organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

Bis(3-hy­dr­oxy­propanaminium) naphthalene-1,5-di­sulfonate

aOrdered Matter Science Research Center, Southeast University, Nanjing 211189, People's Republic of China
*Correspondence e-mail: jinyunihao@yahoo.cn

(Received 9 November 2011; accepted 9 December 2011; online 21 December 2011)

In the title molecular salt, 2C3H10NO+·C10H6O6S22−, the cations and anions are associated via N—H⋯O and O—H⋯O hydrogen-bonding inter­actions, giving rise to a three-dimensional structure with zigzag rows of cations lying between rows of anions. The asymmetric unit contains one cation and one half-anion, which is related to the remainder of the mol­ecule by an inversion center.

Related literature

The title compound was studied as part of a search for simple ferroelectric compounds. For general background to ferroelectric metal-organic frameworks, see: Ye et al. (2006[Ye, Q., Song, Y.-M., Wang, G.-X., Chen, K. & Fu, D.-W. (2006). J. Am. Chem. Soc. 128, 6554-6555.]); Zhang et al. (2008[Zhang, W., Xiong, R.-G. & Huang, S.-P. D. (2008). J. Am. Chem. Soc. 130, 10468-10469.], 2009[Zhang, W., Li, Z.-C., Xiong, R.-G., Nakamura, T. & Huang, S.-P. (2009). J. Am. Chem. Soc. 131, 12544-12545.], 2010[Zhang, W., Ye, H.-Y., Cai, H.-L., Ge, J.-Z. & Xiong, R.-G. (2010). J. Am. Chem. Soc. 132, 7300-7302.]); Fu et al. (2009[Fu, D.-W., Ge, J.-Z., Dai, J., Ye, H.-Y. & Qu, Z.-R. (2009). Inorg. Chem. Commun. 12, 994-997.]).

[Scheme 1]

Experimental

Crystal data
  • 2C3H10NO+·C10H6O6S22−

  • Mr = 438.51

  • Monoclinic, P 21 /c

  • a = 10.004 (2) Å

  • b = 8.8311 (18) Å

  • c = 11.183 (2) Å

  • β = 92.79 (3)°

  • V = 986.8 (3) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.32 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[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.489, Tmax = 1.000

  • 9820 measured reflections

  • 2268 independent reflections

  • 2135 reflections with I > 2σ(I)

  • Rint = 0.029

Refinement
  • R[F2 > 2σ(F2)] = 0.054

  • wR(F2) = 0.156

  • S = 1.08

  • 2268 reflections

  • 128 parameters

  • H-atom parameters constrained

  • Δρmax = 0.58 e Å−3

  • Δρmin = −0.63 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O4—H4A⋯O1i 0.82 1.95 2.772 (3) 177
N1—H1D⋯O3ii 0.89 1.93 2.768 (3) 157
N1—H1C⋯O4iii 0.89 2.07 2.854 (3) 147
Symmetry codes: (i) x-1, y, z; (ii) [-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]; (iii) [x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}].

Data collection: CrystalClear (Rigaku, 2005[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

Ferroelectric compounds have displayed such technical applications as ferroelectric random access memories (FeRAM), ferroelectric field-effect transistors, infrared detectors, piezoelectric sensors, nonlinear optical devices due to their excellent ferroelectric, piezoelectric, pyroelectric, and optical properties. A large number of new ferroelectric metal-organic coordination compounds corresponding to the necessary requirements for ferroelectric properties have been found, yet other necessary conditions, such as a phase transition, a good electric hysteresis loop and electric domain, and a dielectric anomaly, are often missed (Zhang et al., 2009). Therefore pure organic compounds are of great potential and can make up for the drawbacks found in ferroelectric metal-organic coordination compounds. Reversible phase transitions remain one of the prominent properties for ferroelectrics. There exists a series of compounds in which the components can be arranged in a disordered fashion at a relatively high temperature and in an ordered fashion at a relatively low temperature and where the transition is reversible, which is called a reversible structual transition (Fu et al., 2009; Zhang et al., 2010; Zhang et al., 2008; Ye et al., 2006). The transition from the disordered arrangement to the ordered one leads to a sharp change in the physical properties of the compound. As part of our search for simple ferroelectric compounds I have investigated the title compound and report here its room temperature structure.

The centrosymmetric anion and one cation are shown in Fig. 1 with the hydrogen bonds listed in Table 1. The existence of numerous hydrogen-bonding interactions helps to make the substance more stable, so that it forms a three-dimensional layered structure. These interactions tie the cations and anions together in sheets with zigzag rows of cations lying between rows of anions (Fig. 2).

Related literature top

The title compound was studied as part of a search for simple ferroelectric compounds. For general background to ferroelectric metal-organic frameworks, see: Ye et al. (2006); Zhang et al. (2008, 2009, 2010); Fu et al. (2009).

Experimental top

(C3H10NO)2.(C10H6O6S2) was formed from a mixture of NH2(CH2)3OH (150.2 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 78% yield and filtered and washed with distilled water.

Refinement top

H atoms bound to carbon and nitrogen were placed at idealized positions [C—H = 0.93–0.97 Å, O—H = 0.82 Å and N—H = 0.89 Å] and allowed to ride on their parent atoms with Uiso fixed at 1.2 Ueq(C,N).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Crystal structure of the title compound with labelling and displacement ellipsoids drawn at the 30% probability level.
[Figure 2] Fig. 2. Crystal structure of the title compound with a view along the c axis. Intermolecular interactions are shown as dashed lines.
Bis(3-hydroxypropanaminium) naphthalene-1,5-disulfonate top
Crystal data top
2C3H10NO+·C10H6O6S22F(000) = 464
Mr = 438.51Dx = 1.476 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 10.004 (2) ÅCell parameters from 3450 reflections
b = 8.8311 (18) Åθ = 6.2–55.3°
c = 11.183 (2) ŵ = 0.32 mm1
β = 92.79 (3)°T = 293 K
V = 986.8 (3) Å3Block, colorless
Z = 20.3 × 0.3 × 0.2 mm
Data collection top
Rigaku Mercury CCD
diffractometer
2268 independent reflections
Radiation source: fine-focus sealed tube2135 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.029
ω scansθmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
h = 1212
Tmin = 0.489, Tmax = 1.000k = 1111
9820 measured reflectionsl = 1414
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.054H-atom parameters constrained
wR(F2) = 0.156 w = 1/[σ2(Fo2) + (0.0777P)2 + 1.2249P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
2268 reflectionsΔρmax = 0.58 e Å3
128 parametersΔρmin = 0.63 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.254 (15)
Crystal data top
2C3H10NO+·C10H6O6S22V = 986.8 (3) Å3
Mr = 438.51Z = 2
Monoclinic, P21/cMo Kα radiation
a = 10.004 (2) ŵ = 0.32 mm1
b = 8.8311 (18) ÅT = 293 K
c = 11.183 (2) Å0.3 × 0.3 × 0.2 mm
β = 92.79 (3)°
Data collection top
Rigaku Mercury CCD
diffractometer
2268 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
2135 reflections with I > 2σ(I)
Tmin = 0.489, Tmax = 1.000Rint = 0.029
9820 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0540 restraints
wR(F2) = 0.156H-atom parameters constrained
S = 1.08Δρmax = 0.58 e Å3
2268 reflectionsΔρmin = 0.63 e Å3
128 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
C10.4862 (3)0.0066 (3)0.7251 (2)0.0316 (5)
H1B0.46390.02420.80370.038*
C20.5997 (2)0.0809 (3)0.7025 (2)0.0293 (5)
H2A0.65130.12170.76600.035*
C30.6347 (2)0.1062 (2)0.58760 (19)0.0243 (5)
C40.5578 (2)0.0439 (2)0.48811 (18)0.0227 (5)
C50.5915 (2)0.0660 (3)0.36695 (19)0.0274 (5)
H5A0.66750.12160.35050.033*
C60.2313 (3)0.2177 (3)1.0492 (3)0.0468 (7)
H6A0.32130.22611.08490.056*
H6B0.18620.31351.06060.056*
C70.2388 (3)0.1877 (3)0.9175 (3)0.0444 (7)
H7A0.28670.09360.90680.053*
H7B0.29000.26810.88240.053*
C80.1045 (3)0.1771 (3)0.8510 (3)0.0455 (7)
H8A0.11510.12650.77500.055*
H8B0.04480.11630.89710.055*
N10.1620 (2)0.1016 (2)1.10823 (18)0.0337 (5)
H1C0.15960.12361.18580.051*
H1D0.20410.01381.09940.051*
H1E0.07890.09461.07660.051*
O10.8140 (2)0.2850 (3)0.68268 (19)0.0555 (7)
O20.8824 (2)0.1062 (2)0.5327 (2)0.0544 (6)
O30.7522 (2)0.3249 (2)0.4755 (2)0.0477 (6)
O40.0430 (3)0.3286 (3)0.8284 (2)0.0597 (7)
H4A0.02520.31920.78530.090*
S10.78281 (5)0.21407 (7)0.56780 (5)0.0287 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0386 (13)0.0368 (12)0.0198 (10)0.0004 (10)0.0053 (8)0.0012 (9)
C20.0342 (12)0.0317 (11)0.0217 (10)0.0001 (9)0.0020 (8)0.0042 (8)
C30.0247 (10)0.0233 (10)0.0248 (10)0.0014 (8)0.0003 (8)0.0001 (8)
C40.0259 (10)0.0206 (9)0.0217 (10)0.0033 (8)0.0013 (8)0.0001 (7)
C50.0304 (11)0.0281 (11)0.0241 (10)0.0018 (8)0.0051 (8)0.0018 (8)
C60.0530 (17)0.0347 (14)0.0515 (17)0.0034 (12)0.0110 (14)0.0036 (12)
C70.0441 (15)0.0363 (14)0.0541 (17)0.0039 (11)0.0158 (13)0.0092 (12)
C80.0631 (19)0.0346 (14)0.0389 (14)0.0114 (13)0.0047 (13)0.0003 (11)
N10.0504 (12)0.0239 (9)0.0275 (10)0.0065 (9)0.0082 (9)0.0002 (7)
O10.0463 (12)0.0836 (17)0.0363 (11)0.0292 (11)0.0021 (9)0.0123 (10)
O20.0376 (11)0.0419 (11)0.0858 (17)0.0065 (9)0.0251 (11)0.0102 (11)
O30.0583 (13)0.0309 (10)0.0524 (12)0.0130 (9)0.0124 (10)0.0137 (9)
O40.0562 (14)0.0665 (15)0.0552 (13)0.0032 (12)0.0102 (10)0.0073 (12)
S10.0277 (4)0.0296 (4)0.0285 (4)0.0031 (2)0.0004 (2)0.0019 (2)
Geometric parameters (Å, º) top
C1—C5i1.365 (3)C6—H6B0.9700
C1—C21.407 (3)C7—C81.507 (5)
C1—H1B0.9300C7—H7A0.9700
C2—C31.366 (3)C7—H7B0.9700
C2—H2A0.9300C8—O41.489 (4)
C3—C41.432 (3)C8—H8A0.9700
C3—S11.784 (2)C8—H8B0.9700
C4—C51.426 (3)N1—H1C0.8900
C4—C4i1.428 (4)N1—H1D0.8900
C5—C1i1.365 (3)N1—H1E0.8900
C5—H5A0.9300O1—S11.450 (2)
C6—N11.418 (4)O2—S11.446 (2)
C6—C71.502 (4)O3—S11.445 (2)
C6—H6A0.9700O4—H4A0.8200
C5i—C1—C2120.7 (2)C8—C7—H7A108.7
C5i—C1—H1B119.7C6—C7—H7B108.7
C2—C1—H1B119.7C8—C7—H7B108.7
C3—C2—C1120.3 (2)H7A—C7—H7B107.6
C3—C2—H2A119.8O4—C8—C7112.3 (2)
C1—C2—H2A119.8O4—C8—H8A109.1
C2—C3—C4121.0 (2)C7—C8—H8A109.1
C2—C3—S1117.15 (17)O4—C8—H8B109.1
C4—C3—S1121.80 (16)C7—C8—H8B109.1
C5—C4—C4i118.9 (2)H8A—C8—H8B107.9
C5—C4—C3122.9 (2)C6—N1—H1C109.5
C4i—C4—C3118.3 (2)C6—N1—H1D109.5
C1i—C5—C4120.8 (2)H1C—N1—H1D109.5
C1i—C5—H5A119.6C6—N1—H1E109.5
C4—C5—H5A119.6H1C—N1—H1E109.5
N1—C6—C7112.2 (2)H1D—N1—H1E109.5
N1—C6—H6A109.2C8—O4—H4A109.5
C7—C6—H6A109.2O3—S1—O2112.18 (15)
N1—C6—H6B109.2O3—S1—O1111.71 (15)
C7—C6—H6B109.2O2—S1—O1113.79 (16)
H6A—C6—H6B107.9O3—S1—C3107.56 (12)
C6—C7—C8114.2 (3)O2—S1—C3105.61 (12)
C6—C7—H7A108.7O1—S1—C3105.37 (11)
Symmetry code: (i) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4A···O1ii0.821.952.772 (3)177
N1—H1D···O3iii0.891.932.768 (3)157
N1—H1C···O4iv0.892.072.854 (3)147
Symmetry codes: (ii) x1, y, z; (iii) x+1, y1/2, z+3/2; (iv) x, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula2C3H10NO+·C10H6O6S22
Mr438.51
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)10.004 (2), 8.8311 (18), 11.183 (2)
β (°) 92.79 (3)
V3)986.8 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.32
Crystal size (mm)0.3 × 0.3 × 0.2
Data collection
DiffractometerRigaku Mercury CCD
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.489, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
9820, 2268, 2135
Rint0.029
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.054, 0.156, 1.08
No. of reflections2268
No. of parameters128
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.58, 0.63

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4A···O1i0.821.952.772 (3)176.9
N1—H1D···O3ii0.891.932.768 (3)157.1
N1—H1C···O4iii0.892.072.854 (3)147.2
Symmetry codes: (i) x1, y, z; (ii) x+1, y1/2, z+3/2; (iii) x, y+1/2, z+1/2.
 

Acknowledgements

The author thanks the Ordered Matter Science Research Center, Southeast University, for its excellent experimental conditions and its generous financial support.

References

First citationFu, D.-W., Ge, J.-Z., Dai, J., Ye, H.-Y. & Qu, Z.-R. (2009). Inorg. Chem. Commun. 12, 994–997.  Web of Science CSD CrossRef CAS
First citationRigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationYe, Q., Song, Y.-M., Wang, G.-X., Chen, K. & Fu, D.-W. (2006). J. Am. Chem. Soc. 128, 6554–6555.  Web of Science CSD CrossRef PubMed CAS
First citationZhang, W., Li, Z.-C., Xiong, R.-G., Nakamura, T. & Huang, S.-P. (2009). J. Am. Chem. Soc. 131, 12544–12545.  Web of Science CSD CrossRef PubMed CAS
First citationZhang, W., Xiong, R.-G. & Huang, S.-P. D. (2008). J. Am. Chem. Soc. 130, 10468–10469.  Web of Science CSD CrossRef PubMed CAS
First citationZhang, W., Ye, H.-Y., Cai, H.-L., Ge, J.-Z. & Xiong, R.-G. (2010). J. Am. Chem. Soc. 132, 7300–7302.  Web of Science CSD CrossRef CAS PubMed

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