1,1′-Dimethyl-1,1′-(butane-1,4-di­yl)dipyrrolidinium dibromide methanol disolvate

Yang, Y.-L.; Wang, W.-J.; Li, W.-H.; Fan, R.-Q.

doi:10.1107/S1600536808000172

organic compounds

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Volume 64| Part 2| February 2008| Page o417

doi:10.1107/S1600536808000172

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1,1′-Dimethyl-1,1′-(butane-1,4-diyl)dipyrrolidinium dibromide methanol disolvate

Yu-Lin Yang,^a ^* Wen-Jiu Wang,^a Wen-Hui Li ^b and Rui-Qing Fan ^a

^aDepartment of Applied Chemistry, Harbin Institute of Technology, Harbin 150001, People's Republic of China, and ^bCollege of Materials Science and Engineering, Harbin University of Science & Technology, Harbin 150040, People's Republic of China
^*Correspondence e-mail: yangyulin2000@163.com

(Received 18 December 2007; accepted 3 January 2008; online 11 January 2008)

In the title compound, C₁₄H₃₀N₂²⁺·2Br⁻·2CH₃OH, two terminal C atoms of the butane chain are connected to two N atoms of the 1-methylpyrollidines, forming a linear diquaternary ammonium cation. The cation lies across a centre of inversion located between the two central C atoms of the butane chain. The asymmetric unit therefore comprises one half-cation, a bromide anion and a methanol solvent molecule. In the crystal structure, the bromide anions are linked to the methanol solvent molecules by O—H⋯Br hydrogen bonds.

Related literature

For information on the use of organic amines in zeolite synthesis, see: Gramm et al. (2006 ); Hong et al. (2007 ). For a previous synthesis of the title compound, see: Hong et al. (2004 ).

Experimental

Crystal data

C₁₄H₃₀N₂²⁺·2Br⁻·2CH₄O
M_r = 450.30
Monoclinic, P 2₁ /n
a = 6.4919 (7) Å
b = 12.4861 (13) Å
c = 12.9683 (13) Å
β = 90.748 (2)°
V = 1051.10 (19) Å³
Z = 2
Mo Kα radiation
μ = 3.87 mm⁻¹
T = 193 (2) K
0.30 × 0.25 × 0.24 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.390, T_max = 0.457 (expected range = 0.337–0.396)
5618 measured reflections
2013 independent reflections
1681 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.067
S = 1.09
2013 reflections
102 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯Br1	0.82	2.43	3.2453 (18)	172

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); 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, 1997 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808000172/sj2458sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808000172/sj2458Isup2.hkl

checkCIF report

Comment top

The use of zeolites as catalysts or catalyst supports is now widely applied in petrochemical and fine chemical processes. The synthesis of zeolites involves the addition of organic amines and it is proposed that in most cases, the amine acts as a structure-directing agent, helping to shape the framework of the structure. TNU-9 is a complex zeolite (Gramm et al., 2006) and the title compound, (I), is used as structure-directing agent in the synthesis of the TNU-9 zeolite (Hong et al., 2007). In this paper, we report a modified synthesis and the crystal structure of (I), Fig 1.

The structure of (I) consists of a linear diquaternary ammonium cation, two bromide anions and two methanol solvate molecules. The cation lies about an inversion centre at the centroid of the C6—C6A bond in the butane chain. The terminal carbon atoms of the butane are connected to the N atoms of the 1-methylpyrolidines, forming a linear diquaternary ammonium cation. In the crystal structure Br^- anions are linked to methanol molecules by O1—H1···Br1 hydrogen bonds that stabilize the structure (Fig 2, Table 1).

Related literature top

For information on the use of organic amines in zeolite synthesis, see: Gramm et al. (2006); Hong et al. (2007). For a previous synthesis of the title compound, see: Hong et al. (2004).

Experimental top

(I) was prepared by refluxing 1,4-dibromobutane (1 mmol, 99%, Arcos) with an excess of 1-methylpyrrolidine (3 mmol, 97%, Arcos) 24 h in acetone (150 ml, 99%, Arcos), in a modification of the previously reported procedure (Hong et al., 2004). The excess amine was removed by extraction with acetone, and recrystallizations were performed in a methanol-diethylether mixtures (2:1).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 1997).

Figures top

	Fig. 1. View of the molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Labelled atoms are related to unlabelled atoms by the symmetry operation-x + 1,-y,-z + 2.
	Fig. 2. The molecular packing of (I) with hydrogen bonds drawn as dashed lines.

1,1'-Dimethyl-1,1'-(Butane-1,4-diyl)dipyrrolidinium bromide methanol disolvate top

Crystal data top

C₁₄H₃₀N₂²⁺·2Br⁻·2CH₄O	F(000) = 468
M_r = 450.30	D_x = 1.423 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5618 reflections
a = 6.4919 (7) Å	θ = 2.3–26.0°
b = 12.4861 (13) Å	µ = 3.87 mm⁻¹
c = 12.9683 (13) Å	T = 193 K
β = 90.748 (2)°	Block, colorless
V = 1051.10 (19) Å³	0.30 × 0.25 × 0.24 mm
Z = 2

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2013 independent reflections
Radiation source: fine-focus sealed tube	1681 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −5→8
T_min = 0.390, T_max = 0.457	k = −14→15
5618 measured reflections	l = −15→16

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.067	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0335P)² + 0.1193P] where P = (F_o² + 2F_c²)/3
2013 reflections	(Δ/σ)_max < 0.001
102 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₄H₃₀N₂²⁺·2Br⁻·2CH₄O	V = 1051.10 (19) Å³
M_r = 450.30	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.4919 (7) Å	µ = 3.87 mm⁻¹
b = 12.4861 (13) Å	T = 193 K
c = 12.9683 (13) Å	0.30 × 0.25 × 0.24 mm
β = 90.748 (2)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2013 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1681 reflections with I > 2σ(I)
T_min = 0.390, T_max = 0.457	R_int = 0.022
5618 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.067	H-atom parameters constrained
S = 1.09	Δρ_max = 0.42 e Å⁻³
2013 reflections	Δρ_min = −0.21 e Å⁻³
102 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
Br1	0.22798 (4)	0.222545 (19)	0.645609 (19)	0.03899 (11)
N1	0.6827 (3)	0.01906 (14)	0.77454 (14)	0.0279 (4)
C1	0.8754 (4)	−0.04680 (19)	0.79320 (18)	0.0380 (6)
H1A	0.8411	−0.1171	0.8198	0.046*
H1B	0.9671	−0.0113	0.8420	0.046*
C2	0.9755 (4)	−0.0559 (2)	0.68752 (18)	0.0443 (7)
H2A	1.0286	−0.1276	0.6772	0.053*
H2B	1.0884	−0.0054	0.6820	0.053*
C3	0.8074 (4)	−0.0306 (2)	0.60735 (19)	0.0467 (7)
H3A	0.8386	0.0351	0.5708	0.056*
H3B	0.7939	−0.0884	0.5577	0.056*
C4	0.6110 (4)	−0.0184 (2)	0.66926 (17)	0.0385 (6)
H4A	0.5197	0.0339	0.6375	0.046*
H4B	0.5390	−0.0862	0.6741	0.046*
C5	0.5187 (3)	−0.00229 (18)	0.85296 (17)	0.0316 (5)
H5A	0.4768	−0.0767	0.8475	0.038*
H5B	0.3994	0.0415	0.8364	0.038*
C6	0.5842 (3)	0.01998 (18)	0.96372 (16)	0.0319 (5)
H6A	0.6052	0.0962	0.9734	0.038*
H6B	0.7129	−0.0164	0.9792	0.038*
C7	0.7340 (4)	0.13607 (17)	0.77065 (18)	0.0344 (5)
H7A	0.7800	0.1595	0.8376	0.052*
H7B	0.6137	0.1759	0.7503	0.052*
H7C	0.8412	0.1477	0.7216	0.052*
O1	0.5324 (3)	0.32947 (15)	0.47786 (14)	0.0510 (5)
H1	0.4456	0.3057	0.5171	0.076*
C8	0.6858 (4)	0.2517 (2)	0.4620 (2)	0.0478 (7)
H8A	0.7952	0.2615	0.5116	0.072*
H8B	0.7392	0.2590	0.3937	0.072*
H8C	0.6275	0.1816	0.4700	0.072*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.03054 (16)	0.03698 (16)	0.04954 (18)	0.00222 (11)	0.00417 (11)	0.00310 (11)
N1	0.0241 (10)	0.0302 (9)	0.0296 (10)	0.0005 (8)	0.0036 (8)	−0.0010 (8)
C1	0.0336 (13)	0.0414 (14)	0.0390 (14)	0.0110 (11)	0.0052 (11)	0.0050 (11)
C2	0.0438 (16)	0.0413 (14)	0.0482 (16)	0.0130 (12)	0.0163 (13)	0.0038 (12)
C3	0.0487 (16)	0.0560 (17)	0.0359 (14)	0.0039 (14)	0.0113 (13)	−0.0063 (12)
C4	0.0396 (14)	0.0453 (14)	0.0307 (12)	−0.0027 (12)	−0.0011 (11)	−0.0059 (11)
C5	0.0243 (12)	0.0349 (12)	0.0359 (13)	−0.0060 (10)	0.0079 (10)	−0.0032 (10)
C6	0.0265 (12)	0.0337 (12)	0.0356 (13)	−0.0031 (10)	0.0072 (10)	−0.0019 (10)
C7	0.0318 (13)	0.0308 (12)	0.0406 (14)	−0.0050 (10)	0.0041 (11)	0.0040 (10)
O1	0.0450 (12)	0.0590 (12)	0.0492 (12)	0.0083 (10)	0.0092 (9)	0.0080 (9)
C8	0.0447 (17)	0.0497 (15)	0.0492 (17)	0.0009 (13)	0.0048 (14)	−0.0040 (12)

Geometric parameters (Å, º) top

N1—C7	1.500 (3)	C5—C6	1.518 (3)
N1—C5	1.506 (3)	C5—H5A	0.9700
N1—C4	1.511 (3)	C5—H5B	0.9700
N1—C1	1.514 (3)	C6—C6ⁱ	1.535 (4)
C1—C2	1.528 (3)	C6—H6A	0.9700
C1—H1A	0.9700	C6—H6B	0.9700
C1—H1B	0.9700	C7—H7A	0.9600
C2—C3	1.530 (4)	C7—H7B	0.9600
C2—H2A	0.9700	C7—H7C	0.9600
C2—H2B	0.9700	O1—C8	1.408 (3)
C3—C4	1.523 (3)	O1—H1	0.8200
C3—H3A	0.9700	C8—H8A	0.9600
C3—H3B	0.9700	C8—H8B	0.9600
C4—H4A	0.9700	C8—H8C	0.9600
C4—H4B	0.9700

C7—N1—C5	110.76 (17)	C3—C4—H4B	110.8
C7—N1—C4	109.70 (18)	H4A—C4—H4B	108.8
C5—N1—C4	110.08 (17)	N1—C5—C6	114.51 (17)
C7—N1—C1	110.55 (18)	N1—C5—H5A	108.6
C5—N1—C1	112.72 (17)	C6—C5—H5A	108.6
C4—N1—C1	102.75 (17)	N1—C5—H5B	108.6
N1—C1—C2	104.89 (18)	C6—C5—H5B	108.6
N1—C1—H1A	110.8	H5A—C5—H5B	107.6
C2—C1—H1A	110.8	C5—C6—C6ⁱ	109.1 (2)
N1—C1—H1B	110.8	C5—C6—H6A	109.9
C2—C1—H1B	110.8	C6ⁱ—C6—H6A	109.9
H1A—C1—H1B	108.8	C5—C6—H6B	109.9
C1—C2—C3	106.6 (2)	C6ⁱ—C6—H6B	109.9
C1—C2—H2A	110.4	H6A—C6—H6B	108.3
C3—C2—H2A	110.4	N1—C7—H7A	109.5
C1—C2—H2B	110.4	N1—C7—H7B	109.5
C3—C2—H2B	110.4	H7A—C7—H7B	109.5
H2A—C2—H2B	108.6	N1—C7—H7C	109.5
C4—C3—C2	104.9 (2)	H7A—C7—H7C	109.5
C4—C3—H3A	110.8	H7B—C7—H7C	109.5
C2—C3—H3A	110.8	C8—O1—H1	109.5
C4—C3—H3B	110.8	O1—C8—H8A	109.5
C2—C3—H3B	110.8	O1—C8—H8B	109.5
H3A—C3—H3B	108.8	H8A—C8—H8B	109.5
N1—C4—C3	104.9 (2)	O1—C8—H8C	109.5
N1—C4—H4A	110.8	H8A—C8—H8C	109.5
C3—C4—H4A	110.8	H8B—C8—H8C	109.5
N1—C4—H4B	110.8

Symmetry code: (i) −x+1, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Br1	0.82	2.43	3.2453 (18)	172

Experimental details

Crystal data
Chemical formula	C₁₄H₃₀N₂²⁺·2Br⁻·2CH₄O
M_r	450.30
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	193
a, b, c (Å)	6.4919 (7), 12.4861 (13), 12.9683 (13)
β (°)	90.748 (2)
V (Å³)	1051.10 (19)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.87
Crystal size (mm)	0.30 × 0.25 × 0.24

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.390, 0.457
No. of measured, independent and observed [I > 2σ(I)] reflections	5618, 2013, 1681
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.067, 1.09
No. of reflections	2013
No. of parameters	102
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.21

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Br1	0.82	2.43	3.2453 (18)	172.1

Acknowledgements

This work was supported by the National Natural Science Foundation of China (20671025 and 20771030), the Development Program for Outstanding Young Teachers in Harbin Institute of Technology (HITQNJS.2006.029), the Science Innovation Special Foundation of Harbin City in China (2005AFXXJ034), the Young Foundation of Heilongjiang Province in China (QC06C029), and the Heilongjiang Natural Science Foundation (B200603).

References

Bruker (2000). SMART (Version 5.625) and SAINT (Version 6.01) and SADABS (Version?). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Gramm, F., Baerlocher, C., McCusker, L. B., Warrender, S. J., Wright, P. A., Han, B., Hong, S. B., Liu, Z., Ohsuna, T. & Terasaki, O. (2006). Nature (London), 444, 79–81. Web of Science CrossRef PubMed CAS Google Scholar
Hong, S. B., Lear, E. G., Wright, P. A., Zhou, W. Z., Cox, P. A., Shin, C. H., Park, J. H. & Nam, I. S. (2004). J. Am. Chem. Soc. 126, 5817–5826. Web of Science CrossRef PubMed CAS Google Scholar
Hong, S. B., Min, H. K., Shin, C. H., Cox, P. A., Warrender, S. J. & Wright, P. A. (2007). J. Am. Chem. Soc. 129, 10870–10885. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (1997). SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

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Volume 64| Part 2| February 2008| Page o417

doi:10.1107/S1600536808000172

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

1,1′-Di­methyl-1,1′-(butane-1,4-di­yl)dipyrrolidinium dibromide methanol disolvate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

1,1′-Dimethyl-1,1′-(butane-1,4-diyl)dipyrrolidinium dibromide methanol disolvate