organic papers
o1058
Wanget al. C2H10N22+2C7H4NO3S doi:10.1107/S1600536806005046 Acta Cryst.(2006). E62, o1058–o1059
Acta Crystallographica Section E Structure Reports Online
ISSN 1600-5368
Ethylenediammonium disaccharinate
Zi-Liang Wang,aLin-Heng Wei,b Ming-Xue Liaand
Jing-Yang Niua*
aCollege of Chemistry and Chemical
Engineering, Henan University, Kaifeng 475001, People’s Republic of China, andbCollege of
Environment and Planning, Henan University, Kaifeng 475001, People’s Republic of China
Correspondence e-mail: [email protected]
Key indicators
Single-crystal X-ray study
T= 292 K
Mean(C–C) = 0.004 A˚
Rfactor = 0.045
wRfactor = 0.122
Data-to-parameter ratio = 14.2
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
Received 3 January 2006 Accepted 10 February 2006
#2006 International Union of Crystallography
All rights reserved
The asymmetric unit of the title compound, C2H10N2
2+
2C7H4NO3S
, is composed of two saccharinate anions and one doubly protonated ethylenediamine cation. These are linked by N—H O and N—H N hydrogen bonds and aromatic – stacking interactions, leading to a two-dimensional framework structure.
Comment
Saccharin is a versatile polyfunctional ligand which has been used to build novel complexes with transition metals and some ancillary ligands (Falvello et al., 2001; Yilmaz et al., 2002). However, as far as the authors are aware, there are no struc-tures reported in the literature where saccharin interacts with organic bases through hydrogen bonds to form supra-molecular assemblies. Our research groups are currently investigating supramolecular structures of co-crystals containing saccharin and a series of organic bases. Here, we report the title co-crystal of saccharin, (I), incorporating the organic base ethylenediamine.
The structure of (I) is illustrated in Fig. 1. The asymmetric unit consists of two saccharinate anions and one doubly protonated ethylenediamine cation. These ions are linked into a two-dimensional framework structure by a combination of N—H O and N—H N hydrogen bonds (Fig. 2, Table 1). Moreover, – stacking interactions are observed between the C1–C6 benzene ring at (x,y,z) and the C8–C13 benzene rings of centrosymmetrically related molecules at (x, 1y, 1 z) and (1 x, 1 y, 1 z), with centroid–centroid distances of 3.749 (4) and 3.726 (5) A˚ , respectively.
Experimental
Crystal data
C2H10N22+2C7H4NO3S
Mr= 426.46
Triclinic,P1 a= 7.3344 (9) A˚ b= 10.0494 (12) A˚ c= 13.2454 (16) A˚
= 84.741 (2)
= 86.943 (2)
= 73.305 (2) V= 930.8 (2) A˚3
Z= 2
Dx= 1.522 Mg m 3 MoKradiation Cell parameters from 2723
reflections
= 2.5–28.2
= 0.33 mm1 T= 292 (2) K Needle, colourless 0.400.200.10 mm
Data collection
Bruker SMART APEX CCD area-detector diffractometer Thin-slice!scans
Absorption correction: multi-scan (SADABS; Bruker, 2001) Tmin= 0.880,Tmax= 0.968 7288 measured reflections
3612 independent reflections 2944 reflections withI> 2(I) Rint= 0.020
max= 26.0
h=8!9 k=12!12 l=16!16
Refinement
Refinement onF2
R[F2> 2(F2)] = 0.045
wR(F2) = 0.122
S= 1.05 3612 reflections 255 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.0622P)2 + 0.2579P]
whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001
max= 0.37 e A˚
3
min=0.28 e A˚
[image:2.610.45.292.73.247.2]3
Table 1
Hydrogen-bond geometry (A˚ ,).
D—H A D—H H A D A D—H A
N3—H3A O3i 0.89 2.05 2.850 (2) 149 N3—H3B N1ii
0.89 2.00 2.883 (3) 173
N3—H3C N2iii
0.89 2.49 3.085 (3) 125
N4—H4A O3i
0.89 1.97 2.816 (2) 158
N4—H4B N2iv 0.89 2.09 2.867 (2) 146 N4—H4C N1v
0.89 2.28 3.124 (3) 158
N3—H3C O4vi
0.89 2.31 2.886 (3) 123
C11—H11 O2 0.93 2.42 3.280 (3) 154
C15—H15B O6 0.97 2.37 3.083 (3) 130 C15—H15A O4vi
0.97 2.41 2.934 (3) 113
Symmetry codes: (i)x;y;z1; (ii)xþ1;yþ1;zþ1; (iii)xþ1;yþ1;z; (iv)x;yþ1;z; (v)x;yþ1;zþ1; (vi)x;yþ1;z.
All H atoms were placed in calculated positions, with C—H = 0.93– 0.97 A˚ and N–H = 0.89 A˚, and refined as riding, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(N).
Data collection:SMART(Bruker, 2001); cell refinement:SAINT
(Bruker, 2001); data reduction:SAINT; program(s) used to solve structure:SHELXS97(Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
PLATON (Spek, 2003); software used to prepare material for publication:PLATON.
This work was supported by the Basic Research Foundation for Natural Science of Henan University.
References
Bruker (2001).SAINT(Version 6.45),SMART(Version 5.628) andSADABS (Version 2.10). Bruker AXS Inc., Madison, Wisconsin, USA.
Falvello, L. R., Gomez, J., Pascual, I., Tomas, M., Urriolabeitia, E. P. & Schultz, A. J. (2001).Inorg. Chem.40, 4455–4463.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Go¨ttingen, Germany.
Spek, A. L. (2003).J. Appl. Cryst.36, 7–13.
Yilmaz, V. T., Guney, S., Andac, O. & Harrison, W. T. A. (2002).Polyhedron,
[image:2.610.313.565.291.398.2]21, 2393–2402.
Figure 1
The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
Figure 2
A view of the crystal packing of (I) along thebaxis, showing the linkage of the ions by hydrogen-bonding interactions (dashed lines). [Symmetry codes: (A)x,y,z; (B) 1 +x,y,z; (C)x, 1y, 1z; (D) 1x, 1y, 1
[image:2.610.47.295.294.517.2]supporting information
sup-1 Acta Cryst. (2006). E62, o1058–o1059
supporting information
Acta Cryst. (2006). E62, o1058–o1059 [https://doi.org/10.1107/S1600536806005046]
Ethylenediammonium disaccharinate
Zi-Liang Wang, Lin-Heng Wei, Ming-Xue Li and Jing-Yang Niu
Ethylenediammonium disaccharinate
Crystal data
C2H10N22+·2C7H4NO3S−
Mr = 426.46
Triclinic, P1 Hall symbol: -P 1 a = 7.3344 (9) Å b = 10.0494 (12) Å c = 13.2454 (16) Å α = 84.741 (2)° β = 86.943 (2)° γ = 73.305 (2)° V = 930.8 (2) Å3
Z = 2 F(000) = 444 Dx = 1.522 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 2723 reflections θ = 2.5–28.2°
µ = 0.33 mm−1
T = 292 K Needle, colourless 0.40 × 0.20 × 0.10 mm
Data collection
Bruker SMART APEX CCD area-detector diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
0.3° wide ω exposures scans Absorption correction: multi-scan
(SADABS; Bruker, 2001) Tmin = 0.880, Tmax = 0.968
7288 measured reflections 3612 independent reflections 2944 reflections with I > 2σ(I) Rint = 0.020
θmax = 26.0°, θmin = 1.5°
h = −8→9 k = −12→12 l = −16→16
Refinement
Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.045
wR(F2) = 0.122
S = 1.05 3612 reflections 255 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrained w = 1/[σ2(F
o2) + (0.0622P)2 + 0.2579P] where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001 Δρmax = 0.37 e Å−3 Δρmin = −0.28 e Å−3
Special details
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)
x y z Uiso*/Ueq
S1 0.26054 (9) 0.42458 (7) 0.69397 (4) 0.04556 (19) S2 0.48411 (9) 0.06234 (6) 0.13583 (4) 0.04499 (19) N1 0.2815 (3) 0.4573 (2) 0.80964 (13) 0.0428 (5) N2 0.3586 (3) 0.20223 (19) 0.07813 (13) 0.0393 (4) N3 0.3815 (3) 0.6931 (2) 0.08137 (14) 0.0438 (5)
H3A 0.3533 0.6461 0.0336 0.066*
H3B 0.4894 0.6431 0.1102 0.066*
H3C 0.3956 0.7737 0.0536 0.066*
N4 −0.0543 (3) 0.7217 (2) 0.06211 (14) 0.0452 (5)
H4A 0.0254 0.6760 0.0155 0.068*
H4B −0.1573 0.7778 0.0322 0.068*
H4C −0.0883 0.6609 0.1068 0.068*
O1 0.1359 (3) 0.3377 (2) 0.69091 (14) 0.0662 (5) O2 0.4447 (3) 0.3753 (2) 0.64614 (13) 0.0639 (5) O3 0.2158 (2) 0.64616 (19) 0.90294 (12) 0.0527 (4) O4 0.3861 (4) −0.0425 (2) 0.14816 (16) 0.0822 (7) O5 0.6700 (3) 0.0211 (2) 0.08873 (15) 0.0777 (6) O6 0.2165 (3) 0.42760 (17) 0.11134 (13) 0.0628 (5) C1 0.1436 (3) 0.5968 (3) 0.64886 (17) 0.0440 (6) C2 0.0775 (4) 0.6506 (3) 0.55359 (19) 0.0614 (8)
H2 0.0962 0.5949 0.4994 0.074*
C3 −0.0175 (4) 0.7907 (4) 0.5427 (2) 0.0765 (10)
H3 −0.0659 0.8303 0.4799 0.092*
C4 −0.0425 (4) 0.8732 (3) 0.6223 (3) 0.0732 (9)
H4 −0.1079 0.9673 0.6125 0.088*
C5 0.0284 (4) 0.8187 (3) 0.7177 (2) 0.0560 (7)
H5 0.0132 0.8749 0.7713 0.067*
C6 0.1216 (3) 0.6784 (3) 0.72950 (17) 0.0423 (5) C7 0.2097 (3) 0.5940 (3) 0.82257 (16) 0.0401 (5) C8 0.4929 (3) 0.1296 (2) 0.25307 (16) 0.0375 (5) C9 0.5735 (4) 0.0645 (3) 0.34250 (19) 0.0530 (6)
H9 0.6375 −0.0302 0.3486 0.064*
C10 0.5551 (4) 0.1461 (3) 0.42258 (18) 0.0583 (7)
H10 0.6073 0.1057 0.4844 0.070*
C11 0.4611 (4) 0.2861 (3) 0.41301 (18) 0.0552 (7)
H11 0.4536 0.3392 0.4678 0.066*
C12 0.3770 (4) 0.3495 (3) 0.32259 (16) 0.0458 (6)
H12 0.3113 0.4438 0.3166 0.055*
supporting information
sup-3 Acta Cryst. (2006). E62, o1058–o1059
C15 0.2265 (3) 0.7201 (2) 0.15874 (16) 0.0381 (5)
H15A 0.2598 0.7685 0.2119 0.046*
H15B 0.2120 0.6320 0.1891 0.046*
C16 0.0414 (3) 0.8057 (2) 0.11504 (19) 0.0458 (6)
H16A −0.0424 0.8495 0.1692 0.055*
H16B 0.0644 0.8790 0.0676 0.055*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
S1 0.0503 (4) 0.0564 (4) 0.0319 (3) −0.0171 (3) −0.0015 (2) −0.0073 (3) S2 0.0562 (4) 0.0303 (3) 0.0449 (3) −0.0037 (3) −0.0097 (3) −0.0080 (2) N1 0.0457 (11) 0.0495 (12) 0.0284 (9) −0.0056 (9) −0.0037 (8) −0.0017 (8) N2 0.0484 (11) 0.0351 (10) 0.0349 (9) −0.0099 (8) −0.0097 (8) −0.0061 (8) N3 0.0385 (10) 0.0470 (11) 0.0467 (11) −0.0106 (9) −0.0081 (8) −0.0088 (9) N4 0.0359 (10) 0.0558 (12) 0.0420 (10) −0.0102 (9) −0.0046 (8) −0.0013 (9) O1 0.0814 (14) 0.0682 (13) 0.0603 (11) −0.0381 (11) −0.0074 (10) −0.0056 (9) O2 0.0592 (11) 0.0813 (14) 0.0485 (10) −0.0122 (10) 0.0091 (9) −0.0232 (9) O3 0.0608 (11) 0.0653 (12) 0.0356 (9) −0.0212 (9) 0.0018 (8) −0.0143 (8) O4 0.144 (2) 0.0432 (11) 0.0753 (13) −0.0483 (13) −0.0254 (13) −0.0014 (10) O5 0.0615 (12) 0.0836 (15) 0.0677 (13) 0.0193 (11) −0.0024 (10) −0.0305 (11) O6 0.0904 (14) 0.0326 (9) 0.0540 (10) 0.0026 (9) −0.0189 (10) 0.0008 (8) C1 0.0383 (12) 0.0627 (16) 0.0355 (11) −0.0230 (12) −0.0055 (9) 0.0041 (10) C2 0.0628 (17) 0.091 (2) 0.0406 (13) −0.0411 (17) −0.0154 (12) 0.0147 (14) C3 0.0647 (19) 0.104 (3) 0.066 (2) −0.0424 (19) −0.0299 (16) 0.0409 (19) C4 0.0499 (16) 0.0627 (19) 0.102 (3) −0.0179 (14) −0.0157 (16) 0.0344 (18) C5 0.0441 (14) 0.0513 (16) 0.0707 (18) −0.0140 (12) −0.0019 (12) 0.0066 (13) C6 0.0344 (12) 0.0528 (14) 0.0411 (12) −0.0170 (11) −0.0012 (9) 0.0043 (10) C7 0.0354 (12) 0.0532 (14) 0.0326 (11) −0.0146 (11) 0.0016 (9) −0.0027 (10) C8 0.0384 (12) 0.0389 (12) 0.0351 (11) −0.0112 (10) −0.0042 (9) −0.0003 (9) C9 0.0486 (14) 0.0592 (16) 0.0475 (14) −0.0119 (12) −0.0114 (11) 0.0101 (12) C10 0.0536 (15) 0.092 (2) 0.0330 (12) −0.0296 (15) −0.0118 (11) 0.0122 (13) C11 0.0610 (16) 0.084 (2) 0.0322 (12) −0.0362 (16) 0.0036 (11) −0.0139 (12) C12 0.0574 (15) 0.0482 (14) 0.0367 (12) −0.0215 (12) 0.0058 (10) −0.0107 (10) C13 0.0380 (11) 0.0364 (12) 0.0294 (10) −0.0164 (9) −0.0010 (8) −0.0028 (8) C14 0.0460 (13) 0.0338 (12) 0.0354 (11) −0.0121 (10) −0.0050 (9) −0.0007 (9) C15 0.0433 (12) 0.0353 (12) 0.0369 (11) −0.0124 (10) −0.0049 (9) −0.0035 (9) C16 0.0432 (13) 0.0364 (13) 0.0545 (14) −0.0052 (10) −0.0007 (11) −0.0077 (11)
Geometric parameters (Å, º)
S1—O2 1.4325 (19) C3—C4 1.374 (5)
S1—O1 1.4385 (19) C3—H3 0.9300
S1—N1 1.6201 (18) C4—C5 1.395 (4)
S1—C1 1.761 (3) C4—H4 0.9300
S2—O4 1.430 (2) C5—C6 1.377 (3)
S2—O5 1.432 (2) C5—H5 0.9300
S2—C8 1.761 (2) C8—C9 1.375 (3)
N1—C7 1.347 (3) C8—C13 1.378 (3)
N2—C14 1.358 (3) C9—C10 1.377 (4)
N3—C15 1.471 (3) C9—H9 0.9300
N3—H3A 0.8900 C10—C11 1.375 (4)
N3—H3B 0.8900 C10—H10 0.9300
N3—H3C 0.8900 C11—C12 1.390 (4)
N4—C16 1.482 (3) C11—H11 0.9300
N4—H4A 0.8900 C12—C13 1.372 (3)
N4—H4B 0.8900 C12—H12 0.9300
N4—H4C 0.8900 C13—C14 1.502 (3)
O3—C7 1.237 (3) C15—C16 1.497 (3)
O6—C14 1.226 (3) C15—H15A 0.9700
C1—C6 1.381 (3) C15—H15B 0.9700
C1—C2 1.382 (3) C16—H16A 0.9700
C2—C3 1.378 (5) C16—H16B 0.9700
C2—H2 0.9300
O2—S1—O1 116.04 (12) C4—C5—H5 121.3
O2—S1—N1 110.27 (10) C5—C6—C1 120.4 (2)
O1—S1—N1 110.41 (11) C5—C6—C7 128.5 (2)
O2—S1—C1 111.67 (12) C1—C6—C7 111.1 (2)
O1—S1—C1 110.07 (11) O3—C7—N1 123.9 (2)
N1—S1—C1 96.71 (10) O3—C7—C6 122.7 (2)
O4—S2—O5 115.51 (14) N1—C7—C6 113.34 (19)
O4—S2—N2 111.62 (12) C9—C8—C13 122.8 (2)
O5—S2—N2 109.89 (12) C9—C8—S2 130.5 (2)
O4—S2—C8 110.03 (11) C13—C8—S2 106.70 (15)
O5—S2—C8 110.69 (11) C8—C9—C10 116.8 (3)
N2—S2—C8 97.67 (10) C8—C9—H9 121.6
C7—N1—S1 111.53 (15) C10—C9—H9 121.6
C14—N2—S2 111.53 (15) C11—C10—C9 121.3 (2)
C15—N3—H3A 109.5 C11—C10—H10 119.3
C15—N3—H3B 109.5 C9—C10—H10 119.3
H3A—N3—H3B 109.5 C10—C11—C12 121.0 (2)
C15—N3—H3C 109.5 C10—C11—H11 119.5
H3A—N3—H3C 109.5 C12—C11—H11 119.5
H3B—N3—H3C 109.5 C13—C12—C11 118.1 (2)
C16—N4—H4A 109.5 C13—C12—H12 120.9
C16—N4—H4B 109.5 C11—C12—H12 120.9
H4A—N4—H4B 109.5 C12—C13—C8 119.9 (2)
C16—N4—H4C 109.5 C12—C13—C14 128.9 (2)
H4A—N4—H4C 109.5 C8—C13—C14 111.21 (18)
H4B—N4—H4C 109.5 O6—C14—N2 123.5 (2)
C6—C1—C2 122.5 (3) O6—C14—C13 123.59 (19)
C6—C1—S1 107.19 (16) N2—C14—C13 112.86 (19)
C2—C1—S1 130.3 (2) N3—C15—C16 111.97 (18)
supporting information
sup-5 Acta Cryst. (2006). E62, o1058–o1059
C3—C2—H2 121.6 C16—C15—H15A 109.2
C1—C2—H2 121.6 N3—C15—H15B 109.2
C4—C3—C2 121.6 (3) C16—C15—H15B 109.2
C4—C3—H3 119.2 H15A—C15—H15B 107.9
C2—C3—H3 119.2 N4—C16—C15 112.53 (18)
C3—C4—C5 121.3 (3) N4—C16—H16A 109.1
C3—C4—H4 119.4 C15—C16—H16A 109.1
C5—C4—H4 119.4 N4—C16—H16B 109.1
C6—C5—C4 117.5 (3) C15—C16—H16B 109.1
C6—C5—H5 121.3 H16A—C16—H16B 107.8
O2—S1—N1—C7 114.73 (18) C5—C6—C7—N1 176.8 (2) O1—S1—N1—C7 −115.72 (18) C1—C6—C7—N1 −3.3 (3) C1—S1—N1—C7 −1.36 (18) O4—S2—C8—C9 60.8 (3) O4—S2—N2—C14 115.64 (18) O5—S2—C8—C9 −68.1 (3) O5—S2—N2—C14 −114.86 (18) N2—S2—C8—C9 177.2 (2) C8—S2—N2—C14 0.47 (18) O4—S2—C8—C13 −117.49 (17) O2—S1—C1—C6 −115.56 (17) O5—S2—C8—C13 113.62 (17) O1—S1—C1—C6 114.04 (17) N2—S2—C8—C13 −1.07 (17) N1—S1—C1—C6 −0.59 (17) C13—C8—C9—C10 −1.4 (4) O2—S1—C1—C2 65.6 (3) S2—C8—C9—C10 −179.44 (19) O1—S1—C1—C2 −64.8 (3) C8—C9—C10—C11 −0.3 (4) N1—S1—C1—C2 −179.5 (2) C9—C10—C11—C12 1.6 (4) C6—C1—C2—C3 −1.7 (4) C10—C11—C12—C13 −1.3 (4) S1—C1—C2—C3 177.0 (2) C11—C12—C13—C8 −0.4 (3) C1—C2—C3—C4 1.0 (4) C11—C12—C13—C14 178.3 (2) C2—C3—C4—C5 0.3 (4) C9—C8—C13—C12 1.8 (3) C3—C4—C5—C6 −1.0 (4) S2—C8—C13—C12 −179.80 (17) C4—C5—C6—C1 0.4 (4) C9—C8—C13—C14 −177.1 (2) C4—C5—C6—C7 −179.7 (2) S2—C8—C13—C14 1.3 (2) C2—C1—C6—C5 1.1 (4) S2—N2—C14—O6 −179.3 (2) S1—C1—C6—C5 −177.92 (18) S2—N2—C14—C13 0.2 (2) C2—C1—C6—C7 −178.8 (2) C12—C13—C14—O6 −0.3 (4) S1—C1—C6—C7 2.2 (2) C8—C13—C14—O6 178.5 (2) S1—N1—C7—O3 −176.86 (18) C12—C13—C14—N2 −179.8 (2) S1—N1—C7—C6 2.9 (2) C8—C13—C14—N2 −1.1 (3) C5—C6—C7—O3 −3.5 (4) N3—C15—C16—N4 79.7 (2) C1—C6—C7—O3 176.4 (2)
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
N3—H3A···O3i 0.89 2.05 2.850 (2) 149
N3—H3B···N1ii 0.89 2.00 2.883 (3) 173
N3—H3C···N2iii 0.89 2.49 3.085 (3) 125
N4—H4A···O3i 0.89 1.97 2.816 (2) 158
N4—H4B···N2iv 0.89 2.09 2.867 (2) 146
N3—H3C···O4vi 0.89 2.31 2.886 (3) 123
C11—H11···O2 0.93 2.42 3.280 (3) 154
C15—H15B···O6 0.97 2.37 3.083 (3) 130
C15—H15A···O4vi 0.97 2.41 2.934 (3) 113
