Guanidinium bromide-18-crown-6 (2/1).

In the title compound, 2CH(6)N(3) (+)·2Br(-)·C(12)H(24)O(6), the 18-crown-6 mol-ecule lies about an inversion center, whereas the guanidinium cation and bromide anion are in general positions. The guanidinium cations link with the bromide anions and the crown ether mol-ecules via N-H⋯O and N-H⋯Br hydrogen bonds, thus forming a three-dimensional network.

Related literature

For applications of crown ethers, see: Clark et al. (1998 ▶). For ferroelectric metal-organic compounds, see: Fu et al. (2009 ▶, 2011 ▶); Ye et al. (2006 ▶); Zhang et al. (2008 ▶, 2010 ▶). For structures of 18-crown-6 clathrates, see: Zhang & Zhao (2011 ▶); Ge & Zhao (2010 ▶)

Experimental

Crystal data

2CH6N3 +·2Br−·C12H24O6

M = 544.31

Monoclinic,

a = 8.9354 (18) Å

b = 9.860 (2) Å

c = 14.306 (3) Å

β = 101.39 (3)°

V = 1235.6 (4) Å3

Z = 2

Mo Kα radiation

μ = 3.32 mm−1

T = 293 K

0.20 × 0.20 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.936, T max = 0.937

12464 measured reflections

2835 independent reflections

1968 reflections with I > 2σ(I)

R int = 0.077

Refinement

R[F 2 > 2σ(F 2)] = 0.053

wR(F 2) = 0.127

S = 1.11

2835 reflections

127 parameters

H-atom parameters constrained

Δρmax = 0.36 e Å−3

Δρmin = −0.79 e Å−3

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812017394/yk2049sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812017394/yk2049Isup2.hkl

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

2CH6N3+·2Br−·C12H24O6	F(000) = 560
Mr = 544.31	Dx = 1.463 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3638 reflections
a = 8.9354 (18) Å	θ = 3.0–27.5°
b = 9.860 (2) Å	µ = 3.32 mm−1
c = 14.306 (3) Å	T = 293 K
β = 101.39 (3)°	Block, colourless
V = 1235.6 (4) Å3	0.20 × 0.20 × 0.20 mm
Z = 2

Rigaku SCXmini diffractometer	2835 independent reflections
Radiation source: fine-focus sealed tube	1968 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.077
ω scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −11→11
Tmin = 0.936, Tmax = 0.937	k = −12→12
12464 measured reflections	l = −18→18

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127	H-atom parameters constrained
S = 1.11	w = 1/[σ2(Fo2) + (0.0528P)2] where P = (Fo2 + 2Fc2)/3
2835 reflections	(Δ/σ)max = 0.001
127 parameters	Δρmax = 0.36 e Å−3
0 restraints	Δρmin = −0.79 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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.

	x	y	z	Uiso*/Ueq
O2	1.1811 (3)	−0.2005 (3)	0.62582 (18)	0.0572 (7)
O3	1.2804 (3)	0.0677 (3)	0.6025 (2)	0.0649 (8)
O1	0.8672 (3)	−0.2293 (3)	0.5560 (2)	0.0759 (9)
C3	1.3789 (5)	−0.0401 (5)	0.6413 (4)	0.0701 (13)
H3A	1.4677	−0.0043	0.6844	0.084*
H3B	1.4135	−0.0887	0.5905	0.084*
C6	0.9606 (6)	−0.3369 (5)	0.5989 (4)	0.0805 (14)
H6A	1.0024	−0.3854	0.5509	0.097*
H6B	0.9004	−0.4000	0.6282	0.097*
C5	1.0855 (6)	−0.2815 (5)	0.6716 (3)	0.0748 (13)
H5A	1.0439	−0.2269	0.7168	0.090*
H5B	1.1441	−0.3549	0.7061	0.090*
C4	1.2942 (5)	−0.1325 (4)	0.6931 (3)	0.0641 (12)
H4A	1.3635	−0.1980	0.7292	0.077*
H4B	1.2465	−0.0814	0.7372	0.077*
C7	0.7498 (6)	−0.2745 (5)	0.4820 (4)	0.0882 (16)
H7A	0.6934	−0.3471	0.5050	0.106*
H7B	0.7932	−0.3093	0.4298	0.106*
C2	1.3526 (5)	0.1611 (6)	0.5511 (4)	0.0848 (15)
H2A	1.3809	0.1160	0.4969	0.102*
H2B	1.4450	0.1949	0.5917	0.102*
N2	1.1162 (4)	−0.1452 (4)	0.4063 (3)	0.0766 (11)
H2C	1.1030	−0.1300	0.4633	0.092*
H2D	1.0709	−0.0954	0.3599	0.092*
Br1	1.01901 (4)	−0.03281 (4)	0.16380 (3)	0.05407 (18)
N3	1.2257 (4)	−0.2677 (4)	0.3022 (2)	0.0643 (9)
H3C	1.2841	−0.3325	0.2911	0.077*
H3D	1.1801	−0.2174	0.2562	0.077*
C1	1.2061 (4)	−0.2453 (4)	0.3900 (3)	0.0508 (9)
N1	1.2761 (4)	−0.3225 (3)	0.4595 (2)	0.0592 (9)
H1A	1.3344	−0.3871	0.4478	0.071*
H1B	1.2638	−0.3085	0.5168	0.071*

	U11	U22	U33	U12	U13	U23
O2	0.0681 (18)	0.0558 (17)	0.0495 (15)	0.0000 (13)	0.0161 (13)	−0.0003 (13)
O3	0.0545 (17)	0.078 (2)	0.0651 (19)	−0.0106 (15)	0.0176 (14)	0.0009 (16)
O1	0.082 (2)	0.0625 (19)	0.079 (2)	−0.0205 (16)	0.0071 (17)	0.0001 (17)
C3	0.050 (3)	0.087 (3)	0.073 (3)	0.000 (2)	0.010 (2)	−0.027 (3)
C6	0.100 (4)	0.055 (3)	0.091 (4)	−0.019 (3)	0.032 (3)	0.009 (3)
C5	0.095 (3)	0.065 (3)	0.065 (3)	0.005 (3)	0.018 (3)	0.021 (2)
C4	0.071 (3)	0.067 (3)	0.050 (2)	0.017 (2)	0.002 (2)	−0.010 (2)
C7	0.106 (4)	0.087 (4)	0.068 (3)	−0.055 (3)	0.009 (3)	0.002 (3)
C2	0.060 (3)	0.122 (4)	0.074 (3)	−0.040 (3)	0.015 (2)	0.003 (3)
N2	0.101 (3)	0.074 (2)	0.059 (2)	0.034 (2)	0.026 (2)	0.0060 (19)
Br1	0.0649 (3)	0.0498 (3)	0.0474 (3)	0.00012 (18)	0.01084 (19)	0.00461 (18)
N3	0.070 (2)	0.076 (2)	0.045 (2)	0.0250 (18)	0.0076 (16)	0.0070 (17)
C1	0.050 (2)	0.049 (2)	0.052 (2)	−0.0038 (17)	0.0091 (18)	0.000 (2)
N1	0.075 (2)	0.060 (2)	0.0410 (18)	0.0135 (17)	0.0093 (16)	0.0063 (17)

O2—C4	1.418 (5)	C7—C2i	1.464 (7)
O2—C5	1.420 (5)	C7—H7A	0.9700
O3—C2	1.411 (5)	C7—H7B	0.9700
O3—C3	1.421 (5)	C2—C7i	1.464 (7)
O1—C7	1.407 (5)	C2—H2A	0.9700
O1—C6	1.413 (5)	C2—H2B	0.9700
C3—C4	1.474 (6)	N2—C1	1.322 (5)
C3—H3A	0.9700	N2—H2C	0.8600
C3—H3B	0.9700	N2—H2D	0.8600
C6—C5	1.472 (7)	N3—C1	1.320 (5)
C6—H6A	0.9700	N3—H3C	0.8600
C6—H6B	0.9700	N3—H3D	0.8600
C5—H5A	0.9700	C1—N1	1.309 (5)
C5—H5B	0.9700	N1—H1A	0.8600
C4—H4A	0.9700	N1—H1B	0.8600
C4—H4B	0.9700
C4—O2—C5	111.5 (3)	H4A—C4—H4B	108.4
C2—O3—C3	112.3 (4)	O1—C7—C2i	109.1 (4)
C7—O1—C6	112.1 (4)	O1—C7—H7A	109.9
O3—C3—C4	108.6 (3)	C2i—C7—H7A	109.9
O3—C3—H3A	110.0	O1—C7—H7B	109.9
C4—C3—H3A	110.0	C2i—C7—H7B	109.9
O3—C3—H3B	110.0	H7A—C7—H7B	108.3
C4—C3—H3B	110.0	O3—C2—C7i	110.3 (4)
H3A—C3—H3B	108.4	O3—C2—H2A	109.6
O1—C6—C5	109.2 (4)	C7i—C2—H2A	109.6
O1—C6—H6A	109.8	O3—C2—H2B	109.6
C5—C6—H6A	109.8	C7i—C2—H2B	109.6
O1—C6—H6B	109.8	H2A—C2—H2B	108.1
C5—C6—H6B	109.8	C1—N2—H2C	120.0
H6A—C6—H6B	108.3	C1—N2—H2D	120.0
O2—C5—C6	108.9 (4)	H2C—N2—H2D	120.0
O2—C5—H5A	109.9	C1—N3—H3C	120.0
C6—C5—H5A	109.9	C1—N3—H3D	120.0
O2—C5—H5B	109.9	H3C—N3—H3D	120.0
C6—C5—H5B	109.9	N1—C1—N3	119.5 (4)
H5A—C5—H5B	108.3	N1—C1—N2	121.0 (4)
O2—C4—C3	108.6 (3)	N3—C1—N2	119.5 (4)
O2—C4—H4A	110.0	C1—N1—H1A	120.0
C3—C4—H4A	110.0	C1—N1—H1B	120.0
O2—C4—H4B	110.0	H1A—N1—H1B	120.0
C3—C4—H4B	110.0

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Br1ii	0.86	2.68	3.470 (3)	154
N1—H1B···O2	0.86	2.14	2.938 (4)	155
N2—H2C···O2	0.86	2.40	3.127 (5)	143
N2—H2D···Br1	0.86	2.82	3.582 (4)	149
N3—H3D···Br1	0.86	2.53	3.354 (3)	162
N3—H3C···Br1ii	0.86	2.64	3.440 (3)	156

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Br1i	0.86	2.68	3.470 (3)	154
N1—H1B⋯O2	0.86	2.14	2.938 (4)	155
N2—H2C⋯O2	0.86	2.40	3.127 (5)	143
N2—H2D⋯Br1	0.86	2.82	3.582 (4)	149
N3—H3D⋯Br1	0.86	2.53	3.354 (3)	162
N3—H3C⋯Br1i	0.86	2.64	3.440 (3)	156

Symmetry code: (i) .