Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101005789/de1169sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101005789/de1169Isup2.hkl |
CCDC reference: 167006
Compound (I) was obtained from Lancester and was recrystallized from MeOH by slow evaporation of the solvent.
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].
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, C≡C—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 C≡C—H.
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.
Fig. 1. Molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level. | |
Fig. 2. Crystal packing shown in a projection on the yz-plane. |
C3H4N3+·C7H7O3S− | F(000) = 528 |
Mr = 253.28 | Dx = 1.384 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 5.604 (9) Å | Cell parameters from 25 reflections |
b = 25.90 (5) Å | θ = 8.2–14.9° |
c = 8.427 (12) Å | µ = 0.27 mm−1 |
β = 96.40 (14)° | T = 293 K |
V = 1216 (4) Å3 | Plate, colorless |
Z = 4 | 0.8 × 0.3 × 0.05 mm |
STOE for-circle diffractometer | Rint = 0.019 |
Radiation source: fine-focus sealed tube | θmax = 27.0°, θmin = 2.6° |
Graphite monochromator | h = −7→4 |
ω–scans | k = −25→33 |
3001 measured reflections | l = −10→10 |
2660 independent reflections | 3 standard reflections every 90 min |
2162 reflections with I > 2σ(I) | intensity decay: 3% |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.126 | H 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 parameters | Δρmax = 0.45 e Å−3 |
0 restraints | Δρmin = −0.39 e Å−3 |
C3H4N3+·C7H7O3S− | V = 1216 (4) Å3 |
Mr = 253.28 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.604 (9) Å | µ = 0.27 mm−1 |
b = 25.90 (5) Å | T = 293 K |
c = 8.427 (12) Å | 0.8 × 0.3 × 0.05 mm |
β = 96.40 (14)° |
STOE for-circle diffractometer | Rint = 0.019 |
3001 measured reflections | 3 standard reflections every 90 min |
2660 independent reflections | intensity decay: 3% |
2162 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.126 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.45 e Å−3 |
2660 reflections | Δρmin = −0.39 e Å−3 |
171 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.74752 (8) | 0.190589 (19) | 0.62961 (5) | 0.03177 (16) | |
O1 | 0.7303 (3) | 0.22032 (6) | 0.77468 (16) | 0.0393 (4) | |
O2 | 0.5660 (3) | 0.20656 (6) | 0.50249 (17) | 0.0416 (4) | |
O3 | 0.9874 (3) | 0.19285 (6) | 0.58114 (19) | 0.0421 (4) | |
C1 | 0.6888 (4) | 0.12601 (8) | 0.6734 (2) | 0.0376 (4) | |
C2 | 0.4753 (5) | 0.10355 (10) | 0.6150 (3) | 0.0555 (6) | |
H2 | 0.3612 | 0.1220 | 0.5491 | 0.067* | |
C3 | 0.4331 (6) | 0.05303 (12) | 0.6559 (4) | 0.0701 (8) | |
H3 | 0.2887 | 0.0377 | 0.6162 | 0.084* | |
C4 | 0.5962 (6) | 0.02478 (11) | 0.7530 (4) | 0.0649 (8) | |
C5 | 0.8057 (6) | 0.04836 (12) | 0.8096 (4) | 0.0749 (9) | |
H5 | 0.9188 | 0.0300 | 0.8764 | 0.090* | |
C6 | 0.8552 (5) | 0.09854 (11) | 0.7707 (3) | 0.0585 (7) | |
H6 | 1.0002 | 0.1137 | 0.8102 | 0.070* | |
C7 | 0.5440 (8) | −0.03045 (12) | 0.7971 (5) | 0.1013 (14) | |
H7A | 0.4951 | −0.0314 | 0.9027 | 0.152* | |
H7B | 0.6861 | −0.0510 | 0.7942 | 0.152* | |
H7C | 0.4177 | −0.0440 | 0.7224 | 0.152* | |
N1 | 0.7754 (3) | 0.23564 (8) | 1.2375 (2) | 0.0358 (4) | |
H1A | 0.705 (5) | 0.2282 (10) | 1.326 (3) | 0.043 (6)* | |
H1B | 0.694 (5) | 0.2636 (11) | 1.186 (3) | 0.048 (7)* | |
H1C | 0.932 (5) | 0.2464 (10) | 1.261 (3) | 0.057 (8)* | |
N2 | 0.3287 (4) | 0.17136 (10) | 1.0170 (3) | 0.0660 (6) | |
N3 | 0.9688 (5) | 0.11085 (11) | 1.2746 (4) | 0.0798 (8) | |
C8 | 0.7701 (4) | 0.19072 (9) | 1.1300 (2) | 0.0379 (5) | |
H8 | 0.856 (4) | 0.2001 (9) | 1.043 (3) | 0.040 (6)* | |
C9 | 0.5202 (4) | 0.17894 (10) | 1.0673 (3) | 0.0460 (5) | |
C10 | 0.8828 (4) | 0.14550 (10) | 1.2127 (3) | 0.0496 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0255 (3) | 0.0428 (3) | 0.0273 (3) | −0.00154 (19) | 0.00438 (18) | 0.00006 (19) |
O1 | 0.0380 (8) | 0.0492 (9) | 0.0310 (7) | 0.0038 (6) | 0.0044 (6) | −0.0028 (6) |
O2 | 0.0335 (7) | 0.0597 (9) | 0.0309 (7) | −0.0018 (7) | 0.0001 (6) | 0.0078 (7) |
O3 | 0.0287 (7) | 0.0521 (9) | 0.0473 (9) | −0.0057 (6) | 0.0124 (6) | −0.0074 (7) |
C1 | 0.0336 (10) | 0.0438 (11) | 0.0366 (10) | −0.0024 (9) | 0.0093 (8) | −0.0004 (9) |
C2 | 0.0423 (13) | 0.0523 (14) | 0.0703 (17) | −0.0081 (11) | −0.0010 (12) | −0.0042 (12) |
C3 | 0.0586 (16) | 0.0594 (17) | 0.095 (2) | −0.0210 (14) | 0.0188 (16) | −0.0116 (16) |
C4 | 0.0734 (19) | 0.0470 (14) | 0.0802 (19) | −0.0018 (13) | 0.0345 (16) | 0.0030 (13) |
C5 | 0.077 (2) | 0.0641 (18) | 0.084 (2) | 0.0066 (16) | 0.0080 (17) | 0.0273 (16) |
C6 | 0.0463 (14) | 0.0603 (16) | 0.0669 (17) | −0.0037 (12) | −0.0031 (12) | 0.0178 (13) |
C7 | 0.130 (3) | 0.0505 (18) | 0.134 (4) | −0.009 (2) | 0.060 (3) | 0.005 (2) |
N1 | 0.0285 (8) | 0.0471 (10) | 0.0319 (9) | −0.0029 (8) | 0.0032 (7) | 0.0056 (8) |
N2 | 0.0430 (12) | 0.0849 (17) | 0.0677 (15) | −0.0143 (12) | −0.0043 (11) | −0.0044 (13) |
N3 | 0.0799 (18) | 0.0658 (16) | 0.091 (2) | 0.0199 (14) | −0.0045 (15) | 0.0053 (15) |
C8 | 0.0293 (10) | 0.0544 (13) | 0.0305 (10) | −0.0019 (9) | 0.0057 (8) | 0.0023 (9) |
C9 | 0.0399 (12) | 0.0563 (14) | 0.0413 (12) | −0.0063 (10) | 0.0022 (10) | −0.0003 (10) |
C10 | 0.0437 (13) | 0.0535 (14) | 0.0514 (14) | 0.0027 (11) | 0.0043 (11) | −0.0025 (11) |
S1—O3 | 1.449 (3) | C6—H6 | 0.9300 |
S1—O2 | 1.453 (3) | C7—H7A | 0.9600 |
S1—O1 | 1.457 (2) | C7—H7B | 0.9600 |
S1—C1 | 1.752 (4) | C7—H7C | 0.9600 |
C1—C6 | 1.370 (4) | N1—C8 | 1.473 (4) |
C1—C2 | 1.372 (4) | N1—H1A | 0.91 (3) |
C2—C3 | 1.380 (5) | N1—H1B | 0.93 (3) |
C2—H2 | 0.9300 | N1—H1C | 0.92 (3) |
C3—C4 | 1.369 (5) | N2—C9 | 1.127 (4) |
C3—H3 | 0.9300 | N3—C10 | 1.120 (4) |
C4—C5 | 1.362 (5) | C8—C10 | 1.469 (4) |
C4—C7 | 1.515 (5) | C8—C9 | 1.473 (4) |
C5—C6 | 1.376 (5) | C8—H8 | 0.95 (3) |
C5—H5 | 0.9300 | ||
O3—S1—O2 | 112.08 (14) | C1—C6—H6 | 120.3 |
O3—S1—O1 | 111.42 (14) | C5—C6—H6 | 120.3 |
O2—S1—O1 | 111.22 (14) | C4—C7—H7A | 109.5 |
O3—S1—C1 | 107.45 (10) | C4—C7—H7B | 109.5 |
O2—S1—C1 | 107.14 (11) | H7A—C7—H7B | 109.5 |
O1—S1—C1 | 107.24 (14) | C4—C7—H7C | 109.5 |
C6—C1—C2 | 120.2 (3) | H7A—C7—H7C | 109.5 |
C6—C1—S1 | 119.4 (2) | H7B—C7—H7C | 109.5 |
C2—C1—S1 | 120.40 (19) | C8—N1—H1A | 111.0 (16) |
C1—C2—C3 | 118.6 (3) | C8—N1—H1B | 110.5 (16) |
C1—C2—H2 | 120.7 | H1A—N1—H1B | 108 (2) |
C3—C2—H2 | 120.7 | C8—N1—H1C | 108.9 (17) |
C4—C3—C2 | 122.3 (3) | H1A—N1—H1C | 112 (2) |
C4—C3—H3 | 118.8 | H1B—N1—H1C | 105 (2) |
C2—C3—H3 | 118.8 | C10—C8—C9 | 110.3 (2) |
C5—C4—C3 | 117.5 (3) | C10—C8—N1 | 111.1 (2) |
C5—C4—C7 | 121.4 (3) | C9—C8—N1 | 109.7 (2) |
C3—C4—C7 | 121.2 (3) | C10—C8—H8 | 109.8 (14) |
C4—C5—C6 | 122.0 (3) | C9—C8—H8 | 108.7 (15) |
C4—C5—H5 | 119.0 | N1—C8—H8 | 107.1 (14) |
C6—C5—H5 | 119.0 | N2—C9—C8 | 177.8 (3) |
C1—C6—C5 | 119.4 (3) | N3—C10—C8 | 179.5 (3) |
O3—S1—C1—C6 | 48.8 (2) | C2—C3—C4—C7 | 179.5 (3) |
O2—S1—C1—C6 | 169.4 (2) | C3—C4—C5—C6 | −0.5 (5) |
O1—S1—C1—C6 | −71.1 (2) | C7—C4—C5—C6 | −179.9 (3) |
O3—S1—C1—C2 | −133.3 (2) | C2—C1—C6—C5 | −0.2 (4) |
O2—S1—C1—C2 | −12.7 (2) | S1—C1—C6—C5 | 177.8 (2) |
O1—S1—C1—C2 | 106.8 (2) | C4—C5—C6—C1 | 0.5 (5) |
C6—C1—C2—C3 | −0.2 (4) | C10—C8—C9—N2 | −172 (8) |
S1—C1—C2—C3 | −178.2 (2) | N1—C8—C9—N2 | 66 (8) |
C1—C2—C3—C4 | 0.3 (5) | C9—C8—C10—N3 | 72 (36) |
C2—C3—C4—C5 | 0.1 (5) | N1—C8—C10—N3 | −166 (100) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.91 (3) | 1.84 (3) | 2.741 (4) | 175 (2) |
N1—H1B···O3ii | 0.93 (3) | 1.78 (3) | 2.701 (4) | 168 (2) |
N1—H1C···O1iii | 0.92 (3) | 1.87 (3) | 2.778 (5) | 167 (3) |
C8—H8···O1 | 0.95 (3) | 2.35 (2) | 3.075 (5) | 132.3 (19) |
C8—H8···O2iii | 0.95 (3) | 2.73 (2) | 3.373 (5) | 125.8 (17) |
C8—H8···N2iv | 0.95 (3) | 2.78 (3) | 3.409 (6) | 124.2 (17) |
Symmetry codes: (i) x, y, z+1; (ii) x−1/2, −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 formula | C3H4N3+·C7H7O3S− |
Mr | 253.28 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 5.604 (9), 25.90 (5), 8.427 (12) |
β (°) | 96.40 (14) |
V (Å3) | 1216 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.27 |
Crystal size (mm) | 0.8 × 0.3 × 0.05 |
Data collection | |
Diffractometer | STOE for-circle diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3001, 2660, 2162 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.126, 1.03 |
No. of reflections | 2660 |
No. of parameters | 171 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 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.
N1—C8 | 1.473 (4) | C8—C10 | 1.469 (4) |
N2—C9 | 1.127 (4) | C8—C9 | 1.473 (4) |
N3—C10 | 1.120 (4) | ||
C10—C8—C9 | 110.3 (2) | C9—C8—N1 | 109.7 (2) |
C10—C8—N1 | 111.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.91 (3) | 1.84 (3) | 2.741 (4) | 175 (2) |
N1—H1B···O3ii | 0.93 (3) | 1.78 (3) | 2.701 (4) | 168 (2) |
N1—H1C···O1iii | 0.92 (3) | 1.87 (3) | 2.778 (5) | 167 (3) |
C8—H8···O1 | 0.95 (3) | 2.35 (2) | 3.075 (5) | 132.3 (19) |
C8—H8···O2iii | 0.95 (3) | 2.73 (2) | 3.373 (5) | 125.8 (17) |
C8—H8···N2iv | 0.95 (3) | 2.78 (3) | 3.409 (6) | 124.2 (17) |
Symmetry codes: (i) x, y, z+1; (ii) x−1/2, −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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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, C≡C—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 C≡C—H.