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In the crystal of the title mol­ecular salt, 2C7H10N+·C10H6O6S22−, the naphthalene-1,5-disulfonate anion is located on an inversion center and accepts N—H...O hydrogen bonds from the 3-methyl­anilinium cations, forming supra­molecular layers parallel to the ac plane.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536812021290/xu5533sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536812021290/xu5533Isup2.hkl
Contains datablock I

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S1600536812021290/xu5533Isup3.cml
Supplementary material

CCDC reference: 886968

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.007 Å
  • R factor = 0.082
  • wR factor = 0.190
  • Data-to-parameter ratio = 14.8

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT930_ALERT_2_B Check Twin Law ( 0 0 1)[ 0 0 1] Estimated BASF 0.09 PLAT930_ALERT_2_B Check Twin Law ( 0 0 1)[ 0 0 1] Estimated BASF 0.09
Alert level C PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings Differ ? PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for S1 PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds ............... 0.0074 Ang PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) ..... 3
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 ............ 3 PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT Unusually Large. 6.11 PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature 293 K PLAT870_ALERT_4_G ALERTS Related to Twinning Effects Suppressed .. ! PLAT870_ALERT_4_G ALERTS Related to Twinning Effects Suppressed .. ! PLAT931_ALERT_5_G Check Twin Law ( 1 0 0)[ ] Estimated BASF 0.09 PLAT931_ALERT_5_G Check Twin Law ( )[ 1 0 0] Estimated BASF 0.09 PLAT961_ALERT_5_G Dataset Contains no Negative Intensities ....... !
0 ALERT level A = Most likely a serious problem - resolve or explain 2 ALERT level B = A potentially serious problem, consider carefully 4 ALERT level C = Check. Ensure it is not caused by an omission or oversight 10 ALERT level G = General information/check it is not something unexpected 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 5 ALERT type 5 Informative message, check

Comment top

Recently much attention has been devoted to simple molecular-ionic compounds containing inorganic and organic ions due to the tunability of their special structural features and their potential ferroelectrics property. Ferroelectric materials that exhibit reversible electric polarization in response to an external electric field have found many applications such as nonvolatile memory storage, electronics and optics. The freezing of a certain functional group at low temperature forces significant orientational motions of the guest molecules and thus induces the formation of the ferroelectric phase. (Fu et al, 2011; Ye et al. 2009; Zhang et al. 2009; Zhang & Xiong, 2012; Zhang et al. 2010). In our laboratory, the title compound has been synthesized to investigate to its potential ferroelectric properties. However, it was found that the dielectric constant of the compound as a function of temperature indicates that the permittivity is basically temperature-independent (ε = C/(T–T0)), suggesting that this compound is not ferroelectric or there may be no distinct phase transition occurring within the measured temperature (below the melting point).

The title compound,(C7H10N)2.C10H6O6S2, has an asymmetric unit that consists of 3-methylanilinium cation, half an naphthalene-1,5-disulfonate anions, which are linked by an N—H···O hydrogen bond(Fig 1). The non-hydrogen atoms of the cation and the anion are coplanar with the r.m.s deviation are 0.0123Å and 0.0326Å respectively, the angle of the two plane is 114.7°. In the crystal structure, the cations are linked to anions by N—H···O hydrogen bonds to form layer-like structure which is parallel to ac plane (Fig 2).

Related literature top

For background literature concerning ferroelectric complexes, see: Fu et al. (2011); Ye et al. (2009); Zhang & Xiong (2012); Zhang et al. (2009, 2010). For a related structure, see: Liu (2012).

Experimental top

1.07 g (1 mmol) of 3-toluidine was firstly dissolved in 30 ml of ethanol, to which 0.288 g (1 mmol) of 1,5-naphthalene-disulfonic acid was added to give a solution at the ambient temperature. Single crystals suitable for X-ray structure analysis were obtained by the slow evaporation of the above solution after 5 days in air.

Refinement top

H atoms were placed in calculated positions with N—H = 0.89 and C—H = 0.93– 0.96 Å, and refined in riding mode, Uiso(H) = 1.5Ueq(C,N) for methyl and amino H atoms and 1.2Ueq(C) for the others.

Computing details top

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 top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing the atomic numbering scheme with 30% probability displacement ellipsoids. The unlablled atoms are in the asymmetric unit at (1-x,1-y,1-z).
[Figure 2] Fig. 2. The packing of the title compound with view along the a axis. Dashed lines indicate hydrogen bonds.
Bis(3-methylanilinium) naphthalene-1,5-disulfonate top
Crystal data top
2C7H10N+·C10H6O6S22F(000) = 528
Mr = 502.59Dx = 1.423 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2066 reflections
a = 8.3426 (17) Åθ = 3.4–25.0°
b = 19.896 (4) ŵ = 0.27 mm1
c = 7.0670 (14) ÅT = 293 K
β = 90.14 (3)°Block, colourless
V = 1173.0 (4) Å30.36 × 0.32 × 0.28 mm
Z = 2
Data collection top
Rigaku Mercury2
diffractometer
2311 independent reflections
Radiation source: fine-focus sealed tube2131 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.036
Detector resolution: 13.6612 pixels mm-1θmax = 26.0°, θmin = 3.1°
ω scansh = 1010
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
k = 2424
Tmin = 0.901, Tmax = 0.923l = 88
10755 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.082Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.190H-atom parameters constrained
S = 1.22 w = 1/[σ2(Fo2) + (0.0077P)2 + 6.1071P]
where P = (Fo2 + 2Fc2)/3
2311 reflections(Δ/σ)max = 0.034
156 parametersΔρmax = 0.50 e Å3
0 restraintsΔρmin = 0.33 e Å3
Crystal data top
2C7H10N+·C10H6O6S22V = 1173.0 (4) Å3
Mr = 502.59Z = 2
Monoclinic, P21/cMo Kα radiation
a = 8.3426 (17) ŵ = 0.27 mm1
b = 19.896 (4) ÅT = 293 K
c = 7.0670 (14) Å0.36 × 0.32 × 0.28 mm
β = 90.14 (3)°
Data collection top
Rigaku Mercury2
diffractometer
2311 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
2131 reflections with I > 2σ(I)
Tmin = 0.901, Tmax = 0.923Rint = 0.036
10755 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0820 restraints
wR(F2) = 0.190H-atom parameters constrained
S = 1.22Δρmax = 0.50 e Å3
2311 reflectionsΔρmin = 0.33 e Å3
156 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
S10.19559 (14)0.57953 (6)0.74214 (17)0.0295 (3)
O20.2105 (5)0.6206 (2)0.9102 (5)0.0493 (11)
O30.1516 (5)0.6197 (2)0.5795 (6)0.0518 (11)
O10.0920 (5)0.5221 (2)0.7674 (7)0.0554 (12)
N11.0108 (5)0.6117 (2)0.2234 (6)0.0388 (10)
H1A1.06880.61440.32900.058*
H1B1.07480.61600.12360.058*
H1C0.96180.57200.21890.058*
C110.3285 (6)0.4582 (3)0.2293 (7)0.0360 (12)
H110.24640.44790.14470.043*
C80.3919 (5)0.5474 (2)0.6913 (7)0.0288 (10)
C90.4199 (5)0.5100 (2)0.5201 (6)0.0265 (10)
C70.7308 (6)0.6503 (3)0.2401 (7)0.0334 (11)
H70.69880.60570.25050.040*
C100.2950 (6)0.4918 (2)0.3920 (7)0.0317 (11)
H100.18950.50310.42000.038*
C60.8907 (6)0.6655 (3)0.2215 (7)0.0331 (11)
C20.6166 (6)0.7012 (3)0.2436 (7)0.0374 (12)
C120.4886 (6)0.4387 (3)0.1880 (7)0.0360 (11)
H120.51060.41600.07590.043*
C50.9429 (7)0.7315 (3)0.2022 (8)0.0441 (13)
H51.05110.74130.18710.053*
C30.6696 (7)0.7671 (3)0.2287 (8)0.0434 (13)
H30.59540.80190.23420.052*
C40.8297 (8)0.7822 (3)0.2060 (8)0.0461 (14)
H40.86170.82670.19330.055*
C10.4405 (7)0.6864 (4)0.2685 (11)0.0618 (18)
H1D0.41110.69350.39820.093*
H1E0.41960.64040.23460.093*
H1F0.37870.71560.18860.093*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0236 (5)0.0366 (6)0.0282 (6)0.0052 (5)0.0023 (4)0.0040 (5)
O20.050 (2)0.064 (3)0.034 (2)0.007 (2)0.0046 (17)0.0176 (19)
O30.063 (3)0.055 (3)0.037 (2)0.026 (2)0.0026 (19)0.0006 (19)
O10.033 (2)0.051 (3)0.082 (3)0.0064 (18)0.012 (2)0.000 (2)
N10.042 (2)0.038 (2)0.037 (2)0.0038 (19)0.0001 (19)0.0004 (19)
C110.026 (2)0.042 (3)0.039 (3)0.001 (2)0.006 (2)0.012 (2)
C80.026 (2)0.031 (2)0.030 (2)0.0020 (19)0.0028 (19)0.0006 (19)
C90.027 (2)0.026 (2)0.027 (2)0.0007 (18)0.0021 (18)0.0014 (18)
C70.040 (3)0.032 (3)0.028 (2)0.004 (2)0.002 (2)0.004 (2)
C100.026 (2)0.037 (3)0.033 (3)0.003 (2)0.0034 (19)0.002 (2)
C60.037 (3)0.034 (3)0.027 (2)0.003 (2)0.002 (2)0.002 (2)
C20.038 (3)0.045 (3)0.029 (3)0.002 (2)0.001 (2)0.003 (2)
C120.038 (3)0.037 (3)0.033 (3)0.004 (2)0.001 (2)0.006 (2)
C50.042 (3)0.048 (3)0.042 (3)0.011 (3)0.004 (2)0.001 (3)
C30.051 (3)0.035 (3)0.044 (3)0.007 (2)0.003 (3)0.001 (2)
C40.061 (4)0.033 (3)0.045 (3)0.006 (3)0.001 (3)0.006 (2)
C10.037 (3)0.066 (4)0.083 (5)0.002 (3)0.007 (3)0.002 (4)
Geometric parameters (Å, º) top
S1—O11.444 (4)C7—C21.392 (7)
S1—O21.446 (4)C7—H70.9300
S1—O31.446 (4)C10—H100.9300
S1—C81.795 (5)C6—C51.391 (7)
N1—C61.467 (6)C2—C31.387 (8)
N1—H1A0.8900C2—C11.509 (8)
N1—H1B0.8900C12—C8i1.339 (7)
N1—H1C0.8900C12—H120.9300
C11—C101.360 (7)C5—C41.381 (8)
C11—C121.422 (7)C5—H50.9300
C11—H110.9300C3—C41.379 (8)
C8—C12i1.339 (7)C3—H30.9300
C8—C91.440 (6)C4—H40.9300
C9—C101.425 (6)C1—H1D0.9600
C9—C9i1.424 (9)C1—H1E0.9600
C7—C61.374 (7)C1—H1F0.9600
O1—S1—O2113.3 (3)C9—C10—H10119.7
O1—S1—O3112.6 (3)C7—C6—C5121.4 (5)
O2—S1—O3111.3 (2)C7—C6—N1120.2 (5)
O1—S1—C8106.8 (2)C5—C6—N1118.5 (5)
O2—S1—C8106.8 (2)C3—C2—C7117.9 (5)
O3—S1—C8105.5 (2)C3—C2—C1120.3 (5)
C6—N1—H1A109.5C7—C2—C1121.7 (5)
C6—N1—H1B109.5C8i—C12—C11120.7 (5)
H1A—N1—H1B109.5C8i—C12—H12119.6
C6—N1—H1C109.5C11—C12—H12119.6
H1A—N1—H1C109.5C4—C5—C6118.3 (5)
H1B—N1—H1C109.5C4—C5—H5120.9
C10—C11—C12120.2 (5)C6—C5—H5120.9
C10—C11—H11119.9C4—C3—C2121.6 (5)
C12—C11—H11119.9C4—C3—H3119.2
C12i—C8—C9121.3 (4)C2—C3—H3119.2
C12i—C8—S1118.5 (4)C3—C4—C5120.4 (5)
C9—C8—S1120.1 (3)C3—C4—H4119.8
C10—C9—C9i119.2 (5)C5—C4—H4119.8
C10—C9—C8123.0 (4)C2—C1—H1D109.5
C9i—C9—C8117.8 (5)C2—C1—H1E109.5
C6—C7—C2120.5 (5)H1D—C1—H1E109.5
C6—C7—H7119.8C2—C1—H1F109.5
C2—C7—H7119.8H1D—C1—H1F109.5
C11—C10—C9120.7 (4)H1E—C1—H1F109.5
C11—C10—H10119.7
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O3ii0.891.902.779 (6)168
N1—H1B···O2iii0.891.892.779 (6)177
N1—H1C···O1i0.891.932.797 (6)165
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y, z; (iii) x+1, y, z1.

Experimental details

Crystal data
Chemical formula2C7H10N+·C10H6O6S22
Mr502.59
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)8.3426 (17), 19.896 (4), 7.0670 (14)
β (°) 90.14 (3)
V3)1173.0 (4)
Z2
Radiation typeMo Kα
µ (mm1)0.27
Crystal size (mm)0.36 × 0.32 × 0.28
Data collection
DiffractometerRigaku Mercury2
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.901, 0.923
No. of measured, independent and
observed [I > 2σ(I)] reflections
10755, 2311, 2131
Rint0.036
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.082, 0.190, 1.22
No. of reflections2311
No. of parameters156
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.50, 0.33

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

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O3i0.891.902.779 (6)168.3
N1—H1B···O2ii0.891.892.779 (6)177.2
N1—H1C···O1iii0.891.932.797 (6)165.3
Symmetry codes: (i) x+1, y, z; (ii) x+1, y, z1; (iii) x+1, y+1, z+1.
 

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