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We describe the polymorphism of four new bis-hydrazone compounds, namely butane-2,3-dione 2,3-bis{[bis(4-fluorophenyl)methylidene]hydrazone}, C30H22F4N4 (1), butane-2,3-dione 2,3-bis{[bis(4-chlorophenyl)methylidene]hydrazone}, C30H22Cl4N4 (2), butane-2,3-dione 2,3-bis{[bis(4-methylphenyl)methylidene]hydrazone}, C34H34N4 (3), and butane-2,3-dione 2,3-bis({bis[4-(dimethylamino)phenyl]methylidene}hydrazone), C38H46N8 (4), derived by the condensation reaction between substituted benzophenone hydrazone and butane-2,3-dione. Concomitant polymorphism has been observed in 1, 2 and 3. Overlays of molecules of the different polymorphs indicate that there is conformational adjustment in the crystal structures of the polymorphs of 1 and 2, i.e. packing polymorphism, which was confirmed by a computational study. On the other hand, conformational change was observed in the cases of the polymorphs of compounds 3 and 4, i.e. conformational polymorphism.
Supporting information
| Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229618014286/uk3160sup1.cif Contains datablocks 1a, 1b, 1c, 2a, 2b, 3a, 3b, 4a, 4b, gloabal |
| Structure factor file (CIF format) https://doi.org/10.1107/S2053229618014286/uk31601asup2.hkl Contains datablock 1a |
| Structure factor file (CIF format) https://doi.org/10.1107/S2053229618014286/uk31601bsup3.hkl Contains datablock 1b |
| Structure factor file (CIF format) https://doi.org/10.1107/S2053229618014286/uk31601csup4.hkl Contains datablock 1c |
| Structure factor file (CIF format) https://doi.org/10.1107/S2053229618014286/uk31602asup5.hkl Contains datablock 2a |
| Structure factor file (CIF format) https://doi.org/10.1107/S2053229618014286/uk31602bsup6.hkl Contains datablock 2b |
| Structure factor file (CIF format) https://doi.org/10.1107/S2053229618014286/uk31603asup7.hkl Contains datablock 3a |
| Structure factor file (CIF format) https://doi.org/10.1107/S2053229618014286/uk31603bsup8.hkl Contains datablock 3b |
| Structure factor file (CIF format) https://doi.org/10.1107/S2053229618014286/uk31604asup9.hkl Contains datablock 4a |
| Structure factor file (CIF format) https://doi.org/10.1107/S2053229618014286/uk31604bsup10.hkl Contains datablock 4b |
| Portable Document Format (PDF) file https://doi.org/10.1107/S2053229618014286/uk3160sup11.pdf Crystallization details, ellipsoid plots and Hirshfeld analysis |
CCDC references: 1841917; 1841916; 1841911; 1841915; 1841912; 1841918; 1841913; 1841910; 1841914
For all structures, data collection: APEX3 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008). Program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015) for (1a), (1b), (1c), (2a), (2b); SHELXL2014 (Sheldrick, 2015) for (3a), (3b), (4a), (4b). For all structures, molecular graphics: X-SEED (Barbour, 2001).
Butane-2,3-dione 2,3-bis{[bis(4-fluorophenyl)methylidene]hydrazone} (1a)
top
Crystal data top
C30H22F4N4 | F(000) = 532 |
Mr = 514.51 | Dx = 1.327 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 10.1480 (9) Å | Cell parameters from 9988 reflections |
b = 11.2687 (11) Å | θ = 2.6–28.1° |
c = 11.5255 (12) Å | µ = 0.10 mm−1 |
β = 102.371 (3)° | T = 298 K |
V = 1287.4 (2) Å3 | Block, yellow |
Z = 2 | 0.41 × 0.22 × 0.07 mm |
Data collection top
Bruker APEXIII CMOS detector diffractometer | 2291 reflections with I > 2σ(I) |
Radiation source: microfocus | Rint = 0.050 |
phi and ω scans | θmax = 28.3°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | h = −13→10 |
Tmin = 0.974, Tmax = 0.993 | k = −15→15 |
28537 measured reflections | l = −15→15 |
3206 independent reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.049 | w = 1/[σ2(Fo2) + (0.0529P)2 + 0.3545P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.134 | (Δ/σ)max < 0.001 |
S = 1.05 | Δρmax = 0.23 e Å−3 |
3206 reflections | Δρmin = −0.18 e Å−3 |
174 parameters | Extinction correction: SHELXL2016 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.022 (3) |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. The crystal structures of all the polymorphs were determined by
single-crystal X-ray diffraction (SCD) on a Bruker D8 Quest Diffractometer
equipped with a microfocus anode (Mo) and a PHOTON 100 CMOS detector,
employing φ and ω scans. Integration and scaling of data were performed by
SAINT and SADABS program incorporated in the APEXIII suit (Bruker, 2012,
2013). The structures were solved by direct
methods using SHELXS2014
(Sheldrick, 2015a) and refined by full-matrix least-squares on
F2
using SHELX2016 (Sheldrick, 2015b). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
F1 | 0.33187 (13) | −0.14627 (11) | 0.23459 (13) | 0.0933 (4) | |
F2 | 0.53925 (16) | 0.69428 (10) | 0.37182 (13) | 0.0997 (5) | |
N1 | 0.81620 (13) | 0.20065 (11) | 0.46090 (13) | 0.0522 (4) | |
N2 | 0.85191 (12) | 0.08095 (11) | 0.47470 (13) | 0.0495 (3) | |
C1 | 0.69233 (14) | 0.21873 (13) | 0.40757 (14) | 0.0442 (4) | |
C2 | 0.59512 (14) | 0.12473 (13) | 0.35578 (13) | 0.0438 (4) | |
C3 | 0.62408 (17) | 0.04173 (16) | 0.27662 (16) | 0.0564 (4) | |
H3 | 0.705175 | 0.046755 | 0.251631 | 0.068* | |
C4 | 0.53499 (19) | −0.04839 (17) | 0.23399 (18) | 0.0657 (5) | |
H4 | 0.554422 | −0.103115 | 0.179614 | 0.079* | |
C5 | 0.41855 (17) | −0.05546 (16) | 0.27307 (17) | 0.0608 (5) | |
C6 | 0.38553 (17) | 0.02364 (18) | 0.35122 (17) | 0.0625 (5) | |
H6 | 0.305228 | 0.016060 | 0.377134 | 0.075* | |
C7 | 0.47312 (16) | 0.11498 (16) | 0.39115 (16) | 0.0548 (4) | |
H7 | 0.450375 | 0.171136 | 0.442662 | 0.066* | |
C8 | 0.64851 (15) | 0.34474 (13) | 0.39940 (14) | 0.0448 (4) | |
C9 | 0.53820 (17) | 0.38165 (15) | 0.31388 (16) | 0.0545 (4) | |
H9 | 0.488847 | 0.326462 | 0.262168 | 0.065* | |
C10 | 0.50115 (19) | 0.49994 (17) | 0.30501 (17) | 0.0630 (5) | |
H10 | 0.427018 | 0.524759 | 0.247932 | 0.076* | |
C11 | 0.5745 (2) | 0.57903 (16) | 0.38076 (17) | 0.0617 (5) | |
C12 | 0.6831 (2) | 0.54650 (16) | 0.46662 (17) | 0.0632 (5) | |
H12 | 0.731327 | 0.602680 | 0.517847 | 0.076* | |
C13 | 0.71972 (18) | 0.42891 (15) | 0.47574 (16) | 0.0554 (4) | |
H13 | 0.793377 | 0.405400 | 0.534013 | 0.067* | |
C14 | 0.97954 (14) | 0.06282 (12) | 0.49187 (13) | 0.0420 (3) | |
C15 | 1.08342 (16) | 0.15739 (14) | 0.49659 (18) | 0.0583 (5) | |
H15A | 1.090026 | 0.178273 | 0.417278 | 0.087* | |
H15B | 1.169129 | 0.128711 | 0.539551 | 0.087* | |
H15C | 1.057962 | 0.226053 | 0.535962 | 0.087* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
F1 | 0.0740 (8) | 0.0764 (8) | 0.1153 (11) | −0.0186 (6) | −0.0115 (7) | −0.0051 (7) |
F2 | 0.1396 (12) | 0.0509 (7) | 0.1131 (11) | 0.0369 (7) | 0.0366 (9) | 0.0154 (6) |
N1 | 0.0401 (7) | 0.0394 (7) | 0.0752 (10) | 0.0087 (5) | 0.0083 (6) | 0.0027 (6) |
N2 | 0.0379 (7) | 0.0400 (7) | 0.0688 (9) | 0.0073 (5) | 0.0073 (6) | 0.0040 (6) |
C1 | 0.0387 (7) | 0.0436 (8) | 0.0518 (9) | 0.0091 (6) | 0.0131 (6) | 0.0029 (6) |
C2 | 0.0380 (7) | 0.0448 (8) | 0.0482 (8) | 0.0097 (6) | 0.0084 (6) | 0.0042 (6) |
C3 | 0.0482 (9) | 0.0621 (10) | 0.0615 (10) | 0.0051 (8) | 0.0177 (8) | −0.0065 (8) |
C4 | 0.0640 (11) | 0.0610 (11) | 0.0695 (12) | 0.0039 (9) | 0.0085 (9) | −0.0161 (9) |
C5 | 0.0497 (10) | 0.0549 (10) | 0.0691 (11) | −0.0031 (8) | −0.0070 (8) | 0.0036 (9) |
C6 | 0.0394 (8) | 0.0755 (13) | 0.0719 (12) | −0.0013 (8) | 0.0104 (8) | 0.0074 (10) |
C7 | 0.0416 (8) | 0.0629 (10) | 0.0609 (10) | 0.0069 (7) | 0.0128 (7) | −0.0049 (8) |
C8 | 0.0423 (8) | 0.0439 (8) | 0.0509 (9) | 0.0108 (6) | 0.0157 (6) | 0.0038 (7) |
C9 | 0.0502 (9) | 0.0542 (9) | 0.0587 (10) | 0.0136 (7) | 0.0104 (7) | 0.0050 (8) |
C10 | 0.0626 (11) | 0.0615 (11) | 0.0656 (11) | 0.0255 (9) | 0.0153 (9) | 0.0181 (9) |
C11 | 0.0801 (12) | 0.0444 (9) | 0.0683 (11) | 0.0212 (9) | 0.0333 (10) | 0.0102 (8) |
C12 | 0.0790 (12) | 0.0456 (9) | 0.0674 (11) | 0.0056 (9) | 0.0212 (10) | −0.0045 (8) |
C13 | 0.0568 (10) | 0.0496 (9) | 0.0582 (10) | 0.0105 (7) | 0.0086 (8) | 0.0002 (7) |
C14 | 0.0353 (7) | 0.0407 (8) | 0.0490 (8) | 0.0042 (6) | 0.0069 (6) | 0.0036 (6) |
C15 | 0.0434 (9) | 0.0425 (9) | 0.0888 (13) | 0.0022 (7) | 0.0138 (8) | 0.0050 (8) |
Geometric parameters (Å, º) top
F1—C5 | 1.360 (2) | C7—H7 | 0.9300 |
F2—C11 | 1.345 (2) | C8—C13 | 1.387 (2) |
N1—C1 | 1.2917 (19) | C8—C9 | 1.387 (2) |
N1—N2 | 1.3969 (18) | C9—C10 | 1.383 (2) |
N2—C14 | 1.2839 (18) | C9—H9 | 0.9300 |
C1—C2 | 1.483 (2) | C10—C11 | 1.354 (3) |
C1—C8 | 1.485 (2) | C10—H10 | 0.9300 |
C2—C3 | 1.381 (2) | C11—C12 | 1.364 (3) |
C2—C7 | 1.388 (2) | C12—C13 | 1.374 (2) |
C3—C4 | 1.378 (3) | C12—H12 | 0.9300 |
C3—H3 | 0.9300 | C13—H13 | 0.9300 |
C4—C5 | 1.354 (3) | C14—C14i | 1.476 (3) |
C4—H4 | 0.9300 | C14—C15 | 1.492 (2) |
C5—C6 | 1.359 (3) | C15—H15A | 0.9600 |
C6—C7 | 1.373 (2) | C15—H15B | 0.9600 |
C6—H6 | 0.9300 | C15—H15C | 0.9600 |
| | | |
C1—N1—N2 | 114.13 (13) | C9—C8—C1 | 121.12 (15) |
C14—N2—N1 | 113.56 (12) | C10—C9—C8 | 120.44 (17) |
N1—C1—C2 | 125.07 (13) | C10—C9—H9 | 119.8 |
N1—C1—C8 | 115.38 (14) | C8—C9—H9 | 119.8 |
C2—C1—C8 | 119.55 (12) | C11—C10—C9 | 118.93 (17) |
C3—C2—C7 | 118.01 (15) | C11—C10—H10 | 120.5 |
C3—C2—C1 | 122.15 (14) | C9—C10—H10 | 120.5 |
C7—C2—C1 | 119.77 (14) | F2—C11—C10 | 119.06 (18) |
C4—C3—C2 | 121.21 (16) | F2—C11—C12 | 118.37 (19) |
C4—C3—H3 | 119.4 | C10—C11—C12 | 122.56 (16) |
C2—C3—H3 | 119.4 | C11—C12—C13 | 118.54 (18) |
C5—C4—C3 | 118.51 (17) | C11—C12—H12 | 120.7 |
C5—C4—H4 | 120.7 | C13—C12—H12 | 120.7 |
C3—C4—H4 | 120.7 | C12—C13—C8 | 121.03 (17) |
C4—C5—C6 | 122.57 (17) | C12—C13—H13 | 119.5 |
C4—C5—F1 | 119.03 (18) | C8—C13—H13 | 119.5 |
C6—C5—F1 | 118.38 (17) | N2—C14—C14i | 114.79 (16) |
C5—C6—C7 | 118.68 (17) | N2—C14—C15 | 125.00 (13) |
C5—C6—H6 | 120.7 | C14i—C14—C15 | 120.21 (16) |
C7—C6—H6 | 120.7 | C14—C15—H15A | 109.5 |
C6—C7—C2 | 120.98 (16) | C14—C15—H15B | 109.5 |
C6—C7—H7 | 119.5 | H15A—C15—H15B | 109.5 |
C2—C7—H7 | 119.5 | C14—C15—H15C | 109.5 |
C13—C8—C9 | 118.50 (15) | H15A—C15—H15C | 109.5 |
C13—C8—C1 | 120.37 (14) | H15B—C15—H15C | 109.5 |
Symmetry code: (i) −x+2, −y, −z+1. |
Butane-2,3-dione 2,3-bis{[bis(4-fluorophenyl)methylidene]hydrazone} (1b)
top
Crystal data top
C30H22F4N4 | F(000) = 532 |
Mr = 514.51 | Dx = 1.277 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 5.6693 (12) Å | Cell parameters from 3667 reflections |
b = 7.642 (3) Å | θ = 2.6–25.3° |
c = 30.891 (7) Å | µ = 0.10 mm−1 |
β = 90.465 (14)° | T = 298 K |
V = 1338.3 (6) Å3 | Block, yello |
Z = 2 | 0.45 × 0.35 × 0.26 mm |
Data collection top
Bruker APEXIII CMOS detector diffractometer | 1935 reflections with I > 2σ(I) |
Radiation source: microfocus | Rint = 0.033 |
phi and ω scans | θmax = 28.3°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | h = −5→7 |
Tmin = 0.636, Tmax = 0.745 | k = −10→9 |
10103 measured reflections | l = −41→32 |
3061 independent reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.052 | w = 1/[σ2(Fo2) + (0.0584P)2 + 0.3161P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.144 | (Δ/σ)max < 0.001 |
S = 1.03 | Δρmax = 0.17 e Å−3 |
3061 reflections | Δρmin = −0.15 e Å−3 |
174 parameters | Extinction correction: SHELXL2016 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.041 (4) |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
F1 | 0.6152 (2) | 0.3088 (2) | 0.79255 (4) | 0.0928 (5) | |
F2 | −0.0570 (4) | 1.1624 (2) | 0.59694 (6) | 0.1404 (8) | |
N1 | 0.5648 (3) | 0.4745 (2) | 0.59372 (5) | 0.0605 (5) | |
N2 | 0.5523 (3) | 0.5550 (2) | 0.55334 (5) | 0.0624 (5) | |
C1 | 0.4633 (3) | 0.5572 (2) | 0.62460 (5) | 0.0476 (4) | |
C2 | 0.5009 (3) | 0.4877 (2) | 0.66911 (5) | 0.0461 (4) | |
C3 | 0.6985 (3) | 0.3899 (3) | 0.67922 (6) | 0.0619 (5) | |
H3 | 0.807904 | 0.365405 | 0.657788 | 0.074* | |
C4 | 0.7359 (4) | 0.3281 (3) | 0.72052 (7) | 0.0686 (6) | |
H4 | 0.869088 | 0.261993 | 0.727175 | 0.082* | |
C5 | 0.5739 (4) | 0.3657 (3) | 0.75146 (6) | 0.0615 (5) | |
C6 | 0.3757 (4) | 0.4583 (3) | 0.74311 (6) | 0.0610 (5) | |
H6 | 0.265914 | 0.479374 | 0.764705 | 0.073* | |
C7 | 0.3406 (3) | 0.5210 (2) | 0.70149 (5) | 0.0535 (5) | |
H7 | 0.206585 | 0.586761 | 0.695233 | 0.064* | |
C8 | 0.3186 (3) | 0.7161 (2) | 0.61840 (5) | 0.0465 (4) | |
C9 | 0.3905 (3) | 0.8732 (2) | 0.63630 (6) | 0.0593 (5) | |
H9 | 0.525660 | 0.876956 | 0.653542 | 0.071* | |
C10 | 0.2636 (5) | 1.0247 (3) | 0.62881 (7) | 0.0753 (6) | |
H10 | 0.313131 | 1.131248 | 0.640225 | 0.090* | |
C11 | 0.0648 (5) | 1.0132 (3) | 0.60434 (7) | 0.0806 (7) | |
C12 | −0.0153 (4) | 0.8608 (4) | 0.58702 (7) | 0.0821 (7) | |
H12 | −0.154116 | 0.857752 | 0.570795 | 0.098* | |
C13 | 0.1135 (3) | 0.7115 (3) | 0.59404 (6) | 0.0636 (5) | |
H13 | 0.062176 | 0.606026 | 0.582268 | 0.076* | |
C14 | 0.4985 (3) | 0.4570 (3) | 0.52148 (6) | 0.0599 (5) | |
C15 | 0.4332 (7) | 0.2697 (3) | 0.52493 (8) | 0.1123 (10) | |
H15A | 0.506145 | 0.220121 | 0.550263 | 0.168* | |
H15B | 0.486304 | 0.208298 | 0.499700 | 0.168* | |
H15C | 0.264966 | 0.259319 | 0.527049 | 0.168* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
F1 | 0.1043 (10) | 0.1121 (11) | 0.0615 (8) | −0.0147 (8) | −0.0225 (7) | 0.0356 (7) |
F2 | 0.1773 (17) | 0.1235 (14) | 0.1205 (13) | 0.0994 (13) | 0.0055 (12) | 0.0129 (10) |
N1 | 0.0834 (11) | 0.0578 (10) | 0.0405 (8) | 0.0143 (8) | −0.0003 (7) | −0.0040 (7) |
N2 | 0.0882 (11) | 0.0600 (10) | 0.0390 (8) | 0.0121 (8) | 0.0035 (7) | −0.0022 (7) |
C1 | 0.0560 (10) | 0.0475 (10) | 0.0393 (9) | 0.0018 (8) | −0.0041 (7) | −0.0065 (7) |
C2 | 0.0549 (9) | 0.0421 (9) | 0.0412 (9) | 0.0001 (8) | −0.0060 (7) | −0.0045 (7) |
C3 | 0.0644 (11) | 0.0643 (13) | 0.0568 (11) | 0.0153 (10) | −0.0012 (9) | 0.0009 (9) |
C4 | 0.0668 (12) | 0.0679 (14) | 0.0709 (14) | 0.0113 (10) | −0.0160 (11) | 0.0142 (10) |
C5 | 0.0735 (13) | 0.0632 (13) | 0.0474 (11) | −0.0153 (10) | −0.0166 (10) | 0.0164 (9) |
C6 | 0.0656 (11) | 0.0731 (14) | 0.0443 (10) | −0.0059 (10) | 0.0010 (8) | 0.0055 (9) |
C7 | 0.0539 (10) | 0.0610 (12) | 0.0456 (10) | 0.0038 (9) | −0.0034 (8) | 0.0025 (8) |
C8 | 0.0540 (9) | 0.0521 (11) | 0.0334 (8) | 0.0049 (8) | −0.0004 (7) | −0.0005 (7) |
C9 | 0.0697 (12) | 0.0552 (12) | 0.0531 (11) | 0.0029 (10) | −0.0037 (9) | −0.0033 (9) |
C10 | 0.1071 (18) | 0.0498 (12) | 0.0691 (14) | 0.0106 (12) | 0.0096 (13) | −0.0027 (10) |
C11 | 0.0979 (17) | 0.0819 (17) | 0.0622 (13) | 0.0488 (14) | 0.0088 (12) | 0.0118 (12) |
C12 | 0.0702 (13) | 0.114 (2) | 0.0621 (13) | 0.0359 (14) | −0.0100 (11) | −0.0066 (13) |
C13 | 0.0595 (11) | 0.0762 (14) | 0.0551 (11) | 0.0095 (10) | −0.0064 (9) | −0.0108 (10) |
C14 | 0.0810 (13) | 0.0583 (12) | 0.0405 (9) | 0.0098 (10) | 0.0051 (9) | −0.0051 (8) |
C15 | 0.208 (3) | 0.0757 (18) | 0.0530 (13) | −0.0251 (19) | −0.0078 (16) | 0.0033 (12) |
Geometric parameters (Å, º) top
F1—C5 | 1.360 (2) | C7—H7 | 0.9300 |
F2—C11 | 1.351 (3) | C8—C13 | 1.380 (3) |
N1—C1 | 1.284 (2) | C8—C9 | 1.382 (2) |
N1—N2 | 1.392 (2) | C9—C10 | 1.382 (3) |
N2—C14 | 1.272 (2) | C9—H9 | 0.9300 |
C1—C8 | 1.477 (2) | C10—C11 | 1.355 (4) |
C1—C2 | 1.488 (2) | C10—H10 | 0.9300 |
C2—C3 | 1.380 (3) | C11—C12 | 1.359 (4) |
C2—C7 | 1.381 (2) | C12—C13 | 1.371 (3) |
C3—C4 | 1.375 (3) | C12—H12 | 0.9300 |
C3—H3 | 0.9300 | C13—H13 | 0.9300 |
C4—C5 | 1.362 (3) | C14—C14i | 1.481 (4) |
C4—H4 | 0.9300 | C14—C15 | 1.483 (3) |
C5—C6 | 1.351 (3) | C15—H15A | 0.9600 |
C6—C7 | 1.385 (2) | C15—H15B | 0.9600 |
C6—H6 | 0.9300 | C15—H15C | 0.9600 |
| | | |
C1—N1—N2 | 115.37 (15) | C9—C8—C1 | 120.03 (15) |
C14—N2—N1 | 116.34 (17) | C8—C9—C10 | 120.62 (19) |
N1—C1—C8 | 124.04 (15) | C8—C9—H9 | 119.7 |
N1—C1—C2 | 116.69 (16) | C10—C9—H9 | 119.7 |
C8—C1—C2 | 119.26 (14) | C11—C10—C9 | 118.0 (2) |
C3—C2—C7 | 118.28 (16) | C11—C10—H10 | 121.0 |
C3—C2—C1 | 120.83 (15) | C9—C10—H10 | 121.0 |
C7—C2—C1 | 120.89 (16) | F2—C11—C10 | 117.5 (3) |
C4—C3—C2 | 120.98 (18) | F2—C11—C12 | 119.2 (2) |
C4—C3—H3 | 119.5 | C10—C11—C12 | 123.3 (2) |
C2—C3—H3 | 119.5 | C11—C12—C13 | 118.4 (2) |
C5—C4—C3 | 118.61 (18) | C11—C12—H12 | 120.8 |
C5—C4—H4 | 120.7 | C13—C12—H12 | 120.8 |
C3—C4—H4 | 120.7 | C12—C13—C8 | 120.7 (2) |
C6—C5—F1 | 118.82 (19) | C12—C13—H13 | 119.7 |
C6—C5—C4 | 122.77 (17) | C8—C13—H13 | 119.7 |
F1—C5—C4 | 118.40 (19) | N2—C14—C14i | 115.4 (2) |
C5—C6—C7 | 118.12 (18) | N2—C14—C15 | 124.83 (18) |
C5—C6—H6 | 120.9 | C14i—C14—C15 | 119.8 (2) |
C7—C6—H6 | 120.9 | C14—C15—H15A | 109.5 |
C2—C7—C6 | 121.22 (17) | C14—C15—H15B | 109.5 |
C2—C7—H7 | 119.4 | H15A—C15—H15B | 109.5 |
C6—C7—H7 | 119.4 | C14—C15—H15C | 109.5 |
C13—C8—C9 | 119.00 (17) | H15A—C15—H15C | 109.5 |
C13—C8—C1 | 120.95 (16) | H15B—C15—H15C | 109.5 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Butane-2,3-dione 2,3-bis{[bis(4-fluorophenyl)methylidene]hydrazone} (1c)
top
Crystal data top
C30H22F4N4 | Z = 2 |
Mr = 514.51 | F(000) = 532 |
Triclinic, P1 | Dx = 1.309 Mg m−3 |
a = 4.9137 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 15.0053 (9) Å | Cell parameters from 9850 reflections |
c = 17.7776 (10) Å | θ = 2.3–23.7° |
α = 86.452 (2)° | µ = 0.10 mm−1 |
β = 86.481 (3)° | T = 300 K |
γ = 89.888 (3)° | Needle, yellow |
V = 1305.79 (13) Å3 | 0.38 × 0.18 × 0.10 mm |
Data collection top
Bruker APEXIII CMOS detector diffractometer | 3535 reflections with I > 2σ(I) |
Radiation source: microfocus | Rint = 0.045 |
phi and ω scans | θmax = 28.4°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | h = −6→6 |
Tmin = 0.979, Tmax = 0.990 | k = −19→20 |
59436 measured reflections | l = −23→23 |
6507 independent reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.058 | w = 1/[σ2(Fo2) + (0.0732P)2 + 0.3208P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.182 | (Δ/σ)max < 0.001 |
S = 1.04 | Δρmax = 0.22 e Å−3 |
6507 reflections | Δρmin = −0.30 e Å−3 |
346 parameters | Extinction correction: SHELXL2018 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.027 (3) |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | −0.0625 (4) | 0.61118 (10) | 0.01566 (9) | 0.0649 (5) | |
N2 | −0.0073 (4) | 0.67210 (10) | 0.06844 (10) | 0.0676 (5) | |
N3 | 0.4430 (4) | 0.89114 (10) | 0.47815 (10) | 0.0683 (5) | |
N4 | 0.4984 (4) | 0.83655 (10) | 0.41865 (10) | 0.0699 (5) | |
F1 | 0.4301 (5) | 0.81769 (13) | −0.26121 (9) | 0.1344 (7) | |
F2 | 0.2477 (5) | 0.99633 (11) | 0.25609 (11) | 0.1421 (8) | |
F3 | 0.6692 (4) | 0.52028 (10) | 0.20659 (9) | 0.1159 (6) | |
F4 | 0.9214 (5) | 0.64505 (14) | 0.72055 (10) | 0.1472 (8) | |
C1 | 0.0971 (4) | 0.74698 (12) | 0.04243 (12) | 0.0605 (5) | |
C2 | 0.1885 (4) | 0.76696 (12) | −0.03791 (12) | 0.0607 (5) | |
C3 | 0.3912 (5) | 0.71868 (16) | −0.07252 (14) | 0.0822 (7) | |
H3 | 0.475106 | 0.673215 | −0.044540 | 0.099* | |
C4 | 0.4748 (7) | 0.73519 (19) | −0.14731 (15) | 0.1005 (9) | |
H4 | 0.613734 | 0.701825 | −0.169693 | 0.121* | |
C5 | 0.3513 (6) | 0.80058 (18) | −0.18720 (14) | 0.0883 (7) | |
C6 | 0.1536 (7) | 0.85105 (19) | −0.15623 (18) | 0.1039 (9) | |
H6 | 0.071847 | 0.896198 | −0.185102 | 0.125* | |
C7 | 0.0738 (6) | 0.83485 (16) | −0.08091 (16) | 0.0931 (8) | |
H7 | −0.059951 | 0.870442 | −0.058767 | 0.112* | |
C8 | 0.1320 (4) | 0.81511 (12) | 0.09797 (13) | 0.0653 (5) | |
C9 | −0.0207 (6) | 0.81139 (14) | 0.16603 (14) | 0.0816 (7) | |
H9 | −0.151651 | 0.766860 | 0.175980 | 0.098* | |
C10 | 0.0169 (7) | 0.87219 (17) | 0.21947 (15) | 0.0962 (9) | |
H10 | −0.086923 | 0.868915 | 0.265096 | 0.115* | |
C11 | 0.2074 (7) | 0.93668 (17) | 0.20430 (18) | 0.0970 (9) | |
C12 | 0.3599 (7) | 0.94420 (18) | 0.1380 (2) | 0.1075 (10) | |
H12 | 0.488391 | 0.989618 | 0.128781 | 0.129* | |
C13 | 0.3214 (6) | 0.88288 (16) | 0.08367 (16) | 0.0899 (7) | |
H13 | 0.423384 | 0.887654 | 0.037771 | 0.108* | |
C14 | 0.0374 (4) | 0.53296 (12) | 0.02682 (11) | 0.0581 (5) | |
C15 | 0.2218 (5) | 0.50705 (15) | 0.08758 (13) | 0.0818 (7) | |
H15A | 0.406089 | 0.522553 | 0.070871 | 0.123* | |
H15B | 0.209215 | 0.443816 | 0.099296 | 0.123* | |
H15C | 0.169312 | 0.538021 | 0.131841 | 0.123* | |
C16 | 0.5934 (4) | 0.75855 (12) | 0.43574 (12) | 0.0612 (5) | |
C17 | 0.6162 (4) | 0.69574 (12) | 0.37450 (12) | 0.0624 (5) | |
C18 | 0.4562 (5) | 0.70596 (14) | 0.31362 (13) | 0.0757 (6) | |
H18 | 0.333702 | 0.753217 | 0.310964 | 0.091* | |
C19 | 0.4735 (6) | 0.64756 (16) | 0.25641 (14) | 0.0849 (7) | |
H19 | 0.364130 | 0.655069 | 0.215616 | 0.102* | |
C20 | 0.6527 (5) | 0.57934 (15) | 0.26098 (14) | 0.0792 (7) | |
C21 | 0.8165 (5) | 0.56712 (16) | 0.31860 (17) | 0.0905 (8) | |
H21 | 0.940439 | 0.520217 | 0.319799 | 0.109* | |
C22 | 0.7978 (5) | 0.62557 (15) | 0.37631 (15) | 0.0829 (7) | |
H22 | 0.908987 | 0.617282 | 0.416631 | 0.099* | |
C23 | 0.6791 (4) | 0.72864 (12) | 0.51168 (12) | 0.0612 (5) | |
C24 | 0.8740 (5) | 0.77472 (14) | 0.54623 (13) | 0.0739 (6) | |
H24 | 0.950917 | 0.825906 | 0.521501 | 0.089* | |
C25 | 0.9572 (6) | 0.74730 (18) | 0.61563 (16) | 0.0945 (8) | |
H25 | 1.090659 | 0.778726 | 0.637864 | 0.113* | |
C26 | 0.8423 (7) | 0.6740 (2) | 0.65125 (15) | 0.0932 (8) | |
C27 | 0.6506 (7) | 0.6256 (2) | 0.62042 (19) | 0.1107 (10) | |
H27 | 0.574454 | 0.575062 | 0.646462 | 0.133* | |
C28 | 0.5704 (6) | 0.65263 (17) | 0.54948 (17) | 0.0935 (8) | |
H28 | 0.441927 | 0.619301 | 0.527017 | 0.112* | |
C29 | 0.5407 (4) | 0.97041 (12) | 0.46949 (11) | 0.0613 (5) | |
C30 | 0.7279 (6) | 1.00322 (15) | 0.40496 (14) | 0.0932 (8) | |
H30A | 0.901847 | 0.974574 | 0.408653 | 0.140* | |
H30B | 0.750352 | 1.066654 | 0.406092 | 0.140* | |
H30C | 0.652461 | 0.989640 | 0.358446 | 0.140* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0784 (11) | 0.0433 (8) | 0.0745 (11) | 0.0000 (7) | −0.0045 (9) | −0.0164 (8) |
N2 | 0.0838 (12) | 0.0437 (9) | 0.0769 (11) | 0.0010 (8) | −0.0019 (9) | −0.0182 (8) |
N3 | 0.0872 (12) | 0.0394 (8) | 0.0793 (11) | 0.0005 (8) | −0.0050 (9) | −0.0113 (8) |
N4 | 0.0911 (13) | 0.0405 (8) | 0.0796 (11) | −0.0010 (8) | −0.0075 (9) | −0.0123 (8) |
F1 | 0.188 (2) | 0.1292 (15) | 0.0838 (11) | −0.0234 (13) | −0.0030 (11) | 0.0074 (10) |
F2 | 0.206 (2) | 0.0896 (11) | 0.1456 (15) | 0.0253 (12) | −0.0780 (14) | −0.0628 (11) |
F3 | 0.1376 (14) | 0.0938 (11) | 0.1215 (12) | −0.0045 (9) | −0.0004 (10) | −0.0559 (9) |
F4 | 0.211 (2) | 0.1426 (16) | 0.0868 (11) | 0.0630 (15) | −0.0135 (12) | 0.0082 (11) |
C1 | 0.0629 (12) | 0.0417 (10) | 0.0787 (13) | 0.0084 (8) | −0.0090 (10) | −0.0138 (9) |
C2 | 0.0648 (12) | 0.0402 (9) | 0.0790 (13) | 0.0031 (8) | −0.0131 (10) | −0.0111 (9) |
C3 | 0.0949 (17) | 0.0688 (14) | 0.0819 (16) | 0.0245 (12) | −0.0010 (13) | −0.0004 (12) |
C4 | 0.126 (2) | 0.0866 (18) | 0.0863 (18) | 0.0234 (16) | 0.0142 (16) | −0.0051 (15) |
C5 | 0.114 (2) | 0.0803 (17) | 0.0712 (16) | −0.0127 (15) | −0.0109 (14) | −0.0033 (13) |
C6 | 0.120 (2) | 0.0864 (19) | 0.103 (2) | 0.0169 (17) | −0.0211 (18) | 0.0248 (16) |
C7 | 0.0967 (19) | 0.0713 (15) | 0.109 (2) | 0.0259 (13) | −0.0029 (15) | 0.0062 (14) |
C8 | 0.0717 (13) | 0.0420 (10) | 0.0847 (14) | 0.0111 (9) | −0.0139 (11) | −0.0170 (9) |
C9 | 0.1044 (18) | 0.0519 (12) | 0.0904 (16) | 0.0087 (11) | −0.0058 (14) | −0.0208 (11) |
C10 | 0.141 (2) | 0.0629 (15) | 0.0887 (17) | 0.0263 (16) | −0.0186 (16) | −0.0274 (13) |
C11 | 0.133 (2) | 0.0585 (14) | 0.108 (2) | 0.0264 (15) | −0.0512 (19) | −0.0367 (14) |
C12 | 0.112 (2) | 0.0687 (16) | 0.149 (3) | −0.0116 (15) | −0.035 (2) | −0.0385 (18) |
C13 | 0.0904 (17) | 0.0673 (14) | 0.115 (2) | −0.0110 (12) | −0.0064 (15) | −0.0292 (14) |
C14 | 0.0619 (12) | 0.0442 (10) | 0.0689 (12) | −0.0002 (8) | 0.0003 (9) | −0.0134 (8) |
C15 | 0.0986 (17) | 0.0637 (13) | 0.0880 (16) | 0.0161 (12) | −0.0228 (13) | −0.0283 (12) |
C16 | 0.0633 (12) | 0.0395 (9) | 0.0812 (14) | −0.0068 (8) | −0.0011 (10) | −0.0092 (9) |
C17 | 0.0631 (12) | 0.0409 (9) | 0.0836 (14) | −0.0070 (8) | −0.0011 (10) | −0.0121 (9) |
C18 | 0.0856 (16) | 0.0553 (12) | 0.0881 (16) | 0.0034 (11) | −0.0115 (13) | −0.0126 (11) |
C19 | 0.1052 (19) | 0.0679 (14) | 0.0844 (16) | −0.0048 (13) | −0.0156 (14) | −0.0178 (12) |
C20 | 0.0864 (16) | 0.0618 (13) | 0.0912 (17) | −0.0140 (12) | 0.0040 (13) | −0.0298 (12) |
C21 | 0.0833 (17) | 0.0623 (14) | 0.130 (2) | 0.0120 (12) | −0.0069 (16) | −0.0360 (14) |
C22 | 0.0803 (15) | 0.0624 (13) | 0.1107 (19) | 0.0100 (11) | −0.0218 (13) | −0.0288 (13) |
C23 | 0.0623 (12) | 0.0428 (9) | 0.0776 (13) | −0.0025 (8) | 0.0045 (10) | −0.0066 (9) |
C24 | 0.0845 (15) | 0.0556 (12) | 0.0820 (15) | −0.0034 (11) | −0.0084 (12) | −0.0057 (11) |
C25 | 0.119 (2) | 0.0734 (16) | 0.0947 (19) | 0.0108 (15) | −0.0287 (16) | −0.0152 (14) |
C26 | 0.116 (2) | 0.0865 (19) | 0.0752 (17) | 0.0318 (17) | 0.0012 (15) | −0.0014 (14) |
C27 | 0.110 (2) | 0.088 (2) | 0.125 (2) | −0.0017 (17) | 0.0171 (19) | 0.0426 (19) |
C28 | 0.0921 (18) | 0.0668 (14) | 0.119 (2) | −0.0181 (13) | −0.0100 (15) | 0.0181 (14) |
C29 | 0.0745 (13) | 0.0395 (9) | 0.0710 (12) | 0.0041 (9) | −0.0099 (10) | −0.0056 (8) |
C30 | 0.129 (2) | 0.0605 (13) | 0.0886 (17) | −0.0177 (14) | 0.0168 (15) | −0.0175 (12) |
Geometric parameters (Å, º) top
N1—C14 | 1.280 (2) | C14—C14i | 1.478 (4) |
N1—N2 | 1.389 (2) | C14—C15 | 1.485 (3) |
N2—C1 | 1.284 (2) | C15—H15A | 0.9600 |
N3—C29 | 1.280 (2) | C15—H15B | 0.9600 |
N3—N4 | 1.391 (2) | C15—H15C | 0.9600 |
N4—C16 | 1.285 (2) | C16—C23 | 1.482 (3) |
F1—C5 | 1.358 (3) | C16—C17 | 1.482 (3) |
F2—C11 | 1.346 (3) | C17—C18 | 1.377 (3) |
F3—C20 | 1.350 (2) | C17—C22 | 1.379 (3) |
F4—C26 | 1.360 (3) | C18—C19 | 1.382 (3) |
C1—C8 | 1.482 (3) | C18—H18 | 0.9300 |
C1—C2 | 1.483 (3) | C19—C20 | 1.351 (3) |
C2—C3 | 1.368 (3) | C19—H19 | 0.9300 |
C2—C7 | 1.376 (3) | C20—C21 | 1.345 (4) |
C3—C4 | 1.375 (3) | C21—C22 | 1.389 (3) |
C3—H3 | 0.9300 | C21—H21 | 0.9300 |
C4—C5 | 1.341 (4) | C22—H22 | 0.9300 |
C4—H4 | 0.9300 | C23—C24 | 1.378 (3) |
C5—C6 | 1.343 (4) | C23—C28 | 1.379 (3) |
C6—C7 | 1.379 (4) | C24—C25 | 1.363 (3) |
C6—H6 | 0.9300 | C24—H24 | 0.9300 |
C7—H7 | 0.9300 | C25—C26 | 1.343 (4) |
C8—C13 | 1.381 (3) | C25—H25 | 0.9300 |
C8—C9 | 1.382 (3) | C26—C27 | 1.353 (4) |
C9—C10 | 1.378 (3) | C27—C28 | 1.381 (4) |
C9—H9 | 0.9300 | C27—H27 | 0.9300 |
C10—C11 | 1.351 (4) | C28—H28 | 0.9300 |
C10—H10 | 0.9300 | C29—C29ii | 1.480 (4) |
C11—C12 | 1.357 (4) | C29—C30 | 1.485 (3) |
C12—C13 | 1.395 (4) | C30—H30A | 0.9600 |
C12—H12 | 0.9300 | C30—H30B | 0.9600 |
C13—H13 | 0.9300 | C30—H30C | 0.9600 |
| | | |
C14—N1—N2 | 115.98 (17) | H15A—C15—H15C | 109.5 |
C1—N2—N1 | 116.47 (17) | H15B—C15—H15C | 109.5 |
C29—N3—N4 | 116.15 (18) | N4—C16—C23 | 124.23 (18) |
C16—N4—N3 | 116.55 (18) | N4—C16—C17 | 116.69 (19) |
N2—C1—C8 | 116.43 (19) | C23—C16—C17 | 119.08 (16) |
N2—C1—C2 | 123.95 (17) | C18—C17—C22 | 117.8 (2) |
C8—C1—C2 | 119.60 (17) | C18—C17—C16 | 120.78 (18) |
C3—C2—C7 | 117.0 (2) | C22—C17—C16 | 121.4 (2) |
C3—C2—C1 | 121.39 (18) | C17—C18—C19 | 121.5 (2) |
C7—C2—C1 | 121.6 (2) | C17—C18—H18 | 119.3 |
C2—C3—C4 | 122.1 (2) | C19—C18—H18 | 119.3 |
C2—C3—H3 | 118.9 | C20—C19—C18 | 118.6 (2) |
C4—C3—H3 | 118.9 | C20—C19—H19 | 120.7 |
C5—C4—C3 | 118.4 (3) | C18—C19—H19 | 120.7 |
C5—C4—H4 | 120.8 | C21—C20—F3 | 118.0 (2) |
C3—C4—H4 | 120.8 | C21—C20—C19 | 122.3 (2) |
C4—C5—C6 | 122.3 (3) | F3—C20—C19 | 119.7 (2) |
C4—C5—F1 | 119.3 (3) | C20—C21—C22 | 119.0 (2) |
C6—C5—F1 | 118.4 (3) | C20—C21—H21 | 120.5 |
C5—C6—C7 | 118.9 (2) | C22—C21—H21 | 120.5 |
C5—C6—H6 | 120.5 | C17—C22—C21 | 120.8 (2) |
C7—C6—H6 | 120.5 | C17—C22—H22 | 119.6 |
C2—C7—C6 | 121.2 (2) | C21—C22—H22 | 119.6 |
C2—C7—H7 | 119.4 | C24—C23—C28 | 117.8 (2) |
C6—C7—H7 | 119.4 | C24—C23—C16 | 121.20 (18) |
C13—C8—C9 | 118.3 (2) | C28—C23—C16 | 121.0 (2) |
C13—C8—C1 | 120.9 (2) | C25—C24—C23 | 121.8 (2) |
C9—C8—C1 | 120.8 (2) | C25—C24—H24 | 119.1 |
C10—C9—C8 | 121.5 (3) | C23—C24—H24 | 119.1 |
C10—C9—H9 | 119.3 | C26—C25—C24 | 118.6 (3) |
C8—C9—H9 | 119.3 | C26—C25—H25 | 120.7 |
C11—C10—C9 | 118.7 (3) | C24—C25—H25 | 120.7 |
C11—C10—H10 | 120.6 | C25—C26—C27 | 122.6 (3) |
C9—C10—H10 | 120.6 | C25—C26—F4 | 119.9 (3) |
F2—C11—C10 | 119.5 (3) | C27—C26—F4 | 117.5 (3) |
F2—C11—C12 | 118.3 (3) | C26—C27—C28 | 118.7 (3) |
C10—C11—C12 | 122.2 (2) | C26—C27—H27 | 120.7 |
C11—C12—C13 | 119.1 (3) | C28—C27—H27 | 120.7 |
C11—C12—H12 | 120.4 | C23—C28—C27 | 120.6 (3) |
C13—C12—H12 | 120.4 | C23—C28—H28 | 119.7 |
C8—C13—C12 | 120.1 (3) | C27—C28—H28 | 119.7 |
C8—C13—H13 | 119.9 | N3—C29—C29ii | 115.1 (2) |
C12—C13—H13 | 119.9 | N3—C29—C30 | 124.41 (19) |
N1—C14—C14i | 115.5 (2) | C29ii—C29—C30 | 120.5 (2) |
N1—C14—C15 | 124.38 (17) | C29—C30—H30A | 109.5 |
C14i—C14—C15 | 120.1 (2) | C29—C30—H30B | 109.5 |
C14—C15—H15A | 109.5 | H30A—C30—H30B | 109.5 |
C14—C15—H15B | 109.5 | C29—C30—H30C | 109.5 |
H15A—C15—H15B | 109.5 | H30A—C30—H30C | 109.5 |
C14—C15—H15C | 109.5 | H30B—C30—H30C | 109.5 |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, −y+2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···F4iii | 0.93 | 2.58 | 3.451 (3) | 156 |
C6—H6···F2iv | 0.93 | 2.58 | 3.492 (3) | 168 |
C25—H25···F1v | 0.93 | 2.62 | 3.497 (3) | 158 |
Symmetry codes: (iii) x, y, z−1; (iv) −x, −y+2, −z; (v) x+1, y, z+1. |
Butane-2,3-dione 2,3-bis{[bis(4-chloroenyl)methylidene]hydrazone} (2a)
top
Crystal data top
C30H22Cl4N4 | Z = 1 |
Mr = 580.31 | F(000) = 298 |
Triclinic, P1 | Dx = 1.369 Mg m−3 |
a = 6.0349 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.3474 (2) Å | Cell parameters from 9957 reflections |
c = 16.6718 (5) Å | θ = 2.5–28.3° |
α = 93.255 (1)° | µ = 0.45 mm−1 |
β = 98.722 (1)° | T = 100 K |
γ = 104.473 (1)° | Plate, yellow |
V = 704.03 (4) Å3 | 0.35 × 0.22 × 0.12 mm |
Data collection top
Bruker APEXIII CMOS detector diffractometer | 3138 reflections with I > 2σ(I) |
Radiation source: microfocus | Rint = 0.028 |
phi and ω scans | θmax = 28.3°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | h = −8→8 |
Tmin = 0.889, Tmax = 0.948 | k = −9→9 |
19577 measured reflections | l = −22→22 |
3475 independent reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.028 | w = 1/[σ2(Fo2) + (0.0314P)2 + 0.3487P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.074 | (Δ/σ)max = 0.001 |
S = 1.05 | Δρmax = 0.38 e Å−3 |
3475 reflections | Δρmin = −0.23 e Å−3 |
174 parameters | Extinction correction: SHELXL2016 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.020 (2) |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | 0.65058 (6) | −0.13047 (4) | 0.20077 (2) | 0.03010 (10) | |
Cl2 | 0.18551 (6) | 0.84185 (4) | 0.56878 (2) | 0.02592 (9) | |
N1 | 0.03764 (17) | 0.53888 (13) | 0.17732 (5) | 0.01551 (19) | |
N2 | 0.01303 (17) | 0.44601 (14) | 0.10013 (6) | 0.0163 (2) | |
C1 | 0.15155 (19) | 0.47268 (15) | 0.23559 (6) | 0.0136 (2) | |
C2 | 0.27691 (19) | 0.32515 (15) | 0.22542 (6) | 0.0141 (2) | |
C3 | 0.4302 (2) | 0.33351 (16) | 0.17007 (7) | 0.0171 (2) | |
H3 | 0.455486 | 0.435814 | 0.137244 | 0.021* | |
C4 | 0.5463 (2) | 0.19387 (17) | 0.16244 (7) | 0.0195 (2) | |
H4 | 0.651746 | 0.200451 | 0.125118 | 0.023* | |
C5 | 0.5053 (2) | 0.04487 (16) | 0.21028 (7) | 0.0190 (2) | |
C6 | 0.3543 (2) | 0.03229 (17) | 0.26544 (7) | 0.0202 (2) | |
H6 | 0.327770 | −0.071486 | 0.297427 | 0.024* | |
C7 | 0.2422 (2) | 0.17388 (16) | 0.27324 (7) | 0.0176 (2) | |
H7 | 0.140142 | 0.167942 | 0.311729 | 0.021* | |
C8 | 0.15558 (19) | 0.55550 (15) | 0.31924 (6) | 0.0133 (2) | |
C9 | 0.3475 (2) | 0.57382 (16) | 0.38038 (7) | 0.0162 (2) | |
H9 | 0.472162 | 0.524325 | 0.369473 | 0.019* | |
C10 | 0.3583 (2) | 0.66380 (17) | 0.45721 (7) | 0.0182 (2) | |
H10 | 0.490677 | 0.678445 | 0.498335 | 0.022* | |
C11 | 0.1737 (2) | 0.73131 (16) | 0.47265 (7) | 0.0169 (2) | |
C12 | −0.0211 (2) | 0.71241 (17) | 0.41344 (7) | 0.0184 (2) | |
H12 | −0.147164 | 0.759157 | 0.425155 | 0.022* | |
C13 | −0.0289 (2) | 0.62426 (16) | 0.33696 (7) | 0.0166 (2) | |
H13 | −0.161533 | 0.610493 | 0.296054 | 0.020* | |
C14 | 0.02135 (19) | 0.55182 (16) | 0.04111 (6) | 0.0153 (2) | |
C15 | 0.0728 (3) | 0.76265 (17) | 0.04980 (7) | 0.0267 (3) | |
H15A | 0.038933 | 0.805423 | 0.102251 | 0.040* | |
H15B | −0.023845 | 0.803436 | 0.005379 | 0.040* | |
H15C | 0.237169 | 0.817208 | 0.047479 | 0.040* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.02534 (17) | 0.02041 (16) | 0.0472 (2) | 0.01208 (12) | 0.00448 (14) | 0.00242 (13) |
Cl2 | 0.03450 (18) | 0.02809 (17) | 0.01493 (14) | 0.00857 (13) | 0.00564 (11) | −0.00535 (11) |
N1 | 0.0185 (5) | 0.0171 (5) | 0.0101 (4) | 0.0035 (4) | 0.0015 (3) | 0.0015 (3) |
N2 | 0.0196 (5) | 0.0185 (5) | 0.0100 (4) | 0.0048 (4) | 0.0007 (3) | 0.0007 (3) |
C1 | 0.0146 (5) | 0.0140 (5) | 0.0112 (5) | 0.0014 (4) | 0.0026 (4) | 0.0019 (4) |
C2 | 0.0152 (5) | 0.0139 (5) | 0.0114 (5) | 0.0025 (4) | −0.0005 (4) | −0.0004 (4) |
C3 | 0.0197 (6) | 0.0154 (5) | 0.0158 (5) | 0.0033 (4) | 0.0038 (4) | 0.0022 (4) |
C4 | 0.0182 (6) | 0.0187 (5) | 0.0214 (6) | 0.0038 (4) | 0.0049 (4) | −0.0007 (4) |
C5 | 0.0169 (5) | 0.0140 (5) | 0.0246 (6) | 0.0049 (4) | −0.0014 (4) | −0.0019 (4) |
C6 | 0.0227 (6) | 0.0145 (5) | 0.0218 (6) | 0.0033 (4) | 0.0006 (5) | 0.0046 (4) |
C7 | 0.0198 (6) | 0.0172 (5) | 0.0150 (5) | 0.0031 (4) | 0.0031 (4) | 0.0022 (4) |
C8 | 0.0162 (5) | 0.0128 (5) | 0.0108 (5) | 0.0030 (4) | 0.0025 (4) | 0.0029 (4) |
C9 | 0.0169 (5) | 0.0190 (5) | 0.0137 (5) | 0.0071 (4) | 0.0017 (4) | 0.0010 (4) |
C10 | 0.0204 (6) | 0.0203 (5) | 0.0129 (5) | 0.0065 (4) | −0.0015 (4) | 0.0003 (4) |
C11 | 0.0236 (6) | 0.0155 (5) | 0.0114 (5) | 0.0041 (4) | 0.0048 (4) | −0.0001 (4) |
C12 | 0.0179 (6) | 0.0200 (5) | 0.0189 (5) | 0.0069 (4) | 0.0051 (4) | 0.0010 (4) |
C13 | 0.0161 (5) | 0.0187 (5) | 0.0149 (5) | 0.0056 (4) | 0.0007 (4) | 0.0021 (4) |
C14 | 0.0155 (5) | 0.0178 (5) | 0.0116 (5) | 0.0043 (4) | −0.0005 (4) | 0.0010 (4) |
C15 | 0.0471 (8) | 0.0172 (6) | 0.0131 (5) | 0.0061 (6) | 0.0013 (5) | 0.0012 (4) |
Geometric parameters (Å, º) top
Cl1—C5 | 1.7426 (12) | C7—H7 | 0.9500 |
Cl2—C11 | 1.7384 (11) | C8—C13 | 1.3947 (16) |
N1—C1 | 1.2927 (14) | C8—C9 | 1.3952 (15) |
N1—N2 | 1.3911 (13) | C9—C10 | 1.3924 (15) |
N2—C14 | 1.2874 (14) | C9—H9 | 0.9500 |
C1—C8 | 1.4840 (14) | C10—C11 | 1.3792 (17) |
C1—C2 | 1.4846 (15) | C10—H10 | 0.9500 |
C2—C3 | 1.3959 (16) | C11—C12 | 1.3881 (17) |
C2—C7 | 1.3963 (15) | C12—C13 | 1.3858 (16) |
C3—C4 | 1.3896 (16) | C12—H12 | 0.9500 |
C3—H3 | 0.9500 | C13—H13 | 0.9500 |
C4—C5 | 1.3855 (17) | C14—C14i | 1.484 (2) |
C4—H4 | 0.9500 | C14—C15 | 1.4957 (16) |
C5—C6 | 1.3807 (18) | C15—H15A | 0.9800 |
C6—C7 | 1.3857 (17) | C15—H15B | 0.9800 |
C6—H6 | 0.9500 | C15—H15C | 0.9800 |
| | | |
C1—N1—N2 | 115.11 (9) | C9—C8—C1 | 120.80 (10) |
C14—N2—N1 | 115.54 (9) | C10—C9—C8 | 120.76 (11) |
N1—C1—C8 | 115.64 (10) | C10—C9—H9 | 119.6 |
N1—C1—C2 | 125.79 (10) | C8—C9—H9 | 119.6 |
C8—C1—C2 | 118.57 (9) | C11—C10—C9 | 118.92 (11) |
C3—C2—C7 | 118.83 (10) | C11—C10—H10 | 120.5 |
C3—C2—C1 | 122.13 (10) | C9—C10—H10 | 120.5 |
C7—C2—C1 | 119.04 (10) | C10—C11—C12 | 121.60 (10) |
C4—C3—C2 | 120.74 (11) | C10—C11—Cl2 | 119.04 (9) |
C4—C3—H3 | 119.6 | C12—C11—Cl2 | 119.36 (9) |
C2—C3—H3 | 119.6 | C13—C12—C11 | 118.93 (11) |
C5—C4—C3 | 118.74 (11) | C13—C12—H12 | 120.5 |
C5—C4—H4 | 120.6 | C11—C12—H12 | 120.5 |
C3—C4—H4 | 120.6 | C12—C13—C8 | 120.88 (10) |
C6—C5—C4 | 121.90 (11) | C12—C13—H13 | 119.6 |
C6—C5—Cl1 | 119.27 (9) | C8—C13—H13 | 119.6 |
C4—C5—Cl1 | 118.82 (10) | N2—C14—C14i | 114.54 (12) |
C5—C6—C7 | 118.75 (11) | N2—C14—C15 | 125.67 (10) |
C5—C6—H6 | 120.6 | C14i—C14—C15 | 119.78 (12) |
C7—C6—H6 | 120.6 | C14—C15—H15A | 109.5 |
C6—C7—C2 | 121.02 (11) | C14—C15—H15B | 109.5 |
C6—C7—H7 | 119.5 | H15A—C15—H15B | 109.5 |
C2—C7—H7 | 119.5 | C14—C15—H15C | 109.5 |
C13—C8—C9 | 118.88 (10) | H15A—C15—H15C | 109.5 |
C13—C8—C1 | 120.25 (10) | H15B—C15—H15C | 109.5 |
Symmetry code: (i) −x, −y+1, −z. |
Butane-2,3-dione 2,3-bis{[bis(4-chloroenyl)methylidene]hydrazone} (2b)
top
Crystal data top
C30H22Cl4N4 | F(000) = 596 |
Mr = 580.31 | Dx = 1.356 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 10.4200 (8) Å | Cell parameters from 8736 reflections |
b = 12.5276 (11) Å | θ = 2.5–28.0° |
c = 11.2084 (9) Å | µ = 0.44 mm−1 |
β = 103.682 (3)° | T = 298 K |
V = 1421.6 (2) Å3 | Block, orange |
Z = 2 | 0.31 × 0.24 × 0.10 mm |
Data collection top
Bruker APEXIII CMOS detector diffractometer | 2565 reflections with I > 2σ(I) |
Radiation source: microfocus | Rint = 0.032 |
phi and ω scans | θmax = 28.3°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | h = −13→13 |
Tmin = 0.880, Tmax = 0.957 | k = −16→16 |
20477 measured reflections | l = −14→14 |
3527 independent reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.047 | w = 1/[σ2(Fo2) + (0.0572P)2 + 0.4215P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.131 | (Δ/σ)max = 0.001 |
S = 1.03 | Δρmax = 0.29 e Å−3 |
3527 reflections | Δρmin = −0.34 e Å−3 |
174 parameters | Extinction correction: SHELXL2016 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.007 (2) |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | 0.68910 (6) | −0.15371 (5) | 0.74583 (6) | 0.0783 (2) | |
Cl2 | 0.42701 (9) | 0.66559 (5) | 0.62731 (7) | 0.1015 (3) | |
N1 | 0.17766 (14) | 0.18132 (13) | 0.53715 (16) | 0.0579 (4) | |
N2 | 0.14416 (13) | 0.07379 (13) | 0.52138 (15) | 0.0558 (4) | |
C1 | 0.30010 (16) | 0.19985 (15) | 0.59054 (16) | 0.0510 (4) | |
C2 | 0.39945 (16) | 0.11740 (16) | 0.63939 (16) | 0.0499 (4) | |
C3 | 0.37448 (17) | 0.03265 (18) | 0.71109 (17) | 0.0600 (5) | |
H3 | 0.295162 | 0.031146 | 0.735454 | 0.072* | |
C4 | 0.46323 (19) | −0.04851 (18) | 0.74676 (19) | 0.0636 (5) | |
H4 | 0.444873 | −0.103796 | 0.795556 | 0.076* | |
C5 | 0.58018 (17) | −0.04729 (16) | 0.70944 (17) | 0.0565 (5) | |
C6 | 0.61025 (18) | 0.03606 (17) | 0.64137 (19) | 0.0601 (5) | |
H6 | 0.690228 | 0.037005 | 0.618151 | 0.072* | |
C7 | 0.52134 (17) | 0.11832 (16) | 0.60763 (18) | 0.0565 (5) | |
H7 | 0.542768 | 0.175413 | 0.562971 | 0.068* | |
C8 | 0.33619 (17) | 0.31444 (15) | 0.59710 (17) | 0.0520 (4) | |
C9 | 0.44542 (19) | 0.35264 (17) | 0.68290 (19) | 0.0595 (5) | |
H9 | 0.499514 | 0.305072 | 0.735662 | 0.071* | |
C10 | 0.4747 (2) | 0.46018 (18) | 0.6908 (2) | 0.0650 (5) | |
H10 | 0.548248 | 0.485030 | 0.748177 | 0.078* | |
C11 | 0.3947 (2) | 0.52961 (17) | 0.61388 (18) | 0.0630 (5) | |
C12 | 0.2867 (2) | 0.49456 (18) | 0.5279 (2) | 0.0739 (6) | |
H12 | 0.232927 | 0.542760 | 0.475804 | 0.089* | |
C13 | 0.2588 (2) | 0.38763 (18) | 0.51972 (19) | 0.0685 (6) | |
H13 | 0.186058 | 0.363655 | 0.460709 | 0.082* | |
C14 | 0.01973 (15) | 0.05627 (15) | 0.51005 (16) | 0.0504 (4) | |
C15 | −0.08038 (19) | 0.13991 (17) | 0.5156 (2) | 0.0660 (5) | |
H15A | −0.084949 | 0.150286 | 0.599389 | 0.099* | |
H15B | −0.165175 | 0.117663 | 0.467810 | 0.099* | |
H15C | −0.055514 | 0.205672 | 0.483292 | 0.099* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0626 (3) | 0.0707 (4) | 0.0975 (5) | −0.0018 (3) | 0.0108 (3) | −0.0089 (3) |
Cl2 | 0.1450 (7) | 0.0654 (4) | 0.0968 (5) | −0.0455 (4) | 0.0337 (4) | −0.0080 (3) |
N1 | 0.0404 (7) | 0.0577 (10) | 0.0750 (10) | −0.0161 (7) | 0.0121 (7) | −0.0065 (8) |
N2 | 0.0385 (7) | 0.0557 (9) | 0.0717 (10) | −0.0149 (7) | 0.0098 (6) | −0.0051 (8) |
C1 | 0.0413 (8) | 0.0603 (11) | 0.0536 (10) | −0.0172 (8) | 0.0155 (7) | −0.0070 (8) |
C2 | 0.0388 (8) | 0.0616 (11) | 0.0497 (9) | −0.0166 (8) | 0.0114 (7) | −0.0096 (8) |
C3 | 0.0422 (9) | 0.0818 (14) | 0.0597 (11) | −0.0128 (9) | 0.0193 (8) | 0.0027 (10) |
C4 | 0.0532 (10) | 0.0741 (14) | 0.0640 (12) | −0.0131 (10) | 0.0148 (9) | 0.0077 (10) |
C5 | 0.0443 (9) | 0.0644 (12) | 0.0582 (10) | −0.0108 (8) | 0.0069 (8) | −0.0119 (9) |
C6 | 0.0429 (9) | 0.0704 (13) | 0.0704 (12) | −0.0136 (9) | 0.0200 (8) | −0.0096 (10) |
C7 | 0.0452 (9) | 0.0629 (11) | 0.0652 (11) | −0.0183 (9) | 0.0205 (8) | −0.0041 (9) |
C8 | 0.0452 (9) | 0.0616 (11) | 0.0519 (10) | −0.0183 (8) | 0.0165 (7) | −0.0076 (8) |
C9 | 0.0469 (9) | 0.0661 (12) | 0.0639 (11) | −0.0124 (9) | 0.0100 (8) | −0.0114 (9) |
C10 | 0.0543 (10) | 0.0723 (14) | 0.0691 (12) | −0.0237 (10) | 0.0158 (9) | −0.0230 (11) |
C11 | 0.0763 (13) | 0.0597 (12) | 0.0599 (11) | −0.0272 (10) | 0.0297 (10) | −0.0086 (9) |
C12 | 0.0901 (15) | 0.0672 (14) | 0.0598 (12) | −0.0205 (12) | 0.0085 (11) | 0.0088 (10) |
C13 | 0.0682 (12) | 0.0715 (14) | 0.0594 (12) | −0.0269 (11) | 0.0021 (9) | 0.0012 (10) |
C14 | 0.0373 (8) | 0.0576 (11) | 0.0553 (10) | −0.0114 (7) | 0.0089 (7) | −0.0033 (8) |
C15 | 0.0450 (10) | 0.0590 (12) | 0.0943 (15) | −0.0091 (9) | 0.0171 (10) | −0.0047 (11) |
Geometric parameters (Å, º) top
Cl1—C5 | 1.736 (2) | C7—H7 | 0.9300 |
Cl2—C11 | 1.736 (2) | C8—C13 | 1.383 (3) |
N1—C1 | 1.296 (2) | C8—C9 | 1.390 (3) |
N1—N2 | 1.392 (2) | C9—C10 | 1.379 (3) |
N2—C14 | 1.291 (2) | C9—H9 | 0.9300 |
C1—C2 | 1.473 (3) | C10—C11 | 1.362 (3) |
C1—C8 | 1.481 (3) | C10—H10 | 0.9300 |
C2—C3 | 1.393 (3) | C11—C12 | 1.369 (3) |
C2—C7 | 1.398 (2) | C12—C13 | 1.369 (3) |
C3—C4 | 1.369 (3) | C12—H12 | 0.9300 |
C3—H3 | 0.9300 | C13—H13 | 0.9300 |
C4—C5 | 1.379 (3) | C14—C14i | 1.471 (4) |
C4—H4 | 0.9300 | C14—C15 | 1.490 (3) |
C5—C6 | 1.373 (3) | C15—H15A | 0.9600 |
C6—C7 | 1.377 (3) | C15—H15B | 0.9600 |
C6—H6 | 0.9300 | C15—H15C | 0.9600 |
| | | |
C1—N1—N2 | 114.95 (17) | C9—C8—C1 | 121.65 (19) |
C14—N2—N1 | 113.12 (15) | C10—C9—C8 | 120.9 (2) |
N1—C1—C2 | 125.08 (17) | C10—C9—H9 | 119.6 |
N1—C1—C8 | 114.03 (18) | C8—C9—H9 | 119.6 |
C2—C1—C8 | 120.88 (15) | C11—C10—C9 | 119.35 (19) |
C3—C2—C7 | 117.27 (18) | C11—C10—H10 | 120.3 |
C3—C2—C1 | 122.57 (15) | C9—C10—H10 | 120.3 |
C7—C2—C1 | 120.03 (17) | C10—C11—C12 | 121.2 (2) |
C4—C3—C2 | 121.96 (16) | C10—C11—Cl2 | 119.64 (16) |
C4—C3—H3 | 119.0 | C12—C11—Cl2 | 119.09 (19) |
C2—C3—H3 | 119.0 | C11—C12—C13 | 119.2 (2) |
C3—C4—C5 | 119.18 (19) | C11—C12—H12 | 120.4 |
C3—C4—H4 | 120.4 | C13—C12—H12 | 120.4 |
C5—C4—H4 | 120.4 | C12—C13—C8 | 121.57 (19) |
C6—C5—C4 | 120.76 (19) | C12—C13—H13 | 119.2 |
C6—C5—Cl1 | 119.50 (15) | C8—C13—H13 | 119.2 |
C4—C5—Cl1 | 119.73 (16) | N2—C14—C14i | 114.6 (2) |
C5—C6—C7 | 119.64 (17) | N2—C14—C15 | 124.95 (17) |
C5—C6—H6 | 120.2 | C14i—C14—C15 | 120.48 (18) |
C7—C6—H6 | 120.2 | C14—C15—H15A | 109.5 |
C6—C7—C2 | 121.10 (18) | C14—C15—H15B | 109.5 |
C6—C7—H7 | 119.4 | H15A—C15—H15B | 109.5 |
C2—C7—H7 | 119.4 | C14—C15—H15C | 109.5 |
C13—C8—C9 | 117.80 (18) | H15A—C15—H15C | 109.5 |
C13—C8—C1 | 120.52 (16) | H15B—C15—H15C | 109.5 |
Symmetry code: (i) −x, −y, −z+1. |
Butane-2,3-dione 2,3-bis{[bis(4-methylphenyl)methylidene]hydrazone} (3a)
top
Crystal data top
C34H34N4 | Z = 2 |
Mr = 498.65 | F(000) = 532 |
Triclinic, P1 | Dx = 1.210 Mg m−3 |
a = 7.6122 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.7586 (6) Å | Cell parameters from 9990 reflections |
c = 18.3363 (11) Å | θ = 2.6–28.3° |
α = 104.238 (2)° | µ = 0.07 mm−1 |
β = 95.169 (2)° | T = 100 K |
γ = 107.232 (2)° | Plate, orange |
V = 1368.51 (13) Å3 | 0.43 × 0.32 × 0.21 mm |
Data collection top
Bruker APEXII CMOS detector diffractometer | 5759 reflections with I > 2σ(I) |
Radiation source: microfocus | Rint = 0.103 |
phi and ω scans | θmax = 28.3°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | h = −10→10 |
Tmin = 0.973, Tmax = 0.985 | k = −14→14 |
63984 measured reflections | l = −24→24 |
6794 independent reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.051 | w = 1/[σ2(Fo2) + (0.0701P)2 + 0.737P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.142 | (Δ/σ)max < 0.001 |
S = 1.02 | Δρmax = 0.44 e Å−3 |
6794 reflections | Δρmin = −0.37 e Å−3 |
350 parameters | Extinction correction: SHELXL2016 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.011 (2) |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.84962 (15) | 0.63387 (11) | 0.10935 (6) | 0.0180 (2) | |
N2 | 0.66544 (15) | 0.60759 (11) | 0.07965 (6) | 0.0172 (2) | |
N3 | 0.13612 (16) | 0.40732 (12) | 0.40169 (7) | 0.0214 (2) | |
N4 | 0.27424 (15) | 0.39873 (12) | 0.45366 (7) | 0.0204 (2) | |
C1 | 0.96370 (18) | 0.75725 (13) | 0.12820 (7) | 0.0168 (3) | |
C2 | 0.91952 (18) | 0.87240 (13) | 0.10946 (8) | 0.0187 (3) | |
C3 | 0.81904 (19) | 0.85664 (14) | 0.03853 (8) | 0.0217 (3) | |
H3 | 0.781149 | 0.771239 | 0.000670 | 0.026* | |
C4 | 0.7735 (2) | 0.96376 (15) | 0.02239 (9) | 0.0266 (3) | |
H4 | 0.705066 | 0.950665 | −0.026405 | 0.032* | |
C5 | 0.8266 (2) | 1.09010 (15) | 0.07650 (9) | 0.0271 (3) | |
C6 | 0.9273 (2) | 1.10601 (14) | 0.14724 (9) | 0.0269 (3) | |
H6 | 0.963936 | 1.191267 | 0.185176 | 0.032* | |
C7 | 0.97532 (19) | 0.99978 (14) | 0.16348 (8) | 0.0228 (3) | |
H7 | 1.046826 | 1.013784 | 0.211785 | 0.027* | |
C8 | 0.7799 (3) | 1.20670 (18) | 0.05752 (11) | 0.0402 (4) | |
H8A | 0.754818 | 1.188917 | 0.001901 | 0.060* | |
H8B | 0.885460 | 1.290824 | 0.079853 | 0.060* | |
H8C | 0.668950 | 1.216057 | 0.078481 | 0.060* | |
C9 | 1.14988 (18) | 0.77868 (13) | 0.17161 (7) | 0.0178 (3) | |
C10 | 1.31145 (19) | 0.87895 (14) | 0.16780 (8) | 0.0209 (3) | |
H10 | 1.302386 | 0.942279 | 0.140762 | 0.025* | |
C11 | 1.48576 (19) | 0.88710 (15) | 0.20322 (8) | 0.0231 (3) | |
H11 | 1.594442 | 0.955025 | 0.199255 | 0.028* | |
C12 | 1.50330 (19) | 0.79728 (15) | 0.24437 (8) | 0.0224 (3) | |
C13 | 1.3408 (2) | 0.70216 (15) | 0.25123 (8) | 0.0243 (3) | |
H13 | 1.349194 | 0.642960 | 0.281236 | 0.029* | |
C14 | 1.16734 (19) | 0.69197 (14) | 0.21528 (8) | 0.0219 (3) | |
H14 | 1.058767 | 0.625207 | 0.220340 | 0.026* | |
C15 | 1.6908 (2) | 0.79710 (17) | 0.27845 (9) | 0.0281 (3) | |
H15A | 1.717031 | 0.717880 | 0.248309 | 0.042* | |
H15B | 1.689495 | 0.792997 | 0.331207 | 0.042* | |
H15C | 1.787944 | 0.880288 | 0.277995 | 0.042* | |
C16 | 0.60118 (17) | 0.51861 (12) | 0.01387 (7) | 0.0151 (2) | |
C17 | 0.71926 (18) | 0.45751 (14) | −0.03465 (8) | 0.0207 (3) | |
H17A | 0.780168 | 0.519876 | −0.062786 | 0.031* | |
H17B | 0.640382 | 0.371104 | −0.070934 | 0.031* | |
H17C | 0.814574 | 0.441525 | −0.002016 | 0.031* | |
C18 | −0.03297 (18) | 0.33344 (13) | 0.40239 (7) | 0.0180 (3) | |
C19 | −0.08477 (18) | 0.24931 (13) | 0.45555 (8) | 0.0177 (3) | |
C20 | −0.01485 (18) | 0.30044 (13) | 0.53375 (8) | 0.0183 (3) | |
H20 | 0.066721 | 0.391484 | 0.554145 | 0.022* | |
C21 | −0.06325 (18) | 0.21961 (14) | 0.58211 (8) | 0.0198 (3) | |
H21 | −0.015516 | 0.256892 | 0.635337 | 0.024* | |
C22 | −0.18022 (19) | 0.08509 (14) | 0.55435 (8) | 0.0217 (3) | |
C23 | −0.2499 (2) | 0.03424 (14) | 0.47605 (8) | 0.0257 (3) | |
H23 | −0.330241 | −0.057175 | 0.455636 | 0.031* | |
C24 | −0.2039 (2) | 0.11506 (14) | 0.42742 (8) | 0.0236 (3) | |
H24 | −0.254170 | 0.078488 | 0.374380 | 0.028* | |
C25 | −0.2305 (2) | −0.00252 (16) | 0.60721 (9) | 0.0292 (3) | |
H25A | −0.146345 | 0.041377 | 0.656627 | 0.044* | |
H25B | −0.218228 | −0.091447 | 0.584683 | 0.044* | |
H25C | −0.359733 | −0.014395 | 0.614651 | 0.044* | |
C26 | −0.18174 (18) | 0.33972 (13) | 0.34604 (7) | 0.0183 (3) | |
C27 | −0.37042 (19) | 0.29318 (15) | 0.35105 (8) | 0.0239 (3) | |
H27 | −0.406695 | 0.253955 | 0.390749 | 0.029* | |
C28 | −0.5068 (2) | 0.30314 (16) | 0.29892 (9) | 0.0260 (3) | |
H28 | −0.634524 | 0.269812 | 0.303310 | 0.031* | |
C29 | −0.4588 (2) | 0.36094 (14) | 0.24076 (8) | 0.0232 (3) | |
C30 | −0.2695 (2) | 0.41190 (15) | 0.23724 (8) | 0.0246 (3) | |
H30 | −0.233206 | 0.454670 | 0.198852 | 0.030* | |
C31 | −0.13384 (19) | 0.40137 (14) | 0.28852 (8) | 0.0219 (3) | |
H31 | −0.006032 | 0.436571 | 0.284625 | 0.026* | |
C32 | −0.6053 (2) | 0.36927 (18) | 0.18282 (10) | 0.0331 (4) | |
H32A | −0.646836 | 0.285982 | 0.140008 | 0.050* | |
H32B | −0.552296 | 0.447628 | 0.163947 | 0.050* | |
H32C | −0.712059 | 0.379597 | 0.206831 | 0.050* | |
C33 | 0.42487 (17) | 0.50329 (13) | 0.47275 (7) | 0.0189 (3) | |
C34 | 0.45753 (19) | 0.62552 (15) | 0.44365 (9) | 0.0244 (3) | |
H34A | 0.499706 | 0.606948 | 0.394391 | 0.037* | |
H34B | 0.553294 | 0.703459 | 0.480436 | 0.037* | |
H34C | 0.340933 | 0.646008 | 0.437129 | 0.037* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0153 (5) | 0.0179 (5) | 0.0177 (5) | 0.0038 (4) | −0.0009 (4) | 0.0029 (4) |
N2 | 0.0135 (5) | 0.0152 (5) | 0.0198 (5) | 0.0021 (4) | −0.0007 (4) | 0.0039 (4) |
N3 | 0.0161 (5) | 0.0212 (6) | 0.0252 (6) | 0.0040 (4) | −0.0006 (4) | 0.0078 (5) |
N4 | 0.0147 (5) | 0.0222 (6) | 0.0239 (6) | 0.0044 (4) | 0.0006 (4) | 0.0086 (5) |
C1 | 0.0156 (6) | 0.0163 (6) | 0.0153 (6) | 0.0033 (5) | 0.0013 (5) | 0.0017 (5) |
C2 | 0.0143 (6) | 0.0173 (6) | 0.0231 (6) | 0.0033 (5) | 0.0035 (5) | 0.0055 (5) |
C3 | 0.0219 (6) | 0.0176 (6) | 0.0228 (7) | 0.0026 (5) | 0.0012 (5) | 0.0064 (5) |
C4 | 0.0268 (7) | 0.0250 (7) | 0.0283 (7) | 0.0064 (6) | 0.0016 (6) | 0.0121 (6) |
C5 | 0.0261 (7) | 0.0222 (7) | 0.0375 (8) | 0.0092 (6) | 0.0102 (6) | 0.0134 (6) |
C6 | 0.0250 (7) | 0.0176 (6) | 0.0348 (8) | 0.0056 (5) | 0.0066 (6) | 0.0027 (6) |
C7 | 0.0178 (6) | 0.0201 (6) | 0.0259 (7) | 0.0036 (5) | 0.0017 (5) | 0.0022 (5) |
C8 | 0.0504 (11) | 0.0285 (8) | 0.0504 (11) | 0.0196 (8) | 0.0104 (8) | 0.0183 (8) |
C9 | 0.0161 (6) | 0.0185 (6) | 0.0151 (6) | 0.0046 (5) | 0.0005 (5) | 0.0005 (5) |
C10 | 0.0184 (6) | 0.0206 (6) | 0.0215 (6) | 0.0045 (5) | 0.0014 (5) | 0.0048 (5) |
C11 | 0.0163 (6) | 0.0248 (7) | 0.0234 (7) | 0.0031 (5) | 0.0015 (5) | 0.0035 (5) |
C12 | 0.0185 (6) | 0.0280 (7) | 0.0159 (6) | 0.0083 (5) | −0.0019 (5) | −0.0011 (5) |
C13 | 0.0242 (7) | 0.0288 (7) | 0.0191 (6) | 0.0087 (6) | −0.0003 (5) | 0.0073 (5) |
C14 | 0.0193 (6) | 0.0240 (7) | 0.0187 (6) | 0.0036 (5) | 0.0000 (5) | 0.0054 (5) |
C15 | 0.0206 (7) | 0.0380 (8) | 0.0229 (7) | 0.0119 (6) | −0.0011 (5) | 0.0029 (6) |
C16 | 0.0154 (6) | 0.0112 (5) | 0.0183 (6) | 0.0033 (4) | 0.0002 (5) | 0.0058 (4) |
C17 | 0.0167 (6) | 0.0203 (6) | 0.0223 (6) | 0.0071 (5) | −0.0008 (5) | 0.0016 (5) |
C18 | 0.0179 (6) | 0.0145 (6) | 0.0196 (6) | 0.0040 (5) | 0.0013 (5) | 0.0037 (5) |
C19 | 0.0161 (6) | 0.0157 (6) | 0.0206 (6) | 0.0049 (5) | 0.0027 (5) | 0.0045 (5) |
C20 | 0.0145 (6) | 0.0152 (6) | 0.0221 (6) | 0.0042 (5) | 0.0006 (5) | 0.0018 (5) |
C21 | 0.0165 (6) | 0.0224 (6) | 0.0190 (6) | 0.0064 (5) | 0.0006 (5) | 0.0043 (5) |
C22 | 0.0204 (6) | 0.0217 (6) | 0.0243 (7) | 0.0066 (5) | 0.0038 (5) | 0.0092 (5) |
C23 | 0.0278 (7) | 0.0159 (6) | 0.0260 (7) | −0.0010 (5) | 0.0000 (6) | 0.0048 (5) |
C24 | 0.0260 (7) | 0.0185 (6) | 0.0193 (6) | 0.0017 (5) | −0.0014 (5) | 0.0018 (5) |
C25 | 0.0287 (8) | 0.0281 (7) | 0.0305 (8) | 0.0039 (6) | 0.0034 (6) | 0.0153 (6) |
C26 | 0.0183 (6) | 0.0146 (6) | 0.0185 (6) | 0.0035 (5) | −0.0004 (5) | 0.0021 (5) |
C27 | 0.0197 (7) | 0.0276 (7) | 0.0228 (7) | 0.0044 (5) | 0.0025 (5) | 0.0088 (6) |
C28 | 0.0166 (6) | 0.0307 (7) | 0.0272 (7) | 0.0037 (5) | 0.0003 (5) | 0.0082 (6) |
C29 | 0.0210 (7) | 0.0197 (6) | 0.0240 (7) | 0.0035 (5) | −0.0038 (5) | 0.0041 (5) |
C30 | 0.0243 (7) | 0.0226 (7) | 0.0237 (7) | 0.0027 (5) | 0.0003 (5) | 0.0084 (5) |
C31 | 0.0184 (6) | 0.0200 (6) | 0.0241 (7) | 0.0021 (5) | 0.0020 (5) | 0.0061 (5) |
C32 | 0.0257 (8) | 0.0357 (8) | 0.0340 (8) | 0.0051 (6) | −0.0072 (6) | 0.0137 (7) |
C33 | 0.0154 (6) | 0.0207 (6) | 0.0208 (6) | 0.0051 (5) | 0.0032 (5) | 0.0076 (5) |
C34 | 0.0181 (6) | 0.0256 (7) | 0.0288 (7) | 0.0023 (5) | −0.0010 (5) | 0.0147 (6) |
Geometric parameters (Å, º) top
N1—C1 | 1.2934 (16) | C17—H17A | 0.9800 |
N1—N2 | 1.3762 (15) | C17—H17B | 0.9800 |
N2—C16 | 1.2879 (16) | C17—H17C | 0.9800 |
N3—C18 | 1.3002 (17) | C18—C19 | 1.4889 (18) |
N3—N4 | 1.3937 (16) | C18—C26 | 1.4911 (18) |
N4—C33 | 1.2933 (17) | C19—C20 | 1.3939 (18) |
C1—C2 | 1.4837 (18) | C19—C24 | 1.3956 (18) |
C1—C9 | 1.4860 (17) | C20—C21 | 1.3881 (19) |
C2—C3 | 1.3931 (19) | C20—H20 | 0.9500 |
C2—C7 | 1.3968 (19) | C21—C22 | 1.3924 (19) |
C3—C4 | 1.386 (2) | C21—H21 | 0.9500 |
C3—H3 | 0.9500 | C22—C23 | 1.395 (2) |
C4—C5 | 1.391 (2) | C22—C25 | 1.5090 (19) |
C4—H4 | 0.9500 | C23—C24 | 1.390 (2) |
C5—C6 | 1.391 (2) | C23—H23 | 0.9500 |
C5—C8 | 1.509 (2) | C24—H24 | 0.9500 |
C6—C7 | 1.387 (2) | C25—H25A | 0.9800 |
C6—H6 | 0.9500 | C25—H25B | 0.9800 |
C7—H7 | 0.9500 | C25—H25C | 0.9800 |
C8—H8A | 0.9800 | C26—C27 | 1.3937 (19) |
C8—H8B | 0.9800 | C26—C31 | 1.3984 (19) |
C8—H8C | 0.9800 | C27—C28 | 1.393 (2) |
C9—C10 | 1.3956 (18) | C27—H27 | 0.9500 |
C9—C14 | 1.3968 (19) | C28—C29 | 1.385 (2) |
C10—C11 | 1.3921 (19) | C28—H28 | 0.9500 |
C10—H10 | 0.9500 | C29—C30 | 1.395 (2) |
C11—C12 | 1.392 (2) | C29—C32 | 1.5078 (19) |
C11—H11 | 0.9500 | C30—C31 | 1.382 (2) |
C12—C13 | 1.391 (2) | C30—H30 | 0.9500 |
C12—C15 | 1.5066 (19) | C31—H31 | 0.9500 |
C13—C14 | 1.3829 (19) | C32—H32A | 0.9800 |
C13—H13 | 0.9500 | C32—H32B | 0.9800 |
C14—H14 | 0.9500 | C32—H32C | 0.9800 |
C15—H15A | 0.9800 | C33—C33ii | 1.480 (3) |
C15—H15B | 0.9800 | C33—C34 | 1.5003 (18) |
C15—H15C | 0.9800 | C34—H34A | 0.9800 |
C16—C16i | 1.478 (2) | C34—H34B | 0.9800 |
C16—C17 | 1.4960 (18) | C34—H34C | 0.9800 |
| | | |
C1—N1—N2 | 119.22 (11) | H17A—C17—H17C | 109.5 |
C16—N2—N1 | 116.34 (11) | H17B—C17—H17C | 109.5 |
C18—N3—N4 | 114.78 (11) | N3—C18—C19 | 124.93 (12) |
C33—N4—N3 | 113.85 (11) | N3—C18—C26 | 115.32 (12) |
N1—C1—C2 | 124.67 (12) | C19—C18—C26 | 119.73 (11) |
N1—C1—C9 | 114.90 (11) | C20—C19—C24 | 118.24 (12) |
C2—C1—C9 | 120.43 (11) | C20—C19—C18 | 121.63 (12) |
C3—C2—C7 | 118.08 (13) | C24—C19—C18 | 120.13 (12) |
C3—C2—C1 | 121.39 (12) | C21—C20—C19 | 120.64 (12) |
C7—C2—C1 | 120.52 (12) | C21—C20—H20 | 119.7 |
C4—C3—C2 | 120.96 (13) | C19—C20—H20 | 119.7 |
C4—C3—H3 | 119.5 | C20—C21—C22 | 121.46 (12) |
C2—C3—H3 | 119.5 | C20—C21—H21 | 119.3 |
C3—C4—C5 | 121.04 (14) | C22—C21—H21 | 119.3 |
C3—C4—H4 | 119.5 | C21—C22—C23 | 117.75 (13) |
C5—C4—H4 | 119.5 | C21—C22—C25 | 121.12 (13) |
C4—C5—C6 | 118.03 (13) | C23—C22—C25 | 121.13 (13) |
C4—C5—C8 | 120.46 (15) | C24—C23—C22 | 121.11 (13) |
C6—C5—C8 | 121.49 (15) | C24—C23—H23 | 119.4 |
C7—C6—C5 | 121.25 (14) | C22—C23—H23 | 119.4 |
C7—C6—H6 | 119.4 | C23—C24—C19 | 120.80 (13) |
C5—C6—H6 | 119.4 | C23—C24—H24 | 119.6 |
C6—C7—C2 | 120.62 (13) | C19—C24—H24 | 119.6 |
C6—C7—H7 | 119.7 | C22—C25—H25A | 109.5 |
C2—C7—H7 | 119.7 | C22—C25—H25B | 109.5 |
C5—C8—H8A | 109.5 | H25A—C25—H25B | 109.5 |
C5—C8—H8B | 109.5 | C22—C25—H25C | 109.5 |
H8A—C8—H8B | 109.5 | H25A—C25—H25C | 109.5 |
C5—C8—H8C | 109.5 | H25B—C25—H25C | 109.5 |
H8A—C8—H8C | 109.5 | C27—C26—C31 | 117.53 (12) |
H8B—C8—H8C | 109.5 | C27—C26—C18 | 122.14 (12) |
C10—C9—C14 | 118.09 (12) | C31—C26—C18 | 120.21 (12) |
C10—C9—C1 | 122.45 (12) | C28—C27—C26 | 121.20 (13) |
C14—C9—C1 | 119.39 (12) | C28—C27—H27 | 119.4 |
C9—C10—C11 | 120.66 (13) | C26—C27—H27 | 119.4 |
C9—C10—H10 | 119.7 | C29—C28—C27 | 120.96 (13) |
C11—C10—H10 | 119.7 | C29—C28—H28 | 119.5 |
C12—C11—C10 | 121.03 (13) | C27—C28—H28 | 119.5 |
C12—C11—H11 | 119.5 | C28—C29—C30 | 117.93 (13) |
C10—C11—H11 | 119.5 | C28—C29—C32 | 121.48 (13) |
C13—C12—C11 | 117.95 (13) | C30—C29—C32 | 120.58 (14) |
C13—C12—C15 | 119.82 (13) | C31—C30—C29 | 121.28 (13) |
C11—C12—C15 | 122.18 (13) | C31—C30—H30 | 119.4 |
C14—C13—C12 | 121.36 (13) | C29—C30—H30 | 119.4 |
C14—C13—H13 | 119.3 | C30—C31—C26 | 121.03 (13) |
C12—C13—H13 | 119.3 | C30—C31—H31 | 119.5 |
C13—C14—C9 | 120.77 (13) | C26—C31—H31 | 119.5 |
C13—C14—H14 | 119.6 | C29—C32—H32A | 109.5 |
C9—C14—H14 | 119.6 | C29—C32—H32B | 109.5 |
C12—C15—H15A | 109.5 | H32A—C32—H32B | 109.5 |
C12—C15—H15B | 109.5 | C29—C32—H32C | 109.5 |
H15A—C15—H15B | 109.5 | H32A—C32—H32C | 109.5 |
C12—C15—H15C | 109.5 | H32B—C32—H32C | 109.5 |
H15A—C15—H15C | 109.5 | N4—C33—C33ii | 115.20 (15) |
H15B—C15—H15C | 109.5 | N4—C33—C34 | 125.61 (12) |
N2—C16—C16i | 115.75 (14) | C33ii—C33—C34 | 119.18 (14) |
N2—C16—C17 | 123.96 (11) | C33—C34—H34A | 109.5 |
C16i—C16—C17 | 120.26 (14) | C33—C34—H34B | 109.5 |
C16—C17—H17A | 109.5 | H34A—C34—H34B | 109.5 |
C16—C17—H17B | 109.5 | C33—C34—H34C | 109.5 |
H17A—C17—H17B | 109.5 | H34A—C34—H34C | 109.5 |
C16—C17—H17C | 109.5 | H34B—C34—H34C | 109.5 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, −y+1, −z+1. |
Butane-2,3-dione 2,3-bis{[bis(4-methylphenyl)methylidene]hydrazone} (3b)
top
Crystal data top
C34H34N4 | Z = 1 |
Mr = 498.65 | F(000) = 266 |
Triclinic, P1 | Dx = 1.219 Mg m−3 |
a = 7.7270 (15) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.9264 (17) Å | Cell parameters from 9982 reflections |
c = 10.491 (2) Å | θ = 2.8–28.3° |
α = 97.989 (7)° | µ = 0.07 mm−1 |
β = 96.215 (7)° | T = 100 K |
γ = 106.294 (7)° | Plate, yellow |
V = 679.5 (2) Å3 | 0.42 × 0.31 × 0.11 mm |
Data collection top
Bruker APEXII CMOS detector diffractometer | 6027 reflections with I > 2σ(I) |
Radiation source: microfocus | Rint = 0.036 |
phi and ω scans | θmax = 28.3°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | h = −10→10 |
Tmin = 0.974, Tmax = 0.992 | k = −11→11 |
28324 measured reflections | l = −13→13 |
6741 independent reflections | |
Refinement top
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0465P)2 + 0.1308P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.040 | (Δ/σ)max < 0.001 |
wR(F2) = 0.096 | Δρmax = 0.27 e Å−3 |
S = 1.05 | Δρmin = −0.19 e Å−3 |
6741 reflections | Extinction correction: SHELXL2016 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
350 parameters | Extinction coefficient: 0.024 (5) |
3 restraints | Absolute structure: Flack x determined using 2626 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons et al., 2013) |
Hydrogen site location: inferred from neighbouring sites | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.2849 (2) | 0.8199 (2) | 0.96188 (18) | 0.0176 (4) | |
N2 | 0.4717 (2) | 0.8860 (2) | 0.98037 (17) | 0.0173 (4) | |
N3 | 0.8018 (2) | 1.2351 (2) | 1.13372 (18) | 0.0196 (4) | |
N4 | 0.9870 (3) | 1.3077 (2) | 1.14178 (18) | 0.0199 (4) | |
C1 | 0.1954 (3) | 0.7928 (3) | 0.8458 (2) | 0.0157 (4) | |
C2 | 0.2757 (3) | 0.8467 (3) | 0.7304 (2) | 0.0157 (4) | |
C3 | 0.3868 (3) | 1.0007 (3) | 0.7359 (2) | 0.0187 (4) | |
H3 | 0.411328 | 1.075607 | 0.814338 | 0.022* | |
C4 | 0.4620 (3) | 1.0457 (3) | 0.6277 (2) | 0.0220 (5) | |
H4 | 0.536514 | 1.151767 | 0.633168 | 0.026* | |
C5 | 0.4310 (3) | 0.9396 (3) | 0.5116 (2) | 0.0205 (5) | |
C6 | 0.3183 (3) | 0.7860 (3) | 0.5065 (2) | 0.0204 (5) | |
H6 | 0.293756 | 0.711064 | 0.428102 | 0.024* | |
C7 | 0.2415 (3) | 0.7406 (3) | 0.6136 (2) | 0.0191 (5) | |
H7 | 0.164350 | 0.635302 | 0.607238 | 0.023* | |
C8 | 0.5163 (4) | 0.9881 (3) | 0.3951 (2) | 0.0298 (6) | |
H8A | 0.640414 | 0.979132 | 0.403341 | 0.045* | |
H8B | 0.520870 | 1.098116 | 0.390959 | 0.045* | |
H8C | 0.443113 | 0.918554 | 0.315468 | 0.045* | |
C9 | −0.0009 (3) | 0.7005 (3) | 0.8284 (2) | 0.0160 (4) | |
C10 | −0.1297 (3) | 0.7212 (3) | 0.7342 (2) | 0.0170 (4) | |
H10 | −0.090693 | 0.789819 | 0.674496 | 0.020* | |
C11 | −0.3137 (3) | 0.6430 (3) | 0.7265 (2) | 0.0183 (5) | |
H11 | −0.399508 | 0.662026 | 0.663659 | 0.022* | |
C12 | −0.3751 (3) | 0.5372 (3) | 0.8091 (2) | 0.0187 (5) | |
C13 | −0.2460 (3) | 0.5118 (3) | 0.9002 (2) | 0.0200 (5) | |
H13 | −0.284682 | 0.437592 | 0.955829 | 0.024* | |
C14 | −0.0621 (3) | 0.5932 (3) | 0.9112 (2) | 0.0188 (5) | |
H14 | 0.023250 | 0.575867 | 0.975401 | 0.023* | |
C15 | −0.5762 (3) | 0.4550 (3) | 0.8014 (3) | 0.0248 (5) | |
H15A | −0.593314 | 0.376360 | 0.859076 | 0.037* | |
H15B | −0.627855 | 0.401851 | 0.711549 | 0.037* | |
H15C | −0.638001 | 0.533418 | 0.828423 | 0.037* | |
C16 | 0.5370 (3) | 1.0249 (3) | 1.0516 (2) | 0.0163 (4) | |
C17 | 0.4226 (3) | 1.1236 (3) | 1.1010 (2) | 0.0214 (5) | |
H17A | 0.383987 | 1.175746 | 1.031623 | 0.032* | |
H17B | 0.494029 | 1.204154 | 1.175520 | 0.032* | |
H17C | 0.314721 | 1.055630 | 1.128239 | 0.032* | |
C18 | 0.7383 (3) | 1.0905 (3) | 1.0757 (2) | 0.0165 (4) | |
C19 | 0.8547 (3) | 0.9906 (3) | 1.0313 (2) | 0.0217 (5) | |
H19A | 0.953495 | 1.053644 | 0.992027 | 0.033* | |
H19B | 0.779980 | 0.898715 | 0.966703 | 0.033* | |
H19C | 0.906801 | 0.954151 | 1.106126 | 0.033* | |
C20 | 1.0914 (3) | 1.3283 (3) | 1.2505 (2) | 0.0169 (5) | |
C21 | 1.0319 (3) | 1.2697 (3) | 1.3704 (2) | 0.0169 (4) | |
C22 | 1.0717 (3) | 1.1380 (3) | 1.4085 (2) | 0.0208 (5) | |
H22 | 1.122645 | 1.075046 | 1.352183 | 0.025* | |
C23 | 1.0369 (3) | 1.0986 (3) | 1.5287 (2) | 0.0220 (5) | |
H23 | 1.063244 | 1.007815 | 1.553122 | 0.026* | |
C24 | 0.9644 (3) | 1.1892 (3) | 1.6137 (2) | 0.0193 (5) | |
C25 | 0.9394 (4) | 1.1521 (3) | 1.7476 (2) | 0.0284 (5) | |
H25A | 0.932058 | 1.246338 | 1.804353 | 0.043* | |
H25B | 1.043411 | 1.120585 | 1.784006 | 0.043* | |
H25C | 0.826636 | 1.065183 | 1.741549 | 0.043* | |
C26 | 0.9188 (3) | 1.3165 (3) | 1.5731 (2) | 0.0222 (5) | |
H26 | 0.863997 | 1.377250 | 1.628159 | 0.027* | |
C27 | 0.9525 (3) | 1.3562 (3) | 1.4525 (2) | 0.0198 (5) | |
H27 | 0.920493 | 1.443801 | 1.426281 | 0.024* | |
C28 | 1.2850 (3) | 1.4232 (3) | 1.2600 (2) | 0.0168 (4) | |
C29 | 1.4124 (3) | 1.4380 (3) | 1.3691 (2) | 0.0184 (5) | |
H29 | 1.375325 | 1.385962 | 1.439076 | 0.022* | |
C30 | 1.5925 (3) | 1.5275 (3) | 1.3768 (2) | 0.0208 (5) | |
H30 | 1.676778 | 1.536619 | 1.452594 | 0.025* | |
C31 | 1.6526 (3) | 1.6039 (3) | 1.2766 (2) | 0.0214 (5) | |
C32 | 1.5237 (3) | 1.5934 (3) | 1.1688 (2) | 0.0228 (5) | |
H32 | 1.560439 | 1.648487 | 1.100305 | 0.027* | |
C33 | 1.3445 (3) | 1.5046 (3) | 1.1604 (2) | 0.0201 (5) | |
H33 | 1.259713 | 1.498266 | 1.085678 | 0.024* | |
C34 | 1.8497 (4) | 1.6971 (3) | 1.2842 (3) | 0.0324 (6) | |
H34A | 1.914405 | 1.707294 | 1.372077 | 0.049* | |
H34B | 1.857675 | 1.802746 | 1.264524 | 0.049* | |
H34C | 1.905358 | 1.641785 | 1.220790 | 0.049* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0145 (9) | 0.0173 (9) | 0.0194 (9) | 0.0028 (7) | 0.0004 (7) | 0.0034 (7) |
N2 | 0.0136 (9) | 0.0211 (10) | 0.0157 (9) | 0.0030 (7) | −0.0004 (7) | 0.0053 (8) |
N3 | 0.0155 (9) | 0.0220 (10) | 0.0186 (9) | 0.0033 (8) | −0.0009 (7) | 0.0020 (8) |
N4 | 0.0166 (10) | 0.0207 (10) | 0.0200 (10) | 0.0034 (8) | 0.0007 (7) | 0.0017 (8) |
C1 | 0.0161 (11) | 0.0135 (11) | 0.0182 (11) | 0.0051 (9) | 0.0035 (8) | 0.0029 (8) |
C2 | 0.0116 (10) | 0.0178 (11) | 0.0188 (11) | 0.0058 (8) | 0.0009 (8) | 0.0052 (9) |
C3 | 0.0159 (10) | 0.0194 (11) | 0.0177 (11) | 0.0033 (9) | −0.0014 (8) | 0.0008 (9) |
C4 | 0.0174 (11) | 0.0209 (12) | 0.0242 (12) | 0.0004 (9) | 0.0003 (9) | 0.0058 (10) |
C5 | 0.0154 (11) | 0.0283 (12) | 0.0196 (11) | 0.0084 (9) | 0.0021 (8) | 0.0072 (9) |
C6 | 0.0198 (11) | 0.0230 (12) | 0.0182 (11) | 0.0091 (9) | 0.0007 (9) | −0.0006 (9) |
C7 | 0.0169 (11) | 0.0169 (11) | 0.0222 (11) | 0.0050 (9) | −0.0001 (8) | 0.0020 (9) |
C8 | 0.0271 (13) | 0.0381 (15) | 0.0230 (12) | 0.0061 (11) | 0.0058 (10) | 0.0075 (11) |
C9 | 0.0157 (11) | 0.0149 (11) | 0.0170 (10) | 0.0046 (8) | 0.0028 (8) | 0.0008 (8) |
C10 | 0.0185 (11) | 0.0160 (11) | 0.0166 (10) | 0.0050 (9) | 0.0024 (8) | 0.0033 (8) |
C11 | 0.0166 (11) | 0.0213 (12) | 0.0164 (10) | 0.0065 (9) | −0.0001 (8) | 0.0016 (9) |
C12 | 0.0152 (11) | 0.0166 (11) | 0.0225 (12) | 0.0037 (9) | 0.0036 (9) | −0.0008 (9) |
C13 | 0.0182 (12) | 0.0190 (12) | 0.0235 (12) | 0.0041 (9) | 0.0054 (9) | 0.0071 (9) |
C14 | 0.0184 (11) | 0.0198 (12) | 0.0195 (11) | 0.0074 (9) | 0.0011 (9) | 0.0057 (9) |
C15 | 0.0145 (11) | 0.0251 (13) | 0.0316 (13) | 0.0010 (10) | 0.0031 (10) | 0.0052 (10) |
C16 | 0.0161 (10) | 0.0198 (11) | 0.0131 (10) | 0.0053 (9) | 0.0015 (8) | 0.0044 (8) |
C17 | 0.0169 (11) | 0.0257 (12) | 0.0202 (11) | 0.0072 (9) | −0.0002 (9) | −0.0002 (9) |
C18 | 0.0175 (11) | 0.0201 (12) | 0.0112 (9) | 0.0043 (9) | 0.0004 (8) | 0.0043 (8) |
C19 | 0.0167 (11) | 0.0237 (12) | 0.0238 (12) | 0.0049 (9) | 0.0034 (9) | 0.0031 (9) |
C20 | 0.0166 (11) | 0.0150 (11) | 0.0188 (11) | 0.0058 (9) | 0.0016 (8) | 0.0009 (8) |
C21 | 0.0110 (10) | 0.0176 (11) | 0.0186 (11) | 0.0006 (8) | −0.0012 (8) | 0.0014 (9) |
C22 | 0.0200 (11) | 0.0188 (11) | 0.0244 (12) | 0.0069 (9) | 0.0050 (9) | 0.0032 (9) |
C23 | 0.0212 (11) | 0.0203 (12) | 0.0265 (12) | 0.0075 (9) | 0.0036 (9) | 0.0078 (9) |
C24 | 0.0140 (11) | 0.0188 (12) | 0.0216 (11) | −0.0003 (9) | 0.0016 (8) | 0.0034 (9) |
C25 | 0.0298 (14) | 0.0316 (14) | 0.0243 (12) | 0.0067 (11) | 0.0084 (10) | 0.0093 (11) |
C26 | 0.0216 (12) | 0.0186 (12) | 0.0259 (12) | 0.0046 (10) | 0.0083 (9) | 0.0017 (9) |
C27 | 0.0170 (11) | 0.0163 (11) | 0.0263 (12) | 0.0050 (9) | 0.0027 (9) | 0.0047 (9) |
C28 | 0.0181 (11) | 0.0144 (11) | 0.0174 (11) | 0.0050 (9) | 0.0032 (8) | 0.0011 (8) |
C29 | 0.0187 (11) | 0.0192 (11) | 0.0175 (11) | 0.0056 (9) | 0.0035 (9) | 0.0036 (9) |
C30 | 0.0187 (11) | 0.0242 (12) | 0.0174 (11) | 0.0068 (9) | −0.0020 (9) | 0.0000 (9) |
C31 | 0.0171 (11) | 0.0181 (11) | 0.0266 (12) | 0.0028 (9) | 0.0022 (9) | 0.0022 (10) |
C32 | 0.0229 (12) | 0.0217 (12) | 0.0244 (12) | 0.0053 (10) | 0.0045 (9) | 0.0086 (10) |
C33 | 0.0185 (11) | 0.0223 (12) | 0.0189 (11) | 0.0064 (9) | −0.0009 (9) | 0.0039 (9) |
C34 | 0.0214 (13) | 0.0345 (15) | 0.0364 (15) | −0.0016 (11) | 0.0020 (10) | 0.0121 (12) |
Geometric parameters (Å, º) top
N1—C1 | 1.289 (3) | C17—H17A | 0.9800 |
N1—N2 | 1.378 (3) | C17—H17B | 0.9800 |
N2—C16 | 1.288 (3) | C17—H17C | 0.9800 |
N3—C18 | 1.280 (3) | C18—C19 | 1.499 (3) |
N3—N4 | 1.383 (3) | C19—H19A | 0.9800 |
N4—C20 | 1.283 (3) | C19—H19B | 0.9800 |
C1—C9 | 1.487 (3) | C19—H19C | 0.9800 |
C1—C2 | 1.496 (3) | C20—C28 | 1.483 (3) |
C2—C3 | 1.391 (3) | C20—C21 | 1.496 (3) |
C2—C7 | 1.392 (3) | C21—C27 | 1.382 (3) |
C3—C4 | 1.389 (3) | C21—C22 | 1.394 (3) |
C3—H3 | 0.9500 | C22—C23 | 1.389 (3) |
C4—C5 | 1.387 (3) | C22—H22 | 0.9500 |
C4—H4 | 0.9500 | C23—C24 | 1.388 (3) |
C5—C6 | 1.393 (3) | C23—H23 | 0.9500 |
C5—C8 | 1.509 (3) | C24—C26 | 1.386 (3) |
C6—C7 | 1.383 (3) | C24—C25 | 1.507 (3) |
C6—H6 | 0.9500 | C25—H25A | 0.9800 |
C7—H7 | 0.9500 | C25—H25B | 0.9800 |
C8—H8A | 0.9800 | C25—H25C | 0.9800 |
C8—H8B | 0.9800 | C26—C27 | 1.393 (3) |
C8—H8C | 0.9800 | C26—H26 | 0.9500 |
C9—C10 | 1.394 (3) | C27—H27 | 0.9500 |
C9—C14 | 1.400 (3) | C28—C29 | 1.392 (3) |
C10—C11 | 1.385 (3) | C28—C33 | 1.400 (3) |
C10—H10 | 0.9500 | C29—C30 | 1.384 (3) |
C11—C12 | 1.390 (3) | C29—H29 | 0.9500 |
C11—H11 | 0.9500 | C30—C31 | 1.383 (3) |
C12—C13 | 1.393 (3) | C30—H30 | 0.9500 |
C12—C15 | 1.509 (3) | C31—C32 | 1.398 (3) |
C13—C14 | 1.387 (3) | C31—C34 | 1.504 (3) |
C13—H13 | 0.9500 | C32—C33 | 1.376 (3) |
C14—H14 | 0.9500 | C32—H32 | 0.9500 |
C15—H15A | 0.9800 | C33—H33 | 0.9500 |
C15—H15B | 0.9800 | C34—H34A | 0.9800 |
C15—H15C | 0.9800 | C34—H34B | 0.9800 |
C16—C18 | 1.479 (3) | C34—H34C | 0.9800 |
C16—C17 | 1.496 (3) | | |
| | | |
C1—N1—N2 | 118.70 (18) | H17A—C17—H17C | 109.5 |
C16—N2—N1 | 116.71 (18) | H17B—C17—H17C | 109.5 |
C18—N3—N4 | 117.38 (19) | N3—C18—C16 | 115.57 (18) |
C20—N4—N3 | 119.01 (19) | N3—C18—C19 | 124.0 (2) |
N1—C1—C9 | 116.24 (19) | C16—C18—C19 | 120.47 (19) |
N1—C1—C2 | 124.7 (2) | C18—C19—H19A | 109.5 |
C9—C1—C2 | 119.10 (19) | C18—C19—H19B | 109.5 |
C3—C2—C7 | 118.1 (2) | H19A—C19—H19B | 109.5 |
C3—C2—C1 | 122.0 (2) | C18—C19—H19C | 109.5 |
C7—C2—C1 | 119.8 (2) | H19A—C19—H19C | 109.5 |
C4—C3—C2 | 120.5 (2) | H19B—C19—H19C | 109.5 |
C4—C3—H3 | 119.7 | N4—C20—C28 | 117.5 (2) |
C2—C3—H3 | 119.7 | N4—C20—C21 | 125.2 (2) |
C5—C4—C3 | 121.6 (2) | C28—C20—C21 | 117.25 (19) |
C5—C4—H4 | 119.2 | C27—C21—C22 | 118.7 (2) |
C3—C4—H4 | 119.2 | C27—C21—C20 | 119.7 (2) |
C4—C5—C6 | 117.6 (2) | C22—C21—C20 | 121.3 (2) |
C4—C5—C8 | 121.4 (2) | C23—C22—C21 | 120.2 (2) |
C6—C5—C8 | 121.0 (2) | C23—C22—H22 | 119.9 |
C7—C6—C5 | 121.2 (2) | C21—C22—H22 | 119.9 |
C7—C6—H6 | 119.4 | C24—C23—C22 | 121.3 (2) |
C5—C6—H6 | 119.4 | C24—C23—H23 | 119.4 |
C6—C7—C2 | 121.0 (2) | C22—C23—H23 | 119.4 |
C6—C7—H7 | 119.5 | C26—C24—C23 | 118.2 (2) |
C2—C7—H7 | 119.5 | C26—C24—C25 | 121.0 (2) |
C5—C8—H8A | 109.5 | C23—C24—C25 | 120.8 (2) |
C5—C8—H8B | 109.5 | C24—C25—H25A | 109.5 |
H8A—C8—H8B | 109.5 | C24—C25—H25B | 109.5 |
C5—C8—H8C | 109.5 | H25A—C25—H25B | 109.5 |
H8A—C8—H8C | 109.5 | C24—C25—H25C | 109.5 |
H8B—C8—H8C | 109.5 | H25A—C25—H25C | 109.5 |
C10—C9—C14 | 118.1 (2) | H25B—C25—H25C | 109.5 |
C10—C9—C1 | 121.9 (2) | C24—C26—C27 | 120.7 (2) |
C14—C9—C1 | 119.97 (19) | C24—C26—H26 | 119.6 |
C11—C10—C9 | 120.9 (2) | C27—C26—H26 | 119.6 |
C11—C10—H10 | 119.6 | C21—C27—C26 | 120.9 (2) |
C9—C10—H10 | 119.6 | C21—C27—H27 | 119.6 |
C10—C11—C12 | 121.1 (2) | C26—C27—H27 | 119.6 |
C10—C11—H11 | 119.4 | C29—C28—C33 | 117.8 (2) |
C12—C11—H11 | 119.4 | C29—C28—C20 | 121.5 (2) |
C11—C12—C13 | 118.1 (2) | C33—C28—C20 | 120.77 (19) |
C11—C12—C15 | 120.6 (2) | C30—C29—C28 | 120.8 (2) |
C13—C12—C15 | 121.2 (2) | C30—C29—H29 | 119.6 |
C14—C13—C12 | 121.1 (2) | C28—C29—H29 | 119.6 |
C14—C13—H13 | 119.5 | C31—C30—C29 | 121.4 (2) |
C12—C13—H13 | 119.5 | C31—C30—H30 | 119.3 |
C13—C14—C9 | 120.6 (2) | C29—C30—H30 | 119.3 |
C13—C14—H14 | 119.7 | C30—C31—C32 | 117.8 (2) |
C9—C14—H14 | 119.7 | C30—C31—C34 | 121.1 (2) |
C12—C15—H15A | 109.5 | C32—C31—C34 | 121.1 (2) |
C12—C15—H15B | 109.5 | C33—C32—C31 | 121.0 (2) |
H15A—C15—H15B | 109.5 | C33—C32—H32 | 119.5 |
C12—C15—H15C | 109.5 | C31—C32—H32 | 119.5 |
H15A—C15—H15C | 109.5 | C32—C33—C28 | 121.1 (2) |
H15B—C15—H15C | 109.5 | C32—C33—H33 | 119.5 |
N2—C16—C18 | 115.88 (18) | C28—C33—H33 | 119.5 |
N2—C16—C17 | 124.0 (2) | C31—C34—H34A | 109.5 |
C18—C16—C17 | 119.94 (19) | C31—C34—H34B | 109.5 |
C16—C17—H17A | 109.5 | H34A—C34—H34B | 109.5 |
C16—C17—H17B | 109.5 | C31—C34—H34C | 109.5 |
H17A—C17—H17B | 109.5 | H34A—C34—H34C | 109.5 |
C16—C17—H17C | 109.5 | H34B—C34—H34C | 109.5 |
Butane-2,3-dione 2,3-bis((bis[4-(dimethylamino)phenyl]methylidene}hydrazone) (4a)
top
Crystal data top
C38H46N8 | F(000) = 660 |
Mr = 614.83 | Dx = 1.162 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 11.8988 (4) Å | Cell parameters from 9961 reflections |
b = 8.1189 (3) Å | θ = 2.2–23.6° |
c = 18.4205 (6) Å | µ = 0.07 mm−1 |
β = 98.961 (2)° | T = 298 K |
V = 1757.80 (11) Å3 | Needle, yellow |
Z = 2 | 0.43 × 0.31 × 0.11 mm |
Data collection top
Bruker APEXII CMOS detector diffractometer | 4603 reflections with I > 2σ(I) |
Radiation source: microfocus | Rint = 0.046 |
phi and ω scans | θmax = 28.3°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | h = −15→14 |
Tmin = 0.974, Tmax = 0.992 | k = −10→10 |
36024 measured reflections | l = −24→23 |
8685 independent reflections | |
Refinement top
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0643P)2 + 0.1615P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.055 | (Δ/σ)max < 0.001 |
wR(F2) = 0.148 | Δρmax = 0.17 e Å−3 |
S = 1.00 | Δρmin = −0.16 e Å−3 |
8685 reflections | Extinction correction: SHELXL2018 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
426 parameters | Extinction coefficient: 0.017 (2) |
1 restraint | Absolute structure: Flack x determined using 1684 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons et al., 2013) |
Hydrogen site location: inferred from neighbouring sites | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N6 | 0.4781 (2) | 0.3859 (4) | 0.72924 (13) | 0.0610 (7) | |
C19 | 0.4058 (3) | 0.3965 (4) | 0.53219 (16) | 0.0578 (8) | |
N5 | 0.4138 (2) | 0.3805 (4) | 0.65938 (13) | 0.0609 (7) | |
N4 | 0.4525 (2) | 0.4583 (4) | 0.48016 (13) | 0.0663 (8) | |
C22 | 0.4198 (3) | 0.4021 (4) | 0.78299 (15) | 0.0562 (8) | |
N3 | 0.3890 (2) | 0.4394 (4) | 0.41041 (13) | 0.0672 (8) | |
C20 | 0.4694 (3) | 0.4167 (4) | 0.60711 (15) | 0.0567 (8) | |
C31 | 0.4874 (3) | 0.3818 (4) | 0.85710 (15) | 0.0568 (8) | |
C36 | 0.4585 (3) | 0.4594 (5) | 0.91846 (16) | 0.0652 (9) | |
H36 | 0.392454 | 0.522471 | 0.913490 | 0.078* | |
C35 | 0.5241 (3) | 0.4463 (5) | 0.98644 (17) | 0.0701 (10) | |
H35 | 0.501781 | 0.500700 | 1.026268 | 0.084* | |
C1 | 0.4489 (3) | 0.4203 (4) | 0.35800 (15) | 0.0603 (8) | |
C33 | 0.6517 (3) | 0.2733 (5) | 0.93469 (18) | 0.0743 (10) | |
H33 | 0.717003 | 0.208731 | 0.939455 | 0.089* | |
C2 | 0.3818 (3) | 0.4096 (4) | 0.28304 (16) | 0.0597 (8) | |
C23 | 0.2969 (3) | 0.4373 (4) | 0.77484 (15) | 0.0557 (8) | |
C32 | 0.5855 (3) | 0.2884 (5) | 0.86747 (17) | 0.0685 (10) | |
H32 | 0.607171 | 0.233998 | 0.827427 | 0.082* | |
C34 | 0.6228 (3) | 0.3537 (5) | 0.99679 (17) | 0.0674 (9) | |
N8 | 0.6900 (3) | 0.3392 (5) | 1.06460 (16) | 0.0910 (11) | |
C21 | 0.5902 (3) | 0.4709 (6) | 0.61810 (18) | 0.0824 (12) | |
H21A | 0.634736 | 0.392810 | 0.595677 | 0.124* | |
H21B | 0.618367 | 0.477694 | 0.669753 | 0.124* | |
H21C | 0.595411 | 0.577065 | 0.595960 | 0.124* | |
C24 | 0.2441 (3) | 0.5517 (4) | 0.72467 (16) | 0.0632 (9) | |
H24 | 0.287745 | 0.609982 | 0.695709 | 0.076* | |
C26 | 0.0583 (3) | 0.4969 (5) | 0.75800 (18) | 0.0677 (9) | |
C10 | 0.5743 (3) | 0.4109 (4) | 0.36644 (15) | 0.0587 (8) | |
C4 | 0.2153 (3) | 0.4793 (5) | 0.19611 (19) | 0.0772 (10) | |
H4 | 0.147748 | 0.538310 | 0.185291 | 0.093* | |
C3 | 0.2809 (3) | 0.4954 (5) | 0.26469 (18) | 0.0706 (9) | |
H3 | 0.256757 | 0.565412 | 0.299131 | 0.085* | |
C12 | 0.7571 (4) | 0.3398 (5) | 0.43475 (19) | 0.0774 (11) | |
H12 | 0.799390 | 0.282397 | 0.473365 | 0.093* | |
C11 | 0.6408 (3) | 0.3286 (5) | 0.42427 (17) | 0.0693 (10) | |
H11 | 0.605570 | 0.265157 | 0.456261 | 0.083* | |
C6 | 0.3493 (3) | 0.2893 (5) | 0.16170 (18) | 0.0765 (10) | |
H6 | 0.373565 | 0.218106 | 0.127726 | 0.092* | |
C7 | 0.4141 (3) | 0.3068 (5) | 0.22992 (17) | 0.0694 (9) | |
H7 | 0.481641 | 0.247878 | 0.240711 | 0.083* | |
C15 | 0.6315 (3) | 0.4979 (4) | 0.31857 (16) | 0.0627 (9) | |
H15 | 0.589450 | 0.548131 | 0.277744 | 0.075* | |
C18 | 0.2982 (3) | 0.2997 (6) | 0.52233 (19) | 0.0873 (13) | |
H18A | 0.315669 | 0.184191 | 0.523372 | 0.131* | |
H18B | 0.253400 | 0.327145 | 0.475945 | 0.131* | |
H18C | 0.256060 | 0.325280 | 0.561297 | 0.131* | |
C5 | 0.2490 (3) | 0.3752 (5) | 0.14273 (18) | 0.0726 (10) | |
N1 | 0.1843 (3) | 0.3595 (6) | 0.07330 (18) | 0.1027 (13) | |
C28 | 0.2273 (3) | 0.3549 (4) | 0.81664 (17) | 0.0658 (9) | |
H28 | 0.259832 | 0.278814 | 0.851436 | 0.079* | |
C14 | 0.7472 (3) | 0.5124 (5) | 0.32923 (18) | 0.0696 (9) | |
H14 | 0.781870 | 0.574131 | 0.296401 | 0.084* | |
C25 | 0.1280 (3) | 0.5813 (5) | 0.71657 (19) | 0.0702 (10) | |
H25 | 0.095889 | 0.659496 | 0.682633 | 0.084* | |
N7 | −0.0570 (3) | 0.5274 (6) | 0.7496 (2) | 0.0973 (11) | |
C27 | 0.1113 (3) | 0.3819 (5) | 0.80836 (19) | 0.0722 (10) | |
H27 | 0.067725 | 0.322243 | 0.836908 | 0.087* | |
C38 | 0.7965 (4) | 0.2540 (9) | 1.0727 (2) | 0.119 (2) | |
H38A | 0.845773 | 0.306888 | 1.043256 | 0.178* | |
H38B | 0.783905 | 0.141878 | 1.056906 | 0.178* | |
H38C | 0.831215 | 0.255921 | 1.123350 | 0.178* | |
C37 | 0.6538 (5) | 0.4066 (7) | 1.1293 (2) | 0.1071 (15) | |
H37A | 0.575017 | 0.380901 | 1.129142 | 0.161* | |
H37B | 0.663629 | 0.523991 | 1.129781 | 0.161* | |
H37C | 0.698584 | 0.359942 | 1.172251 | 0.161* | |
C13 | 0.8142 (3) | 0.4361 (5) | 0.3885 (2) | 0.0755 (10) | |
C9 | 0.2170 (5) | 0.2410 (9) | 0.0226 (2) | 0.127 (2) | |
H9A | 0.211326 | 0.132078 | 0.042003 | 0.191* | |
H9B | 0.294049 | 0.261415 | 0.015582 | 0.191* | |
H9C | 0.167520 | 0.250283 | −0.023619 | 0.191* | |
C29 | −0.1114 (4) | 0.6310 (8) | 0.6916 (3) | 0.1252 (19) | |
H29A | −0.108750 | 0.578951 | 0.645118 | 0.188* | |
H29B | −0.072541 | 0.734927 | 0.693291 | 0.188* | |
H29C | −0.189171 | 0.648597 | 0.697586 | 0.188* | |
C8 | 0.0749 (4) | 0.4378 (12) | 0.0591 (3) | 0.162 (3) | |
H8A | 0.083779 | 0.554225 | 0.067207 | 0.242* | |
H8B | 0.026730 | 0.393592 | 0.091552 | 0.242* | |
H8C | 0.041090 | 0.418044 | 0.009076 | 0.242* | |
N2 | 0.9305 (3) | 0.4550 (6) | 0.4013 (2) | 0.1051 (12) | |
C30 | −0.1268 (4) | 0.4458 (8) | 0.7949 (3) | 0.132 (2) | |
H30A | −0.098597 | 0.468414 | 0.845606 | 0.198* | |
H30B | −0.125064 | 0.329263 | 0.786409 | 0.198* | |
H30C | −0.203575 | 0.485015 | 0.783058 | 0.198* | |
C17 | 0.9838 (4) | 0.5708 (9) | 0.3580 (3) | 0.131 (2) | |
H17A | 0.949782 | 0.677381 | 0.360718 | 0.197* | |
H17B | 0.973436 | 0.534788 | 0.307734 | 0.197* | |
H17C | 1.063627 | 0.577292 | 0.376642 | 0.197* | |
C16 | 0.9945 (5) | 0.4029 (11) | 0.4701 (3) | 0.158 (3) | |
H16A | 0.992528 | 0.285001 | 0.473375 | 0.238* | |
H16B | 0.961878 | 0.450110 | 0.509845 | 0.238* | |
H16C | 1.071962 | 0.438980 | 0.473121 | 0.238* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N6 | 0.0692 (16) | 0.0719 (19) | 0.0426 (13) | 0.0018 (14) | 0.0106 (12) | 0.0030 (13) |
C19 | 0.061 (2) | 0.065 (2) | 0.0487 (17) | 0.0036 (17) | 0.0145 (15) | 0.0004 (16) |
N5 | 0.0685 (17) | 0.0709 (18) | 0.0444 (14) | 0.0020 (14) | 0.0127 (13) | 0.0010 (13) |
N4 | 0.0804 (19) | 0.078 (2) | 0.0428 (14) | −0.0051 (15) | 0.0172 (13) | −0.0027 (13) |
C22 | 0.066 (2) | 0.0565 (19) | 0.0470 (16) | 0.0002 (16) | 0.0126 (14) | 0.0019 (15) |
N3 | 0.0770 (18) | 0.081 (2) | 0.0454 (14) | −0.0038 (16) | 0.0139 (13) | 0.0045 (14) |
C20 | 0.066 (2) | 0.061 (2) | 0.0458 (16) | 0.0053 (16) | 0.0149 (15) | −0.0011 (15) |
C31 | 0.065 (2) | 0.061 (2) | 0.0459 (16) | 0.0011 (17) | 0.0126 (14) | −0.0009 (15) |
C36 | 0.071 (2) | 0.072 (2) | 0.0527 (18) | 0.0126 (18) | 0.0099 (16) | −0.0033 (16) |
C35 | 0.082 (2) | 0.080 (3) | 0.0484 (18) | 0.007 (2) | 0.0119 (17) | −0.0056 (17) |
C1 | 0.079 (2) | 0.059 (2) | 0.0441 (16) | −0.0006 (17) | 0.0122 (16) | 0.0033 (15) |
C33 | 0.065 (2) | 0.099 (3) | 0.059 (2) | 0.015 (2) | 0.0088 (17) | 0.008 (2) |
C2 | 0.070 (2) | 0.065 (2) | 0.0458 (16) | −0.0045 (18) | 0.0127 (15) | 0.0075 (16) |
C23 | 0.065 (2) | 0.059 (2) | 0.0443 (16) | −0.0014 (16) | 0.0120 (14) | −0.0017 (14) |
C32 | 0.071 (2) | 0.087 (3) | 0.0498 (19) | 0.014 (2) | 0.0148 (17) | −0.0013 (17) |
C34 | 0.070 (2) | 0.082 (3) | 0.0481 (18) | −0.009 (2) | 0.0048 (16) | 0.0097 (17) |
N8 | 0.084 (2) | 0.129 (3) | 0.0555 (19) | 0.001 (2) | −0.0044 (16) | 0.0098 (19) |
C21 | 0.074 (2) | 0.121 (3) | 0.0541 (19) | −0.017 (2) | 0.0142 (17) | −0.007 (2) |
C24 | 0.070 (2) | 0.067 (2) | 0.0537 (18) | −0.0010 (17) | 0.0120 (16) | 0.0096 (16) |
C26 | 0.061 (2) | 0.075 (2) | 0.067 (2) | −0.0052 (19) | 0.0092 (17) | −0.0014 (19) |
C10 | 0.073 (2) | 0.061 (2) | 0.0431 (16) | 0.0045 (17) | 0.0098 (15) | −0.0003 (14) |
C4 | 0.067 (2) | 0.092 (3) | 0.072 (2) | 0.003 (2) | 0.0051 (18) | 0.010 (2) |
C3 | 0.074 (2) | 0.079 (2) | 0.062 (2) | 0.006 (2) | 0.0187 (18) | 0.0048 (18) |
C12 | 0.087 (3) | 0.084 (3) | 0.058 (2) | 0.023 (2) | −0.0003 (19) | −0.0008 (19) |
C11 | 0.094 (3) | 0.066 (2) | 0.0485 (19) | 0.0106 (19) | 0.0126 (18) | 0.0063 (16) |
C6 | 0.088 (3) | 0.087 (3) | 0.053 (2) | 0.003 (2) | 0.0083 (19) | −0.0085 (19) |
C7 | 0.078 (2) | 0.078 (2) | 0.0520 (19) | 0.0086 (19) | 0.0096 (17) | 0.0027 (17) |
C15 | 0.076 (2) | 0.067 (2) | 0.0454 (16) | 0.0058 (18) | 0.0104 (16) | 0.0038 (15) |
C18 | 0.080 (3) | 0.126 (4) | 0.054 (2) | −0.016 (3) | 0.0044 (18) | 0.008 (2) |
C5 | 0.076 (2) | 0.087 (3) | 0.0530 (19) | −0.016 (2) | 0.0057 (18) | 0.0030 (19) |
N1 | 0.094 (3) | 0.136 (4) | 0.071 (2) | −0.008 (2) | −0.0123 (19) | −0.001 (2) |
C28 | 0.075 (2) | 0.067 (2) | 0.0555 (19) | 0.0023 (18) | 0.0113 (17) | 0.0083 (16) |
C14 | 0.080 (3) | 0.072 (2) | 0.058 (2) | 0.0033 (19) | 0.0162 (18) | −0.0016 (17) |
C25 | 0.068 (2) | 0.073 (2) | 0.068 (2) | 0.0037 (19) | 0.0076 (18) | 0.0128 (18) |
N7 | 0.064 (2) | 0.118 (3) | 0.112 (3) | 0.000 (2) | 0.0210 (19) | 0.010 (2) |
C27 | 0.073 (2) | 0.078 (2) | 0.069 (2) | −0.012 (2) | 0.0204 (18) | 0.0022 (19) |
C38 | 0.079 (3) | 0.185 (6) | 0.086 (3) | −0.008 (4) | −0.007 (2) | 0.035 (4) |
C37 | 0.151 (4) | 0.105 (3) | 0.058 (2) | −0.012 (3) | −0.009 (2) | −0.006 (2) |
C13 | 0.075 (3) | 0.079 (3) | 0.073 (2) | 0.011 (2) | 0.011 (2) | −0.011 (2) |
C9 | 0.149 (5) | 0.166 (5) | 0.061 (2) | −0.027 (4) | −0.002 (3) | −0.022 (3) |
C29 | 0.074 (3) | 0.140 (5) | 0.155 (5) | 0.018 (3) | −0.007 (3) | 0.020 (4) |
C8 | 0.079 (3) | 0.280 (10) | 0.114 (4) | −0.019 (5) | −0.021 (3) | 0.008 (5) |
N2 | 0.073 (2) | 0.134 (4) | 0.106 (3) | 0.004 (2) | 0.006 (2) | 0.000 (3) |
C30 | 0.083 (3) | 0.145 (5) | 0.175 (5) | −0.006 (3) | 0.044 (3) | 0.029 (4) |
C17 | 0.091 (3) | 0.156 (6) | 0.150 (5) | −0.017 (4) | 0.030 (3) | −0.011 (5) |
C16 | 0.099 (4) | 0.194 (7) | 0.166 (6) | 0.001 (4) | −0.029 (4) | 0.026 (5) |
Geometric parameters (Å, º) top
N6—C22 | 1.302 (4) | C6—C7 | 1.375 (5) |
N6—N5 | 1.392 (3) | C6—C5 | 1.380 (5) |
C19—N4 | 1.283 (4) | C6—H6 | 0.9300 |
C19—C20 | 1.476 (4) | C7—H7 | 0.9300 |
C19—C18 | 1.489 (5) | C15—C14 | 1.366 (5) |
N5—C20 | 1.284 (4) | C15—H15 | 0.9300 |
N4—N3 | 1.394 (4) | C18—H18A | 0.9600 |
C22—C23 | 1.474 (4) | C18—H18B | 0.9600 |
C22—C31 | 1.482 (4) | C18—H18C | 0.9600 |
N3—C1 | 1.296 (4) | C5—N1 | 1.392 (5) |
C20—C21 | 1.487 (5) | N1—C8 | 1.436 (7) |
C31—C32 | 1.380 (5) | N1—C9 | 1.436 (7) |
C31—C36 | 1.384 (4) | C28—C27 | 1.382 (5) |
C36—C35 | 1.373 (5) | C28—H28 | 0.9300 |
C36—H36 | 0.9300 | C14—C13 | 1.392 (5) |
C35—C34 | 1.382 (5) | C14—H14 | 0.9300 |
C35—H35 | 0.9300 | C25—H25 | 0.9300 |
C1—C10 | 1.478 (5) | N7—C30 | 1.428 (6) |
C1—C2 | 1.486 (4) | N7—C29 | 1.432 (6) |
C33—C32 | 1.366 (4) | C27—H27 | 0.9300 |
C33—C34 | 1.406 (5) | C38—H38A | 0.9600 |
C33—H33 | 0.9300 | C38—H38B | 0.9600 |
C2—C3 | 1.383 (5) | C38—H38C | 0.9600 |
C2—C7 | 1.386 (5) | C37—H37A | 0.9600 |
C23—C28 | 1.387 (4) | C37—H37B | 0.9600 |
C23—C24 | 1.390 (4) | C37—H37C | 0.9600 |
C32—H32 | 0.9300 | C13—N2 | 1.376 (5) |
C34—N8 | 1.380 (4) | C9—H9A | 0.9600 |
N8—C38 | 1.431 (6) | C9—H9B | 0.9600 |
N8—C37 | 1.438 (5) | C9—H9C | 0.9600 |
C21—H21A | 0.9600 | C29—H29A | 0.9600 |
C21—H21B | 0.9600 | C29—H29B | 0.9600 |
C21—H21C | 0.9600 | C29—H29C | 0.9600 |
C24—C25 | 1.387 (5) | C8—H8A | 0.9600 |
C24—H24 | 0.9300 | C8—H8B | 0.9600 |
C26—N7 | 1.379 (4) | C8—H8C | 0.9600 |
C26—C25 | 1.391 (5) | N2—C16 | 1.437 (6) |
C26—C27 | 1.396 (5) | N2—C17 | 1.442 (7) |
C10—C15 | 1.388 (4) | C30—H30A | 0.9600 |
C10—C11 | 1.394 (5) | C30—H30B | 0.9600 |
C4—C3 | 1.384 (5) | C30—H30C | 0.9600 |
C4—C5 | 1.402 (5) | C17—H17A | 0.9600 |
C4—H4 | 0.9300 | C17—H17B | 0.9600 |
C3—H3 | 0.9300 | C17—H17C | 0.9600 |
C12—C11 | 1.371 (5) | C16—H16A | 0.9600 |
C12—C13 | 1.406 (5) | C16—H16B | 0.9600 |
C12—H12 | 0.9300 | C16—H16C | 0.9600 |
C11—H11 | 0.9300 | | |
| | | |
C22—N6—N5 | 115.1 (3) | C19—C18—H18B | 109.5 |
N4—C19—C20 | 115.9 (3) | H18A—C18—H18B | 109.5 |
N4—C19—C18 | 125.4 (3) | C19—C18—H18C | 109.5 |
C20—C19—C18 | 118.6 (3) | H18A—C18—H18C | 109.5 |
C20—N5—N6 | 114.3 (3) | H18B—C18—H18C | 109.5 |
C19—N4—N3 | 114.2 (3) | C6—C5—N1 | 121.3 (4) |
N6—C22—C23 | 125.5 (3) | C6—C5—C4 | 117.3 (3) |
N6—C22—C31 | 114.3 (3) | N1—C5—C4 | 121.5 (4) |
C23—C22—C31 | 120.2 (2) | C5—N1—C8 | 118.9 (4) |
C1—N3—N4 | 114.7 (3) | C5—N1—C9 | 119.4 (4) |
N5—C20—C19 | 115.2 (3) | C8—N1—C9 | 120.6 (4) |
N5—C20—C21 | 124.5 (3) | C27—C28—C23 | 122.3 (3) |
C19—C20—C21 | 120.3 (2) | C27—C28—H28 | 118.8 |
C32—C31—C36 | 116.8 (3) | C23—C28—H28 | 118.8 |
C32—C31—C22 | 121.0 (3) | C15—C14—C13 | 121.0 (3) |
C36—C31—C22 | 122.2 (3) | C15—C14—H14 | 119.5 |
C35—C36—C31 | 122.1 (3) | C13—C14—H14 | 119.5 |
C35—C36—H36 | 119.0 | C24—C25—C26 | 121.6 (3) |
C31—C36—H36 | 119.0 | C24—C25—H25 | 119.2 |
C36—C35—C34 | 121.2 (3) | C26—C25—H25 | 119.2 |
C36—C35—H35 | 119.4 | C26—N7—C30 | 120.7 (4) |
C34—C35—H35 | 119.4 | C26—N7—C29 | 121.0 (4) |
N3—C1—C10 | 126.3 (3) | C30—N7—C29 | 118.2 (4) |
N3—C1—C2 | 114.9 (3) | C28—C27—C26 | 121.3 (3) |
C10—C1—C2 | 118.9 (3) | C28—C27—H27 | 119.4 |
C32—C33—C34 | 121.1 (3) | C26—C27—H27 | 119.4 |
C32—C33—H33 | 119.5 | N8—C38—H38A | 109.5 |
C34—C33—H33 | 119.5 | N8—C38—H38B | 109.5 |
C3—C2—C7 | 117.2 (3) | H38A—C38—H38B | 109.5 |
C3—C2—C1 | 121.2 (3) | N8—C38—H38C | 109.5 |
C7—C2—C1 | 121.5 (3) | H38A—C38—H38C | 109.5 |
C28—C23—C24 | 116.4 (3) | H38B—C38—H38C | 109.5 |
C28—C23—C22 | 121.2 (3) | N8—C37—H37A | 109.5 |
C24—C23—C22 | 122.4 (3) | N8—C37—H37B | 109.5 |
C33—C32—C31 | 122.1 (3) | H37A—C37—H37B | 109.5 |
C33—C32—H32 | 119.0 | N8—C37—H37C | 109.5 |
C31—C32—H32 | 119.0 | H37A—C37—H37C | 109.5 |
N8—C34—C35 | 122.1 (3) | H37B—C37—H37C | 109.5 |
N8—C34—C33 | 121.1 (3) | N2—C13—C14 | 121.5 (4) |
C35—C34—C33 | 116.8 (3) | N2—C13—C12 | 121.7 (4) |
C34—N8—C38 | 121.0 (4) | C14—C13—C12 | 116.8 (3) |
C34—N8—C37 | 120.8 (4) | N1—C9—H9A | 109.5 |
C38—N8—C37 | 118.2 (3) | N1—C9—H9B | 109.5 |
C20—C21—H21A | 109.5 | H9A—C9—H9B | 109.5 |
C20—C21—H21B | 109.5 | N1—C9—H9C | 109.5 |
H21A—C21—H21B | 109.5 | H9A—C9—H9C | 109.5 |
C20—C21—H21C | 109.5 | H9B—C9—H9C | 109.5 |
H21A—C21—H21C | 109.5 | N7—C29—H29A | 109.5 |
H21B—C21—H21C | 109.5 | N7—C29—H29B | 109.5 |
C25—C24—C23 | 121.8 (3) | H29A—C29—H29B | 109.5 |
C25—C24—H24 | 119.1 | N7—C29—H29C | 109.5 |
C23—C24—H24 | 119.1 | H29A—C29—H29C | 109.5 |
N7—C26—C25 | 121.1 (3) | H29B—C29—H29C | 109.5 |
N7—C26—C27 | 122.2 (3) | N1—C8—H8A | 109.5 |
C25—C26—C27 | 116.6 (3) | N1—C8—H8B | 109.5 |
C15—C10—C11 | 117.0 (3) | H8A—C8—H8B | 109.5 |
C15—C10—C1 | 119.6 (3) | N1—C8—H8C | 109.5 |
C11—C10—C1 | 123.2 (3) | H8A—C8—H8C | 109.5 |
C3—C4—C5 | 121.0 (4) | H8B—C8—H8C | 109.5 |
C3—C4—H4 | 119.5 | C13—N2—C16 | 120.0 (4) |
C5—C4—H4 | 119.5 | C13—N2—C17 | 119.6 (4) |
C2—C3—C4 | 121.3 (3) | C16—N2—C17 | 117.5 (5) |
C2—C3—H3 | 119.3 | N7—C30—H30A | 109.5 |
C4—C3—H3 | 119.3 | N7—C30—H30B | 109.5 |
C11—C12—C13 | 121.6 (3) | H30A—C30—H30B | 109.5 |
C11—C12—H12 | 119.2 | N7—C30—H30C | 109.5 |
C13—C12—H12 | 119.2 | H30A—C30—H30C | 109.5 |
C12—C11—C10 | 121.0 (3) | H30B—C30—H30C | 109.5 |
C12—C11—H11 | 119.5 | N2—C17—H17A | 109.5 |
C10—C11—H11 | 119.5 | N2—C17—H17B | 109.5 |
C7—C6—C5 | 121.2 (3) | H17A—C17—H17B | 109.5 |
C7—C6—H6 | 119.4 | N2—C17—H17C | 109.5 |
C5—C6—H6 | 119.4 | H17A—C17—H17C | 109.5 |
C6—C7—C2 | 122.0 (3) | H17B—C17—H17C | 109.5 |
C6—C7—H7 | 119.0 | N2—C16—H16A | 109.5 |
C2—C7—H7 | 119.0 | N2—C16—H16B | 109.5 |
C14—C15—C10 | 122.4 (3) | H16A—C16—H16B | 109.5 |
C14—C15—H15 | 118.8 | N2—C16—H16C | 109.5 |
C10—C15—H15 | 118.8 | H16A—C16—H16C | 109.5 |
C19—C18—H18A | 109.5 | H16B—C16—H16C | 109.5 |
Butane-2,3-dione 2,3-bis((bis[4-(dimethylamino)phenyl]methylidene}hydrazone) (4b)
top
Crystal data top
C38H46N8 | Z = 1 |
Mr = 614.83 | F(000) = 330 |
Triclinic, P1 | Dx = 1.162 Mg m−3 |
a = 7.5278 (8) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.1875 (11) Å | Cell parameters from 9590 reflections |
c = 12.0834 (13) Å | θ = 2.4–23.7° |
α = 104.338 (5)° | µ = 0.07 mm−1 |
β = 95.713 (5)° | T = 293 K |
γ = 98.717 (4)° | Plate, yellow |
V = 878.30 (16) Å3 | 0.24 × 0.22 × 0.12 mm |
Data collection top
Bruker APEXII CMOS detector diffractometer | 2552 reflections with I > 2σ(I) |
Radiation source: microfocus | Rint = 0.039 |
phi and ω scans | θmax = 28.3°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | h = −10→10 |
Tmin = 0.983, Tmax = 0.992 | k = −13→13 |
33918 measured reflections | l = −15→16 |
4357 independent reflections | |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.056 | H-atom parameters constrained |
wR(F2) = 0.168 | w = 1/[σ2(Fo2) + (0.0705P)2 + 0.1719P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
4357 reflections | Δρmax = 0.14 e Å−3 |
213 parameters | Δρmin = −0.14 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.3624 (2) | 0.34915 (16) | 0.41542 (13) | 0.0677 (4) | |
N2 | 0.1901 (2) | 0.27391 (15) | 0.40909 (13) | 0.0695 (4) | |
N3 | −0.5783 (2) | −0.11689 (19) | 0.2999 (2) | 0.0966 (6) | |
N4 | 0.2609 (3) | 0.44009 (19) | −0.07106 (15) | 0.0835 (5) | |
C1 | 0.0876 (2) | 0.23702 (16) | 0.31039 (15) | 0.0586 (4) | |
C2 | −0.0835 (2) | 0.13981 (16) | 0.30181 (15) | 0.0591 (4) | |
C3 | −0.2354 (3) | 0.13202 (19) | 0.22461 (18) | 0.0728 (5) | |
H3 | −0.227864 | 0.184637 | 0.171816 | 0.087* | |
C4 | −0.3975 (3) | 0.0486 (2) | 0.2237 (2) | 0.0805 (6) | |
H4 | −0.497334 | 0.047242 | 0.171212 | 0.097* | |
C5 | −0.4154 (2) | −0.03368 (18) | 0.29941 (18) | 0.0706 (5) | |
C6 | −0.2614 (3) | −0.0310 (2) | 0.37385 (18) | 0.0752 (5) | |
H6 | −0.266482 | −0.087965 | 0.423302 | 0.090* | |
C7 | −0.1016 (3) | 0.05496 (19) | 0.37520 (17) | 0.0727 (5) | |
H7 | −0.001425 | 0.056309 | 0.427455 | 0.087* | |
C8 | −0.5944 (3) | −0.1985 (2) | 0.3812 (2) | 0.0982 (8) | |
H8A | −0.522808 | −0.269437 | 0.363751 | 0.147* | |
H8B | −0.719287 | −0.239895 | 0.376199 | 0.147* | |
H8C | −0.551738 | −0.140712 | 0.457863 | 0.147* | |
C9 | −0.7380 (3) | −0.1081 (3) | 0.2286 (3) | 0.1283 (11) | |
H9A | −0.764742 | −0.016979 | 0.252292 | 0.192* | |
H9B | −0.838511 | −0.173876 | 0.236368 | 0.192* | |
H9C | −0.717532 | −0.127724 | 0.149487 | 0.192* | |
C10 | 0.1296 (2) | 0.28911 (16) | 0.21041 (14) | 0.0555 (4) | |
C11 | 0.1743 (2) | 0.42884 (17) | 0.22023 (15) | 0.0597 (4) | |
H11 | 0.177259 | 0.491068 | 0.291469 | 0.072* | |
C12 | 0.2144 (2) | 0.47844 (18) | 0.12802 (16) | 0.0632 (5) | |
H12 | 0.242078 | 0.573136 | 0.138064 | 0.076* | |
C13 | 0.2145 (2) | 0.39003 (19) | 0.02000 (16) | 0.0619 (4) | |
C14 | 0.1678 (3) | 0.2489 (2) | 0.00894 (17) | 0.0695 (5) | |
H14 | 0.165564 | 0.186292 | −0.062016 | 0.083* | |
C15 | 0.1251 (3) | 0.20148 (18) | 0.10177 (16) | 0.0670 (5) | |
H15 | 0.091955 | 0.107037 | 0.091356 | 0.080* | |
C16 | 0.2513 (4) | 0.3500 (3) | −0.1837 (2) | 0.1117 (9) | |
H16A | 0.305285 | 0.271916 | −0.177900 | 0.168* | |
H16B | 0.315724 | 0.398318 | −0.230697 | 0.168* | |
H16C | 0.126594 | 0.319105 | −0.218060 | 0.168* | |
C17 | 0.2971 (3) | 0.5863 (2) | −0.0596 (2) | 0.0918 (7) | |
H17A | 0.188632 | 0.623014 | −0.046366 | 0.138* | |
H17B | 0.335835 | 0.602632 | −0.129087 | 0.138* | |
H17C | 0.390976 | 0.630482 | 0.004366 | 0.138* | |
C18 | 0.4047 (2) | 0.46470 (18) | 0.49349 (14) | 0.0609 (5) | |
C19 | 0.2762 (3) | 0.5300 (2) | 0.56480 (18) | 0.0861 (6) | |
H19A | 0.218233 | 0.586876 | 0.525626 | 0.129* | |
H19B | 0.341148 | 0.585589 | 0.637841 | 0.129* | |
H19C | 0.185862 | 0.459743 | 0.577117 | 0.129* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0629 (9) | 0.0648 (9) | 0.0663 (9) | −0.0130 (7) | −0.0126 (7) | 0.0241 (8) |
N2 | 0.0660 (9) | 0.0636 (9) | 0.0685 (10) | −0.0180 (7) | −0.0117 (7) | 0.0246 (7) |
N3 | 0.0602 (10) | 0.0755 (11) | 0.1561 (18) | −0.0052 (8) | 0.0054 (11) | 0.0492 (12) |
N4 | 0.0992 (13) | 0.0920 (13) | 0.0733 (11) | 0.0282 (10) | 0.0220 (9) | 0.0374 (10) |
C1 | 0.0601 (10) | 0.0471 (9) | 0.0618 (10) | −0.0045 (7) | −0.0085 (8) | 0.0173 (8) |
C2 | 0.0590 (10) | 0.0463 (9) | 0.0663 (10) | −0.0034 (7) | −0.0070 (8) | 0.0184 (8) |
C3 | 0.0669 (11) | 0.0572 (10) | 0.0921 (14) | −0.0048 (8) | −0.0142 (10) | 0.0354 (10) |
C4 | 0.0613 (11) | 0.0637 (11) | 0.1130 (17) | −0.0019 (9) | −0.0179 (11) | 0.0370 (11) |
C5 | 0.0574 (10) | 0.0491 (9) | 0.0998 (15) | −0.0010 (8) | 0.0047 (10) | 0.0188 (10) |
C6 | 0.0713 (12) | 0.0699 (12) | 0.0805 (13) | −0.0100 (9) | −0.0032 (10) | 0.0323 (10) |
C7 | 0.0672 (11) | 0.0718 (12) | 0.0735 (12) | −0.0121 (9) | −0.0116 (9) | 0.0324 (10) |
C8 | 0.0946 (16) | 0.0774 (14) | 0.1079 (17) | −0.0224 (12) | 0.0319 (13) | 0.0136 (13) |
C9 | 0.0521 (12) | 0.0927 (17) | 0.242 (4) | −0.0002 (11) | 0.0010 (17) | 0.063 (2) |
C10 | 0.0523 (9) | 0.0476 (9) | 0.0608 (10) | −0.0024 (7) | −0.0072 (7) | 0.0163 (8) |
C11 | 0.0663 (10) | 0.0478 (9) | 0.0599 (10) | 0.0007 (7) | 0.0001 (8) | 0.0141 (8) |
C12 | 0.0668 (11) | 0.0508 (9) | 0.0717 (12) | 0.0041 (8) | 0.0043 (9) | 0.0222 (9) |
C13 | 0.0542 (9) | 0.0715 (11) | 0.0650 (11) | 0.0158 (8) | 0.0046 (8) | 0.0267 (9) |
C14 | 0.0765 (12) | 0.0640 (11) | 0.0621 (11) | 0.0136 (9) | 0.0008 (9) | 0.0090 (9) |
C15 | 0.0754 (12) | 0.0477 (9) | 0.0699 (12) | 0.0020 (8) | −0.0070 (9) | 0.0131 (9) |
C16 | 0.127 (2) | 0.139 (2) | 0.0763 (16) | 0.0238 (18) | 0.0304 (14) | 0.0360 (16) |
C17 | 0.0893 (15) | 0.1048 (17) | 0.1042 (17) | 0.0233 (13) | 0.0254 (13) | 0.0624 (14) |
C18 | 0.0610 (10) | 0.0629 (10) | 0.0519 (9) | −0.0118 (8) | −0.0136 (8) | 0.0249 (8) |
C19 | 0.0746 (13) | 0.0938 (15) | 0.0734 (13) | −0.0162 (11) | 0.0016 (10) | 0.0144 (11) |
Geometric parameters (Å, º) top
N1—C18 | 1.286 (2) | C9—H9A | 0.9600 |
N1—N2 | 1.3875 (19) | C9—H9B | 0.9600 |
N2—C1 | 1.291 (2) | C9—H9C | 0.9600 |
N3—C5 | 1.382 (2) | C10—C11 | 1.384 (2) |
N3—C9 | 1.435 (3) | C10—C15 | 1.387 (2) |
N3—C8 | 1.439 (3) | C11—C12 | 1.374 (2) |
N4—C13 | 1.376 (2) | C11—H11 | 0.9300 |
N4—C16 | 1.429 (3) | C12—C13 | 1.390 (3) |
N4—C17 | 1.442 (3) | C12—H12 | 0.9300 |
C1—C10 | 1.478 (2) | C13—C14 | 1.397 (3) |
C1—C2 | 1.479 (2) | C14—C15 | 1.374 (3) |
C2—C3 | 1.381 (2) | C14—H14 | 0.9300 |
C2—C7 | 1.386 (2) | C15—H15 | 0.9300 |
C3—C4 | 1.374 (3) | C16—H16A | 0.9600 |
C3—H3 | 0.9300 | C16—H16B | 0.9600 |
C4—C5 | 1.389 (3) | C16—H16C | 0.9600 |
C4—H4 | 0.9300 | C17—H17A | 0.9600 |
C5—C6 | 1.387 (3) | C17—H17B | 0.9600 |
C6—C7 | 1.373 (2) | C17—H17C | 0.9600 |
C6—H6 | 0.9300 | C18—C18i | 1.479 (3) |
C7—H7 | 0.9300 | C18—C19 | 1.483 (3) |
C8—H8A | 0.9600 | C19—H19A | 0.9600 |
C8—H8B | 0.9600 | C19—H19B | 0.9600 |
C8—H8C | 0.9600 | C19—H19C | 0.9600 |
| | | |
C18—N1—N2 | 116.40 (16) | H9B—C9—H9C | 109.5 |
C1—N2—N1 | 117.37 (15) | C11—C10—C15 | 116.34 (16) |
C5—N3—C9 | 119.31 (19) | C11—C10—C1 | 121.53 (15) |
C5—N3—C8 | 120.72 (19) | C15—C10—C1 | 122.12 (15) |
C9—N3—C8 | 119.49 (18) | C12—C11—C10 | 122.05 (17) |
C13—N4—C16 | 121.2 (2) | C12—C11—H11 | 119.0 |
C13—N4—C17 | 120.79 (18) | C10—C11—H11 | 119.0 |
C16—N4—C17 | 117.48 (19) | C11—C12—C13 | 121.38 (16) |
N2—C1—C10 | 124.01 (14) | C11—C12—H12 | 119.3 |
N2—C1—C2 | 116.03 (15) | C13—C12—H12 | 119.3 |
C10—C1—C2 | 119.94 (14) | N4—C13—C12 | 121.15 (17) |
C3—C2—C7 | 116.31 (16) | N4—C13—C14 | 121.86 (18) |
C3—C2—C1 | 122.56 (15) | C12—C13—C14 | 116.98 (17) |
C7—C2—C1 | 121.08 (15) | C15—C14—C13 | 120.70 (18) |
C4—C3—C2 | 121.79 (17) | C15—C14—H14 | 119.6 |
C4—C3—H3 | 119.1 | C13—C14—H14 | 119.6 |
C2—C3—H3 | 119.1 | C14—C15—C10 | 122.51 (16) |
C3—C4—C5 | 121.44 (18) | C14—C15—H15 | 118.7 |
C3—C4—H4 | 119.3 | C10—C15—H15 | 118.7 |
C5—C4—H4 | 119.3 | N4—C16—H16A | 109.5 |
N3—C5—C6 | 121.01 (19) | N4—C16—H16B | 109.5 |
N3—C5—C4 | 121.84 (18) | H16A—C16—H16B | 109.5 |
C6—C5—C4 | 117.14 (16) | N4—C16—H16C | 109.5 |
C7—C6—C5 | 120.61 (18) | H16A—C16—H16C | 109.5 |
C7—C6—H6 | 119.7 | H16B—C16—H16C | 109.5 |
C5—C6—H6 | 119.7 | N4—C17—H17A | 109.5 |
C6—C7—C2 | 122.61 (17) | N4—C17—H17B | 109.5 |
C6—C7—H7 | 118.7 | H17A—C17—H17B | 109.5 |
C2—C7—H7 | 118.7 | N4—C17—H17C | 109.5 |
N3—C8—H8A | 109.5 | H17A—C17—H17C | 109.5 |
N3—C8—H8B | 109.5 | H17B—C17—H17C | 109.5 |
H8A—C8—H8B | 109.5 | N1—C18—C18i | 115.1 (2) |
N3—C8—H8C | 109.5 | N1—C18—C19 | 124.70 (16) |
H8A—C8—H8C | 109.5 | C18i—C18—C19 | 120.1 (2) |
H8B—C8—H8C | 109.5 | C18—C19—H19A | 109.5 |
N3—C9—H9A | 109.5 | C18—C19—H19B | 109.5 |
N3—C9—H9B | 109.5 | H19A—C19—H19B | 109.5 |
H9A—C9—H9B | 109.5 | C18—C19—H19C | 109.5 |
N3—C9—H9C | 109.5 | H19A—C19—H19C | 109.5 |
H9A—C9—H9C | 109.5 | H19B—C19—H19C | 109.5 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bonding parameters (Å, °) in the crystal structures of
1–4 topCompound | Hydrogen bond | H···A (Å) | D···A (Å) | D—H···A (°) | Packing co-efficient (%) |
1a | C12—H12···F1i | 2.54 | 3.329 (2) | 143 | 65.8 |
| C3—H3···π(Cg2)ii | 2.89 | 3.732 (2) | 151 | |
1b | C7—H7···F1iii | 2.52 | 3.399 (2) | 157 | 63.2 |
1c | C4—H4···F4iv | 2.55 | 3.448 (4) | 156 | 64.8 |
| C6—H6···F2v | 2.58 | 3.492 (4) | 168 | |
2a | C6—H6···π(Cg2)vi | 2.82 | 3.754 (1) | 168 | 66.0 |
3a | C17—H17B···π(Cg2)vii | 2.77 | 3.530 (2) | | 68.6 |
| C34—H34C···π(Cg3)viii | 2.97 | 3.824 (2) | 146 | |
3b | C23—H23···π(Cg1)ix | 2.77 | 3.569 (3) | 142 | 69.2 |
| C19—H19B···π(Cg2)x | 2.85 | 3.652 (3) | 140 | .. |
| C26—H26···π(Cg2)xi | 2.87 | 3.783 (3) | 163 | |
| C17—H17B···π(Cg4)xii | 2.88 | 3.591 (3) | 130 | |
| C6—H6···π(Cg4)xiii | 2.95 | 3.734 (3) | 141 | |
| C8—H8A···π(Cg4)xiv | 2.97 | 3.672 (3) | 130 | |
4a | C18—H18A···π (Cg2)xv | 2.83 | 3.585 (5) | 136 | 65 |
| C24—H24···π(Cg2)xvi | 2.88 | 3.669 (4) | 143 | |
4b | C17—H17A···π(Cg2)xvii | 2.86 | 3.745 (2) | 154 | 64.9 |
Symmetry codes: (i) x+1/2, -y+1/2, z+1/2;
(ii) -x+3/2, y-1/2, -z+1/2;
(iii) -x+1/2, y+1/2, -z+3/2;
(iv) x, y, z-1;
(v) -x, -y+2, -z;
(vi) x, y-1, z;
(vii) -x+2, -y+1, -z;
(viii) -x, -y+1, -z+1;
(ix) x+1, y, z+1;
(x) x+1, y, z;
(xi) x+1, y+1, z+1;
(xii) x-1, y, z;
(xiii) x-1, y-1, z-1;
(xiv) x, y, z-1;
(xv) -x+1, y+1/2, -z+1;
(xvi) -x+1, y-1/2, -z+1;
(xvii) -x, -y+1, -z. |
Torsion angle (°) of –C═N—N═C— unit and dihedral angle (°)
between the mean planes of terminal phenyl rings topCrystal | Torsion angle | Dihedral angle |
1a | 159.15 | 69.03 |
1b | 134.58 | 77.07 |
1c | 127.07, 130.21 | 76.81, 69.37 |
2a | 143.8 | 70.02 |
3a | 123.98, 156.19 | 63.46, 56.89 |
3b | 115.89, -104.07 | 67.87, 78.84 |
4a | -159, 146.51 | 62.55, 70.36 |
4b | 125.81 | 69.89 |
rmsd[r] values of overlays of pairs of molecular structures of
the
polymorphs of 1, 2, 3 and 4 topPair of polymorphs | Overlay diagram (see Fig. 12) | rmsd[r] |
1a and 1b | Part (a) | 0.2892 |
1a and 1c1 (one of the two molecules in the
asymmetric unit of 1c) | Part (b) | 0.3301 |
1a and 1c2 (the second molecule of the asymmetric
unit of 1c) | Part (c) | 0.3013 |
1b and 1c1 (one of the two molecules in the asymmetric unit of
1c) | Part (d) | 0.1271 |
1b and 1c2 (the second molecule of the asymmetric unit of
1c) | Part (e) | 0.1079 |
1c1 and 1c2 | Part (f) | 0.1185 |
2a and 2b | Part (g) | 0.2166 |
3a1 and 3b (3a1 is one of the two moleculesin the
asymmetric unit of 3a) | Part (h) | 0.4626 |
3a2 and 3b (3a2 is the second molecule in the asymmetric unit
of 3a) | Part (i) | 0.5840 |
3a1 and 3a2 | Part (j) | 0.3949 |
4a and 4b | Part (k) | 0.5445 |
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