The crystal structure of the heterocyclic compound 2-(4-methoxyphenyl)-7-phenylpyrazolo[1,5-
c]pyrimidine, C
19H
15N
3O, has been determined and its self-assembly on the surface of graphite has been examined using atomic force microscopy (AFM). The title compound crystallized in the monoclinic space group
P2
1/
c, with two independent molecules in the asymmetric unit. The packing of the L-shaped molecules in the crystal is governed by arene interactions, in the absence of any conventional hydrogen-bonding interactions. The packing arrangement reveals four types of dimeric motifs stabilized by π–π and C—H
π interactions. At low coverage, molecules assemble into long needle-like islands on the graphite surface. High-resolution AFM images reveal that the molecules interact through weak noncovalent interactions between the aromatic H atoms and the methoxy O atoms.
Supporting information
CCDC reference: 2071327
Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).
2-(4-Methoxyphenyl)-7-phenylpyrazolo[1,5-
c]pyrimidine
top
Crystal data top
C19H15N3O | F(000) = 1264 |
Mr = 301.34 | Dx = 1.321 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 5.7626 (4) Å | Cell parameters from 22699 reflections |
b = 36.693 (2) Å | θ = 1.5–26.4° |
c = 14.3279 (10) Å | µ = 0.08 mm−1 |
β = 90.07 (1)° | T = 296 K |
V = 3029.6 (3) Å3 | Platy, colorless |
Z = 8 | 0.3 × 0.1 × 0.01 mm |
Data collection top
Bruker APEX CCD diffractometer | Rint = 0.064 |
Radiation source: Fine-focus sealed tube | θmax = 26.4°, θmin = 1.5° |
ω scans | h = −7→7 |
22699 measured reflections | k = −45→44 |
5727 independent reflections | l = −17→17 |
2694 reflections with I > 2σ(I) | |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.046 | w = 1/[σ2(Fo2) + (0.0478P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.120 | (Δ/σ)max < 0.001 |
S = 0.85 | Δρmax = 0.19 e Å−3 |
5727 reflections | Δρmin = −0.18 e Å−3 |
416 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0033 (4) |
Primary atom site location: structure-invariant direct methods | |
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 | |
O1 | 0.8487 (3) | 0.20497 (4) | 0.23238 (10) | 0.0598 (4) | |
C30 | 1.3534 (4) | 0.22899 (6) | 0.98529 (14) | 0.0454 (5) | |
N4 | 1.1510 (3) | 0.39648 (5) | 0.94352 (12) | 0.0518 (5) | |
O2 | 1.3545 (3) | 0.19176 (4) | 0.98453 (10) | 0.0579 (4) | |
N2 | 0.6303 (3) | 0.37302 (5) | 0.29945 (12) | 0.0522 (5) | |
N5 | 1.1258 (3) | 0.36008 (5) | 0.92836 (12) | 0.0511 (5) | |
C27 | 1.3143 (4) | 0.30474 (6) | 0.98104 (14) | 0.0466 (5) | |
C26 | 1.2927 (4) | 0.34452 (6) | 0.98067 (14) | 0.0484 (5) | |
C7 | 0.8123 (3) | 0.31784 (6) | 0.24246 (13) | 0.0473 (5) | |
C6 | 0.7922 (4) | 0.35763 (6) | 0.24576 (14) | 0.0498 (5) | |
C29 | 1.5272 (4) | 0.25042 (6) | 1.02269 (14) | 0.0531 (6) | |
H011 | 1.6574 | 0.2397 | 1.0495 | 0.064* | |
C10 | 0.8499 (4) | 0.24230 (6) | 0.23371 (14) | 0.0465 (5) | |
C11 | 0.6588 (4) | 0.25829 (6) | 0.27470 (14) | 0.0498 (5) | |
H013 | 0.5420 | 0.2437 | 0.2996 | 0.060* | |
N1 | 0.6557 (3) | 0.40952 (5) | 0.28593 (12) | 0.0547 (5) | |
C4 | 0.8340 (4) | 0.41691 (7) | 0.22376 (17) | 0.0630 (6) | |
C28 | 1.5065 (4) | 0.28785 (6) | 1.02011 (14) | 0.0540 (6) | |
H016 | 1.6244 | 0.3021 | 1.0452 | 0.065* | |
C24 | 1.3332 (4) | 0.40365 (7) | 1.00459 (16) | 0.0575 (6) | |
C12 | 0.6402 (4) | 0.29544 (6) | 0.27897 (13) | 0.0497 (5) | |
H018 | 0.5104 | 0.3059 | 0.3067 | 0.060* | |
C14 | 0.3436 (4) | 0.42863 (6) | 0.39638 (16) | 0.0552 (6) | |
C34 | 0.8304 (4) | 0.41607 (6) | 0.83628 (15) | 0.0519 (6) | |
N6 | 1.0639 (4) | 0.45767 (5) | 0.92405 (15) | 0.0688 (6) | |
C31 | 1.1611 (4) | 0.24536 (6) | 0.94523 (14) | 0.0480 (5) | |
H022 | 1.0441 | 0.2311 | 0.9195 | 0.058* | |
C8 | 1.0031 (4) | 0.30128 (6) | 0.20213 (14) | 0.0534 (6) | |
H023 | 1.1210 | 0.3157 | 0.1778 | 0.064* | |
C1 | 0.5307 (4) | 0.43665 (6) | 0.32902 (17) | 0.0605 (6) | |
C32 | 1.1426 (4) | 0.28256 (6) | 0.94333 (14) | 0.0473 (5) | |
H025 | 1.0125 | 0.2932 | 0.9162 | 0.057* | |
C33 | 1.5527 (5) | 0.17394 (7) | 1.02316 (18) | 0.0757 (7) | |
H02A | 1.5330 | 0.1480 | 1.0186 | 0.114* | |
H02B | 1.6889 | 0.1811 | 0.9893 | 0.114* | |
H02C | 1.5694 | 0.1807 | 1.0875 | 0.114* | |
C18 | 0.0503 (4) | 0.39145 (7) | 0.46527 (19) | 0.0750 (8) | |
H027 | −0.0259 | 0.3691 | 0.4686 | 0.090* | |
C5 | 0.9207 (4) | 0.38373 (6) | 0.19765 (16) | 0.0610 (6) | |
H028 | 1.0415 | 0.3794 | 0.1561 | 0.073* | |
C17 | −0.0167 (5) | 0.41912 (8) | 0.52192 (19) | 0.0788 (8) | |
H029 | −0.1396 | 0.4160 | 0.5632 | 0.095* | |
C39 | 0.7222 (4) | 0.38254 (6) | 0.82604 (16) | 0.0578 (6) | |
H030 | 0.7712 | 0.3628 | 0.8619 | 0.069* | |
C9 | 1.0225 (4) | 0.26386 (6) | 0.19722 (14) | 0.0530 (6) | |
H031 | 1.1517 | 0.2533 | 0.1694 | 0.064* | |
C25 | 1.4248 (4) | 0.37056 (6) | 1.02895 (16) | 0.0589 (6) | |
H032 | 1.5487 | 0.3662 | 1.0691 | 0.071* | |
C36 | 0.5723 (5) | 0.43964 (7) | 0.71826 (19) | 0.0778 (8) | |
H033 | 0.5237 | 0.4591 | 0.6815 | 0.093* | |
C19 | 0.2287 (4) | 0.39592 (6) | 0.40316 (17) | 0.0620 (6) | |
H034 | 0.2725 | 0.3766 | 0.3651 | 0.074* | |
C35 | 0.7492 (5) | 0.44448 (7) | 0.78109 (19) | 0.0712 (7) | |
H035 | 0.8167 | 0.4674 | 0.7869 | 0.085* | |
C21 | 1.0200 (4) | 0.42381 (6) | 0.90320 (16) | 0.0549 (6) | |
C3 | 0.8788 (5) | 0.45372 (7) | 0.20540 (19) | 0.0820 (8) | |
H037 | 0.9957 | 0.4606 | 0.1643 | 0.098* | |
C15 | 0.2757 (5) | 0.45661 (7) | 0.4554 (2) | 0.0842 (8) | |
H038 | 0.3514 | 0.4790 | 0.4526 | 0.101* | |
C13 | 1.0464 (4) | 0.18693 (7) | 0.19591 (18) | 0.0768 (8) | |
H03A | 1.0233 | 0.1610 | 0.1990 | 0.115* | |
H03B | 1.0690 | 0.1941 | 0.1321 | 0.115* | |
H03C | 1.1807 | 0.1934 | 0.2319 | 0.115* | |
N3 | 0.5776 (4) | 0.47053 (5) | 0.31016 (16) | 0.0820 (7) | |
C23 | 1.3771 (5) | 0.44045 (7) | 1.02523 (18) | 0.0726 (7) | |
H041 | 1.4960 | 0.4472 | 1.0657 | 0.087* | |
C38 | 0.5423 (4) | 0.37807 (6) | 0.76320 (18) | 0.0678 (7) | |
H042 | 0.4713 | 0.3554 | 0.7574 | 0.081* | |
C37 | 0.4672 (5) | 0.40661 (7) | 0.70919 (19) | 0.0744 (7) | |
H043 | 0.3461 | 0.4034 | 0.6670 | 0.089* | |
C22 | 1.2402 (5) | 0.46567 (7) | 0.9842 (2) | 0.0795 (8) | |
H044 | 1.2680 | 0.4901 | 0.9979 | 0.095* | |
C16 | 0.0984 (6) | 0.45174 (8) | 0.5178 (2) | 0.0919 (9) | |
H045 | 0.0561 | 0.4706 | 0.5575 | 0.110* | |
C2 | 0.7485 (6) | 0.47879 (7) | 0.2488 (2) | 0.0951 (10) | |
H049 | 0.7770 | 0.5032 | 0.2361 | 0.114* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0581 (9) | 0.0594 (10) | 0.0619 (10) | 0.0064 (8) | 0.0054 (8) | −0.0076 (8) |
C30 | 0.0482 (12) | 0.0494 (14) | 0.0387 (11) | 0.0055 (11) | 0.0044 (10) | −0.0005 (10) |
N4 | 0.0539 (11) | 0.0452 (12) | 0.0563 (12) | −0.0066 (9) | 0.0075 (10) | −0.0054 (9) |
O2 | 0.0597 (9) | 0.0549 (10) | 0.0592 (10) | 0.0099 (8) | −0.0029 (8) | 0.0028 (8) |
N2 | 0.0524 (11) | 0.0470 (11) | 0.0572 (11) | 0.0007 (9) | 0.0059 (9) | 0.0057 (9) |
N5 | 0.0554 (11) | 0.0431 (11) | 0.0548 (11) | −0.0019 (9) | 0.0041 (9) | −0.0020 (9) |
C27 | 0.0450 (12) | 0.0550 (14) | 0.0397 (12) | −0.0005 (11) | 0.0031 (10) | −0.0029 (10) |
C26 | 0.0466 (12) | 0.0566 (15) | 0.0419 (12) | −0.0032 (11) | 0.0032 (10) | −0.0030 (11) |
C7 | 0.0437 (12) | 0.0598 (14) | 0.0384 (12) | 0.0012 (10) | 0.0002 (10) | 0.0012 (10) |
C6 | 0.0478 (12) | 0.0587 (15) | 0.0429 (13) | 0.0014 (11) | −0.0003 (10) | 0.0049 (10) |
C29 | 0.0467 (13) | 0.0660 (16) | 0.0464 (13) | 0.0129 (12) | −0.0069 (11) | −0.0023 (11) |
C10 | 0.0484 (12) | 0.0530 (14) | 0.0379 (11) | 0.0060 (11) | −0.0040 (10) | −0.0067 (10) |
C11 | 0.0435 (12) | 0.0627 (15) | 0.0433 (12) | −0.0035 (11) | 0.0043 (10) | −0.0040 (11) |
N1 | 0.0563 (11) | 0.0515 (12) | 0.0564 (12) | −0.0022 (10) | 0.0067 (10) | 0.0096 (9) |
C4 | 0.0626 (15) | 0.0637 (17) | 0.0627 (15) | −0.0063 (13) | 0.0095 (13) | 0.0150 (13) |
C28 | 0.0453 (12) | 0.0674 (17) | 0.0494 (13) | 0.0020 (12) | −0.0067 (10) | −0.0094 (12) |
C24 | 0.0577 (14) | 0.0593 (16) | 0.0556 (14) | −0.0135 (12) | 0.0059 (12) | −0.0091 (12) |
C12 | 0.0445 (12) | 0.0619 (15) | 0.0428 (12) | 0.0054 (11) | 0.0069 (10) | −0.0058 (11) |
C14 | 0.0571 (13) | 0.0474 (14) | 0.0613 (15) | 0.0070 (12) | 0.0019 (12) | 0.0087 (11) |
C34 | 0.0542 (13) | 0.0422 (13) | 0.0593 (14) | 0.0029 (11) | 0.0104 (11) | 0.0002 (11) |
N6 | 0.0782 (14) | 0.0456 (13) | 0.0825 (15) | −0.0086 (11) | 0.0089 (12) | −0.0077 (11) |
C31 | 0.0443 (12) | 0.0523 (14) | 0.0473 (13) | −0.0019 (11) | −0.0016 (10) | 0.0027 (10) |
C8 | 0.0459 (12) | 0.0670 (16) | 0.0472 (13) | −0.0020 (11) | 0.0080 (10) | 0.0012 (11) |
C1 | 0.0639 (15) | 0.0458 (14) | 0.0719 (16) | 0.0045 (12) | 0.0047 (13) | 0.0051 (12) |
C32 | 0.0431 (11) | 0.0539 (14) | 0.0450 (13) | 0.0024 (10) | −0.0015 (10) | 0.0043 (10) |
C33 | 0.0801 (18) | 0.0672 (17) | 0.0797 (18) | 0.0252 (14) | −0.0122 (15) | 0.0064 (14) |
C18 | 0.0561 (15) | 0.0756 (19) | 0.093 (2) | −0.0097 (14) | 0.0114 (15) | −0.0090 (16) |
C5 | 0.0583 (14) | 0.0713 (17) | 0.0535 (14) | −0.0029 (13) | 0.0115 (12) | 0.0107 (12) |
C17 | 0.0667 (17) | 0.083 (2) | 0.086 (2) | 0.0124 (16) | 0.0194 (15) | 0.0018 (16) |
C39 | 0.0535 (14) | 0.0491 (14) | 0.0708 (16) | −0.0016 (11) | 0.0008 (13) | 0.0077 (11) |
C9 | 0.0425 (12) | 0.0695 (16) | 0.0471 (13) | 0.0057 (11) | 0.0060 (10) | −0.0041 (11) |
C25 | 0.0557 (14) | 0.0687 (17) | 0.0524 (14) | −0.0082 (13) | −0.0041 (11) | −0.0075 (12) |
C36 | 0.0819 (19) | 0.0644 (19) | 0.087 (2) | 0.0194 (15) | −0.0010 (17) | 0.0141 (15) |
C19 | 0.0505 (13) | 0.0611 (16) | 0.0745 (17) | −0.0022 (12) | 0.0037 (12) | −0.0065 (12) |
C35 | 0.0807 (18) | 0.0496 (16) | 0.0833 (18) | 0.0004 (14) | 0.0080 (16) | 0.0065 (14) |
C21 | 0.0621 (15) | 0.0410 (14) | 0.0617 (15) | −0.0033 (12) | 0.0152 (12) | −0.0007 (11) |
C3 | 0.086 (2) | 0.0701 (19) | 0.090 (2) | −0.0131 (16) | 0.0223 (17) | 0.0237 (16) |
C15 | 0.101 (2) | 0.0535 (16) | 0.099 (2) | 0.0023 (15) | 0.0240 (18) | −0.0045 (15) |
C13 | 0.0742 (17) | 0.0698 (17) | 0.0865 (19) | 0.0186 (14) | 0.0174 (15) | −0.0097 (14) |
N3 | 0.0906 (16) | 0.0501 (14) | 0.1053 (18) | −0.0009 (11) | 0.0233 (14) | 0.0178 (12) |
C23 | 0.0767 (18) | 0.0662 (19) | 0.0749 (18) | −0.0213 (15) | 0.0008 (15) | −0.0149 (14) |
C38 | 0.0613 (16) | 0.0593 (16) | 0.0828 (19) | −0.0014 (13) | −0.0047 (15) | 0.0023 (14) |
C37 | 0.0698 (17) | 0.0733 (19) | 0.0799 (19) | 0.0126 (15) | −0.0074 (15) | 0.0049 (15) |
C22 | 0.091 (2) | 0.0565 (18) | 0.091 (2) | −0.0224 (16) | 0.0099 (17) | −0.0175 (15) |
C16 | 0.111 (2) | 0.076 (2) | 0.089 (2) | 0.0215 (19) | 0.0279 (19) | −0.0090 (17) |
C2 | 0.108 (2) | 0.0565 (18) | 0.121 (3) | −0.0088 (18) | 0.026 (2) | 0.0243 (17) |
Geometric parameters (Å, º) top
O1—C10 | 1.370 (2) | N6—C22 | 1.364 (3) |
O1—C13 | 1.418 (3) | C31—C32 | 1.369 (3) |
C30—O2 | 1.366 (2) | C31—H022 | 0.9300 |
C30—C29 | 1.381 (3) | C8—C9 | 1.379 (3) |
C30—C31 | 1.385 (3) | C8—H023 | 0.9300 |
N4—N5 | 1.361 (2) | C1—N3 | 1.301 (3) |
N4—C21 | 1.381 (3) | C32—H025 | 0.9300 |
N4—C24 | 1.391 (3) | C33—H02A | 0.9600 |
O2—C33 | 1.427 (3) | C33—H02B | 0.9600 |
N2—C6 | 1.335 (3) | C33—H02C | 0.9600 |
N2—N1 | 1.361 (2) | C18—C17 | 1.356 (3) |
N5—C26 | 1.346 (3) | C18—C19 | 1.370 (3) |
C27—C28 | 1.386 (3) | C18—H027 | 0.9300 |
C27—C32 | 1.390 (3) | C5—H028 | 0.9300 |
C27—C26 | 1.465 (3) | C17—C16 | 1.370 (4) |
C26—C25 | 1.403 (3) | C17—H029 | 0.9300 |
C7—C8 | 1.383 (3) | C39—C38 | 1.382 (3) |
C7—C12 | 1.391 (3) | C39—H030 | 0.9300 |
C7—C6 | 1.465 (3) | C9—H031 | 0.9300 |
C6—C5 | 1.394 (3) | C25—H032 | 0.9300 |
C29—C28 | 1.379 (3) | C36—C37 | 1.361 (3) |
C29—H011 | 0.9300 | C36—C35 | 1.371 (4) |
C10—C9 | 1.375 (3) | C36—H033 | 0.9300 |
C10—C11 | 1.380 (3) | C19—H034 | 0.9300 |
C11—C12 | 1.369 (3) | C35—H035 | 0.9300 |
C11—H013 | 0.9300 | C3—C2 | 1.341 (4) |
N1—C1 | 1.375 (3) | C3—H037 | 0.9300 |
N1—C4 | 1.388 (3) | C15—C16 | 1.370 (4) |
C4—C5 | 1.368 (3) | C15—H038 | 0.9300 |
C4—C3 | 1.400 (3) | C13—H03A | 0.9600 |
C28—H016 | 0.9300 | C13—H03B | 0.9600 |
C24—C25 | 1.369 (3) | C13—H03C | 0.9600 |
C24—C23 | 1.405 (3) | N3—C2 | 1.355 (3) |
C12—H018 | 0.9300 | C23—C22 | 1.350 (4) |
C14—C19 | 1.374 (3) | C23—H041 | 0.9300 |
C14—C15 | 1.387 (3) | C38—C37 | 1.372 (3) |
C14—C1 | 1.478 (3) | C38—H042 | 0.9300 |
C34—C39 | 1.387 (3) | C37—H043 | 0.9300 |
C34—C35 | 1.389 (3) | C22—H044 | 0.9300 |
C34—C21 | 1.480 (3) | C16—H045 | 0.9300 |
N6—C21 | 1.303 (3) | C2—H049 | 0.9300 |
| | | |
C10—O1—C13 | 117.90 (18) | O2—C33—H02B | 109.5 |
O2—C30—C29 | 124.72 (19) | H02A—C33—H02B | 109.5 |
O2—C30—C31 | 115.72 (19) | O2—C33—H02C | 109.5 |
C29—C30—C31 | 119.6 (2) | H02A—C33—H02C | 109.5 |
N5—N4—C21 | 125.99 (18) | H02B—C33—H02C | 109.5 |
N5—N4—C24 | 111.48 (18) | C17—C18—C19 | 120.9 (3) |
C21—N4—C24 | 122.51 (19) | C17—C18—H027 | 119.6 |
C30—O2—C33 | 117.29 (18) | C19—C18—H027 | 119.6 |
C6—N2—N1 | 104.98 (17) | C4—C5—C6 | 106.4 (2) |
C26—N5—N4 | 104.55 (17) | C4—C5—H028 | 126.8 |
C28—C27—C32 | 117.6 (2) | C6—C5—H028 | 126.8 |
C28—C27—C26 | 121.0 (2) | C18—C17—C16 | 119.4 (3) |
C32—C27—C26 | 121.44 (19) | C18—C17—H029 | 120.3 |
N5—C26—C25 | 111.9 (2) | C16—C17—H029 | 120.3 |
N5—C26—C27 | 119.03 (19) | C38—C39—C34 | 120.7 (2) |
C25—C26—C27 | 129.1 (2) | C38—C39—H030 | 119.6 |
C8—C7—C12 | 117.7 (2) | C34—C39—H030 | 119.6 |
C8—C7—C6 | 120.95 (19) | C10—C9—C8 | 119.6 (2) |
C12—C7—C6 | 121.34 (19) | C10—C9—H031 | 120.2 |
N2—C6—C5 | 111.5 (2) | C8—C9—H031 | 120.2 |
N2—C6—C7 | 119.69 (19) | C24—C25—C26 | 105.6 (2) |
C5—C6—C7 | 128.8 (2) | C24—C25—H032 | 127.2 |
C28—C29—C30 | 119.62 (19) | C26—C25—H032 | 127.2 |
C28—C29—H011 | 120.2 | C37—C36—C35 | 120.6 (2) |
C30—C29—H011 | 120.2 | C37—C36—H033 | 119.7 |
O1—C10—C9 | 124.99 (19) | C35—C36—H033 | 119.7 |
O1—C10—C11 | 115.28 (19) | C18—C19—C14 | 120.8 (2) |
C9—C10—C11 | 119.7 (2) | C18—C19—H034 | 119.6 |
C12—C11—C10 | 120.3 (2) | C14—C19—H034 | 119.6 |
C12—C11—H013 | 119.8 | C36—C35—C34 | 121.8 (2) |
C10—C11—H013 | 119.8 | C36—C35—H035 | 119.1 |
N2—N1—C1 | 126.28 (18) | C34—C35—H035 | 119.1 |
N2—N1—C4 | 111.32 (18) | N6—C21—N4 | 119.4 (2) |
C1—N1—C4 | 122.37 (19) | N6—C21—C34 | 118.3 (2) |
C5—C4—N1 | 105.82 (19) | N4—C21—C34 | 122.27 (19) |
C5—C4—C3 | 137.7 (2) | C2—C3—C4 | 118.1 (3) |
N1—C4—C3 | 116.5 (2) | C2—C3—H037 | 120.9 |
C29—C28—C27 | 121.7 (2) | C4—C3—H037 | 120.9 |
C29—C28—H016 | 119.2 | C16—C15—C14 | 120.8 (3) |
C27—C28—H016 | 119.2 | C16—C15—H038 | 119.6 |
C25—C24—N4 | 106.5 (2) | C14—C15—H038 | 119.6 |
C25—C24—C23 | 136.8 (3) | O1—C13—H03A | 109.5 |
N4—C24—C23 | 116.7 (2) | O1—C13—H03B | 109.5 |
C11—C12—C7 | 121.1 (2) | H03A—C13—H03B | 109.5 |
C11—C12—H018 | 119.5 | O1—C13—H03C | 109.5 |
C7—C12—H018 | 119.5 | H03A—C13—H03C | 109.5 |
C19—C14—C15 | 117.8 (2) | H03B—C13—H03C | 109.5 |
C19—C14—C1 | 124.9 (2) | C1—N3—C2 | 120.0 (2) |
C15—C14—C1 | 117.2 (2) | C22—C23—C24 | 117.5 (2) |
C39—C34—C35 | 117.0 (2) | C22—C23—H041 | 121.2 |
C39—C34—C21 | 124.8 (2) | C24—C23—H041 | 121.2 |
C35—C34—C21 | 118.2 (2) | C37—C38—C39 | 120.9 (2) |
C21—N6—C22 | 119.6 (2) | C37—C38—H042 | 119.6 |
C32—C31—C30 | 120.2 (2) | C39—C38—H042 | 119.6 |
C32—C31—H022 | 119.9 | C36—C37—C38 | 119.1 (3) |
C30—C31—H022 | 119.9 | C36—C37—H043 | 120.5 |
C9—C8—C7 | 121.6 (2) | C38—C37—H043 | 120.5 |
C9—C8—H023 | 119.2 | C23—C22—N6 | 124.2 (2) |
C7—C8—H023 | 119.2 | C23—C22—H044 | 117.9 |
N3—C1—N1 | 119.3 (2) | N6—C22—H044 | 117.9 |
N3—C1—C14 | 118.6 (2) | C17—C16—C15 | 120.2 (3) |
N1—C1—C14 | 122.1 (2) | C17—C16—H045 | 119.9 |
C31—C32—C27 | 121.38 (19) | C15—C16—H045 | 119.9 |
C31—C32—H025 | 119.3 | C3—C2—N3 | 123.7 (3) |
C27—C32—H025 | 119.3 | C3—C2—H049 | 118.1 |
O2—C33—H02A | 109.5 | N3—C2—H049 | 118.1 |
| | | |
C29—C30—O2—C33 | −1.7 (3) | C30—C31—C32—C27 | 0.0 (3) |
C31—C30—O2—C33 | 178.50 (19) | C28—C27—C32—C31 | 0.5 (3) |
C21—N4—N5—C26 | 178.80 (18) | C26—C27—C32—C31 | −178.81 (18) |
C24—N4—N5—C26 | 0.3 (2) | N1—C4—C5—C6 | −0.4 (3) |
N4—N5—C26—C25 | −0.1 (2) | C3—C4—C5—C6 | 178.8 (3) |
N4—N5—C26—C27 | 179.67 (17) | N2—C6—C5—C4 | 0.4 (3) |
C28—C27—C26—N5 | 168.55 (19) | C7—C6—C5—C4 | 179.3 (2) |
C32—C27—C26—N5 | −12.2 (3) | C19—C18—C17—C16 | −1.0 (4) |
C28—C27—C26—C25 | −11.7 (3) | C35—C34—C39—C38 | 0.2 (3) |
C32—C27—C26—C25 | 167.6 (2) | C21—C34—C39—C38 | 178.4 (2) |
N1—N2—C6—C5 | −0.2 (2) | O1—C10—C9—C8 | 179.46 (19) |
N1—N2—C6—C7 | −179.24 (17) | C11—C10—C9—C8 | 0.1 (3) |
C8—C7—C6—N2 | −167.72 (19) | C7—C8—C9—C10 | −0.5 (3) |
C12—C7—C6—N2 | 12.8 (3) | N4—C24—C25—C26 | 0.2 (2) |
C8—C7—C6—C5 | 13.5 (3) | C23—C24—C25—C26 | −179.7 (3) |
C12—C7—C6—C5 | −166.0 (2) | N5—C26—C25—C24 | 0.0 (2) |
O2—C30—C29—C28 | −179.50 (19) | C27—C26—C25—C24 | −179.8 (2) |
C31—C30—C29—C28 | 0.3 (3) | C17—C18—C19—C14 | −0.3 (4) |
C13—O1—C10—C9 | 4.1 (3) | C15—C14—C19—C18 | 1.1 (4) |
C13—O1—C10—C11 | −176.52 (19) | C1—C14—C19—C18 | −177.2 (2) |
O1—C10—C11—C12 | −179.25 (17) | C37—C36—C35—C34 | 1.2 (4) |
C9—C10—C11—C12 | 0.2 (3) | C39—C34—C35—C36 | −0.9 (3) |
C6—N2—N1—C1 | −178.0 (2) | C21—C34—C35—C36 | −179.2 (2) |
C6—N2—N1—C4 | −0.1 (2) | C22—N6—C21—N4 | 0.9 (3) |
N2—N1—C4—C5 | 0.3 (2) | C22—N6—C21—C34 | −178.8 (2) |
C1—N1—C4—C5 | 178.3 (2) | N5—N4—C21—N6 | −179.84 (19) |
N2—N1—C4—C3 | −179.1 (2) | C24—N4—C21—N6 | −1.5 (3) |
C1—N1—C4—C3 | −1.1 (3) | N5—N4—C21—C34 | −0.1 (3) |
C30—C29—C28—C27 | 0.2 (3) | C24—N4—C21—C34 | 178.30 (19) |
C32—C27—C28—C29 | −0.6 (3) | C39—C34—C21—N6 | −161.8 (2) |
C26—C27—C28—C29 | 178.67 (18) | C35—C34—C21—N6 | 16.4 (3) |
N5—N4—C24—C25 | −0.3 (2) | C39—C34—C21—N4 | 18.5 (3) |
C21—N4—C24—C25 | −178.89 (18) | C35—C34—C21—N4 | −163.4 (2) |
N5—N4—C24—C23 | 179.65 (19) | C5—C4—C3—C2 | −179.0 (3) |
C21—N4—C24—C23 | 1.1 (3) | N1—C4—C3—C2 | 0.2 (4) |
C10—C11—C12—C7 | −0.1 (3) | C19—C14—C15—C16 | −0.5 (4) |
C8—C7—C12—C11 | −0.3 (3) | C1—C14—C15—C16 | 177.9 (2) |
C6—C7—C12—C11 | 179.23 (18) | N1—C1—N3—C2 | −0.2 (4) |
O2—C30—C31—C32 | 179.38 (17) | C14—C1—N3—C2 | 179.9 (2) |
C29—C30—C31—C32 | −0.5 (3) | C25—C24—C23—C22 | 179.7 (3) |
C12—C7—C8—C9 | 0.6 (3) | N4—C24—C23—C22 | −0.2 (3) |
C6—C7—C8—C9 | −178.95 (19) | C34—C39—C38—C37 | 0.3 (4) |
N2—N1—C1—N3 | 178.8 (2) | C35—C36—C37—C38 | −0.7 (4) |
C4—N1—C1—N3 | 1.1 (3) | C39—C38—C37—C36 | 0.0 (4) |
N2—N1—C1—C14 | −1.3 (3) | C24—C23—C22—N6 | −0.3 (4) |
C4—N1—C1—C14 | −178.9 (2) | C21—N6—C22—C23 | −0.1 (4) |
C19—C14—C1—N3 | 159.8 (2) | C18—C17—C16—C15 | 1.6 (4) |
C15—C14—C1—N3 | −18.5 (3) | C14—C15—C16—C17 | −0.8 (4) |
C19—C14—C1—N1 | −20.1 (4) | C4—C3—C2—N3 | 0.7 (5) |
C15—C14—C1—N1 | 161.6 (2) | C1—N3—C2—C3 | −0.8 (5) |
Relevant parameters for the intermolecular interactions in the crystal
structure of 1 topπ–π interactions | | | | | |
Type | No. | Interaction | Cg···Cga,b (Å) | Interplanar angle γ (°) | Symmetry code |
Py···Ph | 1 | Cg1···Cg4 | 3.894 (2) | 19.6 (1) | x+1, y, z |
| 2 | Cg5···Cg8 | 3.849 (2) | 17.6 (1) | x+1, y, z |
| | | | | |
C—H···π/O interactions | | | | | |
Type | No. | Interaction | C···Cg/C···O (Å) | \angleC—H···Cg/O (°) | Symmetry code |
Ph···Ph | 1 | C17—H···Cg8 | 4.087 (3) | 136.1 | x-1, y, z |
| 2 | C37—H···Cg4 | 4.026 (3) | 144.1 | x, y, z |
OPh···OPh | 3 | C11—H···Cg7 | 3.645 (3) | 136.1 | x-1, -y+1/2, z-1/2 |
| 4 | C12—H···O2 | 3.408 (3)b | 133.2 | x-1, -y+1/2, z-1/2 |
| 5 | C31—H···Cg3 | 3.645 (3) | 137.6 | x, -y+1/2, z+1/2 |
| 6 | C32—H···O2 | 3.493 (2)c | 132.4 | x, -y+1/2, z+1/2 |
Py···Py | 7 | C5—H···Cg6 | 3.751 (4) | 156.6 | x, y, z-1 |
| 8 | C3—H···Cg5 | 4.007 (4) | 136.2 | x, y, z-1 |
| 9 | C25—H···Cg2 | 3.795 (4) | 144.3 | x+1, y, z+1 |
| 10 | C23—H···Cg1 | 3.943 (3) | 147.8 | x+1, y, z+1 |
Notes: (a) Cg = centroid and the centroids of the rings are
labelled
as follows: (MOL-1/MOL-2) Py (six-membered ring) = Cg1/Cg5,
Py (five-memebred ring) = Cg2/Cg6,
OPh = Cg3/Cg7,
Ph = Cg4/Cg8.
Atoms labels are as shown in Fig. 1.
(b) H···O = 2.70 Å;
(c) H···O = 2.79 Å. |
Interaction energies of the dimers shown in Fig. 3.
Calculations are performed using DFT GGA/BLYP with van der Waals correction
(DFT-D3) implemented in Quantumwise (Schneider et al.,
2017) topCompound 1 | Energy of dimer (eV) | Energy of monomer (eV) | ΔE (eV) |
Dimer 1 | -8881.142 | -4440.508 | -0.128 |
Dimer 2 | -8881.566 | -4440.508 | -0.552 |
Dimer 3 | -8881.790 | -4440.508 | -0.776 |
Dimer 4 | -8882.941 | -4440.508 | -1.927 |