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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o129.
Published online 2007 December 6. doi:  10.1107/S1600536807063027
PMCID: PMC2915199

N,N′-Dibenzyl-N,N,N′,N′-tetra­methyl­ethylenediammonium dibromide dihydrate

Abstract

In the title compound, C20H30N2 2+·2Br·2H2O, the asymmetric unit consists of half of the N,N′-dibenzyl-N,N,N′,N′-tetra­methyl­ethylenediammonium cation lying across an inversion center, a bromide ion and a water mol­ecule of solvation. There is an eight-membered dibromide dihydrate ring, which is formed via hydrogen bonds of the type O—H(...)Br.

Related literature

For related literature, see: Chen et al. (2006 [triangle]); Jayaraman et al. (2002 [triangle]); Kabak et al. (2000 [triangle]); Li et al. (2006 [triangle]); Mathew et al. (2002 [triangle]); Misra et al. (2007 [triangle]); Nastase et al. (2007 [triangle]); Pan et al. (2007 [triangle]); Srinivasan et al. (2003 [triangle], 2005 [triangle], 2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0o129-scheme1.jpg

Experimental

Crystal data

  • C20H30N2 2+·2Br·2H2O
  • M r = 494.31
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o129-efi1.jpg
  • a = 6.7897 (14) Å
  • b = 22.774 (5) Å
  • c = 7.7069 (15) Å
  • β = 110.15 (3)°
  • V = 1118.8 (5) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 3.64 mm−1
  • T = 298 (2) K
  • 0.30 × 0.20 × 0.15 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: multi-scan (RAPID-AUTO; Rigaku Corporation, 1998 [triangle]) T min = 0.421, T max = 0.582
  • 10562 measured reflections
  • 2547 independent reflections
  • 1792 reflections with I > 2.0 σ(I)
  • R int = 0.074

Refinement

  • R[F 2 > 2σ(F 2)] = 0.046
  • wR(F 2) = 0.126
  • S = 1.06
  • 2547 reflections
  • 184 parameters
  • 3 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.51 e Å−3
  • Δρmin = −0.72 e Å−3

Data collection: RAPID-AUTO (Rigaku Corporation, 1998 [triangle]); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: SHELXTL/PC (Sheldrick, 1993 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807063027/pv2053sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807063027/pv2053Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported financially by the Natural Science Project of Jinggangshan University (JZ0731).

supplementary crystallographic information

Comment

It is well known that organic amines, such as ethylenediamine (en), 1,3-propanediamine (1,3-pnen), N,N,N',N'-tetramethylethylenediamine (tmen), piperazine (pip), etc, have been widely used as structure-directing agents for the construction of novel supramolecular assemblies (Misra et al., 2007, Nastase et al., 2007, Pan et al., 2007, Srinivasan et al., 2007, Li et al., 2006, Chen et al., 2006, Mathew et al., 2002, Jayaraman et al., 2002, Kabak et al., 2000). In a search for more organic surpramolecur amines, we have synthesized the title compound, (I), the structure of which is presented in this paper.

In the structure of (I), the asymmetric unit consists of a half molecule of N,N'-dibenzyl-N,N,N',N'-tetramethylethylenediammonium cation lying about an inversion center, a bromide ion and a water of solvation (Fig. 1). The C—C and C—N bond lengths are in good agreement with those found in other compounds containing the tmen moiety (Srinivasan et al., 2003; 2005; 2007). The water molecules in (I) are hydrogen-bonded with two bromide ions forming a novel eight membered cyclic dibromide. The two phenyl rings in each cation lie parallel to each other. The phenyl rings are arranged in layers. The dihedral angle between the two pheny rings is 16.3 (5)°. The shortest distance between adjacent phenyl rings is about 3.6441 Å, which indicates the existence of stacking interactions (Fig. 2).

Experimental

Tetramethylethylenediamine (tmen) (2.6 ml, 17.23 mmol) was dissolved in 15 ml of CH3CN, and benzyl bromide (4.8 ml, 40.36 mmol) was added dropwise with continuous stirring over 20–30 min. White crystaline solid was filtrated from the mixture after cooling to room temperature which was dissolved in glacial acetic acid. Colourless crystal of the title compound grew from the cetic acid solution on standing for several days at room temperature.

Refinement

All hydrogen atoms were found from difference Fourier maps and were refined with isotropic displacement parameters. H atoms of the water molecule were restrained at O—H bond lengths (O—H = 0.84 (1) Å) during the refinements.

Figures

Fig. 1.
A view of (I) with atom labels and 50% probability displacement ellipsoids. [symmetry codes: (i) -x + 1, -y, -z + 1]
Fig. 2.
Packing diagram of (I) viewed down the a axis; H-bonding interactions are shown as dashed lines.

Crystal data

C20H30N22+·2Br·2H2OF000 = 508
Mr = 494.31Dx = 1.467 Mg m3
Monoclinic, P21/nMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 6.7897 (14) Åθ = 12–18º
b = 22.774 (5) ŵ = 3.64 mm1
c = 7.7069 (15) ÅT = 298 (2) K
β = 110.15 (3)ºParallelepiped, colourless
V = 1118.8 (5) Å30.30 × 0.20 × 0.15 mm
Z = 2

Data collection

Rigaku R-AXIS RAPID diffractometer2547 independent reflections
Radiation source: fine-focus sealed tube1792 reflections with I > 2.0 σ(I)
Monochromator: graphiteRint = 0.074
T = 298(2) Kθmax = 27.5º
Oscillation scansθmin = 3.3º
Absorption correction: MULTI-SCAN(RAPID-AUTO; Rigaku Corporation, 1998)h = −8→8
Tmin = 0.421, Tmax = 0.582k = −29→29
10562 measured reflectionsl = −9→10

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.126  w = 1/[σ2(Fo2) + (0.0552P)2 + 0.2784P] where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.002
2547 reflectionsΔρmax = 0.51 e Å3
184 parametersΔρmin = −0.72 e Å3
3 restraintsExtinction correction: None
Primary atom site location: structure-invariant direct methods

Special details

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)

xyzUiso*/Ueq
Br10.89391 (7)0.065641 (16)0.24054 (6)0.05367 (19)
OW10.2419 (7)0.04996 (18)1.0319 (6)0.0917 (12)
N10.5346 (5)0.07807 (11)0.6087 (4)0.0371 (7)
C10.7021 (7)0.19997 (16)0.4469 (6)0.0531 (10)
C20.7549 (9)0.25943 (18)0.4717 (7)0.0681 (13)
C30.6231 (10)0.29803 (17)0.5114 (6)0.0705 (15)
C40.4387 (10)0.27891 (18)0.5281 (6)0.0654 (14)
C50.3847 (8)0.21992 (18)0.5030 (6)0.0547 (10)
C60.5200 (6)0.17978 (14)0.4658 (5)0.0408 (8)
C70.4612 (6)0.11582 (14)0.4341 (5)0.0404 (8)
C80.4532 (7)0.01555 (14)0.5633 (6)0.0411 (9)
C90.7673 (7)0.07937 (18)0.6952 (7)0.0472 (9)
C100.4404 (9)0.10009 (19)0.7456 (7)0.0547 (12)
H10.801 (6)0.1761 (16)0.433 (5)0.049 (11)*
H20.885 (9)0.272 (2)0.457 (7)0.082 (17)*
H30.652 (7)0.338 (2)0.530 (6)0.068 (13)*
H40.336 (7)0.3058 (19)0.532 (6)0.057 (12)*
H50.254 (8)0.207 (2)0.515 (7)0.069 (14)*
H60.540 (6)0.0962 (18)0.361 (6)0.056 (11)*
H70.300 (7)0.1093 (16)0.378 (5)0.051 (11)*
H80.306 (6)0.0181 (16)0.511 (5)0.044 (11)*
H90.488 (6)−0.0026 (15)0.678 (5)0.036 (9)*
H100.806 (7)0.0550 (17)0.791 (6)0.051 (12)*
H110.823 (8)0.0694 (18)0.609 (7)0.067 (15)*
H120.804 (7)0.1197 (18)0.736 (6)0.054 (11)*
H130.485 (7)0.0805 (19)0.840 (7)0.049 (12)*
H140.284 (8)0.0988 (19)0.684 (6)0.058 (13)*
H150.487 (7)0.137 (2)0.777 (6)0.057 (12)*
HWA0.211 (6)0.0193 (13)0.962 (5)0.068*
HWB0.143 (5)0.0568 (17)1.074 (6)0.068*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0612 (3)0.0525 (3)0.0569 (3)0.00285 (18)0.0325 (2)0.00037 (16)
OW10.109 (3)0.088 (3)0.092 (3)−0.014 (2)0.053 (3)−0.014 (2)
N10.0483 (18)0.0294 (13)0.0354 (16)−0.0048 (12)0.0166 (14)−0.0002 (10)
C10.066 (3)0.0360 (18)0.062 (3)0.0025 (19)0.028 (2)0.0058 (17)
C20.083 (4)0.042 (2)0.074 (3)−0.013 (2)0.021 (3)0.008 (2)
C30.108 (4)0.0284 (19)0.061 (3)−0.006 (2)0.010 (3)−0.0005 (17)
C40.095 (4)0.039 (2)0.057 (3)0.021 (3)0.020 (3)0.0005 (17)
C50.061 (3)0.046 (2)0.055 (3)0.012 (2)0.019 (2)0.0028 (17)
C60.052 (2)0.0329 (16)0.0333 (19)0.0021 (15)0.0099 (17)0.0025 (13)
C70.048 (2)0.0320 (16)0.041 (2)−0.0019 (15)0.0143 (19)−0.0020 (14)
C80.054 (3)0.0313 (17)0.045 (2)−0.0043 (16)0.025 (2)−0.0008 (14)
C90.049 (3)0.042 (2)0.045 (2)−0.0009 (17)0.009 (2)0.0017 (17)
C100.086 (4)0.039 (2)0.051 (3)−0.001 (2)0.040 (3)−0.0040 (19)

Geometric parameters (Å, °)

OW1—HWA0.86 (3)C5—C61.394 (6)
OW1—HWB0.86 (3)C5—H50.97 (5)
N1—C91.488 (5)C6—C71.508 (5)
N1—C101.496 (5)C7—H61.00 (4)
N1—C81.524 (4)C7—H71.04 (4)
N1—C71.528 (4)C8—C8i1.511 (7)
C1—C61.374 (6)C8—H80.94 (4)
C1—C21.397 (6)C8—H90.93 (4)
C1—H10.90 (4)C9—H100.89 (4)
C2—C31.362 (8)C9—H110.90 (5)
C2—H20.97 (6)C9—H120.97 (4)
C3—C41.373 (8)C10—H130.82 (5)
C3—H30.94 (5)C10—H141.00 (5)
C4—C51.388 (6)C10—H150.90 (4)
C4—H40.94 (5)
HWA—OW1—HWB109.2 (17)C6—C7—N1114.4 (3)
C9—N1—C10108.9 (3)C6—C7—H6111 (2)
C9—N1—C8111.5 (3)N1—C7—H6100 (2)
C10—N1—C8105.4 (3)C6—C7—H7113 (2)
C9—N1—C7110.9 (3)N1—C7—H7105 (2)
C10—N1—C7110.1 (3)H6—C7—H7113 (3)
C8—N1—C7109.9 (3)C8i—C8—N1112.7 (4)
C6—C1—C2120.5 (4)C8i—C8—H8112 (2)
C6—C1—H1123 (2)N1—C8—H8107 (2)
C2—C1—H1116 (2)C8i—C8—H9112 (2)
C3—C2—C1119.9 (5)N1—C8—H9104 (2)
C3—C2—H2122 (3)H8—C8—H9109 (3)
C1—C2—H2118 (3)N1—C9—H10109 (3)
C2—C3—C4120.5 (4)N1—C9—H11109 (3)
C2—C3—H3123 (3)H10—C9—H11112 (4)
C4—C3—H3117 (3)N1—C9—H12106 (3)
C3—C4—C5120.0 (4)H10—C9—H12111 (4)
C3—C4—H4121 (3)H11—C9—H12110 (4)
C5—C4—H4118 (3)N1—C10—H13109 (3)
C4—C5—C6120.2 (5)N1—C10—H14107 (3)
C4—C5—H5119 (3)H13—C10—H14115 (4)
C6—C5—H5120 (3)N1—C10—H15108 (3)
C1—C6—C5118.9 (3)H13—C10—H15106 (4)
C1—C6—C7120.3 (3)H14—C10—H15112 (4)
C5—C6—C7120.7 (4)

Symmetry codes: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
OW1—HWA···Br1i0.86 (3)2.434 (11)3.295 (4)177 (4)
OW1—HWB···Br1ii0.86 (3)2.456 (14)3.304 (4)170 (5)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PV2053).

References

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