organic compounds
of 1-methoxy-2,2,2-tris(pyrazol-1-yl)ethane
aDepartment of Biochemistry and Chemistry, Southern Arkansas University, Magnolia, AR 71753, USA, and bDepartment of Chemistry, University of Kentucky, Lexington, KY 40506, USA
*Correspondence e-mail: GannaLyubartseva@saumag.edu
The title compound, C12H14N6O, consists of three pyrazole rings bound via nitrogen to the distal ethane carbon of methoxy ethane. The dihedral angles between the three pyrazole rings are 67.62 (14), 73.74 (14), and 78.92 (12)°. In the crystal, molecules are linked by bifurcated C—H,H⋯N hydrogen bonds, forming double-stranded chains along [001]. The chains are linked via C—H⋯O hydrogen bonds, forming a three-dimensional framework structure. The crystal was refined as a perfect (0.5:0.5) inversion twin.
CCDC reference: 1019968
1. Related literature
For properties of pyrazole-based tridentate ligands, see: Paulo et al. (2004); Bigmore et al. (2005). For nickel and cobalt complexes of N-donor tridentate scorpionate ligands, see: Lyubartseva et al. (2011, 2012, 2013a,b); Lyubartseva & Parkin (2009). For the synthesis of the title compound, see: Maria et al. (2007).
2. Experimental
2.1. Crystal data
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2.3. Refinement
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Data collection: COLLECT (Nonius, 1998); cell SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014 and PLATON (Spek, 2009).
Supporting information
CCDC reference: 1019968
10.1107/S1600536814018789/su2774sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814018789/su2774Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814018789/su2774Isup3.cml
The title compound was prepared using the published procedure (Maria et al., 2007). Colourless block-like crystals were obtained by slow evaporation of a diethyl ether solution of pure product. Spectral and other characterizations are in good accordance with the previously reported data (Maria et al., 2007).
Data collection: COLLECT (Nonius, 1998); cell
SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2008) and PLATON (Spek, 2009).Fig. 1. View of molecular structure of the title molecule, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. |
C12H14N6O | F(000) = 544 |
Mr = 258.29 | Dx = 1.330 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
a = 12.5828 (3) Å | Cell parameters from 1549 reflections |
b = 12.3847 (3) Å | θ = 1.0–27.5° |
c = 8.4807 (2) Å | µ = 0.09 mm−1 |
β = 102.5635 (11)° | T = 90 K |
V = 1289.94 (5) Å3 | Block, colourless |
Z = 4 | 0.28 × 0.20 × 0.16 mm |
Nonius KappaCCD diffractometer | 2934 independent reflections |
Radiation source: fine-focus sealed-tube | 2386 reflections with I > 2σ(I) |
Detector resolution: 9.1 pixels mm-1 | Rint = 0.032 |
ϕ and ω scans at fixed χ = 55° | θmax = 27.5°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −16→16 |
Tmin = 0.749, Tmax = 0.942 | k = −16→16 |
11397 measured reflections | l = −10→11 |
Refinement on F2 | Hydrogen site location: difference Fourier map |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.042 | w = 1/[σ2(Fo2) + (0.0453P)2 + 0.5917P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.102 | (Δ/σ)max < 0.001 |
S = 1.10 | Δρmax = 0.23 e Å−3 |
2934 reflections | Δρmin = −0.18 e Å−3 |
174 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
2 restraints | Extinction coefficient: 0.0127 (19) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Refined as a perfect (i.e. 50:50) inversion twin. |
Secondary atom site location: difference Fourier map |
C12H14N6O | V = 1289.94 (5) Å3 |
Mr = 258.29 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 12.5828 (3) Å | µ = 0.09 mm−1 |
b = 12.3847 (3) Å | T = 90 K |
c = 8.4807 (2) Å | 0.28 × 0.20 × 0.16 mm |
β = 102.5635 (11)° |
Nonius KappaCCD diffractometer | 2934 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2386 reflections with I > 2σ(I) |
Tmin = 0.749, Tmax = 0.942 | Rint = 0.032 |
11397 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 2 restraints |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.23 e Å−3 |
2934 reflections | Δρmin = −0.18 e Å−3 |
174 parameters | Absolute structure: Refined as a perfect (i.e. 50:50) inversion twin. |
Experimental. The crystal was mounted with polyisobutene oil on the tip of a fine glass fibre, which was fastened in a copper mounting pin with electrical solder. It was placed directly into the cold gas stream of a liquid nitrogen based cryostat, according to published methods (Hope, 1994; Parkin & Hope, 1998). Diffraction data were collected with the crystal at 90 K, which is standard practice in this laboratory for the majority of flash-cooled crystals. |
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 progress was checked using PLATON (Spek, 2009) and by an R-tensor (Parkin, 2000). The final model was further checked with the IUCr utility checkCIF. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.34875 (17) | 0.16856 (16) | 0.5089 (3) | 0.0305 (5) | |
N1 | 0.62903 (19) | 0.25690 (19) | 0.5191 (3) | 0.0229 (5) | |
N2 | 0.6299 (2) | 0.2508 (2) | 0.3598 (3) | 0.0291 (6) | |
N3 | 0.4892 (2) | 0.35743 (18) | 0.5996 (3) | 0.0255 (6) | |
N4 | 0.5617 (2) | 0.4320 (2) | 0.6770 (4) | 0.0378 (7) | |
N5 | 0.5520 (2) | 0.1924 (2) | 0.7270 (3) | 0.0236 (5) | |
N6 | 0.5898 (2) | 0.0891 (2) | 0.7266 (3) | 0.0296 (6) | |
C1 | 0.5280 (2) | 0.2497 (2) | 0.5740 (3) | 0.0212 (6) | |
C2 | 0.7343 (3) | 0.2658 (3) | 0.3557 (4) | 0.0336 (7) | |
H2A | 0.7610 | 0.2658 | 0.2591 | 0.040* | |
C3 | 0.8001 (2) | 0.2816 (2) | 0.5100 (4) | 0.0318 (7) | |
H3A | 0.8765 | 0.2933 | 0.5376 | 0.038* | |
C4 | 0.7295 (3) | 0.2762 (2) | 0.6118 (4) | 0.0303 (7) | |
H4A | 0.7475 | 0.2845 | 0.7259 | 0.036* | |
C5 | 0.5010 (3) | 0.5170 (3) | 0.6921 (5) | 0.0426 (9) | |
H5A | 0.5290 | 0.5831 | 0.7406 | 0.051* | |
C6 | 0.3900 (3) | 0.4977 (3) | 0.6277 (5) | 0.0394 (8) | |
H6A | 0.3311 | 0.5461 | 0.6252 | 0.047* | |
C7 | 0.3848 (3) | 0.3954 (3) | 0.5699 (4) | 0.0307 (7) | |
H7A | 0.3210 | 0.3574 | 0.5187 | 0.037* | |
C8 | 0.6077 (3) | 0.0592 (3) | 0.8804 (4) | 0.0330 (7) | |
H8A | 0.6344 | −0.0098 | 0.9187 | 0.040* | |
C9 | 0.5825 (3) | 0.1410 (3) | 0.9791 (4) | 0.0379 (8) | |
H9A | 0.5884 | 0.1385 | 1.0927 | 0.045* | |
C10 | 0.5474 (2) | 0.2258 (3) | 0.8775 (4) | 0.0324 (7) | |
H10A | 0.5244 | 0.2946 | 0.9067 | 0.039* | |
C11 | 0.4437 (2) | 0.1869 (2) | 0.4498 (4) | 0.0252 (6) | |
H11A | 0.4249 | 0.2284 | 0.3478 | 0.030* | |
H11B | 0.4751 | 0.1169 | 0.4266 | 0.030* | |
C12 | 0.3184 (3) | 0.0580 (3) | 0.5101 (5) | 0.0384 (8) | |
H12A | 0.2517 | 0.0515 | 0.5511 | 0.058* | |
H12B | 0.3770 | 0.0171 | 0.5800 | 0.058* | |
H12C | 0.3057 | 0.0291 | 0.4000 | 0.058* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0238 (11) | 0.0263 (11) | 0.0426 (13) | −0.0028 (9) | 0.0099 (9) | −0.0036 (9) |
N1 | 0.0226 (13) | 0.0254 (12) | 0.0214 (13) | 0.0009 (10) | 0.0062 (10) | 0.0004 (10) |
N2 | 0.0335 (15) | 0.0325 (14) | 0.0239 (13) | 0.0045 (11) | 0.0115 (11) | 0.0029 (11) |
N3 | 0.0233 (12) | 0.0213 (12) | 0.0324 (13) | −0.0003 (10) | 0.0072 (10) | −0.0024 (11) |
N4 | 0.0282 (14) | 0.0256 (14) | 0.0600 (19) | −0.0051 (12) | 0.0103 (13) | −0.0140 (13) |
N5 | 0.0247 (12) | 0.0237 (12) | 0.0227 (12) | −0.0018 (10) | 0.0058 (10) | −0.0001 (10) |
N6 | 0.0359 (15) | 0.0213 (13) | 0.0294 (14) | 0.0003 (10) | 0.0025 (11) | 0.0033 (10) |
C1 | 0.0197 (14) | 0.0219 (14) | 0.0233 (15) | 0.0004 (10) | 0.0074 (12) | −0.0010 (11) |
C2 | 0.0357 (17) | 0.0306 (17) | 0.0400 (19) | 0.0029 (14) | 0.0203 (15) | 0.0051 (14) |
C3 | 0.0222 (15) | 0.0285 (15) | 0.048 (2) | 0.0000 (12) | 0.0143 (15) | 0.0000 (14) |
C4 | 0.0257 (16) | 0.0316 (17) | 0.0334 (17) | 0.0020 (13) | 0.0057 (13) | −0.0024 (13) |
C5 | 0.0370 (18) | 0.0272 (18) | 0.064 (2) | −0.0032 (14) | 0.0130 (17) | −0.0149 (16) |
C6 | 0.0308 (17) | 0.0274 (17) | 0.061 (2) | 0.0062 (14) | 0.0116 (16) | −0.0077 (15) |
C7 | 0.0249 (15) | 0.0287 (16) | 0.0374 (17) | 0.0024 (12) | 0.0042 (13) | −0.0008 (13) |
C8 | 0.0248 (16) | 0.0364 (18) | 0.0353 (18) | −0.0083 (14) | 0.0009 (13) | 0.0113 (15) |
C9 | 0.0300 (17) | 0.060 (2) | 0.0246 (16) | −0.0035 (16) | 0.0075 (13) | 0.0056 (15) |
C10 | 0.0260 (16) | 0.0457 (19) | 0.0282 (16) | −0.0028 (14) | 0.0122 (13) | −0.0058 (14) |
C11 | 0.0214 (15) | 0.0256 (14) | 0.0280 (15) | 0.0008 (11) | 0.0041 (12) | −0.0027 (12) |
C12 | 0.038 (2) | 0.0282 (17) | 0.051 (2) | −0.0059 (14) | 0.0126 (17) | 0.0031 (16) |
O1—C11 | 1.411 (3) | C3—H3A | 0.9500 |
O1—C12 | 1.423 (4) | C4—H4A | 0.9500 |
N1—N2 | 1.356 (3) | C5—C6 | 1.405 (5) |
N1—C4 | 1.357 (4) | C5—H5A | 0.9500 |
N1—C1 | 1.448 (3) | C6—C7 | 1.355 (5) |
N2—C2 | 1.335 (4) | C6—H6A | 0.9500 |
N3—N4 | 1.363 (4) | C7—H7A | 0.9500 |
N3—C7 | 1.365 (4) | C8—C9 | 1.394 (5) |
N3—C1 | 1.454 (3) | C8—H8A | 0.9500 |
N4—C5 | 1.323 (4) | C9—C10 | 1.369 (5) |
N5—C10 | 1.354 (4) | C9—H9A | 0.9500 |
N5—N6 | 1.364 (3) | C10—H10A | 0.9500 |
N5—C1 | 1.452 (4) | C11—H11A | 0.9900 |
N6—C8 | 1.327 (4) | C11—H11B | 0.9900 |
C1—C11 | 1.534 (4) | C12—H12A | 0.9800 |
C2—C3 | 1.402 (5) | C12—H12B | 0.9800 |
C2—H2A | 0.9500 | C12—H12C | 0.9800 |
C3—C4 | 1.369 (4) | ||
C11—O1—C12 | 114.0 (2) | N4—C5—H5A | 124.0 |
N2—N1—C4 | 112.3 (2) | C6—C5—H5A | 124.0 |
N2—N1—C1 | 121.0 (2) | C7—C6—C5 | 105.3 (3) |
C4—N1—C1 | 126.7 (2) | C7—C6—H6A | 127.3 |
C2—N2—N1 | 103.8 (3) | C5—C6—H6A | 127.3 |
N4—N3—C7 | 111.9 (2) | C6—C7—N3 | 106.7 (3) |
N4—N3—C1 | 118.8 (2) | C6—C7—H7A | 126.7 |
C7—N3—C1 | 129.0 (2) | N3—C7—H7A | 126.7 |
C5—N4—N3 | 104.2 (3) | N6—C8—C9 | 112.0 (3) |
C10—N5—N6 | 112.0 (3) | N6—C8—H8A | 124.0 |
C10—N5—C1 | 130.5 (3) | C9—C8—H8A | 124.0 |
N6—N5—C1 | 117.4 (2) | C10—C9—C8 | 105.3 (3) |
C8—N6—N5 | 104.1 (3) | C10—C9—H9A | 127.4 |
N1—C1—N5 | 106.9 (2) | C8—C9—H9A | 127.4 |
N1—C1—N3 | 109.8 (2) | N5—C10—C9 | 106.6 (3) |
N5—C1—N3 | 109.0 (2) | N5—C10—H10A | 126.7 |
N1—C1—C11 | 109.6 (2) | C9—C10—H10A | 126.7 |
N5—C1—C11 | 110.1 (2) | O1—C11—C1 | 110.5 (2) |
N3—C1—C11 | 111.3 (2) | O1—C11—H11A | 109.5 |
N2—C2—C3 | 112.3 (3) | C1—C11—H11A | 109.5 |
N2—C2—H2A | 123.8 | O1—C11—H11B | 109.5 |
C3—C2—H2A | 123.8 | C1—C11—H11B | 109.5 |
C4—C3—C2 | 104.4 (3) | H11A—C11—H11B | 108.1 |
C4—C3—H3A | 127.8 | O1—C12—H12A | 109.5 |
C2—C3—H3A | 127.8 | O1—C12—H12B | 109.5 |
N1—C4—C3 | 107.1 (3) | H12A—C12—H12B | 109.5 |
N1—C4—H4A | 126.4 | O1—C12—H12C | 109.5 |
C3—C4—H4A | 126.4 | H12A—C12—H12C | 109.5 |
N4—C5—C6 | 112.0 (3) | H12B—C12—H12C | 109.5 |
C4—N1—N2—C2 | 0.6 (3) | N4—N3—C1—C11 | −165.4 (3) |
C1—N1—N2—C2 | 177.0 (3) | C7—N3—C1—C11 | 21.3 (4) |
C7—N3—N4—C5 | −1.0 (4) | N1—N2—C2—C3 | −0.1 (3) |
C1—N3—N4—C5 | −175.4 (3) | N2—C2—C3—C4 | −0.4 (4) |
C10—N5—N6—C8 | 0.5 (3) | N2—N1—C4—C3 | −0.9 (3) |
C1—N5—N6—C8 | 178.0 (2) | C1—N1—C4—C3 | −177.1 (3) |
N2—N1—C1—N5 | 144.6 (2) | C2—C3—C4—N1 | 0.8 (3) |
C4—N1—C1—N5 | −39.6 (4) | N3—N4—C5—C6 | 0.9 (4) |
N2—N1—C1—N3 | −97.3 (3) | N4—C5—C6—C7 | −0.5 (5) |
C4—N1—C1—N3 | 78.6 (3) | C5—C6—C7—N3 | −0.2 (4) |
N2—N1—C1—C11 | 25.2 (3) | N4—N3—C7—C6 | 0.8 (4) |
C4—N1—C1—C11 | −158.9 (3) | C1—N3—C7—C6 | 174.4 (3) |
C10—N5—C1—N1 | 115.6 (3) | N5—N6—C8—C9 | −0.2 (3) |
N6—N5—C1—N1 | −61.3 (3) | N6—C8—C9—C10 | −0.2 (4) |
C10—N5—C1—N3 | −3.0 (4) | N6—N5—C10—C9 | −0.6 (3) |
N6—N5—C1—N3 | −179.9 (2) | C1—N5—C10—C9 | −177.7 (3) |
C10—N5—C1—C11 | −125.4 (3) | C8—C9—C10—N5 | 0.4 (3) |
N6—N5—C1—C11 | 57.7 (3) | C12—O1—C11—C1 | −124.7 (3) |
N4—N3—C1—N1 | −43.9 (3) | N1—C1—C11—O1 | 173.5 (2) |
C7—N3—C1—N1 | 142.8 (3) | N5—C1—C11—O1 | 56.2 (3) |
N4—N3—C1—N5 | 72.9 (3) | N3—C1—C11—O1 | −64.8 (3) |
C7—N3—C1—N5 | −100.4 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5A···N2i | 0.95 | 2.51 | 3.453 (4) | 171 |
C9—H9A···N2ii | 0.95 | 2.61 | 3.433 (4) | 145 |
C4—H4A···O1iii | 0.95 | 2.53 | 3.444 (4) | 162 |
Symmetry codes: (i) x, −y+1, z+1/2; (ii) x, y, z+1; (iii) x+1/2, −y+1/2, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5A···N2i | 0.95 | 2.51 | 3.453 (4) | 171 |
C9—H9A···N2ii | 0.95 | 2.61 | 3.433 (4) | 145 |
C4—H4A···O1iii | 0.95 | 2.53 | 3.444 (4) | 162 |
Symmetry codes: (i) x, −y+1, z+1/2; (ii) x, y, z+1; (iii) x+1/2, −y+1/2, z+1/2. |
Acknowledgements
GL is grateful to the Southern Arkansas University Faculty Research Grant for financial support.
References
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