5H-Imidazo[4,5-f][1,10]phenanthroline

Tong, S.-W.; Song, W.-D.; Miao, D.-L.; An, J.-B.

doi:10.1107/S1600536812016595

organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page o1448

doi:10.1107/S1600536812016595

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5H-Imidazo[4,5-f][1,10]phenanthroline

Shao-Wei Tong,^a Wen-Dong Song,^b ^* Dong-Liang Miao ^a and Jing-Bo An ^a

^aCollege of Food Science and Technology, Guangdong Ocean University, Zhanjiang 524088, People's Republic of China, and ^bCollege of Science, Guangdong Ocean University, Zhanjiang 524088, People's Republic of China
^*Correspondence e-mail: songwd60@163.com

(Received 5 April 2012; accepted 16 April 2012; online 21 April 2012)

The title molecule, C₁₃H₈N₄, is is essentially planar [r.m.s. deviation for all non-H atoms = 0.025 (3) Å]. In the crystal, molecules are connected through one weak bifurcated N—H⋯(N,N) hydrogen bond and three π–π stacking interactions between pyridine and imidazole rings [centroid–centroid distance = 3.631 (8) Å] and between pyridine and benzene rings [centroid–centroid distances = 3.675 (5) and 3.666 (2) Å].

Related literature

For our previous work based on 1,10-phenanthroline as anauxiliary ligand, see: Song et al. (2009 ); Hao et al. (2008 ). For background to 1,10-phenanthroline complexes, see: Chesnut et al. (1999 ).

Experimental

Crystal data

C₁₃H₈N₄
M_r = 220.23
Orthorhombic, P b c a
a = 14.569 (2) Å
b = 7.8623 (12) Å
c = 17.042 (3) Å
V = 1952.1 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.26 × 0.18 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.980, T_max = 0.985
5772 measured reflections
1756 independent reflections
1025 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.123
S = 1.00
1756 reflections
186 parameters
All H-atom parameters refined
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H8⋯N1ⁱ	0.92 (3)	2.47 (3)	3.104 (3)	126 (2)
N3—H8⋯N2ⁱ	0.92 (3)	2.18 (3)	3.017 (3)	150 (2)
Symmetry code: (i) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812016595/bx2404sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812016595/bx2404Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812016595/bx2404Isup3.cml

checkCIF report

Comment top

(1,10)phenanthroline is widely used to synthetize metal-complex as a auxiliary ligand. In our laboratory earlier studies, we have successfully obtained some metal-complex with (1,10)phenanthroline.We report here the crystal structure of the title compound, Fig. 1. The title compound, is essentially planar (r.m.s. deviation for all non-H atoms = 0.025 (3)Å). In the crystal the molecules are connected through one weak bifurcated N—H···N hydrogen bonds, Fig. 2, Table 1 and π-π stacking interactions between pyridine and imidazole rings [distance centroid – centroid 3.631 (8) Å] and between pyridine and benzene rings [distance centroid–centroid 3.675 (5); 3.666 (2) Å] respectively.

Related literature top

For our previous work based on 1,10-phenanthroline as anauxiliary ligand, see: Song et al. (2009); Hao et al. (2008). For background to 1,10-phenanthroline complexes, see: Chesnut et al. (1999).

Experimental top

Imidazo(4,5-f)(1,10)phenanthroline was purchased from Jinan Henghua science and technology limited company and recristallized of an alkaline solution.

Computing details top

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: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular configuration and atom numbering scheme for the title complex showing 30% probability ellipsoids.
	Fig. 2. Part of the crystal structure showing one dimensional chain along (100).

5H-Imidazo[4,5-f][1,10]phenanthroline top

Crystal data top

C₁₃H₈N₄	F(000) = 912
M_r = 220.23	D_x = 1.499 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 799 reflections
a = 14.569 (2) Å	θ = 2.2–27.5°
b = 7.8623 (12) Å	µ = 0.10 mm⁻¹
c = 17.042 (3) Å	T = 296 K
V = 1952.1 (5) Å³	Block, yellow
Z = 8	0.26 × 0.18 × 0.16 mm

Data collection top

Bruker APEXII CCD diffractometer	1756 independent reflections
Radiation source: fine-focus sealed tube	1025 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
ϕ and ω scans	θ_max = 25.2°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −17→10
T_min = 0.980, T_max = 0.985	k = −9→9
5772 measured reflections	l = −20→20

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	All H-atom parameters refined
S = 1.00	w = 1/[σ²(F_o²) + (0.0606P)²] where P = (F_o² + 2F_c²)/3
1756 reflections	(Δ/σ)_max < 0.001
186 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₁₃H₈N₄	V = 1952.1 (5) Å³
M_r = 220.23	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 14.569 (2) Å	µ = 0.10 mm⁻¹
b = 7.8623 (12) Å	T = 296 K
c = 17.042 (3) Å	0.26 × 0.18 × 0.16 mm

Data collection top

Bruker APEXII CCD diffractometer	1756 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	1025 reflections with I > 2σ(I)
T_min = 0.980, T_max = 0.985	R_int = 0.053
5772 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.123	All H-atom parameters refined
S = 1.00	Δρ_max = 0.18 e Å⁻³
1756 reflections	Δρ_min = −0.15 e Å⁻³
186 parameters

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. 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 > 2sigma(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	U_iso*/U_eq
N2	0.08583 (13)	0.0741 (3)	0.18218 (11)	0.0428 (6)
C13	0.17857 (16)	0.0868 (3)	0.18200 (12)	0.0349 (6)
C4	0.22247 (15)	0.1620 (3)	0.25102 (12)	0.0347 (6)
N1	0.16716 (13)	0.2161 (3)	0.30974 (10)	0.0423 (6)
C5	0.31923 (15)	0.1740 (3)	0.25518 (12)	0.0355 (6)
N3	0.46339 (14)	0.1051 (3)	0.17574 (13)	0.0471 (6)
N4	0.39502 (14)	−0.0018 (3)	0.06803 (11)	0.0449 (6)
C11	0.09449 (19)	−0.0623 (4)	0.05615 (15)	0.0487 (7)
C12	0.04717 (19)	−0.0004 (3)	0.12071 (16)	0.0494 (7)
C3	0.20665 (19)	0.2840 (3)	0.37251 (14)	0.0460 (7)
C2	0.30087 (18)	0.3045 (3)	0.38092 (14)	0.0439 (7)
C1	0.35746 (19)	0.2504 (3)	0.32252 (13)	0.0416 (6)
C6	0.37040 (15)	0.1101 (3)	0.18996 (12)	0.0365 (6)
C7	0.4727 (2)	0.0392 (3)	0.10225 (15)	0.0514 (7)
C8	0.32970 (16)	0.0437 (3)	0.12418 (12)	0.0373 (6)
C9	0.23250 (15)	0.0280 (3)	0.11878 (12)	0.0356 (6)
C10	0.18762 (19)	−0.0478 (3)	0.05489 (14)	0.0445 (7)
H7	0.5396 (16)	0.027 (3)	0.0759 (12)	0.042 (6)*
H6	0.2264 (16)	−0.088 (3)	0.0121 (15)	0.056 (8)*
H4	−0.0192 (17)	−0.012 (3)	0.1232 (13)	0.045 (7)*
H1	0.4230 (16)	0.270 (3)	0.3229 (13)	0.051 (8)*
H5	0.0590 (16)	−0.125 (3)	0.0140 (15)	0.063 (8)*
H3	0.1640 (15)	0.322 (3)	0.4153 (13)	0.046 (7)*
H2	0.3235 (16)	0.353 (3)	0.4266 (14)	0.053 (7)*
H8	0.5057 (19)	0.136 (4)	0.2135 (18)	0.074 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N2	0.0304 (12)	0.0574 (14)	0.0407 (12)	−0.0012 (10)	−0.0020 (9)	0.0005 (10)
C13	0.0326 (13)	0.0403 (15)	0.0318 (12)	−0.0009 (11)	−0.0029 (11)	0.0052 (10)
C4	0.0343 (13)	0.0379 (14)	0.0319 (11)	0.0024 (12)	0.0035 (11)	0.0054 (10)
N1	0.0396 (12)	0.0519 (14)	0.0355 (11)	0.0021 (10)	0.0037 (10)	0.0001 (9)
C5	0.0350 (14)	0.0389 (14)	0.0326 (12)	−0.0016 (11)	−0.0027 (11)	0.0075 (10)
N3	0.0308 (12)	0.0644 (15)	0.0462 (13)	0.0046 (11)	−0.0024 (11)	0.0001 (11)
N4	0.0334 (12)	0.0646 (15)	0.0368 (11)	0.0021 (11)	0.0034 (10)	0.0000 (10)
C11	0.0435 (17)	0.0584 (18)	0.0441 (15)	−0.0023 (14)	−0.0125 (13)	−0.0028 (13)
C12	0.0326 (15)	0.0651 (19)	0.0505 (15)	−0.0029 (14)	−0.0084 (13)	−0.0022 (13)
C3	0.0488 (17)	0.0546 (18)	0.0346 (14)	0.0041 (13)	0.0018 (12)	−0.0029 (11)
C2	0.0511 (17)	0.0462 (16)	0.0344 (13)	−0.0027 (13)	−0.0045 (12)	−0.0036 (11)
C1	0.0403 (15)	0.0443 (15)	0.0403 (14)	−0.0014 (13)	−0.0053 (13)	0.0029 (11)
C6	0.0305 (13)	0.0445 (15)	0.0344 (12)	0.0013 (11)	0.0015 (10)	0.0047 (11)
C7	0.0401 (17)	0.0647 (19)	0.0495 (15)	0.0122 (15)	0.0068 (14)	0.0010 (13)
C8	0.0335 (14)	0.0447 (16)	0.0338 (12)	0.0021 (12)	0.0013 (11)	0.0039 (10)
C9	0.0375 (14)	0.0372 (14)	0.0321 (12)	0.0020 (11)	−0.0006 (10)	0.0048 (10)
C10	0.0471 (17)	0.0518 (17)	0.0346 (13)	0.0026 (14)	−0.0025 (12)	0.0009 (11)

Geometric parameters (Å, º) top

N2—C12	1.326 (3)	C11—C10	1.362 (4)
N2—C13	1.355 (3)	C11—C12	1.387 (4)
C13—C9	1.411 (3)	C11—H5	1.01 (3)
C13—C4	1.464 (3)	C12—H4	0.97 (2)
C4—N1	1.353 (3)	C3—C2	1.390 (4)
C4—C5	1.415 (3)	C3—H3	1.00 (2)
N1—C3	1.327 (3)	C2—C1	1.360 (3)
C5—C1	1.410 (3)	C2—H2	0.93 (2)
C5—C6	1.429 (3)	C1—H1	0.97 (2)
N3—C7	1.362 (3)	C6—C8	1.372 (3)
N3—C6	1.377 (3)	C7—H7	1.08 (2)
N3—H8	0.92 (3)	C8—C9	1.424 (3)
N4—C7	1.314 (3)	C9—C10	1.403 (3)
N4—C8	1.396 (3)	C10—H6	0.98 (3)

C12—N2—C13	117.0 (2)	C2—C3—H3	120.2 (13)
N2—C13—C9	122.2 (2)	C1—C2—C3	119.2 (2)
N2—C13—C4	117.63 (19)	C1—C2—H2	121.8 (15)
C9—C13—C4	120.2 (2)	C3—C2—H2	119.0 (15)
N1—C4—C5	122.4 (2)	C2—C1—C5	119.3 (2)
N1—C4—C13	117.4 (2)	C2—C1—H1	123.0 (14)
C5—C4—C13	120.16 (19)	C5—C1—H1	117.5 (14)
C3—N1—C4	117.7 (2)	C8—C6—N3	105.7 (2)
C1—C5—C4	117.6 (2)	C8—C6—C5	122.9 (2)
C1—C5—C6	125.2 (2)	N3—C6—C5	131.3 (2)
C4—C5—C6	117.2 (2)	N4—C7—N3	114.5 (2)
C7—N3—C6	105.7 (2)	N4—C7—H7	124.9 (11)
C7—N3—H8	132.4 (17)	N3—C7—H7	120.5 (11)
C6—N3—H8	121.7 (17)	C6—C8—N4	111.3 (2)
C7—N4—C8	102.7 (2)	C6—C8—C9	121.0 (2)
C10—C11—C12	118.6 (2)	N4—C8—C9	127.7 (2)
C10—C11—H5	122.6 (13)	C10—C9—C13	118.2 (2)
C12—C11—H5	118.7 (13)	C10—C9—C8	123.4 (2)
N2—C12—C11	124.8 (2)	C13—C9—C8	118.4 (2)
N2—C12—H4	115.4 (14)	C11—C10—C9	119.2 (2)
C11—C12—H4	119.7 (14)	C11—C10—H6	124.2 (14)
N1—C3—C2	123.9 (2)	C9—C10—H6	116.6 (14)
N1—C3—H3	115.9 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H8···N1ⁱ	0.92 (3)	2.47 (3)	3.104 (3)	126 (2)
N3—H8···N2ⁱ	0.92 (3)	2.18 (3)	3.017 (3)	150 (2)

Symmetry code: (i) x+1/2, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₈N₄
M_r	220.23
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	14.569 (2), 7.8623 (12), 17.042 (3)
V (Å³)	1952.1 (5)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.26 × 0.18 × 0.16

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.980, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	5772, 1756, 1025
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.123, 1.00
No. of reflections	1756
No. of parameters	186
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.15

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H8···N1ⁱ	0.92 (3)	2.47 (3)	3.104 (3)	126 (2)
N3—H8···N2ⁱ	0.92 (3)	2.18 (3)	3.017 (3)	150 (2)

Symmetry code: (i) x+1/2, y, −z+1/2.

Acknowledgements

We acknowledge the Public Science and Technology Research Funds Projects of Ocean (grant No. 2000905021), the Guangdong Oceanic Fisheries Technology Promotion Project [grant No. A2009003–018(c)], the Guangdong Chinese Academy of Science Comprehensive Strategic Cooperation Project (grant No. 2009B091300121) and the Guangdong Province Key Project in the Field of Social Development [grant No. A2009011–007(c)].

References

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