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In the title compound, C3H4N3+·C7H7O3S, the activated C—H group of the cation forms a short but bent C—H...O hydrogen bond with a sulfonate O atom of the anion; C...O = 3.075 (5) Å and C—H...O = 130°.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101005789/de1169sup1.cif
Contains datablocks malono, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101005789/de1169Isup2.hkl
Contains datablock I

CCDC reference: 167006

Comment top

C—H···O hydrogen bonds are known to have a very wide range of geometries and strengths. With highly polar C—H groups such as in CHCl3, CC—H, CH(NO2)3, etc, C—H···O interactions may have similar geometries as conventional O/N—H···O hydrogen bonds. On the other hand, with the weakly polar methyl groups, C—H···O interactions have long contact distances and are only slightly directional. All intermediate situations exist between these extremes (see e.g. Steiner, 1997; Steiner & Desiraju, 1998; Desiraju & Steiner, 1999). When studying the stronger kinds of C—H···O interactions, methyl groups are of interest which carry two or even three strongly electron-withdrawing substituents (Pedireddi & Desiraju, 1992). In this context, the (dicyanomethyl)ammonium cation is of obvious interest. In the p-toluenesulfonate salt, (I), formation of a short C—H···O hydrogen bond may be expected. \sch

In the crystal structure of (I), the three ammonium H atoms form N—H···O hydrogen bonds with the sulfonate group (Table 2). As expected, the highly activated C—H group of the cation interacts with a sulfonate O-atom too (Fig. 1). The C···O distance is very short with 3.075 (5) Å, but the geometry is strongly bent. Based on a normalized H atom position (C—H = 1.08 Å), the H···O distance is 2.27 Å, and the C—H···O angle is 130°. When compared to the shortest C—H···O interactions known, which have H···O distances around and below 2.0 Å (e.g. Bock et al., 1993; Kariuki et al., 1997), this may not appear to be so short. However, upon closer examination, it is seen that the C—H donor is involved in two additional intermolecular interactions with hydrogen-bond geometry, but both have substantially longer distances (Table 2). The crystal packing as a whole is shown in Fig. 2 to illustrate the typical segregation of polar and apolar groups in the lattice. An important factor responsible for the poor C—H···O angle might be the competition of C—H and the neighboring ammonium group for acceptors. The ammonium group certainly plays the more dominant role in determining intermolecular geometries, and optimizing N—H···O geometries might prevent the C—H···O angle to be linear.

To see how the C—H···O hydrogen bond in (I) compares with related interactions of dicyanomethyl C—H donors, a short database search was performed (CSD, update 5.20, Allen & Kennard, 1993). In the 15 relevant crystal structures found, the shortest occurring (C)H···O distance is 2.12 Å (in a crown-ether complex of dicyanomethane; Grootenhuis et al., 1986), with the more typical values > 2.2 Å. This indicates that (CN)2C—H is a good hydrogen bond donor in general, but clearly falls behind the classical strong C—H donors like CHCl3 and CC—H.

Experimental top

Compound (I) was obtained from Lancester and was recrystallized from MeOH by slow evaporation of the solvent.

Refinement top

H atoms bonded to C of the anion were treated in the default riding model with U values allowed to vary. The cation H atoms were located in difference Fourier calculations and refined isotropically [U values of the cation H atoms: H(N1) = 0.043–0.057, H(C8) = 0.040 Å2, respectively].

Structure description top

C—H···O hydrogen bonds are known to have a very wide range of geometries and strengths. With highly polar C—H groups such as in CHCl3, CC—H, CH(NO2)3, etc, C—H···O interactions may have similar geometries as conventional O/N—H···O hydrogen bonds. On the other hand, with the weakly polar methyl groups, C—H···O interactions have long contact distances and are only slightly directional. All intermediate situations exist between these extremes (see e.g. Steiner, 1997; Steiner & Desiraju, 1998; Desiraju & Steiner, 1999). When studying the stronger kinds of C—H···O interactions, methyl groups are of interest which carry two or even three strongly electron-withdrawing substituents (Pedireddi & Desiraju, 1992). In this context, the (dicyanomethyl)ammonium cation is of obvious interest. In the p-toluenesulfonate salt, (I), formation of a short C—H···O hydrogen bond may be expected. \sch

In the crystal structure of (I), the three ammonium H atoms form N—H···O hydrogen bonds with the sulfonate group (Table 2). As expected, the highly activated C—H group of the cation interacts with a sulfonate O-atom too (Fig. 1). The C···O distance is very short with 3.075 (5) Å, but the geometry is strongly bent. Based on a normalized H atom position (C—H = 1.08 Å), the H···O distance is 2.27 Å, and the C—H···O angle is 130°. When compared to the shortest C—H···O interactions known, which have H···O distances around and below 2.0 Å (e.g. Bock et al., 1993; Kariuki et al., 1997), this may not appear to be so short. However, upon closer examination, it is seen that the C—H donor is involved in two additional intermolecular interactions with hydrogen-bond geometry, but both have substantially longer distances (Table 2). The crystal packing as a whole is shown in Fig. 2 to illustrate the typical segregation of polar and apolar groups in the lattice. An important factor responsible for the poor C—H···O angle might be the competition of C—H and the neighboring ammonium group for acceptors. The ammonium group certainly plays the more dominant role in determining intermolecular geometries, and optimizing N—H···O geometries might prevent the C—H···O angle to be linear.

To see how the C—H···O hydrogen bond in (I) compares with related interactions of dicyanomethyl C—H donors, a short database search was performed (CSD, update 5.20, Allen & Kennard, 1993). In the 15 relevant crystal structures found, the shortest occurring (C)H···O distance is 2.12 Å (in a crown-ether complex of dicyanomethane; Grootenhuis et al., 1986), with the more typical values > 2.2 Å. This indicates that (CN)2C—H is a good hydrogen bond donor in general, but clearly falls behind the classical strong C—H donors like CHCl3 and CC—H.

Computing details top

Data collection: STOE Diffractometer Software (Stoe & Cie, 1993); cell refinement: STOE Diffractometer Software; data reduction: STOE Diffractometer Software; program(s) used to solve structure: SHELXS86 (Sheldrick, 1986); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1990); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. Molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. Crystal packing shown in a projection on the yz-plane.
Ammonio-malononitrile p-toluenesulfonate top
Crystal data top
C3H4N3+·C7H7O3SF(000) = 528
Mr = 253.28Dx = 1.384 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 5.604 (9) ÅCell parameters from 25 reflections
b = 25.90 (5) Åθ = 8.2–14.9°
c = 8.427 (12) ŵ = 0.27 mm1
β = 96.40 (14)°T = 293 K
V = 1216 (4) Å3Plate, colorless
Z = 40.8 × 0.3 × 0.05 mm
Data collection top
STOE for-circle
diffractometer
Rint = 0.019
Radiation source: fine-focus sealed tubeθmax = 27.0°, θmin = 2.6°
Graphite monochromatorh = 74
ω–scansk = 2533
3001 measured reflectionsl = 1010
2660 independent reflections3 standard reflections every 90 min
2162 reflections with I > 2σ(I) intensity decay: 3%
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)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.126H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0656P)2 + 0.4531P]
where P = (Fo2 + 2Fc2)/3
2660 reflections(Δ/σ)max < 0.001
171 parametersΔρmax = 0.45 e Å3
0 restraintsΔρmin = 0.39 e Å3
Crystal data top
C3H4N3+·C7H7O3SV = 1216 (4) Å3
Mr = 253.28Z = 4
Monoclinic, P21/nMo Kα radiation
a = 5.604 (9) ŵ = 0.27 mm1
b = 25.90 (5) ÅT = 293 K
c = 8.427 (12) Å0.8 × 0.3 × 0.05 mm
β = 96.40 (14)°
Data collection top
STOE for-circle
diffractometer
Rint = 0.019
3001 measured reflections3 standard reflections every 90 min
2660 independent reflections intensity decay: 3%
2162 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.126H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.45 e Å3
2660 reflectionsΔρmin = 0.39 e Å3
171 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
S10.74752 (8)0.190589 (19)0.62961 (5)0.03177 (16)
O10.7303 (3)0.22032 (6)0.77468 (16)0.0393 (4)
O20.5660 (3)0.20656 (6)0.50249 (17)0.0416 (4)
O30.9874 (3)0.19285 (6)0.58114 (19)0.0421 (4)
C10.6888 (4)0.12601 (8)0.6734 (2)0.0376 (4)
C20.4753 (5)0.10355 (10)0.6150 (3)0.0555 (6)
H20.36120.12200.54910.067*
C30.4331 (6)0.05303 (12)0.6559 (4)0.0701 (8)
H30.28870.03770.61620.084*
C40.5962 (6)0.02478 (11)0.7530 (4)0.0649 (8)
C50.8057 (6)0.04836 (12)0.8096 (4)0.0749 (9)
H50.91880.03000.87640.090*
C60.8552 (5)0.09854 (11)0.7707 (3)0.0585 (7)
H61.00020.11370.81020.070*
C70.5440 (8)0.03045 (12)0.7971 (5)0.1013 (14)
H7A0.49510.03140.90270.152*
H7B0.68610.05100.79420.152*
H7C0.41770.04400.72240.152*
N10.7754 (3)0.23564 (8)1.2375 (2)0.0358 (4)
H1A0.705 (5)0.2282 (10)1.326 (3)0.043 (6)*
H1B0.694 (5)0.2636 (11)1.186 (3)0.048 (7)*
H1C0.932 (5)0.2464 (10)1.261 (3)0.057 (8)*
N20.3287 (4)0.17136 (10)1.0170 (3)0.0660 (6)
N30.9688 (5)0.11085 (11)1.2746 (4)0.0798 (8)
C80.7701 (4)0.19072 (9)1.1300 (2)0.0379 (5)
H80.856 (4)0.2001 (9)1.043 (3)0.040 (6)*
C90.5202 (4)0.17894 (10)1.0673 (3)0.0460 (5)
C100.8828 (4)0.14550 (10)1.2127 (3)0.0496 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0255 (3)0.0428 (3)0.0273 (3)0.00154 (19)0.00438 (18)0.00006 (19)
O10.0380 (8)0.0492 (9)0.0310 (7)0.0038 (6)0.0044 (6)0.0028 (6)
O20.0335 (7)0.0597 (9)0.0309 (7)0.0018 (7)0.0001 (6)0.0078 (7)
O30.0287 (7)0.0521 (9)0.0473 (9)0.0057 (6)0.0124 (6)0.0074 (7)
C10.0336 (10)0.0438 (11)0.0366 (10)0.0024 (9)0.0093 (8)0.0004 (9)
C20.0423 (13)0.0523 (14)0.0703 (17)0.0081 (11)0.0010 (12)0.0042 (12)
C30.0586 (16)0.0594 (17)0.095 (2)0.0210 (14)0.0188 (16)0.0116 (16)
C40.0734 (19)0.0470 (14)0.0802 (19)0.0018 (13)0.0345 (16)0.0030 (13)
C50.077 (2)0.0641 (18)0.084 (2)0.0066 (16)0.0080 (17)0.0273 (16)
C60.0463 (14)0.0603 (16)0.0669 (17)0.0037 (12)0.0031 (12)0.0178 (13)
C70.130 (3)0.0505 (18)0.134 (4)0.009 (2)0.060 (3)0.005 (2)
N10.0285 (8)0.0471 (10)0.0319 (9)0.0029 (8)0.0032 (7)0.0056 (8)
N20.0430 (12)0.0849 (17)0.0677 (15)0.0143 (12)0.0043 (11)0.0044 (13)
N30.0799 (18)0.0658 (16)0.091 (2)0.0199 (14)0.0045 (15)0.0053 (15)
C80.0293 (10)0.0544 (13)0.0305 (10)0.0019 (9)0.0057 (8)0.0023 (9)
C90.0399 (12)0.0563 (14)0.0413 (12)0.0063 (10)0.0022 (10)0.0003 (10)
C100.0437 (13)0.0535 (14)0.0514 (14)0.0027 (11)0.0043 (11)0.0025 (11)
Geometric parameters (Å, º) top
S1—O31.449 (3)C6—H60.9300
S1—O21.453 (3)C7—H7A0.9600
S1—O11.457 (2)C7—H7B0.9600
S1—C11.752 (4)C7—H7C0.9600
C1—C61.370 (4)N1—C81.473 (4)
C1—C21.372 (4)N1—H1A0.91 (3)
C2—C31.380 (5)N1—H1B0.93 (3)
C2—H20.9300N1—H1C0.92 (3)
C3—C41.369 (5)N2—C91.127 (4)
C3—H30.9300N3—C101.120 (4)
C4—C51.362 (5)C8—C101.469 (4)
C4—C71.515 (5)C8—C91.473 (4)
C5—C61.376 (5)C8—H80.95 (3)
C5—H50.9300
O3—S1—O2112.08 (14)C1—C6—H6120.3
O3—S1—O1111.42 (14)C5—C6—H6120.3
O2—S1—O1111.22 (14)C4—C7—H7A109.5
O3—S1—C1107.45 (10)C4—C7—H7B109.5
O2—S1—C1107.14 (11)H7A—C7—H7B109.5
O1—S1—C1107.24 (14)C4—C7—H7C109.5
C6—C1—C2120.2 (3)H7A—C7—H7C109.5
C6—C1—S1119.4 (2)H7B—C7—H7C109.5
C2—C1—S1120.40 (19)C8—N1—H1A111.0 (16)
C1—C2—C3118.6 (3)C8—N1—H1B110.5 (16)
C1—C2—H2120.7H1A—N1—H1B108 (2)
C3—C2—H2120.7C8—N1—H1C108.9 (17)
C4—C3—C2122.3 (3)H1A—N1—H1C112 (2)
C4—C3—H3118.8H1B—N1—H1C105 (2)
C2—C3—H3118.8C10—C8—C9110.3 (2)
C5—C4—C3117.5 (3)C10—C8—N1111.1 (2)
C5—C4—C7121.4 (3)C9—C8—N1109.7 (2)
C3—C4—C7121.2 (3)C10—C8—H8109.8 (14)
C4—C5—C6122.0 (3)C9—C8—H8108.7 (15)
C4—C5—H5119.0N1—C8—H8107.1 (14)
C6—C5—H5119.0N2—C9—C8177.8 (3)
C1—C6—C5119.4 (3)N3—C10—C8179.5 (3)
O3—S1—C1—C648.8 (2)C2—C3—C4—C7179.5 (3)
O2—S1—C1—C6169.4 (2)C3—C4—C5—C60.5 (5)
O1—S1—C1—C671.1 (2)C7—C4—C5—C6179.9 (3)
O3—S1—C1—C2133.3 (2)C2—C1—C6—C50.2 (4)
O2—S1—C1—C212.7 (2)S1—C1—C6—C5177.8 (2)
O1—S1—C1—C2106.8 (2)C4—C5—C6—C10.5 (5)
C6—C1—C2—C30.2 (4)C10—C8—C9—N2172 (8)
S1—C1—C2—C3178.2 (2)N1—C8—C9—N266 (8)
C1—C2—C3—C40.3 (5)C9—C8—C10—N372 (36)
C2—C3—C4—C50.1 (5)N1—C8—C10—N3166 (100)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.91 (3)1.84 (3)2.741 (4)175 (2)
N1—H1B···O3ii0.93 (3)1.78 (3)2.701 (4)168 (2)
N1—H1C···O1iii0.92 (3)1.87 (3)2.778 (5)167 (3)
C8—H8···O10.95 (3)2.35 (2)3.075 (5)132.3 (19)
C8—H8···O2iii0.95 (3)2.73 (2)3.373 (5)125.8 (17)
C8—H8···N2iv0.95 (3)2.78 (3)3.409 (6)124.2 (17)
Symmetry codes: (i) x, y, z+1; (ii) x1/2, y+1/2, z+1/2; (iii) x+1/2, y+1/2, z+1/2; (iv) x+1, y, z.

Experimental details

Crystal data
Chemical formulaC3H4N3+·C7H7O3S
Mr253.28
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)5.604 (9), 25.90 (5), 8.427 (12)
β (°) 96.40 (14)
V3)1216 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.27
Crystal size (mm)0.8 × 0.3 × 0.05
Data collection
DiffractometerSTOE for-circle
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
3001, 2660, 2162
Rint0.019
(sin θ/λ)max1)0.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.126, 1.03
No. of reflections2660
No. of parameters171
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.45, 0.39

Computer programs: STOE Diffractometer Software (Stoe & Cie, 1993), STOE Diffractometer Software, SHELXS86 (Sheldrick, 1986), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1990), SHELXL97.

Selected geometric parameters (Å, º) top
N1—C81.473 (4)C8—C101.469 (4)
N2—C91.127 (4)C8—C91.473 (4)
N3—C101.120 (4)
C10—C8—C9110.3 (2)C9—C8—N1109.7 (2)
C10—C8—N1111.1 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.91 (3)1.84 (3)2.741 (4)175 (2)
N1—H1B···O3ii0.93 (3)1.78 (3)2.701 (4)168 (2)
N1—H1C···O1iii0.92 (3)1.87 (3)2.778 (5)167 (3)
C8—H8···O10.95 (3)2.35 (2)3.075 (5)132.3 (19)
C8—H8···O2iii0.95 (3)2.73 (2)3.373 (5)125.8 (17)
C8—H8···N2iv0.95 (3)2.78 (3)3.409 (6)124.2 (17)
Symmetry codes: (i) x, y, z+1; (ii) x1/2, y+1/2, z+1/2; (iii) x+1/2, y+1/2, z+1/2; (iv) x+1, y, z.
 

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