Bis(3-amino­propan-1-aminium) naphthalene-1,5-disulfonate dihydrate

Gao, S.; Ng, S.W.

doi:10.1107/S1600536812018296

organic compounds

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Volume 68| Part 5| May 2012| Page o1575

doi:10.1107/S1600536812018296

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Bis(3-aminopropan-1-aminium) naphthalene-1,5-disulfonate dihydrate

Shan Gao ^a and Seik Weng Ng ^b,^c ^*

^aKey Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, Heilongjiang University, Harbin 150080, People's Republic of China, ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^cChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 23 April 2012; accepted 24 April 2012; online 28 April 2012)

In the title hydrated salt, 2C₃H₁₁N₂⁺·C₁₀H₆O₆S₂²⁻·2H₂O, the anion lies on a center of inversion; its sulfonate –SO₃ group features one S—O bond that is longer than the other two. The O atom of this longer bond is the hydrogen-bond acceptor to the amino H atom of one cation and the ammonium H atom of another cation. In the crystal, N—H⋯O and O—H⋯O hydrogen bonds link the cations, anions and water molecules into a three-dimensional network.

Related literature

For a related structure, see: Gao & Ng (2012 ).

Experimental

Crystal data

2C₃H₁₁N₂⁺·C₁₀H₆O₆S₂²⁻·2H₂O
M_r = 472.58
Triclinic, $[P \overline 1]$
a = 8.0913 (16) Å
b = 8.1917 (16) Å
c = 9.8062 (18) Å
α = 71.182 (5)°
β = 65.950 (5)°
γ = 79.945 (5)°
V = 561.12 (19) Å³
Z = 1
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 293 K
0.21 × 0.17 × 0.17 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.942, T_max = 0.953
5584 measured reflections
2552 independent reflections
2268 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.127
S = 1.05
2552 reflections
165 parameters
7 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1w—H1w1⋯O1	0.84 (1)	2.00 (1)	2.826 (2)	166 (3)
O1w—H1w2⋯N1	0.84 (1)	1.91 (1)	2.736 (2)	172 (3)
N1—H12⋯O3ⁱ	0.88 (1)	2.55 (2)	3.317 (2)	147 (2)
N2—H21⋯O1wⁱⁱ	0.89 (1)	1.84 (1)	2.715 (2)	172 (2)
N2—H22⋯O2ⁱⁱⁱ	0.89 (1)	1.98 (1)	2.845 (2)	165 (3)
N2—H23⋯O3^iv	0.88 (1)	1.97 (1)	2.825 (2)	164 (2)
Symmetry codes: (i) -x+1, -y+1, -z; (ii) x, y-1, z; (iii) -x+1, -y, -z+1; (iv) x+1, y-1, z.

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812018296/xu5521sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812018296/xu5521Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812018296/xu5521Isup3.cml

checkCIF report

Comment top

The study continues with the preceding study on ammonium naphthalene-1,5-disulfonates (Gao & Ng, 2012). The synthesis of the propane-1,3-diammonium derivative yielded instead the bis(3-aminopropylammonium) salt, which exists as a dihydrate (Scheme I), i.e., only one of the two amino groups is protonated so that the cation has a monopositive charge only. The anion of 2(C₃H₁₁N₂)^2+.(C₁₀H₆O₆S₂)^2-.2H₂O lies on a center-of-inversion (Fig. 1). The sulfonate –SO₃ group features one S–O bond that is longer than the other two; the O atom of this longer bond is hydrogen-bond acceptor two the amino H atom of one cation and the ammonium H atom of another cation. Hydrogen bonds link the cation, anion and water molecule into a three-dimensional network.

Related literature top

For a related structure, see: Gao & Ng (2012).

Experimental top

A methanol solution (5 ml) of 1,3-propanediamine (98% pure, 1 mmol, 0.08 ml) was added to an aqueous solution (5 ml) of 1,5-naphthalenedisulfonic acid tetrahydrate (0.5 mmol, 180 mg). The mixture heated at 343 K until the reacctants dissolved completely; colorless crystals were isolated from the filtrate after several days. three days.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of 2(C₃H₁₁N₂)^2+.(C₁₀H₆O₆S₂)^2-.2H₂O at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. Symmetry-related atoms are not labeled.

Bis(3-aminopropan-1-aminium) naphthalene-1,5-disulfonate dihydrate top

Crystal data top

2C₃H₁₁N₂⁺·C₁₀H₆O₆S₂²⁻·2H₂O	Z = 1
M_r = 472.58	F(000) = 252
Triclinic, P1	D_x = 1.399 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.0913 (16) Å	Cell parameters from 3803 reflections
b = 8.1917 (16) Å	θ = 3.0–27.5°
c = 9.8062 (18) Å	µ = 0.29 mm⁻¹
α = 71.182 (5)°	T = 293 K
β = 65.950 (5)°	Prism, colorless
γ = 79.945 (5)°	0.21 × 0.17 × 0.17 mm
V = 561.12 (19) Å³

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	2552 independent reflections
Radiation source: fine-focus sealed tube	2268 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
ω scan	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −10→9
T_min = 0.942, T_max = 0.953	k = −10→10
5584 measured reflections	l = −12→12

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.044	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.127	w = 1/[σ²(F_o²) + (0.0736P)² + 0.1592P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
2552 reflections	Δρ_max = 0.44 e Å⁻³
165 parameters	Δρ_min = −0.39 e Å⁻³
7 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.081 (12)

Crystal data top

2C₃H₁₁N₂⁺·C₁₀H₆O₆S₂²⁻·2H₂O	γ = 79.945 (5)°
M_r = 472.58	V = 561.12 (19) Å³
Triclinic, P1	Z = 1
a = 8.0913 (16) Å	Mo Kα radiation
b = 8.1917 (16) Å	µ = 0.29 mm⁻¹
c = 9.8062 (18) Å	T = 293 K
α = 71.182 (5)°	0.21 × 0.17 × 0.17 mm
β = 65.950 (5)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	2552 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2268 reflections with I > 2σ(I)
T_min = 0.942, T_max = 0.953	R_int = 0.039
5584 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	7 restraints
wR(F²) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.44 e Å⁻³
2552 reflections	Δρ_min = −0.39 e Å⁻³
165 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.27701 (5)	0.72860 (5)	0.28439 (4)	0.02880 (18)
O1	0.40860 (17)	0.78029 (17)	0.12668 (14)	0.0406 (3)
O2	0.35741 (17)	0.62846 (16)	0.39549 (15)	0.0402 (3)
O3	0.12666 (17)	0.64501 (17)	0.29413 (17)	0.0425 (3)
O1W	0.75757 (19)	0.63049 (19)	0.10446 (16)	0.0421 (3)
H1W1	0.6524 (18)	0.661 (3)	0.106 (3)	0.057 (7)*
H1W2	0.766 (4)	0.5307 (17)	0.096 (3)	0.063 (8)*
N1	0.8221 (3)	0.3040 (2)	0.0702 (2)	0.0437 (4)
H11	0.9387 (16)	0.288 (3)	0.053 (3)	0.063 (8)*
H12	0.792 (4)	0.294 (4)	−0.003 (2)	0.067 (8)*
N2	0.7492 (2)	−0.3142 (2)	0.36576 (18)	0.0367 (4)
H21	0.744 (3)	−0.340 (3)	0.287 (2)	0.059 (7)*
H22	0.701 (3)	−0.400 (3)	0.450 (2)	0.065 (7)*
H23	0.8614 (16)	−0.323 (3)	0.361 (3)	0.046 (6)*
C1	0.1830 (2)	0.9236 (2)	0.33721 (18)	0.0269 (3)
C2	0.2538 (2)	1.0749 (2)	0.23475 (18)	0.0320 (4)
H2	0.3496	1.0745	0.1411	0.038*
C3	0.1822 (2)	1.2322 (2)	0.27039 (19)	0.0341 (4)
H3	0.2318	1.3352	0.2003	0.041*
C4	0.0411 (2)	1.2350 (2)	0.40653 (18)	0.0297 (4)
H4A	−0.0057	1.3403	0.4274	0.036*
C5	−0.03570 (19)	1.08034 (19)	0.51689 (17)	0.0251 (3)
C6	0.7250 (3)	0.1771 (2)	0.2140 (2)	0.0387 (4)
H6A	0.5962	0.1970	0.2356	0.046*
H6B	0.7462	0.1951	0.2985	0.046*
C7	0.7781 (3)	−0.0097 (2)	0.2119 (2)	0.0385 (4)
H7A	0.7530	−0.0300	0.1302	0.046*
H7B	0.9073	−0.0301	0.1882	0.046*
C8	0.6774 (2)	−0.1352 (2)	0.3650 (2)	0.0360 (4)
H8A	0.6896	−0.1063	0.4488	0.043*
H8B	0.5496	−0.1262	0.3825	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0281 (3)	0.0244 (2)	0.0307 (3)	−0.00188 (15)	−0.00813 (18)	−0.00714 (17)
O1	0.0406 (7)	0.0360 (7)	0.0315 (6)	0.0011 (5)	−0.0028 (5)	−0.0076 (5)
O2	0.0405 (7)	0.0329 (7)	0.0413 (7)	0.0000 (5)	−0.0168 (6)	−0.0019 (5)
O3	0.0366 (7)	0.0390 (7)	0.0580 (8)	−0.0049 (5)	−0.0135 (6)	−0.0256 (6)
O1W	0.0412 (7)	0.0395 (8)	0.0456 (8)	0.0018 (6)	−0.0141 (6)	−0.0169 (6)
N1	0.0528 (10)	0.0322 (8)	0.0420 (9)	−0.0036 (7)	−0.0147 (8)	−0.0085 (7)
N2	0.0376 (8)	0.0327 (8)	0.0368 (8)	−0.0065 (6)	−0.0146 (7)	−0.0028 (6)
C1	0.0298 (7)	0.0245 (8)	0.0278 (7)	−0.0035 (6)	−0.0122 (6)	−0.0063 (6)
C2	0.0339 (8)	0.0307 (9)	0.0262 (7)	−0.0073 (6)	−0.0066 (6)	−0.0047 (6)
C3	0.0418 (9)	0.0238 (8)	0.0311 (8)	−0.0107 (7)	−0.0097 (7)	−0.0011 (6)
C4	0.0368 (8)	0.0210 (8)	0.0297 (8)	−0.0063 (6)	−0.0110 (7)	−0.0043 (6)
C5	0.0273 (7)	0.0233 (8)	0.0265 (7)	−0.0050 (6)	−0.0123 (6)	−0.0046 (6)
C6	0.0396 (9)	0.0340 (9)	0.0424 (9)	−0.0042 (7)	−0.0133 (8)	−0.0123 (8)
C7	0.0425 (9)	0.0321 (9)	0.0390 (9)	−0.0020 (7)	−0.0143 (8)	−0.0087 (7)
C8	0.0337 (8)	0.0347 (9)	0.0395 (9)	−0.0041 (7)	−0.0125 (7)	−0.0106 (7)

Geometric parameters (Å, º) top

S1—O1	1.4484 (13)	C2—H2	0.9300
S1—O2	1.4484 (13)	C3—C4	1.362 (2)
S1—O3	1.4532 (13)	C3—H3	0.9300
S1—C1	1.7848 (16)	C4—C5	1.416 (2)
O1W—H1W1	0.840 (10)	C4—H4A	0.9300
O1W—H1W2	0.837 (10)	C5—C5ⁱ	1.427 (3)
N1—C6	1.457 (2)	C5—C1ⁱ	1.436 (2)
N1—H11	0.883 (10)	C6—C7	1.520 (2)
N1—H12	0.879 (10)	C6—H6A	0.9700
N2—C8	1.479 (2)	C6—H6B	0.9700
N2—H21	0.886 (10)	C7—C8	1.508 (2)
N2—H22	0.885 (10)	C7—H7A	0.9700
N2—H23	0.881 (9)	C7—H7B	0.9700
C1—C2	1.360 (2)	C8—H8A	0.9700
C1—C5ⁱ	1.436 (2)	C8—H8B	0.9700
C2—C3	1.408 (2)

O1—S1—O2	113.11 (8)	C3—C4—C5	121.11 (15)
O1—S1—O3	111.96 (8)	C3—C4—H4A	119.4
O2—S1—O3	112.63 (8)	C5—C4—H4A	119.4
O1—S1—C1	106.07 (7)	C4—C5—C5ⁱ	119.01 (17)
O2—S1—C1	106.32 (8)	C4—C5—C1ⁱ	123.18 (14)
O3—S1—C1	106.10 (7)	C5ⁱ—C5—C1ⁱ	117.81 (16)
H1W1—O1W—H1W2	100 (2)	N1—C6—C7	114.59 (16)
C6—N1—H11	108.1 (17)	N1—C6—H6A	108.6
C6—N1—H12	107.7 (18)	C7—C6—H6A	108.6
H11—N1—H12	115 (3)	N1—C6—H6B	108.6
C8—N2—H21	110.4 (16)	C7—C6—H6B	108.6
C8—N2—H22	119.3 (18)	H6A—C6—H6B	107.6
H21—N2—H22	107 (2)	C8—C7—C6	112.28 (15)
C8—N2—H23	108.1 (15)	C8—C7—H7A	109.1
H21—N2—H23	111 (2)	C6—C7—H7A	109.1
H22—N2—H23	101 (2)	C8—C7—H7B	109.1
C2—C1—C5ⁱ	121.35 (15)	C6—C7—H7B	109.1
C2—C1—S1	118.04 (13)	H7A—C7—H7B	107.9
C5ⁱ—C1—S1	120.60 (12)	N2—C8—C7	110.76 (14)
C1—C2—C3	120.06 (15)	N2—C8—H8A	109.5
C1—C2—H2	120.0	C7—C8—H8A	109.5
C3—C2—H2	120.0	N2—C8—H8B	109.5
C4—C3—C2	120.65 (15)	C7—C8—H8B	109.5
C4—C3—H3	119.7	H8A—C8—H8B	108.1
C2—C3—H3	119.7

O1—S1—C1—C2	−4.68 (15)	S1—C1—C2—C3	179.05 (12)
O2—S1—C1—C2	115.97 (14)	C1—C2—C3—C4	−0.5 (3)
O3—S1—C1—C2	−123.91 (14)	C2—C3—C4—C5	1.0 (3)
O1—S1—C1—C5ⁱ	174.63 (12)	C3—C4—C5—C5ⁱ	−0.7 (3)
O2—S1—C1—C5ⁱ	−64.71 (14)	C3—C4—C5—C1ⁱ	179.21 (15)
O3—S1—C1—C5ⁱ	55.41 (14)	N1—C6—C7—C8	178.34 (16)
C5ⁱ—C1—C2—C3	−0.3 (2)	C6—C7—C8—N2	−172.59 (15)

Symmetry code: (i) −x, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H1w1···O1	0.84 (1)	2.00 (1)	2.826 (2)	166 (3)
O1w—H1w2···N1	0.84 (1)	1.91 (1)	2.736 (2)	172 (3)
N1—H12···O3ⁱⁱ	0.88 (1)	2.55 (2)	3.317 (2)	147 (2)
N2—H21···O1wⁱⁱⁱ	0.89 (1)	1.84 (1)	2.715 (2)	172 (2)
N2—H22···O2^iv	0.89 (1)	1.98 (1)	2.845 (2)	165 (3)
N2—H23···O3^v	0.88 (1)	1.97 (1)	2.825 (2)	164 (2)

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

Experimental details

Crystal data
Chemical formula	2C₃H₁₁N₂⁺·C₁₀H₆O₆S₂²⁻·2H₂O
M_r	472.58
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.0913 (16), 8.1917 (16), 9.8062 (18)
α, β, γ (°)	71.182 (5), 65.950 (5), 79.945 (5)
V (Å³)	561.12 (19)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.21 × 0.17 × 0.17

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.942, 0.953
No. of measured, independent and observed [I > 2σ(I)] reflections	5584, 2552, 2268
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.127, 1.05
No. of reflections	2552
No. of parameters	165
No. of restraints	7
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.39

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalClear (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H1w1···O1	0.84 (1)	2.00 (1)	2.826 (2)	166 (3)
O1w—H1w2···N1	0.84 (1)	1.91 (1)	2.736 (2)	172 (3)
N1—H12···O3ⁱ	0.88 (1)	2.55 (2)	3.317 (2)	147 (2)
N2—H21···O1wⁱⁱ	0.89 (1)	1.84 (1)	2.715 (2)	172 (2)
N2—H22···O2ⁱⁱⁱ	0.89 (1)	1.98 (1)	2.845 (2)	165 (3)
N2—H23···O3^iv	0.88 (1)	1.97 (1)	2.825 (2)	164 (2)

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

Acknowledgements

This work was supported by the Key Project of the Natural Science Foundation of Heilongjiang Province (No. ZD200903), the Key Project of the Education Bureau of Heilongjiang Province (Nos. 12511z023, 2011CJHB006), the Innovation Team of the Education Bureau of Heilongjiang Province (No. 2010 t d03), Heilongjiang University (Hdtd2010–04), and the Ministry of Higher Education of Malaysia (grant No. UM.C/HIR/MOHE/SC/12).

References

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