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The reaction of 1,10-phenanthroline-5,6-dione and diethylenetriamine unexpectedly yielded the title compound, C
16H
15N
5, which is a non-planar and chiral fused-ring system composed of two pyridine rings and three non-aromatic rings. Crystal symmetry results in a racemic mixture of enantiomers. Aromatic π–π stacking interactions exist between adjacent molecules and weak bifurcated N—H
(N,N) hydrogen bonds lead to dimeric associations of molecules, generated by inversion.
Supporting information
CCDC reference: 621326
Key indicators
- Single-crystal X-ray study
- T = 273 K
- Mean (C-C)= 0.002 Å
- R factor = 0.038
- wR factor = 0.117
- Data-to-parameter ratio = 12.6
checkCIF/PLATON results
No syntax errors found
No errors found in this datablock
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.
(1
R)-6,9,15,18,21-Pentaazapentacyclo[12.7.0.0
1,18.0
2,7.0
8,13]henicosa- 2,4,6,8(13),9,11,14-heptaene
top
Crystal data top
C16H15N5 | F(000) = 584 |
Mr = 277.33 | Dx = 1.385 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4400 reflections |
a = 10.7254 (2) Å | θ = 2.6–28.2° |
b = 13.0587 (3) Å | µ = 0.09 mm−1 |
c = 10.2122 (2) Å | T = 273 K |
β = 111.609 (1)° | Block, yellow |
V = 1329.79 (5) Å3 | 0.3 × 0.3 × 0.2 mm |
Z = 4 | |
Data collection top
Bruker SMART CCD diffractometer | 1963 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.021 |
Graphite monochromator | θmax = 25.2°, θmin = 2.0° |
ω scans | h = −12→12 |
11156 measured reflections | k = −15→15 |
2402 independent reflections | l = −10→12 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.038 | Hydrogen site location: difmap and geom |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0692P)2 + 0.1716P] where P = (Fo2 + 2Fc2)/3 |
2402 reflections | (Δ/σ)max < 0.001 |
190 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.41925 (12) | 0.01619 (9) | 0.74776 (12) | 0.0429 (3) | |
N2 | 0.55717 (11) | 0.14851 (10) | 0.95816 (13) | 0.0426 (3) | |
N3 | 0.02596 (12) | 0.13131 (10) | 0.81013 (13) | 0.0458 (3) | |
N4 | 0.17382 (12) | 0.18151 (10) | 1.10369 (13) | 0.0448 (3) | |
N5 | 0.24898 (11) | 0.01627 (9) | 1.09360 (12) | 0.0413 (3) | |
H5 | 0.3256 | −0.0162 | 1.0992 | 0.049* | |
C1 | 0.34671 (16) | −0.03749 (12) | 0.63435 (16) | 0.0496 (4) | |
H1 | 0.3913 | −0.0679 | 0.5817 | 0.060* | |
C2 | 0.21002 (16) | −0.05081 (13) | 0.59002 (16) | 0.0506 (4) | |
H2 | 0.1642 | −0.0889 | 0.5098 | 0.061* | |
C3 | 0.14281 (15) | −0.00651 (12) | 0.66698 (16) | 0.0452 (4) | |
H3 | 0.0505 | −0.0144 | 0.6398 | 0.054* | |
C4 | 0.21466 (13) | 0.05019 (10) | 0.78585 (14) | 0.0373 (3) | |
C5 | 0.35317 (13) | 0.05934 (10) | 0.82252 (14) | 0.0356 (3) | |
C6 | 0.43114 (13) | 0.12464 (10) | 0.94416 (14) | 0.0354 (3) | |
C7 | 0.37051 (13) | 0.16083 (10) | 1.03489 (14) | 0.0376 (3) | |
C8 | 0.44208 (16) | 0.22953 (12) | 1.13869 (16) | 0.0475 (4) | |
H8 | 0.4038 | 0.2572 | 1.1990 | 0.057* | |
C9 | 0.57037 (17) | 0.25655 (13) | 1.15188 (18) | 0.0536 (4) | |
H9 | 0.6194 | 0.3034 | 1.2199 | 0.064* | |
C10 | 0.62417 (15) | 0.21253 (13) | 1.06203 (17) | 0.0499 (4) | |
H10 | 0.7124 | 0.2283 | 1.0745 | 0.060* | |
C11 | 0.14718 (13) | 0.10318 (10) | 0.87070 (14) | 0.0379 (3) | |
C12 | 0.23465 (13) | 0.11806 (10) | 1.02534 (15) | 0.0379 (3) | |
C13 | −0.03535 (15) | 0.18784 (14) | 0.89479 (18) | 0.0548 (4) | |
H13A | −0.0824 | 0.1400 | 0.9329 | 0.066* | |
H13B | −0.1008 | 0.2355 | 0.8345 | 0.066* | |
C14 | 0.06562 (16) | 0.24626 (13) | 1.01435 (18) | 0.0522 (4) | |
H14A | 0.1032 | 0.3009 | 0.9760 | 0.063* | |
H14B | 0.0204 | 0.2773 | 1.0710 | 0.063* | |
C15 | 0.1405 (2) | 0.11580 (14) | 1.2012 (2) | 0.0631 (5) | |
H15A | 0.0515 | 0.0867 | 1.1575 | 0.076* | |
H15B | 0.1458 | 0.1528 | 1.2854 | 0.076* | |
C16 | 0.24701 (18) | 0.03467 (14) | 1.23358 (17) | 0.0548 (4) | |
H16A | 0.3329 | 0.0595 | 1.2982 | 0.066* | |
H16B | 0.2222 | −0.0264 | 1.2722 | 0.066* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0486 (7) | 0.0444 (7) | 0.0382 (7) | 0.0014 (5) | 0.0189 (6) | −0.0043 (6) |
N2 | 0.0441 (6) | 0.0469 (7) | 0.0372 (7) | −0.0043 (5) | 0.0153 (5) | 0.0004 (6) |
N3 | 0.0421 (6) | 0.0538 (8) | 0.0425 (7) | 0.0015 (5) | 0.0168 (6) | 0.0014 (6) |
N4 | 0.0528 (7) | 0.0469 (7) | 0.0399 (7) | 0.0057 (5) | 0.0230 (6) | −0.0024 (6) |
N5 | 0.0482 (7) | 0.0426 (7) | 0.0391 (7) | 0.0029 (5) | 0.0231 (5) | 0.0034 (5) |
C1 | 0.0600 (9) | 0.0510 (9) | 0.0411 (9) | 0.0015 (7) | 0.0225 (7) | −0.0097 (7) |
C2 | 0.0591 (9) | 0.0517 (9) | 0.0376 (9) | −0.0046 (7) | 0.0140 (7) | −0.0121 (7) |
C3 | 0.0453 (8) | 0.0493 (9) | 0.0380 (8) | −0.0031 (6) | 0.0118 (6) | −0.0032 (7) |
C4 | 0.0447 (7) | 0.0364 (7) | 0.0298 (7) | 0.0006 (5) | 0.0125 (6) | 0.0027 (6) |
C5 | 0.0450 (7) | 0.0328 (7) | 0.0308 (7) | 0.0015 (5) | 0.0161 (6) | 0.0030 (6) |
C6 | 0.0426 (7) | 0.0334 (7) | 0.0297 (7) | 0.0006 (5) | 0.0127 (6) | 0.0034 (6) |
C7 | 0.0448 (7) | 0.0353 (7) | 0.0327 (7) | 0.0002 (6) | 0.0141 (6) | 0.0007 (6) |
C8 | 0.0570 (9) | 0.0452 (9) | 0.0420 (9) | −0.0039 (7) | 0.0204 (7) | −0.0095 (7) |
C9 | 0.0610 (10) | 0.0511 (9) | 0.0456 (9) | −0.0159 (7) | 0.0162 (8) | −0.0125 (8) |
C10 | 0.0476 (8) | 0.0556 (10) | 0.0448 (9) | −0.0139 (7) | 0.0150 (7) | −0.0019 (8) |
C11 | 0.0417 (7) | 0.0380 (7) | 0.0352 (8) | −0.0013 (6) | 0.0158 (6) | 0.0017 (6) |
C12 | 0.0444 (7) | 0.0374 (7) | 0.0346 (8) | 0.0006 (6) | 0.0177 (6) | −0.0017 (6) |
C13 | 0.0472 (8) | 0.0668 (11) | 0.0529 (10) | 0.0122 (7) | 0.0215 (8) | 0.0024 (8) |
C14 | 0.0584 (9) | 0.0509 (9) | 0.0540 (10) | 0.0109 (7) | 0.0287 (8) | −0.0007 (8) |
C15 | 0.0848 (12) | 0.0696 (12) | 0.0507 (10) | 0.0143 (9) | 0.0434 (10) | 0.0061 (9) |
C16 | 0.0707 (10) | 0.0605 (10) | 0.0389 (9) | 0.0052 (8) | 0.0268 (8) | 0.0065 (8) |
Geometric parameters (Å, º) top
N1—C1 | 1.3321 (19) | C5—C6 | 1.4848 (19) |
N1—C5 | 1.3422 (18) | C6—C7 | 1.3960 (19) |
N2—C10 | 1.334 (2) | C7—C8 | 1.385 (2) |
N2—C6 | 1.3425 (18) | C7—C12 | 1.5298 (19) |
N3—C11 | 1.2710 (18) | C8—C9 | 1.378 (2) |
N3—C13 | 1.464 (2) | C8—H8 | 0.9300 |
N4—C14 | 1.454 (2) | C9—C10 | 1.377 (2) |
N4—C15 | 1.455 (2) | C9—H9 | 0.9300 |
N4—C12 | 1.4618 (18) | C10—H10 | 0.9300 |
N5—C16 | 1.4574 (19) | C11—C12 | 1.523 (2) |
N5—C12 | 1.4824 (18) | C13—C14 | 1.507 (2) |
N5—H5 | 0.9074 | C13—H13A | 0.9700 |
C1—C2 | 1.377 (2) | C13—H13B | 0.9700 |
C1—H1 | 0.9300 | C14—H14A | 0.9700 |
C2—C3 | 1.375 (2) | C14—H14B | 0.9700 |
C2—H2 | 0.9300 | C15—C16 | 1.503 (2) |
C3—C4 | 1.388 (2) | C15—H15A | 0.9700 |
C3—H3 | 0.9300 | C15—H15B | 0.9700 |
C4—C5 | 1.3970 (19) | C16—H16A | 0.9700 |
C4—C11 | 1.4884 (19) | C16—H16B | 0.9700 |
| | | |
C1—N1—C5 | 116.99 (12) | N2—C10—C9 | 123.81 (14) |
C10—N2—C6 | 117.17 (13) | N2—C10—H10 | 118.1 |
C11—N3—C13 | 117.37 (13) | C9—C10—H10 | 118.1 |
C14—N4—C15 | 115.57 (13) | N3—C11—C4 | 118.73 (12) |
C14—N4—C12 | 113.59 (11) | N3—C11—C12 | 126.63 (13) |
C15—N4—C12 | 108.18 (12) | C4—C11—C12 | 114.64 (11) |
C16—N5—C12 | 106.08 (12) | N4—C12—N5 | 103.93 (11) |
C16—N5—H5 | 110.8 | N4—C12—C11 | 114.28 (11) |
C12—N5—H5 | 112.5 | N5—C12—C11 | 106.90 (11) |
N1—C1—C2 | 124.24 (14) | N4—C12—C7 | 111.39 (11) |
N1—C1—H1 | 117.9 | N5—C12—C7 | 111.47 (11) |
C2—C1—H1 | 117.9 | C11—C12—C7 | 108.74 (11) |
C3—C2—C1 | 118.56 (14) | N3—C13—C14 | 112.87 (13) |
C3—C2—H2 | 120.7 | N3—C13—H13A | 109.0 |
C1—C2—H2 | 120.7 | C14—C13—H13A | 109.0 |
C2—C3—C4 | 119.03 (14) | N3—C13—H13B | 109.0 |
C2—C3—H3 | 120.5 | C14—C13—H13B | 109.0 |
C4—C3—H3 | 120.5 | H13A—C13—H13B | 107.8 |
C3—C4—C5 | 118.24 (13) | N4—C14—C13 | 112.54 (13) |
C3—C4—C11 | 121.65 (13) | N4—C14—H14A | 109.1 |
C5—C4—C11 | 120.08 (12) | C13—C14—H14A | 109.1 |
N1—C5—C4 | 122.94 (12) | N4—C14—H14B | 109.1 |
N1—C5—C6 | 117.66 (12) | C13—C14—H14B | 109.1 |
C4—C5—C6 | 119.29 (12) | H14A—C14—H14B | 107.8 |
N2—C6—C7 | 123.20 (13) | N4—C15—C16 | 102.00 (13) |
N2—C6—C5 | 117.21 (12) | N4—C15—H15A | 111.4 |
C7—C6—C5 | 119.55 (12) | C16—C15—H15A | 111.4 |
C8—C7—C6 | 117.70 (13) | N4—C15—H15B | 111.4 |
C8—C7—C12 | 122.13 (13) | C16—C15—H15B | 111.4 |
C6—C7—C12 | 119.98 (12) | H15A—C15—H15B | 109.2 |
C9—C8—C7 | 119.52 (15) | N5—C16—C15 | 100.64 (13) |
C9—C8—H8 | 120.2 | N5—C16—H16A | 111.6 |
C7—C8—H8 | 120.2 | C15—C16—H16A | 111.6 |
C10—C9—C8 | 118.45 (14) | N5—C16—H16B | 111.6 |
C10—C9—H9 | 120.8 | C15—C16—H16B | 111.6 |
C8—C9—H9 | 120.8 | H16A—C16—H16B | 109.4 |
| | | |
C5—N1—C1—C2 | 0.2 (2) | C3—C4—C11—N3 | −27.4 (2) |
C1—N1—C5—C4 | −0.2 (2) | C3—C4—C11—C12 | 152.69 (13) |
C1—N1—C5—C6 | −176.36 (12) | C5—C4—C11—N3 | 150.58 (14) |
C10—N2—C6—C5 | 175.77 (13) | C5—C4—C11—C12 | −29.30 (18) |
C10—N2—C6—C7 | −2.1 (2) | N1—C5—C6—N2 | 9.80 (18) |
C6—N2—C10—C9 | −1.6 (2) | N1—C5—C6—C7 | −172.26 (12) |
C13—N3—C11—C4 | −176.95 (13) | C4—C5—C6—N2 | −166.52 (13) |
C13—N3—C11—C12 | 2.9 (2) | C4—C5—C6—C7 | 11.43 (19) |
C11—N3—C13—C14 | 27.2 (2) | N2—C6—C7—C8 | 4.0 (2) |
C14—N4—C12—N5 | −136.08 (13) | N2—C6—C7—C12 | −171.07 (13) |
C14—N4—C12—C7 | 103.77 (14) | C5—C6—C7—C8 | −173.79 (13) |
C14—N4—C12—C11 | −19.95 (17) | C5—C6—C7—C12 | 11.12 (19) |
C15—N4—C12—N5 | −6.34 (16) | C6—C7—C8—C9 | −2.3 (2) |
C15—N4—C12—C7 | −126.49 (14) | C12—C7—C8—C9 | 172.70 (14) |
C15—N4—C12—C11 | 109.79 (14) | C6—C7—C12—N4 | −166.39 (12) |
C12—N4—C14—C13 | 49.36 (18) | C6—C7—C12—N5 | 78.02 (16) |
C15—N4—C14—C13 | −76.54 (18) | C6—C7—C12—C11 | −39.58 (16) |
C12—N4—C15—C16 | 30.55 (17) | C8—C7—C12—N4 | 18.74 (18) |
C14—N4—C15—C16 | 159.17 (14) | C8—C7—C12—N5 | −96.85 (15) |
C16—N5—C12—N4 | −21.52 (15) | C8—C7—C12—C11 | 145.55 (13) |
C16—N5—C12—C7 | 98.58 (14) | C7—C8—C9—C10 | −1.1 (2) |
C16—N5—C12—C11 | −142.72 (13) | C8—C9—C10—N2 | 3.2 (3) |
C12—N5—C16—C15 | 39.80 (16) | N3—C11—C12—N4 | −7.4 (2) |
N1—C1—C2—C3 | −0.2 (2) | N3—C11—C12—N5 | 107.03 (16) |
C1—C2—C3—C4 | 0.3 (2) | N3—C11—C12—C7 | −132.51 (15) |
C2—C3—C4—C5 | −0.3 (2) | C4—C11—C12—N4 | 172.50 (11) |
C2—C3—C4—C11 | 177.76 (14) | C4—C11—C12—N5 | −73.10 (15) |
C3—C4—C5—N1 | 0.3 (2) | C4—C11—C12—C7 | 47.36 (15) |
C3—C4—C5—C6 | 176.38 (13) | N3—C13—C14—N4 | −54.03 (19) |
C11—C4—C5—N1 | −177.82 (12) | N4—C15—C16—N5 | −42.54 (16) |
C11—C4—C5—C6 | −1.70 (19) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5···N1i | 0.91 | 2.60 | 3.3497 (18) | 140 |
N5—H5···N2i | 0.91 | 2.33 | 3.1689 (18) | 153 |
C8—H8···N4 | 0.93 | 2.50 | 2.836 (2) | 102 |
Symmetry code: (i) −x+1, −y, −z+2. |
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