A new sulfate acid polymorph of 1,3-dihydrobenzotriazole,
viz. 1,3-dihydrobenzotriazolium hydrogensulfate, C
6H
6N
3+·HSO
4-, differs from an existing polymorph in that the polymeric interaction between the HSO
4- anions, together with different classical (
D-H
A) and nonclassical (C-H
A) interactions, changes the space group.
Supporting information
CCDC reference: 661793
A mixture of (I) (400 mg, 3.36 mmol) and dry THF (10 ml) was cooled at 223 K;
H2SO4 (0.18 ml, 329 mg, 3.36 mmol) was added, and the mixture was stirred
for half an hour. The mixture was then filtered and the white powdered product
(II) (98% yield, m.p. 437–439 K) was partially dissolved for crystallization
in a THF/hexane mixture. m/z (intensity, %): 207 (1) 133.35 (100),
105 (100). IR (KBr), νmax: 2100–3600 (OH), 3300 (NH), 1723 (N═N), 1612
(C═C). Analysis calcualted: C 33.18, H 3.25, N 19.35, S 14.76%; observed:
C 33.53, H 3.30, N 19.02, S 13.24%. The structure of (I) (Scheme 2) was
analyzed by 1H and 13C NMR spectroscopy, which showed a symmetrical
molecule, three signals for 1H and four for 13C. The N—H chemical shift
in (II) was shifted to lower frequency (2.62 p.p.m) compared to N—H for (I).
Double protonation was not observed for (I); in fact, atom N2 is not a basic
position, because no different –NH signal was observed in the 1H NMR
spectrum. No significant changes were observed in the 13C NMR spectrum
because there were no changes in the aromatic ring.
All H atoms were refined freely [C—H = 0.09 (2)–0.97 (3) Å].
Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
1,3-dihydrobenzotriazolium hydrogensulfate
top
Crystal data top
C6H6N3+·HO4S− | F(000) = 448 |
Mr = 217.21 | Dx = 1.675 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 600 reflections |
a = 12.715 (3) Å | θ = 20–25° |
b = 5.133 (1) Å | µ = 0.37 mm−1 |
c = 14.406 (4) Å | T = 273 K |
β = 113.63 (1)° | Block, colorless |
V = 861.4 (4) Å3 | 0.25 × 0.20 × 0.20 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD diffractometer | 1969 independent reflections |
Radiation source: Enraf Nonius FR590 | 1637 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
Detector resolution: 9 pixels mm-1 | θmax = 27.5°, θmin = 3.5° |
CCD rotation images, thick slices scans | h = −16→16 |
Absorption correction: multi-scan (Blessing, 1995) | k = −6→6 |
Tmin = 0.913, Tmax = 0.930 | l = −18→18 |
9336 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.035 | All H-atom parameters refined |
wR(F2) = 0.095 | w = 1/[σ2(Fo2) + (0.0447P)2 + 0.3606P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
1969 reflections | Δρmax = 0.26 e Å−3 |
156 parameters | Δρmin = −0.34 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.135 (7) |
Crystal data top
C6H6N3+·HO4S− | V = 861.4 (4) Å3 |
Mr = 217.21 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.715 (3) Å | µ = 0.37 mm−1 |
b = 5.133 (1) Å | T = 273 K |
c = 14.406 (4) Å | 0.25 × 0.20 × 0.20 mm |
β = 113.63 (1)° | |
Data collection top
Nonius KappaCCD diffractometer | 1969 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 1637 reflections with I > 2σ(I) |
Tmin = 0.913, Tmax = 0.930 | Rint = 0.038 |
9336 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.095 | All H-atom parameters refined |
S = 1.07 | Δρmax = 0.26 e Å−3 |
1969 reflections | Δρmin = −0.34 e Å−3 |
156 parameters | |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded
fractional coordinates. All su's are estimated from the variances of the
(full) variance-covariance matrix. The cell e.s.d.'s are taken into account in
the estimation of distances, angles and torsion angles |
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 | x | y | z | Uiso*/Ueq | |
N1 | 0.14597 (13) | 0.8878 (3) | 0.00723 (11) | 0.0321 (5) | |
N2 | 0.08082 (13) | 0.7651 (3) | 0.04460 (11) | 0.0366 (5) | |
N3 | 0.14782 (13) | 0.5896 (3) | 0.10613 (11) | 0.0334 (5) | |
C4 | 0.35565 (17) | 0.4474 (4) | 0.16183 (15) | 0.0407 (6) | |
C5 | 0.44902 (17) | 0.5100 (4) | 0.14226 (17) | 0.0476 (7) | |
C6 | 0.44675 (17) | 0.7097 (5) | 0.07465 (17) | 0.0479 (7) | |
C7 | 0.35075 (17) | 0.8556 (4) | 0.02349 (16) | 0.0413 (6) | |
C8 | 0.25480 (14) | 0.7932 (3) | 0.04328 (12) | 0.0298 (5) | |
C9 | 0.25652 (14) | 0.5955 (3) | 0.10966 (12) | 0.0300 (5) | |
S1 | 0.15446 (3) | 0.11578 (8) | 0.30659 (3) | 0.0292 (2) | |
O1 | 0.13681 (12) | −0.1847 (3) | 0.29554 (10) | 0.0347 (4) | |
O2 | 0.27038 (12) | 0.1591 (3) | 0.32186 (13) | 0.0570 (5) | |
O3 | 0.12529 (14) | 0.1896 (3) | 0.39017 (10) | 0.0487 (5) | |
O4 | 0.07252 (11) | 0.2299 (3) | 0.21155 (9) | 0.0376 (4) | |
H1 | 0.1165 (19) | 1.005 (5) | −0.0350 (18) | 0.046 (6)* | |
H3 | 0.119 (2) | 0.483 (5) | 0.1368 (19) | 0.056 (7)* | |
H4 | 0.3575 (19) | 0.325 (5) | 0.2068 (18) | 0.050 (6)* | |
H5 | 0.517 (2) | 0.413 (5) | 0.1736 (18) | 0.055 (7)* | |
H6 | 0.517 (2) | 0.747 (5) | 0.0673 (18) | 0.062 (7)* | |
H7 | 0.347 (2) | 0.989 (5) | −0.0255 (18) | 0.054 (6)* | |
H1A | 0.070 (3) | −0.205 (6) | 0.289 (2) | 0.074 (9)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0353 (8) | 0.0319 (8) | 0.0310 (8) | 0.0022 (6) | 0.0154 (6) | 0.0063 (6) |
N2 | 0.0359 (8) | 0.0425 (9) | 0.0348 (8) | 0.0021 (7) | 0.0179 (7) | 0.0039 (7) |
N3 | 0.0364 (8) | 0.0360 (8) | 0.0310 (8) | −0.0026 (6) | 0.0169 (6) | 0.0047 (6) |
C4 | 0.0419 (10) | 0.0387 (11) | 0.0366 (10) | 0.0014 (8) | 0.0105 (8) | 0.0069 (8) |
C5 | 0.0338 (10) | 0.0523 (13) | 0.0505 (12) | 0.0051 (9) | 0.0104 (9) | 0.0018 (10) |
C6 | 0.0339 (10) | 0.0588 (13) | 0.0544 (13) | −0.0074 (9) | 0.0213 (9) | −0.0016 (10) |
C7 | 0.0398 (10) | 0.0455 (11) | 0.0431 (10) | −0.0091 (8) | 0.0214 (8) | 0.0037 (9) |
C8 | 0.0316 (8) | 0.0297 (8) | 0.0280 (8) | −0.0038 (7) | 0.0117 (7) | −0.0024 (7) |
C9 | 0.0334 (8) | 0.0311 (9) | 0.0252 (8) | −0.0038 (7) | 0.0113 (7) | −0.0011 (7) |
S1 | 0.0303 (3) | 0.0279 (3) | 0.0293 (3) | −0.0019 (2) | 0.0118 (2) | 0.0006 (2) |
O1 | 0.0394 (7) | 0.0272 (7) | 0.0399 (7) | 0.0034 (5) | 0.0183 (6) | −0.0016 (5) |
O2 | 0.0309 (7) | 0.0626 (10) | 0.0726 (11) | −0.0077 (7) | 0.0156 (7) | 0.0123 (8) |
O3 | 0.0758 (10) | 0.0371 (8) | 0.0391 (8) | 0.0002 (7) | 0.0292 (7) | −0.0092 (6) |
O4 | 0.0383 (7) | 0.0378 (7) | 0.0359 (7) | 0.0016 (5) | 0.0139 (6) | 0.0101 (5) |
Geometric parameters (Å, º) top
S1—O3 | 1.4453 (17) | C4—C9 | 1.404 (3) |
S1—O1 | 1.5576 (17) | C4—C5 | 1.364 (3) |
S1—O2 | 1.4179 (18) | C5—C6 | 1.406 (3) |
S1—O4 | 1.4696 (14) | C6—C7 | 1.369 (3) |
O1—H1A | 0.82 (4) | C7—C8 | 1.397 (3) |
N1—N2 | 1.315 (2) | C8—C9 | 1.389 (2) |
N1—C8 | 1.358 (3) | C4—H4 | 0.90 (2) |
N2—N3 | 1.311 (2) | C5—H5 | 0.94 (3) |
N3—C9 | 1.363 (3) | C6—H6 | 0.96 (3) |
N1—H1 | 0.83 (2) | C7—H7 | 0.97 (3) |
N3—H3 | 0.87 (3) | | |
| | | |
S1···O4i | 3.4229 (18) | N1···O3x | 2.695 (2) |
S1···H1Aii | 2.78 (4) | N2···N2viii | 3.094 (2) |
S1···H3 | 2.98 (3) | N2···O3ii | 3.143 (3) |
S1···H1iii | 3.18 (3) | N2···N1viii | 3.213 (3) |
O1···N3iv | 3.019 (2) | N3···O1vii | 3.019 (2) |
O1···O4iv | 3.220 (2) | N3···O4 | 2.792 (2) |
O1···O4i | 2.659 (2) | N2···H1viii | 2.73 (3) |
O1···N1v | 3.181 (2) | C4···O2 | 3.269 (3) |
O1···C8v | 3.318 (2) | C6···O2xi | 3.306 (3) |
O2···C4 | 3.269 (3) | C8···O3ix | 3.287 (2) |
O2···C6vi | 3.306 (3) | C8···O1ix | 3.318 (2) |
O3···C9v | 3.270 (2) | C9···O3ix | 3.270 (2) |
O3···N2i | 3.143 (3) | C5···H4xi | 3.02 (3) |
O3···C8v | 3.287 (2) | H1···N2viii | 2.73 (3) |
O3···N1iii | 2.695 (2) | H1···S1x | 3.18 (2) |
O4···O1vii | 3.220 (2) | H1···O3x | 1.93 (3) |
O4···S1ii | 3.4229 (18) | H1A···S1i | 2.78 (4) |
O4···N3 | 2.792 (2) | H1A···O3i | 2.83 (3) |
O4···O1ii | 2.659 (2) | H1A···O4i | 1.84 (4) |
O1···H3iv | 2.79 (3) | H3···O4 | 1.93 (3) |
O2···H6vi | 2.57 (3) | H3···S1 | 2.98 (3) |
O2···H7iii | 2.71 (2) | H3···O1vii | 2.79 (3) |
O2···H4 | 2.48 (3) | H4···O2 | 2.48 (3) |
O3···H1iii | 1.93 (3) | H4···C5vi | 3.02 (3) |
O3···H1Aii | 2.83 (3) | H6···H7xii | 2.45 (4) |
O4···H3 | 1.93 (3) | H6···O2xi | 2.57 (3) |
O4···H1Aii | 1.84 (4) | H7···O2x | 2.71 (2) |
N1···N2viii | 3.213 (3) | H7···H6xii | 2.45 (4) |
N1···O1ix | 3.181 (2) | | |
| | | |
O3—S1—O4 | 110.41 (9) | C5—C6—C7 | 122.6 (2) |
O1—S1—O3 | 105.68 (9) | C6—C7—C8 | 115.35 (19) |
O1—S1—O4 | 106.27 (8) | N1—C8—C7 | 132.80 (16) |
O1—S1—O2 | 105.63 (9) | N1—C8—C9 | 104.90 (16) |
O2—S1—O4 | 112.75 (9) | C7—C8—C9 | 122.29 (17) |
O2—S1—O3 | 115.31 (10) | N3—C9—C4 | 133.41 (17) |
S1—O1—H1A | 104 (2) | N3—C9—C8 | 104.76 (15) |
N2—N1—C8 | 112.62 (15) | C4—C9—C8 | 121.82 (18) |
N1—N2—N3 | 105.11 (16) | C5—C4—H4 | 122.8 (17) |
N2—N3—C9 | 112.61 (15) | C9—C4—H4 | 121.6 (17) |
N2—N1—H1 | 118.3 (18) | C4—C5—H5 | 119.0 (16) |
C8—N1—H1 | 129.1 (18) | C6—C5—H5 | 118.5 (16) |
C9—N3—H3 | 128.4 (18) | C5—C6—H6 | 117.4 (15) |
N2—N3—H3 | 118.9 (18) | C7—C6—H6 | 120.0 (15) |
C5—C4—C9 | 115.51 (18) | C6—C7—H7 | 123.4 (16) |
C4—C5—C6 | 122.5 (2) | C8—C7—H7 | 121.2 (16) |
| | | |
C8—N1—N2—N3 | 0.36 (19) | C4—C5—C6—C7 | −0.1 (4) |
N2—N1—C8—C7 | 177.92 (19) | C5—C6—C7—C8 | 0.2 (3) |
N2—N1—C8—C9 | −0.57 (19) | C6—C7—C8—C9 | −0.5 (3) |
N1—N2—N3—C9 | 0.0 (2) | C6—C7—C8—N1 | −178.76 (19) |
N2—N3—C9—C4 | −178.91 (19) | N1—C8—C9—N3 | 0.53 (17) |
N2—N3—C9—C8 | −0.34 (19) | C7—C8—C9—C4 | 0.6 (3) |
C5—C4—C9—C8 | −0.4 (3) | N1—C8—C9—C4 | 179.30 (16) |
C5—C4—C9—N3 | 177.95 (19) | C7—C8—C9—N3 | −178.17 (16) |
C9—C4—C5—C6 | 0.2 (3) | | |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x, y+1/2, −z+1/2; (iii) x, −y+3/2, z+1/2; (iv) x, y−1, z; (v) x, −y+1/2, z+1/2; (vi) −x+1, y−1/2, −z+1/2; (vii) x, y+1, z; (viii) −x, −y+2, −z; (ix) x, −y+1/2, z−1/2; (x) x, −y+3/2, z−1/2; (xi) −x+1, y+1/2, −z+1/2; (xii) −x+1, −y+2, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O3x | 0.83 (2) | 1.93 (3) | 2.695 (2) | 153 (2) |
O1—H1A···O4i | 0.82 (4) | 1.84 (4) | 2.659 (2) | 173 (3) |
N3—H3···O4 | 0.87 (3) | 1.93 (3) | 2.792 (2) | 173 (3) |
C4—H4···O2 | 0.90 (2) | 2.48 (3) | 3.269 (3) | 146 (2) |
C6—H6···O2xi | 0.96 (3) | 2.57 (3) | 3.306 (3) | 133.7 (19) |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (x) x, −y+3/2, z−1/2; (xi) −x+1, y+1/2, −z+1/2. |
Experimental details
Crystal data |
Chemical formula | C6H6N3+·HO4S− |
Mr | 217.21 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 273 |
a, b, c (Å) | 12.715 (3), 5.133 (1), 14.406 (4) |
β (°) | 113.63 (1) |
V (Å3) | 861.4 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.37 |
Crystal size (mm) | 0.25 × 0.20 × 0.20 |
|
Data collection |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.913, 0.930 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9336, 1969, 1637 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.095, 1.07 |
No. of reflections | 1969 |
No. of parameters | 156 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.26, −0.34 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O3i | 0.83 (2) | 1.93 (3) | 2.695 (2) | 153 (2) |
O1—H1A···O4ii | 0.82 (4) | 1.84 (4) | 2.659 (2) | 173 (3) |
N3—H3···O4 | 0.87 (3) | 1.93 (3) | 2.792 (2) | 173 (3) |
C4—H4···O2 | 0.90 (2) | 2.48 (3) | 3.269 (3) | 146 (2) |
C6—H6···O2iii | 0.96 (3) | 2.57 (3) | 3.306 (3) | 133.7 (19) |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x, y−1/2, −z+1/2; (iii) −x+1, y+1/2, −z+1/2. |
Table 1. Selected values of bond distances of (II) in comparison with
(III) and (IV) topatoms distances, (Å) | molecule 2a (esd) | molecule 3b | molecule 4c (esd) |
N1-N2 | 1.315 (2) | 1.310 | 1.317 (3) |
N2-N3 | 1.311 (2) | 1.312 | 1.314 (3) |
C4-C5 | 1.364 (3) | 1.365 | 1.368 (4) |
C5-C6 | 1.406 (3) | 1.416 | 1.414 (4) |
C6-C7 | 1.369 (3) | 1.356 | 1.370 (4) |
C7-C8 | 1.397 (3) | 1.391 | 1.402 (4) |
C8-C9 | 1.389 (2) | 1.391 | 1.390 (3) |
C4-C9 | 1.404 (3) | 1.392 | 1.400 (4) |
C9-N3 | 1.363 (3) | 1.367 | 1.364 (3) |
C8-N1 | 1.358 (3) | 1.362 | 1.365 (3) |
O1-S1 | 1.5576 (17) | 1.539 | – |
O2-S1 | 1.4179 (18) | 1.431 | – |
O3-S1 | 1.4453 (17) | 1.435 | – |
O4-S1 | 1.4696 (14) | 1.449 | – |
(a) This work, monoclinic; (b) Giordano (1980), orthorhombic;
(c) Emsley et al. (1988), triclinic. |
Heterocyclic molecule (I) (Scheme 1) contains acidic H atoms and N atoms with lone electron pairs. The presence of both acidic and basic characteristics gives the molecule the ability to participate in a wide variety of interactions. Moreover, tautomerism in (I) can change the reactivity depending on the starting material (Scheme 1) (Jagerovic et al., 2002; Katritzky et al., 1998; Gallinek, 1897; Elderfiel, 1957). This diversity gives rise to the possibility of different structural arrangements or polymorphs. For aliphatic amines this outcome is expected, but in this case the molecule is planar and polymorphs are not common (Bladengen or Blagden & Davey, 2003; Davey, 2003; Mak & Zhou, 1992; Dunitz, 1979).
The title compound, C6H4N3H2+·HSO4-, (II), crystallized in the monoclinic space group P21/c from a mixture of tetrahydrofuran (THF) and hexane. The structure (Fig. 1) shows the presence of acidic H atoms on atom N3 (Scheme 1) and on the counter-ion HSO4-. The crystal packing (Fig. 2) is structured by classical and nonclassical hydrogen bonds, the most important of which are listed in Table 1. Three of these are classical hydrogen bonds (N—H···O), while the others are nonclassical (C—H···O). Two particularly strong interactions are H3···O4 and H1···O3. Some of the hydrogen bonds are complex. For example, the N1/H1 group is considered a bifurcated donor because it is interacting with atoms N2 and O3. Atom O2 is considered as a trifurcated acceptor because it is interacting with the C6—H6, C4—H4 and C7—H7 bonds. All such interactions are important because they contribute to the geometry of the lattice. The HSO4- ions are joined together by strong O—H···O═S hydrogen bonds that are nearly ideal in geometry (Steiner, 1998, 2002; Jeffrey, 1997).
As a result of these interactions, the 1,3-dihydrobenzotriazole cations pack in a herringbone pattern in the ab plane with the hydrogen sulfate anions interspersed (Fig. 3). A polymorphic structure of (II) was reported by Giordano (1980), which crystallizes in the orthorhombic space group Pbcn. The phosphoric acid salt of 1,3-dihydrobenzotriazole, (IV) (Scheme 1), is also known (Emsley et al., 1988) and crystallizes in the triclinic space group P1 with similar packing to (II).
In Table 1, the bond distances for polymorphs (II) and (III) (Giordano, 1980) and molecule (IV) (Emsley et al., 1988) are compared. Polymorphs (II) and (III) show similar bond distances, while in compound (IV) they are slightly longer. It can also be observed that the distances decrease in the crystal system order triclinic → monoclinic → orthorhombic. This reflects better packing as the symmetry increases. Fig. 4 shows the rearrangement of the HSO4- anion corresponding to polymorphs (II) and (III). The hydrogen bond [S—O—H···O═S = 1.84 (4) and 1.478 Å] is in fact the reason that the HSO4- ions stay together in the supramolecular polymeric structure. We can conclude that these interactions are stronger in (III) than in (II). Consequently, the chains in (III) have almost linear shape, while those in (II) have a zigzag shape; and the distances are shorter, stronger and more efficient in the orthorhombic lattice in (III) compared with the monoclinic lattice in (II).