Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103007042/kb1000sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103007042/kb1000Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103007042/kb1000IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103007042/kb1000IIIAsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103007042/kb1000IIIBsup5.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103007042/kb1000IIICsup6.hkl |
CCDC references: 214174; 214175; 214176; 214177; 214178
The (1H-pyrrol-2-yl)pyridines (I)–(III) are well known compounds, and (I) is an inhibitor of prolyl 4-hydroxylase (Dowell et al., 1993). We chose methods that were (a) inexpensive, (b) relatively high-yielding, and (c) easily applied to acetophenones in order to generate a large variety of 2-aryl-1H-pyrroles for medicinal chemistry studies. A variation of the Knorr pyrrole synthesis (see Scheme below, method A) was suitable for easy formation of (II) and (III) (Kruse et al., 1987). The starting methyl ketones are, in general, inexpensive and readily available, and the intermediates require minimal purification. The synthesis of (I) was more difficult. Method A failed due to a very poor yield in the alkylation step and failure of the N,N-dimethylhydrazone to hydrolyze under several conditions. The problem was solved by preparing and utilizing 1-aryl-4-(N,N-dimethylhydrazono)-2-buten-1-ones (Severin et al., 1975) in two steps (see Scheme below, method B). The aldol step is rapid, but the cyclization step proceeded in lower yield, due in part, at least, to loss of product (I) because of its extremely high volatility. The literature melting points follow the usual pattern for aromatic compounds, with the para-isomer having the highest melting point, viz. 447–448 K (CCl4; Afonin et al., 2000); cf. the meta-isomer 373–375 K (benzene–petroleum ether; Pictet & Crepieux, 1895), and the ortho-isomer 361–362 K (petroleum ether;Petrova et al., 1997). The RF values (SiO2, 1:1 EtOAc, hexanes) among the isomers rose sharply from para (0.04) to meta (0.16) to ortho (0.49).
The initial attempt to grow crystals of (III) was made by recrystallization of a slightly impure sample (light brown in color) from methanol. The crystals were a mixture of dendrites and tear-shaped crystals. The sample was purified further; new crystals grown from acetonitrile appeared to be satisfactory for X-ray diffraction and the structure of (IIIA) was determined. It was then decided to check the unit cells on the original crystals. A needle, cut from a dendrite, had a different cell; the structure was determined as (IIIB). A tear-shaped crystal had a still different cell; the structure was determined as (IIIC). The melting point of (IIIA) was 445–447 K, in agreement with the literature value. The melting points of (IIIB) and (IIIC) were essentially the same, viz. 444–446 and 442–443 K, respectively, although both samples had shown some decomposition at about 430 K.
In all of the determinations, the H atoms were placed in idealized positions with respect to the attached atoms, except for those on the pyrrole N atoms; these were refined with isotropic displacement parameters. The ortho compound, (I), occurred in a non-centrosymmetric space group. However, with no atoms heavier than nitrogen in the structure, the absolute configuration could not be determined. The Friedel pairs were averaged for the final refinement. Disorder was found for the pyridine rings of molecule A in the (IIIC) polymorph; refinement using an ordered model with large anisotropic displacement parameters increased R from 0.057 to 0.061. The disorder parameter 0.475 (7) for the lesser component is not convincingly different from complete disorder. An intermolecular contact distance of 3.116 Å between atoms C2A' and C5A' in the next molecule along the a direction suggests the the two orientations probably alternate in adjacent molecules in this direction but are random between molecules in other directions.
For all compounds, data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C9H8N2 | Dx = 1.235 Mg m−3 |
Mr = 144.17 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P43212 | Cell parameters from 3961 reflections |
Hall symbol: P 4nw 2abw | θ = 2.6–26.4° |
a = 8.123 (2) Å | µ = 0.08 mm−1 |
c = 23.502 (6) Å | T = 173 K |
V = 1550.7 (7) Å3 | Prism, colorless |
Z = 8 | 0.50 × 0.20 × 0.20 mm |
F(000) = 608 |
Siemens SMART area-detector diffractometer | 1115 independent reflections |
Radiation source: fine-focus sealed tube | 1052 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
ω scans | θmax = 27.5°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995) | h = −10→10 |
Tmin = 0.97, Tmax = 0.99 | k = −10→10 |
18079 measured reflections | l = −30→30 |
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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.100 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.16 | w = 1/[σ2(Fo2) + (0.044P)2 + 0.304P] where P = (Fo2 + 2Fc2)/3 |
1115 reflections | (Δ/σ)max = 0.006 |
104 parameters | Δρmax = 0.13 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
C9H8N2 | Z = 8 |
Mr = 144.17 | Mo Kα radiation |
Tetragonal, P43212 | µ = 0.08 mm−1 |
a = 8.123 (2) Å | T = 173 K |
c = 23.502 (6) Å | 0.50 × 0.20 × 0.20 mm |
V = 1550.7 (7) Å3 |
Siemens SMART area-detector diffractometer | 1115 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995) | 1052 reflections with I > 2σ(I) |
Tmin = 0.97, Tmax = 0.99 | Rint = 0.048 |
18079 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.100 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.16 | Δρmax = 0.13 e Å−3 |
1115 reflections | Δρmin = −0.16 e Å−3 |
104 parameters |
Refinement. Since there are no atoms heavier than N, the Friedel pairs were averaged and no attempt was made to find the correct chirality. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.4647 (2) | 0.4615 (2) | 0.18006 (6) | 0.0336 (4) | |
C2 | 0.3648 (2) | 0.3306 (2) | 0.17355 (7) | 0.0311 (4) | |
C3 | 0.2546 (3) | 0.3197 (3) | 0.12807 (8) | 0.0401 (5) | |
H3 | 0.1837 | 0.2273 | 0.1245 | 0.048* | |
C4 | 0.2502 (3) | 0.4441 (3) | 0.08864 (8) | 0.0468 (5) | |
H4 | 0.1781 | 0.4370 | 0.0569 | 0.056* | |
C5 | 0.3505 (3) | 0.5793 (3) | 0.09517 (8) | 0.0436 (5) | |
H5 | 0.3484 | 0.6671 | 0.0685 | 0.052* | |
C6 | 0.4545 (3) | 0.5837 (3) | 0.14170 (8) | 0.0387 (5) | |
H6 | 0.5222 | 0.6779 | 0.1468 | 0.046* | |
C7 | 0.3808 (2) | 0.1975 (2) | 0.21452 (7) | 0.0322 (4) | |
N8 | 0.4717 (2) | 0.2180 (2) | 0.26351 (6) | 0.0339 (4) | |
H8 | 0.512 (3) | 0.316 (3) | 0.2768 (8) | 0.041 (6)* | |
C9 | 0.4817 (3) | 0.0717 (2) | 0.29148 (8) | 0.0393 (5) | |
H9 | 0.5377 | 0.0536 | 0.3264 | 0.047* | |
C10 | 0.3981 (3) | −0.0451 (3) | 0.26108 (8) | 0.0406 (5) | |
H10 | 0.3856 | −0.1579 | 0.2708 | 0.049* | |
C11 | 0.3340 (3) | 0.0339 (3) | 0.21249 (8) | 0.0397 (5) | |
H11 | 0.2700 | −0.0163 | 0.1835 | 0.048* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0348 (8) | 0.0359 (9) | 0.0302 (7) | −0.0003 (7) | 0.0003 (7) | −0.0018 (6) |
C2 | 0.0295 (9) | 0.0351 (10) | 0.0287 (8) | 0.0025 (7) | 0.0013 (7) | −0.0065 (8) |
C3 | 0.0387 (11) | 0.0418 (11) | 0.0397 (9) | −0.0025 (9) | −0.0069 (9) | −0.0039 (9) |
C4 | 0.0449 (13) | 0.0558 (14) | 0.0398 (10) | 0.0000 (11) | −0.0128 (9) | 0.0032 (10) |
C5 | 0.0431 (12) | 0.0488 (12) | 0.0389 (10) | 0.0021 (10) | −0.0050 (9) | 0.0105 (10) |
C6 | 0.0382 (11) | 0.0383 (10) | 0.0396 (9) | −0.0031 (9) | 0.0004 (9) | 0.0015 (8) |
C7 | 0.0307 (9) | 0.0359 (10) | 0.0300 (8) | −0.0010 (8) | −0.0003 (7) | −0.0042 (8) |
N8 | 0.0377 (9) | 0.0349 (9) | 0.0291 (7) | −0.0030 (7) | −0.0017 (7) | −0.0011 (6) |
C9 | 0.0416 (11) | 0.0415 (11) | 0.0348 (9) | −0.0017 (9) | 0.0005 (9) | 0.0040 (8) |
C10 | 0.0463 (12) | 0.0328 (10) | 0.0427 (10) | −0.0030 (9) | 0.0010 (9) | 0.0049 (9) |
C11 | 0.0428 (11) | 0.0382 (11) | 0.0381 (9) | −0.0040 (9) | −0.0021 (9) | −0.0037 (9) |
N1—C6 | 1.343 (2) | C6—H6 | 0.9500 |
N1—C2 | 1.347 (2) | C7—N8 | 1.378 (2) |
C2—C3 | 1.397 (2) | C7—C11 | 1.383 (3) |
C2—C7 | 1.453 (3) | N8—C9 | 1.361 (2) |
C3—C4 | 1.372 (3) | N8—H8 | 0.91 (2) |
C3—H3 | 0.9500 | C9—C10 | 1.369 (3) |
C4—C5 | 1.376 (3) | C9—H9 | 0.9500 |
C4—H4 | 0.9500 | C10—C11 | 1.410 (3) |
C5—C6 | 1.382 (3) | C10—H10 | 0.9500 |
C5—H5 | 0.9500 | C11—H11 | 0.9500 |
C6—N1—C2 | 118.07 (16) | N8—C7—C11 | 107.00 (17) |
N1—C2—C3 | 121.51 (18) | N8—C7—C2 | 120.79 (17) |
N1—C2—C7 | 117.26 (16) | C11—C7—C2 | 131.83 (17) |
C3—C2—C7 | 121.18 (17) | C9—N8—C7 | 109.28 (17) |
C4—C3—C2 | 119.17 (19) | C9—N8—H8 | 124.9 (12) |
C4—C3—H3 | 120.4 | C7—N8—H8 | 125.6 (13) |
C2—C3—H3 | 120.4 | N8—C9—C10 | 108.90 (17) |
C3—C4—C5 | 119.80 (19) | N8—C9—H9 | 125.6 |
C3—C4—H4 | 120.1 | C10—C9—H9 | 125.6 |
C5—C4—H4 | 120.1 | C9—C10—C11 | 106.86 (18) |
C4—C5—C6 | 118.1 (2) | C9—C10—H10 | 126.6 |
C4—C5—H5 | 121.0 | C11—C10—H10 | 126.6 |
C6—C5—H5 | 121.0 | C7—C11—C10 | 107.96 (18) |
N1—C6—C5 | 123.33 (19) | C7—C11—H11 | 126.0 |
N1—C6—H6 | 118.3 | C10—C11—H11 | 126.0 |
C5—C6—H6 | 118.3 | ||
C6—N1—C2—C3 | 0.7 (3) | N1—C2—C7—C11 | −160.2 (2) |
C6—N1—C2—C7 | 178.28 (16) | C3—C2—C7—C11 | 17.4 (3) |
N1—C2—C3—C4 | 1.1 (3) | C11—C7—N8—C9 | 0.0 (2) |
C7—C2—C3—C4 | −176.36 (19) | C2—C7—N8—C9 | −173.71 (17) |
C2—C3—C4—C5 | −1.7 (3) | C7—N8—C9—C10 | 0.1 (2) |
C3—C4—C5—C6 | 0.6 (3) | N8—C9—C10—C11 | −0.2 (2) |
C2—N1—C6—C5 | −2.0 (3) | N8—C7—C11—C10 | −0.1 (2) |
C4—C5—C6—N1 | 1.4 (3) | C2—C7—C11—C10 | 172.6 (2) |
N1—C2—C7—N8 | 11.7 (3) | C9—C10—C11—C7 | 0.1 (2) |
C3—C2—C7—N8 | −170.74 (17) |
C9H8N2 | F(000) = 304 |
Mr = 144.17 | Dx = 1.293 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2058 reflections |
a = 5.3537 (13) Å | θ = 2.4–27.0° |
b = 11.654 (3) Å | µ = 0.08 mm−1 |
c = 11.990 (3) Å | T = 174 K |
β = 98.10 (1)° | Needle, colorless |
V = 740.6 (3) Å3 | 0.35 × 0.15 × 0.05 mm |
Z = 4 |
Siemens SMART area-detector diffractometer | 1681 independent reflections |
Radiation source: fine-focus sealed tube | 1232 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ω scans | θmax = 27.5°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995) | h = −6→6 |
Tmin = 0.97, Tmax = 0.99 | k = −11→15 |
4676 measured reflections | l = −15→14 |
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)] = 0.044 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.114 | w = 1/[σ2(Fo2) + (0.058P)2 + 0.116P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
1681 reflections | Δρmax = 0.19 e Å−3 |
105 parameters | Δρmin = −0.17 e Å−3 |
0 restraints | Extinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.022 (6) |
C9H8N2 | V = 740.6 (3) Å3 |
Mr = 144.17 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.3537 (13) Å | µ = 0.08 mm−1 |
b = 11.654 (3) Å | T = 174 K |
c = 11.990 (3) Å | 0.35 × 0.15 × 0.05 mm |
β = 98.10 (1)° |
Siemens SMART area-detector diffractometer | 1681 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995) | 1232 reflections with I > 2σ(I) |
Tmin = 0.97, Tmax = 0.99 | Rint = 0.030 |
4676 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.114 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.19 e Å−3 |
1681 reflections | Δρmin = −0.17 e Å−3 |
105 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.1570 (2) | 0.18720 (11) | 0.49705 (10) | 0.0382 (4) | |
C2 | 0.3451 (3) | 0.26068 (13) | 0.53070 (12) | 0.0353 (4) | |
H2 | 0.4423 | 0.2876 | 0.4756 | 0.042* | |
C3 | 0.4083 (2) | 0.30048 (12) | 0.64082 (11) | 0.0288 (3) | |
C4 | 0.2632 (3) | 0.25840 (13) | 0.72014 (12) | 0.0315 (4) | |
H4 | 0.2980 | 0.2822 | 0.7965 | 0.038* | |
C5 | 0.0695 (3) | 0.18224 (13) | 0.68719 (12) | 0.0343 (4) | |
H5 | −0.0298 | 0.1530 | 0.7405 | 0.041* | |
C6 | 0.0218 (3) | 0.14906 (13) | 0.57566 (12) | 0.0361 (4) | |
H6 | −0.1126 | 0.0970 | 0.5536 | 0.043* | |
C7 | 0.6152 (3) | 0.38164 (12) | 0.66867 (11) | 0.0296 (3) | |
N8 | 0.7188 (2) | 0.40504 (10) | 0.77786 (10) | 0.0309 (3) | |
H8 | 0.678 (3) | 0.3731 (15) | 0.8438 (14) | 0.044 (5)* | |
C9 | 0.9103 (3) | 0.48217 (13) | 0.77801 (13) | 0.0352 (4) | |
H9 | 1.0127 | 0.5115 | 0.8429 | 0.042* | |
C10 | 0.9299 (3) | 0.51011 (14) | 0.66894 (13) | 0.0381 (4) | |
H10 | 1.0463 | 0.5627 | 0.6443 | 0.046* | |
C11 | 0.7455 (3) | 0.44653 (13) | 0.59991 (13) | 0.0354 (4) | |
H11 | 0.7160 | 0.4480 | 0.5199 | 0.042* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0423 (7) | 0.0413 (8) | 0.0305 (7) | −0.0014 (6) | 0.0027 (5) | −0.0030 (6) |
C2 | 0.0404 (8) | 0.0382 (8) | 0.0278 (8) | −0.0003 (7) | 0.0071 (6) | 0.0006 (6) |
C3 | 0.0313 (7) | 0.0268 (7) | 0.0279 (7) | 0.0065 (6) | 0.0030 (5) | 0.0023 (6) |
C4 | 0.0349 (7) | 0.0333 (8) | 0.0262 (7) | 0.0041 (6) | 0.0041 (6) | −0.0017 (6) |
C5 | 0.0346 (8) | 0.0368 (8) | 0.0321 (8) | −0.0001 (7) | 0.0075 (6) | 0.0016 (6) |
C6 | 0.0348 (7) | 0.0355 (8) | 0.0373 (8) | −0.0011 (7) | 0.0026 (6) | −0.0027 (7) |
C7 | 0.0326 (7) | 0.0300 (7) | 0.0263 (7) | 0.0058 (6) | 0.0047 (6) | 0.0005 (6) |
N8 | 0.0348 (6) | 0.0325 (7) | 0.0257 (7) | 0.0014 (5) | 0.0057 (5) | −0.0004 (5) |
C9 | 0.0326 (8) | 0.0349 (8) | 0.0384 (9) | −0.0001 (7) | 0.0056 (6) | −0.0055 (6) |
C10 | 0.0372 (8) | 0.0359 (8) | 0.0429 (9) | −0.0017 (7) | 0.0120 (7) | 0.0002 (7) |
C11 | 0.0394 (8) | 0.0370 (8) | 0.0306 (8) | 0.0023 (7) | 0.0077 (6) | 0.0013 (6) |
N1—C2 | 1.340 (2) | C6—H6 | 0.9500 |
N1—C6 | 1.342 (2) | C7—N8 | 1.375 (2) |
C2—C3 | 1.395 (2) | C7—C11 | 1.379 (2) |
C2—H2 | 0.9500 | N8—C9 | 1.364 (2) |
C3—C4 | 1.399 (2) | N8—H8 | 0.93 (2) |
C3—C7 | 1.459 (2) | C9—C10 | 1.366 (2) |
C4—C5 | 1.380 (2) | C9—H9 | 0.9500 |
C4—H4 | 0.9500 | C10—C11 | 1.406 (2) |
C5—C6 | 1.381 (2) | C10—H10 | 0.9500 |
C5—H5 | 0.9500 | C11—H11 | 0.9500 |
C2—N1—C6 | 117.18 (13) | N8—C7—C11 | 106.86 (13) |
N1—C2—C3 | 124.70 (14) | N8—C7—C3 | 122.54 (12) |
N1—C2—H2 | 117.6 | C11—C7—C3 | 130.60 (13) |
C3—C2—H2 | 117.6 | C9—N8—C7 | 109.54 (12) |
C2—C3—C4 | 116.28 (13) | C9—N8—H8 | 122.1 (10) |
C2—C3—C7 | 120.49 (13) | C7—N8—H8 | 128.3 (10) |
C4—C3—C7 | 123.23 (13) | N8—C9—C10 | 108.36 (13) |
C5—C4—C3 | 119.87 (13) | N8—C9—H9 | 125.8 |
C5—C4—H4 | 120.1 | C10—C9—H9 | 125.8 |
C3—C4—H4 | 120.1 | C9—C10—C11 | 107.20 (14) |
C4—C5—C6 | 119.09 (14) | C9—C10—H10 | 126.4 |
C4—C5—H5 | 120.5 | C11—C10—H10 | 126.4 |
C6—C5—H5 | 120.5 | C7—C11—C10 | 108.04 (13) |
N1—C6—C5 | 122.88 (14) | C7—C11—H11 | 126.0 |
N1—C6—H6 | 118.6 | C10—C11—H11 | 126.0 |
C5—C6—H6 | 118.6 | ||
C6—N1—C2—C3 | −0.4 (2) | C2—C3—C7—C11 | 13.0 (2) |
N1—C2—C3—C4 | 0.6 (2) | C4—C3—C7—C11 | −166.92 (15) |
N1—C2—C3—C7 | −179.29 (13) | C11—C7—N8—C9 | −0.31 (16) |
C2—C3—C4—C5 | −0.3 (2) | C3—C7—N8—C9 | 178.97 (12) |
C7—C3—C4—C5 | 179.61 (13) | C7—N8—C9—C10 | 0.67 (17) |
C3—C4—C5—C6 | −0.2 (2) | N8—C9—C10—C11 | −0.75 (17) |
C2—N1—C6—C5 | −0.1 (2) | N8—C7—C11—C10 | −0.15 (16) |
C4—C5—C6—N1 | 0.4 (2) | C3—C7—C11—C10 | −179.36 (14) |
C2—C3—C7—N8 | −166.14 (13) | C9—C10—C11—C7 | 0.56 (17) |
C4—C3—C7—N8 | 14.0 (2) |
C9H8N2 | F(000) = 608 |
Mr = 144.17 | Dx = 1.281 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2036 reflections |
a = 7.402 (2) Å | θ = 2.9–25.4° |
b = 11.480 (3) Å | µ = 0.08 mm−1 |
c = 17.705 (4) Å | T = 173 K |
β = 96.23 (1)° | Needle, colorless |
V = 1495.6 (7) Å3 | 0.50 × 0.10 × 0.06 mm |
Z = 8 |
Siemens SMART area-detector diffractometer | 3412 independent reflections |
Radiation source: fine-focus sealed tube | 1933 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
ω scans | θmax = 27.5°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995) | h = −9→9 |
Tmin = 0.97, Tmax = 0.99 | k = −14→14 |
9224 measured reflections | l = −14→22 |
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)] = 0.047 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.118 | w = 1/[σ2(Fo2) + (0.058P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.92 | (Δ/σ)max = 0.001 |
3412 reflections | Δρmax = 0.22 e Å−3 |
208 parameters | Δρmin = −0.21 e Å−3 |
0 restraints | Extinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0061 (13) |
C9H8N2 | V = 1495.6 (7) Å3 |
Mr = 144.17 | Z = 8 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.402 (2) Å | µ = 0.08 mm−1 |
b = 11.480 (3) Å | T = 173 K |
c = 17.705 (4) Å | 0.50 × 0.10 × 0.06 mm |
β = 96.23 (1)° |
Siemens SMART area-detector diffractometer | 3412 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995) | 1933 reflections with I > 2σ(I) |
Tmin = 0.97, Tmax = 0.99 | Rint = 0.052 |
9224 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.118 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.92 | Δρmax = 0.22 e Å−3 |
3412 reflections | Δρmin = −0.21 e Å−3 |
208 parameters |
x | y | z | Uiso*/Ueq | ||
N1A | 0.51651 (19) | 1.03326 (13) | 0.36614 (8) | 0.0342 (4) | |
C2A | 0.4940 (2) | 0.91726 (16) | 0.36095 (10) | 0.0339 (4) | |
H2A | 0.4105 | 0.8881 | 0.3209 | 0.041* | |
C3A | 0.5842 (2) | 0.83744 (15) | 0.40998 (10) | 0.0310 (4) | |
H3A | 0.5628 | 0.7564 | 0.4029 | 0.037* | |
C4A | 0.7073 (2) | 0.87705 (14) | 0.47014 (9) | 0.0269 (4) | |
C5A | 0.7320 (2) | 0.99727 (15) | 0.47522 (10) | 0.0313 (4) | |
H5A | 0.8152 | 1.0292 | 0.5144 | 0.038* | |
C6A | 0.6363 (2) | 1.06976 (16) | 0.42358 (10) | 0.0349 (5) | |
H6A | 0.6563 | 1.1512 | 0.4289 | 0.042* | |
C7A | 0.8068 (2) | 0.79937 (15) | 0.52473 (10) | 0.0284 (4) | |
N8A | 0.82073 (19) | 0.68110 (13) | 0.51256 (9) | 0.0320 (4) | |
H8A | 0.766 (3) | 0.6376 (18) | 0.4691 (13) | 0.069 (7)* | |
C9A | 0.9270 (2) | 0.63296 (17) | 0.57209 (11) | 0.0383 (5) | |
H9A | 0.9588 | 0.5529 | 0.5772 | 0.046* | |
C10A | 0.9804 (2) | 0.71855 (18) | 0.62330 (11) | 0.0419 (5) | |
H10A | 1.0546 | 0.7090 | 0.6701 | 0.050* | |
C11A | 0.9051 (2) | 0.82348 (16) | 0.59361 (10) | 0.0364 (5) | |
H11A | 0.9193 | 0.8979 | 0.6169 | 0.044* | |
N1B | 0.66800 (19) | 0.52851 (13) | 0.39051 (9) | 0.0370 (4) | |
C2B | 0.5705 (2) | 0.43542 (15) | 0.40684 (10) | 0.0326 (4) | |
H2B | 0.5490 | 0.4241 | 0.4583 | 0.039* | |
C3B | 0.4990 (2) | 0.35478 (14) | 0.35406 (9) | 0.0273 (4) | |
H3B | 0.4279 | 0.2918 | 0.3692 | 0.033* | |
C4B | 0.5318 (2) | 0.36635 (14) | 0.27840 (9) | 0.0256 (4) | |
C5B | 0.6355 (2) | 0.46278 (15) | 0.26074 (10) | 0.0328 (4) | |
H5B | 0.6624 | 0.4749 | 0.2101 | 0.039* | |
C6B | 0.6980 (2) | 0.53971 (16) | 0.31713 (11) | 0.0379 (5) | |
H6B | 0.7666 | 0.6049 | 0.3035 | 0.045* | |
C7B | 0.4594 (2) | 0.28416 (15) | 0.21977 (9) | 0.0270 (4) | |
N8B | 0.38293 (19) | 0.17978 (13) | 0.23726 (9) | 0.0315 (4) | |
H8B | 0.402 (3) | 0.1393 (17) | 0.2827 (12) | 0.064 (7)* | |
C9B | 0.3209 (2) | 0.12374 (17) | 0.17161 (11) | 0.0381 (5) | |
H9B | 0.2644 | 0.0493 | 0.1680 | 0.046* | |
C10B | 0.3541 (2) | 0.19336 (17) | 0.11157 (11) | 0.0401 (5) | |
H10B | 0.3230 | 0.1767 | 0.0592 | 0.048* | |
C11B | 0.4425 (2) | 0.29391 (16) | 0.14198 (10) | 0.0345 (5) | |
H11B | 0.4834 | 0.3573 | 0.1138 | 0.041* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1A | 0.0338 (8) | 0.0355 (10) | 0.0341 (9) | 0.0028 (7) | 0.0068 (7) | 0.0054 (7) |
C2A | 0.0327 (10) | 0.0365 (11) | 0.0323 (11) | −0.0014 (8) | 0.0020 (8) | −0.0013 (8) |
C3A | 0.0330 (9) | 0.0274 (10) | 0.0325 (10) | −0.0021 (8) | 0.0029 (8) | 0.0000 (8) |
C4A | 0.0270 (8) | 0.0255 (9) | 0.0291 (10) | −0.0013 (7) | 0.0073 (7) | 0.0009 (7) |
C5A | 0.0337 (9) | 0.0273 (10) | 0.0325 (10) | −0.0017 (8) | 0.0019 (8) | −0.0015 (8) |
C6A | 0.0359 (10) | 0.0286 (11) | 0.0411 (12) | −0.0009 (8) | 0.0076 (9) | 0.0008 (9) |
C7A | 0.0271 (9) | 0.0265 (10) | 0.0318 (10) | −0.0024 (7) | 0.0043 (8) | 0.0016 (8) |
N8A | 0.0342 (8) | 0.0254 (8) | 0.0366 (10) | 0.0007 (7) | 0.0053 (7) | 0.0025 (7) |
C9A | 0.0376 (10) | 0.0336 (11) | 0.0445 (12) | 0.0052 (9) | 0.0085 (9) | 0.0107 (9) |
C10A | 0.0355 (10) | 0.0480 (13) | 0.0404 (12) | −0.0012 (9) | −0.0050 (9) | 0.0142 (10) |
C11A | 0.0356 (10) | 0.0341 (11) | 0.0387 (11) | −0.0057 (8) | 0.0002 (8) | 0.0003 (9) |
N1B | 0.0357 (8) | 0.0275 (9) | 0.0466 (10) | 0.0004 (7) | −0.0002 (7) | −0.0040 (7) |
C2B | 0.0350 (10) | 0.0306 (11) | 0.0319 (10) | 0.0050 (8) | 0.0027 (8) | −0.0014 (8) |
C3B | 0.0285 (9) | 0.0228 (9) | 0.0308 (10) | 0.0012 (7) | 0.0047 (7) | 0.0016 (7) |
C4B | 0.0234 (8) | 0.0230 (9) | 0.0300 (10) | 0.0062 (7) | 0.0010 (7) | 0.0013 (7) |
C5B | 0.0332 (9) | 0.0300 (10) | 0.0356 (11) | 0.0002 (8) | 0.0054 (8) | 0.0040 (8) |
C6B | 0.0352 (10) | 0.0267 (11) | 0.0518 (13) | −0.0054 (8) | 0.0054 (9) | 0.0041 (9) |
C7B | 0.0261 (9) | 0.0271 (10) | 0.0281 (10) | 0.0029 (7) | 0.0048 (7) | 0.0015 (8) |
N8B | 0.0371 (8) | 0.0295 (9) | 0.0276 (9) | −0.0038 (7) | 0.0027 (7) | −0.0024 (7) |
C9B | 0.0383 (10) | 0.0383 (12) | 0.0369 (11) | −0.0032 (9) | 0.0001 (9) | −0.0117 (9) |
C10B | 0.0381 (10) | 0.0508 (13) | 0.0299 (11) | 0.0086 (9) | −0.0033 (8) | −0.0068 (10) |
C11B | 0.0354 (10) | 0.0384 (11) | 0.0299 (11) | 0.0065 (8) | 0.0047 (8) | 0.0031 (8) |
N1A—C6A | 1.342 (2) | N1B—C2B | 1.339 (2) |
N1A—C2A | 1.344 (2) | N1B—C6B | 1.348 (2) |
C2A—C3A | 1.383 (2) | C2B—C3B | 1.379 (2) |
C2A—H2A | 0.9500 | C2B—H2B | 0.9500 |
C3A—C4A | 1.400 (2) | C3B—C4B | 1.393 (2) |
C3A—H3A | 0.9500 | C3B—H3B | 0.9500 |
C4A—C5A | 1.394 (2) | C4B—C5B | 1.402 (2) |
C4A—C7A | 1.455 (2) | C4B—C7B | 1.461 (2) |
C5A—C6A | 1.375 (2) | C5B—C6B | 1.375 (2) |
C5A—H5A | 0.9500 | C5B—H5B | 0.9500 |
C6A—H6A | 0.9500 | C6B—H6B | 0.9500 |
C7A—C11A | 1.379 (2) | C7B—C11B | 1.374 (2) |
C7A—N8A | 1.380 (2) | C7B—N8B | 1.375 (2) |
N8A—C9A | 1.362 (2) | N8B—C9B | 1.364 (2) |
N8A—H8A | 0.97 (2) | N8B—H8B | 0.93 (2) |
C9A—C10A | 1.366 (3) | C9B—C10B | 1.373 (3) |
C9A—H9A | 0.9500 | C9B—H9B | 0.9500 |
C10A—C11A | 1.405 (2) | C10B—C11B | 1.405 (2) |
C10A—H10A | 0.9500 | C10B—H10B | 0.9500 |
C11A—H11A | 0.9500 | C11B—H11B | 0.9500 |
C6A—N1A—C2A | 115.35 (15) | C2B—N1B—C6B | 115.68 (16) |
N1A—C2A—C3A | 124.46 (17) | N1B—C2B—C3B | 124.44 (17) |
N1A—C2A—H2A | 117.8 | N1B—C2B—H2B | 117.8 |
C3A—C2A—H2A | 117.8 | C3B—C2B—H2B | 117.8 |
C2A—C3A—C4A | 119.47 (16) | C2B—C3B—C4B | 119.56 (16) |
C2A—C3A—H3A | 120.3 | C2B—C3B—H3B | 120.2 |
C4A—C3A—H3A | 120.3 | C4B—C3B—H3B | 120.2 |
C5A—C4A—C3A | 116.16 (16) | C3B—C4B—C5B | 116.51 (16) |
C5A—C4A—C7A | 120.68 (15) | C3B—C4B—C7B | 122.20 (15) |
C3A—C4A—C7A | 123.16 (15) | C5B—C4B—C7B | 121.28 (16) |
C6A—C5A—C4A | 120.11 (16) | C6B—C5B—C4B | 119.64 (17) |
C6A—C5A—H5A | 119.9 | C6B—C5B—H5B | 120.2 |
C4A—C5A—H5A | 119.9 | C4B—C5B—H5B | 120.2 |
N1A—C6A—C5A | 124.44 (17) | N1B—C6B—C5B | 124.14 (17) |
N1A—C6A—H6A | 117.8 | N1B—C6B—H6B | 117.9 |
C5A—C6A—H6A | 117.8 | C5B—C6B—H6B | 117.9 |
C11A—C7A—N8A | 107.11 (16) | C11B—C7B—N8B | 107.58 (15) |
C11A—C7A—C4A | 130.17 (16) | C11B—C7B—C4B | 130.24 (16) |
N8A—C7A—C4A | 122.70 (15) | N8B—C7B—C4B | 122.08 (15) |
C9A—N8A—C7A | 108.97 (16) | C9B—N8B—C7B | 109.14 (16) |
C9A—N8A—H8A | 124.2 (12) | C9B—N8B—H8B | 120.6 (13) |
C7A—N8A—H8A | 126.8 (12) | C7B—N8B—H8B | 127.3 (13) |
N8A—C9A—C10A | 108.84 (17) | N8B—C9B—C10B | 108.26 (17) |
N8A—C9A—H9A | 125.6 | N8B—C9B—H9B | 125.9 |
C10A—C9A—H9A | 125.6 | C10B—C9B—H9B | 125.9 |
C9A—C10A—C11A | 107.08 (17) | C9B—C10B—C11B | 107.25 (17) |
C9A—C10A—H10A | 126.5 | C9B—C10B—H10B | 126.4 |
C11A—C10A—H10A | 126.5 | C11B—C10B—H10B | 126.4 |
C7A—C11A—C10A | 107.99 (17) | C7B—C11B—C10B | 107.76 (16) |
C7A—C11A—H11A | 126.0 | C7B—C11B—H11B | 126.1 |
C10A—C11A—H11A | 126.0 | C10B—C11B—H11B | 126.1 |
C6A—N1A—C2A—C3A | 0.2 (2) | C6B—N1B—C2B—C3B | −1.3 (2) |
N1A—C2A—C3A—C4A | 0.5 (3) | N1B—C2B—C3B—C4B | 1.8 (2) |
C2A—C3A—C4A—C5A | −1.0 (2) | C2B—C3B—C4B—C5B | −1.0 (2) |
C2A—C3A—C4A—C7A | 179.47 (15) | C2B—C3B—C4B—C7B | −179.76 (15) |
C3A—C4A—C5A—C6A | 0.9 (2) | C3B—C4B—C5B—C6B | −0.2 (2) |
C7A—C4A—C5A—C6A | −179.57 (15) | C7B—C4B—C5B—C6B | 178.56 (15) |
C2A—N1A—C6A—C5A | −0.3 (2) | C2B—N1B—C6B—C5B | −0.1 (3) |
C4A—C5A—C6A—N1A | −0.3 (3) | C4B—C5B—C6B—N1B | 0.8 (3) |
C5A—C4A—C7A—C11A | 13.8 (3) | C3B—C4B—C7B—C11B | 164.02 (16) |
C3A—C4A—C7A—C11A | −166.72 (17) | C5B—C4B—C7B—C11B | −14.7 (3) |
C5A—C4A—C7A—N8A | −164.32 (16) | C3B—C4B—C7B—N8B | −11.9 (2) |
C3A—C4A—C7A—N8A | 15.1 (2) | C5B—C4B—C7B—N8B | 169.35 (14) |
C11A—C7A—N8A—C9A | −0.69 (19) | C11B—C7B—N8B—C9B | 0.77 (19) |
C4A—C7A—N8A—C9A | 177.82 (14) | C4B—C7B—N8B—C9B | 177.53 (14) |
C7A—N8A—C9A—C10A | 0.7 (2) | C7B—N8B—C9B—C10B | −1.2 (2) |
N8A—C9A—C10A—C11A | −0.5 (2) | N8B—C9B—C10B—C11B | 1.2 (2) |
N8A—C7A—C11A—C10A | 0.38 (19) | N8B—C7B—C11B—C10B | −0.01 (19) |
C4A—C7A—C11A—C10A | −177.98 (16) | C4B—C7B—C11B—C10B | −176.42 (16) |
C9A—C10A—C11A—C7A | 0.1 (2) | C9B—C10B—C11B—C7B | −0.7 (2) |
C9H8N2 | F(000) = 608 |
Mr = 144.17 | Dx = 1.265 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2651 reflections |
a = 15.139 (4) Å | θ = 2.2–25.8° |
b = 5.4945 (14) Å | µ = 0.08 mm−1 |
c = 18.736 (5) Å | T = 173 K |
β = 103.76 (1)° | Needle, pale yellow |
V = 1513.8 (7) Å3 | 0.50 × 0.05 × 0.05 mm |
Z = 8 |
Siemens SMART area-detector diffractometer | 3452 independent reflections |
Radiation source: fine-focus sealed tube | 2385 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.049 |
ω scans | θmax = 27.5°, θmin = 1.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995) | h = −19→19 |
Tmin = 0.98, Tmax = 1.00 | k = −7→7 |
14309 measured reflections | l = −24→24 |
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.039P)2 + 0.333P] where P = (Fo2 + 2Fc2)/3 |
3452 reflections | (Δ/σ)max = 0.004 |
207 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
C9H8N2 | V = 1513.8 (7) Å3 |
Mr = 144.17 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.139 (4) Å | µ = 0.08 mm−1 |
b = 5.4945 (14) Å | T = 173 K |
c = 18.736 (5) Å | 0.50 × 0.05 × 0.05 mm |
β = 103.76 (1)° |
Siemens SMART area-detector diffractometer | 3452 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995) | 2385 reflections with I > 2σ(I) |
Tmin = 0.98, Tmax = 1.00 | Rint = 0.049 |
14309 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.21 e Å−3 |
3452 reflections | Δρmin = −0.17 e Å−3 |
207 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. |
x | y | z | Uiso*/Ueq | ||
N1A | 0.27576 (9) | 0.3961 (3) | 0.53606 (7) | 0.0384 (3) | |
C2A | 0.29091 (10) | 0.1884 (3) | 0.50396 (8) | 0.0345 (4) | |
H2A | 0.3516 | 0.1294 | 0.5137 | 0.041* | |
C3A | 0.22412 (10) | 0.0537 (3) | 0.45747 (8) | 0.0323 (4) | |
H3A | 0.2395 | −0.0919 | 0.4359 | 0.039* | |
C4A | 0.13355 (10) | 0.1330 (3) | 0.44233 (8) | 0.0313 (3) | |
C5A | 0.11799 (11) | 0.3500 (3) | 0.47555 (9) | 0.0396 (4) | |
H5A | 0.0581 | 0.4138 | 0.4671 | 0.047* | |
C6A | 0.18896 (11) | 0.4721 (3) | 0.52049 (9) | 0.0428 (4) | |
H6A | 0.1758 | 0.6202 | 0.5420 | 0.051* | |
C7A | 0.05897 (10) | −0.0024 (3) | 0.39618 (8) | 0.0333 (4) | |
N8A | 0.07100 (9) | −0.1964 (3) | 0.35351 (7) | 0.0346 (3) | |
H8A | 0.1266 (12) | −0.251 (3) | 0.3465 (9) | 0.049 (5)* | |
C9A | −0.01126 (11) | −0.2884 (3) | 0.31821 (9) | 0.0410 (4) | |
H9A | −0.0210 | −0.4226 | 0.2853 | 0.049* | |
C10A | −0.07738 (11) | −0.1543 (4) | 0.33842 (10) | 0.0492 (5) | |
H10A | −0.1412 | −0.1788 | 0.3224 | 0.059* | |
C11A | −0.03390 (11) | 0.0253 (4) | 0.38697 (10) | 0.0486 (5) | |
H11A | −0.0630 | 0.1457 | 0.4097 | 0.058* | |
N1B | 0.23424 (9) | 0.8359 (3) | 0.80902 (7) | 0.0379 (3) | |
C2B | 0.23462 (11) | 0.6726 (3) | 0.75637 (9) | 0.0394 (4) | |
H2B | 0.1943 | 0.5381 | 0.7524 | 0.047* | |
C3B | 0.28941 (10) | 0.6856 (3) | 0.70726 (8) | 0.0349 (4) | |
H3B | 0.2865 | 0.5623 | 0.6712 | 0.042* | |
C4B | 0.34898 (9) | 0.8809 (3) | 0.71097 (8) | 0.0285 (3) | |
C5B | 0.34858 (10) | 1.0534 (3) | 0.76572 (9) | 0.0347 (4) | |
H5B | 0.3875 | 1.1911 | 0.7707 | 0.042* | |
C6B | 0.29178 (10) | 1.0235 (3) | 0.81231 (9) | 0.0380 (4) | |
H6B | 0.2933 | 1.1432 | 0.8492 | 0.046* | |
C7B | 0.41214 (9) | 0.9031 (3) | 0.66349 (8) | 0.0289 (3) | |
N8B | 0.41667 (9) | 0.7352 (3) | 0.60987 (7) | 0.0335 (3) | |
H8B | 0.3747 (12) | 0.614 (4) | 0.5915 (10) | 0.057 (6)* | |
C9B | 0.48412 (11) | 0.8000 (3) | 0.57681 (9) | 0.0387 (4) | |
H9B | 0.5004 | 0.7153 | 0.5376 | 0.046* | |
C10B | 0.52452 (10) | 1.0078 (3) | 0.60954 (9) | 0.0385 (4) | |
H10B | 0.5739 | 1.0918 | 0.5976 | 0.046* | |
C11B | 0.47941 (10) | 1.0736 (3) | 0.66395 (8) | 0.0342 (4) | |
H11B | 0.4927 | 1.2109 | 0.6955 | 0.041* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1A | 0.0398 (8) | 0.0369 (8) | 0.0374 (7) | −0.0027 (6) | 0.0068 (6) | −0.0036 (6) |
C2A | 0.0307 (8) | 0.0378 (9) | 0.0341 (8) | 0.0008 (7) | 0.0064 (6) | −0.0003 (7) |
C3A | 0.0326 (8) | 0.0335 (9) | 0.0312 (8) | 0.0010 (7) | 0.0081 (6) | −0.0028 (7) |
C4A | 0.0317 (8) | 0.0362 (9) | 0.0273 (7) | −0.0002 (7) | 0.0098 (6) | 0.0019 (7) |
C5A | 0.0330 (8) | 0.0416 (10) | 0.0435 (9) | 0.0058 (7) | 0.0080 (7) | −0.0036 (8) |
C6A | 0.0464 (10) | 0.0359 (10) | 0.0465 (10) | 0.0016 (8) | 0.0120 (8) | −0.0081 (8) |
C7A | 0.0310 (8) | 0.0375 (9) | 0.0320 (8) | −0.0011 (7) | 0.0088 (6) | −0.0022 (7) |
N8A | 0.0307 (7) | 0.0407 (8) | 0.0322 (7) | −0.0007 (6) | 0.0075 (6) | −0.0034 (6) |
C9A | 0.0370 (9) | 0.0462 (10) | 0.0368 (9) | −0.0079 (8) | 0.0030 (7) | −0.0057 (8) |
C10A | 0.0294 (8) | 0.0605 (12) | 0.0553 (11) | −0.0045 (8) | 0.0053 (8) | −0.0081 (10) |
C11A | 0.0317 (9) | 0.0568 (12) | 0.0585 (11) | 0.0004 (8) | 0.0129 (8) | −0.0153 (10) |
N1B | 0.0360 (7) | 0.0435 (8) | 0.0352 (7) | 0.0003 (6) | 0.0106 (6) | 0.0025 (7) |
C2B | 0.0361 (8) | 0.0404 (10) | 0.0416 (9) | −0.0105 (7) | 0.0088 (7) | 0.0001 (8) |
C3B | 0.0370 (8) | 0.0338 (9) | 0.0334 (8) | −0.0064 (7) | 0.0077 (7) | −0.0058 (7) |
C4B | 0.0260 (7) | 0.0302 (8) | 0.0270 (7) | 0.0020 (6) | 0.0018 (6) | 0.0034 (6) |
C5B | 0.0341 (8) | 0.0321 (9) | 0.0375 (9) | −0.0040 (7) | 0.0078 (7) | −0.0034 (7) |
C6B | 0.0397 (9) | 0.0383 (10) | 0.0361 (9) | −0.0002 (7) | 0.0095 (7) | −0.0043 (7) |
C7B | 0.0293 (7) | 0.0284 (8) | 0.0264 (7) | 0.0003 (6) | 0.0016 (6) | 0.0006 (6) |
N8B | 0.0337 (7) | 0.0346 (8) | 0.0320 (7) | −0.0011 (6) | 0.0073 (6) | −0.0017 (6) |
C9B | 0.0358 (8) | 0.0487 (11) | 0.0335 (8) | 0.0060 (8) | 0.0121 (7) | 0.0030 (8) |
C10B | 0.0301 (8) | 0.0502 (11) | 0.0351 (9) | −0.0033 (7) | 0.0072 (7) | 0.0075 (8) |
C11B | 0.0302 (8) | 0.0382 (9) | 0.0311 (8) | −0.0054 (7) | 0.0014 (6) | 0.0017 (7) |
N1A—C2A | 1.335 (2) | N1B—C2B | 1.335 (2) |
N1A—C6A | 1.343 (2) | N1B—C6B | 1.341 (2) |
C2A—C3A | 1.382 (2) | C2B—C3B | 1.379 (2) |
C2A—H2A | 0.9500 | C2B—H2B | 0.9500 |
C3A—C4A | 1.402 (2) | C3B—C4B | 1.393 (2) |
C3A—H3A | 0.9500 | C3B—H3B | 0.9500 |
C4A—C5A | 1.391 (2) | C4B—C5B | 1.398 (2) |
C4A—C7A | 1.453 (2) | C4B—C7B | 1.458 (2) |
C5A—C6A | 1.372 (2) | C5B—C6B | 1.373 (2) |
C5A—H5A | 0.9500 | C5B—H5B | 0.9500 |
C6A—H6A | 0.9500 | C6B—H6B | 0.9500 |
C7A—N8A | 1.370 (2) | C7B—N8B | 1.377 (2) |
C7A—C11A | 1.384 (2) | C7B—C11B | 1.382 (2) |
N8A—C9A | 1.361 (2) | N8B—C9B | 1.362 (2) |
N8A—H8A | 0.931 (18) | N8B—H8B | 0.929 (19) |
C9A—C10A | 1.367 (2) | C9B—C10B | 1.369 (2) |
C9A—H9A | 0.9500 | C9B—H9B | 0.9500 |
C10A—C11A | 1.397 (2) | C10B—C11B | 1.403 (2) |
C10A—H10A | 0.9500 | C10B—H10B | 0.9500 |
C11A—H11A | 0.9500 | C11B—H11B | 0.9500 |
C2A—N1A—C6A | 115.60 (14) | C2B—N1B—C6B | 115.69 (14) |
N1A—C2A—C3A | 124.30 (14) | N1B—C2B—C3B | 124.57 (15) |
N1A—C2A—H2A | 117.8 | N1B—C2B—H2B | 117.7 |
C3A—C2A—H2A | 117.8 | C3B—C2B—H2B | 117.7 |
C2A—C3A—C4A | 119.64 (15) | C2B—C3B—C4B | 119.44 (15) |
C2A—C3A—H3A | 120.2 | C2B—C3B—H3B | 120.3 |
C4A—C3A—H3A | 120.2 | C4B—C3B—H3B | 120.3 |
C5A—C4A—C3A | 115.95 (14) | C3B—C4B—C5B | 116.31 (14) |
C5A—C4A—C7A | 120.99 (14) | C3B—C4B—C7B | 123.02 (14) |
C3A—C4A—C7A | 123.05 (14) | C5B—C4B—C7B | 120.61 (14) |
C6A—C5A—C4A | 120.18 (15) | C6B—C5B—C4B | 119.88 (15) |
C6A—C5A—H5A | 119.9 | C6B—C5B—H5B | 120.1 |
C4A—C5A—H5A | 119.9 | C4B—C5B—H5B | 120.1 |
N1A—C6A—C5A | 124.33 (16) | N1B—C6B—C5B | 124.11 (15) |
N1A—C6A—H6A | 117.8 | N1B—C6B—H6B | 117.9 |
C5A—C6A—H6A | 117.8 | C5B—C6B—H6B | 117.9 |
N8A—C7A—C11A | 106.56 (14) | N8B—C7B—C11B | 107.10 (13) |
N8A—C7A—C4A | 123.58 (14) | N8B—C7B—C4B | 122.87 (14) |
C11A—C7A—C4A | 129.83 (15) | C11B—C7B—C4B | 129.94 (14) |
C9A—N8A—C7A | 109.84 (14) | C9B—N8B—C7B | 109.24 (14) |
C9A—N8A—H8A | 124.4 (11) | C9B—N8B—H8B | 122.7 (12) |
C7A—N8A—H8A | 125.6 (11) | C7B—N8B—H8B | 127.1 (12) |
N8A—C9A—C10A | 108.11 (15) | N8B—C9B—C10B | 108.52 (15) |
N8A—C9A—H9A | 125.9 | N8B—C9B—H9B | 125.7 |
C10A—C9A—H9A | 125.9 | C10B—C9B—H9B | 125.7 |
C9A—C10A—C11A | 107.37 (15) | C9B—C10B—C11B | 107.30 (14) |
C9A—C10A—H10A | 126.3 | C9B—C10B—H10B | 126.3 |
C11A—C10A—H10A | 126.3 | C11B—C10B—H10B | 126.3 |
C7A—C11A—C10A | 108.12 (15) | C7B—C11B—C10B | 107.82 (14) |
C7A—C11A—H11A | 125.9 | C7B—C11B—H11B | 126.1 |
C10A—C11A—H11A | 125.9 | C10B—C11B—H11B | 126.1 |
C6A—N1A—C2A—C3A | −0.1 (2) | C6B—N1B—C2B—C3B | 0.4 (2) |
N1A—C2A—C3A—C4A | −0.7 (2) | N1B—C2B—C3B—C4B | −0.4 (3) |
C2A—C3A—C4A—C5A | 1.0 (2) | C2B—C3B—C4B—C5B | 0.0 (2) |
C2A—C3A—C4A—C7A | −177.77 (15) | C2B—C3B—C4B—C7B | 177.12 (14) |
C3A—C4A—C5A—C6A | −0.5 (2) | C3B—C4B—C5B—C6B | 0.4 (2) |
C7A—C4A—C5A—C6A | 178.31 (15) | C7B—C4B—C5B—C6B | −176.81 (14) |
C2A—N1A—C6A—C5A | 0.7 (2) | C2B—N1B—C6B—C5B | 0.1 (2) |
C4A—C5A—C6A—N1A | −0.4 (3) | C4B—C5B—C6B—N1B | −0.4 (2) |
C5A—C4A—C7A—N8A | 169.99 (15) | C3B—C4B—C7B—N8B | 1.5 (2) |
C3A—C4A—C7A—N8A | −11.3 (2) | C5B—C4B—C7B—N8B | 178.50 (14) |
C5A—C4A—C7A—C11A | −12.1 (3) | C3B—C4B—C7B—C11B | −174.60 (15) |
C3A—C4A—C7A—C11A | 166.58 (17) | C5B—C4B—C7B—C11B | 2.4 (2) |
C11A—C7A—N8A—C9A | 0.17 (18) | C11B—C7B—N8B—C9B | −0.78 (17) |
C4A—C7A—N8A—C9A | 178.48 (15) | C4B—C7B—N8B—C9B | −177.66 (13) |
C7A—N8A—C9A—C10A | −0.38 (19) | C7B—N8B—C9B—C10B | 0.92 (18) |
N8A—C9A—C10A—C11A | 0.4 (2) | N8B—C9B—C10B—C11B | −0.68 (18) |
N8A—C7A—C11A—C10A | 0.1 (2) | N8B—C7B—C11B—C10B | 0.35 (17) |
C4A—C7A—C11A—C10A | −178.07 (17) | C4B—C7B—C11B—C10B | 176.93 (14) |
C9A—C10A—C11A—C7A | −0.3 (2) | C9B—C10B—C11B—C7B | 0.20 (18) |
C9H8N2 | F(000) = 608 |
Mr = 144.17 | Dx = 1.287 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2761 reflections |
a = 5.1519 (13) Å | θ = 2.8–26.2° |
b = 19.739 (5) Å | µ = 0.08 mm−1 |
c = 14.694 (4) Å | T = 173 K |
β = 95.26 (1)° | Irregular, pale yellow |
V = 1488.0 (7) Å3 | 0.45 × 0.15 × 0.05 mm |
Z = 8 |
Siemens SMART area-detector diffractometer | 2920 independent reflections |
Radiation source: fine-focus sealed tube | 1985 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
ω scans | θmax = 26.0°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995) | h = −6→6 |
Tmin = 0.98, Tmax = 1.00 | k = −21→24 |
8607 measured reflections | l = −18→14 |
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)] = 0.058 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.111 | w = 1/[σ2(Fo2) + (0.034P)2 + 0.258P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.002 |
2920 reflections | Δρmax = 0.15 e Å−3 |
227 parameters | Δρmin = −0.12 e Å−3 |
12 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0059 (13) |
C9H8N2 | V = 1488.0 (7) Å3 |
Mr = 144.17 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.1519 (13) Å | µ = 0.08 mm−1 |
b = 19.739 (5) Å | T = 173 K |
c = 14.694 (4) Å | 0.45 × 0.15 × 0.05 mm |
β = 95.26 (1)° |
Siemens SMART area-detector diffractometer | 2920 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995) | 1985 reflections with I > 2σ(I) |
Tmin = 0.98, Tmax = 1.00 | Rint = 0.042 |
8607 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 12 restraints |
wR(F2) = 0.111 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | Δρmax = 0.15 e Å−3 |
2920 reflections | Δρmin = −0.12 e Å−3 |
227 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
N1A | 0.559 (4) | 0.3845 (15) | 0.3992 (5) | 0.046 (3) | 0.525 (7) |
C2A | 0.4897 (15) | 0.4178 (4) | 0.4718 (5) | 0.0510 (15) | 0.525 (7) |
H2A | 0.3639 | 0.4529 | 0.4618 | 0.061* | 0.525 (7) |
C3A | 0.5876 (16) | 0.4051 (4) | 0.5606 (5) | 0.0489 (16) | 0.525 (7) |
H3A | 0.5355 | 0.4324 | 0.6089 | 0.059* | 0.525 (7) |
C4A | 0.763 (6) | 0.3520 (19) | 0.5797 (7) | 0.0395 (15) | 0.525 (7) |
C5A | 0.832 (2) | 0.3153 (6) | 0.5038 (10) | 0.050 (3) | 0.525 (7) |
H5A | 0.9520 | 0.2788 | 0.5119 | 0.060* | 0.525 (7) |
C6A | 0.725 (3) | 0.3324 (9) | 0.4178 (8) | 0.056 (3) | 0.525 (7) |
H6A | 0.7710 | 0.3057 | 0.3679 | 0.067* | 0.525 (7) |
N1A' | 0.540 (5) | 0.3729 (16) | 0.3969 (6) | 0.046 (3) | 0.475 (7) |
C2A' | 0.4238 (17) | 0.3930 (4) | 0.4694 (6) | 0.0510 (15) | 0.475 (7) |
H2A' | 0.2637 | 0.4169 | 0.4588 | 0.061* | 0.475 (7) |
C3A' | 0.5191 (18) | 0.3817 (5) | 0.5589 (6) | 0.0489 (16) | 0.475 (7) |
H3A' | 0.4237 | 0.3970 | 0.6073 | 0.059* | 0.475 (7) |
C4A' | 0.755 (7) | 0.348 (2) | 0.5784 (8) | 0.0395 (15) | 0.475 (7) |
C5A' | 0.887 (2) | 0.3297 (7) | 0.5025 (11) | 0.050 (3) | 0.475 (7) |
H5A' | 1.0513 | 0.3078 | 0.5110 | 0.060* | 0.475 (7) |
C6A' | 0.776 (3) | 0.3435 (10) | 0.4159 (9) | 0.056 (3) | 0.475 (7) |
H6A' | 0.8709 | 0.3315 | 0.3660 | 0.067* | 0.475 (7) |
C7A | 0.8633 (4) | 0.33406 (9) | 0.67166 (13) | 0.0393 (5) | |
N8A | 0.7479 (3) | 0.35683 (9) | 0.74647 (11) | 0.0444 (4) | |
H8A | 0.612 (4) | 0.3867 (11) | 0.7484 (13) | 0.056 (6)* | |
C9A | 0.8816 (4) | 0.33289 (11) | 0.82370 (14) | 0.0512 (6) | |
H9A | 0.8412 | 0.3415 | 0.8844 | 0.061* | |
C10A | 1.0844 (4) | 0.29430 (11) | 0.79918 (14) | 0.0536 (6) | |
H10A | 1.2097 | 0.2714 | 0.8395 | 0.064* | |
C11A | 1.0730 (4) | 0.29477 (10) | 0.70346 (14) | 0.0484 (5) | |
H11A | 1.1891 | 0.2721 | 0.6671 | 0.058* | |
N1B | 0.3322 (3) | 0.45933 (8) | 0.76455 (11) | 0.0455 (4) | |
C2B | 0.1425 (4) | 0.48763 (10) | 0.70906 (14) | 0.0465 (5) | |
H2B | 0.1323 | 0.4760 | 0.6461 | 0.056* | |
C3B | −0.0396 (4) | 0.53260 (10) | 0.73675 (13) | 0.0440 (5) | |
H3B | −0.1703 | 0.5504 | 0.6934 | 0.053* | |
C4B | −0.0322 (3) | 0.55191 (9) | 0.82781 (12) | 0.0372 (5) | |
C5B | 0.1636 (4) | 0.52192 (10) | 0.88640 (13) | 0.0446 (5) | |
H5B | 0.1777 | 0.5322 | 0.9498 | 0.054* | |
C6B | 0.3359 (4) | 0.47750 (10) | 0.85222 (14) | 0.0465 (5) | |
H6B | 0.4673 | 0.4583 | 0.8940 | 0.056* | |
C7B | −0.2144 (4) | 0.60047 (9) | 0.86040 (12) | 0.0381 (5) | |
N8B | −0.4080 (3) | 0.63014 (8) | 0.80317 (11) | 0.0402 (4) | |
H8B | −0.447 (4) | 0.6232 (9) | 0.7393 (13) | 0.049 (6)* | |
C9B | −0.5502 (4) | 0.67238 (10) | 0.85214 (14) | 0.0465 (5) | |
H9B | −0.6957 | 0.6985 | 0.8284 | 0.056* | |
C10B | −0.4484 (4) | 0.67091 (11) | 0.94137 (15) | 0.0529 (6) | |
H10B | −0.5093 | 0.6958 | 0.9905 | 0.063* | |
C11B | −0.2371 (4) | 0.62571 (10) | 0.94692 (13) | 0.0477 (5) | |
H11B | −0.1289 | 0.6145 | 1.0007 | 0.057* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1A | 0.054 (3) | 0.036 (8) | 0.0480 (11) | −0.003 (5) | 0.0045 (10) | −0.0035 (13) |
C2A | 0.051 (3) | 0.048 (4) | 0.0532 (16) | 0.009 (3) | 0.003 (2) | 0.000 (3) |
C3A | 0.047 (4) | 0.053 (5) | 0.0469 (14) | 0.010 (3) | 0.003 (2) | −0.003 (3) |
C4A | 0.0388 (17) | 0.030 (3) | 0.0497 (12) | −0.005 (2) | 0.0030 (10) | −0.0004 (11) |
C5A | 0.053 (4) | 0.042 (5) | 0.0563 (16) | 0.009 (4) | 0.006 (3) | −0.003 (3) |
C6A | 0.065 (5) | 0.050 (5) | 0.0518 (15) | 0.010 (5) | 0.009 (2) | −0.006 (2) |
N1A' | 0.054 (3) | 0.036 (8) | 0.0480 (11) | −0.003 (5) | 0.0045 (10) | −0.0035 (13) |
C2A' | 0.051 (3) | 0.048 (4) | 0.0532 (16) | 0.009 (3) | 0.003 (2) | 0.000 (3) |
C3A' | 0.047 (4) | 0.053 (5) | 0.0469 (14) | 0.010 (3) | 0.003 (2) | −0.003 (3) |
C4A' | 0.0388 (17) | 0.030 (3) | 0.0497 (12) | −0.005 (2) | 0.0030 (10) | −0.0004 (11) |
C5A' | 0.053 (4) | 0.042 (5) | 0.0563 (16) | 0.009 (4) | 0.006 (3) | −0.003 (3) |
C6A' | 0.065 (5) | 0.050 (5) | 0.0518 (15) | 0.010 (5) | 0.009 (2) | −0.006 (2) |
C7A | 0.0388 (11) | 0.0318 (11) | 0.0471 (12) | −0.0019 (9) | 0.0026 (9) | −0.0013 (9) |
N8A | 0.0437 (10) | 0.0438 (11) | 0.0453 (10) | 0.0009 (9) | 0.0024 (8) | 0.0032 (8) |
C9A | 0.0501 (13) | 0.0549 (14) | 0.0475 (13) | −0.0066 (11) | −0.0016 (10) | 0.0082 (10) |
C10A | 0.0484 (13) | 0.0487 (13) | 0.0613 (15) | −0.0026 (11) | −0.0087 (11) | 0.0132 (11) |
C11A | 0.0441 (12) | 0.0384 (12) | 0.0620 (14) | 0.0026 (10) | 0.0017 (10) | 0.0021 (10) |
N1B | 0.0419 (10) | 0.0415 (10) | 0.0533 (11) | −0.0023 (8) | 0.0047 (8) | 0.0028 (8) |
C2B | 0.0476 (12) | 0.0453 (13) | 0.0467 (12) | −0.0022 (11) | 0.0045 (10) | −0.0039 (10) |
C3B | 0.0415 (12) | 0.0464 (12) | 0.0440 (12) | 0.0032 (10) | 0.0022 (9) | −0.0003 (9) |
C4B | 0.0353 (11) | 0.0347 (11) | 0.0417 (11) | −0.0077 (9) | 0.0040 (9) | 0.0011 (8) |
C5B | 0.0451 (12) | 0.0462 (13) | 0.0425 (12) | −0.0027 (10) | 0.0043 (9) | 0.0025 (9) |
C6B | 0.0416 (12) | 0.0475 (13) | 0.0501 (13) | −0.0014 (10) | 0.0024 (10) | 0.0073 (10) |
C7B | 0.0366 (11) | 0.0354 (11) | 0.0422 (11) | −0.0068 (9) | 0.0029 (9) | −0.0006 (9) |
N8B | 0.0410 (10) | 0.0362 (10) | 0.0437 (10) | −0.0023 (8) | 0.0054 (8) | −0.0021 (8) |
C9B | 0.0464 (12) | 0.0380 (12) | 0.0566 (14) | 0.0017 (10) | 0.0123 (10) | −0.0016 (10) |
C10B | 0.0584 (14) | 0.0446 (13) | 0.0579 (14) | −0.0054 (11) | 0.0176 (11) | −0.0096 (11) |
C11B | 0.0504 (13) | 0.0487 (13) | 0.0441 (12) | −0.0085 (11) | 0.0050 (10) | −0.0023 (10) |
N1A—C2A | 1.331 (6) | C9A—C10A | 1.368 (3) |
N1A—C6A | 1.349 (9) | C9A—H9A | 0.9500 |
C2A—C3A | 1.378 (3) | C10A—C11A | 1.402 (3) |
C2A—H2A | 0.9500 | C10A—H10A | 0.9500 |
C3A—C4A | 1.394 (9) | C11A—H11A | 0.9500 |
C3A—H3A | 0.9500 | N1B—C6B | 1.336 (2) |
C4A—C5A | 1.403 (9) | N1B—C2B | 1.336 (2) |
C4A—C7A | 1.447 (9) | C2B—C3B | 1.380 (3) |
C5A—C6A | 1.374 (3) | C2B—H2B | 0.9500 |
C5A—H5A | 0.9500 | C3B—C4B | 1.388 (2) |
C6A—H6A | 0.9500 | C3B—H3B | 0.9500 |
N1A'—C2A' | 1.331 (5) | C4B—C5B | 1.396 (3) |
N1A'—C6A' | 1.349 (10) | C4B—C7B | 1.453 (3) |
C2A'—C3A' | 1.378 (3) | C5B—C6B | 1.375 (3) |
C2A'—H2A' | 0.9500 | C5B—H5B | 0.9500 |
C3A'—C4A' | 1.394 (9) | C6B—H6B | 0.9500 |
C3A'—H3A' | 0.9500 | C7B—N8B | 1.375 (2) |
C4A'—C5A' | 1.403 (9) | C7B—C11B | 1.380 (3) |
C5A'—C6A' | 1.374 (3) | N8B—C9B | 1.358 (2) |
C5A'—H5A' | 0.9500 | N8B—H8B | 0.952 (19) |
C6A'—H6A' | 0.9500 | C9B—C10B | 1.367 (3) |
C7A—N8A | 1.372 (2) | C9B—H9B | 0.9500 |
C7A—C11A | 1.377 (3) | C10B—C11B | 1.404 (3) |
N8A—C9A | 1.357 (2) | C10B—H10B | 0.9500 |
N8A—H8A | 0.92 (2) | C11B—H11B | 0.9500 |
C2A—N1A—C6A | 115.2 (3) | C10A—C9A—H9A | 125.8 |
N1A—C2A—C3A | 124.6 (3) | C9A—C10A—C11A | 107.33 (18) |
N1A—C2A—H2A | 117.7 | C9A—C10A—H10A | 126.3 |
C3A—C2A—H2A | 117.7 | C11A—C10A—H10A | 126.3 |
C2A—C3A—C4A | 120.1 (3) | C7A—C11A—C10A | 107.66 (19) |
C2A—C3A—H3A | 119.9 | C7A—C11A—H11A | 126.2 |
C4A—C3A—H3A | 119.9 | C10A—C11A—H11A | 126.2 |
C3A—C4A—C5A | 115.8 (2) | C6B—N1B—C2B | 114.92 (17) |
C3A—C4A—C7A | 122.8 (9) | N1B—C2B—C3B | 124.61 (19) |
C5A—C4A—C7A | 121.4 (11) | N1B—C2B—H2B | 117.7 |
C6A—C5A—C4A | 119.6 (4) | C3B—C2B—H2B | 117.7 |
C6A—C5A—H5A | 120.2 | C2B—C3B—C4B | 120.09 (18) |
C4A—C5A—H5A | 120.2 | C2B—C3B—H3B | 120.0 |
N1A—C6A—C5A | 124.5 (5) | C4B—C3B—H3B | 120.0 |
N1A—C6A—H6A | 117.7 | C3B—C4B—C5B | 115.61 (18) |
C5A—C6A—H6A | 117.7 | C3B—C4B—C7B | 122.49 (17) |
C2A'—N1A'—C6A' | 115.2 (3) | C5B—C4B—C7B | 121.89 (17) |
N1A'—C2A'—C3A' | 124.6 (3) | C6B—C5B—C4B | 119.95 (18) |
N1A'—C2A'—H2A' | 117.7 | C6B—C5B—H5B | 120.0 |
C3A'—C2A'—H2A' | 117.7 | C4B—C5B—H5B | 120.0 |
C2A'—C3A'—C4A' | 120.1 (3) | N1B—C6B—C5B | 124.80 (19) |
C2A'—C3A'—H3A' | 119.9 | N1B—C6B—H6B | 117.6 |
C4A'—C3A'—H3A' | 119.9 | C5B—C6B—H6B | 117.6 |
C3A'—C4A'—C5A' | 115.8 (2) | N8B—C7B—C11B | 106.94 (17) |
C6A'—C5A'—C4A' | 119.6 (5) | N8B—C7B—C4B | 122.25 (16) |
C6A'—C5A'—H5A' | 120.2 | C11B—C7B—C4B | 130.81 (18) |
C4A'—C5A'—H5A' | 120.2 | C9B—N8B—C7B | 109.49 (16) |
N1A'—C6A'—C5A' | 124.5 (5) | C9B—N8B—H8B | 122.5 (12) |
N1A'—C6A'—H6A' | 117.7 | C7B—N8B—H8B | 128.0 (12) |
C5A'—C6A'—H6A' | 117.7 | N8B—C9B—C10B | 108.48 (19) |
N8A—C7A—C11A | 107.27 (17) | N8B—C9B—H9B | 125.8 |
N8A—C7A—C4A | 121.6 (5) | C10B—C9B—H9B | 125.8 |
C11A—C7A—C4A | 131.1 (5) | C9B—C10B—C11B | 107.24 (19) |
C9A—N8A—C7A | 109.38 (18) | C9B—C10B—H10B | 126.4 |
C9A—N8A—H8A | 121.8 (12) | C11B—C10B—H10B | 126.4 |
C7A—N8A—H8A | 128.5 (12) | C7B—C11B—C10B | 107.86 (18) |
N8A—C9A—C10A | 108.36 (19) | C7B—C11B—H11B | 126.1 |
N8A—C9A—H9A | 125.8 | C10B—C11B—H11B | 126.1 |
C6A—N1A—C2A—C3A | 4 (3) | N8A—C7A—C11A—C10A | −0.3 (2) |
N1A—C2A—C3A—C4A | −3 (3) | C4A—C7A—C11A—C10A | 180 (2) |
C2A—C3A—C4A—C5A | 1 (4) | C9A—C10A—C11A—C7A | 0.3 (2) |
C2A—C3A—C4A—C7A | −177 (2) | C6B—N1B—C2B—C3B | 0.2 (3) |
C3A—C4A—C5A—C6A | −1 (4) | N1B—C2B—C3B—C4B | 0.6 (3) |
C7A—C4A—C5A—C6A | 178 (3) | C2B—C3B—C4B—C5B | −1.3 (3) |
C2A—N1A—C6A—C5A | −4 (4) | C2B—C3B—C4B—C7B | 178.26 (18) |
C4A—C5A—C6A—N1A | 2 (4) | C3B—C4B—C5B—C6B | 1.2 (3) |
C6A'—N1A'—C2A'—C3A' | −4 (4) | C7B—C4B—C5B—C6B | −178.35 (18) |
N1A'—C2A'—C3A'—C4A' | 1 (3) | C2B—N1B—C6B—C5B | −0.3 (3) |
C2A'—C3A'—C4A'—C5A' | 2 (5) | C4B—C5B—C6B—N1B | −0.4 (3) |
C3A'—C4A'—C5A'—C6A' | −2 (5) | C3B—C4B—C7B—N8B | 0.6 (3) |
C2A'—N1A'—C6A'—C5A' | 5 (4) | C5B—C4B—C7B—N8B | −179.88 (17) |
C4A'—C5A'—C6A'—N1A' | −2 (4) | C3B—C4B—C7B—C11B | −179.8 (2) |
C3A—C4A—C7A—N8A | 16 (5) | C5B—C4B—C7B—C11B | −0.3 (3) |
C5A—C4A—C7A—N8A | −162 (2) | C11B—C7B—N8B—C9B | −0.5 (2) |
C3A—C4A—C7A—C11A | −164.1 (19) | C4B—C7B—N8B—C9B | 179.16 (17) |
C5A—C4A—C7A—C11A | 18 (5) | C7B—N8B—C9B—C10B | 0.5 (2) |
C11A—C7A—N8A—C9A | 0.3 (2) | N8B—C9B—C10B—C11B | −0.3 (2) |
C4A—C7A—N8A—C9A | −180 (2) | N8B—C7B—C11B—C10B | 0.3 (2) |
C7A—N8A—C9A—C10A | −0.1 (2) | C4B—C7B—C11B—C10B | −179.33 (19) |
N8A—C9A—C10A—C11A | −0.1 (2) | C9B—C10B—C11B—C7B | 0.0 (2) |
Experimental details
(I) | (II) | (IIIA) | (IIIB) | |
Crystal data | ||||
Chemical formula | C9H8N2 | C9H8N2 | C9H8N2 | C9H8N2 |
Mr | 144.17 | 144.17 | 144.17 | 144.17 |
Crystal system, space group | Tetragonal, P43212 | Monoclinic, P21/n | Monoclinic, P21/n | Monoclinic, P21/c |
Temperature (K) | 173 | 174 | 173 | 173 |
a, b, c (Å) | 8.123 (2), 8.123 (2), 23.502 (6) | 5.3537 (13), 11.654 (3), 11.990 (3) | 7.402 (2), 11.480 (3), 17.705 (4) | 15.139 (4), 5.4945 (14), 18.736 (5) |
α, β, γ (°) | 90, 90, 90 | 90, 98.10 (1), 90 | 90, 96.23 (1), 90 | 90, 103.76 (1), 90 |
V (Å3) | 1550.7 (7) | 740.6 (3) | 1495.6 (7) | 1513.8 (7) |
Z | 8 | 4 | 8 | 8 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.08 | 0.08 | 0.08 |
Crystal size (mm) | 0.50 × 0.20 × 0.20 | 0.35 × 0.15 × 0.05 | 0.50 × 0.10 × 0.06 | 0.50 × 0.05 × 0.05 |
Data collection | ||||
Diffractometer | Siemens SMART area-detector diffractometer | Siemens SMART area-detector diffractometer | Siemens SMART area-detector diffractometer | Siemens SMART area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995) | Multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995) | Multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995) | Multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995) |
Tmin, Tmax | 0.97, 0.99 | 0.97, 0.99 | 0.97, 0.99 | 0.98, 1.00 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18079, 1115, 1052 | 4676, 1681, 1232 | 9224, 3412, 1933 | 14309, 3452, 2385 |
Rint | 0.048 | 0.030 | 0.052 | 0.049 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 | 0.649 | 0.650 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.100, 1.16 | 0.044, 0.114, 1.02 | 0.047, 0.118, 0.92 | 0.047, 0.098, 1.03 |
No. of reflections | 1115 | 1681 | 3412 | 3452 |
No. of parameters | 104 | 105 | 208 | 207 |
No. of restraints | 0 | 0 | 0 | 0 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.13, −0.16 | 0.19, −0.17 | 0.22, −0.21 | 0.21, −0.17 |
(IIIC) | |
Crystal data | |
Chemical formula | C9H8N2 |
Mr | 144.17 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 5.1519 (13), 19.739 (5), 14.694 (4) |
α, β, γ (°) | 90, 95.26 (1), 90 |
V (Å3) | 1488.0 (7) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.45 × 0.15 × 0.05 |
Data collection | |
Diffractometer | Siemens SMART area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995) |
Tmin, Tmax | 0.98, 1.00 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8607, 2920, 1985 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.111, 1.09 |
No. of reflections | 2920 |
No. of parameters | 227 |
No. of restraints | 12 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.15, −0.12 |
Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL.
D | A | D—H | D—H···A | H···A | D···A | |
(I) | N8 | N1i | 0.91 | 163 | 2.06 | 2.949 |
(II) | N8 | N1ii | 0.93 | 169 | 1.99 | 2.901 |
(IIIA) | N8A | N1B | 0.97 | 171 | 1.95 | 2.913 |
(IIIA) | N8B | N1iii | 0.93 | 161 | 2.03 | 2.920 |
(IIIB) | N8A | N1Biv | 0.96 | 168 | 1.94 | 2.891 |
(IIIB) | N8B | N1A | 0.95 | 167 | 1.99 | 2.920 |
(IIIC) | N8A | N1B | 0.91 | 174 | 2.07 | 2.976 |
(IIIC) | N8B | N1Av | 0.95 | 174 | 2.08 | 3.021 |
(IIIC) | N8B | N1A'v | 0.95 | 169 | 2.02 | 2.956 |
The s.u. values are N8—H and H.·N1 0.02 Å, N8—H···N1 1° and N8···N1 0.002–0.003 Å. Symmetry codes: (i) 1 − y, 1 − x, 1/2 − z; (ii) −1/2 + x, 1/2 − y, −1/2 + z; (iii) x, −1 + y, z; (iv) x, 1/2 − y, −1/2 + z; (v) −x, 1 − y, 1 − z. |
Pyrroles and other simple heteroaromatic nuclei are of interest in biology and medicine, and are used widely as ligands for transition metal complexes, including porphyrins and synthetic analogs (Klappa et al., 2002). Polypyrroles are of interest as conducting polymers (Wilson, 1997; de Jesus, 1996; Kanatzidis, 1990). We became interested in the (1H-pyrrol-2-yl)pyridines substituted in the ortho, (I), meta, (II), and para, (III), positions with respect to the N atom of the pyridine nucleus. We report here the crystal structures of (I), (II), and three polymorphs (III), viz. (IIIA), (IIIB) and (IIIC). In all three polymorphs, there are two molecules in the asymmetric unit.
The atomic labelling and the anisotropic displacement ellipsoids for the five structures are shown as part of the packing diagrams in Figs. 1–5. The bond lengths and angles are normal, and vary slightly in the pyridine rings, depending, in a reasonable way, on the point of attachment of the pyrrole ring. They agreed, within experimental error, in all eight determinations of the pyrrole-ring geometry.
The rings were all planar, with dihedral angles between the rings in (I) of 12.1 (2) and 5.0 (2)°, and between the rings in (IIIC) of 16.8 (5) and 8.3 (5)° for the two orientations of the disordered ring and 0.8 (2)° for the other. The disordered rings in (IIIC) are tilted in opposite directions to the plane of the pyrrole ring.
In all five structures, the molecules are held together by N8—H···N1 hydrogen bonds. The metrical parameters for these bonds are given in Table 1. A l l of the N—H···N bonds are close to linear and of average length.
In (I), there is an intramolecular N8—H···N1 contact, with N—H···N = 93°, H···N = 2.06 Å, and N···N = 2.786(?)Å. Although the N···N distance in this contact is shorter than the intermolecular N···N distances in all of the compounds, the geometry of the arrangement, with an N—H···N angle of 93°, suggests that it is less important. The intermolecular hydrogen-bond arrangement is shown in Fig. 1. Two molecules form a dimer across a twofold axis. In graph-set notation (Etter et al., 1990), this is an R22(10) arrangement.
The hydrogen bonding in (II) is shown in Fig. 2. There are chains, graph set C(6), lying along the [101] direction, with the molecules related by the n glide.
The hydrogen bonding in polymorph A of (III) is shown in Fig. 3. There are chains, graph set C(7), parallel to the b axis alternating between the crystallographically independent A and B molecules. The A and B molecules are not related by any pseudosymmetry. Pairs of molecules in the chain are related by translation along b. Although the molecules are crystallographically independent, there is no significant difference in their hydrogen-bonding behavior.
The hydrogen bonding in polymorph B of (III) is shown in Fig. 4. There are chains, graph set C(7), parallel to the c axis alternating between the crystallographically independent A and B molecules. As in polymorph A, there is no pseudosymmetry relating the two independent molecules and no significant difference in their hydrogen-bonding behavior. Adjacent pairs of A and B molecules in the chain are related by the c glide.
The bonding in polymorph C of (III) is shown in Fig. 5. There are four-membered rings, graph set R44(28), surrounding a center of symmetry, with alternating crystallographically independent A and B molecules. As a consequence of the molecular ring, the A and B molecules are related by a pseudo-fourfold symmetry axis, but this does not lead to more extended pseudosymmetry.
A comparison of the cell volumes of (IIIA), (IIIB), and (IIIC) [1495.6 (7), 1513.8 (7), and 1488.0 (7) Å3, respectively] suggests that the (IIIC) form is the most stable at low temperature and the (IIIB) form the least stable at low temperature (Dunitz, 1995).