Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680301078X/lh6063sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680301078X/lh60631sup2.hkl |
CCDC reference: 214853
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.003 Å
- R factor = 0.043
- wR factor = 0.092
- Data-to-parameter ratio = 14.0
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
The title compound was synthesized according to literature procedures (Buchner & Hachumian, 1902). X-ray quality crystals were obtained after recrystallization from CH3OH at ambient temperature.
All H atoms could be located by difference Fourier synthesis and were refined with fixed individual displacement parameters [Uiso(H) = 1.2Ueq(N,C)] using a riding model, with N—H = 0.88 Å and C—H = 0.95 Å.
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991).
C9H8N2 | Z = 8 |
Mr = 144.17 | F(000) = 608 |
Triclinic, P1 | Dx = 1.226 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.5745 (13) Å | Cell parameters from 7377 reflections |
b = 10.3359 (12) Å | θ = 3.5–25.2° |
c = 17.132 (2) Å | µ = 0.08 mm−1 |
α = 85.693 (10)° | T = 173 K |
β = 75.609 (10)° | Block, colourless |
γ = 72.102 (10)° | 0.31 × 0.15 × 0.11 mm |
V = 1562.7 (3) Å3 |
Stoe IPDS II two-circle diffractometer | 3329 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.059 |
Graphite monochromator | θmax = 25.2°, θmin = 3.7° |
ω scans | h = −11→11 |
12794 measured reflections | k = −11→12 |
5573 independent reflections | l = −20→20 |
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)] = 0.043 | H-atom parameters constrained |
wR(F2) = 0.092 | w = 1/[σ2(Fo2) + (0.0337P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.88 | (Δ/σ)max < 0.001 |
5573 reflections | Δρmax = 0.19 e Å−3 |
398 parameters | Δρmin = −0.20 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: 0.0084 (9) |
C9H8N2 | γ = 72.102 (10)° |
Mr = 144.17 | V = 1562.7 (3) Å3 |
Triclinic, P1 | Z = 8 |
a = 9.5745 (13) Å | Mo Kα radiation |
b = 10.3359 (12) Å | µ = 0.08 mm−1 |
c = 17.132 (2) Å | T = 173 K |
α = 85.693 (10)° | 0.31 × 0.15 × 0.11 mm |
β = 75.609 (10)° |
Stoe IPDS II two-circle diffractometer | 3329 reflections with I > 2σ(I) |
12794 measured reflections | Rint = 0.059 |
5573 independent reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.092 | H-atom parameters constrained |
S = 0.88 | Δρmax = 0.19 e Å−3 |
5573 reflections | Δρmin = −0.20 e Å−3 |
398 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 | ||
N1A | 0.72060 (19) | 0.50293 (18) | 0.66325 (10) | 0.0454 (4) | |
H1A | 0.7674 | 0.4585 | 0.6998 | 0.055* | |
N2A | 0.57164 (19) | 0.52776 (17) | 0.66703 (10) | 0.0415 (4) | |
C3A | 0.5439 (2) | 0.59738 (19) | 0.60057 (11) | 0.0350 (4) | |
C4A | 0.6783 (2) | 0.6170 (2) | 0.55374 (13) | 0.0447 (5) | |
H4A | 0.6920 | 0.6629 | 0.5036 | 0.054* | |
C5A | 0.7858 (2) | 0.5558 (2) | 0.59585 (13) | 0.0479 (5) | |
H5A | 0.8894 | 0.5517 | 0.5797 | 0.057* | |
C11A | 0.3918 (2) | 0.63991 (19) | 0.58505 (11) | 0.0354 (4) | |
C12A | 0.2654 (2) | 0.6299 (2) | 0.64409 (12) | 0.0419 (5) | |
H12A | 0.2769 | 0.5943 | 0.6957 | 0.050* | |
C13A | 0.1229 (2) | 0.6715 (2) | 0.62799 (13) | 0.0475 (5) | |
H13A | 0.0376 | 0.6651 | 0.6688 | 0.057* | |
C14A | 0.1045 (2) | 0.7216 (2) | 0.55360 (14) | 0.0469 (5) | |
H14A | 0.0069 | 0.7496 | 0.5429 | 0.056* | |
C15A | 0.2291 (2) | 0.7314 (2) | 0.49397 (13) | 0.0468 (5) | |
H15A | 0.2168 | 0.7657 | 0.4423 | 0.056* | |
C16A | 0.3710 (2) | 0.6912 (2) | 0.50986 (12) | 0.0411 (5) | |
H16A | 0.4556 | 0.6987 | 0.4689 | 0.049* | |
N1B | 0.87194 (19) | 0.23731 (19) | 0.81058 (11) | 0.0472 (4) | |
H1B | 0.8384 | 0.1829 | 0.7880 | 0.057* | |
N2B | 0.83500 (18) | 0.37365 (18) | 0.80097 (10) | 0.0415 (4) | |
C3B | 0.9092 (2) | 0.4191 (2) | 0.84500 (11) | 0.0389 (5) | |
C4B | 0.9933 (2) | 0.3095 (2) | 0.88281 (14) | 0.0501 (5) | |
H4B | 1.0558 | 0.3119 | 0.9176 | 0.060* | |
C5B | 0.9662 (3) | 0.1972 (2) | 0.85898 (14) | 0.0535 (6) | |
H5B | 1.0080 | 0.1060 | 0.8745 | 0.064* | |
C11B | 0.8919 (2) | 0.5653 (2) | 0.84920 (11) | 0.0397 (5) | |
C12B | 0.9943 (3) | 0.6094 (3) | 0.87726 (14) | 0.0533 (6) | |
H12B | 1.0773 | 0.5447 | 0.8929 | 0.064* | |
C13B | 0.9757 (3) | 0.7473 (3) | 0.88251 (16) | 0.0634 (7) | |
H13B | 1.0448 | 0.7765 | 0.9028 | 0.076* | |
C14B | 0.8584 (3) | 0.8413 (3) | 0.85864 (15) | 0.0576 (6) | |
H14B | 0.8485 | 0.9354 | 0.8604 | 0.069* | |
C15B | 0.7542 (3) | 0.7992 (2) | 0.83185 (14) | 0.0526 (6) | |
H15B | 0.6712 | 0.8645 | 0.8166 | 0.063* | |
C16B | 0.7711 (2) | 0.6625 (2) | 0.82739 (13) | 0.0443 (5) | |
H16B | 0.6992 | 0.6342 | 0.8091 | 0.053* | |
N1C | 0.7461 (2) | 0.10275 (18) | 0.71827 (11) | 0.0473 (4) | |
N2C | 0.59896 (19) | 0.15166 (17) | 0.71608 (10) | 0.0419 (4) | |
H2C | 0.5327 | 0.2200 | 0.7455 | 0.050* | |
C3C | 0.5673 (2) | 0.0821 (2) | 0.66291 (12) | 0.0396 (5) | |
C4C | 0.6999 (2) | −0.0170 (2) | 0.62927 (13) | 0.0479 (5) | |
H4C | 0.7141 | −0.0827 | 0.5898 | 0.057* | |
C5C | 0.8071 (3) | 0.0000 (2) | 0.66515 (14) | 0.0518 (6) | |
H5C | 0.9100 | −0.0537 | 0.6538 | 0.062* | |
C11C | 0.4156 (2) | 0.1170 (2) | 0.64758 (12) | 0.0409 (5) | |
C12C | 0.3744 (3) | 0.0244 (3) | 0.60911 (14) | 0.0557 (6) | |
H12C | 0.4459 | −0.0611 | 0.5919 | 0.067* | |
C13C | 0.2310 (3) | 0.0559 (3) | 0.59594 (15) | 0.0656 (7) | |
H13C | 0.2048 | −0.0078 | 0.5696 | 0.079* | |
C14C | 0.1264 (3) | 0.1784 (3) | 0.62062 (14) | 0.0598 (7) | |
H14C | 0.0276 | 0.1989 | 0.6120 | 0.072* | |
C15C | 0.1645 (2) | 0.2723 (3) | 0.65820 (13) | 0.0534 (6) | |
H15C | 0.0923 | 0.3577 | 0.6747 | 0.064* | |
C16C | 0.3083 (2) | 0.2415 (2) | 0.67172 (12) | 0.0444 (5) | |
H16C | 0.3337 | 0.3062 | 0.6977 | 0.053* | |
N1D | 0.4294 (2) | 0.34644 (18) | 0.84401 (10) | 0.0441 (4) | |
N2D | 0.42569 (18) | 0.47755 (17) | 0.82706 (10) | 0.0388 (4) | |
H2D | 0.4501 | 0.5095 | 0.7782 | 0.047* | |
C3D | 0.3795 (2) | 0.5528 (2) | 0.89507 (11) | 0.0356 (4) | |
C4D | 0.3518 (2) | 0.4660 (2) | 0.95892 (12) | 0.0473 (5) | |
H4D | 0.3177 | 0.4882 | 1.0147 | 0.057* | |
C5D | 0.3841 (3) | 0.3408 (2) | 0.92421 (13) | 0.0505 (6) | |
H5D | 0.3753 | 0.2608 | 0.9535 | 0.061* | |
C11D | 0.3621 (2) | 0.6986 (2) | 0.89432 (12) | 0.0405 (5) | |
C12D | 0.3446 (3) | 0.7645 (2) | 0.96551 (15) | 0.0571 (6) | |
H12D | 0.3455 | 0.7144 | 1.0143 | 0.069* | |
C13D | 0.3259 (3) | 0.9033 (3) | 0.9657 (2) | 0.0779 (8) | |
H13D | 0.3162 | 0.9469 | 1.0145 | 0.093* | |
C14D | 0.3214 (3) | 0.9777 (3) | 0.8964 (2) | 0.0749 (8) | |
H14D | 0.3064 | 1.0728 | 0.8971 | 0.090* | |
C15D | 0.3387 (3) | 0.9136 (3) | 0.82618 (18) | 0.0658 (7) | |
H15D | 0.3360 | 0.9650 | 0.7779 | 0.079* | |
C16D | 0.3599 (3) | 0.7758 (2) | 0.82422 (14) | 0.0510 (5) | |
H16D | 0.3731 | 0.7330 | 0.7746 | 0.061* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1A | 0.0458 (11) | 0.0523 (12) | 0.0402 (10) | −0.0132 (9) | −0.0165 (8) | 0.0025 (8) |
N2A | 0.0441 (10) | 0.0432 (10) | 0.0361 (9) | −0.0084 (8) | −0.0141 (8) | 0.0024 (8) |
C3A | 0.0388 (11) | 0.0352 (11) | 0.0321 (10) | −0.0113 (9) | −0.0093 (9) | −0.0017 (8) |
C4A | 0.0462 (12) | 0.0525 (14) | 0.0405 (11) | −0.0225 (10) | −0.0125 (10) | 0.0102 (10) |
C5A | 0.0424 (12) | 0.0583 (15) | 0.0478 (13) | −0.0226 (11) | −0.0108 (10) | 0.0032 (11) |
C11A | 0.0408 (11) | 0.0306 (11) | 0.0356 (10) | −0.0101 (9) | −0.0106 (9) | −0.0012 (8) |
C12A | 0.0436 (12) | 0.0455 (13) | 0.0359 (11) | −0.0140 (10) | −0.0082 (9) | 0.0036 (9) |
C13A | 0.0378 (12) | 0.0529 (14) | 0.0494 (13) | −0.0148 (10) | −0.0034 (10) | −0.0032 (10) |
C14A | 0.0378 (12) | 0.0440 (13) | 0.0604 (14) | −0.0089 (10) | −0.0180 (11) | −0.0011 (11) |
C15A | 0.0516 (13) | 0.0433 (13) | 0.0480 (12) | −0.0129 (10) | −0.0195 (11) | 0.0055 (10) |
C16A | 0.0437 (12) | 0.0424 (12) | 0.0382 (11) | −0.0141 (9) | −0.0110 (9) | 0.0035 (9) |
N1B | 0.0430 (10) | 0.0498 (12) | 0.0499 (11) | −0.0127 (9) | −0.0143 (9) | −0.0012 (9) |
N2B | 0.0371 (9) | 0.0469 (11) | 0.0417 (9) | −0.0130 (8) | −0.0111 (8) | −0.0002 (8) |
C3B | 0.0304 (10) | 0.0515 (13) | 0.0336 (10) | −0.0107 (9) | −0.0070 (8) | −0.0012 (9) |
C4B | 0.0463 (13) | 0.0568 (15) | 0.0520 (13) | −0.0135 (11) | −0.0235 (11) | 0.0015 (11) |
C5B | 0.0502 (13) | 0.0516 (15) | 0.0570 (14) | −0.0066 (11) | −0.0224 (11) | 0.0065 (11) |
C11B | 0.0335 (10) | 0.0536 (14) | 0.0310 (10) | −0.0151 (9) | −0.0026 (8) | −0.0021 (9) |
C12B | 0.0441 (13) | 0.0636 (17) | 0.0570 (14) | −0.0183 (11) | −0.0179 (11) | 0.0003 (12) |
C13B | 0.0604 (16) | 0.0708 (19) | 0.0744 (17) | −0.0364 (14) | −0.0213 (13) | −0.0040 (14) |
C14B | 0.0612 (15) | 0.0499 (15) | 0.0636 (15) | −0.0239 (13) | −0.0085 (12) | −0.0023 (12) |
C15B | 0.0481 (13) | 0.0510 (15) | 0.0563 (14) | −0.0145 (11) | −0.0091 (11) | 0.0013 (11) |
C16B | 0.0387 (12) | 0.0505 (14) | 0.0459 (12) | −0.0155 (10) | −0.0113 (10) | 0.0004 (10) |
N1C | 0.0421 (10) | 0.0401 (11) | 0.0589 (11) | −0.0087 (8) | −0.0152 (9) | 0.0006 (9) |
N2C | 0.0410 (10) | 0.0348 (10) | 0.0498 (10) | −0.0084 (8) | −0.0123 (8) | −0.0066 (8) |
C3C | 0.0475 (12) | 0.0373 (12) | 0.0368 (10) | −0.0166 (10) | −0.0105 (9) | 0.0014 (9) |
C4C | 0.0543 (14) | 0.0407 (13) | 0.0473 (12) | −0.0105 (11) | −0.0117 (10) | −0.0073 (10) |
C5C | 0.0475 (13) | 0.0405 (13) | 0.0613 (14) | −0.0044 (10) | −0.0128 (11) | −0.0010 (11) |
C11C | 0.0444 (12) | 0.0483 (13) | 0.0326 (10) | −0.0202 (10) | −0.0061 (9) | 0.0013 (9) |
C12C | 0.0605 (15) | 0.0607 (16) | 0.0534 (14) | −0.0262 (13) | −0.0139 (12) | −0.0102 (12) |
C13C | 0.0716 (18) | 0.089 (2) | 0.0541 (15) | −0.0456 (17) | −0.0166 (13) | −0.0073 (14) |
C14C | 0.0481 (14) | 0.094 (2) | 0.0464 (13) | −0.0339 (15) | −0.0120 (11) | 0.0029 (13) |
C15C | 0.0398 (12) | 0.0731 (17) | 0.0457 (13) | −0.0171 (12) | −0.0065 (10) | −0.0011 (11) |
C16C | 0.0438 (12) | 0.0523 (14) | 0.0389 (11) | −0.0186 (11) | −0.0070 (9) | −0.0031 (10) |
N1D | 0.0512 (11) | 0.0414 (11) | 0.0434 (10) | −0.0150 (8) | −0.0171 (8) | 0.0017 (8) |
N2D | 0.0422 (9) | 0.0400 (10) | 0.0333 (9) | −0.0111 (8) | −0.0094 (7) | 0.0015 (7) |
C3D | 0.0313 (10) | 0.0434 (12) | 0.0318 (10) | −0.0104 (9) | −0.0077 (8) | −0.0003 (9) |
C4D | 0.0566 (14) | 0.0582 (15) | 0.0308 (10) | −0.0234 (11) | −0.0096 (10) | 0.0024 (10) |
C5D | 0.0635 (15) | 0.0522 (15) | 0.0430 (12) | −0.0273 (12) | −0.0162 (11) | 0.0103 (11) |
C11D | 0.0297 (10) | 0.0442 (13) | 0.0451 (12) | −0.0083 (9) | −0.0063 (9) | −0.0057 (9) |
C12D | 0.0586 (15) | 0.0569 (16) | 0.0531 (14) | −0.0083 (12) | −0.0157 (11) | −0.0138 (11) |
C13D | 0.081 (2) | 0.0609 (19) | 0.089 (2) | −0.0083 (15) | −0.0219 (17) | −0.0312 (16) |
C14D | 0.0654 (17) | 0.0417 (16) | 0.115 (3) | −0.0100 (13) | −0.0211 (17) | −0.0090 (16) |
C15D | 0.0654 (17) | 0.0482 (16) | 0.0814 (19) | −0.0191 (13) | −0.0124 (14) | 0.0075 (14) |
C16D | 0.0538 (14) | 0.0474 (14) | 0.0492 (13) | −0.0175 (11) | −0.0050 (11) | 0.0016 (10) |
N1A—C5A | 1.333 (3) | N1C—C5C | 1.340 (3) |
N1A—N2A | 1.355 (2) | N1C—N2C | 1.352 (2) |
N1A—H1A | 0.8800 | N2C—C3C | 1.345 (2) |
N2A—C3A | 1.339 (2) | N2C—H2C | 0.8800 |
C3A—C4A | 1.401 (3) | C3C—C4C | 1.385 (3) |
C3A—C11A | 1.472 (3) | C3C—C11C | 1.471 (3) |
C4A—C5A | 1.372 (3) | C4C—C5C | 1.379 (3) |
C4A—H4A | 0.9500 | C4C—H4C | 0.9500 |
C5A—H5A | 0.9500 | C5C—H5C | 0.9500 |
C11A—C16A | 1.393 (3) | C11C—C16C | 1.393 (3) |
C11A—C12A | 1.397 (3) | C11C—C12C | 1.401 (3) |
C12A—C13A | 1.389 (3) | C12C—C13C | 1.382 (3) |
C12A—H12A | 0.9500 | C12C—H12C | 0.9500 |
C13A—C14A | 1.371 (3) | C13C—C14C | 1.369 (4) |
C13A—H13A | 0.9500 | C13C—H13C | 0.9500 |
C14A—C15A | 1.389 (3) | C14C—C15C | 1.385 (3) |
C14A—H14A | 0.9500 | C14C—H14C | 0.9500 |
C15A—C16A | 1.383 (3) | C15C—C16C | 1.389 (3) |
C15A—H15A | 0.9500 | C15C—H15C | 0.9500 |
C16A—H16A | 0.9500 | C16C—H16C | 0.9500 |
N1B—C5B | 1.328 (3) | N1D—C5D | 1.337 (3) |
N1B—N2B | 1.351 (2) | N1D—N2D | 1.356 (2) |
N1B—H1B | 0.8800 | N2D—C3D | 1.351 (2) |
N2B—C3B | 1.348 (2) | N2D—H2D | 0.8800 |
C3B—C4B | 1.393 (3) | C3D—C4D | 1.388 (3) |
C3B—C11B | 1.474 (3) | C3D—C11D | 1.464 (3) |
C4B—C5B | 1.375 (3) | C4D—C5D | 1.380 (3) |
C4B—H4B | 0.9500 | C4D—H4D | 0.9500 |
C5B—H5B | 0.9500 | C5D—H5D | 0.9500 |
C11B—C16B | 1.389 (3) | C11D—C12D | 1.390 (3) |
C11B—C12B | 1.394 (3) | C11D—C16D | 1.392 (3) |
C12B—C13B | 1.388 (3) | C12D—C13D | 1.390 (4) |
C12B—H12B | 0.9500 | C12D—H12D | 0.9500 |
C13B—C14B | 1.367 (4) | C13D—C14D | 1.367 (4) |
C13B—H13B | 0.9500 | C13D—H13D | 0.9500 |
C14B—C15B | 1.386 (3) | C14D—C15D | 1.366 (4) |
C14B—H14B | 0.9500 | C14D—H14D | 0.9500 |
C15B—C16B | 1.378 (3) | C15D—C16D | 1.378 (3) |
C15B—H15B | 0.9500 | C15D—H15D | 0.9500 |
C16B—H16B | 0.9500 | C16D—H16D | 0.9500 |
C5A—N1A—N2A | 109.91 (17) | C5C—N1C—N2C | 105.80 (17) |
C5A—N1A—H1A | 125.0 | C3C—N2C—N1C | 110.97 (18) |
N2A—N1A—H1A | 125.0 | C3C—N2C—H2C | 124.5 |
C3A—N2A—N1A | 107.10 (16) | N1C—N2C—H2C | 124.5 |
N2A—C3A—C4A | 109.13 (17) | N2C—C3C—C4C | 107.14 (18) |
N2A—C3A—C11A | 121.33 (17) | N2C—C3C—C11C | 121.89 (19) |
C4A—C3A—C11A | 129.54 (18) | C4C—C3C—C11C | 130.96 (19) |
C5A—C4A—C3A | 105.24 (18) | C5C—C4C—C3C | 105.38 (19) |
C5A—C4A—H4A | 127.4 | C5C—C4C—H4C | 127.3 |
C3A—C4A—H4A | 127.4 | C3C—C4C—H4C | 127.3 |
N1A—C5A—C4A | 108.62 (18) | N1C—C5C—C4C | 110.7 (2) |
N1A—C5A—H5A | 125.7 | N1C—C5C—H5C | 124.6 |
C4A—C5A—H5A | 125.7 | C4C—C5C—H5C | 124.6 |
C16A—C11A—C12A | 118.21 (18) | C16C—C11C—C12C | 118.1 (2) |
C16A—C11A—C3A | 120.08 (18) | C16C—C11C—C3C | 121.30 (18) |
C12A—C11A—C3A | 121.71 (17) | C12C—C11C—C3C | 120.6 (2) |
C13A—C12A—C11A | 120.53 (19) | C13C—C12C—C11C | 120.7 (2) |
C13A—C12A—H12A | 119.7 | C13C—C12C—H12C | 119.6 |
C11A—C12A—H12A | 119.7 | C11C—C12C—H12C | 119.6 |
C14A—C13A—C12A | 120.5 (2) | C14C—C13C—C12C | 120.4 (2) |
C14A—C13A—H13A | 119.8 | C14C—C13C—H13C | 119.8 |
C12A—C13A—H13A | 119.8 | C12C—C13C—H13C | 119.8 |
C13A—C14A—C15A | 119.8 (2) | C13C—C14C—C15C | 120.0 (2) |
C13A—C14A—H14A | 120.1 | C13C—C14C—H14C | 120.0 |
C15A—C14A—H14A | 120.1 | C15C—C14C—H14C | 120.0 |
C16A—C15A—C14A | 120.0 (2) | C14C—C15C—C16C | 120.0 (2) |
C16A—C15A—H15A | 120.0 | C14C—C15C—H15C | 120.0 |
C14A—C15A—H15A | 120.0 | C16C—C15C—H15C | 120.0 |
C15A—C16A—C11A | 121.0 (2) | C15C—C16C—C11C | 120.7 (2) |
C15A—C16A—H16A | 119.5 | C15C—C16C—H16C | 119.6 |
C11A—C16A—H16A | 119.5 | C11C—C16C—H16C | 119.6 |
C5B—N1B—N2B | 110.24 (17) | C5D—N1D—N2D | 105.44 (17) |
C5B—N1B—H1B | 124.9 | C3D—N2D—N1D | 111.17 (16) |
N2B—N1B—H1B | 124.9 | C3D—N2D—H2D | 124.4 |
C3B—N2B—N1B | 106.64 (16) | N1D—N2D—H2D | 124.4 |
N2B—C3B—C4B | 109.33 (19) | N2D—C3D—C4D | 106.78 (17) |
N2B—C3B—C11B | 120.96 (18) | N2D—C3D—C11D | 122.76 (17) |
C4B—C3B—C11B | 129.70 (18) | C4D—C3D—C11D | 130.44 (19) |
C5B—C4B—C3B | 105.12 (18) | C5D—C4D—C3D | 105.31 (18) |
C5B—C4B—H4B | 127.4 | C5D—C4D—H4D | 127.3 |
C3B—C4B—H4B | 127.4 | C3D—C4D—H4D | 127.3 |
N1B—C5B—C4B | 108.7 (2) | N1D—C5D—C4D | 111.29 (18) |
N1B—C5B—H5B | 125.7 | N1D—C5D—H5D | 124.4 |
C4B—C5B—H5B | 125.7 | C4D—C5D—H5D | 124.4 |
C16B—C11B—C12B | 118.4 (2) | C12D—C11D—C16D | 118.0 (2) |
C16B—C11B—C3B | 120.92 (17) | C12D—C11D—C3D | 119.9 (2) |
C12B—C11B—C3B | 120.68 (19) | C16D—C11D—C3D | 122.11 (19) |
C13B—C12B—C11B | 120.4 (2) | C11D—C12D—C13D | 120.4 (3) |
C13B—C12B—H12B | 119.8 | C11D—C12D—H12D | 119.8 |
C11B—C12B—H12B | 119.8 | C13D—C12D—H12D | 119.8 |
C14B—C13B—C12B | 120.4 (2) | C14D—C13D—C12D | 120.7 (3) |
C14B—C13B—H13B | 119.8 | C14D—C13D—H13D | 119.7 |
C12B—C13B—H13B | 119.8 | C12D—C13D—H13D | 119.7 |
C13B—C14B—C15B | 120.0 (2) | C15D—C14D—C13D | 119.3 (3) |
C13B—C14B—H14B | 120.0 | C15D—C14D—H14D | 120.4 |
C15B—C14B—H14B | 120.0 | C13D—C14D—H14D | 120.4 |
C16B—C15B—C14B | 119.9 (2) | C14D—C15D—C16D | 121.1 (3) |
C16B—C15B—H15B | 120.1 | C14D—C15D—H15D | 119.5 |
C14B—C15B—H15B | 120.1 | C16D—C15D—H15D | 119.5 |
C15B—C16B—C11B | 121.01 (19) | C15D—C16D—C11D | 120.6 (2) |
C15B—C16B—H16B | 119.5 | C15D—C16D—H16D | 119.7 |
C11B—C16B—H16B | 119.5 | C11D—C16D—H16D | 119.7 |
C5A—N1A—N2A—C3A | 0.0 (2) | C5C—N1C—N2C—C3C | −0.1 (2) |
N1A—N2A—C3A—C4A | 0.0 (2) | N1C—N2C—C3C—C4C | 0.2 (2) |
N1A—N2A—C3A—C11A | 179.35 (16) | N1C—N2C—C3C—C11C | −178.57 (18) |
N2A—C3A—C4A—C5A | 0.0 (2) | N2C—C3C—C4C—C5C | −0.3 (2) |
C11A—C3A—C4A—C5A | −179.3 (2) | C11C—C3C—C4C—C5C | 178.4 (2) |
N2A—N1A—C5A—C4A | −0.1 (2) | N2C—N1C—C5C—C4C | −0.1 (2) |
C3A—C4A—C5A—N1A | 0.1 (2) | C3C—C4C—C5C—N1C | 0.2 (3) |
N2A—C3A—C11A—C16A | −169.01 (19) | N2C—C3C—C11C—C16C | 15.8 (3) |
C4A—C3A—C11A—C16A | 10.2 (3) | C4C—C3C—C11C—C16C | −162.7 (2) |
N2A—C3A—C11A—C12A | 10.7 (3) | N2C—C3C—C11C—C12C | −163.2 (2) |
C4A—C3A—C11A—C12A | −170.1 (2) | C4C—C3C—C11C—C12C | 18.3 (3) |
C16A—C11A—C12A—C13A | −0.7 (3) | C16C—C11C—C12C—C13C | −0.3 (3) |
C3A—C11A—C12A—C13A | 179.63 (19) | C3C—C11C—C12C—C13C | 178.8 (2) |
C11A—C12A—C13A—C14A | 0.7 (3) | C11C—C12C—C13C—C14C | −0.2 (4) |
C12A—C13A—C14A—C15A | −0.2 (3) | C12C—C13C—C14C—C15C | 0.8 (4) |
C13A—C14A—C15A—C16A | −0.3 (3) | C13C—C14C—C15C—C16C | −0.8 (4) |
C14A—C15A—C16A—C11A | 0.4 (3) | C14C—C15C—C16C—C11C | 0.3 (3) |
C12A—C11A—C16A—C15A | 0.1 (3) | C12C—C11C—C16C—C15C | 0.3 (3) |
C3A—C11A—C16A—C15A | 179.83 (18) | C3C—C11C—C16C—C15C | −178.8 (2) |
C5B—N1B—N2B—C3B | 0.0 (2) | C5D—N1D—N2D—C3D | 0.2 (2) |
N1B—N2B—C3B—C4B | −0.2 (2) | N1D—N2D—C3D—C4D | −0.2 (2) |
N1B—N2B—C3B—C11B | −178.90 (17) | N1D—N2D—C3D—C11D | −178.70 (17) |
N2B—C3B—C4B—C5B | 0.3 (2) | N2D—C3D—C4D—C5D | 0.1 (2) |
C11B—C3B—C4B—C5B | 178.8 (2) | C11D—C3D—C4D—C5D | 178.43 (19) |
N2B—N1B—C5B—C4B | 0.2 (3) | N2D—N1D—C5D—C4D | −0.2 (2) |
C3B—C4B—C5B—N1B | −0.3 (3) | C3D—C4D—C5D—N1D | 0.1 (3) |
N2B—C3B—C11B—C16B | 17.8 (3) | N2D—C3D—C11D—C12D | −166.85 (19) |
C4B—C3B—C11B—C16B | −160.7 (2) | C4D—C3D—C11D—C12D | 15.0 (3) |
N2B—C3B—C11B—C12B | −163.98 (19) | N2D—C3D—C11D—C16D | 14.2 (3) |
C4B—C3B—C11B—C12B | 17.6 (3) | C4D—C3D—C11D—C16D | −163.9 (2) |
C16B—C11B—C12B—C13B | −0.5 (3) | C16D—C11D—C12D—C13D | −0.1 (3) |
C3B—C11B—C12B—C13B | −178.8 (2) | C3D—C11D—C12D—C13D | −179.1 (2) |
C11B—C12B—C13B—C14B | −1.4 (4) | C11D—C12D—C13D—C14D | 1.3 (4) |
C12B—C13B—C14B—C15B | 2.4 (4) | C12D—C13D—C14D—C15D | −1.4 (4) |
C13B—C14B—C15B—C16B | −1.7 (4) | C13D—C14D—C15D—C16D | 0.3 (4) |
C14B—C15B—C16B—C11B | −0.2 (3) | C14D—C15D—C16D—C11D | 0.9 (4) |
C12B—C11B—C16B—C15B | 1.2 (3) | C12D—C11D—C16D—C15D | −0.9 (3) |
C3B—C11B—C16B—C15B | 179.5 (2) | C3D—C11D—C16D—C15D | 178.0 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···N2B | 0.88 | 2.04 | 2.909 (2) | 168 |
N1B—H1B···N1C | 0.88 | 2.00 | 2.863 (2) | 165 |
N2C—H2C···N1D | 0.88 | 2.06 | 2.894 (3) | 158 |
N2D—H2D···N2A | 0.88 | 2.00 | 2.840 (2) | 160 |
Experimental details
Crystal data | |
Chemical formula | C9H8N2 |
Mr | 144.17 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 9.5745 (13), 10.3359 (12), 17.132 (2) |
α, β, γ (°) | 85.693 (10), 75.609 (10), 72.102 (10) |
V (Å3) | 1562.7 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.31 × 0.15 × 0.11 |
Data collection | |
Diffractometer | Stoe IPDS II two-circle diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12794, 5573, 3329 |
Rint | 0.059 |
(sin θ/λ)max (Å−1) | 0.600 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.092, 0.88 |
No. of reflections | 5573 |
No. of parameters | 398 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.20 |
Computer programs: X-AREA (Stoe & Cie, 2001), X-AREA, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP in SHELXTL-Plus (Sheldrick, 1991).
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···N2B | 0.88 | 2.04 | 2.909 (2) | 168 |
N1B—H1B···N1C | 0.88 | 2.00 | 2.863 (2) | 165 |
N2C—H2C···N1D | 0.88 | 2.06 | 2.894 (3) | 158 |
N2D—H2D···N2A | 0.88 | 2.00 | 2.840 (2) | 160 |
Recently, we have reported the X-ray crystal structure analysis of 3-phenylpyrazole, C9H8N2, (1) (Haghiri et al., 2002). Here we describe the X-ray crystal structure analysis of a new polymorph of 3-phenylpyrazole, (1). Tris(1-pyrazolyl)borates (`scorpinates') were invented by Trofimenko more than 30 years ago and are today well established as ligands in coordination chemistry (Trofimenko, 1993). Scorpinates now find applications in a wide range of chemistry, from modelling the active site of metal–enzymes, through analytical chemistry and organic synthesis to catalysis and materials science (Edelmann, 2001).
Given this background, we are interested in the synthesis of transition metal complexes (3) with hydrotris(3-phenylpyrazol-1-yl)borate, (2), as the ligand (see Scheme). Therefore, we have prepared 3-phenylpyrazole as a starting material several times. A new polymorph of 3-phenylpyrazol was obtained after recrystallization from CH3OH instead of from CH2Cl2.
The asymmetric unit of (1) contains four independent molecules, labeled A to D. It is interesting to note, that in molecules A and B the N atoms in position 1 carries a H atom whereas in molecules C and D its the N atoms in position 2, which carries the H atom. The pyrazole and phenyl groups of each molecule are approximately planar. The angles between the planes of the pyrazole and phenyl rings are 10.7 (1), 17.4 (1), 16.9 (1) and 14.95 (6)° for molecules A to D, respectively. The crystal structure is built up by circular clusters of these four molecules which are held together by N—H.·N hydrogen bonds (Fig. 1 and Table 1).