Dimethyl­ammonium guanidinium naphthalene-1,5-disulfonate

The asymmetric unit of the title salt, CH₆N₃⁺·C₂H₈N⁺·C₁₀H₆O₆S₂²⁻, consists of one dimethyl­ammonium cation, one guanidinium cation, and two half naphthalene-1,5-disulfonate anions, which lie on inversion centers. N—H...O hydrogen bonds link the cations and anions into layers parallel to the ab plane. The layers have a sandwich-like structure, with the sulfonate groups and cations forming outer slices and the naphthalene ring systems inside.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.046
• wR factor = 0.121
• Data-to-parameter ratio = 18.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors of          C3
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors of          N4
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          6
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600          6

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT007_ALERT_5_G Note: Number of Unrefined D-H Atoms ............          8
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal ..........    0.03000 Deg.
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   5 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   5 ALERT level G = General information/check it is not something unexpected

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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S1. Comment

Recently a series of nanoporous materials has been reported, which have two-dimensional hydrogen-bond networks and adjustable porosity (Russell et al., 1997). Guanidinium ions and the sulfonate groups of arenedisulfonate ions can form rich variety of H-bonds. We prepared the title compound in attempts to find new hydrogen-bonded dielectric materials consisting of guanidinium and naphthalene-1,5-disulfonate ions. Unfortunately, the study of dielectric permeability of the title compound indicated that its dielectric constant is essentially temperature-independent below its melting point (388 — 390 K). Thus we have found that the title compound has no dielectric disuniform from 80 K to 405 K.

At room temperature (25°C), the asymmetric unit of the title compound consists of one dimethylammonium cation, one guanidinium cation, and two halves of naphthalene-1,5-disulfonate anions, which lie at inversion centers (Fig. 1). The N—H···O hydrogen bonds join cations and anions into layers parallel to the ab plane. Layers have sandwich-like structure: sulfonate groups and cations form outer slices and naphthalene bicycles are inside. (Fig. 2).

Related literature

For nanoporous materials with two-dimensional hydrogen-bonded networks, see: Russell et al. (1997). For recent studies of organic and organic–inorganic salts with ferroelectric properties, see: Fu et al. (2009); Wu et al. (2011). For general background to structure phase transitions in closely related compounds, see: Ye et al. (2009); Zhang et al. (2010).

S2. Experimental

The 1,5-naphthalenedisulfonic acid (1.824 g 8 mmol) and guanidinium tetrafluoroborate (0.588 g 4 mmol) were combined in 30 ml aqueous solution, and methanol solution of dimethylamine (0.326 g 4 mmol) was added to the mixture. The solution was stirred for 30 min to complete the reaction, and good quality blocky single crystals were obtained by slow evaporation of the filtrate after two weeks (chemical yield is 62%).

S3. Refinement

All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H = 0.91—0.93 Å, N—H = 0.86 Å and with U_iso(H) = 1.2 U_iso(C, N) or 1.5 U_iso(C) for methyl H atoms.

Computing details

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

Figures

	Fig. 1. Asymmetric unit of the title compound, with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view of the packing of the title compound. Dashed lines indicate hydrogen bonds.

Dimethylammonium guanidinium naphthalene-1,5-disulfonate

Crystal data

CH6N3^+·C2H8N^+·C10H6O6S2^2^−	Z = 2
Mr = 392.45	F(000) = 412
Triclinic, P1	Dx = 1.431 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.7782 (18) Å	Cell parameters from 3638 reflections
b = 9.0316 (18) Å	θ = 3.0–27.5°
c = 11.923 (2) Å	µ = 0.33 mm^−1
α = 87.10 (3)°	T = 293 K
β = 74.74 (3)°	Block, colourless
γ = 88.77 (3)°	0.20 × 0.20 × 0.20 mm
V = 910.7 (3) Å^3

Data collection

Rigaku SCXmini diffractometer	4168 independent reflections
Radiation source: fine-focus sealed tube	3097 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
ω scans	θmax = 27.5°, θmin = 3.3°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −11→11
Tmin = 0.936, Tmax = 0.937	k = −11→11
9502 measured reflections	l = −15→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.121	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0492P)^2 + 0.289P] where P = (Fo^2 + 2Fc^2)/3
4168 reflections	(Δ/σ)max < 0.001
228 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.29 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.56454 (6)	0.60040 (6)	0.20852 (5)	0.04580 (17)
O1	0.72470 (18)	0.64764 (18)	0.19535 (15)	0.0537 (4)
O2	0.47542 (19)	0.71224 (18)	0.15867 (15)	0.0554 (4)
O3	0.5537 (2)	0.45431 (18)	0.16728 (16)	0.0605 (5)
C4	0.4733 (2)	0.5921 (2)	0.3610 (2)	0.0444 (5)
C5	0.3440 (3)	0.6794 (3)	0.4035 (2)	0.0574 (6)
H5	0.3017	0.7376	0.3523	0.069*
C6	0.2749 (3)	0.6819 (3)	0.5227 (3)	0.0650 (7)
H6	0.1878	0.7430	0.5500	0.078*
C7	0.3320 (3)	0.5973 (3)	0.5998 (2)	0.0523 (6)
H7	0.2843	0.6018	0.6791	0.063*
C8	0.4640 (2)	0.5017 (2)	0.5607 (2)	0.0427 (5)
C3	0.1383 (3)	0.4844 (2)	0.12679 (19)	0.0427 (5)
C1	0.6168 (4)	0.1027 (3)	0.0828 (3)	0.0689 (7)
H1A	0.5056	0.1163	0.0916	0.103*
H1B	0.6669	0.0753	0.0049	0.103*
H1C	0.6613	0.1934	0.0978	0.103*
C2	0.5666 (4)	0.0162 (4)	0.2865 (3)	0.0827 (9)
H2A	0.6138	0.1018	0.3077	0.124*
H2B	0.5807	−0.0678	0.3355	0.124*
H2C	0.4559	0.0344	0.2961	0.124*
N1	−0.0065 (2)	0.4450 (2)	0.1321 (2)	0.0606 (6)
H1D	−0.0779	0.5115	0.1317	0.073*
H1E	−0.0300	0.3526	0.1361	0.073*
N2	0.1747 (3)	0.6261 (2)	0.12075 (19)	0.0590 (5)
H2D	0.1034	0.6928	0.1203	0.071*
H2E	0.2697	0.6517	0.1173	0.071*
N3	0.2482 (2)	0.3819 (2)	0.12657 (18)	0.0556 (5)
H3A	0.2247	0.2896	0.1299	0.067*
H3B	0.3432	0.4077	0.1231	0.067*
N4	0.6420 (3)	−0.0140 (2)	0.1648 (2)	0.0598 (6)
H4A	0.7465	−0.0261	0.1558	0.072*
H4B	0.6042	−0.0995	0.1478	0.072*
C9	−0.0137 (2)	−0.0556 (2)	0.3530 (2)	0.0429 (5)
C10	−0.0994 (3)	−0.1839 (2)	0.3832 (2)	0.0513 (6)
H10	−0.1247	−0.2368	0.3256	0.062*
C11	−0.1487 (3)	−0.2353 (3)	0.4988 (2)	0.0553 (6)
H11	−0.2053	−0.3231	0.5174	0.066*
C12	−0.1155 (3)	−0.1596 (2)	0.5852 (2)	0.0471 (5)
H12	−0.1513	−0.1950	0.6622	0.057*
C13	−0.0266 (2)	−0.0268 (2)	0.55895 (19)	0.0400 (5)
S2	0.03040 (7)	0.01286 (6)	0.20605 (5)	0.04819 (17)
O4	0.1966 (2)	0.0447 (2)	0.16779 (16)	0.0668 (5)
O5	−0.0671 (2)	0.14568 (17)	0.20878 (16)	0.0590 (5)
O6	−0.0188 (2)	−0.10150 (18)	0.14233 (15)	0.0602 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0427 (3)	0.0350 (3)	0.0622 (4)	−0.0011 (2)	−0.0178 (3)	−0.0047 (2)
O1	0.0424 (9)	0.0513 (10)	0.0678 (11)	−0.0067 (7)	−0.0152 (8)	−0.0002 (8)
O2	0.0584 (10)	0.0448 (9)	0.0686 (11)	0.0028 (7)	−0.0273 (9)	0.0006 (8)
O3	0.0678 (11)	0.0400 (9)	0.0772 (12)	−0.0006 (8)	−0.0229 (9)	−0.0146 (8)
C4	0.0360 (11)	0.0324 (11)	0.0651 (15)	0.0022 (8)	−0.0140 (10)	−0.0035 (10)
C5	0.0471 (13)	0.0504 (14)	0.0751 (18)	0.0144 (11)	−0.0185 (12)	0.0007 (12)
C6	0.0512 (14)	0.0605 (16)	0.0755 (19)	0.0291 (12)	−0.0060 (13)	−0.0005 (13)
C7	0.0422 (12)	0.0445 (13)	0.0643 (16)	0.0123 (10)	−0.0045 (11)	−0.0032 (11)
C8	0.0332 (10)	0.0270 (10)	0.0672 (14)	0.0005 (8)	−0.0113 (9)	−0.0049 (9)
C3	0.0430 (12)	0.0413 (12)	0.0410 (12)	−0.0017 (9)	−0.0073 (9)	0.0038 (9)
C1	0.083 (2)	0.0507 (16)	0.0703 (19)	0.0003 (14)	−0.0156 (15)	−0.0022 (13)
C2	0.091 (2)	0.087 (2)	0.069 (2)	−0.0184 (18)	−0.0177 (17)	−0.0047 (16)
N1	0.0445 (11)	0.0447 (11)	0.0905 (16)	−0.0045 (9)	−0.0166 (11)	0.0133 (11)
N2	0.0546 (12)	0.0397 (11)	0.0831 (16)	−0.0032 (9)	−0.0198 (11)	0.0034 (10)
N3	0.0431 (11)	0.0402 (11)	0.0812 (15)	−0.0005 (8)	−0.0131 (10)	0.0006 (10)
N4	0.0527 (12)	0.0479 (12)	0.0803 (16)	0.0023 (9)	−0.0204 (11)	−0.0036 (10)
C9	0.0386 (11)	0.0312 (10)	0.0617 (14)	0.0016 (8)	−0.0181 (10)	−0.0046 (9)
C10	0.0539 (13)	0.0364 (12)	0.0693 (17)	−0.0070 (10)	−0.0249 (12)	−0.0084 (11)
C11	0.0559 (14)	0.0379 (12)	0.0763 (18)	−0.0165 (10)	−0.0238 (13)	−0.0006 (11)
C12	0.0428 (12)	0.0356 (11)	0.0636 (15)	−0.0065 (9)	−0.0151 (10)	−0.0003 (10)
C13	0.0296 (10)	0.0284 (10)	0.0645 (14)	0.0024 (8)	−0.0162 (9)	−0.0051 (9)
S2	0.0479 (3)	0.0357 (3)	0.0614 (4)	−0.0034 (2)	−0.0142 (3)	−0.0054 (2)
O4	0.0489 (10)	0.0736 (13)	0.0720 (12)	−0.0070 (9)	−0.0026 (8)	−0.0166 (10)
O5	0.0647 (11)	0.0373 (9)	0.0733 (12)	0.0020 (8)	−0.0168 (9)	0.0048 (8)
O6	0.0807 (12)	0.0417 (9)	0.0647 (11)	−0.0087 (8)	−0.0296 (9)	−0.0050 (8)

Geometric parameters (Å, º)

S1—O1	1.4442 (16)	C2—H2C	0.9600
S1—O3	1.4448 (17)	N1—H1D	0.8600
S1—O2	1.4614 (17)	N1—H1E	0.8600
S1—C4	1.782 (3)	N2—H2D	0.8600
C4—C5	1.366 (3)	N2—H2E	0.8600
C4—C8^i	1.436 (3)	N3—H3A	0.8600
C5—C6	1.392 (4)	N3—H3B	0.8600
C5—H5	0.9300	N4—H4A	0.9000
C6—C7	1.354 (4)	N4—H4B	0.9000
C6—H6	0.9300	C9—C10	1.375 (3)
C7—C8	1.421 (3)	C9—C13^ii	1.437 (3)
C7—H7	0.9300	C9—S2	1.774 (2)
C8—C8^i	1.421 (5)	C10—C11	1.391 (3)
C8—C4^i	1.436 (3)	C10—H10	0.9300
C3—N1	1.312 (3)	C11—C12	1.362 (3)
C3—N2	1.320 (3)	C11—H11	0.9300
C3—N3	1.322 (3)	C12—C13	1.421 (3)
C1—N4	1.454 (3)	C12—H12	0.9300
C1—H1A	0.9600	C13—C13^ii	1.422 (4)
C1—H1B	0.9600	C13—C9^ii	1.437 (3)
C1—H1C	0.9600	S2—O4	1.4404 (18)
C2—N4	1.465 (4)	S2—O6	1.4496 (17)
C2—H2A	0.9600	S2—O5	1.4552 (17)
C2—H2B	0.9600
O1—S1—O3	113.70 (11)	C3—N1—H1D	120.0
O1—S1—O2	111.13 (10)	C3—N1—H1E	120.0
O3—S1—O2	112.70 (11)	H1D—N1—H1E	120.0
O1—S1—C4	105.95 (10)	C3—N2—H2D	120.0
O3—S1—C4	107.12 (11)	C3—N2—H2E	120.0
O2—S1—C4	105.59 (10)	H2D—N2—H2E	120.0
C5—C4—C8^i	120.0 (2)	C3—N3—H3A	120.0
C5—C4—S1	118.99 (19)	C3—N3—H3B	120.0
C8^i—C4—S1	121.01 (16)	H3A—N3—H3B	120.0
C4—C5—C6	120.5 (2)	C1—N4—C2	113.6 (2)
C4—C5—H5	119.7	C1—N4—H4A	108.9
C6—C5—H5	119.7	C2—N4—H4A	108.9
C7—C6—C5	121.4 (2)	C1—N4—H4B	108.9
C7—C6—H6	119.3	C2—N4—H4B	108.9
C5—C6—H6	119.3	H4A—N4—H4B	107.7
C6—C7—C8	120.6 (2)	C10—C9—C13^ii	120.2 (2)
C6—C7—H7	119.7	C10—C9—S2	118.36 (18)
C8—C7—H7	119.7	C13^ii—C9—S2	121.21 (16)
C8^i—C8—C7	118.6 (3)	C9—C10—C11	120.6 (2)
C8^i—C8—C4^i	118.8 (2)	C9—C10—H10	119.7
C7—C8—C4^i	122.6 (2)	C11—C10—H10	119.7
N1—C3—N2	120.1 (2)	C12—C11—C10	121.2 (2)
N1—C3—N3	119.9 (2)	C12—C11—H11	119.4
N2—C3—N3	119.9 (2)	C10—C11—H11	119.4
N4—C1—H1A	109.5	C11—C12—C13	120.5 (2)
N4—C1—H1B	109.5	C11—C12—H12	119.7
H1A—C1—H1B	109.5	C13—C12—H12	119.7
N4—C1—H1C	109.5	C12—C13—C13^ii	119.2 (2)
H1A—C1—H1C	109.5	C12—C13—C9^ii	122.6 (2)
H1B—C1—H1C	109.5	C13^ii—C13—C9^ii	118.3 (2)
N4—C2—H2A	109.5	O4—S2—O6	113.80 (11)
N4—C2—H2B	109.5	O4—S2—O5	112.38 (11)
H2A—C2—H2B	109.5	O6—S2—O5	111.31 (11)
N4—C2—H2C	109.5	O4—S2—C9	108.35 (11)
H2A—C2—H2C	109.5	O6—S2—C9	105.83 (10)
H2B—C2—H2C	109.5	O5—S2—C9	104.46 (10)
O1—S1—C4—C5	119.8 (2)	C13^ii—C9—C10—C11	0.3 (3)
O3—S1—C4—C5	−118.5 (2)	S2—C9—C10—C11	−174.47 (18)
O2—S1—C4—C5	1.8 (2)	C9—C10—C11—C12	0.9 (4)
O1—S1—C4—C8^i	−58.72 (19)	C10—C11—C12—C13	−1.2 (4)
O3—S1—C4—C8^i	62.98 (19)	C11—C12—C13—C13^ii	0.4 (4)
O2—S1—C4—C8^i	−176.68 (16)	C11—C12—C13—C9^ii	−178.9 (2)
C8^i—C4—C5—C6	2.1 (4)	C10—C9—S2—O4	−130.74 (19)
S1—C4—C5—C6	−176.5 (2)	C13^ii—C9—S2—O4	54.60 (19)
C4—C5—C6—C7	−0.8 (4)	C10—C9—S2—O6	−8.3 (2)
C5—C6—C7—C8	−0.7 (4)	C13^ii—C9—S2—O6	177.01 (16)
C6—C7—C8—C8^i	0.8 (4)	C10—C9—S2—O5	109.27 (19)
C6—C7—C8—C4^i	−178.7 (2)	C13^ii—C9—S2—O5	−65.39 (18)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···O1^iii	0.86	2.10	2.916 (3)	159
N1—H1E···O5	0.86	2.02	2.825 (3)	157
N2—H2D···O6^iv	0.86	2.12	2.942 (3)	160
N2—H2E···O2	0.86	2.08	2.921 (3)	164
N3—H3A···O4	0.86	2.24	3.084 (3)	167
N3—H3B···O3	0.86	2.11	2.940 (3)	163
N4—H4A···O6^v	0.90	2.12	3.011 (3)	168
N4—H4A···O5^v	0.90	2.50	3.133 (3)	128
N4—H4B···O1^vi	0.90	2.60	3.152 (3)	121
N4—H4B···O2^vi	0.90	2.04	2.914 (3)	163

Symmetry codes: (iii) x−1, y, z; (iv) x, y+1, z; (v) x+1, y, z; (vi) x, y−1, z.