(1R)-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

The reaction of 1,10-phenanthroline-5,6-dione and diethyl­enetriamine unexpectedly yielded the title compound, C₁₆H₁₅N₅, 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.

Key indicators

• Single-crystal X-ray study
• T = 273 K
• Mean [sigma](C-C)= 0.002 Å
• R factor = 0.038
• wR factor = 0.117
• Data-to-parameter ratio = 12.6

checkCIF/PLATON results

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Computing details

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.

(1R)-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

Crystal data

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) Å^3	0.3 × 0.3 × 0.2 mm
Z = 4

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: difmap and geom
wR(F^2) = 0.117	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0692P)^2 + 0.1716P] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···N1^i	0.91	2.60	3.3497 (18)	140
N5—H5···N2^i	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.