Bis-(guanidinium) naphthalene-1,5-di-sulfonate-18-crown-6 (1/1).

In the crystal of the title compound, 2CH(6)N(3) (+)·C(10)H(6)O(6)S(2) (2-)·C(12)H(24)O(6), the 1,5-naphthnalenedisulfonate anion and the 18-crown-6 mol-ecule lie across inversion centers. The guanidin-ium cation links with the 1,5-naphthnalenedisulfonate anion and 18-crown-6 mol-ecule via N-H⋯O hydrogen bonds.

Related literature

For applications of crown ethers, see: Clark et al. (1998 ▶). The title compound was obtained during a search for new hydrogen-bonding-type dielectric materials. For ferroelectric metal-organic 18-crown-6 clathrates, see: Fu et al. (2009 ▶, 2011 ▶); Ye et al. (2006 ▶); Zhang et al. (2008 ▶, 2010 ▶).

Experimental

Crystal data

2CH6N3 +·C10H6O6S2 −·C12H24O6

M = 670.76

Triclinic,

a = 8.5275 (17) Å

b = 9.1291 (18) Å

c = 11.470 (2) Å

α = 111.97 (3)°

β = 96.10 (3)°

γ = 99.38 (3)°

V = 803.3 (3) Å3

Z = 1

Mo Kα radiation

μ = 0.23 mm−1

T = 293 K

0.20 × 0.20 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer

8245 measured reflections

3638 independent reflections

3070 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.104

S = 1.05

3638 reflections

223 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.34 e Å−3

Δρmin = −0.46 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/S1600536812009154/xu5475sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812009154/xu5475Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812009154/xu5475Isup3.cml

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

2CH6N3+·C10H6O6S2−·C12H24O6	Z = 1
Mr = 670.76	F(000) = 356
Triclinic, P1	Dx = 1.387 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.5275 (17) Å	Cell parameters from 3638 reflections
b = 9.1291 (18) Å	θ = 3.0–27.5°
c = 11.470 (2) Å	µ = 0.23 mm−1
α = 111.97 (3)°	T = 293 K
β = 96.10 (3)°	Block, colorless
γ = 99.38 (3)°	0.20 × 0.20 × 0.20 mm
V = 803.3 (3) Å3

Rigaku SCXmini diffractometer	3070 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.025
Graphite monochromator	θmax = 27.4°, θmin = 3.1°
CCD_Profile_fitting scans	h = −11→10
8245 measured reflections	k = −11→11
3638 independent reflections	l = −14→14

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0379P)2 + 0.3633P] where P = (Fo2 + 2Fc2)/3
3638 reflections	(Δ/σ)max < 0.001
223 parameters	Δρmax = 0.34 e Å−3
0 restraints	Δρmin = −0.46 e Å−3

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.

	x	y	z	Uiso*/Ueq
S1	0.11339 (5)	0.65053 (5)	0.31289 (4)	0.03167 (13)
O3	0.09429 (17)	0.50066 (14)	0.33254 (12)	0.0414 (3)
O4	0.63864 (17)	−0.01790 (16)	0.23799 (13)	0.0459 (3)
O5	0.47238 (18)	0.22644 (16)	0.24927 (13)	0.0490 (4)
C3	0.02394 (19)	0.78364 (18)	0.43259 (15)	0.0277 (3)
O6	0.40620 (17)	0.26914 (16)	0.01217 (13)	0.0468 (3)
C4	0.03593 (18)	0.94983 (18)	0.45050 (15)	0.0263 (3)
C1	−0.1274 (2)	0.8214 (2)	0.60430 (18)	0.0387 (4)
H1	−0.1821	0.7782	0.6541	0.046*
O1	0.28092 (17)	0.73046 (16)	0.33171 (17)	0.0608 (5)
C2	−0.0571 (2)	0.7217 (2)	0.50692 (17)	0.0345 (4)
H2	−0.0658	0.6134	0.4931	0.041*
O2	0.0209 (2)	0.62768 (18)	0.19082 (13)	0.0574 (4)
C12	0.7991 (2)	0.1911 (2)	0.04975 (18)	0.0415 (4)
N3	0.8556 (3)	0.2086 (3)	0.16648 (19)	0.0569 (5)
C5	0.1159 (2)	1.0194 (2)	0.37412 (17)	0.0349 (4)
H5	0.1611	0.9550	0.3085	0.042*
N2	0.6973 (3)	0.0547 (2)	−0.0292 (2)	0.0626 (6)
C8	0.5725 (3)	0.2333 (3)	0.35990 (19)	0.0539 (5)
H8A	0.5319	0.2912	0.4361	0.065*
H8B	0.6820	0.2903	0.3672	0.065*
C11	0.3022 (3)	0.2636 (3)	−0.0967 (2)	0.0532 (5)
H11A	0.2955	0.3727	−0.0865	0.064*
H11B	0.1943	0.2037	−0.1034	0.064*
C9	0.4799 (3)	0.3797 (2)	0.2418 (2)	0.0575 (6)
H9A	0.5878	0.4217	0.2326	0.069*
H9B	0.4563	0.4558	0.3197	0.069*
C7	0.5717 (3)	0.0633 (3)	0.34750 (19)	0.0493 (5)
H7A	0.6351	0.0655	0.4238	0.059*
H7B	0.4619	0.0058	0.3382	0.059*
C6	0.6336 (3)	−0.1836 (3)	0.2156 (2)	0.0501 (5)
H6A	0.5231	−0.2393	0.2066	0.060*
H6B	0.6981	−0.1898	0.2879	0.060*
N1	0.8482 (3)	0.3087 (3)	0.0127 (2)	0.0653 (6)
C10	0.3593 (3)	0.3611 (3)	0.1293 (2)	0.0552 (6)
H10A	0.2537	0.3070	0.1334	0.066*
H10B	0.3520	0.4672	0.1318	0.066*
H20	0.928 (3)	0.299 (3)	0.219 (2)	0.066 (7)*
H21	0.819 (3)	0.142 (3)	0.193 (2)	0.065 (8)*
H25	0.903 (3)	0.399 (3)	0.065 (3)	0.074 (9)*
H22	0.670 (3)	−0.012 (3)	0.000 (3)	0.070 (9)*
H24	0.829 (3)	0.289 (3)	−0.057 (3)	0.059 (8)*
H23	0.659 (4)	0.047 (4)	−0.099 (3)	0.094 (11)*

	U11	U22	U33	U12	U13	U23
S1	0.0417 (2)	0.0225 (2)	0.0323 (2)	0.00950 (16)	0.01195 (17)	0.01017 (16)
O3	0.0617 (9)	0.0267 (6)	0.0411 (7)	0.0161 (6)	0.0153 (6)	0.0150 (5)
O4	0.0520 (8)	0.0399 (7)	0.0458 (8)	0.0041 (6)	0.0122 (6)	0.0188 (6)
O5	0.0553 (9)	0.0386 (7)	0.0412 (7)	0.0067 (6)	−0.0003 (6)	0.0068 (6)
C3	0.0293 (8)	0.0254 (8)	0.0291 (8)	0.0073 (6)	0.0054 (6)	0.0108 (6)
O6	0.0498 (8)	0.0426 (7)	0.0513 (8)	0.0232 (6)	0.0100 (6)	0.0168 (6)
C4	0.0264 (8)	0.0250 (7)	0.0294 (8)	0.0065 (6)	0.0055 (6)	0.0126 (6)
C1	0.0454 (10)	0.0369 (9)	0.0487 (11)	0.0129 (8)	0.0237 (9)	0.0279 (8)
O1	0.0477 (8)	0.0351 (7)	0.0928 (12)	0.0100 (6)	0.0374 (8)	0.0111 (7)
C2	0.0409 (9)	0.0260 (8)	0.0425 (10)	0.0091 (7)	0.0125 (8)	0.0182 (7)
O2	0.0952 (12)	0.0506 (8)	0.0305 (7)	0.0300 (8)	0.0092 (7)	0.0157 (6)
C12	0.0424 (10)	0.0352 (9)	0.0421 (10)	0.0033 (8)	0.0097 (8)	0.0118 (8)
N3	0.0583 (12)	0.0525 (11)	0.0517 (11)	−0.0154 (9)	−0.0037 (9)	0.0265 (10)
C5	0.0416 (10)	0.0326 (9)	0.0391 (9)	0.0140 (7)	0.0197 (8)	0.0182 (7)
N2	0.0723 (14)	0.0400 (11)	0.0573 (13)	−0.0042 (10)	−0.0098 (11)	0.0118 (10)
C8	0.0543 (13)	0.0537 (13)	0.0358 (11)	0.0051 (10)	0.0011 (9)	0.0027 (9)
C11	0.0518 (12)	0.0508 (12)	0.0676 (14)	0.0241 (10)	0.0093 (11)	0.0305 (11)
C9	0.0706 (15)	0.0356 (10)	0.0540 (13)	0.0146 (10)	0.0116 (11)	0.0031 (9)
C7	0.0464 (11)	0.0597 (13)	0.0354 (10)	0.0030 (10)	0.0027 (9)	0.0169 (9)
C6	0.0518 (12)	0.0495 (12)	0.0577 (13)	0.0097 (9)	0.0050 (10)	0.0328 (10)
N1	0.0971 (18)	0.0497 (12)	0.0444 (12)	−0.0041 (11)	0.0146 (12)	0.0215 (10)
C10	0.0662 (14)	0.0402 (11)	0.0608 (14)	0.0278 (10)	0.0200 (11)	0.0133 (10)

S1—O1	1.4481 (15)	C5—C1i	1.365 (2)
S1—O3	1.4544 (12)	C5—H5	0.9300
S1—O2	1.4556 (15)	N2—H22	0.81 (3)
S1—C3	1.7943 (17)	N2—H23	0.80 (3)
O4—C6	1.429 (2)	C8—C7	1.504 (3)
O4—C7	1.430 (2)	C8—H8A	0.9700
O5—C9	1.425 (3)	C8—H8B	0.9700
O5—C8	1.427 (2)	C11—C6ii	1.496 (3)
C3—C2	1.372 (2)	C11—H11A	0.9700
C3—C4	1.437 (2)	C11—H11B	0.9700
O6—C10	1.431 (2)	C9—C10	1.499 (3)
O6—C11	1.432 (2)	C9—H9A	0.9700
C4—C5	1.428 (2)	C9—H9B	0.9700
C4—C4i	1.434 (3)	C7—H7A	0.9700
C1—C5i	1.365 (2)	C7—H7B	0.9700
C1—C2	1.412 (2)	C6—C11ii	1.496 (3)
C1—H1	0.9300	C6—H6A	0.9700
C2—H2	0.9300	C6—H6B	0.9700
C12—N3	1.314 (3)	N1—H25	0.84 (3)
C12—N1	1.319 (3)	N1—H24	0.75 (3)
C12—N2	1.327 (3)	C10—H10A	0.9700
N3—H20	0.90 (3)	C10—H10B	0.9700
N3—H21	0.81 (3)
O1—S1—O3	113.09 (9)	O5—C8—H8B	110.0
O1—S1—O2	112.57 (11)	C7—C8—H8B	110.0
O3—S1—O2	111.83 (9)	H8A—C8—H8B	108.3
O1—S1—C3	107.06 (9)	O6—C11—C6ii	109.94 (16)
O3—S1—C3	106.12 (8)	O6—C11—H11A	109.7
O2—S1—C3	105.53 (8)	C6ii—C11—H11A	109.7
C6—O4—C7	112.50 (15)	O6—C11—H11B	109.7
C9—O5—C8	113.94 (16)	C6ii—C11—H11B	109.7
C2—C3—C4	120.72 (15)	H11A—C11—H11B	108.2
C2—C3—S1	117.84 (12)	O5—C9—C10	109.51 (17)
C4—C3—S1	121.44 (12)	O5—C9—H9A	109.8
C10—O6—C11	111.63 (15)	C10—C9—H9A	109.8
C5—C4—C4i	118.55 (17)	O5—C9—H9B	109.8
C5—C4—C3	122.97 (14)	C10—C9—H9B	109.8
C4i—C4—C3	118.48 (17)	H9A—C9—H9B	108.2
C5i—C1—C2	120.57 (15)	O4—C7—C8	109.21 (17)
C5i—C1—H1	119.7	O4—C7—H7A	109.8
C2—C1—H1	119.7	C8—C7—H7A	109.8
C3—C2—C1	120.44 (15)	O4—C7—H7B	109.8
C3—C2—H2	119.8	C8—C7—H7B	109.8
C1—C2—H2	119.8	H7A—C7—H7B	108.3
N3—C12—N1	119.0 (2)	O4—C6—C11ii	109.89 (17)
N3—C12—N2	119.6 (2)	O4—C6—H6A	109.7
N1—C12—N2	121.4 (2)	C11ii—C6—H6A	109.7
C12—N3—H20	119.7 (16)	O4—C6—H6B	109.7
C12—N3—H21	119.9 (18)	C11ii—C6—H6B	109.7
H20—N3—H21	120 (2)	H6A—C6—H6B	108.2
C1i—C5—C4	121.22 (16)	C12—N1—H25	120.7 (19)
C1i—C5—H5	119.4	C12—N1—H24	116 (2)
C4—C5—H5	119.4	H25—N1—H24	123 (3)
C12—N2—H22	116.7 (19)	O6—C10—C9	110.54 (17)
C12—N2—H23	119 (2)	O6—C10—H10A	109.5
H22—N2—H23	124 (3)	C9—C10—H10A	109.5
O5—C8—C7	108.65 (16)	O6—C10—H10B	109.5
O5—C8—H8A	110.0	C9—C10—H10B	109.5
C7—C8—H8A	110.0	H10A—C10—H10B	108.1

D—H···A	D—H	H···A	D···A	D—H···A
N1—H24···O2iii	0.75 (3)	2.36 (3)	2.897 (3)	131 (2)
N1—H25···O2iv	0.84 (3)	2.05 (3)	2.887 (3)	175 (3)
N2—H22···O6ii	0.81 (3)	2.28 (3)	3.029 (3)	154 (3)
N2—H23···O5ii	0.80 (3)	2.43 (3)	2.867 (3)	115 (3)
N3—H20···O3iv	0.90 (3)	2.01 (3)	2.913 (3)	179 (2)
N3—H21···O4	0.81 (3)	2.18 (3)	2.952 (3)	159 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H24⋯O2i	0.75 (3)	2.36 (3)	2.897 (3)	131 (2)
N1—H25⋯O2ii	0.84 (3)	2.05 (3)	2.887 (3)	175 (3)
N2—H22⋯O6iii	0.81 (3)	2.28 (3)	3.029 (3)	154 (3)
N2—H23⋯O5iii	0.80 (3)	2.43 (3)	2.867 (3)	115 (3)
N3—H20⋯O3ii	0.90 (3)	2.01 (3)	2.913 (3)	179 (2)
N3—H21⋯O4	0.81 (3)	2.18 (3)	2.952 (3)	159 (2)

Symmetry codes: (i) ; (ii) ; (iii) .