1ⁱⁱ	0.88 (2)	2.30 (2)	3.1853 (13)	178 (1)
N5—H52⋯Cl1ⁱⁱⁱ	0.89 (2)	2.58 (2)	3.4104 (13)	156 (2)
N5—H53⋯Cl1^iv	0.85 (2)	2.61 (2)	3.4344 (13)	164 (2)
Symmetry codes: (i) x+1, y, z+1; (ii) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x+1, -y, -z+1; (iv) x, y, z-1.

H atoms were located in difference maps and their positions were freely refined; U_iso(H) = 1.2U_eq(carrier).

Data collection: APEX2 (Bruker, 2005 ); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ); molecular graphics: ATOMS (Dowty, 2000 ); software used to prepare material for publication: CRYSTALS.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536806020988/hb2078sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806020988/hb2078Isup2.hkl

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: ATOMS (Dowty, 2000); software used to prepare material for publication: CRYSTALS.

3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-aminium chloride top

Crystal data top

C₁₀H₂₅N₄⁺·Cl⁻	F(000) = 520
M_r = 236.79	D_x = 1.155 Mg m⁻³
Monoclinic, P2₁/c	Melting point: not measured K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 10.9035 (9) Å	Cell parameters from 3967 reflections
b = 15.9679 (13) Å	θ = 2–30°
c = 7.8750 (6) Å	µ = 0.26 mm⁻¹
β = 96.693 (4)°	T = 293 K
V = 1361.74 (19) Å³	Needle, colourless
Z = 4	0.50 × 0.10 × 0.10 mm

Data collection top

Bruker-Nonius APEX-2 CCD area-detector diffractometer	2257 reflections with I > 3.00σ(I)
Graphite monochromator	R_int = 0.023
ω/2θ scans	θ_max = 30.1°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→15
T_min = 0.811, T_max = 0.974	k = −22→22
18638 measured reflections	l = −11→9
3967 independent reflections

Refinement top

Refinement on F	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.029	Only H-atom coordinates refined
wR(F²) = 0.033	W = [1-(δF/6σF)²]²/[0.491T₀(x) + 0.340T₁(x) + 0.263T_n-1(x)] where T_i are Chebychev polynomials and x = F /F_max (Watkin, 1994; Prince, 1982)
S = 1.11	(Δ/σ)_max = 0.0004
2257 reflections	Δρ_max = 0.32 e Å⁻³
211 parameters	Δρ_min = −0.18 e Å⁻³
0 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.43536 (4)	0.14304 (2)	0.77225 (4)	0.0211
N2	1.37324 (11)	0.16961 (8)	1.37176 (15)	0.0161
N3	1.01135 (10)	0.15643 (7)	0.92003 (14)	0.0139
N4	0.87488 (11)	0.09259 (7)	0.60663 (14)	0.0143
N5	0.50436 (12)	0.06571 (8)	0.17912 (15)	0.0177
C6	1.24057 (12)	0.14862 (11)	1.32522 (16)	0.0170
C7	1.19916 (13)	0.16654 (10)	1.13825 (17)	0.0171
C8	1.06443 (12)	0.14127 (10)	1.09743 (16)	0.0153
C9	1.07007 (13)	0.10325 (9)	0.79997 (18)	0.0152
C10	1.00747 (13)	0.11313 (9)	0.61937 (18)	0.0152
C11	0.87922 (12)	0.13626 (10)	0.90503 (17)	0.0156
C12	0.81727 (12)	0.14716 (10)	0.72436 (16)	0.0160
C13	0.81963 (13)	0.10454 (10)	0.42929 (17)	0.0164
C14	0.68553 (14)	0.07703 (10)	0.39558 (18)	0.0191
C15	0.63633 (14)	0.08777 (11)	0.20778 (18)	0.0203
H21	1.3947 (17)	0.1627 (11)	1.486 (2)	0.0196*
H22	1.3889 (16)	0.2220 (12)	1.346 (2)	0.0196*
H23	1.4214 (17)	0.1352 (11)	1.312 (2)	0.0196*
H52	0.4953 (17)	0.0114 (13)	0.197 (2)	0.0212*
H53	0.4781 (17)	0.0758 (12)	0.075 (2)	0.0212*
H61	1.1909 (17)	0.1794 (12)	1.393 (2)	0.0208*
H62	1.2318 (17)	0.0890 (12)	1.348 (2)	0.0208*
H71	1.2089 (16)	0.2262 (12)	1.116 (2)	0.0207*
H72	1.2516 (16)	0.1385 (12)	1.070 (2)	0.0207*
H81	1.0146 (17)	0.1737 (11)	1.169 (2)	0.0185*
H82	1.0563 (16)	0.0845 (12)	1.126 (2)	0.0185*
H91	1.1566 (17)	0.1191 (11)	0.802 (2)	0.0185*
H92	1.0675 (16)	0.0438 (11)	0.833 (2)	0.0185*
H101	1.0199 (16)	0.1713 (12)	0.581 (2)	0.0188*
H102	1.0471 (16)	0.0765 (12)	0.544 (2)	0.0188*
H111	0.8371 (16)	0.1737 (11)	0.983 (2)	0.0188*
H112	0.8672 (17)	0.0789 (12)	0.937 (2)	0.0188*
H121	0.8258 (16)	0.2078 (12)	0.692 (2)	0.0194*
H122	0.7347 (17)	0.1342 (12)	0.721 (2)	0.0194*
H131	0.8670 (17)	0.0735 (12)	0.359 (2)	0.0198*
H132	0.8277 (17)	0.1639 (12)	0.398 (2)	0.0198*
H141	0.6795 (16)	0.0183 (12)	0.423 (2)	0.0230*
H142	0.6324 (18)	0.1086 (12)	0.464 (2)	0.0230*
H151	0.6878 (18)	0.0556 (12)	0.137 (2)	0.0245*
H152	0.6447 (17)	0.1454 (13)	0.174 (2)	0.0245*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.03055 (18)	0.01941 (15)	0.01294 (14)	0.00514 (16)	0.00035 (11)	0.00047 (15)
N2	0.0184 (6)	0.0186 (6)	0.0111 (5)	0.0001 (5)	0.0004 (4)	−0.0006 (4)
N3	0.0122 (5)	0.0168 (6)	0.0130 (5)	−0.0006 (4)	0.0021 (4)	−0.0011 (4)
N4	0.0128 (5)	0.0170 (6)	0.0133 (5)	−0.0009 (4)	0.0019 (4)	−0.0012 (4)
N5	0.0192 (6)	0.0206 (6)	0.0123 (5)	0.0026 (5)	−0.0027 (4)	−0.0017 (4)
C6	0.0159 (6)	0.0222 (7)	0.0130 (5)	−0.0020 (6)	0.0014 (4)	−0.0008 (5)
C7	0.0165 (6)	0.0212 (7)	0.0136 (6)	−0.0013 (5)	0.0019 (5)	0.0026 (5)
C8	0.0151 (6)	0.0163 (6)	0.0142 (5)	−0.0020 (6)	0.0013 (4)	0.0012 (6)
C9	0.0128 (6)	0.0162 (6)	0.0170 (6)	−0.0007 (5)	0.0033 (5)	−0.0020 (5)
C10	0.0131 (6)	0.0184 (6)	0.0149 (6)	−0.0014 (5)	0.0050 (5)	−0.0025 (5)
C11	0.0125 (6)	0.0184 (7)	0.0161 (6)	0.0000 (5)	0.0029 (4)	0.0001 (5)
C12	0.0132 (6)	0.0188 (6)	0.0161 (6)	0.0015 (5)	0.0025 (5)	−0.0005 (5)
C13	0.0173 (6)	0.0197 (7)	0.0125 (6)	−0.0005 (5)	0.0023 (5)	−0.0012 (5)
C14	0.0173 (7)	0.0251 (8)	0.0144 (6)	−0.0022 (5)	−0.0007 (5)	0.0008 (5)
C15	0.0199 (7)	0.0281 (8)	0.0130 (6)	0.0017 (6)	0.0019 (5)	0.0005 (5)

Geometric parameters (Å, º) top

N2—C6	1.4884 (18)	C8—H82	0.942 (19)
N2—H21	0.911 (19)	C9—C10	1.512 (2)
N2—H22	0.882 (19)	C9—H91	0.975 (18)
N2—H23	0.927 (19)	C9—H92	0.984 (18)
N3—C8	1.4686 (17)	C10—H101	0.991 (18)
N3—C9	1.4717 (17)	C10—H102	0.972 (18)
N3—C11	1.4676 (17)	C11—C12	1.5122 (19)
N4—C10	1.4744 (18)	C11—H111	1.005 (18)
N4—C12	1.4659 (17)	C11—H112	0.962 (19)
N4—C13	1.4675 (18)	C12—H121	1.009 (18)
N5—C15	1.473 (2)	C12—H122	0.921 (18)
N5—H52	0.88 (2)	C13—C14	1.520 (2)
N5—H53	0.853 (19)	C13—H131	0.941 (19)
C6—C7	1.5162 (19)	C13—H132	0.986 (18)
C6—H61	0.942 (19)	C14—C15	1.523 (2)
C6—H62	0.975 (19)	C14—H141	0.967 (19)
C7—C8	1.5212 (19)	C14—H142	0.978 (19)
C7—H71	0.978 (18)	C15—H151	0.979 (19)
C7—H72	0.943 (18)	C15—H152	0.97 (2)
C8—H81	0.974 (18)

C6—N2—H21	110.3 (11)	H91—C9—H92	107.6 (15)
C6—N2—H22	111.4 (12)	C9—C10—N4	111.86 (11)
H21—N2—H22	108.1 (16)	C9—C10—H101	108.7 (10)
C6—N2—H23	109.4 (11)	N4—C10—H101	110.8 (10)
H21—N2—H23	109.7 (16)	C9—C10—H102	109.3 (10)
H22—N2—H23	107.9 (16)	N4—C10—H102	109.0 (10)
C8—N3—C9	111.30 (11)	H101—C10—H102	107.0 (14)
C8—N3—C11	108.35 (10)	N3—C11—C12	112.16 (11)
C9—N3—C11	108.55 (11)	N3—C11—H111	109.6 (10)
C10—N4—C12	108.29 (11)	C12—C11—H111	108.7 (10)
C10—N4—C13	109.05 (11)	N3—C11—H112	110.5 (11)
C12—N4—C13	111.47 (11)	C12—C11—H112	107.2 (11)
C15—N5—H52	109.6 (12)	H111—C11—H112	108.7 (15)
C15—N5—H53	108.4 (13)	C11—C12—N4	110.45 (12)
H52—N5—H53	107.6 (17)	C11—C12—H121	107.8 (10)
N2—C6—C7	111.56 (11)	N4—C12—H121	110.5 (10)
N2—C6—H61	110.4 (11)	C11—C12—H122	109.3 (11)
C7—C6—H61	109.1 (11)	N4—C12—H122	109.7 (11)
N2—C6—H62	106.8 (11)	H121—C12—H122	109.1 (15)
C7—C6—H62	109.6 (11)	N4—C13—C14	114.11 (11)
H61—C6—H62	109.4 (15)	N4—C13—H131	107.4 (11)
C6—C7—C8	109.03 (11)	C14—C13—H131	109.2 (11)
C6—C7—H71	109.4 (11)	N4—C13—H132	108.8 (11)
C8—C7—H71	110.1 (11)	C14—C13—H132	110.3 (11)
C6—C7—H72	109.5 (11)	H131—C13—H132	106.8 (15)
C8—C7—H72	112.8 (11)	C13—C14—C15	111.09 (12)
H71—C7—H72	105.8 (15)	C13—C14—H141	109.3 (11)
C7—C8—N3	114.90 (11)	C15—C14—H141	107.6 (11)
C7—C8—H81	109.1 (11)	C13—C14—H142	112.0 (11)
N3—C8—H81	106.0 (11)	C15—C14—H142	108.3 (11)
C7—C8—H82	108.7 (11)	H141—C14—H142	108.4 (16)
N3—C8—H82	110.6 (11)	C14—C15—N5	110.43 (12)
H81—C8—H82	107.4 (15)	C14—C15—H151	109.3 (11)
N3—C9—C10	111.19 (12)	N5—C15—H151	113.7 (11)
N3—C9—H91	109.4 (11)	C14—C15—H152	110.0 (11)
C10—C9—H91	108.5 (11)	N5—C15—H152	107.9 (11)
N3—C9—H92	111.2 (10)	H151—C15—H152	105.3 (15)
C10—C9—H92	108.8 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H23···N5ⁱ	0.926 (18)	1.834 (17)	2.7574 (18)	174.7 (17)
N2—H21···Cl1ⁱ	0.910 (16)	2.268 (16)	3.1761 (12)	176.3 (17)
N2—H22···Cl1ⁱⁱ	0.882 (19)	2.304 (19)	3.1853 (13)	177.8 (14)
N5—H52···Cl1ⁱⁱⁱ	0.89 (2)	2.58 (2)	3.4104 (13)	155.9 (16)
N5—H53···Cl1^iv	0.852 (16)	2.607 (16)	3.4344 (13)	164.3 (16)

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

Acknowledgements

The author thanks the UK EPSRC for an Advanced Research Fellowship.

References

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