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Acta Cryst. (2008). E64, o1981    [ doi:10.1107/S1600536808029759 ]

2-Phenyl-1H-1,3,7,8-tetraazacyclopenta[l]phenanthrene

H.-M. Xi

Abstract top

There are two molecules in the asymmetric unit of the title compound, C19H12N4. One is almost planar [dihedral angle between the fused-ring system and the phenyl ring = 2.16 (13)°] and one is somewhat twisted [dihedral angle = 13.30 (14)°]. In the crystal, the molecules are linked by N-H...N hydrogen bonds to result in chains.

Comment top

1,10-Phenanthroline and its derivatives are widely utilized as ligands in metal complexes (Zhang et al., 2008). I report here the crystal structure of the title compound, which was synthesized from 1,10-phenanthroline-5,6-dione. In this compound, all the bond lengths are within normal ranges (Yin, 2008). The asymmetric unit consists of two independent molecules (Fig. 1), which are connected by N—H···N hydrogen bonds to form a one-dimensional chain (Table 1).

Related literature top

For related literature, see Zhang et al. (2008); Yin (2008).

Experimental top

1,10-Phenanthroline-5,6-dione (1.5 mmol) and benzaldehyde (1.5 mmol) were dissolved in CH3COOHCH3COONH4 (1:1) solution (30 ml). The mixture was refluxed for 3 h under argon, after cooling, this mixture was diluted with water and neutralized with concentrated aqueous ammonia, immediately resulting a yellow precipitate, which was washed with water, acetone and diethyl ether respectively. Crystals of the title compound were obtained by recrystallization from dichloromethane.

Refinement top

C– and N-bound H atoms were positioned geometrically (N—H = 0.86 Å and C—H= 0.93 Å) and refined as riding, with Uiso(H)= 1.2 Ueq(carrier).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of (I), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
2-Phenyl-1H-1,3,7,8-tetraazacyclopenta[l]phenanthrene top
Crystal data top
C19H12N4F(000) = 1232
Mr = 296.33Dx = 1.352 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5721 reflections
a = 12.3326 (15) Åθ = 1.1–26.0°
b = 12.2334 (15) ŵ = 0.08 mm−1
c = 19.885 (2) ÅT = 293 K
β = 104.010 (2)°Block, pale yellow
V = 2910.9 (6) Å30.24 × 0.21 × 0.19 mm
Z = 8
Data collection top
Bruker APEX CCD area-detector
diffractometer		5721 independent reflections
Radiation source: fine-focus sealed tube2627 reflections with I > 2σ(I)
graphiteRint = 0.089
φ and ω scansθmax = 26.0°, θmin = 1.7°
Absorption correction: multi-scan
(SAINT; Bruker, 1998)		h = −15→15
Tmin = 0.981, Tmax = 0.982k = −15→14
23942 measured reflectionsl = −24→24
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.060Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.167H-atom parameters constrained
S = 0.97 w = 1/[σ2(Fo2) + (0.0719P)2]
where P = (Fo2 + 2Fc2)/3
5721 reflections(Δ/σ)max < 0.001
415 parametersΔρmax = 0.62 e Å−3
0 restraintsΔρmin = −0.26 e Å−3
Crystal data top
C19H12N4V = 2910.9 (6) Å3
Mr = 296.33Z = 8
Monoclinic, P21/cMo Kα radiation
a = 12.3326 (15) ŵ = 0.08 mm−1
b = 12.2334 (15) ÅT = 293 K
c = 19.885 (2) Å0.24 × 0.21 × 0.19 mm
β = 104.010 (2)°
Data collection top
Bruker APEX CCD area-detector
diffractometer		5721 independent reflections
Absorption correction: multi-scan
(SAINT; Bruker, 1998)		2627 reflections with I > 2σ(I)
Tmin = 0.981, Tmax = 0.982Rint = 0.089
23942 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.060H-atom parameters constrained
wR(F2) = 0.167Δρmax = 0.62 e Å−3
S = 0.97Δρmin = −0.26 e Å−3
5721 reflectionsAbsolute structure: ?
415 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
C11.8134 (3)−0.7259 (3)1.53329 (17)0.0535 (9)
H11.8713−0.76281.56340.064*
C21.7966 (3)−0.6167 (2)1.54683 (16)0.0504 (8)
H21.8415−0.58221.58530.061*
C31.7134 (2)−0.5611 (2)1.50287 (16)0.0475 (8)
H31.7017−0.48751.51030.057*
C41.6452 (2)−0.6157 (2)1.44615 (15)0.0400 (7)
C51.6667 (2)−0.7273 (2)1.43635 (15)0.0399 (7)
C61.5946 (2)−0.7898 (2)1.38033 (15)0.0405 (7)
C71.5008 (2)−0.7402 (2)1.33678 (15)0.0423 (7)
C81.4329 (3)−0.8051 (3)1.28464 (16)0.0510 (8)
H81.3714−0.77481.25370.061*
C91.4585 (3)−0.9123 (3)1.28015 (17)0.0558 (9)
H91.4135−0.95711.24700.067*
C101.5533 (3)−0.9541 (3)1.32599 (18)0.0567 (9)
H101.5704−1.02741.32160.068*
C111.4801 (2)−0.6274 (2)1.34767 (15)0.0423 (7)
C121.5524 (2)−0.5691 (2)1.39835 (16)0.0417 (7)
C131.4147 (3)−0.4650 (2)1.34191 (16)0.0465 (8)
C141.3452 (3)−0.3683 (3)1.32024 (17)0.0509 (8)
C151.2420 (3)−0.3792 (3)1.27505 (18)0.0676 (10)
H151.2177−0.44741.25680.081*
C161.1741 (3)−0.2880 (4)1.25679 (19)0.0840 (13)
H161.1044−0.29591.22620.101*
C171.2078 (4)−0.1869 (3)1.2829 (2)0.0820 (12)
H171.1615−0.12661.27010.098*
C181.3100 (4)−0.1754 (3)1.3277 (2)0.0866 (13)
H181.3334−0.10701.34610.104*
C191.3788 (3)−0.2654 (3)1.3460 (2)0.0755 (12)
H191.4488−0.25671.37610.091*
C201.1864 (3)−0.9545 (3)1.14281 (18)0.0627 (10)
H201.2040−1.02821.15000.075*
C211.1001 (3)−0.9129 (3)1.16926 (18)0.0620 (10)
H211.0615−0.95751.19340.074*
C221.0735 (3)−0.8046 (3)1.15866 (17)0.0549 (9)
H221.0172−0.77411.17640.066*
C231.1315 (2)−0.7401 (2)1.12107 (15)0.0441 (8)
C241.2181 (2)−0.7894 (2)1.09701 (15)0.0425 (7)
C251.2812 (2)−0.7264 (2)1.05692 (15)0.0421 (7)
C261.4170 (3)−0.7220 (3)0.99579 (17)0.0548 (9)
H261.4723−0.75790.97970.066*
C271.3965 (3)−0.6129 (2)0.97781 (17)0.0540 (9)
H271.4362−0.57740.95000.065*
C281.3169 (3)−0.5593 (2)1.00190 (16)0.0486 (8)
H281.3023−0.48600.99120.058*
C291.2573 (2)−0.6147 (2)1.04264 (15)0.0409 (7)
C301.1711 (2)−0.5686 (2)1.06952 (15)0.0424 (8)
C311.1082 (2)−0.6270 (2)1.10553 (15)0.0429 (7)
C321.0428 (2)−0.4646 (3)1.09756 (16)0.0446 (8)
C330.9771 (2)−0.3676 (2)1.10415 (16)0.0458 (8)
C340.8959 (3)−0.3745 (3)1.14149 (18)0.0628 (10)
H340.8819−0.44111.16030.075*
C350.8357 (3)−0.2833 (3)1.1510 (2)0.0745 (11)
H350.7819−0.28871.17650.089*
C360.8546 (3)−0.1844 (3)1.1231 (2)0.0762 (12)
H360.8143−0.12281.12990.091*
C370.9327 (3)−0.1776 (3)1.0856 (2)0.0741 (11)
H370.9449−0.11111.06600.089*
C380.9945 (3)−0.2677 (3)1.07615 (18)0.0614 (9)
H381.0482−0.26121.05070.074*
N11.6202 (2)−0.8969 (2)1.37510 (13)0.0491 (7)
N21.7522 (2)−0.78066 (19)1.48026 (13)0.0470 (7)
N31.5101 (2)−0.46462 (19)1.39421 (13)0.0499 (7)
H3A1.5380−0.40981.41960.060*
N41.3927 (2)−0.5633 (2)1.31277 (13)0.0501 (7)
N51.2449 (2)−0.8967 (2)1.10833 (14)0.0530 (7)
N61.3630 (2)−0.7781 (2)1.03437 (13)0.0504 (7)
N71.0279 (2)−0.5624 (2)1.12287 (13)0.0488 (7)
N81.12765 (19)−0.46471 (18)1.06446 (12)0.0439 (6)
H8A1.1498−0.40991.04420.053*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.051 (2)0.051 (2)0.053 (2)0.0050 (17)0.0021 (18)−0.0024 (17)
C20.050 (2)0.048 (2)0.049 (2)−0.0014 (17)0.0046 (17)−0.0064 (16)
C30.0459 (19)0.0405 (18)0.056 (2)−0.0025 (15)0.0121 (17)−0.0003 (16)
C40.0371 (17)0.0367 (18)0.0460 (19)−0.0029 (14)0.0099 (15)0.0026 (15)
C50.0350 (17)0.0377 (17)0.0485 (19)0.0002 (14)0.0130 (15)0.0009 (15)
C60.0411 (18)0.0381 (18)0.0437 (19)−0.0043 (14)0.0133 (16)−0.0010 (14)
C70.0394 (18)0.049 (2)0.0398 (19)−0.0057 (15)0.0126 (15)−0.0012 (15)
C80.048 (2)0.052 (2)0.052 (2)−0.0050 (16)0.0106 (17)−0.0021 (17)
C90.054 (2)0.054 (2)0.058 (2)−0.0138 (17)0.0112 (19)−0.0162 (17)
C100.062 (2)0.048 (2)0.061 (2)−0.0018 (18)0.016 (2)−0.0136 (17)
C110.0397 (18)0.0403 (18)0.048 (2)−0.0015 (15)0.0126 (16)0.0049 (15)
C120.0385 (17)0.0366 (18)0.050 (2)0.0002 (15)0.0111 (16)0.0039 (15)
C130.0422 (19)0.045 (2)0.052 (2)0.0008 (16)0.0107 (17)0.0044 (16)
C140.044 (2)0.053 (2)0.056 (2)0.0071 (17)0.0129 (17)0.0060 (17)
C150.063 (2)0.073 (3)0.059 (2)0.018 (2)0.000 (2)−0.008 (2)
C160.068 (3)0.101 (3)0.070 (3)0.032 (3)−0.007 (2)−0.004 (3)
C170.083 (3)0.070 (3)0.088 (3)0.033 (2)0.011 (3)0.014 (2)
C180.075 (3)0.055 (3)0.121 (4)0.015 (2)0.006 (3)0.006 (2)
C190.051 (2)0.054 (2)0.113 (3)0.0055 (19)0.002 (2)0.010 (2)
C200.066 (2)0.042 (2)0.082 (3)−0.0017 (18)0.022 (2)0.0144 (18)
C210.058 (2)0.060 (2)0.074 (3)−0.0027 (18)0.027 (2)0.0179 (19)
C220.050 (2)0.054 (2)0.064 (2)−0.0010 (17)0.0192 (18)0.0095 (17)
C230.0398 (18)0.0437 (19)0.048 (2)−0.0021 (15)0.0099 (16)0.0029 (15)
C240.0448 (18)0.0329 (17)0.049 (2)−0.0007 (14)0.0094 (16)0.0009 (14)
C250.0377 (17)0.0419 (18)0.0472 (19)−0.0007 (14)0.0112 (15)−0.0022 (15)
C260.053 (2)0.051 (2)0.066 (2)0.0059 (17)0.0263 (19)−0.0033 (18)
C270.057 (2)0.044 (2)0.070 (2)−0.0008 (16)0.0334 (19)0.0021 (17)
C280.054 (2)0.0377 (18)0.057 (2)−0.0006 (15)0.0200 (18)−0.0022 (15)
C290.0383 (17)0.0378 (18)0.047 (2)−0.0013 (14)0.0105 (15)−0.0022 (14)
C300.0387 (17)0.0376 (18)0.051 (2)−0.0024 (14)0.0116 (16)−0.0017 (14)
C310.0387 (17)0.0407 (18)0.0492 (19)0.0026 (15)0.0102 (15)−0.0006 (15)
C320.0407 (18)0.049 (2)0.047 (2)−0.0007 (15)0.0164 (16)−0.0027 (16)
C330.0369 (18)0.047 (2)0.052 (2)0.0052 (15)0.0083 (16)−0.0033 (16)
C340.058 (2)0.059 (2)0.076 (3)0.0065 (19)0.027 (2)0.0014 (19)
C350.062 (2)0.084 (3)0.085 (3)0.016 (2)0.032 (2)−0.003 (2)
C360.075 (3)0.066 (3)0.091 (3)0.029 (2)0.025 (2)−0.009 (2)
C370.076 (3)0.055 (2)0.096 (3)0.020 (2)0.031 (3)0.009 (2)
C380.059 (2)0.050 (2)0.079 (3)0.0112 (18)0.027 (2)0.0061 (19)
N10.0507 (16)0.0428 (16)0.0552 (18)0.0009 (13)0.0153 (14)−0.0079 (13)
N20.0444 (15)0.0413 (15)0.0538 (17)0.0008 (13)0.0091 (14)−0.0011 (13)
N30.0468 (16)0.0396 (16)0.0610 (18)0.0006 (13)0.0083 (15)0.0011 (13)
N40.0453 (16)0.0502 (17)0.0529 (17)0.0029 (13)0.0081 (14)0.0054 (14)
N50.0517 (16)0.0394 (16)0.0678 (19)0.0027 (13)0.0144 (15)0.0081 (13)
N60.0471 (16)0.0431 (16)0.0648 (19)0.0005 (13)0.0213 (15)0.0005 (13)
N70.0453 (16)0.0458 (16)0.0578 (18)0.0015 (13)0.0171 (14)0.0024 (13)
N80.0429 (15)0.0357 (15)0.0558 (17)0.0044 (12)0.0171 (14)0.0027 (12)
Geometric parameters (Å, °) top
C1—N21.321 (4)C20—C211.393 (4)
C1—C21.388 (4)C20—H200.9300
C1—H10.9300C21—C221.369 (4)
C2—C31.359 (4)C21—H210.9300
C2—H20.9300C22—C231.397 (4)
C3—C41.402 (4)C22—H220.9300
C3—H30.9300C23—C241.407 (4)
C4—C51.413 (4)C23—C311.432 (4)
C4—C121.419 (4)C24—N51.359 (3)
C5—N21.362 (3)C24—C251.461 (4)
C5—C61.462 (4)C25—N61.356 (3)
C6—N11.357 (3)C25—C291.412 (4)
C6—C71.405 (4)C26—N61.323 (4)
C7—C81.409 (4)C26—C271.389 (4)
C7—C111.429 (4)C26—H260.9300
C8—C91.357 (4)C27—C281.361 (4)
C8—H80.9300C27—H270.9300
C9—C101.394 (4)C28—C291.394 (4)
C9—H90.9300C28—H280.9300
C10—N11.317 (4)C29—C301.418 (4)
C10—H100.9300C30—N81.374 (3)
C11—C121.373 (4)C30—C311.376 (4)
C11—N41.377 (3)C31—N71.375 (3)
C12—N31.375 (3)C32—N71.327 (3)
C13—N41.334 (3)C32—N81.364 (3)
C13—N31.368 (4)C32—C331.462 (4)
C13—C141.464 (4)C33—C381.380 (4)
C14—C151.375 (4)C33—C341.386 (4)
C14—C191.384 (4)C34—C351.378 (4)
C15—C161.390 (5)C34—H340.9300
C15—H150.9300C35—C361.374 (5)
C16—C171.365 (5)C35—H350.9300
C16—H160.9300C36—C371.356 (5)
C17—C181.364 (5)C36—H360.9300
C17—H170.9300C37—C381.378 (4)
C18—C191.385 (4)C37—H370.9300
C18—H180.9300C38—H380.9300
C19—H190.9300N3—H3A0.8600
C20—N51.315 (4)N8—H8A0.8600
N2—C1—C2124.0 (3)C21—C22—C23119.7 (3)
N2—C1—H1118.0C21—C22—H22120.2
C2—C1—H1118.0C23—C22—H22120.2
C3—C2—C1118.8 (3)C22—C23—C24118.0 (3)
C3—C2—H2120.6C22—C23—C31124.0 (3)
C1—C2—H2120.6C24—C23—C31118.0 (3)
C2—C3—C4119.4 (3)N5—C24—C23122.1 (3)
C2—C3—H3120.3N5—C24—C25117.4 (3)
C4—C3—H3120.3C23—C24—C25120.5 (3)
C3—C4—C5118.4 (3)N6—C25—C29121.4 (3)
C3—C4—C12125.2 (3)N6—C25—C24118.1 (3)
C5—C4—C12116.4 (3)C29—C25—C24120.5 (3)
N2—C5—C4121.1 (3)N6—C26—C27124.1 (3)
N2—C5—C6118.1 (3)N6—C26—H26117.9
C4—C5—C6120.7 (3)C27—C26—H26117.9
N1—C6—C7122.9 (3)C28—C27—C26118.3 (3)
N1—C6—C5117.0 (3)C28—C27—H27120.8
C7—C6—C5120.1 (3)C26—C27—H27120.8
C6—C7—C8117.6 (3)C27—C28—C29119.8 (3)
C6—C7—C11118.4 (3)C27—C28—H28120.1
C8—C7—C11124.0 (3)C29—C28—H28120.1
C9—C8—C7119.1 (3)C28—C29—C25118.3 (3)
C9—C8—H8120.4C28—C29—C30125.1 (3)
C7—C8—H8120.4C25—C29—C30116.6 (3)
C8—C9—C10118.9 (3)N8—C30—C31105.0 (3)
C8—C9—H9120.5N8—C30—C29130.9 (3)
C10—C9—H9120.5C31—C30—C29124.0 (3)
N1—C10—C9124.4 (3)N7—C31—C30111.3 (3)
N1—C10—H10117.8N7—C31—C23128.4 (3)
C9—C10—H10117.8C30—C31—C23120.3 (3)
C12—C11—N4111.4 (3)N7—C32—N8112.1 (3)
C12—C11—C7120.3 (3)N7—C32—C33124.5 (3)
N4—C11—C7128.3 (3)N8—C32—C33123.4 (3)
C11—C12—N3105.6 (3)C38—C33—C34118.2 (3)
C11—C12—C4123.9 (3)C38—C33—C32122.6 (3)
N3—C12—C4130.3 (3)C34—C33—C32119.1 (3)
N4—C13—N3112.4 (3)C35—C34—C33120.4 (3)
N4—C13—C14123.9 (3)C35—C34—H34119.8
N3—C13—C14123.8 (3)C33—C34—H34119.8
C15—C14—C19118.5 (3)C36—C35—C34120.6 (3)
C15—C14—C13119.8 (3)C36—C35—H35119.7
C19—C14—C13121.6 (3)C34—C35—H35119.7
C14—C15—C16119.8 (4)C37—C36—C35119.2 (3)
C14—C15—H15120.1C37—C36—H36120.4
C16—C15—H15120.1C35—C36—H36120.4
C17—C16—C15121.3 (4)C36—C37—C38121.1 (4)
C17—C16—H16119.4C36—C37—H37119.5
C15—C16—H16119.4C38—C37—H37119.5
C18—C17—C16119.4 (3)C37—C38—C33120.5 (3)
C18—C17—H17120.3C37—C38—H38119.7
C16—C17—H17120.3C33—C38—H38119.7
C17—C18—C19120.0 (4)C10—N1—C6117.0 (3)
C17—C18—H18120.0C1—N2—C5118.2 (3)
C19—C18—H18120.0C13—N3—C12106.6 (2)
C14—C19—C18121.1 (4)C13—N3—H3A126.7
C14—C19—H19119.4C12—N3—H3A126.7
C18—C19—H19119.4C13—N4—C11104.0 (3)
N5—C20—C21124.5 (3)C20—N5—C24117.6 (3)
N5—C20—H20117.8C26—N6—C25118.0 (3)
C21—C20—H20117.8C32—N7—C31104.4 (2)
C22—C21—C20118.1 (3)C32—N8—C30107.2 (2)
C22—C21—H21120.9C32—N8—H8A126.4
C20—C21—H21120.9C30—N8—H8A126.4
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···N6i0.862.092.932 (4)165.
N8—H8A···N2i0.862.122.948 (3)163.
Symmetry codes: (i) −x+3, y+1/2, −z+5/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···N6i0.862.092.932 (4)165.
N8—H8A···N2i0.862.122.948 (3)163.
Symmetry codes: (i) −x+3, y+1/2, −z+5/2.
Acknowledgements top

The author thanks Beihua University for supporting this work.

references
References top

Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Yin, G.-Q. (2008). Acta Cryst. E64, o1236.

Zhang, W.-Z., Li, L. & Xiao, Y.-H. (2008). Acta Cryst. E64, o1331.