Crystal structures are reported for three substituted 1
H-imidazole-4,5-dicarbonitrile compounds used as catalysts for the coupling reaction of nucleoside methyl phosphonamidites, namely 2-(3′,5′-dimethylbiphenyl-2-yl)-1
H-imidazole-4,5-dicarbonitrile, C
19H
14N
4, (I), 2-(2′,4′,6′-trimethylbiphenyl-2-yl)-1
H-imidazole-4,5-dicarbonitrile, C
20H
16N
4, (II), and 2-[8-(3,5-dimethylphenyl)naphthalen-1-yl]-1
H-imidazole-4,5-dicarbonitrile, C
23H
16N
4, (III). The asymmetric unit of (I) contains two independent molecules with similar conformations. There is steric repulsion between the imidazole group and the terminal phenyl group in all three compounds, resulting in the nonplanarity of the molecules. The naphthalene group of (III) shows significant deviation from planarity. The C—N bond lengths in the imidazole rings range from 1.325 (2) to 1.377 (2) Å. The molecules are connected into zigzag chains by intermolecular N—H
N
imidazole [for (I)] or N—H
·N
cyano [for (II) and (III)] hydrogen bonds.
Supporting information
CCDC references: 950366; 950367; 950368
The starting materials for the preparation of the compounds were
2-cyano-3',5'-dimethylbiphenyl for (I), 2-cyano-2',4',6'-trimethylbiphenyl for
(II) and 1-cyano-8-(3,5-dimethylphenyl)-naphthalene for (III). The starting
material [How much?] was reacted for 2 h with
diisobutylaluminiumhydride [How much?] in ether [How much?], and
then for 5 min with 2,3-diaminomaleonitrile [How much?] and
concentrated H2SO4 [How much?] in tetrahydrofuran [How
much?]. Thus, the cyano group of the starting compound was replaced by a
2-amino-3-methylideneamino-but-2-enedinitrile chain (Begland et al.,
1974). The products were purified by recrystallization from
dichloromethane–n-hexane [Solvent ratio?]. Subsequently, they
were further reacted with nicotinamide [How much?] and
N-chlorosuccinimide [How much?], resulting in the cyclization of
the 2-amino-3-methylideneamino-but-2-enedinitrile chain to form the desired
1H-imidazole-4,5-dicarbonitrile group (Moriya et al., 1984).
The final products
were recrystallized from dichloromethane/n-hexane [Solvent
ratio?], resulting in colourless crystals of (I), (II) or (III). The
yields of the three products were 74, 77 and 63%, respectively. [Please
give quantities of all reagents, or at least mole ratios]
Friedel opposites were merged for data set (III) and no attempt was made to
determine the direction of the c axis for the polar space group.
C-bound H atoms were positioned geometrically and treated as riding, with
Cplanar—H = 0.95 Å for (I) and (II) and 0.93 Å for (III), and
Cmethyl—H = 0.98 Å for (I) and (II) and 0.96 Å for (III), with
Uiso(H) = 1.2Ueq(planar parent C atom) or
1.5Ueq(methyl parent C atom). N-bound H atoms were located from
difference Fourier syntheses and their coordinates and isotropic displacement
parameters were refined.
Data collection: SMART (Siemens, 1995) for (I), (II); CAD-4 Software (Enraf–Nonius, 1989) for (III). Cell refinement: SMART (Siemens, 1995) for (I), (II); CAD-4 Software (Enraf–Nonius, 1989) for (III). Data reduction: SAINT (Siemens, 1995) for (I), (II); MolEN (Fair, 1990) for (III). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
(I) 2-(3',5'-Dimethylbiphenyl-2-yl)-1
H-imidazole-4,5-dicarbonitrile
top
Crystal data top
C19H14N4 | F(000) = 1248 |
Mr = 298.34 | Dx = 1.229 Mg m−3 |
Monoclinic, P21/n | Melting point: 425(1) K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 9.771 (2) Å | Cell parameters from 244 reflections |
b = 16.807 (2) Å | θ = 3–23° |
c = 19.692 (2) Å | µ = 0.08 mm−1 |
β = 93.976 (7)° | T = 134 K |
V = 3226.1 (8) Å3 | Block, colourless |
Z = 8 | 0.36 × 0.30 × 0.15 mm |
Data collection top
Siemens SMART 1K CCD area-detector diffractometer | 7317 independent reflections |
Radiation source: normal-focus sealed tube | 3808 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.067 |
ω scans | θmax = 27.5°, θmin = 2.1° |
Absorption correction: multi-scan SADABS (Sheldrick, 1996) | h = −12→12 |
Tmin = 0.867, Tmax = 0.989 | k = −21→21 |
47542 measured reflections | l = −25→25 |
Refinement top
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)] = 0.052 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.093 | w = 1/[σ2(Fo2) + (0.03P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.92 | (Δ/σ)max = 0.002 |
7317 reflections | Δρmax = 0.22 e Å−3 |
428 parameters | Δρmin = −0.17 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0032 (2) |
Crystal data top
C19H14N4 | V = 3226.1 (8) Å3 |
Mr = 298.34 | Z = 8 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.771 (2) Å | µ = 0.08 mm−1 |
b = 16.807 (2) Å | T = 134 K |
c = 19.692 (2) Å | 0.36 × 0.30 × 0.15 mm |
β = 93.976 (7)° | |
Data collection top
Siemens SMART 1K CCD area-detector diffractometer | 7317 independent reflections |
Absorption correction: multi-scan SADABS (Sheldrick, 1996) | 3808 reflections with I > 2σ(I) |
Tmin = 0.867, Tmax = 0.989 | Rint = 0.067 |
47542 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.093 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.92 | Δρmax = 0.22 e Å−3 |
7317 reflections | Δρmin = −0.17 e Å−3 |
428 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R-factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.65061 (16) | 0.31498 (8) | 0.18696 (7) | 0.0262 (4) | |
N2 | 0.66519 (16) | 0.42836 (9) | 0.13001 (8) | 0.0240 (4) | |
N3 | 0.32788 (19) | 0.22942 (10) | 0.14701 (9) | 0.0458 (5) | |
N4 | 0.35949 (17) | 0.46877 (10) | 0.03112 (9) | 0.0386 (5) | |
N5 | 0.83027 (16) | 0.68623 (9) | 0.21618 (8) | 0.0244 (4) | |
N6 | 0.78633 (15) | 0.58594 (8) | 0.14454 (7) | 0.0246 (4) | |
N7 | 1.14192 (19) | 0.77904 (11) | 0.18084 (9) | 0.0463 (5) | |
N8 | 1.05867 (19) | 0.57761 (10) | 0.03535 (9) | 0.0473 (5) | |
C1 | 0.8832 (2) | 0.30175 (11) | 0.36994 (10) | 0.0394 (6) | |
H1A | 0.9654 | 0.2729 | 0.3648 | 0.047* | |
C2 | 0.8079 (3) | 0.28650 (12) | 0.42548 (11) | 0.0461 (6) | |
C3 | 0.6906 (3) | 0.33087 (13) | 0.43355 (11) | 0.0524 (7) | |
H3A | 0.6398 | 0.3217 | 0.4722 | 0.063* | |
C4 | 0.6451 (2) | 0.38853 (12) | 0.38642 (11) | 0.0436 (6) | |
C5 | 0.7203 (2) | 0.40035 (11) | 0.33000 (10) | 0.0331 (5) | |
H5A | 0.6886 | 0.4380 | 0.2965 | 0.040* | |
C6 | 0.8407 (2) | 0.35880 (11) | 0.32105 (10) | 0.0306 (5) | |
C7 | 0.9277 (2) | 0.37580 (10) | 0.26369 (10) | 0.0291 (5) | |
C8 | 1.0694 (2) | 0.38304 (12) | 0.27705 (12) | 0.0412 (6) | |
H8A | 1.1080 | 0.3738 | 0.3220 | 0.049* | |
C9 | 1.1549 (2) | 0.40316 (13) | 0.22702 (13) | 0.0490 (6) | |
H9A | 1.2507 | 0.4080 | 0.2380 | 0.059* | |
C10 | 1.1024 (2) | 0.41641 (12) | 0.16112 (12) | 0.0448 (6) | |
H10A | 1.1613 | 0.4311 | 0.1268 | 0.054* | |
C11 | 0.9627 (2) | 0.40803 (11) | 0.14577 (11) | 0.0349 (5) | |
H11A | 0.9257 | 0.4163 | 0.1004 | 0.042* | |
C12 | 0.87566 (19) | 0.38757 (10) | 0.19627 (10) | 0.0267 (5) | |
C13 | 0.73079 (19) | 0.37624 (10) | 0.17362 (9) | 0.0239 (4) | |
C14 | 0.52892 (19) | 0.32911 (10) | 0.14981 (9) | 0.0248 (4) | |
C15 | 0.53520 (18) | 0.39910 (10) | 0.11427 (9) | 0.0237 (4) | |
C16 | 0.8508 (3) | 0.22143 (13) | 0.47562 (11) | 0.0680 (9) | |
H16A | 0.9500 | 0.2245 | 0.4868 | 0.102* | |
H16B | 0.8279 | 0.1694 | 0.4553 | 0.102* | |
H16C | 0.8024 | 0.2282 | 0.5172 | 0.102* | |
C17 | 0.5192 (3) | 0.43783 (13) | 0.39721 (12) | 0.0625 (8) | |
H17A | 0.5472 | 0.4893 | 0.4170 | 0.094* | |
H17B | 0.4614 | 0.4098 | 0.4282 | 0.094* | |
H17C | 0.4674 | 0.4464 | 0.3534 | 0.094* | |
C18 | 0.4169 (2) | 0.27400 (11) | 0.14893 (9) | 0.0301 (5) | |
C19 | 0.4373 (2) | 0.43810 (11) | 0.06859 (10) | 0.0276 (5) | |
C20 | 0.8040 (2) | 0.59259 (10) | 0.34993 (10) | 0.0291 (5) | |
H20A | 0.8222 | 0.5587 | 0.3130 | 0.035* | |
C21 | 0.8987 (2) | 0.59682 (11) | 0.40554 (10) | 0.0332 (5) | |
C22 | 0.8713 (2) | 0.64726 (12) | 0.45888 (10) | 0.0389 (5) | |
H22A | 0.9344 | 0.6499 | 0.4978 | 0.047* | |
C23 | 0.7535 (2) | 0.69400 (12) | 0.45661 (10) | 0.0390 (5) | |
C24 | 0.6598 (2) | 0.68791 (11) | 0.40072 (10) | 0.0341 (5) | |
H24A | 0.5785 | 0.7191 | 0.3991 | 0.041* | |
C25 | 0.6828 (2) | 0.63663 (11) | 0.34664 (9) | 0.0274 (5) | |
C26 | 0.5753 (2) | 0.62615 (10) | 0.28950 (10) | 0.0291 (5) | |
C27 | 0.4381 (2) | 0.62121 (12) | 0.30480 (11) | 0.0400 (6) | |
H27A | 0.4155 | 0.6290 | 0.3505 | 0.048* | |
C28 | 0.3347 (2) | 0.60536 (12) | 0.25553 (12) | 0.0466 (6) | |
H28A | 0.2423 | 0.6027 | 0.2676 | 0.056* | |
C29 | 0.3642 (2) | 0.59334 (12) | 0.18868 (12) | 0.0428 (6) | |
H29A | 0.2933 | 0.5807 | 0.1549 | 0.051* | |
C30 | 0.4988 (2) | 0.59996 (11) | 0.17173 (11) | 0.0342 (5) | |
H30A | 0.5197 | 0.5930 | 0.1257 | 0.041* | |
C31 | 0.60429 (19) | 0.61677 (10) | 0.22107 (10) | 0.0262 (4) | |
C32 | 0.74044 (19) | 0.62799 (10) | 0.19571 (9) | 0.0236 (4) | |
C33 | 0.93823 (19) | 0.68201 (10) | 0.17594 (9) | 0.0252 (4) | |
C34 | 0.9100 (2) | 0.61976 (11) | 0.13207 (9) | 0.0260 (4) | |
C35 | 1.0268 (2) | 0.54699 (12) | 0.40878 (11) | 0.0449 (6) | |
H35A | 1.0887 | 0.5644 | 0.4472 | 0.067* | |
H35B | 1.0726 | 0.5531 | 0.3664 | 0.067* | |
H35C | 1.0027 | 0.4910 | 0.4149 | 0.067* | |
C36 | 0.7284 (2) | 0.75154 (14) | 0.51375 (11) | 0.0598 (8) | |
H36A | 0.7686 | 0.8034 | 0.5040 | 0.090* | |
H36B | 0.7708 | 0.7308 | 0.5567 | 0.090* | |
H36C | 0.6294 | 0.7576 | 0.5175 | 0.090* | |
C37 | 1.0505 (2) | 0.73625 (12) | 0.17970 (10) | 0.0325 (5) | |
C38 | 0.9908 (2) | 0.59460 (11) | 0.07831 (10) | 0.0329 (5) | |
H2A | 0.700 (2) | 0.4799 (12) | 0.1180 (10) | 0.056 (7)* | |
H5B | 0.8208 (19) | 0.7254 (11) | 0.2505 (10) | 0.050 (7)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0317 (10) | 0.0219 (8) | 0.0251 (9) | −0.0011 (7) | 0.0020 (8) | 0.0026 (7) |
N2 | 0.0248 (10) | 0.0200 (8) | 0.0270 (9) | −0.0018 (7) | −0.0001 (7) | 0.0029 (7) |
N3 | 0.0473 (13) | 0.0432 (12) | 0.0479 (12) | −0.0167 (10) | 0.0091 (10) | 0.0003 (9) |
N4 | 0.0347 (11) | 0.0396 (10) | 0.0405 (11) | −0.0026 (9) | −0.0049 (9) | 0.0061 (9) |
N5 | 0.0305 (10) | 0.0192 (8) | 0.0234 (9) | −0.0011 (7) | 0.0012 (7) | −0.0035 (7) |
N6 | 0.0295 (10) | 0.0209 (8) | 0.0233 (9) | −0.0021 (7) | 0.0009 (7) | −0.0020 (7) |
N7 | 0.0491 (13) | 0.0484 (12) | 0.0416 (12) | −0.0197 (10) | 0.0049 (9) | −0.0053 (9) |
N8 | 0.0564 (14) | 0.0427 (11) | 0.0451 (12) | −0.0145 (10) | 0.0186 (10) | −0.0117 (10) |
C1 | 0.0572 (15) | 0.0248 (11) | 0.0334 (13) | −0.0024 (10) | −0.0162 (11) | −0.0026 (10) |
C2 | 0.0819 (19) | 0.0290 (12) | 0.0248 (12) | −0.0129 (13) | −0.0139 (12) | −0.0009 (10) |
C3 | 0.095 (2) | 0.0366 (13) | 0.0263 (13) | −0.0214 (14) | 0.0097 (13) | −0.0066 (11) |
C4 | 0.0660 (17) | 0.0256 (12) | 0.0405 (14) | −0.0087 (11) | 0.0128 (12) | −0.0057 (10) |
C5 | 0.0478 (14) | 0.0218 (11) | 0.0294 (12) | −0.0031 (10) | −0.0002 (10) | 0.0004 (9) |
C6 | 0.0422 (13) | 0.0209 (10) | 0.0269 (11) | −0.0022 (10) | −0.0108 (10) | −0.0018 (9) |
C7 | 0.0303 (12) | 0.0197 (10) | 0.0362 (12) | 0.0028 (9) | −0.0049 (10) | −0.0006 (9) |
C8 | 0.0407 (15) | 0.0332 (12) | 0.0479 (14) | 0.0065 (11) | −0.0111 (11) | 0.0016 (11) |
C9 | 0.0285 (13) | 0.0482 (15) | 0.0694 (18) | 0.0048 (11) | −0.0040 (13) | 0.0016 (13) |
C10 | 0.0316 (14) | 0.0458 (14) | 0.0578 (16) | 0.0026 (11) | 0.0097 (12) | 0.0040 (12) |
C11 | 0.0342 (13) | 0.0296 (11) | 0.0406 (13) | 0.0037 (10) | 0.0006 (10) | 0.0025 (10) |
C12 | 0.0272 (11) | 0.0194 (10) | 0.0331 (12) | 0.0036 (9) | −0.0017 (9) | 0.0011 (9) |
C13 | 0.0292 (12) | 0.0219 (10) | 0.0207 (10) | 0.0023 (9) | 0.0021 (9) | 0.0003 (8) |
C14 | 0.0307 (12) | 0.0232 (10) | 0.0210 (10) | −0.0035 (9) | 0.0050 (9) | −0.0006 (8) |
C15 | 0.0254 (11) | 0.0239 (10) | 0.0218 (10) | −0.0009 (9) | 0.0009 (9) | 0.0003 (8) |
C16 | 0.126 (3) | 0.0427 (14) | 0.0311 (14) | −0.0179 (15) | −0.0274 (15) | 0.0123 (11) |
C17 | 0.084 (2) | 0.0422 (15) | 0.0654 (18) | −0.0048 (14) | 0.0372 (16) | −0.0085 (13) |
C18 | 0.0373 (13) | 0.0285 (11) | 0.0249 (11) | −0.0026 (10) | 0.0049 (9) | 0.0022 (9) |
C19 | 0.0282 (12) | 0.0268 (11) | 0.0281 (11) | −0.0073 (9) | 0.0046 (9) | 0.0023 (9) |
C20 | 0.0371 (12) | 0.0234 (10) | 0.0272 (11) | −0.0022 (9) | 0.0051 (9) | −0.0010 (9) |
C21 | 0.0414 (13) | 0.0283 (11) | 0.0297 (12) | −0.0018 (10) | 0.0016 (10) | 0.0026 (9) |
C22 | 0.0527 (15) | 0.0368 (12) | 0.0265 (12) | −0.0021 (11) | −0.0032 (11) | 0.0017 (10) |
C23 | 0.0571 (16) | 0.0340 (12) | 0.0270 (12) | 0.0001 (11) | 0.0099 (11) | −0.0022 (10) |
C24 | 0.0405 (14) | 0.0291 (11) | 0.0340 (12) | 0.0039 (10) | 0.0127 (10) | 0.0021 (10) |
C25 | 0.0322 (12) | 0.0235 (10) | 0.0275 (11) | −0.0021 (9) | 0.0082 (9) | 0.0018 (9) |
C26 | 0.0314 (12) | 0.0199 (10) | 0.0366 (12) | 0.0025 (9) | 0.0065 (10) | −0.0009 (9) |
C27 | 0.0349 (13) | 0.0386 (13) | 0.0478 (14) | 0.0038 (11) | 0.0114 (11) | −0.0053 (11) |
C28 | 0.0261 (13) | 0.0474 (15) | 0.0673 (17) | 0.0026 (11) | 0.0103 (12) | −0.0083 (13) |
C29 | 0.0291 (13) | 0.0420 (13) | 0.0560 (16) | 0.0042 (11) | −0.0056 (11) | −0.0132 (12) |
C30 | 0.0346 (13) | 0.0262 (11) | 0.0416 (13) | 0.0042 (10) | 0.0009 (10) | −0.0069 (9) |
C31 | 0.0264 (11) | 0.0181 (10) | 0.0341 (11) | 0.0023 (8) | 0.0015 (9) | −0.0030 (9) |
C32 | 0.0290 (12) | 0.0176 (10) | 0.0235 (10) | 0.0000 (8) | −0.0038 (9) | 0.0009 (8) |
C33 | 0.0299 (12) | 0.0231 (10) | 0.0225 (10) | −0.0035 (9) | 0.0017 (9) | −0.0009 (8) |
C34 | 0.0330 (12) | 0.0232 (10) | 0.0221 (10) | −0.0003 (9) | 0.0040 (9) | −0.0008 (8) |
C35 | 0.0462 (15) | 0.0429 (14) | 0.0439 (14) | 0.0080 (11) | −0.0083 (11) | −0.0007 (11) |
C36 | 0.080 (2) | 0.0621 (17) | 0.0377 (15) | 0.0078 (15) | 0.0100 (14) | −0.0177 (13) |
C37 | 0.0399 (13) | 0.0319 (12) | 0.0257 (12) | −0.0049 (10) | 0.0036 (10) | −0.0042 (9) |
C38 | 0.0400 (14) | 0.0279 (11) | 0.0317 (12) | −0.0095 (10) | 0.0072 (10) | −0.0054 (9) |
Geometric parameters (Å, º) top
N1—C13 | 1.331 (2) | C15—C19 | 1.426 (3) |
N1—C14 | 1.373 (2) | C16—H16A | 0.9800 |
N2—C13 | 1.356 (2) | C16—H16B | 0.9800 |
N2—C15 | 1.377 (2) | C16—H16C | 0.9800 |
N2—H2A | 0.97 (2) | C17—H17A | 0.9800 |
N3—C18 | 1.147 (2) | C17—H17B | 0.9800 |
N4—C19 | 1.145 (2) | C17—H17C | 0.9800 |
N5—C32 | 1.357 (2) | C20—C21 | 1.386 (3) |
N5—C33 | 1.365 (2) | C20—C25 | 1.395 (3) |
N5—H5B | 0.953 (19) | C20—H20A | 0.9500 |
N6—C32 | 1.334 (2) | C21—C22 | 1.390 (3) |
N6—C34 | 1.373 (2) | C21—C35 | 1.504 (3) |
N7—C37 | 1.146 (2) | C22—C23 | 1.392 (3) |
N8—C38 | 1.147 (2) | C22—H22A | 0.9500 |
C1—C2 | 1.383 (3) | C23—C24 | 1.386 (3) |
C1—C6 | 1.401 (2) | C23—C36 | 1.516 (3) |
C1—H1A | 0.9500 | C24—C25 | 1.400 (2) |
C2—C3 | 1.386 (3) | C24—H24A | 0.9500 |
C2—C16 | 1.513 (3) | C25—C26 | 1.495 (3) |
C3—C4 | 1.393 (3) | C26—C27 | 1.397 (3) |
C3—H3A | 0.9500 | C26—C31 | 1.405 (2) |
C4—C5 | 1.388 (3) | C27—C28 | 1.377 (3) |
C4—C17 | 1.510 (3) | C27—H27A | 0.9500 |
C5—C6 | 1.390 (3) | C28—C29 | 1.382 (3) |
C5—H5A | 0.9500 | C28—H28A | 0.9500 |
C6—C7 | 1.488 (3) | C29—C30 | 1.383 (3) |
C7—C8 | 1.397 (3) | C29—H29A | 0.9500 |
C7—C12 | 1.402 (2) | C30—C31 | 1.396 (2) |
C8—C9 | 1.377 (3) | C30—H30A | 0.9500 |
C8—H8A | 0.9500 | C31—C32 | 1.465 (2) |
C9—C10 | 1.380 (3) | C33—C34 | 1.372 (2) |
C9—H9A | 0.9500 | C33—C37 | 1.424 (3) |
C10—C11 | 1.385 (3) | C34—C38 | 1.428 (3) |
C10—H10A | 0.9500 | C35—H35A | 0.9800 |
C11—C12 | 1.395 (3) | C35—H35B | 0.9800 |
C11—H11A | 0.9500 | C35—H35C | 0.9800 |
C12—C13 | 1.467 (2) | C36—H36A | 0.9800 |
C14—C15 | 1.372 (2) | C36—H36B | 0.9800 |
C14—C18 | 1.433 (3) | C36—H36C | 0.9800 |
| | | |
C13—N1—C14 | 105.12 (14) | H17A—C17—H17C | 109.5 |
C13—N2—C15 | 107.45 (15) | H17B—C17—H17C | 109.5 |
C13—N2—H2A | 125.0 (12) | N3—C18—C14 | 178.7 (2) |
C15—N2—H2A | 126.9 (12) | N4—C19—C15 | 179.0 (2) |
C32—N5—C33 | 107.46 (16) | C21—C20—C25 | 121.88 (18) |
C32—N5—H5B | 128.0 (12) | C21—C20—H20A | 119.1 |
C33—N5—H5B | 124.5 (12) | C25—C20—H20A | 119.1 |
C32—N6—C34 | 105.18 (15) | C20—C21—C22 | 118.4 (2) |
C2—C1—C6 | 121.5 (2) | C20—C21—C35 | 120.88 (18) |
C2—C1—H1A | 119.3 | C22—C21—C35 | 120.73 (19) |
C6—C1—H1A | 119.3 | C21—C22—C23 | 121.5 (2) |
C1—C2—C3 | 118.7 (2) | C21—C22—H22A | 119.3 |
C1—C2—C16 | 120.8 (2) | C23—C22—H22A | 119.3 |
C3—C2—C16 | 120.5 (2) | C24—C23—C22 | 118.90 (19) |
C2—C3—C4 | 121.7 (2) | C24—C23—C36 | 120.3 (2) |
C2—C3—H3A | 119.1 | C22—C23—C36 | 120.8 (2) |
C4—C3—H3A | 119.1 | C23—C24—C25 | 121.2 (2) |
C5—C4—C3 | 118.1 (2) | C23—C24—H24A | 119.4 |
C5—C4—C17 | 121.0 (2) | C25—C24—H24A | 119.4 |
C3—C4—C17 | 120.9 (2) | C20—C25—C24 | 118.15 (19) |
C4—C5—C6 | 122.0 (2) | C20—C25—C26 | 121.49 (17) |
C4—C5—H5A | 119.0 | C24—C25—C26 | 120.24 (18) |
C6—C5—H5A | 119.0 | C27—C26—C31 | 117.42 (19) |
C5—C6—C1 | 118.0 (2) | C27—C26—C25 | 118.62 (18) |
C5—C6—C7 | 122.20 (17) | C31—C26—C25 | 123.88 (18) |
C1—C6—C7 | 119.72 (19) | C28—C27—C26 | 121.9 (2) |
C8—C7—C12 | 117.13 (19) | C28—C27—H27A | 119.1 |
C8—C7—C6 | 119.00 (18) | C26—C27—H27A | 119.1 |
C12—C7—C6 | 123.85 (17) | C27—C28—C29 | 120.5 (2) |
C9—C8—C7 | 121.9 (2) | C27—C28—H28A | 119.7 |
C9—C8—H8A | 119.0 | C29—C28—H28A | 119.7 |
C7—C8—H8A | 119.0 | C28—C29—C30 | 118.9 (2) |
C8—C9—C10 | 120.6 (2) | C28—C29—H29A | 120.6 |
C8—C9—H9A | 119.7 | C30—C29—H29A | 120.6 |
C10—C9—H9A | 119.7 | C29—C30—C31 | 121.1 (2) |
C9—C10—C11 | 119.0 (2) | C29—C30—H30A | 119.4 |
C9—C10—H10A | 120.5 | C31—C30—H30A | 119.4 |
C11—C10—H10A | 120.5 | C30—C31—C26 | 120.14 (18) |
C10—C11—C12 | 120.6 (2) | C30—C31—C32 | 115.67 (17) |
C10—C11—H11A | 119.7 | C26—C31—C32 | 124.10 (17) |
C12—C11—H11A | 119.7 | N6—C32—N5 | 111.24 (17) |
C11—C12—C7 | 120.69 (18) | N6—C32—C31 | 123.37 (16) |
C11—C12—C13 | 115.99 (17) | N5—C32—C31 | 125.13 (17) |
C7—C12—C13 | 123.27 (18) | N5—C33—C34 | 105.98 (16) |
N1—C13—N2 | 111.46 (16) | N5—C33—C37 | 124.07 (17) |
N1—C13—C12 | 127.54 (16) | C34—C33—C37 | 129.88 (18) |
N2—C13—C12 | 120.83 (16) | C33—C34—N6 | 110.14 (16) |
C15—C14—N1 | 110.63 (16) | C33—C34—C38 | 126.50 (18) |
C15—C14—C18 | 127.52 (18) | N6—C34—C38 | 123.28 (16) |
N1—C14—C18 | 121.81 (16) | C21—C35—H35A | 109.5 |
C14—C15—N2 | 105.33 (16) | C21—C35—H35B | 109.5 |
C14—C15—C19 | 131.59 (18) | H35A—C35—H35B | 109.5 |
N2—C15—C19 | 123.06 (16) | C21—C35—H35C | 109.5 |
C2—C16—H16A | 109.5 | H35A—C35—H35C | 109.5 |
C2—C16—H16B | 109.5 | H35B—C35—H35C | 109.5 |
H16A—C16—H16B | 109.5 | C23—C36—H36A | 109.5 |
C2—C16—H16C | 109.5 | C23—C36—H36B | 109.5 |
H16A—C16—H16C | 109.5 | H36A—C36—H36B | 109.5 |
H16B—C16—H16C | 109.5 | C23—C36—H36C | 109.5 |
C4—C17—H17A | 109.5 | H36A—C36—H36C | 109.5 |
C4—C17—H17B | 109.5 | H36B—C36—H36C | 109.5 |
H17A—C17—H17B | 109.5 | N7—C37—C33 | 177.9 (2) |
C4—C17—H17C | 109.5 | N8—C38—C34 | 176.9 (2) |
| | | |
C6—C1—C2—C3 | −2.1 (3) | C25—C20—C21—C22 | −0.6 (3) |
C6—C1—C2—C16 | 176.46 (18) | C25—C20—C21—C35 | 178.24 (18) |
C1—C2—C3—C4 | 1.7 (3) | C20—C21—C22—C23 | −1.3 (3) |
C16—C2—C3—C4 | −176.88 (19) | C35—C21—C22—C23 | 179.77 (19) |
C2—C3—C4—C5 | 0.5 (3) | C21—C22—C23—C24 | 2.1 (3) |
C2—C3—C4—C17 | −178.2 (2) | C21—C22—C23—C36 | −177.13 (19) |
C3—C4—C5—C6 | −2.5 (3) | C22—C23—C24—C25 | −0.9 (3) |
C17—C4—C5—C6 | 176.30 (19) | C36—C23—C24—C25 | 178.36 (19) |
C4—C5—C6—C1 | 2.1 (3) | C21—C20—C25—C24 | 1.8 (3) |
C4—C5—C6—C7 | −174.95 (18) | C21—C20—C25—C26 | −174.31 (17) |
C2—C1—C6—C5 | 0.3 (3) | C23—C24—C25—C20 | −1.0 (3) |
C2—C1—C6—C7 | 177.39 (18) | C23—C24—C25—C26 | 175.13 (18) |
C5—C6—C7—C8 | 133.6 (2) | C20—C25—C26—C27 | 135.43 (19) |
C1—C6—C7—C8 | −43.3 (3) | C24—C25—C26—C27 | −40.6 (3) |
C5—C6—C7—C12 | −44.4 (3) | C20—C25—C26—C31 | −41.1 (3) |
C1—C6—C7—C12 | 138.66 (19) | C24—C25—C26—C31 | 142.82 (19) |
C12—C7—C8—C9 | 1.9 (3) | C31—C26—C27—C28 | 2.0 (3) |
C6—C7—C8—C9 | −176.26 (19) | C25—C26—C27—C28 | −174.83 (18) |
C7—C8—C9—C10 | −0.5 (3) | C26—C27—C28—C29 | 0.3 (3) |
C8—C9—C10—C11 | −0.9 (3) | C27—C28—C29—C30 | −2.0 (3) |
C9—C10—C11—C12 | 0.9 (3) | C28—C29—C30—C31 | 1.4 (3) |
C10—C11—C12—C7 | 0.6 (3) | C29—C30—C31—C26 | 0.9 (3) |
C10—C11—C12—C13 | −176.92 (18) | C29—C30—C31—C32 | −175.68 (17) |
C8—C7—C12—C11 | −1.9 (3) | C27—C26—C31—C30 | −2.5 (3) |
C6—C7—C12—C11 | 176.11 (17) | C25—C26—C31—C30 | 174.06 (17) |
C8—C7—C12—C13 | 175.41 (17) | C27—C26—C31—C32 | 173.76 (17) |
C6—C7—C12—C13 | −6.6 (3) | C25—C26—C31—C32 | −9.6 (3) |
C14—N1—C13—N2 | 0.2 (2) | C34—N6—C32—N5 | −0.5 (2) |
C14—N1—C13—C12 | −174.96 (18) | C34—N6—C32—C31 | 173.90 (16) |
C15—N2—C13—N1 | 0.0 (2) | C33—N5—C32—N6 | 0.6 (2) |
C15—N2—C13—C12 | 175.52 (16) | C33—N5—C32—C31 | −173.62 (17) |
C11—C12—C13—N1 | 130.2 (2) | C30—C31—C32—N6 | −37.1 (3) |
C7—C12—C13—N1 | −47.2 (3) | C26—C31—C32—N6 | 146.47 (18) |
C11—C12—C13—N2 | −44.5 (2) | C30—C31—C32—N5 | 136.51 (18) |
C7—C12—C13—N2 | 138.05 (18) | C26—C31—C32—N5 | −39.9 (3) |
C13—N1—C14—C15 | −0.3 (2) | C32—N5—C33—C34 | −0.5 (2) |
C13—N1—C14—C18 | 177.64 (17) | C32—N5—C33—C37 | 176.68 (18) |
N1—C14—C15—N2 | 0.3 (2) | N5—C33—C34—N6 | 0.2 (2) |
C18—C14—C15—N2 | −177.49 (18) | C37—C33—C34—N6 | −176.73 (19) |
N1—C14—C15—C19 | 179.01 (19) | N5—C33—C34—C38 | 177.10 (18) |
C18—C14—C15—C19 | 1.2 (3) | C37—C33—C34—C38 | 0.1 (3) |
C13—N2—C15—C14 | −0.2 (2) | C32—N6—C34—C33 | 0.1 (2) |
C13—N2—C15—C19 | −179.03 (17) | C32—N6—C34—C38 | −176.85 (18) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···N6 | 0.97 (2) | 2.02 (2) | 2.907 (2) | 150.9 (17) |
N5—H5B···N1i | 0.953 (19) | 1.95 (2) | 2.882 (2) | 164.4 (17) |
C11—H11A···N8ii | 0.95 | 2.69 | 3.567 (3) | 154 |
C16—H16B···N6iii | 0.98 | 2.60 | 3.484 (3) | 150 |
C16—H16C···N3iv | 0.98 | 2.65 | 3.497 (3) | 145 |
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x+2, −y+1, −z; (iii) −x+3/2, y−1/2, −z+1/2; (iv) x+1/2, −y+1/2, z+1/2. |
(II) 2-(2',4',6'-Trimethylbiphenyl-2-yl)-1
H-imidazole-4,5-dicarbonitrile
top
Crystal data top
C20H16N4 | F(000) = 656 |
Mr = 312.37 | Dx = 1.227 Mg m−3 |
Monoclinic, P21/c | Melting point: 486(1) K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 12.373 (1) Å | Cell parameters from 247 reflections |
b = 10.303 (2) Å | θ = 3–23° |
c = 13.279 (2) Å | µ = 0.08 mm−1 |
β = 92.578 (7)° | T = 133 K |
V = 1691.1 (4) Å3 | Plate, colourless |
Z = 4 | 0.60 × 0.40 × 0.10 mm |
Data collection top
Siemens SMART 1K CCD area-detector diffractometer | 4381 independent reflections |
Radiation source: normal-focus sealed tube | 3014 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ω scans | θmax = 29.0°, θmin = 2.5° |
Absorption correction: multi-scan SADABS (Sheldrick, 1996) | h = −14→16 |
Tmin = 0.784, Tmax = 0.993 | k = −12→14 |
25406 measured reflections | l = −18→18 |
Refinement top
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)] = 0.040 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.104 | w = 1/[σ2(Fo2) + (0.045P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
4381 reflections | Δρmax = 0.23 e Å−3 |
225 parameters | Δρmin = −0.20 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0160 (17) |
Crystal data top
C20H16N4 | V = 1691.1 (4) Å3 |
Mr = 312.37 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.373 (1) Å | µ = 0.08 mm−1 |
b = 10.303 (2) Å | T = 133 K |
c = 13.279 (2) Å | 0.60 × 0.40 × 0.10 mm |
β = 92.578 (7)° | |
Data collection top
Siemens SMART 1K CCD area-detector diffractometer | 4381 independent reflections |
Absorption correction: multi-scan SADABS (Sheldrick, 1996) | 3014 reflections with I > 2σ(I) |
Tmin = 0.784, Tmax = 0.993 | Rint = 0.033 |
25406 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.104 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.23 e Å−3 |
4381 reflections | Δρmin = −0.20 e Å−3 |
225 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R-factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.71987 (8) | 0.43078 (10) | 0.52011 (7) | 0.0234 (2) | |
N2 | 0.64706 (8) | 0.49068 (11) | 0.37197 (7) | 0.0280 (2) | |
N3 | 0.69072 (11) | 0.23410 (13) | 0.20203 (8) | 0.0476 (3) | |
N4 | 0.83141 (11) | 0.11688 (13) | 0.50582 (9) | 0.0430 (3) | |
C1 | 0.66536 (9) | 0.52552 (12) | 0.46789 (8) | 0.0232 (3) | |
C2 | 0.69141 (10) | 0.36986 (13) | 0.36458 (8) | 0.0264 (3) | |
C3 | 0.73685 (9) | 0.33054 (12) | 0.45601 (8) | 0.0241 (3) | |
C4 | 0.68981 (11) | 0.29635 (14) | 0.27323 (9) | 0.0341 (3) | |
C5 | 0.78988 (10) | 0.21276 (14) | 0.48468 (9) | 0.0287 (3) | |
C6 | 0.62895 (9) | 0.64746 (12) | 0.51227 (8) | 0.0240 (3) | |
C7 | 0.53525 (10) | 0.70443 (13) | 0.46939 (10) | 0.0306 (3) | |
H7A | 0.4992 | 0.6654 | 0.4124 | 0.037* | |
C8 | 0.49484 (11) | 0.81694 (14) | 0.50929 (11) | 0.0373 (3) | |
H8A | 0.4313 | 0.8555 | 0.4797 | 0.045* | |
C9 | 0.54702 (11) | 0.87375 (14) | 0.59256 (11) | 0.0392 (3) | |
H9A | 0.5179 | 0.9499 | 0.6212 | 0.047* | |
C10 | 0.64133 (11) | 0.82023 (13) | 0.63424 (10) | 0.0334 (3) | |
H10A | 0.6772 | 0.8612 | 0.6904 | 0.040* | |
C11 | 0.68438 (10) | 0.70702 (12) | 0.59482 (9) | 0.0254 (3) | |
C12 | 0.78750 (9) | 0.65169 (12) | 0.63979 (8) | 0.0237 (3) | |
C13 | 0.78784 (10) | 0.59029 (12) | 0.73408 (9) | 0.0260 (3) | |
C14 | 0.88263 (10) | 0.53157 (13) | 0.77167 (9) | 0.0289 (3) | |
H14A | 0.8830 | 0.4901 | 0.8356 | 0.035* | |
C15 | 0.97678 (10) | 0.53191 (13) | 0.71823 (9) | 0.0287 (3) | |
C16 | 0.97493 (10) | 0.59668 (13) | 0.62640 (9) | 0.0284 (3) | |
H16A | 1.0391 | 0.5991 | 0.5897 | 0.034* | |
C17 | 0.88270 (10) | 0.65811 (12) | 0.58621 (9) | 0.0254 (3) | |
C18 | 0.68692 (11) | 0.58439 (15) | 0.79433 (10) | 0.0367 (3) | |
H18A | 0.7000 | 0.5280 | 0.8531 | 0.055* | |
H18B | 0.6269 | 0.5495 | 0.7520 | 0.055* | |
H18C | 0.6685 | 0.6719 | 0.8170 | 0.055* | |
C19 | 1.07663 (11) | 0.46266 (16) | 0.75969 (10) | 0.0403 (4) | |
H19A | 1.1352 | 0.4733 | 0.7131 | 0.060* | |
H19B | 1.0607 | 0.3701 | 0.7674 | 0.060* | |
H19C | 1.0988 | 0.4996 | 0.8254 | 0.060* | |
C20 | 0.88650 (11) | 0.73054 (14) | 0.48770 (10) | 0.0350 (3) | |
H20A | 0.9601 | 0.7271 | 0.4634 | 0.053* | |
H20B | 0.8657 | 0.8212 | 0.4979 | 0.053* | |
H20C | 0.8362 | 0.6904 | 0.4378 | 0.053* | |
H1A | 0.7366 (12) | 0.4278 (15) | 0.5868 (11) | 0.045 (4)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0270 (5) | 0.0252 (6) | 0.0177 (5) | −0.0006 (4) | −0.0014 (4) | 0.0000 (4) |
N2 | 0.0321 (5) | 0.0295 (6) | 0.0221 (5) | −0.0040 (5) | −0.0020 (4) | 0.0028 (4) |
N3 | 0.0669 (9) | 0.0493 (9) | 0.0261 (6) | −0.0069 (7) | −0.0025 (6) | −0.0069 (6) |
N4 | 0.0577 (8) | 0.0368 (8) | 0.0343 (6) | 0.0118 (6) | −0.0016 (6) | −0.0040 (6) |
C1 | 0.0204 (5) | 0.0263 (7) | 0.0227 (5) | −0.0040 (5) | 0.0000 (4) | 0.0040 (5) |
C2 | 0.0303 (6) | 0.0285 (7) | 0.0205 (5) | −0.0056 (5) | 0.0007 (5) | −0.0005 (5) |
C3 | 0.0257 (6) | 0.0248 (7) | 0.0219 (5) | −0.0035 (5) | 0.0013 (4) | −0.0019 (5) |
C4 | 0.0441 (8) | 0.0345 (8) | 0.0235 (6) | −0.0069 (6) | −0.0016 (5) | 0.0013 (6) |
C5 | 0.0342 (7) | 0.0303 (7) | 0.0213 (6) | −0.0003 (6) | −0.0004 (5) | −0.0038 (5) |
C6 | 0.0226 (6) | 0.0236 (7) | 0.0260 (6) | −0.0020 (5) | 0.0026 (5) | 0.0054 (5) |
C7 | 0.0237 (6) | 0.0324 (8) | 0.0357 (7) | −0.0040 (6) | 0.0007 (5) | 0.0111 (6) |
C8 | 0.0246 (6) | 0.0329 (8) | 0.0547 (8) | 0.0034 (6) | 0.0066 (6) | 0.0159 (7) |
C9 | 0.0363 (7) | 0.0262 (8) | 0.0564 (9) | 0.0059 (6) | 0.0159 (7) | 0.0048 (7) |
C10 | 0.0352 (7) | 0.0266 (7) | 0.0388 (7) | 0.0008 (6) | 0.0072 (6) | −0.0024 (6) |
C11 | 0.0255 (6) | 0.0234 (7) | 0.0276 (6) | −0.0010 (5) | 0.0045 (5) | 0.0020 (5) |
C12 | 0.0265 (6) | 0.0206 (6) | 0.0239 (6) | −0.0018 (5) | 0.0001 (5) | −0.0047 (5) |
C13 | 0.0298 (6) | 0.0254 (7) | 0.0228 (6) | −0.0042 (5) | 0.0022 (5) | −0.0051 (5) |
C14 | 0.0345 (7) | 0.0299 (7) | 0.0221 (6) | −0.0033 (6) | −0.0013 (5) | 0.0008 (5) |
C15 | 0.0287 (6) | 0.0286 (7) | 0.0282 (6) | −0.0029 (5) | −0.0047 (5) | −0.0004 (5) |
C16 | 0.0228 (6) | 0.0329 (7) | 0.0297 (6) | −0.0026 (5) | 0.0027 (5) | −0.0001 (5) |
C17 | 0.0276 (6) | 0.0240 (7) | 0.0245 (6) | −0.0052 (5) | −0.0002 (5) | −0.0007 (5) |
C18 | 0.0376 (7) | 0.0433 (9) | 0.0298 (7) | 0.0013 (6) | 0.0099 (6) | 0.0021 (6) |
C19 | 0.0331 (7) | 0.0486 (10) | 0.0386 (7) | 0.0041 (7) | −0.0048 (6) | 0.0059 (7) |
C20 | 0.0313 (7) | 0.0423 (9) | 0.0318 (7) | −0.0029 (6) | 0.0037 (5) | 0.0088 (6) |
Geometric parameters (Å, º) top
N1—C1 | 1.3588 (15) | C11—C12 | 1.4969 (17) |
N1—C3 | 1.3606 (15) | C12—C13 | 1.4027 (16) |
N1—H1A | 0.901 (14) | C12—C17 | 1.4048 (16) |
N2—C1 | 1.3329 (15) | C13—C14 | 1.3921 (17) |
N2—C2 | 1.3657 (17) | C13—C18 | 1.5142 (17) |
N3—C4 | 1.1429 (17) | C14—C15 | 1.3911 (17) |
N4—C5 | 1.1427 (17) | C14—H14A | 0.9500 |
C1—C6 | 1.4672 (17) | C15—C16 | 1.3895 (17) |
C2—C3 | 1.3758 (16) | C15—C19 | 1.5090 (18) |
C2—C4 | 1.4294 (17) | C16—C17 | 1.3902 (17) |
C3—C5 | 1.4232 (18) | C16—H16A | 0.9500 |
C6—C7 | 1.3976 (17) | C17—C20 | 1.5086 (17) |
C6—C11 | 1.4075 (17) | C18—H18A | 0.9800 |
C7—C8 | 1.3778 (19) | C18—H18B | 0.9800 |
C7—H7A | 0.9500 | C18—H18C | 0.9800 |
C8—C9 | 1.385 (2) | C19—H19A | 0.9800 |
C8—H8A | 0.9500 | C19—H19B | 0.9800 |
C9—C10 | 1.3834 (19) | C19—H19C | 0.9800 |
C9—H9A | 0.9500 | C20—H20A | 0.9800 |
C10—C11 | 1.3940 (18) | C20—H20B | 0.9800 |
C10—H10A | 0.9500 | C20—H20C | 0.9800 |
| | | |
C1—N1—C3 | 108.24 (10) | C17—C12—C11 | 119.94 (10) |
C1—N1—H1A | 127.8 (10) | C14—C13—C12 | 119.00 (11) |
C3—N1—H1A | 123.6 (10) | C14—C13—C18 | 119.64 (11) |
C1—N2—C2 | 105.23 (10) | C12—C13—C18 | 121.35 (11) |
N2—C1—N1 | 110.69 (11) | C15—C14—C13 | 121.83 (11) |
N2—C1—C6 | 124.92 (11) | C15—C14—H14A | 119.1 |
N1—C1—C6 | 124.37 (10) | C13—C14—H14A | 119.1 |
N2—C2—C3 | 110.76 (11) | C16—C15—C14 | 117.89 (11) |
N2—C2—C4 | 123.62 (11) | C16—C15—C19 | 121.88 (12) |
C3—C2—C4 | 125.62 (12) | C14—C15—C19 | 120.22 (12) |
N1—C3—C2 | 105.08 (11) | C15—C16—C17 | 122.44 (11) |
N1—C3—C5 | 124.20 (10) | C15—C16—H16A | 118.8 |
C2—C3—C5 | 130.72 (11) | C17—C16—H16A | 118.8 |
N3—C4—C2 | 177.46 (16) | C16—C17—C12 | 118.47 (11) |
N4—C5—C3 | 178.45 (14) | C16—C17—C20 | 120.06 (11) |
C7—C6—C11 | 120.03 (12) | C12—C17—C20 | 121.47 (11) |
C7—C6—C1 | 117.39 (11) | C13—C18—H18A | 109.5 |
C11—C6—C1 | 122.58 (11) | C13—C18—H18B | 109.5 |
C8—C7—C6 | 120.35 (13) | H18A—C18—H18B | 109.5 |
C8—C7—H7A | 119.8 | C13—C18—H18C | 109.5 |
C6—C7—H7A | 119.8 | H18A—C18—H18C | 109.5 |
C7—C8—C9 | 119.90 (13) | H18B—C18—H18C | 109.5 |
C7—C8—H8A | 120.1 | C15—C19—H19A | 109.5 |
C9—C8—H8A | 120.1 | C15—C19—H19B | 109.5 |
C10—C9—C8 | 120.36 (13) | H19A—C19—H19B | 109.5 |
C10—C9—H9A | 119.8 | C15—C19—H19C | 109.5 |
C8—C9—H9A | 119.8 | H19A—C19—H19C | 109.5 |
C9—C10—C11 | 120.87 (13) | H19B—C19—H19C | 109.5 |
C9—C10—H10A | 119.6 | C17—C20—H20A | 109.5 |
C11—C10—H10A | 119.6 | C17—C20—H20B | 109.5 |
C10—C11—C6 | 118.44 (11) | H20A—C20—H20B | 109.5 |
C10—C11—C12 | 120.14 (11) | C17—C20—H20C | 109.5 |
C6—C11—C12 | 121.42 (11) | H20A—C20—H20C | 109.5 |
C13—C12—C17 | 120.29 (11) | H20B—C20—H20C | 109.5 |
C13—C12—C11 | 119.74 (10) | | |
| | | |
C2—N2—C1—N1 | 0.25 (13) | C1—C6—C11—C10 | −177.61 (11) |
C2—N2—C1—C6 | −177.98 (11) | C7—C6—C11—C12 | −177.38 (11) |
C3—N1—C1—N2 | −0.45 (13) | C1—C6—C11—C12 | 2.69 (18) |
C3—N1—C1—C6 | 177.79 (10) | C10—C11—C12—C13 | 72.88 (16) |
C1—N2—C2—C3 | 0.04 (14) | C6—C11—C12—C13 | −107.42 (13) |
C1—N2—C2—C4 | −179.89 (12) | C10—C11—C12—C17 | −108.95 (14) |
C1—N1—C3—C2 | 0.45 (13) | C6—C11—C12—C17 | 70.75 (16) |
C1—N1—C3—C5 | −178.74 (11) | C17—C12—C13—C14 | −2.52 (18) |
N2—C2—C3—N1 | −0.31 (13) | C11—C12—C13—C14 | 175.64 (11) |
C4—C2—C3—N1 | 179.63 (12) | C17—C12—C13—C18 | 178.75 (12) |
N2—C2—C3—C5 | 178.80 (12) | C11—C12—C13—C18 | −3.09 (18) |
C4—C2—C3—C5 | −1.3 (2) | C12—C13—C14—C15 | −0.14 (19) |
N2—C1—C6—C7 | 28.19 (17) | C18—C13—C14—C15 | 178.61 (12) |
N1—C1—C6—C7 | −149.80 (12) | C13—C14—C15—C16 | 1.96 (19) |
N2—C1—C6—C11 | −151.88 (12) | C13—C14—C15—C19 | −177.59 (12) |
N1—C1—C6—C11 | 30.13 (17) | C14—C15—C16—C17 | −1.2 (2) |
C11—C6—C7—C8 | −1.86 (18) | C19—C15—C16—C17 | 178.37 (12) |
C1—C6—C7—C8 | 178.07 (11) | C15—C16—C17—C12 | −1.41 (19) |
C6—C7—C8—C9 | −0.24 (19) | C15—C16—C17—C20 | 178.07 (12) |
C7—C8—C9—C10 | 1.9 (2) | C13—C12—C17—C16 | 3.27 (18) |
C8—C9—C10—C11 | −1.4 (2) | C11—C12—C17—C16 | −174.89 (11) |
C9—C10—C11—C6 | −0.73 (19) | C13—C12—C17—C20 | −176.21 (12) |
C9—C10—C11—C12 | 178.97 (12) | C11—C12—C17—C20 | 5.63 (18) |
C7—C6—C11—C10 | 2.32 (17) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N3i | 0.901 (14) | 2.351 (15) | 2.9883 (16) | 127.7 (12) |
C14—H14A···N4i | 0.95 | 2.62 | 3.5476 (17) | 166 |
C19—H19C···N4ii | 0.98 | 2.66 | 3.6327 (19) | 175 |
C16—H16A···C3iii | 0.95 | 2.96 | 3.8507 (17) | 158 |
C16—H16A···C5iii | 0.95 | 3.07 | 3.8580 (18) | 142 |
C19—H19A···C2iii | 0.98 | 2.91 | 3.7899 (19) | 150 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+2, y+1/2, −z+3/2; (iii) −x+2, −y+1, −z+1. |
(III) 2-[8-(3,5-Dimethylphenyl)naphthalen-1-yl]-1
H-imidazole-4,5-dicarbonitrile
top
Crystal data top
C23H16N4 | Dx = 1.285 Mg m−3 |
Mr = 348.40 | Melting point: 514(1) K |
Orthorhombic, Pca21 | Cu Kα radiation, λ = 1.54180 Å |
Hall symbol: P 2c -2ac | Cell parameters from 25 reflections |
a = 16.7042 (14) Å | θ = 46–62° |
b = 7.1632 (7) Å | µ = 0.62 mm−1 |
c = 15.0528 (11) Å | T = 294 K |
V = 1801.2 (3) Å3 | Block, colourless |
Z = 4 | 0.60 × 0.40 × 0.25 mm |
F(000) = 728 | |
Data collection top
Enraf–Nonius CAD-4 diffractometer | 1753 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.019 |
Graphite monochromator | θmax = 69.9°, θmin = 5.3° |
ω scans | h = −20→20 |
Absorption correction: ψ scan MolEN (Fair, 1990) | k = 0→8 |
Tmin = 0.776, Tmax = 0.857 | l = −18→18 |
3815 measured reflections | 3 standard reflections every 90 min |
1781 independent reflections | intensity decay: 2.0% |
Refinement top
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)] = 0.027 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.070 | w = 1/[σ2(Fo2) + (0.046P)2 + 0.15P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
1781 reflections | Δρmax = 0.13 e Å−3 |
251 parameters | Δρmin = −0.12 e Å−3 |
1 restraint | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0137 (6) |
Crystal data top
C23H16N4 | V = 1801.2 (3) Å3 |
Mr = 348.40 | Z = 4 |
Orthorhombic, Pca21 | Cu Kα radiation |
a = 16.7042 (14) Å | µ = 0.62 mm−1 |
b = 7.1632 (7) Å | T = 294 K |
c = 15.0528 (11) Å | 0.60 × 0.40 × 0.25 mm |
Data collection top
Enraf–Nonius CAD-4 diffractometer | 1753 reflections with I > 2σ(I) |
Absorption correction: ψ scan MolEN (Fair, 1990) | Rint = 0.019 |
Tmin = 0.776, Tmax = 0.857 | 3 standard reflections every 90 min |
3815 measured reflections | intensity decay: 2.0% |
1781 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.027 | 1 restraint |
wR(F2) = 0.070 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.13 e Å−3 |
1781 reflections | Δρmin = −0.12 e Å−3 |
251 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R-factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.39034 (9) | 0.03608 (19) | 0.39285 (9) | 0.0420 (3) | |
N2 | 0.48444 (8) | 0.0795 (2) | 0.49401 (9) | 0.0394 (3) | |
N3 | 0.47805 (12) | 0.0167 (3) | 0.18351 (11) | 0.0665 (5) | |
N4 | 0.66997 (11) | 0.1656 (3) | 0.38986 (14) | 0.0759 (6) | |
C1 | 0.33666 (9) | 0.1751 (2) | 0.62080 (10) | 0.0393 (3) | |
C2 | 0.37449 (10) | 0.3547 (2) | 0.62529 (11) | 0.0432 (4) | |
C3 | 0.36311 (12) | 0.4641 (3) | 0.70001 (13) | 0.0534 (4) | |
H3A | 0.3887 | 0.5791 | 0.7032 | 0.064* | |
C4 | 0.31469 (13) | 0.4082 (3) | 0.77064 (14) | 0.0593 (5) | |
H4A | 0.3093 | 0.4842 | 0.8204 | 0.071* | |
C5 | 0.27531 (11) | 0.2422 (3) | 0.76655 (13) | 0.0550 (5) | |
H5A | 0.2421 | 0.2062 | 0.8130 | 0.066* | |
C6 | 0.28460 (10) | 0.1244 (3) | 0.69229 (12) | 0.0456 (4) | |
C7 | 0.24059 (12) | −0.0446 (3) | 0.68892 (15) | 0.0551 (5) | |
H7A | 0.2076 | −0.0769 | 0.7362 | 0.066* | |
C8 | 0.24593 (14) | −0.1599 (3) | 0.61781 (15) | 0.0605 (5) | |
H8A | 0.2144 | −0.2667 | 0.6148 | 0.073* | |
C9 | 0.29923 (11) | −0.1173 (3) | 0.54884 (13) | 0.0516 (4) | |
H9A | 0.3033 | −0.1982 | 0.5007 | 0.062* | |
C10 | 0.34525 (10) | 0.0400 (2) | 0.55056 (11) | 0.0409 (3) | |
C11 | 0.42305 (11) | 0.4389 (2) | 0.55251 (12) | 0.0426 (4) | |
C12 | 0.39158 (11) | 0.4619 (2) | 0.46758 (12) | 0.0438 (4) | |
H12A | 0.3397 | 0.4219 | 0.4557 | 0.053* | |
C13 | 0.43646 (12) | 0.5437 (2) | 0.40042 (12) | 0.0462 (4) | |
C14 | 0.51353 (12) | 0.6051 (2) | 0.41944 (13) | 0.0501 (4) | |
H14A | 0.5440 | 0.6588 | 0.3745 | 0.060* | |
C15 | 0.54637 (11) | 0.5882 (3) | 0.50413 (14) | 0.0503 (4) | |
C16 | 0.49942 (13) | 0.5053 (3) | 0.56997 (13) | 0.0486 (4) | |
H16A | 0.5200 | 0.4943 | 0.6272 | 0.058* | |
C17 | 0.40170 (15) | 0.5662 (3) | 0.30870 (15) | 0.0640 (6) | |
H17A | 0.3921 | 0.4454 | 0.2832 | 0.096* | |
H17B | 0.4387 | 0.6340 | 0.2720 | 0.096* | |
H17C | 0.3522 | 0.6337 | 0.3124 | 0.096* | |
C18 | 0.62974 (14) | 0.6562 (4) | 0.52483 (18) | 0.0712 (6) | |
H18A | 0.6681 | 0.5668 | 0.5037 | 0.107* | |
H18B | 0.6355 | 0.6711 | 0.5879 | 0.107* | |
H18C | 0.6386 | 0.7740 | 0.4960 | 0.107* | |
C19 | 0.40546 (10) | 0.0538 (2) | 0.47883 (11) | 0.0384 (3) | |
C20 | 0.46288 (11) | 0.0564 (2) | 0.35248 (10) | 0.0414 (4) | |
C21 | 0.52226 (11) | 0.0854 (2) | 0.41370 (11) | 0.0404 (3) | |
C22 | 0.47209 (12) | 0.0383 (3) | 0.25815 (12) | 0.0486 (4) | |
C23 | 0.60471 (11) | 0.1274 (3) | 0.40170 (12) | 0.0501 (4) | |
H2A | 0.5051 (13) | 0.085 (3) | 0.5428 (16) | 0.047 (5)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0488 (7) | 0.0474 (7) | 0.0300 (7) | 0.0024 (6) | −0.0010 (6) | −0.0004 (6) |
N2 | 0.0462 (7) | 0.0457 (7) | 0.0262 (7) | 0.0063 (6) | −0.0019 (6) | −0.0015 (5) |
N3 | 0.0735 (12) | 0.0953 (13) | 0.0307 (8) | 0.0048 (10) | 0.0045 (8) | −0.0014 (9) |
N4 | 0.0537 (9) | 0.1049 (15) | 0.0692 (12) | −0.0031 (10) | 0.0037 (9) | 0.0089 (12) |
C1 | 0.0414 (7) | 0.0462 (8) | 0.0303 (7) | 0.0045 (6) | 0.0005 (6) | 0.0025 (7) |
C2 | 0.0496 (8) | 0.0474 (9) | 0.0326 (8) | 0.0027 (7) | 0.0007 (7) | 0.0002 (7) |
C3 | 0.0627 (11) | 0.0539 (10) | 0.0437 (10) | −0.0017 (8) | 0.0045 (8) | −0.0079 (8) |
C4 | 0.0665 (12) | 0.0699 (12) | 0.0414 (10) | 0.0048 (9) | 0.0095 (9) | −0.0134 (10) |
C5 | 0.0570 (10) | 0.0697 (12) | 0.0383 (9) | 0.0047 (8) | 0.0131 (8) | −0.0004 (9) |
C6 | 0.0445 (8) | 0.0542 (9) | 0.0380 (9) | 0.0050 (7) | 0.0046 (7) | 0.0044 (8) |
C7 | 0.0539 (10) | 0.0593 (10) | 0.0522 (11) | −0.0027 (8) | 0.0127 (9) | 0.0087 (9) |
C8 | 0.0622 (10) | 0.0530 (10) | 0.0664 (13) | −0.0115 (9) | 0.0110 (10) | 0.0020 (10) |
C9 | 0.0590 (10) | 0.0486 (9) | 0.0473 (10) | −0.0011 (8) | 0.0024 (8) | −0.0045 (8) |
C10 | 0.0444 (8) | 0.0455 (8) | 0.0327 (8) | 0.0047 (6) | 0.0000 (7) | 0.0026 (6) |
C11 | 0.0524 (9) | 0.0378 (8) | 0.0377 (8) | 0.0022 (6) | 0.0030 (7) | 0.0011 (6) |
C12 | 0.0521 (9) | 0.0383 (8) | 0.0410 (9) | 0.0020 (7) | −0.0002 (7) | 0.0011 (7) |
C13 | 0.0624 (10) | 0.0369 (8) | 0.0393 (9) | 0.0035 (7) | 0.0033 (8) | 0.0024 (7) |
C14 | 0.0628 (11) | 0.0396 (8) | 0.0478 (10) | −0.0004 (7) | 0.0108 (8) | 0.0040 (8) |
C15 | 0.0549 (10) | 0.0416 (8) | 0.0543 (10) | −0.0027 (7) | 0.0031 (8) | 0.0015 (8) |
C16 | 0.0568 (9) | 0.0479 (8) | 0.0411 (9) | −0.0023 (7) | −0.0043 (8) | 0.0010 (8) |
C17 | 0.0856 (15) | 0.0629 (12) | 0.0436 (10) | −0.0065 (11) | −0.0042 (10) | 0.0110 (9) |
C18 | 0.0625 (12) | 0.0749 (15) | 0.0762 (16) | −0.0162 (11) | −0.0018 (11) | 0.0082 (12) |
C19 | 0.0454 (8) | 0.0400 (8) | 0.0299 (8) | 0.0047 (6) | −0.0017 (6) | −0.0004 (6) |
C20 | 0.0533 (9) | 0.0430 (8) | 0.0279 (8) | 0.0043 (7) | −0.0006 (7) | 0.0009 (6) |
C21 | 0.0486 (9) | 0.0413 (8) | 0.0314 (8) | 0.0067 (7) | 0.0005 (6) | 0.0008 (6) |
C22 | 0.0557 (9) | 0.0576 (10) | 0.0326 (9) | 0.0020 (8) | 0.0004 (8) | 0.0007 (7) |
C23 | 0.0517 (10) | 0.0600 (10) | 0.0386 (9) | 0.0051 (8) | 0.0003 (7) | 0.0011 (8) |
Geometric parameters (Å, º) top
N1—C19 | 1.325 (2) | C9—C10 | 1.365 (3) |
N1—C20 | 1.363 (2) | C9—H9A | 0.9300 |
N2—C19 | 1.352 (2) | C10—C19 | 1.479 (2) |
N2—C21 | 1.365 (2) | C11—C16 | 1.387 (3) |
N2—H2A | 0.81 (2) | C11—C12 | 1.392 (2) |
N3—C22 | 1.138 (2) | C12—C13 | 1.388 (2) |
N4—C23 | 1.138 (3) | C12—H12A | 0.9300 |
C1—C6 | 1.430 (2) | C13—C14 | 1.390 (3) |
C1—C2 | 1.435 (2) | C13—C17 | 1.506 (3) |
C1—C10 | 1.440 (2) | C14—C15 | 1.393 (3) |
C2—C3 | 1.384 (3) | C14—H14A | 0.9300 |
C2—C11 | 1.491 (2) | C15—C16 | 1.397 (3) |
C3—C4 | 1.394 (3) | C15—C18 | 1.508 (3) |
C3—H3A | 0.9300 | C16—H16A | 0.9300 |
C4—C5 | 1.361 (3) | C17—H17A | 0.9600 |
C4—H4A | 0.9300 | C17—H17B | 0.9600 |
C5—C6 | 1.409 (3) | C17—H17C | 0.9600 |
C5—H5A | 0.9300 | C18—H18A | 0.9600 |
C6—C7 | 1.417 (3) | C18—H18B | 0.9600 |
C7—C8 | 1.355 (3) | C18—H18C | 0.9600 |
C7—H7A | 0.9300 | C20—C21 | 1.370 (2) |
C8—C9 | 1.401 (3) | C20—C22 | 1.434 (2) |
C8—H8A | 0.9300 | C21—C23 | 1.421 (3) |
| | | |
C19—N1—C20 | 104.82 (14) | C13—C12—H12A | 119.5 |
C19—N2—C21 | 107.84 (14) | C11—C12—H12A | 119.5 |
C19—N2—H2A | 125.1 (15) | C12—C13—C14 | 118.92 (17) |
C21—N2—H2A | 127.0 (15) | C12—C13—C17 | 120.30 (17) |
C6—C1—C2 | 117.37 (14) | C14—C13—C17 | 120.77 (17) |
C6—C1—C10 | 116.25 (15) | C13—C14—C15 | 121.71 (17) |
C2—C1—C10 | 126.37 (14) | C13—C14—H14A | 119.1 |
C3—C2—C1 | 119.04 (16) | C15—C14—H14A | 119.1 |
C3—C2—C11 | 116.30 (16) | C14—C15—C16 | 117.73 (17) |
C1—C2—C11 | 124.59 (15) | C14—C15—C18 | 121.65 (19) |
C2—C3—C4 | 122.47 (18) | C16—C15—C18 | 120.62 (19) |
C2—C3—H3A | 118.8 | C11—C16—C15 | 121.86 (18) |
C4—C3—H3A | 118.8 | C11—C16—H16A | 119.1 |
C5—C4—C3 | 119.78 (18) | C15—C16—H16A | 119.1 |
C5—C4—H4A | 120.1 | C13—C17—H17A | 109.5 |
C3—C4—H4A | 120.1 | C13—C17—H17B | 109.5 |
C4—C5—C6 | 120.41 (18) | H17A—C17—H17B | 109.5 |
C4—C5—H5A | 119.8 | C13—C17—H17C | 109.5 |
C6—C5—H5A | 119.8 | H17A—C17—H17C | 109.5 |
C5—C6—C7 | 118.87 (17) | H17B—C17—H17C | 109.5 |
C5—C6—C1 | 120.78 (16) | C15—C18—H18A | 109.5 |
C7—C6—C1 | 120.35 (16) | C15—C18—H18B | 109.5 |
C8—C7—C6 | 120.99 (18) | H18A—C18—H18B | 109.5 |
C8—C7—H7A | 119.5 | C15—C18—H18C | 109.5 |
C6—C7—H7A | 119.5 | H18A—C18—H18C | 109.5 |
C7—C8—C9 | 119.63 (18) | H18B—C18—H18C | 109.5 |
C7—C8—H8A | 120.2 | N1—C19—N2 | 111.36 (15) |
C9—C8—H8A | 120.2 | N1—C19—C10 | 125.26 (15) |
C10—C9—C8 | 121.58 (18) | N2—C19—C10 | 123.33 (14) |
C10—C9—H9A | 119.2 | N1—C20—C21 | 111.10 (14) |
C8—C9—H9A | 119.2 | N1—C20—C22 | 121.80 (16) |
C9—C10—C1 | 120.84 (16) | C21—C20—C22 | 127.02 (17) |
C9—C10—C19 | 115.11 (15) | N2—C21—C20 | 104.83 (15) |
C1—C10—C19 | 123.98 (14) | N2—C21—C23 | 124.60 (16) |
C16—C11—C12 | 118.75 (16) | C20—C21—C23 | 130.42 (16) |
C16—C11—C2 | 120.00 (16) | N3—C22—C20 | 177.1 (2) |
C12—C11—C2 | 121.15 (16) | N4—C23—C21 | 177.5 (2) |
C13—C12—C11 | 120.98 (17) | | |
| | | |
C6—C1—C2—C3 | 4.0 (2) | C16—C11—C12—C13 | 2.3 (2) |
C10—C1—C2—C3 | −176.64 (17) | C2—C11—C12—C13 | 178.74 (15) |
C6—C1—C2—C11 | −172.89 (16) | C11—C12—C13—C14 | −0.9 (2) |
C10—C1—C2—C11 | 6.5 (3) | C11—C12—C13—C17 | 179.54 (17) |
C1—C2—C3—C4 | −1.5 (3) | C12—C13—C14—C15 | −0.6 (2) |
C11—C2—C3—C4 | 175.69 (18) | C17—C13—C14—C15 | 178.99 (17) |
C2—C3—C4—C5 | −1.4 (3) | C13—C14—C15—C16 | 0.6 (3) |
C3—C4—C5—C6 | 1.5 (3) | C13—C14—C15—C18 | −179.54 (19) |
C4—C5—C6—C7 | −177.90 (19) | C12—C11—C16—C15 | −2.3 (3) |
C4—C5—C6—C1 | 1.2 (3) | C2—C11—C16—C15 | −178.80 (17) |
C2—C1—C6—C5 | −3.9 (2) | C14—C15—C16—C11 | 0.9 (3) |
C10—C1—C6—C5 | 176.62 (16) | C18—C15—C16—C11 | −178.97 (19) |
C2—C1—C6—C7 | 175.19 (16) | C20—N1—C19—N2 | −1.6 (2) |
C10—C1—C6—C7 | −4.2 (2) | C20—N1—C19—C10 | −179.23 (14) |
C5—C6—C7—C8 | 178.2 (2) | C21—N2—C19—N1 | 2.2 (2) |
C1—C6—C7—C8 | −0.9 (3) | C21—N2—C19—C10 | 179.93 (14) |
C6—C7—C8—C9 | 3.8 (3) | C9—C10—C19—N1 | 52.5 (2) |
C7—C8—C9—C10 | −1.2 (3) | C1—C10—C19—N1 | −130.50 (18) |
C8—C9—C10—C1 | −4.3 (3) | C9—C10—C19—N2 | −124.88 (18) |
C8—C9—C10—C19 | 172.79 (18) | C1—C10—C19—N2 | 52.1 (2) |
C6—C1—C10—C9 | 6.8 (2) | C19—N1—C20—C21 | 0.35 (19) |
C2—C1—C10—C9 | −172.56 (17) | C19—N1—C20—C22 | 177.34 (16) |
C6—C1—C10—C19 | −170.01 (15) | C19—N2—C21—C20 | −1.85 (17) |
C2—C1—C10—C19 | 10.6 (3) | C19—N2—C21—C23 | 174.04 (16) |
C3—C2—C11—C16 | 55.2 (2) | N1—C20—C21—N2 | 0.94 (18) |
C1—C2—C11—C16 | −127.87 (19) | C22—C20—C21—N2 | −175.85 (18) |
C3—C2—C11—C12 | −121.27 (19) | N1—C20—C21—C23 | −174.61 (17) |
C1—C2—C11—C12 | 55.7 (2) | C22—C20—C21—C23 | 8.6 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···N3i | 0.81 (2) | 2.26 (2) | 3.001 (2) | 152 (2) |
Symmetry code: (i) −x+1, −y, z+1/2. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C19H14N4 | C20H16N4 | C23H16N4 |
Mr | 298.34 | 312.37 | 348.40 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/c | Orthorhombic, Pca21 |
Temperature (K) | 134 | 133 | 294 |
a, b, c (Å) | 9.771 (2), 16.807 (2), 19.692 (2) | 12.373 (1), 10.303 (2), 13.279 (2) | 16.7042 (14), 7.1632 (7), 15.0528 (11) |
α, β, γ (°) | 90, 93.976 (7), 90 | 90, 92.578 (7), 90 | 90, 90, 90 |
V (Å3) | 3226.1 (8) | 1691.1 (4) | 1801.2 (3) |
Z | 8 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Cu Kα |
µ (mm−1) | 0.08 | 0.08 | 0.62 |
Crystal size (mm) | 0.36 × 0.30 × 0.15 | 0.60 × 0.40 × 0.10 | 0.60 × 0.40 × 0.25 |
|
Data collection |
Diffractometer | Siemens SMART 1K CCD area-detector diffractometer | Siemens SMART 1K CCD area-detector diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | Multi-scan SADABS (Sheldrick, 1996) | Multi-scan SADABS (Sheldrick, 1996) | ψ scan MolEN (Fair, 1990) |
Tmin, Tmax | 0.867, 0.989 | 0.784, 0.993 | 0.776, 0.857 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 47542, 7317, 3808 | 25406, 4381, 3014 | 3815, 1781, 1753 |
Rint | 0.067 | 0.033 | 0.019 |
(sin θ/λ)max (Å−1) | 0.650 | 0.682 | 0.609 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.093, 0.92 | 0.040, 0.104, 1.04 | 0.027, 0.070, 1.05 |
No. of reflections | 7317 | 4381 | 1781 |
No. of parameters | 428 | 225 | 251 |
No. of restraints | 0 | 0 | 1 |
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 |
Δρmax, Δρmin (e Å−3) | 0.22, −0.17 | 0.23, −0.20 | 0.13, −0.12 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···N6 | 0.97 (2) | 2.02 (2) | 2.907 (2) | 150.9 (17) |
N5—H5B···N1i | 0.953 (19) | 1.95 (2) | 2.882 (2) | 164.4 (17) |
C11—H11A···N8ii | 0.95 | 2.69 | 3.567 (3) | 153.6 |
C16—H16B···N6iii | 0.98 | 2.60 | 3.484 (3) | 149.6 |
C16—H16C···N3iv | 0.98 | 2.65 | 3.497 (3) | 144.9 |
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x+2, −y+1, −z; (iii) −x+3/2, y−1/2, −z+1/2; (iv) x+1/2, −y+1/2, z+1/2. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N3i | 0.901 (14) | 2.351 (15) | 2.9883 (16) | 127.7 (12) |
C14—H14A···N4i | 0.95 | 2.62 | 3.5476 (17) | 165.6 |
C19—H19C···N4ii | 0.98 | 2.66 | 3.6327 (19) | 174.6 |
C16—H16A···C3iii | 0.95 | 2.96 | 3.8507 (17) | 157.6 |
C16—H16A···C5iii | 0.95 | 3.07 | 3.8580 (18) | 141.8 |
C19—H19A···C2iii | 0.98 | 2.91 | 3.7899 (19) | 149.7 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+2, y+1/2, −z+3/2; (iii) −x+2, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···N3i | 0.81 (2) | 2.26 (2) | 3.001 (2) | 152 (2) |
Symmetry code: (i) −x+1, −y, z+1/2. |
Methylphosphonate oligonucleotides differ from conventional oligonucleotides by the replacement of a negatively charged O atom at the phosphonate linkage by a methyl group. They are more stable to degradation by cellular nucleases than conventional oligonucleotides and can be applied in the antisense concept to control gene expression in mammalian cells (Uhlmann & Peyman, 1990). The P atoms in methylphosphonate oligonucleotides are chiral. RP-configured molecules bind better to their target strand than SP-configured ones (Lebedev & Wickstrom, 1996). The phosphoramidite approach can be used for the synthesis of methylphosphonate oligonucleotides (Jäger & Engels, 1984). The reaction is activated by the use of tetrazole but no stereocontrol occurs at the P atom. Also, the use of tetrazoles with a chiral substituent shows only weak selectivity (Schell & Engels, 1997). Therefore, substituted 1H-imidazole-4,5-dicarbonitriles were tested as activators for stereoselection during the synthesis of dinucleoside methylphosphonates. Selectivities up to 84/16 (RP/SP) have been reported by Schell & Engels (1998). Single crystals were obtained for three different substituted 1H-imidazole-4,5-dicarbonitriles used for these experiments and the crystal structures of these three compounds, (I), (II) and (III), are reported here.
The crystal structure of (I) contains two crystallographically independent molecules, A and B (Fig. 1), which have very similar conformations. The angle between the planes of the six-membered rings of the biphenyl group is 44.91 (6)° for molecule A and 42.09 (6)° for molecule B. The angle between the plane of the imidazole group and the plane of the central phenyl group is 46.02 (7)° for molecule A and 39.57 (7)° for molecule B. There is significant steric repulsion between the dimethylphenyl group and the imidazole group [shortest contacts: C5···C13 = 3.115 (3) Å, N5···C20 = 3.094 (3) Å, N5···C25 = 3.144 (2) Å and C20···C32 = 3.115 (3) Å]. These steric contacts are not only responsible for the non-planar conformation of the biphenyl group, but also result in an out-of-plane distortion of the dimethylphenyl and imidazole groups with respect to the plane of the central phenyl ring. Consequently, the C6—C7—C12—C13 and C25—C26—C31—C32 torsion angles are -6.6 (3) and -9.6 (3)°, respectively. The amino N atoms are planar, the sums of the three valence angles about atoms N2 and N5 being 359.4 (8) and 360.0 (9)°, respectively. The molecules are connected by N—H···N hydrogen bonds (Fig. 2, Table 1) between the imidazole groups to form zigzag chains parallel to the b axis direction. These chains are connected by weak intermolecular C—H···N contacts (Table 1) to give a three-dimensional structure.
The molecular structure of (II) is shown in Fig. 3. The angle between the planes of the six-membered rings of the biphenyl group is 71.20 (4)°, almost 30° larger than the corresponding values in (I), and it results from steric repulsions between the ortho methyl groups and the imidazole group and C10—H10A bond [shortest contacts: C10···C18 = 3.261 (2) Å and C1···H20C = 2.75 Å]. The angle between the planes of the imidazole ring and the central phenyl ring is 29.39 (6)°, slightly smaller than the corresponding value observed in (I), despite the short intramolecular contact distance of 2.879 (2) Å between atoms N1 and C12. The C1—C6—C11—C12 torsion angle of 2.7 (2)° again shows a small out-of-plane distortion of the trimethylphenyl and imidazole groups from the plane of the central phenyl ring, but this distortion is smaller than the corresponding distortion observed in (I). The amino N atom is planar, the sum of the three valence angles about atom N1 being 359.6 (7)°. The crystal packing of (II) is shown in Fig. 4. The molecules are connected by rather weak intermolecular hydrogen bonds between the N—H bond and a cyano N atom of a neighbouring molecule (Table 2) to form zigzag chains along the c axis direction. The long H···N distance of 2.351 (15) Å and the small N—H—N angle of 127.7 (12)° show this hydrogen bond to be rather weak. The crystal packing also shows two weak intermolecular C—H···Ncyano contacts (Table 2). One of these results in an additional stabilization of the hydrogen-bonded chain and the other connects the chains along the b axis direction. Along the a axis direction the molecules are only connected by intermolecular C—H···πimidazole contacts (final three entries of Table 2) These contacts are very weak. Consequently, the crystal habit is a (100) plate.
The molecular structure of (III) is shown in Fig. 5. The naphthalene group shows considerable deviation from planarity (mean deviation from best plane = 0.041 Å). Ring atoms C2 and C10 deviate by 0.0567 (14) and 0.0788 (14) Å, respectively, in opposite directions from the best plane of the naphthalene group. The out-of-plane deviation from the naphthalene plane is even more pronounced for substituent atoms C11 and C19 [deviations of 0.221 (2) and 0.299 (2) Å, respectively] as a result of steric interactions between the dimethylphenyl group and the imidazole group. The shortest contact distances are: C11···N2 = 2.908 (2) Å, C11···C19 = 2.988 (2) Å and C12···C19 = 2.937 (2) Å. Steric repulsion between the dimethylphenyl and imidazole groups also results in rather large values of the C1—C2—C11, C2—C1—C10 and C1—C10—C19 bond angles [124.59 (15), 126.37 (14) and 123.98 (14)°, respectively]. The angle between the naphthalene plane and the dimethylphenyl plane is 55.20 (4)°. The angle between the naphthalene plane and the imidazole plane is 54.11 (6)°. The angle between the dimethylphenyl plane and the imidazole plane is 22.71 (5)°. The amino N atom again is planar, the sum of the three valence angles about atom N2 being 359.9 (10)°. The crystal packing of (III) is shown in Fig. 6. The molecules are connected by intermolecular N—H···Ncyano hydrogen bonds (Table 3) to form zigzag chains parallel to the c axis direction. There are no other short intermolecular contact distances. The shortest intermolecular C—H···N contact has an H···N distance of 2.74 Å.
The bond lengths and angles in the dicyanoimidazole groups of (I), (II) and (III) are in excellent agreement. They are also very similar to the corresponding bond lengths and angles observed in the crystal structure of 1H-imidazole-4,5-dicarbonitrile (Barni et al., 1997). The C—N bond lengths in the imidazole rings range from 1.325 (2) to 1.377 (2) Å, thus showing a considerable degree of delocalization of the double bonds in the ring. The N—H···Nimidazole hydrogen bond in (I) is considerably shorter than the N—H···Ncyano hydrogen bonds in (II) and (III).
The three title compounds have been tested as activators in the coupling reaction to produce a protected thymine dinucleoside methylphosphonate TpT (Schell & Engels, 1998). The RP/SP stereoselectivities were 65/35 for (I) and 77/23 for (II), while no reaction occurred for (III). Thus, the stereoselectivity of these compounds depends very much on the substituent of the imidazole group.