3-(1H-Imidazo[4,5-f][1,10]phenanthrolin-2-yl)benzonitrile methanol solvate

Wang, W.-L.

doi:10.1107/S1600536809051472

organic compounds

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Volume 66| Part 1| January 2010| Page o55

doi:10.1107/S1600536809051472

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3-(1H-Imidazo[4,5-f][1,10]phenanthrolin-2-yl)benzonitrile methanol solvate

Wen-Lan Wang ^a ^*

^aCollege of Chemistry and Biology, Beihua University, Jilin City 132013, People's Republic of China
^*Correspondence e-mail: wenlan1964@yeah.net

(Received 28 November 2009; accepted 29 November 2009; online 4 December 2009)

In the title compound, C₂₀H₁₁N₅·CH₃OH, the benzene ring is twisted by a small dihedral angle of 1.89 (11)° with respect to the imidazo[4,5-f][1,10]phenanthroline ring system. N—H⋯O and O—H⋯N hydrogen bonding is present in the crystal structure.

Related literature

For related structures, see: Sun et al. (2007 ); Yin (2008 ); Zhang et al. (2008 ).

Experimental

Crystal data

C₂₀H₁₁N₅·CH₄O
M_r = 353.38
Monoclinic, P 2₁ /n
a = 7.115 (1) Å
b = 18.385 (2) Å
c = 13.5576 (12) Å
β = 99.956 (19)°
V = 1746.7 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.30 × 0.28 × 0.26 mm

Data collection

Rigaku, SCXmini diffractometer
15971 measured reflections
3432 independent reflections
2018 reflections with I > 2σ(I)
R_int = 0.099

Refinement

R[F² > 2σ(F²)] = 0.072
wR(F²) = 0.179
S = 1.04
3432 reflections
245 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3B⋯O1	0.86	1.95	2.803 (3)	174
O1—H1E⋯N5ⁱ	0.98	1.89	2.857 (3)	168
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809051472/xu2700sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809051472/xu2700Isup2.hkl

checkCIF report

Comment top

1,10-Phenanthroline and its derivatives are commonly used as ligands in metal-organic coordination polymers (Sun et al., 2007; Yin, 2008; Zhang et al., 2008). The title compound was synthesized from 1,10-phenanthroline-5,6-dione.

The asymmetric unit of the title compound, C₂₀H₁₁N₅.CH₃OH, contains one organic molecule and one solvent methanol molecule (Fig.1). The molecules are connected by N—H···O and O—H···N hydrogen bonding to form a one-dimensional chain (Fig. 2). The organic molecule is essentially planar.

Related literature top

For applications of phenanthroline derivatives, see: Yin (2008); Zhang et al. (2008). For a related structure, see: Sun et al. (2007).

Experimental top

1,10-Phenanthroline-5,6-dione (1.5 mmol) and 3-cyanobenzaldehyde (1.5 mmol) were dissolved in CH₃COOH and CH₃COONH₄ (1:1) solution (30 ml). The mixture was refluxed for 1.5 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-methanol solution.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound with atom labels. Displacement ellipsoids were drawn at the 30% probability level.
	Fig. 2. The packing viewed along the b axis. Hydrogen bonds are drawn as dashed lines

3-(1H-Imidazo[4,5-f][1,10]phenanthrolin-2-yl)benzonitrile methanol solvate top

Crystal data top

C₂₀H₁₁N₅·CH₄O	F(000) = 736
M_r = 353.38	D_x = 1.344 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2018 reflections
a = 7.115 (1) Å	θ = 3.0–26.0°
b = 18.385 (2) Å	µ = 0.09 mm⁻¹
c = 13.5576 (12) Å	T = 293 K
β = 99.956 (19)°	Block, colorless
V = 1746.7 (4) Å³	0.30 × 0.28 × 0.26 mm
Z = 4

Data collection top

Rigaku, SCXmini diffractometer	2018 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.099
Graphite monochromator	θ_max = 26.0°, θ_min = 3.0°
Detector resolution: 13.6612 pixels mm^-1	h = −8→8
ω scan	k = −22→22
15971 measured reflections	l = −16→16
3432 independent reflections

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)] = 0.072	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.179	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0784P)² + 0.0647P] where P = (F_o² + 2F_c²)/3
3432 reflections	(Δ/σ)_max < 0.001
245 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₂₀H₁₁N₅·CH₄O	V = 1746.7 (4) Å³
M_r = 353.38	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.115 (1) Å	µ = 0.09 mm⁻¹
b = 18.385 (2) Å	T = 293 K
c = 13.5576 (12) Å	0.30 × 0.28 × 0.26 mm
β = 99.956 (19)°

Data collection top

Rigaku, SCXmini diffractometer	2018 reflections with I > 2σ(I)
15971 measured reflections	R_int = 0.099
3432 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.072	0 restraints
wR(F²) = 0.179	H-atom parameters constrained
S = 1.04	Δρ_max = 0.18 e Å⁻³
3432 reflections	Δρ_min = −0.19 e Å⁻³
245 parameters

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	U_iso*/U_eq
C1	0.6541 (5)	−0.05805 (18)	0.7761 (3)	0.0518 (8)
C2	0.6702 (4)	−0.07430 (16)	0.6737 (2)	0.0430 (7)
C3	0.6441 (4)	−0.14493 (17)	0.6377 (3)	0.0510 (8)
H3A	0.6173	−0.1822	0.6795	0.061*
C4	0.6581 (5)	−0.15944 (17)	0.5396 (3)	0.0538 (9)
H4A	0.6398	−0.2066	0.5152	0.065*
C5	0.6993 (4)	−0.10430 (17)	0.4769 (2)	0.0501 (8)
H5A	0.7079	−0.1149	0.4107	0.060*
C6	0.7281 (4)	−0.03325 (15)	0.5117 (2)	0.0386 (7)
C7	0.7123 (4)	−0.01864 (16)	0.6113 (2)	0.0407 (7)
H7A	0.7300	0.0285	0.6360	0.049*
C8	0.7695 (4)	0.02402 (15)	0.4435 (2)	0.0391 (7)
C9	0.8262 (4)	0.08115 (15)	0.3144 (2)	0.0388 (7)
C10	0.8600 (4)	0.10077 (16)	0.2162 (2)	0.0391 (7)
C11	0.8394 (4)	0.05275 (17)	0.1346 (2)	0.0490 (8)
H11A	0.7998	0.0051	0.1413	0.059*
C12	0.8787 (5)	0.07721 (19)	0.0448 (2)	0.0567 (9)
H12A	0.8629	0.0470	−0.0110	0.068*
C13	0.9430 (5)	0.14836 (19)	0.0393 (2)	0.0596 (10)
H13A	0.9758	0.1633	−0.0210	0.072*
C14	0.9157 (4)	0.17313 (16)	0.2013 (2)	0.0411 (7)
C15	0.9232 (4)	0.22708 (16)	0.2820 (2)	0.0407 (7)
C16	0.9749 (5)	0.34573 (18)	0.3349 (3)	0.0622 (10)
H16A	1.0103	0.3930	0.3221	0.075*
C17	0.9213 (5)	0.33164 (18)	0.4271 (2)	0.0592 (9)
H17A	0.9197	0.3687	0.4737	0.071*
C18	0.8714 (5)	0.26248 (17)	0.4477 (2)	0.0511 (8)
H18A	0.8365	0.2515	0.5090	0.061*
C19	0.8732 (4)	0.20771 (15)	0.3752 (2)	0.0388 (7)
C20	0.8320 (4)	0.13278 (15)	0.3885 (2)	0.0371 (7)
C21	0.9291 (6)	0.1623 (3)	0.7300 (3)	0.1045 (16)
H21A	0.9003	0.1877	0.7875	0.157*
H21B	1.0353	0.1853	0.7075	0.157*
H21C	0.9610	0.1127	0.7478	0.157*
N1	0.6392 (5)	−0.04524 (19)	0.8570 (2)	0.0749 (9)
N2	0.7870 (3)	0.01301 (12)	0.34899 (16)	0.0406 (6)
N3	0.7950 (3)	0.09555 (12)	0.47126 (17)	0.0390 (6)
H3B	0.7891	0.1137	0.5291	0.047*
N4	0.9610 (4)	0.19635 (14)	0.11301 (19)	0.0550 (7)
N5	0.9787 (4)	0.29620 (13)	0.26399 (19)	0.0513 (7)
O1	0.7700 (4)	0.16399 (13)	0.65327 (16)	0.0640 (7)
H1E	0.6578	0.1781	0.6823	0.14 (2)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.050 (2)	0.061 (2)	0.044 (2)	−0.0024 (16)	0.0072 (16)	0.0113 (16)
C2	0.0349 (16)	0.050 (2)	0.0432 (18)	0.0017 (13)	0.0034 (14)	0.0069 (14)
C3	0.051 (2)	0.0400 (19)	0.063 (2)	−0.0021 (14)	0.0118 (17)	0.0147 (16)
C4	0.055 (2)	0.0383 (19)	0.070 (2)	−0.0027 (14)	0.0155 (18)	−0.0017 (17)
C5	0.0488 (19)	0.050 (2)	0.052 (2)	−0.0018 (15)	0.0117 (16)	−0.0018 (16)
C6	0.0300 (16)	0.0410 (17)	0.0446 (17)	0.0024 (12)	0.0063 (13)	0.0044 (13)
C7	0.0409 (17)	0.0381 (17)	0.0426 (18)	−0.0026 (13)	0.0060 (14)	0.0031 (13)
C8	0.0345 (16)	0.0416 (17)	0.0414 (17)	0.0021 (12)	0.0074 (13)	0.0001 (13)
C9	0.0359 (16)	0.0419 (18)	0.0382 (16)	−0.0003 (12)	0.0051 (13)	0.0016 (13)
C10	0.0351 (16)	0.0460 (18)	0.0361 (16)	0.0024 (13)	0.0062 (13)	−0.0013 (13)
C11	0.053 (2)	0.0483 (19)	0.0457 (19)	0.0018 (15)	0.0095 (16)	−0.0034 (15)
C12	0.070 (2)	0.062 (2)	0.0386 (19)	0.0111 (17)	0.0105 (17)	−0.0064 (16)
C13	0.078 (3)	0.066 (2)	0.0375 (19)	0.0088 (19)	0.0183 (17)	0.0087 (17)
C14	0.0407 (17)	0.0470 (19)	0.0357 (16)	0.0054 (13)	0.0071 (13)	0.0038 (13)
C15	0.0378 (17)	0.0422 (18)	0.0422 (17)	0.0020 (13)	0.0077 (14)	0.0027 (13)
C16	0.087 (3)	0.0392 (19)	0.063 (2)	−0.0115 (17)	0.021 (2)	−0.0003 (17)
C17	0.079 (3)	0.049 (2)	0.052 (2)	−0.0060 (17)	0.0183 (18)	−0.0075 (16)
C18	0.064 (2)	0.049 (2)	0.0429 (18)	−0.0016 (16)	0.0161 (16)	−0.0037 (15)
C19	0.0389 (17)	0.0409 (18)	0.0377 (16)	0.0005 (12)	0.0099 (13)	−0.0005 (13)
C20	0.0347 (16)	0.0436 (18)	0.0345 (16)	0.0030 (12)	0.0103 (13)	0.0041 (13)
C21	0.082 (3)	0.134 (4)	0.092 (3)	0.011 (3)	−0.002 (3)	−0.042 (3)
N1	0.071 (2)	0.100 (3)	0.053 (2)	−0.0063 (18)	0.0090 (17)	0.0078 (18)
N2	0.0423 (15)	0.0424 (15)	0.0386 (14)	−0.0004 (11)	0.0114 (11)	0.0001 (11)
N3	0.0434 (14)	0.0430 (15)	0.0322 (13)	0.0006 (11)	0.0110 (11)	−0.0003 (11)
N4	0.073 (2)	0.0573 (18)	0.0366 (15)	0.0024 (14)	0.0161 (14)	0.0035 (13)
N5	0.0651 (18)	0.0425 (16)	0.0489 (16)	−0.0064 (13)	0.0171 (13)	−0.0016 (12)
O1	0.0695 (17)	0.0778 (17)	0.0474 (14)	0.0083 (13)	0.0177 (13)	−0.0119 (12)

Geometric parameters (Å, º) top

C1—N1	1.145 (4)	C12—H12A	0.9300
C1—C2	1.444 (4)	C13—N4	1.323 (4)
C2—C3	1.388 (4)	C13—H13A	0.9300
C2—C7	1.393 (4)	C14—N4	1.361 (4)
C3—C4	1.376 (4)	C14—C15	1.471 (4)
C3—H3A	0.9300	C15—N5	1.365 (4)
C4—C5	1.387 (4)	C15—C19	1.416 (4)
C4—H4A	0.9300	C16—N5	1.328 (4)
C5—C6	1.392 (4)	C16—C17	1.393 (4)
C5—H5A	0.9300	C16—H16A	0.9300
C6—C7	1.400 (4)	C17—C18	1.362 (4)
C6—C8	1.465 (4)	C17—H17A	0.9300
C7—H7A	0.9300	C18—C19	1.409 (4)
C8—N2	1.324 (3)	C18—H18A	0.9300
C8—N3	1.371 (3)	C19—C20	1.426 (4)
C9—C20	1.378 (4)	C20—N3	1.377 (3)
C9—N2	1.383 (3)	C21—O1	1.400 (4)
C9—C10	1.439 (4)	C21—H21A	0.9600
C10—C11	1.403 (4)	C21—H21B	0.9600
C10—C14	1.412 (4)	C21—H21C	0.9600
C11—C12	1.371 (4)	N3—H3B	0.8600
C11—H11A	0.9300	O1—H1E	0.9842
C12—C13	1.392 (5)

N1—C1—C2	179.2 (4)	C12—C13—H13A	117.4
C3—C2—C7	120.2 (3)	N4—C14—C10	122.4 (3)
C3—C2—C1	120.2 (3)	N4—C14—C15	117.3 (3)
C7—C2—C1	119.5 (3)	C10—C14—C15	120.3 (3)
C4—C3—C2	119.6 (3)	N5—C15—C19	121.3 (3)
C4—C3—H3A	120.2	N5—C15—C14	118.0 (3)
C2—C3—H3A	120.2	C19—C15—C14	120.8 (3)
C3—C4—C5	120.6 (3)	N5—C16—C17	124.4 (3)
C3—C4—H4A	119.7	N5—C16—H16A	117.8
C5—C4—H4A	119.7	C17—C16—H16A	117.8
C4—C5—C6	120.8 (3)	C18—C17—C16	118.6 (3)
C4—C5—H5A	119.6	C18—C17—H17A	120.7
C6—C5—H5A	119.6	C16—C17—H17A	120.7
C5—C6—C7	118.4 (3)	C17—C18—C19	119.3 (3)
C5—C6—C8	119.6 (3)	C17—C18—H18A	120.3
C7—C6—C8	122.0 (3)	C19—C18—H18A	120.3
C2—C7—C6	120.4 (3)	C18—C19—C15	118.5 (3)
C2—C7—H7A	119.8	C18—C19—C20	125.1 (3)
C6—C7—H7A	119.8	C15—C19—C20	116.4 (3)
N2—C8—N3	112.4 (2)	N3—C20—C9	105.4 (2)
N2—C8—C6	124.3 (3)	N3—C20—C19	131.0 (3)
N3—C8—C6	123.2 (3)	C9—C20—C19	123.6 (3)
C20—C9—N2	111.0 (3)	O1—C21—H21A	109.5
C20—C9—C10	120.9 (3)	O1—C21—H21B	109.5
N2—C9—C10	128.1 (3)	H21A—C21—H21B	109.5
C11—C10—C14	118.3 (3)	O1—C21—H21C	109.5
C11—C10—C9	124.1 (3)	H21A—C21—H21C	109.5
C14—C10—C9	117.6 (3)	H21B—C21—H21C	109.5
C12—C11—C10	119.0 (3)	C8—N2—C9	104.4 (2)
C12—C11—H11A	120.5	C8—N3—C20	106.8 (2)
C10—C11—H11A	120.5	C8—N3—H3B	126.6
C11—C12—C13	118.4 (3)	C20—N3—H3B	126.6
C11—C12—H12A	120.8	C13—N4—C14	116.7 (3)
C13—C12—H12A	120.8	C16—N5—C15	117.8 (3)
N4—C13—C12	125.2 (3)	C21—O1—H1E	108.4
N4—C13—H13A	117.4

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···O1	0.86	1.95	2.803 (3)	174
O1—H1E···N5ⁱ	0.98	1.89	2.857 (3)	168

Symmetry code: (i) x−1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₀H₁₁N₅·CH₄O
M_r	353.38
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	7.115 (1), 18.385 (2), 13.5576 (12)
β (°)	99.956 (19)
V (Å³)	1746.7 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.28 × 0.26

Data collection
Diffractometer	Rigaku, SCXmini diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	15971, 3432, 2018
R_int	0.099
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.072, 0.179, 1.04
No. of reflections	3432
No. of parameters	245
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.19

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···O1	0.86	1.95	2.803 (3)	174.2
O1—H1E···N5ⁱ	0.98	1.89	2.857 (3)	167.9

Symmetry code: (i) x−1/2, −y+1/2, z+1/2.

Acknowledgements

This work was supported by a start-up grant from Beihua University, China.

References

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