Bis(butan-1-aminium) naphthalene-1,5-disulfonate

Abstract

In the title compound, 2C₄H₁₂N⁺·C₁₀H₆O₆S₂ ²⁻, the anion lies on an inversion center, so the asymmetric unit contains half an anion and one cation which are linked by a strong N—H⋯O hydrogen bond. The crystal structure comprises discrete ions, which are linked into centrosymmetric R ₄ ⁴(12) loops by N—H⋯O inter­actions.

Related literature  

For related structures, see: Jin (2011a ▶,b ▶, 2012 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental  

Crystal data  

• 2C₄H₁₂N⁺·C₁₀H₆O₆S₂ ²⁻

• M _r = 434.56

• Monoclinic,

• a = 8.1532 (16) Å

• b = 9.2582 (19) Å

• c = 14.108 (5) Å

• β = 108.02 (3)°

• V = 1012.7 (5) ų

• Z = 2

• Mo Kα radiation

• μ = 0.30 mm⁻¹

• T = 293 K

• 0.3 × 0.3 × 0.2 mm

Data collection  

• Rigaku Mercury CCD diffractometer

• Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.489, T _max = 1.000

• 10171 measured reflections

• 2316 independent reflections

• 2039 reflections with I > 2σ(I)

• R _int = 0.034

Refinement  

• R[F ² > 2σ(F ²)] = 0.038

• wR(F ²) = 0.094

• S = 1.14

• 2316 reflections

• 128 parameters

• H-atom parameters constrained

• Δρ_max = 0.24 e Å⁻³

• Δρ_min = −0.43 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812018880/bx2406Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1	0.89	1.95	2.840 (2)	177
N1—H1C⋯O2i	0.89	1.97	2.857 (2)	177
N1—H1B⋯O3ii	0.89	2.05	2.911 (2)	162

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

As an extension of the research about naphthalene-1,5-disulfonate salts (Jin, 2011a; Jin, 2011b; Jin, 2012), I report here the synthesis and the crystal structure of the title complex, 2C₄H₁₂N⁺C₁₀H₆S₂O₆^2-. In the title compound 2 C₄H₁₂N⁺ . C₁₀H₆S₂O₆² , the anion lies on inversion center, so the asymmetric unit contains one-half anion and one cation which are linked by one strong N—H···O hydrogen bond interaction, Fig 1. The crystal structure comprises discrete ions which are linked into centrosymmetric R₄⁴(12) dimers by simple N—H···O interactions, (Bernstein, et al., 1995), Fig 2, Table1.

Experimental

2C₄H₁₂N⁺•C₁₀H₆S₂O₆^2- was synthetized from a mixture of CH₃(CH₂)₃NH₂ (146.28 mg, 2.00 mmol), C₁₀H₈O₆S₂ (288.28 mg, 1.00 mmol), and distilled water (10 ml), which was stirred a few minutes at room temperature, giving a clear transparent solution. After evaporation for a few days, block colorless crystals suitable for X-ray diffraction were obtained in about 88% yield and filtered and washed with distilled water.

Refinement

H atoms bound to carbon and nitrogen were placed at idealized positions [C—H =0.93 to 0.97 Å and N—H = 0.89 Å] and allowed to ride on their parent atoms with U_iso fixed at 1.2 U_eq(C,N).

Figures

Fig. 1.

A view of the title compound showing the labelling of the non-H atoms. Displacement ellipsoids drawn at the 30% probability level. [Symmetry code: (a) 1-x, 2-y, 2-z]

Fig. 2.

Part of the crystal structure of (I) , showing discrete ions which are linked into centrosymmetric R44(12) dimers.[Symmetry codes : (i) x, 3/2-y, -1/2+z; (ii) -x, 1/2+y, 3/2-z; (iii) -x,2-y,1-z]

Crystal data

2C4H12N+·C10H6O6S22−	F(000) = 464
Mr = 434.56	Dx = 1.425 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3450 reflections
a = 8.1532 (16) Å	θ = 6.2–55.3°
b = 9.2582 (19) Å	µ = 0.30 mm−1
c = 14.108 (5) Å	T = 293 K
β = 108.02 (3)°	Block, colourless
V = 1012.7 (5) Å3	0.3 × 0.3 × 0.2 mm
Z = 2

Data collection

Rigaku Mercury CCD diffractometer	2316 independent reflections
Radiation source: fine-focus sealed tube	2039 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
ω scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −10→10
Tmin = 0.489, Tmax = 1.000	k = −12→12
10171 measured reflections	l = −18→18

Refinement

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094	H-atom parameters constrained
S = 1.14	w = 1/[σ2(Fo2) + (0.0379P)2 + 0.4216P] where P = (Fo2 + 2Fc2)/3
2316 reflections	(Δ/σ)max = 0.001
128 parameters	Δρmax = 0.24 e Å−3
0 restraints	Δρmin = −0.43 e Å−3

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.2319 (2)	1.0297 (2)	0.69402 (14)	0.0364 (4)
H1D	0.2261	1.0939	0.7473	0.044*
H1E	0.2235	1.0880	0.6356	0.044*
C2	0.4015 (2)	0.95077 (19)	0.72490 (13)	0.0332 (4)
H2A	0.4062	0.8866	0.6714	0.040*
H2B	0.4085	0.8919	0.7829	0.040*
C3	0.5553 (3)	1.0519 (2)	0.74938 (15)	0.0405 (5)
H3A	0.5439	1.1157	0.6932	0.049*
H3B	0.5553	1.1112	0.8061	0.049*
C4	0.7256 (3)	0.9722 (3)	0.77313 (17)	0.0524 (6)
H4A	0.7286	0.9168	0.7161	0.079*
H4B	0.7376	0.9087	0.8286	0.079*
H4C	0.8186	1.0406	0.7896	0.079*
C5	0.2728 (2)	1.06642 (17)	0.97032 (12)	0.0253 (3)
H5	0.1617	1.0294	0.9555	0.030*
C6	0.41452 (18)	0.97062 (16)	0.98793 (11)	0.0198 (3)
C7	0.39614 (19)	0.81664 (16)	0.98343 (11)	0.0204 (3)
C8	0.5368 (2)	0.72878 (17)	1.00271 (12)	0.0259 (3)
H8	0.5228	0.6290	1.0009	0.031*
C9	0.2973 (2)	1.21166 (18)	0.97477 (13)	0.0286 (4)
H9	0.2025	1.2727	0.9627	0.034*
N1	0.0850 (2)	0.92591 (16)	0.67115 (11)	0.0338 (3)
H1A	0.0840	0.8815	0.7269	0.041*
H1B	−0.0136	0.9735	0.6455	0.041*
H1C	0.0971	0.8608	0.6274	0.041*
O1	0.09524 (16)	0.78595 (15)	0.85199 (9)	0.0380 (3)
O2	0.11042 (16)	0.77995 (14)	1.02545 (9)	0.0343 (3)
O3	0.21663 (16)	0.57911 (13)	0.95327 (10)	0.0353 (3)
S1	0.18812 (5)	0.73440 (4)	0.95082 (3)	0.02387 (13)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0436 (11)	0.0273 (9)	0.0380 (10)	0.0057 (8)	0.0123 (8)	0.0024 (7)
C2	0.0409 (10)	0.0277 (9)	0.0313 (9)	0.0033 (7)	0.0118 (8)	−0.0002 (7)
C3	0.0491 (12)	0.0362 (10)	0.0351 (10)	−0.0046 (9)	0.0113 (9)	0.0010 (8)
C4	0.0407 (12)	0.0699 (16)	0.0470 (12)	−0.0053 (11)	0.0139 (10)	−0.0027 (11)
C5	0.0186 (7)	0.0255 (8)	0.0320 (8)	−0.0005 (6)	0.0078 (6)	0.0015 (6)
C6	0.0197 (7)	0.0203 (7)	0.0206 (7)	−0.0011 (6)	0.0081 (6)	0.0008 (5)
C7	0.0212 (7)	0.0202 (7)	0.0204 (7)	−0.0037 (6)	0.0073 (6)	0.0008 (6)
C8	0.0282 (8)	0.0166 (7)	0.0333 (8)	−0.0006 (6)	0.0101 (7)	0.0011 (6)
C9	0.0225 (8)	0.0235 (8)	0.0400 (9)	0.0052 (6)	0.0100 (7)	0.0025 (7)
N1	0.0363 (8)	0.0338 (8)	0.0320 (8)	0.0092 (6)	0.0116 (6)	0.0033 (6)
O1	0.0318 (7)	0.0443 (8)	0.0306 (7)	−0.0089 (6)	−0.0010 (5)	0.0079 (5)
O2	0.0315 (6)	0.0355 (7)	0.0417 (7)	−0.0059 (5)	0.0198 (6)	−0.0001 (5)
O3	0.0332 (7)	0.0219 (6)	0.0481 (8)	−0.0085 (5)	0.0084 (6)	−0.0019 (5)
S1	0.0220 (2)	0.0218 (2)	0.0267 (2)	−0.00585 (14)	0.00604 (15)	0.00118 (15)

Geometric parameters (Å, º)

C1—N1	1.491 (2)	C5—H5	0.9300
C1—C2	1.505 (3)	C6—C7	1.433 (2)
C1—H1D	0.9700	C6—C6i	1.436 (3)
C1—H1E	0.9700	C7—C8	1.363 (2)
C2—C3	1.517 (3)	C7—S1	1.7847 (15)
C2—H2A	0.9700	C8—C9i	1.403 (2)
C2—H2B	0.9700	C8—H8	0.9300
C3—C4	1.516 (3)	C9—C8i	1.403 (2)
C3—H3A	0.9700	C9—H9	0.9300
C3—H3B	0.9700	N1—H1A	0.8900
C4—H4A	0.9600	N1—H1B	0.8900
C4—H4B	0.9600	N1—H1C	0.8900
C4—H4C	0.9600	O1—S1	1.4464 (14)
C5—C9	1.358 (2)	O2—S1	1.4493 (13)
C5—C6	1.416 (2)	O3—S1	1.4550 (13)
N1—C1—C2	110.73 (15)	C6—C5—H5	119.6
N1—C1—H1D	109.5	C5—C6—C7	123.16 (14)
C2—C1—H1D	109.5	C5—C6—C6i	118.93 (17)
N1—C1—H1E	109.5	C7—C6—C6i	117.91 (17)
C2—C1—H1E	109.5	C8—C7—C6	120.99 (14)
H1D—C1—H1E	108.1	C8—C7—S1	118.08 (12)
C1—C2—C3	112.76 (16)	C6—C7—S1	120.93 (11)
C1—C2—H2A	109.0	C7—C8—C9i	120.22 (15)
C3—C2—H2A	109.0	C7—C8—H8	119.9
C1—C2—H2B	109.0	C9i—C8—H8	119.9
C3—C2—H2B	109.0	C5—C9—C8i	121.16 (15)
H2A—C2—H2B	107.8	C5—C9—H9	119.4
C4—C3—C2	112.72 (18)	C8i—C9—H9	119.4
C4—C3—H3A	109.0	C1—N1—H1A	109.5
C2—C3—H3A	109.0	C1—N1—H1B	109.5
C4—C3—H3B	109.0	H1A—N1—H1B	109.5
C2—C3—H3B	109.0	C1—N1—H1C	109.5
H3A—C3—H3B	107.8	H1A—N1—H1C	109.5
C3—C4—H4A	109.5	H1B—N1—H1C	109.5
C3—C4—H4B	109.5	O1—S1—O2	112.83 (9)
H4A—C4—H4B	109.5	O1—S1—O3	112.40 (8)
C3—C4—H4C	109.5	O2—S1—O3	111.89 (8)
H4A—C4—H4C	109.5	O1—S1—C7	106.27 (8)
H4B—C4—H4C	109.5	O2—S1—C7	106.42 (8)
C9—C5—C6	120.77 (15)	O3—S1—C7	106.46 (7)
C9—C5—H5	119.6
N1—C1—C2—C3	−179.79 (15)	S1—C7—C8—C9i	177.76 (13)
C1—C2—C3—C4	−175.79 (16)	C6—C5—C9—C8i	−0.3 (3)
C9—C5—C6—C7	−179.48 (15)	C8—C7—S1—O1	−119.32 (13)
C9—C5—C6—C6i	0.9 (3)	C6—C7—S1—O1	59.88 (14)
C5—C6—C7—C8	−178.83 (15)	C8—C7—S1—O2	120.19 (13)
C6i—C6—C7—C8	0.8 (3)	C6—C7—S1—O2	−60.61 (14)
C5—C6—C7—S1	2.0 (2)	C8—C7—S1—O3	0.70 (15)
C6i—C6—C7—S1	−178.37 (13)	C6—C7—S1—O3	179.90 (12)
C6—C7—C8—C9i	−1.4 (2)

Symmetry code: (i) −x+1, −y+2, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.89	1.95	2.840 (2)	177
N1—H1C···O2ii	0.89	1.97	2.857 (2)	177
N1—H1B···O3iii	0.89	2.05	2.911 (2)	162

Symmetry codes: (ii) x, −y+3/2, z−1/2; (iii) −x, y+1/2, −z+3/2.