Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109025165/fg3095sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109025165/fg3095Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109025165/fg3095IIsup3.hkl |
CCDC references: 746088; 746089
1-H-Phenanthro[9,10-d]imidazole, (I), was prepared according to the procedure of Steck & Day (1943). Into a 250 ml round-bottomed flask, phenanthroquinone (2.08 g, 9.99 mmol), hexamethylenetetramine (2.80 g, 20.0 mmol) and ammonium acetate (15.5 g) were placed. The solids were suspended in glacial acetic acid and refluxed for 1 h. The mixture was cooled and neutralized with concentrated ammonium hydroxide, followed by the addition of water to precipitate the product fully. The product was collected by filtration, washed with water and dried to constant weight in a vacuum oven to give the product as an off-white solid (yield 2.01 g, 92.2%; m.p. 564 K). Analysis: C15H10N2, Mr = 218.25; 1H NMR (400 MHz, CD3SOCD3, 298 K, δ, p.p.m.): 8.86 (br m, 2H), 8.51 (br m, 2H), 8.37 (s, 1H), 7.72 (br m, 2H), 7.64 (br m, 2H); 13C NMR (CD3SOCD3, δ, p.p.m.): 139.6, 136.2, 127.9, 127.8, 127.4, 125.4, 124.3, 122.0; Rf = 0.38 (ethyl acetate/silica). Single crystals of (I) were obtained by slow evaporation of a dimethylsulfoxide (DMSO) solution of the compound (m.p. 581 K).
Crystals of 3,6-dibromo-1-H-phenanthro[9,10-d]imidazole hemihydrate, (II), were prepared by following a procedure similar to that for (I). Into a 250 ml round-bottomed flask, 3,6-dibromophenanthro-9,10-quinone (2.08 g, 5.68 mmol) (Schmidt & Eitel, 1932; Bhatt, 1964), hexamethylenetetramine (1.59 g, 11.34 mmol) and ammonium acetate (14.0 g) were placed. The solids were suspended in glacial acetic acid and refluxed for 1 h. The mixture was cooled and neutralized with concentrated ammonium hydroxide, followed by the addition of water to precipitate the product fully. The product was collected by filtration, washed with water and dried to constant weight in a vacuum oven to give anhydrous (II) as a pale-gray solid (yield 2.02 g, 94.4%; m.p. 546 K). Analysis: C15H8Br2N2, Mr = 376.91; 1H NMR (400 MHz, 323 K, CD3SOCD3, δ, p.p.m.): 8.85 (s, 2H), 8.19 (d, J = 6.4 Hz, 2H), 8.04 (s, 1H), 7.78 (dd, J = 1.8 and 8.6 Hz, 2H); 13C NMR (CD3SOCD3, 323 K, δ, p.p.m.): 139.7, 139.5, 130.6, 128.6, 126.7, 124.3, 119.1. Rf = 0.37 (ethyl acetate/silica). Single crystals of (II) were obtained by slow evaporation of a DMSO solution of of the compound [m.p. 453 K (opaque), 572 K (soften), 583 K (melt)]. The hemihydrate formed owing to the adventitious presence of water in the DMSO solvent.
C-bound H atoms were positioned geometrically using a riding model, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). The H atoms of the water molecule in (II) were located in a difference Fourier map and were allowed to refine with O—H distance restraints.
Friedel pairs in structure (I) were merged. Disordered atoms H11 and H43 (Fig. 1), which participate in the N—H···N hydrogen bonds, were located in a difference Fourier map. Their occupancy factors were constrained to add to unity and refined to 0.60 (3) and 0.40 (3). Refinement of the two-site model reduced the weighted R factor, wRF2(all), from 0.116 for the one-site model to 0.112. In several other structures containing benzimidazole units incapable of forming hydrogen bonds, residuals (Q-peaks) were located 0.44 to 0.88 Å from the N(imine) atoms and in the planes of the imidazole rings, and were refined for comparison with the present structure. Refinement as H atoms decreased the R factors in some instances and increased them in others. In imidazole-containing structures, approximate differences between the C2—N(amine) and C2—N(imine) bond lengths are 0.04 Å for systems with no amine–imine hydrogen bonding, while for dialkyl-substituted imidazolium ions, there is essentially no difference within experimental error. In the present structure, the difference is 0.020 Å, which is not inconsistent with the two-site disordered model described above. Taken together, these data provide moderate support for the disordered/twinned model.
For both compounds, data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-32 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
C15H10N2 | Dx = 1.426 Mg m−3 |
Mr = 218.25 | Melting point: 581 K |
Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2n | Cell parameters from 966 reflections |
a = 19.559 (3) Å | θ = 2.9–25.0° |
b = 5.2321 (8) Å | µ = 0.09 mm−1 |
c = 19.871 (3) Å | T = 298 K |
V = 2033.5 (5) Å3 | Plate, pale-brown |
Z = 8 | 0.47 × 0.37 × 0.10 mm |
F(000) = 912 |
Bruker SMART CCD area-detector diffractometer | 2095 independent reflections |
Radiation source: sealed tube | 1803 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
ϕ and ω scans | θmax = 26.1°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Blessing, 1995) | h = −23→24 |
Tmin = 0.856, Tmax = 1.000 | k = −6→6 |
18138 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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.076P)2 + 0.260P] where P = (Fo2 + 2Fc2)/3 |
2095 reflections | (Δ/σ)max < 0.001 |
308 parameters | Δρmax = 0.22 e Å−3 |
1 restraint | Δρmin = −0.12 e Å−3 |
C15H10N2 | V = 2033.5 (5) Å3 |
Mr = 218.25 | Z = 8 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 19.559 (3) Å | µ = 0.09 mm−1 |
b = 5.2321 (8) Å | T = 298 K |
c = 19.871 (3) Å | 0.47 × 0.37 × 0.10 mm |
Bruker SMART CCD area-detector diffractometer | 2095 independent reflections |
Absorption correction: multi-scan (SADABS; Blessing, 1995) | 1803 reflections with I > 2σ(I) |
Tmin = 0.856, Tmax = 1.000 | Rint = 0.035 |
18138 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 1 restraint |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.22 e Å−3 |
2095 reflections | Δρmin = −0.12 e Å−3 |
308 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. Friedel pairs in structure (I) were merged. Disordered atoms H11 and H43 (Fig. 1), which participate in the N—H···N hydrogen bonds, were located in a difference Fourier map. Their occupancy factors were constrained to add to unity and refined to 0.60 (3) and 0.40 (3). Refinement of the two-site model reduced the weighted R factor, wRF2(all), from 0.116 for the one-site model to 0.112. In several other structures containing benzimidazole units incapable of forming hydrogen bonds, residuals (Q-peaks) were located 0.44 to 0.88 Å from the N(imine) atoms and in the planes of the imidazole rings, and were refined for comparison with the present structure. Refinement as H atoms decreased the R factors in some instances and increased them in others. In imidazole-containing structures, approximate differences between the C2—N(amine) and C2—N(imine) bond lengths are 0.04 Å for systems with no amine–imine hydrogen bonding, while for dialkyl-substituted imidazolium ions, there is essentially no difference within experimental error. In the present structure, the difference is 0.020 Å, which is not inconsistent with the two-site disordered model described above. Taken together, these data provide moderate support for the disordered/twinned model. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
N11 | 0.14125 (13) | 0.4788 (5) | 0.17659 (14) | 0.0430 (6) | |
H11 | 0.1836 | 0.4700 | 0.1878 | 0.052* | 0.60 (3) |
N13 | 0.02974 (13) | 0.3877 (5) | 0.17243 (14) | 0.0444 (6) | |
H13 | −0.0089 | 0.3148 | 0.1801 | 0.053* | 0.40 (3) |
C11 | 0.11102 (13) | 0.6514 (6) | 0.13345 (15) | 0.0370 (6) | |
C12 | 0.08998 (15) | 0.3276 (6) | 0.19714 (17) | 0.0461 (7) | |
H12 | 0.0965 | 0.1913 | 0.2265 | 0.055* | |
C13 | 0.04282 (15) | 0.5965 (6) | 0.13091 (16) | 0.0385 (7) | |
C14 | −0.00325 (16) | 0.7413 (6) | 0.08938 (15) | 0.0402 (7) | |
C15 | 0.02497 (16) | 0.9427 (6) | 0.05082 (17) | 0.0418 (7) | |
C16 | 0.09839 (16) | 0.9970 (6) | 0.05263 (16) | 0.0409 (7) | |
C17 | 0.14227 (15) | 0.8501 (6) | 0.09424 (16) | 0.0376 (7) | |
C21 | −0.01985 (17) | 1.0895 (6) | 0.01158 (18) | 0.0483 (8) | |
H21 | −0.0026 | 1.2243 | −0.0137 | 0.058* | |
C22 | −0.08843 (18) | 1.0389 (7) | 0.0097 (2) | 0.0555 (9) | |
H22 | −0.1170 | 1.1391 | −0.0169 | 0.067* | |
C23 | −0.11560 (17) | 0.8415 (7) | 0.0467 (2) | 0.0555 (9) | |
H23 | −0.1623 | 0.8079 | 0.0449 | 0.067* | |
C24 | −0.07379 (16) | 0.6944 (7) | 0.08605 (17) | 0.0479 (8) | |
H24 | −0.0924 | 0.5613 | 0.1110 | 0.057* | |
C31 | 0.12841 (18) | 1.1899 (6) | 0.01361 (18) | 0.0480 (8) | |
H31 | 0.1009 | 1.2888 | −0.0143 | 0.058* | |
C32 | 0.19750 (18) | 1.2364 (7) | 0.01560 (18) | 0.0518 (8) | |
H32 | 0.2160 | 1.3649 | −0.0111 | 0.062* | |
C33 | 0.23962 (17) | 1.0944 (7) | 0.05677 (19) | 0.0521 (9) | |
H33 | 0.2862 | 1.1288 | 0.0581 | 0.062* | |
C34 | 0.21293 (15) | 0.9026 (7) | 0.09573 (17) | 0.0469 (8) | |
H34 | 0.2416 | 0.8068 | 0.1233 | 0.056* | |
N41 | 0.40116 (12) | 0.4153 (4) | 0.22151 (14) | 0.0409 (6) | |
H41 | 0.4398 | 0.3433 | 0.2131 | 0.049* | 0.60 (3) |
N43 | 0.28930 (12) | 0.4958 (5) | 0.21919 (13) | 0.0417 (6) | |
H43 | 0.2466 | 0.4844 | 0.2094 | 0.050* | 0.40 (3) |
C41 | 0.38937 (14) | 0.6213 (5) | 0.26271 (15) | 0.0366 (6) | |
C42 | 0.33959 (15) | 0.3502 (6) | 0.19720 (17) | 0.0453 (7) | |
H42 | 0.3330 | 0.2149 | 0.1676 | 0.054* | |
C43 | 0.32034 (14) | 0.6706 (5) | 0.26146 (15) | 0.0378 (6) | |
C44 | 0.28936 (14) | 0.8671 (6) | 0.30040 (15) | 0.0380 (7) | |
C45 | 0.33355 (15) | 1.0193 (6) | 0.34101 (16) | 0.0379 (6) | |
C46 | 0.40754 (14) | 0.9693 (5) | 0.34161 (15) | 0.0375 (6) | |
C47 | 0.43603 (15) | 0.7688 (6) | 0.30290 (15) | 0.0364 (7) | |
C51 | 0.45302 (16) | 1.1174 (6) | 0.38034 (18) | 0.0458 (8) | |
H51 | 0.4358 | 1.2523 | 0.4056 | 0.055* | |
C52 | 0.52135 (16) | 1.0693 (6) | 0.38192 (19) | 0.0498 (8) | |
H52 | 0.5500 | 1.1700 | 0.4083 | 0.060* | |
C53 | 0.54821 (16) | 0.8708 (7) | 0.3443 (2) | 0.0504 (8) | |
H53 | 0.5949 | 0.8382 | 0.3454 | 0.060* | |
C54 | 0.50629 (16) | 0.7226 (6) | 0.30570 (17) | 0.0453 (7) | |
H54 | 0.5248 | 0.5888 | 0.2809 | 0.054* | |
C61 | 0.30349 (16) | 1.2136 (6) | 0.38032 (17) | 0.0455 (7) | |
H61 | 0.3313 | 1.3174 | 0.4067 | 0.055* | |
C62 | 0.23426 (17) | 1.2528 (7) | 0.38043 (18) | 0.0517 (8) | |
H62 | 0.2155 | 1.3812 | 0.4070 | 0.062* | |
C63 | 0.19211 (17) | 1.1015 (7) | 0.3411 (2) | 0.0521 (8) | |
H63 | 0.1451 | 1.1281 | 0.3416 | 0.063* | |
C64 | 0.21929 (14) | 0.9128 (7) | 0.30129 (17) | 0.0462 (8) | |
H64 | 0.1905 | 0.8142 | 0.2746 | 0.055* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N11 | 0.0403 (14) | 0.0430 (14) | 0.0459 (15) | 0.0000 (11) | −0.0001 (12) | 0.0044 (12) |
N13 | 0.0416 (14) | 0.0466 (15) | 0.0451 (15) | −0.0023 (11) | 0.0009 (11) | −0.0014 (12) |
C11 | 0.0338 (14) | 0.0385 (14) | 0.0388 (16) | 0.0020 (12) | 0.0003 (13) | −0.0004 (13) |
C12 | 0.0493 (19) | 0.0446 (16) | 0.0446 (18) | 0.0004 (14) | 0.0015 (14) | 0.0044 (14) |
C13 | 0.0370 (14) | 0.0405 (15) | 0.0382 (16) | −0.0010 (12) | 0.0030 (13) | −0.0042 (14) |
C14 | 0.0374 (16) | 0.0423 (16) | 0.0407 (16) | 0.0009 (12) | 0.0022 (13) | −0.0068 (14) |
C15 | 0.0407 (16) | 0.0435 (16) | 0.0410 (17) | 0.0044 (13) | −0.0033 (14) | −0.0089 (15) |
C16 | 0.0435 (16) | 0.0402 (15) | 0.0389 (16) | 0.0005 (13) | −0.0008 (14) | −0.0034 (13) |
C17 | 0.0383 (16) | 0.0371 (15) | 0.0376 (16) | −0.0007 (12) | −0.0024 (13) | −0.0055 (13) |
C21 | 0.0485 (18) | 0.0458 (16) | 0.0507 (19) | 0.0037 (14) | −0.0056 (15) | 0.0026 (15) |
C22 | 0.049 (2) | 0.059 (2) | 0.058 (2) | 0.0119 (16) | −0.0134 (17) | −0.0048 (18) |
C23 | 0.0354 (17) | 0.066 (2) | 0.065 (2) | 0.0020 (15) | −0.0019 (16) | −0.0080 (19) |
C24 | 0.0411 (17) | 0.0527 (18) | 0.0497 (19) | −0.0048 (14) | 0.0011 (15) | −0.0009 (16) |
C31 | 0.053 (2) | 0.0431 (16) | 0.048 (2) | −0.0005 (14) | −0.0038 (17) | 0.0061 (15) |
C32 | 0.055 (2) | 0.0472 (18) | 0.054 (2) | −0.0101 (16) | 0.0039 (16) | 0.0090 (17) |
C33 | 0.0368 (17) | 0.0548 (19) | 0.065 (2) | −0.0083 (14) | −0.0005 (16) | 0.0019 (18) |
C34 | 0.0401 (18) | 0.0491 (18) | 0.0514 (19) | −0.0020 (13) | −0.0006 (15) | 0.0049 (16) |
N41 | 0.0403 (13) | 0.0412 (13) | 0.0410 (14) | 0.0030 (11) | 0.0016 (12) | 0.0021 (12) |
N43 | 0.0347 (13) | 0.0452 (13) | 0.0451 (15) | 0.0010 (10) | −0.0045 (12) | 0.0020 (12) |
C41 | 0.0379 (15) | 0.0353 (14) | 0.0365 (15) | 0.0012 (11) | 0.0026 (12) | 0.0064 (13) |
C42 | 0.0491 (19) | 0.0463 (17) | 0.0405 (17) | −0.0014 (14) | −0.0021 (14) | −0.0037 (14) |
C43 | 0.0354 (14) | 0.0366 (14) | 0.0413 (16) | −0.0018 (12) | 0.0009 (13) | 0.0069 (13) |
C44 | 0.0355 (15) | 0.0361 (15) | 0.0425 (16) | 0.0001 (12) | 0.0039 (13) | 0.0056 (13) |
C45 | 0.0414 (15) | 0.0354 (14) | 0.0369 (15) | 0.0014 (12) | 0.0035 (14) | 0.0085 (13) |
C46 | 0.0382 (16) | 0.0367 (14) | 0.0376 (15) | −0.0025 (11) | 0.0012 (13) | 0.0060 (13) |
C47 | 0.0327 (15) | 0.0371 (15) | 0.0394 (17) | −0.0018 (12) | 0.0010 (13) | 0.0082 (13) |
C51 | 0.0481 (18) | 0.0407 (16) | 0.0487 (19) | −0.0023 (13) | −0.0012 (15) | 0.0014 (15) |
C52 | 0.0424 (18) | 0.0523 (19) | 0.055 (2) | −0.0122 (14) | −0.0033 (16) | 0.0025 (17) |
C53 | 0.0324 (15) | 0.062 (2) | 0.056 (2) | −0.0027 (14) | −0.0029 (16) | 0.0069 (19) |
C54 | 0.0376 (16) | 0.0452 (17) | 0.0531 (18) | 0.0021 (13) | 0.0038 (14) | 0.0025 (16) |
C61 | 0.0489 (18) | 0.0416 (16) | 0.0461 (18) | 0.0030 (13) | 0.0015 (15) | −0.0004 (15) |
C62 | 0.0535 (19) | 0.0487 (18) | 0.0529 (19) | 0.0135 (16) | 0.0088 (17) | −0.0020 (17) |
C63 | 0.0371 (16) | 0.058 (2) | 0.061 (2) | 0.0116 (14) | 0.0067 (16) | 0.0024 (18) |
C64 | 0.0314 (16) | 0.0520 (19) | 0.055 (2) | 0.0019 (12) | 0.0006 (15) | −0.0011 (17) |
N11—C12 | 1.341 (4) | N41—C42 | 1.341 (4) |
N11—C11 | 1.379 (4) | N41—C41 | 1.373 (4) |
N11—H11 | 0.8600 | N41—H41 | 0.8600 |
N13—C12 | 1.315 (4) | N43—C42 | 1.318 (4) |
N13—C13 | 1.393 (4) | N43—C43 | 1.382 (4) |
N13—H13 | 0.8600 | N43—H43 | 0.8600 |
C11—C13 | 1.365 (4) | C41—C43 | 1.375 (4) |
C11—C17 | 1.436 (4) | C41—C47 | 1.437 (4) |
C12—H12 | 0.9300 | C42—H42 | 0.9300 |
C13—C14 | 1.438 (4) | C43—C44 | 1.422 (4) |
C14—C24 | 1.403 (5) | C44—C64 | 1.391 (4) |
C14—C15 | 1.415 (4) | C44—C45 | 1.426 (4) |
C15—C21 | 1.402 (4) | C45—C61 | 1.411 (4) |
C15—C16 | 1.464 (4) | C45—C46 | 1.471 (4) |
C16—C31 | 1.402 (5) | C46—C51 | 1.409 (4) |
C16—C17 | 1.418 (4) | C46—C47 | 1.415 (4) |
C17—C34 | 1.409 (4) | C47—C54 | 1.396 (4) |
C21—C22 | 1.368 (5) | C51—C52 | 1.360 (5) |
C21—H21 | 0.9300 | C51—H51 | 0.9300 |
C22—C23 | 1.374 (5) | C52—C53 | 1.383 (5) |
C22—H22 | 0.9300 | C52—H52 | 0.9300 |
C23—C24 | 1.369 (5) | C53—C54 | 1.365 (5) |
C23—H23 | 0.9300 | C53—H53 | 0.9300 |
C24—H24 | 0.9300 | C54—H54 | 0.9300 |
C31—C32 | 1.374 (5) | C61—C62 | 1.369 (4) |
C31—H31 | 0.9300 | C61—H61 | 0.9300 |
C32—C33 | 1.378 (5) | C62—C63 | 1.385 (5) |
C32—H32 | 0.9300 | C62—H62 | 0.9300 |
C33—C34 | 1.371 (5) | C63—C64 | 1.372 (5) |
C33—H33 | 0.9300 | C63—H63 | 0.9300 |
C34—H34 | 0.9300 | C64—H64 | 0.9300 |
C12—N11—C11 | 104.8 (2) | C42—N41—C41 | 105.3 (2) |
C12—N11—H11 | 127.6 | C42—N41—H41 | 127.4 |
C11—N11—H11 | 127.6 | C41—N41—H41 | 127.4 |
C12—N13—C13 | 104.1 (3) | C42—N43—C43 | 104.8 (2) |
C12—N13—H13 | 127.9 | C42—N43—H43 | 127.6 |
C13—N13—H13 | 127.9 | C43—N43—H43 | 127.6 |
C13—C11—N11 | 107.7 (3) | N41—C41—C43 | 107.5 (3) |
C13—C11—C17 | 123.2 (3) | N41—C41—C47 | 130.3 (3) |
N11—C11—C17 | 129.0 (3) | C43—C41—C47 | 122.2 (3) |
N13—C12—N11 | 114.6 (3) | N43—C42—N41 | 113.8 (3) |
N13—C12—H12 | 122.7 | N43—C42—H42 | 123.1 |
N11—C12—H12 | 122.7 | N41—C42—H42 | 123.1 |
C11—C13—N13 | 108.8 (3) | C41—C43—N43 | 108.5 (3) |
C11—C13—C14 | 121.5 (3) | C41—C43—C44 | 123.0 (3) |
N13—C13—C14 | 129.7 (3) | N43—C43—C44 | 128.5 (2) |
C24—C14—C15 | 119.2 (3) | C64—C44—C43 | 123.4 (3) |
C24—C14—C13 | 123.5 (3) | C64—C44—C45 | 119.6 (3) |
C15—C14—C13 | 117.3 (3) | C43—C44—C45 | 117.0 (2) |
C21—C15—C14 | 117.7 (3) | C61—C45—C44 | 117.6 (3) |
C21—C15—C16 | 121.4 (3) | C61—C45—C46 | 122.3 (3) |
C14—C15—C16 | 120.9 (3) | C44—C45—C46 | 120.1 (3) |
C31—C16—C17 | 117.3 (3) | C51—C46—C47 | 117.1 (3) |
C31—C16—C15 | 122.5 (3) | C51—C46—C45 | 121.9 (3) |
C17—C16—C15 | 120.2 (3) | C47—C46—C45 | 121.0 (3) |
C34—C17—C16 | 120.0 (3) | C54—C47—C46 | 119.6 (3) |
C34—C17—C11 | 123.2 (3) | C54—C47—C41 | 123.6 (3) |
C16—C17—C11 | 116.8 (3) | C46—C47—C41 | 116.7 (3) |
C22—C21—C15 | 121.5 (3) | C52—C51—C46 | 122.1 (3) |
C22—C21—H21 | 119.3 | C52—C51—H51 | 118.9 |
C15—C21—H21 | 119.3 | C46—C51—H51 | 118.9 |
C21—C22—C23 | 120.7 (3) | C51—C52—C53 | 120.0 (3) |
C21—C22—H22 | 119.7 | C51—C52—H52 | 120.0 |
C23—C22—H22 | 119.7 | C53—C52—H52 | 120.0 |
C24—C23—C22 | 119.8 (3) | C54—C53—C52 | 120.1 (3) |
C24—C23—H23 | 120.1 | C54—C53—H53 | 119.9 |
C22—C23—H23 | 120.1 | C52—C53—H53 | 119.9 |
C23—C24—C14 | 121.1 (3) | C53—C54—C47 | 121.0 (3) |
C23—C24—H24 | 119.5 | C53—C54—H54 | 119.5 |
C14—C24—H24 | 119.5 | C47—C54—H54 | 119.5 |
C32—C31—C16 | 121.6 (3) | C62—C61—C45 | 121.4 (3) |
C32—C31—H31 | 119.2 | C62—C61—H61 | 119.3 |
C16—C31—H31 | 119.2 | C45—C61—H61 | 119.3 |
C31—C32—C33 | 120.6 (3) | C61—C62—C63 | 120.2 (3) |
C31—C32—H32 | 119.7 | C61—C62—H62 | 119.9 |
C33—C32—H32 | 119.7 | C63—C62—H62 | 119.9 |
C34—C33—C32 | 120.2 (3) | C64—C63—C62 | 120.4 (3) |
C34—C33—H33 | 119.9 | C64—C63—H63 | 119.8 |
C32—C33—H33 | 119.9 | C62—C63—H63 | 119.8 |
C33—C34—C17 | 120.3 (3) | C63—C64—C44 | 120.8 (3) |
C33—C34—H34 | 119.9 | C63—C64—H64 | 119.6 |
C17—C34—H34 | 119.9 | C44—C64—H64 | 119.6 |
C12—N11—C11—C13 | 0.7 (3) | C42—N41—C41—C43 | 0.2 (3) |
C12—N11—C11—C17 | −176.7 (3) | C42—N41—C41—C47 | 179.1 (3) |
C13—N13—C12—N11 | 0.8 (4) | C43—N43—C42—N41 | −0.1 (4) |
C11—N11—C12—N13 | −1.0 (4) | C41—N41—C42—N43 | −0.1 (4) |
N11—C11—C13—N13 | −0.2 (3) | N41—C41—C43—N43 | −0.3 (3) |
C17—C11—C13—N13 | 177.4 (3) | C47—C41—C43—N43 | −179.2 (3) |
N11—C11—C13—C14 | −179.3 (3) | N41—C41—C43—C44 | 177.8 (3) |
C17—C11—C13—C14 | −1.7 (4) | C47—C41—C43—C44 | −1.1 (4) |
C12—N13—C13—C11 | −0.4 (3) | C42—N43—C43—C41 | 0.2 (3) |
C12—N13—C13—C14 | 178.6 (3) | C42—N43—C43—C44 | −177.8 (3) |
C11—C13—C14—C24 | −178.9 (3) | C41—C43—C44—C64 | −177.7 (3) |
N13—C13—C14—C24 | 2.2 (5) | N43—C43—C44—C64 | 0.0 (5) |
C11—C13—C14—C15 | 0.3 (4) | C41—C43—C44—C45 | 1.2 (4) |
N13—C13—C14—C15 | −178.5 (3) | N43—C43—C44—C45 | 178.9 (3) |
C24—C14—C15—C21 | 1.0 (4) | C64—C44—C45—C61 | −0.6 (4) |
C13—C14—C15—C21 | −178.3 (3) | C43—C44—C45—C61 | −179.5 (3) |
C24—C14—C15—C16 | −179.7 (3) | C64—C44—C45—C46 | 178.7 (3) |
C13—C14—C15—C16 | 1.0 (4) | C43—C44—C45—C46 | −0.3 (4) |
C21—C15—C16—C31 | −2.6 (5) | C61—C45—C46—C51 | −1.6 (4) |
C14—C15—C16—C31 | 178.1 (3) | C44—C45—C46—C51 | 179.1 (3) |
C21—C15—C16—C17 | 178.2 (3) | C61—C45—C46—C47 | 178.4 (3) |
C14—C15—C16—C17 | −1.1 (4) | C44—C45—C46—C47 | −0.8 (4) |
C31—C16—C17—C34 | 0.7 (5) | C51—C46—C47—C54 | 1.4 (4) |
C15—C16—C17—C34 | 179.9 (3) | C45—C46—C47—C54 | −178.6 (3) |
C31—C16—C17—C11 | −179.4 (3) | C51—C46—C47—C41 | −179.0 (3) |
C15—C16—C17—C11 | −0.2 (4) | C45—C46—C47—C41 | 0.9 (4) |
C13—C11—C17—C34 | −178.5 (3) | N41—C41—C47—C54 | 0.8 (5) |
N11—C11—C17—C34 | −1.5 (5) | C43—C41—C47—C54 | 179.5 (3) |
C13—C11—C17—C16 | 1.6 (4) | N41—C41—C47—C46 | −178.7 (3) |
N11—C11—C17—C16 | 178.6 (3) | C43—C41—C47—C46 | 0.0 (4) |
C14—C15—C21—C22 | −0.8 (5) | C47—C46—C51—C52 | −1.1 (5) |
C16—C15—C21—C22 | 179.9 (3) | C45—C46—C51—C52 | 178.9 (3) |
C15—C21—C22—C23 | 0.2 (5) | C46—C51—C52—C53 | 0.4 (5) |
C21—C22—C23—C24 | 0.3 (6) | C51—C52—C53—C54 | −0.1 (5) |
C22—C23—C24—C14 | −0.1 (5) | C52—C53—C54—C47 | 0.4 (5) |
C15—C14—C24—C23 | −0.6 (5) | C46—C47—C54—C53 | −1.1 (5) |
C13—C14—C24—C23 | 178.7 (3) | C41—C47—C54—C53 | 179.4 (3) |
C17—C16—C31—C32 | −0.3 (5) | C44—C45—C61—C62 | 1.0 (5) |
C15—C16—C31—C32 | −179.4 (3) | C46—C45—C61—C62 | −178.2 (3) |
C16—C31—C32—C33 | −0.5 (6) | C45—C61—C62—C63 | −0.5 (5) |
C31—C32—C33—C34 | 0.7 (5) | C61—C62—C63—C64 | −0.5 (6) |
C32—C33—C34—C17 | −0.3 (5) | C62—C63—C64—C44 | 0.9 (5) |
C16—C17—C34—C33 | −0.4 (5) | C43—C44—C64—C63 | 178.5 (3) |
C11—C17—C34—C33 | 179.7 (3) | C45—C44—C64—C63 | −0.4 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11···N43 | 0.86 | 2.16 | 3.018 (3) | 173 |
N41—H41···N13i | 0.86 | 2.28 | 3.129 (3) | 168 |
N13—H13···N41ii | 0.86 | 2.28 | 3.129 (3) | 167 |
N43—H43···N11 | 0.86 | 2.16 | 3.018 (3) | 175 |
Symmetry codes: (i) x+1/2, −y+1/2, z; (ii) x−1/2, −y+1/2, z. |
C15H8Br2N2·0.5H2O | Z = 4 |
Mr = 385.04 | F(000) = 748 |
Triclinic, P1 | Dx = 1.898 Mg m−3 |
Hall symbol: -P 1 | Melting point: 583 K |
a = 8.415 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.139 (2) Å | Cell parameters from 824 reflections |
c = 17.227 (4) Å | θ = 2.2–23.9° |
α = 101.683 (4)° | µ = 6.00 mm−1 |
β = 101.398 (5)° | T = 298 K |
γ = 104.109 (5)° | Plate, pale-yellow |
V = 1347.9 (5) Å3 | 0.40 × 0.37 × 0.19 mm |
Bruker SMART CCD area-detector diffractometer | 5330 independent reflections |
Radiation source: sealed tube | 3658 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
ϕ and ω scans | θmax = 26.1°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Blessing, 1995) | h = −10→10 |
Tmin = 0.359, Tmax = 1.000 | k = −12→12 |
12857 measured reflections | l = −21→21 |
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) = 0.128 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0728P)2] where P = (Fo2 + 2Fc2)/3 |
5330 reflections | (Δ/σ)max < 0.001 |
360 parameters | Δρmax = 1.29 e Å−3 |
2 restraints | Δρmin = −0.77 e Å−3 |
C15H8Br2N2·0.5H2O | γ = 104.109 (5)° |
Mr = 385.04 | V = 1347.9 (5) Å3 |
Triclinic, P1 | Z = 4 |
a = 8.415 (2) Å | Mo Kα radiation |
b = 10.139 (2) Å | µ = 6.00 mm−1 |
c = 17.227 (4) Å | T = 298 K |
α = 101.683 (4)° | 0.40 × 0.37 × 0.19 mm |
β = 101.398 (5)° |
Bruker SMART CCD area-detector diffractometer | 5330 independent reflections |
Absorption correction: multi-scan (SADABS; Blessing, 1995) | 3658 reflections with I > 2σ(I) |
Tmin = 0.359, Tmax = 1.000 | Rint = 0.040 |
12857 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 2 restraints |
wR(F2) = 0.128 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 1.29 e Å−3 |
5330 reflections | Δρmin = −0.77 e Å−3 |
360 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 | ||
O1 | 1.1756 (6) | 0.6635 (7) | 0.2421 (4) | 0.1129 (19) | |
H1O | 1.112 (11) | 0.724 (9) | 0.244 (7) | 0.18 (5)* | |
H2O | 1.201 (13) | 0.718 (10) | 0.208 (5) | 0.20 (5)* | |
Br53 | 0.43103 (6) | 0.24240 (6) | 0.61777 (3) | 0.06234 (18) | |
Br63 | 1.04163 (10) | 0.97232 (6) | 0.67120 (4) | 0.0945 (3) | |
N41 | 0.9268 (4) | 0.5002 (4) | 0.2891 (2) | 0.0479 (9) | |
H41 | 1.0010 | 0.5656 | 0.2795 | 0.057* | |
N43 | 0.7364 (5) | 0.2939 (4) | 0.2688 (2) | 0.0508 (9) | |
C41 | 0.8716 (5) | 0.5075 (4) | 0.3588 (3) | 0.0427 (10) | |
C42 | 0.8439 (5) | 0.3722 (5) | 0.2384 (3) | 0.0521 (11) | |
H42 | 0.8607 | 0.3417 | 0.1869 | 0.063* | |
C43 | 0.7523 (5) | 0.3785 (4) | 0.3461 (3) | 0.0438 (10) | |
C44 | 0.6710 (5) | 0.3458 (4) | 0.4076 (3) | 0.0417 (10) | |
C45 | 0.7172 (5) | 0.4499 (4) | 0.4833 (2) | 0.0376 (9) | |
C46 | 0.8385 (5) | 0.5888 (4) | 0.4952 (3) | 0.0409 (10) | |
C47 | 0.9164 (5) | 0.6165 (4) | 0.4320 (3) | 0.0413 (10) | |
C51 | 0.5564 (6) | 0.2153 (5) | 0.3976 (3) | 0.0526 (12) | |
H51 | 0.5274 | 0.1475 | 0.3478 | 0.063* | |
C52 | 0.4848 (6) | 0.1836 (5) | 0.4588 (3) | 0.0535 (12) | |
H52 | 0.4068 | 0.0963 | 0.4510 | 0.064* | |
C53 | 0.5320 (5) | 0.2856 (5) | 0.5329 (3) | 0.0473 (11) | |
C54 | 0.6426 (5) | 0.4157 (4) | 0.5453 (3) | 0.0435 (10) | |
H54 | 0.6687 | 0.4823 | 0.5953 | 0.052* | |
C61 | 1.0320 (6) | 0.7490 (5) | 0.4423 (3) | 0.0497 (11) | |
H61 | 1.0837 | 0.7659 | 0.4009 | 0.060* | |
C62 | 1.0686 (6) | 0.8534 (5) | 0.5135 (3) | 0.0570 (12) | |
H62 | 1.1447 | 0.9413 | 0.5208 | 0.068* | |
C63 | 0.9901 (6) | 0.8255 (5) | 0.5743 (3) | 0.0530 (12) | |
C64 | 0.8789 (6) | 0.6966 (4) | 0.5671 (3) | 0.0494 (11) | |
H64 | 0.8309 | 0.6814 | 0.6100 | 0.059* | |
Br23 | −0.32947 (6) | −0.35521 (6) | −0.23022 (3) | 0.06483 (18) | |
Br33 | 0.33555 (9) | 0.34459 (6) | −0.16606 (4) | 0.0839 (2) | |
N11 | 0.4763 (5) | 0.0408 (4) | 0.1674 (2) | 0.0502 (9) | |
H11 | 0.5635 | 0.1130 | 0.1911 | 0.060* | |
N13 | 0.2838 (5) | −0.1650 (4) | 0.1477 (2) | 0.0537 (10) | |
C11 | 0.3671 (5) | 0.0154 (4) | 0.0922 (2) | 0.0413 (9) | |
C12 | 0.4198 (7) | −0.0696 (5) | 0.1969 (3) | 0.0591 (13) | |
H12 | 0.4728 | −0.0776 | 0.2477 | 0.071* | |
C13 | 0.2492 (5) | −0.1118 (4) | 0.0804 (3) | 0.0434 (10) | |
C14 | 0.1146 (5) | −0.1736 (4) | 0.0077 (3) | 0.0420 (10) | |
C15 | 0.1036 (5) | −0.0967 (4) | −0.0522 (3) | 0.0412 (9) | |
C16 | 0.2310 (5) | 0.0396 (4) | −0.0397 (3) | 0.0419 (10) | |
C17 | 0.3651 (5) | 0.0964 (4) | 0.0336 (3) | 0.0412 (9) | |
C21 | −0.0044 (6) | −0.3057 (4) | −0.0068 (3) | 0.0491 (11) | |
H21 | 0.0052 | −0.3570 | 0.0320 | 0.059* | |
C22 | −0.1333 (6) | −0.3602 (5) | −0.0765 (3) | 0.0542 (12) | |
H22 | −0.2115 | −0.4479 | −0.0856 | 0.065* | |
C23 | −0.1457 (5) | −0.2820 (4) | −0.1340 (3) | 0.0461 (10) | |
C24 | −0.0316 (5) | −0.1545 (4) | −0.1234 (3) | 0.0479 (11) | |
H24 | −0.0431 | −0.1056 | −0.1634 | 0.057* | |
C31 | 0.4856 (6) | 0.2249 (4) | 0.0442 (3) | 0.0476 (11) | |
H31 | 0.5726 | 0.2617 | 0.0924 | 0.057* | |
C32 | 0.4793 (6) | 0.2983 (5) | −0.0141 (3) | 0.0534 (12) | |
H32 | 0.5611 | 0.3835 | −0.0064 | 0.064* | |
C33 | 0.3486 (6) | 0.2427 (5) | −0.0847 (3) | 0.0515 (11) | |
C34 | 0.2254 (6) | 0.1181 (4) | −0.0980 (3) | 0.0505 (11) | |
H34 | 0.1377 | 0.0853 | −0.1459 | 0.061* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.078 (3) | 0.144 (5) | 0.131 (5) | 0.005 (3) | 0.031 (3) | 0.098 (4) |
Br53 | 0.0566 (3) | 0.0768 (4) | 0.0568 (3) | 0.0101 (2) | 0.0176 (2) | 0.0336 (3) |
Br63 | 0.1571 (7) | 0.0495 (3) | 0.0525 (4) | 0.0014 (3) | 0.0144 (4) | 0.0078 (3) |
N41 | 0.045 (2) | 0.049 (2) | 0.053 (2) | 0.0097 (16) | 0.0176 (17) | 0.0227 (18) |
N43 | 0.049 (2) | 0.054 (2) | 0.046 (2) | 0.0104 (17) | 0.0133 (17) | 0.0111 (18) |
C41 | 0.034 (2) | 0.046 (2) | 0.052 (3) | 0.0137 (18) | 0.0075 (19) | 0.021 (2) |
C42 | 0.047 (3) | 0.062 (3) | 0.048 (3) | 0.015 (2) | 0.018 (2) | 0.014 (2) |
C43 | 0.039 (2) | 0.048 (3) | 0.042 (3) | 0.0104 (19) | 0.0065 (19) | 0.013 (2) |
C44 | 0.034 (2) | 0.046 (2) | 0.043 (2) | 0.0109 (18) | 0.0053 (18) | 0.0149 (19) |
C45 | 0.031 (2) | 0.043 (2) | 0.041 (2) | 0.0126 (17) | 0.0049 (17) | 0.0182 (18) |
C46 | 0.040 (2) | 0.039 (2) | 0.044 (2) | 0.0150 (18) | 0.0012 (18) | 0.0155 (19) |
C47 | 0.037 (2) | 0.042 (2) | 0.046 (2) | 0.0132 (18) | 0.0036 (18) | 0.0185 (19) |
C51 | 0.050 (3) | 0.054 (3) | 0.044 (3) | 0.002 (2) | 0.011 (2) | 0.007 (2) |
C52 | 0.046 (3) | 0.053 (3) | 0.052 (3) | −0.001 (2) | 0.009 (2) | 0.016 (2) |
C53 | 0.042 (2) | 0.063 (3) | 0.046 (3) | 0.015 (2) | 0.0166 (19) | 0.028 (2) |
C54 | 0.042 (2) | 0.049 (2) | 0.040 (2) | 0.0146 (19) | 0.0077 (18) | 0.0153 (19) |
C61 | 0.050 (3) | 0.046 (2) | 0.056 (3) | 0.014 (2) | 0.012 (2) | 0.022 (2) |
C62 | 0.066 (3) | 0.042 (3) | 0.057 (3) | 0.010 (2) | 0.004 (2) | 0.019 (2) |
C63 | 0.067 (3) | 0.041 (2) | 0.041 (3) | 0.012 (2) | −0.002 (2) | 0.011 (2) |
C64 | 0.058 (3) | 0.046 (2) | 0.042 (3) | 0.013 (2) | 0.003 (2) | 0.018 (2) |
Br23 | 0.0575 (3) | 0.0680 (3) | 0.0549 (3) | 0.0085 (2) | 0.0037 (2) | 0.0080 (2) |
Br33 | 0.1271 (5) | 0.0599 (3) | 0.0626 (4) | 0.0119 (3) | 0.0183 (3) | 0.0372 (3) |
N11 | 0.058 (2) | 0.043 (2) | 0.041 (2) | 0.0030 (17) | 0.0073 (17) | 0.0143 (17) |
N13 | 0.064 (2) | 0.051 (2) | 0.045 (2) | 0.0088 (19) | 0.0119 (19) | 0.0224 (18) |
C11 | 0.047 (2) | 0.042 (2) | 0.039 (2) | 0.0146 (18) | 0.0145 (19) | 0.0152 (18) |
C12 | 0.074 (3) | 0.057 (3) | 0.046 (3) | 0.013 (3) | 0.013 (2) | 0.024 (2) |
C13 | 0.057 (3) | 0.038 (2) | 0.042 (2) | 0.0156 (19) | 0.021 (2) | 0.0170 (19) |
C14 | 0.048 (2) | 0.035 (2) | 0.044 (2) | 0.0115 (18) | 0.0160 (19) | 0.0123 (18) |
C15 | 0.048 (2) | 0.039 (2) | 0.040 (2) | 0.0149 (18) | 0.0150 (19) | 0.0104 (18) |
C16 | 0.050 (2) | 0.041 (2) | 0.041 (2) | 0.0162 (19) | 0.0190 (19) | 0.0137 (19) |
C17 | 0.047 (2) | 0.039 (2) | 0.040 (2) | 0.0146 (18) | 0.0152 (19) | 0.0098 (18) |
C21 | 0.059 (3) | 0.044 (2) | 0.049 (3) | 0.014 (2) | 0.018 (2) | 0.019 (2) |
C22 | 0.056 (3) | 0.044 (3) | 0.060 (3) | 0.006 (2) | 0.018 (2) | 0.014 (2) |
C23 | 0.043 (2) | 0.047 (2) | 0.043 (3) | 0.0118 (19) | 0.0102 (19) | 0.0045 (19) |
C24 | 0.055 (3) | 0.047 (3) | 0.044 (3) | 0.017 (2) | 0.014 (2) | 0.012 (2) |
C31 | 0.054 (3) | 0.043 (2) | 0.043 (3) | 0.007 (2) | 0.013 (2) | 0.0134 (19) |
C32 | 0.065 (3) | 0.038 (2) | 0.061 (3) | 0.010 (2) | 0.023 (2) | 0.019 (2) |
C33 | 0.074 (3) | 0.045 (3) | 0.043 (3) | 0.015 (2) | 0.024 (2) | 0.022 (2) |
C34 | 0.068 (3) | 0.046 (2) | 0.037 (2) | 0.015 (2) | 0.013 (2) | 0.015 (2) |
O1—H1O | 0.91 (10) | C64—H64 | 0.9300 |
O1—H2O | 0.91 (10) | Br23—C23 | 1.903 (4) |
Br53—C53 | 1.902 (4) | Br33—C33 | 1.904 (4) |
Br63—C63 | 1.894 (5) | N11—C12 | 1.343 (6) |
N41—C42 | 1.339 (6) | N11—C11 | 1.367 (5) |
N41—C41 | 1.366 (5) | N11—H11 | 0.8600 |
N41—H41 | 0.8600 | N13—C12 | 1.307 (6) |
N43—C42 | 1.314 (6) | N13—C13 | 1.384 (5) |
N43—C43 | 1.392 (5) | C11—C13 | 1.371 (5) |
C41—C43 | 1.387 (6) | C11—C17 | 1.425 (6) |
C41—C47 | 1.413 (6) | C12—H12 | 0.9300 |
C42—H42 | 0.9300 | C13—C14 | 1.422 (6) |
C43—C44 | 1.421 (6) | C14—C21 | 1.403 (5) |
C44—C51 | 1.389 (6) | C14—C15 | 1.415 (6) |
C44—C45 | 1.418 (6) | C15—C24 | 1.405 (6) |
C45—C54 | 1.400 (6) | C15—C16 | 1.473 (5) |
C45—C46 | 1.472 (5) | C16—C34 | 1.403 (6) |
C46—C64 | 1.396 (6) | C16—C17 | 1.423 (6) |
C46—C47 | 1.419 (6) | C17—C31 | 1.394 (6) |
C47—C61 | 1.407 (6) | C21—C22 | 1.360 (6) |
C51—C52 | 1.369 (6) | C21—H21 | 0.9300 |
C51—H51 | 0.9300 | C22—C23 | 1.391 (6) |
C52—C53 | 1.386 (6) | C22—H22 | 0.9300 |
C52—H52 | 0.9300 | C23—C24 | 1.363 (6) |
C53—C54 | 1.364 (6) | C24—H24 | 0.9300 |
C54—H54 | 0.9300 | C31—C32 | 1.367 (6) |
C61—C62 | 1.373 (7) | C31—H31 | 0.9300 |
C61—H61 | 0.9300 | C32—C33 | 1.377 (6) |
C62—C63 | 1.383 (7) | C32—H32 | 0.9300 |
C62—H62 | 0.9300 | C33—C34 | 1.369 (6) |
C63—C64 | 1.375 (6) | C34—H34 | 0.9300 |
H1O—O1—H2O | 72 (8) | C12—N11—C11 | 106.1 (4) |
C42—N41—C41 | 107.2 (4) | C12—N11—H11 | 126.9 |
C42—N41—H41 | 126.4 | C11—N11—H11 | 126.9 |
C41—N41—H41 | 126.4 | C12—N13—C13 | 103.8 (4) |
C42—N43—C43 | 104.5 (4) | N11—C11—C13 | 106.0 (3) |
N41—C41—C43 | 105.8 (4) | N11—C11—C17 | 130.7 (4) |
N41—C41—C47 | 131.4 (4) | C13—C11—C17 | 123.3 (4) |
C43—C41—C47 | 122.8 (4) | N13—C12—N11 | 114.0 (4) |
N43—C42—N41 | 113.4 (4) | N13—C12—H12 | 123.0 |
N43—C42—H42 | 123.3 | N11—C12—H12 | 123.0 |
N41—C42—H42 | 123.3 | C11—C13—N13 | 110.1 (4) |
C41—C43—N43 | 109.2 (4) | C11—C13—C14 | 122.1 (4) |
C41—C43—C44 | 121.7 (4) | N13—C13—C14 | 127.8 (4) |
N43—C43—C44 | 129.1 (4) | C21—C14—C15 | 119.6 (4) |
C51—C44—C45 | 119.6 (4) | C21—C14—C13 | 123.1 (4) |
C51—C44—C43 | 122.8 (4) | C15—C14—C13 | 117.3 (4) |
C45—C44—C43 | 117.5 (4) | C24—C15—C14 | 118.0 (4) |
C54—C45—C44 | 117.6 (4) | C24—C15—C16 | 121.4 (4) |
C54—C45—C46 | 121.9 (4) | C14—C15—C16 | 120.6 (4) |
C44—C45—C46 | 120.5 (4) | C34—C16—C17 | 117.6 (4) |
C64—C46—C47 | 118.1 (4) | C34—C16—C15 | 122.2 (4) |
C64—C46—C45 | 122.1 (4) | C17—C16—C15 | 120.2 (4) |
C47—C46—C45 | 119.8 (4) | C31—C17—C16 | 119.5 (4) |
C61—C47—C41 | 121.9 (4) | C31—C17—C11 | 123.9 (4) |
C61—C47—C46 | 120.5 (4) | C16—C17—C11 | 116.6 (4) |
C41—C47—C46 | 117.6 (4) | C22—C21—C14 | 121.4 (4) |
C52—C51—C44 | 122.0 (4) | C22—C21—H21 | 119.3 |
C52—C51—H51 | 119.0 | C14—C21—H21 | 119.3 |
C44—C51—H51 | 119.0 | C21—C22—C23 | 118.5 (4) |
C51—C52—C53 | 117.9 (4) | C21—C22—H22 | 120.7 |
C51—C52—H52 | 121.0 | C23—C22—H22 | 120.7 |
C53—C52—H52 | 121.0 | C24—C23—C22 | 122.3 (4) |
C54—C53—C52 | 122.2 (4) | C24—C23—Br23 | 118.9 (3) |
C54—C53—Br53 | 119.8 (3) | C22—C23—Br23 | 118.8 (3) |
C52—C53—Br53 | 118.0 (3) | C23—C24—C15 | 120.1 (4) |
C53—C54—C45 | 120.6 (4) | C23—C24—H24 | 119.9 |
C53—C54—H54 | 119.7 | C15—C24—H24 | 119.9 |
C45—C54—H54 | 119.7 | C32—C31—C17 | 121.8 (4) |
C62—C61—C47 | 120.1 (4) | C32—C31—H31 | 119.1 |
C62—C61—H61 | 119.9 | C17—C31—H31 | 119.1 |
C47—C61—H61 | 119.9 | C31—C32—C33 | 118.2 (4) |
C61—C62—C63 | 118.8 (4) | C31—C32—H32 | 120.9 |
C61—C62—H62 | 120.6 | C33—C32—H32 | 120.9 |
C63—C62—H62 | 120.6 | C34—C33—C32 | 122.6 (4) |
C64—C63—C62 | 122.8 (4) | C34—C33—Br33 | 118.5 (3) |
C64—C63—Br63 | 119.5 (4) | C32—C33—Br33 | 118.9 (3) |
C62—C63—Br63 | 117.7 (3) | C33—C34—C16 | 120.2 (4) |
C63—C64—C46 | 119.7 (4) | C33—C34—H34 | 119.9 |
C63—C64—H64 | 120.2 | C16—C34—H34 | 119.9 |
C46—C64—H64 | 120.2 | ||
C42—N41—C41—C43 | −0.4 (5) | C12—N11—C11—C13 | −0.2 (5) |
C42—N41—C41—C47 | 179.6 (4) | C12—N11—C11—C17 | −179.9 (5) |
C43—N43—C42—N41 | −0.5 (5) | C13—N13—C12—N11 | 0.0 (6) |
C41—N41—C42—N43 | 0.6 (5) | C11—N11—C12—N13 | 0.1 (6) |
N41—C41—C43—N43 | 0.1 (5) | N11—C11—C13—N13 | 0.2 (5) |
C47—C41—C43—N43 | −179.9 (4) | C17—C11—C13—N13 | 180.0 (4) |
N41—C41—C43—C44 | 177.8 (4) | N11—C11—C13—C14 | −179.5 (4) |
C47—C41—C43—C44 | −2.2 (6) | C17—C11—C13—C14 | 0.3 (7) |
C42—N43—C43—C41 | 0.2 (5) | C12—N13—C13—C11 | −0.2 (5) |
C42—N43—C43—C44 | −177.3 (4) | C12—N13—C13—C14 | 179.6 (5) |
C41—C43—C44—C51 | −177.3 (4) | C11—C13—C14—C21 | 177.9 (4) |
N43—C43—C44—C51 | −0.1 (7) | N13—C13—C14—C21 | −1.8 (7) |
C41—C43—C44—C45 | −0.5 (6) | C11—C13—C14—C15 | −1.6 (6) |
N43—C43—C44—C45 | 176.7 (4) | N13—C13—C14—C15 | 178.7 (4) |
C51—C44—C45—C54 | −0.4 (6) | C21—C14—C15—C24 | 2.3 (6) |
C43—C44—C45—C54 | −177.3 (4) | C13—C14—C15—C24 | −178.2 (4) |
C51—C44—C45—C46 | 180.0 (4) | C21—C14—C15—C16 | −177.6 (4) |
C43—C44—C45—C46 | 3.1 (6) | C13—C14—C15—C16 | 1.9 (6) |
C54—C45—C46—C64 | −3.5 (6) | C24—C15—C16—C34 | −0.5 (6) |
C44—C45—C46—C64 | 176.0 (4) | C14—C15—C16—C34 | 179.3 (4) |
C54—C45—C46—C47 | 177.2 (4) | C24—C15—C16—C17 | 179.1 (4) |
C44—C45—C46—C47 | −3.2 (6) | C14—C15—C16—C17 | −1.0 (6) |
N41—C41—C47—C61 | 3.0 (7) | C34—C16—C17—C31 | −0.8 (6) |
C43—C41—C47—C61 | −177.0 (4) | C15—C16—C17—C31 | 179.5 (4) |
N41—C41—C47—C46 | −177.9 (4) | C34—C16—C17—C11 | 179.4 (4) |
C43—C41—C47—C46 | 2.1 (6) | C15—C16—C17—C11 | −0.3 (6) |
C64—C46—C47—C61 | 0.4 (6) | N11—C11—C17—C31 | 0.7 (7) |
C45—C46—C47—C61 | 179.7 (4) | C13—C11—C17—C31 | −179.1 (4) |
C64—C46—C47—C41 | −178.7 (4) | N11—C11—C17—C16 | −179.6 (4) |
C45—C46—C47—C41 | 0.6 (6) | C13—C11—C17—C16 | 0.7 (6) |
C45—C44—C51—C52 | 0.4 (7) | C15—C14—C21—C22 | −1.8 (7) |
C43—C44—C51—C52 | 177.1 (4) | C13—C14—C21—C22 | 178.8 (4) |
C44—C51—C52—C53 | −1.0 (7) | C14—C21—C22—C23 | 0.0 (7) |
C51—C52—C53—C54 | 1.8 (7) | C21—C22—C23—C24 | 1.3 (7) |
C51—C52—C53—Br53 | 179.4 (4) | C21—C22—C23—Br23 | −178.3 (3) |
C52—C53—C54—C45 | −1.9 (7) | C22—C23—C24—C15 | −0.8 (7) |
Br53—C53—C54—C45 | −179.5 (3) | Br23—C23—C24—C15 | 178.8 (3) |
C44—C45—C54—C53 | 1.1 (6) | C14—C15—C24—C23 | −1.1 (6) |
C46—C45—C54—C53 | −179.3 (4) | C16—C15—C24—C23 | 178.8 (4) |
C41—C47—C61—C62 | 178.2 (4) | C16—C17—C31—C32 | −0.3 (7) |
C46—C47—C61—C62 | −0.8 (6) | C11—C17—C31—C32 | 179.4 (4) |
C47—C61—C62—C63 | 0.0 (7) | C17—C31—C32—C33 | 0.6 (7) |
C61—C62—C63—C64 | 1.2 (7) | C31—C32—C33—C34 | 0.4 (7) |
C61—C62—C63—Br63 | −179.4 (3) | C31—C32—C33—Br33 | 179.1 (4) |
C62—C63—C64—C46 | −1.6 (7) | C32—C33—C34—C16 | −1.6 (7) |
Br63—C63—C64—C46 | 179.0 (3) | Br33—C33—C34—C16 | 179.7 (3) |
C47—C46—C64—C63 | 0.7 (6) | C17—C16—C34—C33 | 1.8 (6) |
C45—C46—C64—C63 | −178.5 (4) | C15—C16—C34—C33 | −178.5 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11···N43 | 0.86 | 2.05 | 2.892 (5) | 165 |
N41—H41···O1 | 0.86 | 1.87 | 2.702 (5) | 164 |
O1—H2O···N13i | 0.91 (10) | 1.83 (10) | 2.731 (8) | 172 (13) |
Symmetry code: (i) x+1, y+1, z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C15H10N2 | C15H8Br2N2·0.5H2O |
Mr | 218.25 | 385.04 |
Crystal system, space group | Orthorhombic, Pna21 | Triclinic, P1 |
Temperature (K) | 298 | 298 |
a, b, c (Å) | 19.559 (3), 5.2321 (8), 19.871 (3) | 8.415 (2), 10.139 (2), 17.227 (4) |
α, β, γ (°) | 90, 90, 90 | 101.683 (4), 101.398 (5), 104.109 (5) |
V (Å3) | 2033.5 (5) | 1347.9 (5) |
Z | 8 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 6.00 |
Crystal size (mm) | 0.47 × 0.37 × 0.10 | 0.40 × 0.37 × 0.19 |
Data collection | ||
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Blessing, 1995) | Multi-scan (SADABS; Blessing, 1995) |
Tmin, Tmax | 0.856, 1.000 | 0.359, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18138, 2095, 1803 | 12857, 5330, 3658 |
Rint | 0.035 | 0.040 |
(sin θ/λ)max (Å−1) | 0.620 | 0.619 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.112, 1.00 | 0.047, 0.128, 1.00 |
No. of reflections | 2095 | 5330 |
No. of parameters | 308 | 360 |
No. of restraints | 1 | 2 |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.22, −0.12 | 1.29, −0.77 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-32 (Farrugia, 1997), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11···N43 | 0.86 | 2.16 | 3.018 (3) | 173 |
N41—H41···N13i | 0.86 | 2.28 | 3.129 (3) | 168 |
N13—H13···N41ii | 0.86 | 2.28 | 3.129 (3) | 167 |
N43—H43···N11 | 0.86 | 2.16 | 3.018 (3) | 175 |
Symmetry codes: (i) x+1/2, −y+1/2, z; (ii) x−1/2, −y+1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11···N43 | 0.86 | 2.05 | 2.892 (5) | 165 |
N41—H41···O1 | 0.86 | 1.87 | 2.702 (5) | 164 |
O1—H2O···N13i | 0.91 (10) | 1.83 (10) | 2.731 (8) | 172 (13) |
Symmetry code: (i) x+1, y+1, z. |
Structure | Cg | Cg/Atom | Distance | Angle |
(I) | Cg(I)1 | Cg(I)2i | 3.581 (2) | 2.8 (2) |
(I) | Cg(I)3 | Cg(I)4ii | 3.604 (2) | 2.8 (2) |
(II) | Cg(II)1 | Cg(II)2iii | 3.594 (3) | 1.0 (3) |
(II) | Cg(II)3 | Cg(II)4iv | 3.689 (3) | 1.7 (2) |
(II) | Cg(II)4 | Cg(II)2iv | 3.631 (3) | 2.5 (3) |
(II) | Cg(II)5 | Cg(II)6v | 3.536 (3) | 2.5 (2) |
(II) | Cg(II)4 | H42vi | 2.89 (1) | 159 |
(II) | Cg(II)6 | Br53vi | 3.639 (2) | 86.1 (1) |
Symmetry codes: (i) x, -1 + y, z; (ii) x, 1 + y, z; (iii) 1 - x, -y, -z; (iv) 1 - x, -y, -z; (v) 2 - x, -y, -z; (vi) 2 - x, 2 - y, 1 - z. Cg(I)1 is the centroid of N11/C11/C13/N13/C12. Cg(I)2 is the centroid of C16/C17/C34/C33/C32/C31 Cg(I)3 is the centroid of C44/C45/C61–C64 Cg(I)4 is the centroid of N41/C41/C43/N43/C42 Cg(II)1 is the centroid of N11/C11/C13/N13/C12 Cg(II)2 is the centroid of C16/C17/C31–C34 Cg(II)3 is the centroid of C11/C13–C17 Cg(II)4 is the centroid of C14/C15/C24/C23/C22/C21 Cg(II)5 is the centroid of C41/C43–C47 Cg(II)6 is the centroid of C46/C47/C61–C64 |
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Bis(imidazoles) and bis(benzimidazoles) are versatile species with numerous applications. Structurally, they have been used as geometrically constraining ligands (Stibrany et al., 2004) and in the formation of metal–organic copolymers (Stibrany & Potenza, 2008). Functionally, they have been shown to act as proton sponges (Stibrany et al., 2002), and when complexed to copper, as polymerization catalysts (Stibrany et al., 2003; Stibrany & Kacker, 2002). Analytically, they have been used as agents in the study of electron transfer (Knapp et al., 1990), and fluorinated versions have been used as 19F NMR probes to study the active sites of copper polymerization catalysts (Stibrany, 2003). In the present study, we have investigated the structures of 1-H-phenanthroimidazoles, expanded-ring imidazoles, as potential building blocks for bis(phenanthroimidazoles). We have previously shown that 1-methylbenzimidazole can be used in the synthesis of bis(benzimidazole)ketones, which were found to be useful ligands for the chelation of metals (Gorun et al., 1996).
Crystals of 1-H-phenanthro[9,10-d]imidazole, (I), contain two independent molecules, (Ia) and (Ib), in the asymmetric unit, linked by N(amine)—H···N(imine) hydrogen bonds (Fig. 1, Table 1). Analysis of the structure reveals a two-site H-atom disorder, corresponding to overlapping N(imine)···H—N(amine) and N(amine)—H···N(imine) bonds and their associated molecules. Occupancy factors for the two H atoms, which were refined and constrained to add to 1, were 0.60 (3) and 0.40 (3). These data and the structure described below are consistent with racemic twinning in which the twins are related by rotation of 180° about the a unit-cell axis. We describe the structure below using the major component (60% occupancy) twin.
In the structure of (I), alternating molecules of (Ia) and I(b) are essentially planar, canted by 79.07 (3)°, and linked by the hydrogen bonds mentioned above to create zigzag polymeric chains which extend along the a cell direction (Fig. 2). In these chains, molecules of (Ia) and (Ib) stack along the b cell direction to yield columns in which the phenanthroimidazole planes are separated by interplanar distances consistent with π–π interactions, which have been taken as inter-ring contacts less than 3.8 Å (Janiak, 2000). The inter-ring contacts are listed in Table 3 and the several rings are enumerated in the second scheme. In each column, the planes of the rings are canted with respect to the ac plane such that, when viewed down the a axis along the polymer chains, the phenanthroimidazole columns appear as a criss-cross array of molecules of (Ia) and (Ib) in profile.
Crystals of 3,6-dibromo-1-H-phenanthro[9,10-d]imidazole hemihydrate, (II), contain a water molecule and two independent phenanthroimidazole molecules, (IIa) and (IIb), in the asymmetric unit (Fig. 3). The water molecule acts as both a donor (O—H) and an acceptor (O) to form two hydrogen bonds (Table 2), one to the N(amine) H atom of molecule (IIb) and the other to the N(imine) atom of molecule (IIa). In (II), the N···O distances (Table 2) in the N(imine)···H—O(H2O)···H—N(amine) fragments are shorter than the corresponding N(imine)···O(H2O) and N(amine)···O(H2O) distances in similar hydrogen-bond networks, in which they range from 2.770–2.914 and 2.802–2.946 Å, respectively, for the imine and amine linkages [Cambridge Structural database (CSD), Version 5.30; Allen, 2002] (Botana et al., 2007; Freire et al., 2003; Fridman et al., 2006; Meng et al., 2006; Molina et al., 1998; Zhang et al., 2005). In (II), the hydrogen bonds lead to polymer chains consisting sequentially of molecules of (IIa), (IIb) and water. These hydrogen-bond chains extend along the [110] direction (Fig. 4), while centrosymmetrically related molecules of (IIa) and (IIb) stack in columns along the a-axis direction. The planes of (IIa) and (IIb) are canted by 48.27 (3)°. In the structure of (II), there are four π–π interactions and two short atom-to-ring interactions (Table 3; see also second scheme).
Compounds (I) and (II) are technically defined as extended-ring imidazole systems. The title compounds, which are 1,2-dihydro-substituted, are the first such to be structurally characterized. A total of 22 crystal structures containing phenanthroimidazoles reported in the CSD contain aromatic substitution at the 2-position. Synthetically, aromatic aldehydes facilitate the formation of phenanthroimidazole ring systems.