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The mol­ecules of the title compound, C20H22N6, are linked together forming a C(8) chain extending along the c axis by an N—H...N hydrogen bond.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801020670/na6114sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801020670/na6114Isup2.hkl
Contains datablock I

CCDC reference: 180544

Key indicators

  • Single-crystal X-ray study
  • T = 100 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.061
  • wR factor = 0.150
  • Data-to-parameter ratio = 16.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_420 Alert C D-H Without Acceptor N(51) - H(52) ?
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

The title compound, (I), was obtained by acid catalyzed rearragement from 5-N-(benzotriazol-1-ylmethyl)amino-1-phenyl-3-tert-butylpyrazole.

The main supramolecular stuctural feature is a hydrogen bond, N51–H51···N43, 3.190 Å, which links the molecules by unit translations along the c axis forming C(8) chains (Bernstein et al., 1995). H52 does not form a hydrogen bond. Details of the hydrogen bonding are given in Table 1. There are no weak C–H hydrogen bonds nor is there any ππ base-stacking. Examination of the structure with PLATON (Spek, 2001) showed that there were no solvent-accessible voids in the crystal lattice.

Experimental top

To a solution of 0.3 g (0.867 mmol) of compound 5-N-(benzotriazol-1-ylmethyl)amino-1-phenyl-3-tert-butylpyrazole in 15 ml of absolute methanol were added 20–30 mg of p-toluensulfonic acid, and was stirred at room temperature for 1 h (TLC control). The solvent was removed under reduced pressure, the residue was re-dissolved in ethyl acetate, washed with a 10% NaOH solution and dried with anhydrous sodium sulfate. The solution was concentrated and purified by column chromatography on silica gel an a mixture 80:20 (hexane–ethyl acetate) as eluent, yielding 0.27 g (90%) of title compound as white crystals, which resulted suitable for X-ray diffraction. M.p. 397 K.

Refinement top

H atoms attached to C atoms were included at calculated positions and treated as riding atoms with C—H 0.95–0.99 Å., The H atoms attached to the N atoms were included at positions based on those found on a difference map were initially DFIXED to a value of 0.87 Å and then allowed to ride on the parent N atom.

Computing details top

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and PLATON (Spek, 2001); software used to prepare material for publication: SHELXL97 and WORDPERFECT macro PRPKAPPA (Ferguson, 1999).

Figures top
[Figure 1] Fig. 1. A view of (I) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. A view of the crystal structure showing the C(8) chain running along the c axis. The molecule labelled with an asterisk (*) is at (x, y, 1 + z) and that labelled with a hash (#) is at (x, y, -1 + z).
5-Amino-4-(benzotriazol-1-ylmethyl)-1-phenyl-3-tert-butylpyrazole top
Crystal data top
C20H22N6Dx = 1.303 Mg m3
Mr = 346.44Melting point: 397K K
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 13.465 (3) ÅCell parameters from 4002 reflections
b = 15.135 (3) Åθ = 3.1–27.5°
c = 9.1558 (18) ŵ = 0.08 mm1
β = 108.86 (3)°T = 100 K
V = 1765.8 (6) Å3Block, colourless
Z = 40.15 × 0.15 × 0.10 mm
F(000) = 736
Data collection top
KappaCCD
diffractometer
4002 independent reflections
Radiation source: fine-focus sealed X-ray tube2136 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.077
ϕ scans, and ω scans with κ offsetsθmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
h = 1717
Tmin = 0.988, Tmax = 0.992k = 1919
10902 measured reflectionsl = 1111
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)] = 0.061Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.150H-atom parameters constrained
S = 0.95 w = 1/[σ2(Fo2) + (0.0599P)2]
where P = (Fo2 + 2Fc2)/3
4002 reflections(Δ/σ)max < 0.001
244 parametersΔρmax = 0.27 e Å3
2 restraintsΔρmin = 0.39 e Å3
Crystal data top
C20H22N6V = 1765.8 (6) Å3
Mr = 346.44Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.465 (3) ŵ = 0.08 mm1
b = 15.135 (3) ÅT = 100 K
c = 9.1558 (18) Å0.15 × 0.15 × 0.10 mm
β = 108.86 (3)°
Data collection top
KappaCCD
diffractometer
4002 independent reflections
Absorption correction: multi-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
2136 reflections with I > 2σ(I)
Tmin = 0.988, Tmax = 0.992Rint = 0.077
10902 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0612 restraints
wR(F2) = 0.150H-atom parameters constrained
S = 0.95Δρmax = 0.27 e Å3
4002 reflectionsΔρmin = 0.39 e Å3
244 parameters
Special details top

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm (Fox & Holmes, 1966) which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.22730 (13)0.03333 (12)0.69269 (19)0.0172 (4)
C110.27550 (16)0.07547 (15)0.8375 (2)0.0177 (5)
C120.35843 (17)0.03735 (15)0.9512 (2)0.0208 (5)
C130.40553 (17)0.08237 (16)1.0868 (2)0.0237 (6)
C140.37268 (18)0.16631 (16)1.1102 (3)0.0239 (6)
C150.28992 (18)0.20431 (15)0.9951 (3)0.0245 (6)
C160.24104 (18)0.15984 (15)0.8595 (3)0.0208 (5)
N20.17458 (13)0.08611 (12)0.56890 (19)0.0189 (4)
C30.13923 (15)0.03215 (14)0.4493 (2)0.0161 (5)
C310.07902 (17)0.07128 (15)0.2936 (2)0.0198 (5)
C3110.15601 (18)0.08983 (17)0.2048 (3)0.0268 (6)
C3120.00729 (17)0.00835 (16)0.1993 (3)0.0256 (6)
C3130.02710 (18)0.15873 (15)0.3159 (3)0.0260 (6)
C40.16794 (16)0.05694 (15)0.4945 (2)0.0169 (5)
C410.15031 (18)0.13986 (15)0.4001 (3)0.0210 (5)
N410.21879 (14)0.14572 (12)0.3031 (2)0.0211 (5)
N420.17663 (16)0.16008 (13)0.1497 (2)0.0256 (5)
N430.25208 (16)0.16117 (13)0.0880 (2)0.0270 (5)
C43A0.34558 (19)0.14769 (15)0.2043 (3)0.0224 (6)
C440.44820 (19)0.14220 (15)0.1991 (3)0.0270 (6)
C450.5256 (2)0.12518 (16)0.3343 (3)0.0298 (6)
C460.50479 (19)0.11511 (16)0.4743 (3)0.0289 (6)
C470.40509 (18)0.12115 (16)0.4821 (3)0.0247 (6)
C47A0.32551 (17)0.13719 (15)0.3428 (3)0.0204 (5)
C50.22172 (16)0.05349 (15)0.6496 (2)0.0182 (5)
N510.26680 (16)0.12086 (13)0.7537 (2)0.0230 (5)
H120.38280.01970.93590.025*
H130.46150.05541.16550.028*
H140.40620.19731.20340.029*
H150.26660.26181.00990.029*
H160.18430.18640.78160.025*
H31A0.20930.13210.26290.040*
H31B0.11770.11460.10330.040*
H31C0.19020.03460.19160.040*
H31D0.02460.04100.16120.038*
H31E0.05530.04030.11170.038*
H31F0.04630.01450.26490.038*
H31G0.02240.14730.37210.039*
H31H0.01050.18440.21480.039*
H31I0.08120.20010.37500.039*
H41A0.16340.19150.47000.025*
H41B0.07610.14210.33300.025*
H440.46310.15000.10530.032*
H450.59590.11990.33420.036*
H460.56140.10380.56600.035*
H470.39090.11480.57670.030*
H510.25790.11610.84340.028*
H520.24280.17080.70920.028*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0158 (10)0.0177 (11)0.0168 (9)0.0002 (8)0.0036 (8)0.0008 (9)
C110.0158 (12)0.0199 (12)0.0180 (12)0.0020 (10)0.0063 (9)0.0001 (10)
C120.0193 (12)0.0207 (13)0.0202 (12)0.0008 (10)0.0036 (10)0.0025 (11)
C130.0196 (12)0.0256 (14)0.0222 (13)0.0012 (10)0.0018 (10)0.0000 (11)
C140.0238 (13)0.0238 (14)0.0209 (12)0.0047 (11)0.0028 (10)0.0026 (11)
C150.0270 (13)0.0191 (13)0.0257 (13)0.0002 (11)0.0061 (11)0.0025 (11)
C160.0170 (11)0.0220 (13)0.0203 (12)0.0005 (10)0.0019 (10)0.0020 (11)
N20.0150 (9)0.0202 (11)0.0196 (10)0.0013 (8)0.0028 (8)0.0032 (9)
C30.0104 (11)0.0200 (13)0.0188 (11)0.0023 (9)0.0058 (9)0.0019 (10)
C310.0137 (11)0.0229 (13)0.0205 (12)0.0022 (10)0.0024 (9)0.0003 (10)
C3110.0228 (13)0.0313 (15)0.0263 (13)0.0045 (11)0.0082 (11)0.0035 (12)
C3120.0172 (12)0.0291 (14)0.0253 (12)0.0025 (11)0.0001 (10)0.0006 (11)
C3130.0210 (13)0.0241 (14)0.0278 (13)0.0017 (11)0.0007 (10)0.0041 (11)
C40.0117 (11)0.0197 (12)0.0183 (11)0.0011 (9)0.0033 (9)0.0010 (10)
C410.0196 (12)0.0212 (13)0.0213 (12)0.0016 (10)0.0052 (10)0.0004 (10)
N410.0233 (11)0.0212 (11)0.0167 (10)0.0022 (9)0.0036 (9)0.0027 (8)
N420.0327 (12)0.0234 (11)0.0187 (10)0.0011 (9)0.0056 (9)0.0027 (9)
N430.0323 (12)0.0271 (12)0.0224 (11)0.0031 (10)0.0099 (10)0.0010 (9)
C43A0.0285 (14)0.0171 (13)0.0215 (13)0.0042 (10)0.0077 (11)0.0019 (10)
C440.0319 (15)0.0254 (14)0.0289 (14)0.0093 (11)0.0170 (12)0.0074 (11)
C450.0232 (13)0.0302 (15)0.0390 (15)0.0080 (11)0.0141 (12)0.0115 (12)
C460.0202 (13)0.0316 (15)0.0309 (14)0.0033 (11)0.0029 (11)0.0067 (12)
C470.0220 (13)0.0283 (14)0.0238 (13)0.0040 (11)0.0075 (11)0.0008 (11)
C47A0.0187 (12)0.0165 (12)0.0252 (13)0.0023 (10)0.0060 (10)0.0010 (10)
C50.0135 (11)0.0187 (12)0.0222 (12)0.0010 (10)0.0055 (9)0.0009 (10)
N510.0299 (12)0.0181 (11)0.0195 (11)0.0010 (9)0.0060 (10)0.0011 (9)
Geometric parameters (Å, º) top
N1—C51.367 (3)C313—H31G0.9800
N1—N21.381 (2)C313—H31H0.9800
N1—C111.425 (3)C313—H31I0.9800
C11—C121.383 (3)C4—C51.371 (3)
C11—C161.395 (3)C4—C411.499 (3)
C12—C131.378 (3)C41—N411.475 (3)
C12—H120.9500C41—H41A0.9900
C13—C141.385 (3)C41—H41B0.9900
C13—H130.9500N41—N421.352 (2)
C14—C151.387 (3)N41—C47A1.370 (3)
C14—H140.9500N42—N431.312 (3)
C15—C161.378 (3)N43—C43A1.376 (3)
C15—H150.9500C43A—C47A1.388 (3)
C16—H160.9500C43A—C441.401 (3)
N2—C31.325 (3)C44—C451.361 (3)
C3—C41.427 (3)C44—H440.9500
C3—C311.514 (3)C45—C461.405 (3)
C31—C3121.534 (3)C45—H450.9500
C31—C3111.536 (3)C46—C471.370 (3)
C31—C3131.541 (3)C46—H460.9500
C311—H31A0.9800C47—C47A1.396 (3)
C311—H31B0.9800C47—H470.9500
C311—H31C0.9800C5—N511.394 (3)
C312—H31D0.9800N51—H510.87
C312—H31E0.9800N51—H520.87
C312—H31F0.9800
C5—N1—N2110.70 (16)C31—C313—H31H109.5
C5—N1—C11131.67 (18)H31G—C313—H31H109.5
N2—N1—C11117.62 (17)C31—C313—H31I109.5
C12—C11—C16119.9 (2)H31G—C313—H31I109.5
C12—C11—N1121.9 (2)H31H—C313—H31I109.5
C16—C11—N1118.13 (19)C5—C4—C3105.51 (19)
C13—C12—C11119.8 (2)C5—C4—C41124.2 (2)
C13—C12—H12120.1C3—C4—C41130.30 (19)
C11—C12—H12120.1N41—C41—C4112.59 (18)
C12—C13—C14121.1 (2)N41—C41—H41A109.1
C12—C13—H13119.5C4—C41—H41A109.1
C14—C13—H13119.5N41—C41—H41B109.1
C13—C14—C15118.8 (2)C4—C41—H41B109.1
C13—C14—H14120.6H41A—C41—H41B107.8
C15—C14—H14120.6N42—N41—C47A110.04 (19)
C16—C15—C14121.0 (2)N42—N41—C41120.06 (18)
C16—C15—H15119.5C47A—N41—C41129.89 (19)
C14—C15—H15119.5N43—N42—N41109.01 (18)
C15—C16—C11119.5 (2)N42—N43—C43A107.89 (17)
C15—C16—H16120.2N43—C43A—C47A108.9 (2)
C11—C16—H16120.2N43—C43A—C44130.4 (2)
C3—N2—N1105.89 (17)C47A—C43A—C44120.7 (2)
N2—C3—C4110.58 (18)C45—C44—C43A117.0 (2)
N2—C3—C31118.49 (19)C45—C44—H44121.5
C4—C3—C31130.92 (19)C43A—C44—H44121.5
C3—C31—C312111.37 (19)C44—C45—C46122.1 (2)
C3—C31—C311108.79 (18)C44—C45—H45119.0
C312—C31—C311109.52 (18)C46—C45—H45119.0
C3—C31—C313109.81 (18)C47—C46—C45121.8 (2)
C312—C31—C313108.31 (18)C47—C46—H46119.1
C311—C31—C313109.0 (2)C45—C46—H46119.1
C31—C311—H31A109.5C46—C47—C47A116.1 (2)
C31—C311—H31B109.5C46—C47—H47122.0
H31A—C311—H31B109.5C47A—C47—H47122.0
C31—C311—H31C109.5N41—C47A—C43A104.1 (2)
H31A—C311—H31C109.5N41—C47A—C47133.5 (2)
H31B—C311—H31C109.5C43A—C47A—C47122.4 (2)
C31—C312—H31D109.5N1—C5—C4107.27 (19)
C31—C312—H31E109.5N1—C5—N51122.33 (19)
H31D—C312—H31E109.5C4—C5—N51130.4 (2)
C31—C312—H31F109.5C5—N51—H51114.9
H31D—C312—H31F109.5C5—N51—H52107.6
H31E—C312—H31F109.5H51—N51—H52112.0
C31—C313—H31G109.5
C5—N1—C11—C1224.1 (3)C4—C41—N41—C47A52.1 (3)
N2—N1—C11—C12156.6 (2)C47A—N41—N42—N430.0 (2)
C5—N1—C11—C16159.8 (2)C41—N41—N42—N43178.92 (18)
N2—N1—C11—C1619.6 (3)N41—N42—N43—C43A0.3 (2)
C16—C11—C12—C131.0 (3)N42—N43—C43A—C47A0.5 (3)
N1—C11—C12—C13177.1 (2)N42—N43—C43A—C44179.3 (2)
C11—C12—C13—C141.4 (3)N43—C43A—C44—C45177.8 (2)
C12—C13—C14—C150.9 (4)C47A—C43A—C44—C450.8 (3)
C13—C14—C15—C160.1 (4)C43A—C44—C45—C461.2 (4)
C14—C15—C16—C110.2 (3)C44—C45—C46—C470.6 (4)
C12—C11—C16—C150.2 (3)C45—C46—C47—C47A0.5 (4)
N1—C11—C16—C15176.5 (2)N42—N41—C47A—C43A0.3 (2)
C5—N1—N2—C31.7 (2)C41—N41—C47A—C43A179.1 (2)
C11—N1—N2—C3178.84 (17)N42—N41—C47A—C47179.2 (2)
N1—N2—C3—C40.5 (2)C41—N41—C47A—C470.4 (4)
N1—N2—C3—C31178.85 (17)N43—C43A—C47A—N410.5 (2)
N2—C3—C31—C312145.9 (2)C44—C43A—C47A—N41179.4 (2)
C4—C3—C31—C31234.9 (3)N43—C43A—C47A—C47179.1 (2)
N2—C3—C31—C31193.3 (2)C44—C43A—C47A—C470.2 (3)
C4—C3—C31—C31185.9 (3)C46—C47—C47A—N41178.6 (2)
N2—C3—C31—C31326.0 (3)C46—C47—C47A—C43A0.8 (3)
C4—C3—C31—C313154.8 (2)N2—N1—C5—C42.2 (2)
N2—C3—C4—C50.8 (2)C11—N1—C5—C4178.4 (2)
C31—C3—C4—C5180.0 (2)N2—N1—C5—N51178.71 (19)
N2—C3—C4—C41177.0 (2)C11—N1—C5—N510.7 (3)
C31—C3—C4—C412.3 (4)C3—C4—C5—N11.8 (2)
C5—C4—C41—N41104.1 (2)C41—C4—C5—N1176.19 (19)
C3—C4—C41—N4173.3 (3)C3—C4—C5—N51179.2 (2)
C4—C41—N41—N42126.6 (2)C41—C4—C5—N512.8 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N51—H51···N43i0.872.373.190 (3)158
Symmetry code: (i) x, y, z+1.

Experimental details

Crystal data
Chemical formulaC20H22N6
Mr346.44
Crystal system, space groupMonoclinic, P21/c
Temperature (K)100
a, b, c (Å)13.465 (3), 15.135 (3), 9.1558 (18)
β (°) 108.86 (3)
V3)1765.8 (6)
Z4
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.15 × 0.15 × 0.10
Data collection
DiffractometerKappaCCD
diffractometer
Absorption correctionMulti-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
Tmin, Tmax0.988, 0.992
No. of measured, independent and
observed [I > 2σ(I)] reflections
10902, 4002, 2136
Rint0.077
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.061, 0.150, 0.95
No. of reflections4002
No. of parameters244
No. of restraints2
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.27, 0.39

Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976) and PLATON (Spek, 2001), SHELXL97 and WORDPERFECT macro PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N51—H51···N43i0.872.373.190 (3)158
Symmetry code: (i) x, y, z+1.
 

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