In the title compound, C
11H
14N
4, the dihedral angle between the ring planes is 74.76 (8)°. In the crystal structure, N—H
N hydrogen bonds result in centrosymmetric dimers.
Supporting information
CCDC reference: 672797
Key indicators
- Single-crystal X-ray study
- T = 300 K
- Mean (C-C) = 0.002 Å
- R factor = 0.045
- wR factor = 0.136
- Data-to-parameter ratio = 18.4
checkCIF/PLATON results
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Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
1 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
0 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
Compound (I) was made by the method of Touzani et al. (2003) from a
mixture of 0.941 g (10 mmol) of 2-aminopyridine and 2.522 g (20 mmol) of
(3,5-Dimethyl-pyrazol-1-yl)-methanol.
The N-bound H atom was located in a differnce map and freely refined. The
C-bound H atoms were geometrically placed and refined as riding with
Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
N-(3,5-Dimethylpyrazol-1-ylmethyl)pyridin-2-ylamine
top
Crystal data top
C11H14N4 | V = 536.77 (15) Å3 |
Mr = 202.26 | Z = 2 |
Triclinic, P1 | F(000) = 216 |
Hall symbol: -P 1 | Dx = 1.251 Mg m−3 |
a = 8.4299 (13) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.5720 (14) Å | µ = 0.08 mm−1 |
c = 9.1803 (15) Å | T = 300 K |
α = 70.283 (3)° | Prism, colourless |
β = 89.506 (3)° | 0.50 × 0.30 × 0.30 mm |
γ = 61.056 (2)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2265 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.042 |
Graphite monochromator | θmax = 28.3°, θmin = 2.4° |
ω scans | h = −11→11 |
8403 measured reflections | k = −11→11 |
2614 independent reflections | l = −12→12 |
Refinement top
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: difmap and geom |
wR(F2) = 0.136 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0764P)2 + 0.0625P] where P = (Fo2 + 2Fc2)/3 |
2614 reflections | (Δ/σ)max = 0.001 |
142 parameters | Δρmax = 0.18 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
Crystal data top
C11H14N4 | γ = 61.056 (2)° |
Mr = 202.26 | V = 536.77 (15) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.4299 (13) Å | Mo Kα radiation |
b = 8.5720 (14) Å | µ = 0.08 mm−1 |
c = 9.1803 (15) Å | T = 300 K |
α = 70.283 (3)° | 0.50 × 0.30 × 0.30 mm |
β = 89.506 (3)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2265 reflections with I > 2σ(I) |
8403 measured reflections | Rint = 0.042 |
2614 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.136 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.18 e Å−3 |
2614 reflections | Δρmin = −0.21 e Å−3 |
142 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 | x | y | z | Uiso*/Ueq | |
N1 | 0.10021 (13) | 0.48900 (13) | 0.77976 (10) | 0.0416 (2) | |
C1 | 0.18977 (15) | 0.18891 (16) | 0.87738 (13) | 0.0438 (3) | |
N2 | 0.08931 (13) | 0.34849 (14) | 0.75052 (11) | 0.0445 (2) | |
C2 | 0.26401 (16) | 0.22673 (17) | 0.98808 (13) | 0.0461 (3) | |
H2A | 0.3382 | 0.1389 | 1.0861 | 0.055* | |
N3 | 0.06940 (16) | 0.70247 (16) | 0.51613 (12) | 0.0521 (3) | |
H3A | 0.030 (2) | 0.672 (2) | 0.4467 (19) | 0.060 (4)* | |
C3 | 0.20498 (15) | 0.42005 (17) | 0.92246 (12) | 0.0419 (3) | |
N4 | 0.28260 (16) | 0.76674 (16) | 0.59911 (12) | 0.0522 (3) | |
C4 | 0.2099 (2) | 0.00185 (19) | 0.88881 (17) | 0.0576 (3) | |
H4A | 0.1581 | 0.0163 | 0.7891 | 0.086* | |
H4B | 0.1462 | −0.0351 | 0.9682 | 0.086* | |
H4C | 0.3383 | −0.0958 | 0.9164 | 0.086* | |
C5 | 0.24125 (19) | 0.5422 (2) | 0.98353 (16) | 0.0543 (3) | |
H5A | 0.2914 | 0.6065 | 0.9084 | 0.082* | |
H5B | 0.3279 | 0.4626 | 1.0814 | 0.082* | |
H5C | 0.1279 | 0.6363 | 1.0002 | 0.082* | |
C6 | 0.00114 (16) | 0.68493 (17) | 0.65997 (14) | 0.0486 (3) | |
H6A | −0.1283 | 0.7257 | 0.6382 | 0.058* | |
H6B | 0.0100 | 0.7711 | 0.7016 | 0.058* | |
C7 | 0.21626 (16) | 0.72951 (15) | 0.49199 (12) | 0.0440 (3) | |
C8 | 0.29132 (19) | 0.71889 (18) | 0.35594 (14) | 0.0526 (3) | |
H8A | 0.2427 | 0.6925 | 0.2829 | 0.063* | |
C9 | 0.4366 (2) | 0.74785 (19) | 0.33276 (16) | 0.0594 (3) | |
H9A | 0.4893 | 0.7396 | 0.2442 | 0.071* | |
C10 | 0.5052 (2) | 0.7897 (2) | 0.44195 (18) | 0.0627 (4) | |
H10A | 0.6030 | 0.8118 | 0.4281 | 0.075* | |
C11 | 0.4238 (2) | 0.7973 (2) | 0.57054 (17) | 0.0607 (3) | |
H11A | 0.4695 | 0.8258 | 0.6437 | 0.073* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0475 (5) | 0.0452 (5) | 0.0381 (5) | −0.0274 (4) | 0.0095 (4) | −0.0170 (4) |
C1 | 0.0472 (5) | 0.0465 (6) | 0.0436 (5) | −0.0269 (5) | 0.0140 (4) | −0.0193 (5) |
N2 | 0.0526 (5) | 0.0507 (5) | 0.0412 (5) | −0.0321 (4) | 0.0111 (4) | −0.0208 (4) |
C2 | 0.0489 (6) | 0.0489 (6) | 0.0400 (5) | −0.0261 (5) | 0.0066 (4) | −0.0145 (5) |
N3 | 0.0675 (6) | 0.0596 (6) | 0.0377 (5) | −0.0414 (5) | 0.0050 (4) | −0.0141 (5) |
C3 | 0.0431 (5) | 0.0514 (6) | 0.0385 (5) | −0.0276 (5) | 0.0118 (4) | −0.0202 (5) |
N4 | 0.0662 (6) | 0.0564 (6) | 0.0467 (5) | −0.0383 (5) | 0.0119 (5) | −0.0227 (5) |
C4 | 0.0681 (8) | 0.0502 (7) | 0.0617 (8) | −0.0341 (6) | 0.0133 (6) | −0.0233 (6) |
C5 | 0.0630 (7) | 0.0629 (7) | 0.0522 (7) | −0.0390 (6) | 0.0108 (5) | −0.0282 (6) |
C6 | 0.0477 (6) | 0.0457 (6) | 0.0485 (6) | −0.0235 (5) | 0.0066 (5) | −0.0141 (5) |
C7 | 0.0559 (6) | 0.0361 (5) | 0.0367 (5) | −0.0243 (5) | 0.0041 (4) | −0.0089 (4) |
C8 | 0.0685 (7) | 0.0492 (6) | 0.0384 (6) | −0.0302 (6) | 0.0076 (5) | −0.0146 (5) |
C9 | 0.0670 (8) | 0.0547 (7) | 0.0481 (7) | −0.0290 (6) | 0.0171 (6) | −0.0138 (6) |
C10 | 0.0623 (8) | 0.0638 (8) | 0.0636 (8) | −0.0387 (7) | 0.0131 (6) | −0.0159 (7) |
C11 | 0.0717 (8) | 0.0675 (8) | 0.0585 (8) | −0.0459 (7) | 0.0094 (6) | −0.0252 (7) |
Geometric parameters (Å, º) top
N1—C3 | 1.3557 (14) | C4—H4B | 0.9600 |
N1—N2 | 1.3626 (13) | C4—H4C | 0.9600 |
N1—C6 | 1.4627 (15) | C5—H5A | 0.9600 |
C1—N2 | 1.3287 (15) | C5—H5B | 0.9600 |
C1—C2 | 1.3998 (16) | C5—H5C | 0.9600 |
C1—C4 | 1.4948 (17) | C6—H6A | 0.9700 |
C2—C3 | 1.3747 (16) | C6—H6B | 0.9700 |
C2—H2A | 0.9300 | C7—C8 | 1.4057 (17) |
N3—C7 | 1.3689 (16) | C8—C9 | 1.364 (2) |
N3—C6 | 1.4263 (16) | C8—H8A | 0.9300 |
N3—H3A | 0.885 (17) | C9—C10 | 1.386 (2) |
C3—C5 | 1.4876 (16) | C9—H9A | 0.9300 |
N4—C7 | 1.3325 (15) | C10—C11 | 1.365 (2) |
N4—C11 | 1.3435 (17) | C10—H10A | 0.9300 |
C4—H4A | 0.9600 | C11—H11A | 0.9300 |
| | | |
C3—N1—N2 | 111.98 (9) | H5A—C5—H5B | 109.5 |
C3—N1—C6 | 129.84 (10) | C3—C5—H5C | 109.5 |
N2—N1—C6 | 118.18 (9) | H5A—C5—H5C | 109.5 |
N2—C1—C2 | 110.81 (10) | H5B—C5—H5C | 109.5 |
N2—C1—C4 | 120.70 (11) | N3—C6—N1 | 113.48 (10) |
C2—C1—C4 | 128.49 (11) | N3—C6—H6A | 108.9 |
C1—N2—N1 | 105.12 (9) | N1—C6—H6A | 108.9 |
C3—C2—C1 | 106.05 (10) | N3—C6—H6B | 108.9 |
C3—C2—H2A | 127.0 | N1—C6—H6B | 108.9 |
C1—C2—H2A | 127.0 | H6A—C6—H6B | 107.7 |
C7—N3—C6 | 123.05 (10) | N4—C7—N3 | 118.30 (10) |
C7—N3—H3A | 117.4 (10) | N4—C7—C8 | 122.12 (11) |
C6—N3—H3A | 118.4 (10) | N3—C7—C8 | 119.58 (10) |
N1—C3—C2 | 106.05 (10) | C9—C8—C7 | 118.93 (12) |
N1—C3—C5 | 123.20 (11) | C9—C8—H8A | 120.5 |
C2—C3—C5 | 130.74 (11) | C7—C8—H8A | 120.5 |
C7—N4—C11 | 117.04 (11) | C8—C9—C10 | 119.59 (12) |
C1—C4—H4A | 109.5 | C8—C9—H9A | 120.2 |
C1—C4—H4B | 109.5 | C10—C9—H9A | 120.2 |
H4A—C4—H4B | 109.5 | C11—C10—C9 | 117.53 (13) |
C1—C4—H4C | 109.5 | C11—C10—H10A | 121.2 |
H4A—C4—H4C | 109.5 | C9—C10—H10A | 121.2 |
H4B—C4—H4C | 109.5 | N4—C11—C10 | 124.77 (13) |
C3—C5—H5A | 109.5 | N4—C11—H11A | 117.6 |
C3—C5—H5B | 109.5 | C10—C11—H11A | 117.6 |
| | | |
C2—C1—N2—N1 | 0.36 (12) | C3—N1—C6—N3 | 115.73 (13) |
C4—C1—N2—N1 | 179.74 (10) | N2—N1—C6—N3 | −64.89 (13) |
C3—N1—N2—C1 | −0.19 (12) | C11—N4—C7—N3 | −178.41 (11) |
C6—N1—N2—C1 | −179.67 (9) | C11—N4—C7—C8 | 1.09 (18) |
N2—C1—C2—C3 | −0.40 (12) | C6—N3—C7—N4 | −9.23 (17) |
C4—C1—C2—C3 | −179.72 (11) | C6—N3—C7—C8 | 171.26 (11) |
N2—N1—C3—C2 | −0.06 (12) | N4—C7—C8—C9 | −0.08 (19) |
C6—N1—C3—C2 | 179.35 (10) | N3—C7—C8—C9 | 179.42 (11) |
N2—N1—C3—C5 | 179.43 (9) | C7—C8—C9—C10 | −0.9 (2) |
C6—N1—C3—C5 | −1.17 (17) | C8—C9—C10—C11 | 0.9 (2) |
C1—C2—C3—N1 | 0.27 (12) | C7—N4—C11—C10 | −1.2 (2) |
C1—C2—C3—C5 | −179.16 (11) | C9—C10—C11—N4 | 0.2 (2) |
C7—N3—C6—N1 | −84.59 (14) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···N2i | 0.886 (17) | 2.177 (17) | 3.0524 (17) | 169.8 (15) |
Symmetry code: (i) −x, −y+1, −z+1. |
Experimental details
Crystal data |
Chemical formula | C11H14N4 |
Mr | 202.26 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 300 |
a, b, c (Å) | 8.4299 (13), 8.5720 (14), 9.1803 (15) |
α, β, γ (°) | 70.283 (3), 89.506 (3), 61.056 (2) |
V (Å3) | 536.77 (15) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.50 × 0.30 × 0.30 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8403, 2614, 2265 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.668 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.136, 1.06 |
No. of reflections | 2614 |
No. of parameters | 142 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.18, −0.21 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···N2i | 0.886 (17) | 2.177 (17) | 3.0524 (17) | 169.8 (15) |
Symmetry code: (i) −x, −y+1, −z+1. |
Polypyrazolyl-containing ligands are used in models for copper proteins to mimic active sites (Sorrell et al., 1987). As part of our studies in this area, we prepared the title compound, (I), which contains amine, pyrazolyl and pyridyl functionalities.
The molecule of (I) is not planar (Fig. 1), the dihedral angle between the aromatic ring planes being 74.76 (8)°. Slight differences between (I) and the known 3,5-dimethylpyrazole, (II), (Baldy et al., 1985) are reflected in the C3—N1 bond length, the angle C3—N1—N2 and the torsion angle C2—C1—N2—N1. These have the values 1.3557 (14) Å, 112.17 (8)° and -0.35 (2)° in (I) and 1.3442 (16) Å, 108.64 (9)° and 0.45 (16)° in (II), respectively.
The packing in (I) is consolidated by N—H···N hydrogen bonds (Table 1) resulting in centrosymmetric dimers (Fig. 2).