PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o346.
Published online 2007 December 21. doi:  10.1107/S1600536807066573
PMCID: PMC2915387

Redetermination of ethyl­ene­diammonium bis­(p-methyl­benzene­sulfonate) monohydrate

Abstract

In the asymmetric unit of the title compound, C2H10N2 2+·2C7H7O3S·H2O, there are two independent 4-methyl­benzene­sulfonate anions, one ethyl­enediammonium cation and a water mol­ecule. The present redetermination was carried out to improve the treatment of disorder, which was not refined in the previous study [Ahn & Kim (1985 [triangle]). J. Korean Chem. Soc. 29, 335–340]. One of the sulfonate groups is disordered over two positions, with site-occupancy factors of 0.588 (14) and 0.412 (14). Inter­molecular N—H(...)O and O—H(...)O hydrogen bonds hold the three components together, affording a layer structure extending parallel to the (001) plane.

Related literature

The crystal structure of the title compound has been reported previously by Ahn & Kim (1985 [triangle]). For related compounds, see: Edwards et al. (2001 [triangle]); Bryant et al. (1993 [triangle]); Nakamura & Iitaka (1978 [triangle]); Nethaji et al. (1992 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0o346-scheme1.jpg

Experimental

Crystal data

  • C2H10N2 2+·2C7H7O3S·H2O
  • M r = 422.53
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o346-efi1.jpg
  • a = 11.302 (2) Å
  • b = 7.724 (1) Å
  • c = 12.648 (2) Å
  • β = 111.77 (1)°
  • V = 1025.4 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.30 mm−1
  • T = 293 (2) K
  • 0.56 × 0.44 × 0.44 mm

Data collection

  • Siemens P4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.865, T max = 0.877
  • 2942 measured reflections
  • 2693 independent reflections
  • 2293 reflections with I > 2σ(I)
  • R int = 0.015
  • 3 standard reflections every 97 reflections intensity decay: 5.0%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.053
  • wR(F 2) = 0.151
  • S = 1.06
  • 2693 reflections
  • 273 parameters
  • 7 restraints
  • H-atom parameters constrained
  • Δρmax = 0.46 e Å−3
  • Δρmin = −0.45 e Å−3
  • Absolute structure: Flack (1983 [triangle]), with 631 Friedel pairs
  • Flack parameter: −0.13 (14)

Data collection: XSCANS (Siemens, 1994 [triangle]); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 1998 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807066573/is2252sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807066573/is2252Isup2.hkl

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

supplementary crystallographic information

Comment

Previously, Ahn and Kim (1985) have reported X-ray diffraction study of the title compound, (I), with R = 0.060. The present redetermination of (I) gives improvement in the treatment of disorder.

In compound (I), one of sulfonate groups of 4-methylbenzenesulfonate anions is disordered (Fig. 1). In the previous paper (Ahn & Kim, 1985), these occupancy factors were not refined and for each disordered O atom a different occupancy factor was given, which could not be accepted from the chemical point of view. The shortest S—O bond lengths in the disorder sulfonate group is of [1.410 (8) Å], it deviates greatly from the shortest one observed in the previous study [1.380 (16) Å]. The present C—N bond lengths [1.468 (8) and 1.480 (7) Å] are smaller obviously than the previous result [1.502 (12) and 1.527 (14) Å]. All C—C bond lengths by our redetermination are consistent with those observed in the Ahn & Kim's result, correspondingly. The present bond lengths and angles of (I) are coherent with those observed in tosylate (Bryant et al., 1993; Nakamura & Iitaka, 1978) and ethylenediammonium (Edwards et al., 2001; Nethaji et al., 1992).

Experimental

4-Methylbenzenesulfonic acid (0.02 mol, 3.12 g), ethylenediamine (0.01 mol, 0.60 g) and sufficient water were added together at 373 K with stirring. The resulting solution was allowed to stand for 5 days at room temperature to give single crystals of (I).

Refinement

The sulfonate O atoms in one of 4-methylbenzenesulfonates are disordered over two sites, with occupancies of 0.412 (14) and 0.588 (14). S2—O4 and S2—O4', S2—O5 and S2—O5', and S2—O6 and S2—O6' are restrained to be identical with 0.01 Å deviation. The water H atoms were located in a difference Fourier map and the positions were fiexed, with Uiso(H) = 1.2Ueq(O). Other H atoms were placed in calculated positions (C—H = 0.93–0.96 Å and N—H = 0.89 Å), and allowed to ride on their parent atoms, with Uiso(H) values 1.2–1.5 times Ueq of the parent atoms.

Figures

Fig. 1.
A view of (I), showing 40% probability displacement ellipsoids.

Crystal data

C2H10N22+·2C7H7O3S·H2OF000 = 448
Mr = 422.53Dx = 1.368 Mg m3
Monoclinic, P21Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 31 reflections
a = 11.302 (2) Åθ = 3.3–18.3º
b = 7.724 (1) ŵ = 0.30 mm1
c = 12.648 (2) ÅT = 293 (2) K
β = 111.77 (1)ºRod, colorless
V = 1025.4 (3) Å30.56 × 0.44 × 0.44 mm
Z = 2

Data collection

Siemens P4 diffractometerRint = 0.015
Radiation source: fine-focus sealed tubeθmax = 25.5º
Monochromator: graphiteθmin = 1.7º
T = 293(2) Kh = −13→13
ω scansk = −8→9
Absorption correction: ψ scan(North et al., 1968)l = −15→14
Tmin = 0.865, Tmax = 0.8773 standard reflections
2942 measured reflections every 97 reflections
2693 independent reflections intensity decay: 5.0%
2293 reflections with I > 2σ(I)

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.053  w = 1/[σ2(Fo2) + (0.0975P)2 + 0.2733P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.151(Δ/σ)max < 0.001
S = 1.06Δρmax = 0.46 e Å3
2693 reflectionsΔρmin = −0.45 e Å3
273 parametersExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
7 restraintsExtinction coefficient: 0.041 (7)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 631 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: −0.13 (14)

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 (Å2)

xyzUiso*/UeqOcc. (<1)
S10.39487 (9)1.37382 (17)0.69865 (8)0.0449 (3)
S20.23545 (10)0.3854 (2)0.30145 (8)0.0486 (3)
N10.1694 (3)1.0595 (6)0.4993 (3)0.0493 (9)
H1A0.08761.04930.48980.074*
H1B0.17591.11890.44150.074*
H1C0.21081.11510.56420.074*
N20.4215 (4)0.7319 (6)0.5269 (4)0.0572 (10)
H2A0.50310.74560.53650.086*
H2B0.38160.67340.46290.086*
H2C0.41630.67340.58560.086*
O30.4599 (3)1.3428 (6)0.6225 (3)0.0651 (11)
O10.3297 (4)1.5388 (6)0.6770 (4)0.0644 (11)
O20.3079 (4)1.2347 (7)0.6970 (4)0.0806 (14)
O40.3036 (16)0.5455 (15)0.3399 (9)0.074 (4)0.412 (14)
O50.1256 (9)0.3402 (16)0.3317 (8)0.073 (4)0.412 (14)
O60.3193 (14)0.2405 (15)0.3414 (10)0.074 (4)0.412 (14)
O4'0.3607 (7)0.4619 (15)0.3379 (6)0.072 (3)0.588 (14)
O5'0.1431 (8)0.4885 (14)0.3320 (7)0.090 (4)0.588 (14)
O6'0.2406 (12)0.2116 (11)0.3368 (8)0.091 (3)0.588 (14)
O70.0703 (3)0.4716 (7)0.5140 (3)0.0804 (14)
H7D0.07820.49330.45330.097*
H7E0.13490.48410.57130.097*
C10.5101 (3)1.3818 (7)0.8381 (3)0.0373 (7)
C20.4835 (4)1.4629 (7)0.9233 (4)0.0482 (10)
H20.40661.52060.90700.058*
C30.5726 (4)1.4581 (7)1.0342 (4)0.0531 (11)
H30.55441.51371.09160.064*
C40.6870 (4)1.3731 (8)1.0608 (3)0.0462 (9)
C50.7114 (4)1.2905 (7)0.9742 (4)0.0496 (11)
H50.78791.23130.99110.060*
C60.6248 (4)1.2935 (7)0.8628 (4)0.0463 (10)
H60.64291.23750.80550.056*
C70.7803 (5)1.3664 (10)1.1808 (4)0.0645 (13)
H7A0.74751.43051.22900.097*
H7B0.85971.41611.18480.097*
H7C0.79371.24811.20580.097*
C80.1792 (3)0.3870 (7)0.1514 (3)0.0392 (8)
C90.0644 (4)0.4651 (7)0.0900 (4)0.0467 (10)
H90.01670.51670.12750.056*
C100.0205 (4)0.4663 (8)−0.0284 (4)0.0529 (12)
H10−0.05640.5204−0.06960.063*
C110.0887 (4)0.3890 (8)−0.0854 (3)0.0514 (10)
C120.2040 (4)0.3120 (7)−0.0222 (4)0.0515 (11)
H120.25200.2607−0.05950.062*
C130.2487 (4)0.3101 (7)0.0948 (4)0.0484 (10)
H130.32590.25680.13580.058*
C140.0403 (7)0.3881 (13)−0.2143 (4)0.0838 (18)
H14A−0.04050.4460−0.24420.126*
H14B0.03070.2707−0.24110.126*
H14C0.10020.4470−0.23910.126*
C150.2250 (4)0.8868 (9)0.5035 (4)0.0552 (11)
H15A0.17970.82540.43320.066*
H15B0.21700.82090.56590.066*
C160.3611 (5)0.9038 (9)0.5199 (6)0.0727 (16)
H16A0.40540.96790.58930.087*
H16B0.36840.96830.45680.087*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0487 (5)0.0482 (6)0.0368 (5)0.0021 (6)0.0147 (4)0.0040 (6)
S20.0539 (5)0.0557 (7)0.0343 (5)−0.0051 (6)0.0141 (4)0.0083 (6)
N10.0506 (19)0.048 (2)0.051 (2)0.0041 (17)0.0214 (17)0.0042 (19)
N20.060 (2)0.051 (2)0.067 (3)0.011 (2)0.032 (2)0.008 (2)
O30.0771 (19)0.080 (3)0.0425 (16)0.011 (2)0.0271 (15)−0.0027 (19)
O10.073 (2)0.060 (2)0.056 (2)0.0253 (19)0.0182 (18)0.0121 (19)
O20.081 (2)0.088 (3)0.056 (2)−0.035 (3)0.0054 (19)0.010 (2)
O40.106 (10)0.064 (8)0.039 (6)−0.012 (7)0.013 (6)0.002 (5)
O50.099 (7)0.069 (10)0.039 (5)−0.010 (6)0.014 (5)0.004 (5)
O60.102 (9)0.067 (7)0.040 (6)−0.006 (7)0.012 (6)0.003 (5)
O4'0.076 (4)0.091 (7)0.053 (4)0.003 (4)0.030 (3)0.013 (4)
O5'0.109 (6)0.111 (10)0.053 (4)0.010 (6)0.032 (4)0.012 (5)
O6'0.112 (8)0.108 (8)0.054 (5)0.007 (7)0.033 (5)0.015 (5)
O70.0564 (18)0.118 (4)0.066 (2)0.011 (2)0.0218 (17)0.002 (3)
C10.0422 (16)0.0346 (19)0.0365 (17)0.003 (2)0.0164 (14)0.001 (2)
C20.046 (2)0.051 (3)0.051 (2)0.009 (2)0.0222 (18)−0.003 (2)
C30.063 (3)0.053 (3)0.049 (2)−0.001 (2)0.028 (2)−0.012 (2)
C40.0514 (19)0.041 (2)0.045 (2)−0.005 (3)0.0171 (16)−0.001 (3)
C50.047 (2)0.047 (3)0.055 (3)0.006 (2)0.0192 (19)0.003 (2)
C60.048 (2)0.050 (3)0.045 (2)0.006 (2)0.0227 (18)−0.005 (2)
C70.069 (3)0.065 (3)0.051 (3)−0.003 (3)0.013 (2)0.000 (3)
C80.0416 (16)0.036 (2)0.0402 (19)−0.006 (2)0.0154 (14)0.004 (2)
C90.0431 (19)0.051 (3)0.048 (2)0.0043 (19)0.0192 (17)0.004 (2)
C100.041 (2)0.063 (3)0.046 (2)0.001 (2)0.0061 (17)0.011 (2)
C110.065 (2)0.046 (3)0.041 (2)−0.007 (3)0.0169 (18)−0.004 (3)
C120.059 (2)0.054 (3)0.047 (2)0.002 (2)0.026 (2)−0.002 (2)
C130.0444 (19)0.050 (3)0.050 (2)0.0083 (19)0.0172 (18)0.005 (2)
C140.108 (4)0.096 (5)0.040 (2)−0.016 (5)0.018 (2)0.006 (4)
C150.058 (2)0.051 (3)0.057 (3)0.000 (3)0.0215 (19)0.005 (3)
C160.070 (3)0.054 (4)0.107 (4)0.009 (3)0.048 (3)0.011 (3)

Geometric parameters (Å, °)

S1—O31.432 (3)C4—C51.381 (7)
S1—O11.446 (4)C4—C71.494 (6)
S1—O21.451 (4)C5—C61.386 (7)
S1—C11.762 (4)C5—H50.9300
S2—O6'1.410 (8)C6—H60.9300
S2—O61.432 (9)C7—H7A0.9600
S2—O41.442 (8)C7—H7B0.9600
S2—O4'1.442 (7)C7—H7C0.9600
S2—O51.471 (8)C8—C131.379 (6)
S2—O5'1.473 (7)C8—C91.379 (6)
S2—C81.764 (4)C9—C101.392 (6)
N1—C151.468 (8)C9—H90.9300
N1—H1A0.8900C10—C111.372 (7)
N1—H1B0.8900C10—H100.9300
N1—H1C0.8900C11—C121.385 (7)
N2—C161.480 (7)C11—C141.515 (6)
N2—H2A0.8900C12—C131.374 (7)
N2—H2B0.8900C12—H120.9300
N2—H2C0.8900C13—H130.9300
O7—H7D0.8228C14—H14A0.9600
O7—H7E0.8218C14—H14B0.9600
C1—C21.372 (6)C14—H14C0.9600
C1—C61.394 (6)C15—C161.480 (7)
C2—C31.391 (7)C15—H15A0.9700
C2—H20.9300C15—H15B0.9700
C3—C41.376 (7)C16—H16A0.9700
C3—H30.9300C16—H16B0.9700
O3—S1—O1111.9 (2)C5—C6—C1118.9 (4)
O3—S1—O2112.4 (3)C5—C6—H6120.5
O1—S1—O2110.8 (3)C1—C6—H6120.5
O3—S1—C1107.82 (18)C4—C7—H7A109.5
O1—S1—C1107.1 (2)C4—C7—H7B109.5
O2—S1—C1106.6 (2)H7A—C7—H7B109.5
O6—S2—O4110.5 (8)C4—C7—H7C109.5
O6—S2—O5103.5 (8)H7A—C7—H7C109.5
O4—S2—O5120.8 (8)H7B—C7—H7C109.5
O6'—S2—O4'111.6 (6)C13—C8—C9119.6 (4)
O6'—S2—O5'112.4 (6)C13—C8—S2120.6 (3)
O4'—S2—O5'113.7 (6)C9—C8—S2119.8 (3)
O6'—S2—C8107.7 (4)C8—C9—C10119.6 (4)
O6—S2—C8108.2 (5)C8—C9—H9120.2
O4—S2—C8107.0 (5)C10—C9—H9120.2
O4'—S2—C8105.1 (3)C11—C10—C9121.1 (4)
O5—S2—C8106.2 (4)C11—C10—H10119.4
O5'—S2—C8105.7 (3)C9—C10—H10119.4
C15—N1—H1A109.5C10—C11—C12118.4 (4)
C15—N1—H1B109.5C10—C11—C14121.2 (5)
H1A—N1—H1B109.5C12—C11—C14120.4 (5)
C15—N1—H1C109.5C13—C12—C11121.2 (4)
H1A—N1—H1C109.5C13—C12—H12119.4
H1B—N1—H1C109.5C11—C12—H12119.4
C16—N2—H2A109.5C12—C13—C8120.1 (4)
C16—N2—H2B109.5C12—C13—H13119.9
H2A—N2—H2B109.5C8—C13—H13119.9
C16—N2—H2C109.5C11—C14—H14A109.5
H2A—N2—H2C109.5C11—C14—H14B109.5
H2B—N2—H2C109.5H14A—C14—H14B109.5
H7D—O7—H7E115.5C11—C14—H14C109.5
C2—C1—C6120.2 (4)H14A—C14—H14C109.5
C2—C1—S1120.4 (3)H14B—C14—H14C109.5
C6—C1—S1119.2 (3)N1—C15—C16109.5 (5)
C1—C2—C3119.5 (4)N1—C15—H15A109.8
C1—C2—H2120.2C16—C15—H15A109.8
C3—C2—H2120.2N1—C15—H15B109.8
C4—C3—C2121.5 (4)C16—C15—H15B109.8
C4—C3—H3119.2H15A—C15—H15B108.2
C2—C3—H3119.2C15—C16—N2111.2 (5)
C3—C4—C5118.2 (4)C15—C16—H16A109.4
C3—C4—C7120.7 (4)N2—C16—H16A109.4
C5—C4—C7121.1 (4)C15—C16—H16B109.4
C4—C5—C6121.7 (4)N2—C16—H16B109.4
C4—C5—H5119.2H16A—C16—H16B108.0
C6—C5—H5119.2
O3—S1—C1—C2158.9 (4)O5—S2—C8—C13−135.5 (7)
O1—S1—C1—C238.3 (5)O5'—S2—C8—C13176.0 (6)
O2—S1—C1—C2−80.3 (5)O6'—S2—C8—C9116.2 (7)
O3—S1—C1—C6−26.0 (5)O6—S2—C8—C9154.9 (8)
O1—S1—C1—C6−146.6 (4)O4—S2—C8—C9−86.0 (9)
O2—S1—C1—C694.8 (4)O4'—S2—C8—C9−124.7 (6)
C6—C1—C2—C30.8 (7)O5—S2—C8—C944.3 (7)
S1—C1—C2—C3175.9 (4)O5'—S2—C8—C9−4.2 (6)
C1—C2—C3—C4−0.3 (8)C13—C8—C9—C10−0.4 (7)
C2—C3—C4—C5−0.5 (8)S2—C8—C9—C10179.9 (4)
C2—C3—C4—C7−178.8 (5)C8—C9—C10—C110.8 (8)
C3—C4—C5—C60.7 (8)C9—C10—C11—C12−1.2 (9)
C7—C4—C5—C6179.0 (5)C9—C10—C11—C14179.2 (6)
C4—C5—C6—C1−0.2 (8)C10—C11—C12—C131.0 (9)
C2—C1—C6—C5−0.6 (7)C14—C11—C12—C13−179.4 (6)
S1—C1—C6—C5−175.7 (4)C11—C12—C13—C8−0.6 (8)
O6'—S2—C8—C13−63.6 (7)C9—C8—C13—C120.2 (7)
O6—S2—C8—C13−24.9 (9)S2—C8—C13—C12180.0 (4)
O4—S2—C8—C1394.2 (9)N1—C15—C16—N2178.9 (4)
O4'—S2—C8—C1355.5 (7)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···O7i0.891.872.736 (7)165
N1—H1B···O5ii0.892.142.942 (8)149
N1—H1B···O6ii0.892.573.365 (5)148
N1—H1B···O6'ii0.891.882.735 (8)162
N1—H1C···O20.891.872.761 (6)176
N2—H2A···O6iii0.892.032.780 (7)142
N2—H2B···O40.891.782.665 (5)177
N2—H2C···O1iv0.892.052.893 (6)157
O7—H7D···O50.822.152.793 (5)134
O7—H7E···O1iv0.822.152.938 (9)160

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IS2252).

References

  • Ahn, C.-T. & Kim, E.-S. (1985). J. Korean Chem. Soc.29, 335–340.
  • Bruker (1998). SHELXTL Bruker AXS Inc., Madison, Wisconsin, USA.
  • Edwards, S. H., Kahwa, I. A. & Mague, J. T. (2001). Acta Cryst. E57, o20–o21.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Bryant, G. L., Yakymyshyn, C. P. & Stewart, K. R. (1993). Acta Cryst. C49, 350–351.
  • Nakamura, H. & Iitaka, Y. (1978). Acta Cryst. B34, 3384–3387.
  • Nethaji, M., Pattabhi, V., Chhabra, N. & Poonia, N. S. (1992). Acta Cryst. C48, 2207–2209.
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Sheldrick, G. M. (1997). SHELXS97 and SHELXL97 University of Göttingen, Germany.
  • Siemens (1994). XSCANS Version 2.1. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography