organic compounds
2-(3,4-Dimethoxyphenyl)-1H-benzimidazole
aDepartment of Chemistry, Faculty of Science, Golestan University, Gorgan, Iran, bDepartment of Chemistry, Islamic Azad University, Qaemshahr, Iran, and cInstitute of Physics of the ASCR, v.v.i, Na Slovance 2, 182 21 Praha 8, Czech Republic
*Correspondence e-mail: fejfarov@fzu.cz
In title compound, C15H14N2O2, the dihedral angle between the 3,4-dimethoxyphenyl group and the benzimidazole system is 26.47 (6)°. In the crystal, neighbouring molecules are linked by N—H⋯N hydrogen bonds into C(4) chains propagating along the c-axis direction. The also features weak C—H⋯O interactions.
Related literature
For a related structure, further synthetic details and background references to imidazolines, see: Khalaji et al. (2008). For related structures, see: Kia et al. (2008, 2009); Rashid et al. (2007).
Experimental
Crystal data
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Refinement
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Data collection: CrysAlis PRO (Agilent, 2010); cell CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: JANA2006 (Petříček et al., 2006); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: JANA2006.
Supporting information
https://doi.org/10.1107/S1600536811046897/hb6490sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811046897/hb6490Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536811046897/hb6490Isup3.cml
The synthetic method used for the preparation of (I) was based on previous work (Khalaji et al., 2008), except that 3,4-dimethoxybenzaldehyde (2 mmol) was used. Light yellow slabs of (I) were obtained by evaporation of a methanol solution of (I) held at room temperature. Anal. Calc. for C15H14N2O2 (MW: 254.30): C, 70.85; H, 5.55; N, 11.01%. Found: C, 70.92; H, 5.65; N, 11.08%. Yield: 73%. IR (KBr pellet, cm-1): 2941, 2977, 3006 (CH aliphatic and aromatic), 3054 (s, –C—HN–), 1624 (s, C=N), 1504, 1588, 1606 (C—C aromatic). 1H-NMR (500 MHz, CDCl3, δ(p.p.m.)): 3.82 (s, 3H), 3.87 (s, 3H), 7.11 (d, 1H), 7.17 (dd, 2H), 7.57 (s, 2H), 7.57–7.79 (m, 2H), 12.78 (s, 1H).
All hydrogen atoms were discernible in difference Fourier maps and could be refined to reasonable geometry. According to common practice they were nevertheless kept in ideal positions with C–H distance 0.96 Å during the
The isotropic atomic displacement parameters of hydrogen atoms were evaluated as 1.5×Ueq(C) for methyl groups and 1.2×Ueq(C, N) for all other hydrogen atoms.As part of our ongoing studies of imidazoline derivatives (Khalaji et al., 2008), we now report the synthesis and structure of the title compound, (I).
The dihedral angle between the N1/N2/C1—C7 and C8—C13 aromatic ring planes in (I) is 26.47 (6)°, which is comparable with related structures (Khalaji et al., 2008; Kia et al., 2008, 2009; Rashid et al., 2007). Atoms C14 and C15 in (I) are displaced from the mean plane of the C8—C13 ring by 0.1134 (17) Å and 0.1756 (18) Å, respectively.
In the crystal of (I), an N—H···N hydrogen bond links the molecules into chains propagating in [001] direction (Fig. 2). There are no aromatic π-π stacking interactions in (I) as the closest centroid-centroid separation of aromatic rings is 4.419 (1) Å, which contrasts with the situation in 2-(4-fluorophenyl)-1H-benzimidazole (Rashid et al., 2007) in which both N—H···N and π-π stacking help to establish the packing. The of (I) is further stabilized by weak C—H···O interactions.
For a related structure, further synthetic details and background references to imidazolines, see: Khalaji et al. (2008). For related structures, see: Kia et al. (2008, 2009); Rashid et al. (2007).
Data collection: CrysAlis PRO (Agilent, 2010); cell
CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: JANA2006 (Petříček et al., 2006); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: JANA2006 (Petříček et al., 2006).C15H14N2O2 | F(000) = 536 |
Mr = 254.3 | Dx = 1.315 Mg m−3 |
Orthorhombic, Pca21 | Cu Kα radiation, λ = 1.5418 Å |
Hall symbol: P 2c -2ac | Cell parameters from 8286 reflections |
a = 9.2274 (8) Å | θ = 2.9–67° |
b = 15.0109 (9) Å | µ = 0.72 mm−1 |
c = 9.2681 (3) Å | T = 120 K |
V = 1283.74 (14) Å3 | Slab, light yellow |
Z = 4 | 0.40 × 0.21 × 0.09 mm |
Agilent Xcalibur diffractometer with an Atlas (Gemini ultra Cu) detector | 1982 independent reflections |
Radiation source: Enhance Ultra (Cu) X-ray Source | 1919 reflections with I > 3σ(I) |
Mirror monochromator | Rint = 0.024 |
Detector resolution: 10.3784 pixels mm-1 | θmax = 67.1°, θmin = 2.9° |
Rotation method data acquisition using ω scans | h = −11→11 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010) | k = −17→17 |
Tmin = 0.75, Tmax = 1 | l = −9→11 |
12506 measured reflections |
Refinement on F2 | 54 constraints |
R[F > 3σ(F)] = 0.026 | H atoms treated by a mixture of independent and constrained refinement |
wR(F) = 0.072 | Weighting scheme based on measured s.u.'s w = 1/[σ2(I) + 0.0016I2] |
S = 1.46 | (Δ/σ)max = 0.047 |
1982 reflections | Δρmax = 0.08 e Å−3 |
174 parameters | Δρmin = −0.11 e Å−3 |
0 restraints |
C15H14N2O2 | V = 1283.74 (14) Å3 |
Mr = 254.3 | Z = 4 |
Orthorhombic, Pca21 | Cu Kα radiation |
a = 9.2274 (8) Å | µ = 0.72 mm−1 |
b = 15.0109 (9) Å | T = 120 K |
c = 9.2681 (3) Å | 0.40 × 0.21 × 0.09 mm |
Agilent Xcalibur diffractometer with an Atlas (Gemini ultra Cu) detector | 1982 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010) | 1919 reflections with I > 3σ(I) |
Tmin = 0.75, Tmax = 1 | Rint = 0.024 |
12506 measured reflections |
R[F > 3σ(F)] = 0.026 | 0 restraints |
wR(F) = 0.072 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.46 | Δρmax = 0.08 e Å−3 |
1982 reflections | Δρmin = −0.11 e Å−3 |
174 parameters |
Experimental. CrysAlisPro, Agilent Technologies (2010), Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. |
Refinement. The refinement was carried out against all reflections. The conventional R-factor is always based on F. The goodness of fit as well as the weighted R-factor are based on F and F2 for refinement carried out on F and F2, respectively. The threshold expression is used only for calculating R-factors etc. and it is not relevant to the choice of reflections for refinement. The program used for refinement, Jana2006, uses the weighting scheme based on the experimental expectations, see _refine_ls_weighting_details, that does not force S to be one. Therefore the values of S are usually larger than the ones from the SHELX program. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.50788 (10) | 0.93193 (6) | 0.50931 (11) | 0.0289 (3) | |
O2 | 0.26137 (11) | 0.89618 (7) | 0.39223 (16) | 0.0325 (3) | |
N1 | 0.77384 (12) | 0.66702 (8) | 0.08732 (18) | 0.0233 (3) | |
N2 | 0.86211 (11) | 0.69056 (8) | 0.30939 (17) | 0.0238 (3) | |
C1 | 0.75266 (14) | 0.70471 (9) | 0.21870 (18) | 0.0226 (4) | |
C2 | 0.90804 (14) | 0.62618 (9) | 0.09065 (19) | 0.0228 (4) | |
C3 | 0.98463 (15) | 0.57777 (9) | −0.01205 (19) | 0.0264 (4) | |
C4 | 1.11744 (15) | 0.54402 (10) | 0.0297 (2) | 0.0281 (4) | |
C5 | 1.17424 (16) | 0.55964 (9) | 0.1677 (2) | 0.0285 (4) | |
C6 | 1.09725 (15) | 0.60805 (9) | 0.2701 (2) | 0.0268 (4) | |
C7 | 0.96186 (14) | 0.64097 (9) | 0.2299 (2) | 0.0228 (4) | |
C8 | 0.62258 (13) | 0.75563 (9) | 0.25552 (18) | 0.0238 (4) | |
C9 | 0.63170 (14) | 0.82035 (9) | 0.36407 (19) | 0.0238 (4) | |
C10 | 0.51002 (15) | 0.86699 (9) | 0.4062 (2) | 0.0244 (4) | |
C11 | 0.37543 (14) | 0.84855 (10) | 0.34023 (19) | 0.0261 (4) | |
C12 | 0.36736 (14) | 0.78589 (11) | 0.2312 (2) | 0.0293 (4) | |
C13 | 0.49052 (15) | 0.73941 (10) | 0.1886 (2) | 0.0277 (4) | |
C14 | 0.63841 (15) | 0.94452 (11) | 0.5909 (2) | 0.0311 (4) | |
C15 | 0.12101 (16) | 0.87431 (12) | 0.3367 (2) | 0.0413 (5) | |
H3 | 0.947018 | 0.568253 | −0.107386 | 0.0316* | |
H4 | 1.172283 | 0.508955 | −0.037558 | 0.0337* | |
H5 | 1.268095 | 0.53647 | 0.191941 | 0.0342* | |
H6 | 1.135836 | 0.618397 | 0.364821 | 0.0322* | |
H9 | 0.723198 | 0.832316 | 0.409397 | 0.0286* | |
H12 | 0.276306 | 0.774417 | 0.184648 | 0.0352* | |
H13 | 0.48424 | 0.696024 | 0.112722 | 0.0333* | |
H14a | 0.62263 | 0.989168 | 0.663353 | 0.0467* | |
H14b | 0.665129 | 0.889441 | 0.636306 | 0.0467* | |
H14c | 0.714823 | 0.963371 | 0.527559 | 0.0467* | |
H15a | 0.049359 | 0.91136 | 0.381853 | 0.062* | |
H15b | 0.119532 | 0.883995 | 0.234322 | 0.062* | |
H15c | 0.10002 | 0.812894 | 0.356683 | 0.062* | |
H1 | 0.7167 (18) | 0.6702 (11) | 0.008 (2) | 0.028* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0310 (5) | 0.0286 (5) | 0.0270 (6) | 0.0021 (4) | −0.0007 (4) | −0.0067 (4) |
O2 | 0.0253 (5) | 0.0362 (6) | 0.0359 (6) | 0.0074 (4) | −0.0002 (4) | −0.0064 (5) |
N1 | 0.0238 (5) | 0.0285 (6) | 0.0176 (6) | 0.0003 (4) | −0.0005 (5) | −0.0009 (5) |
N2 | 0.0239 (5) | 0.0289 (6) | 0.0186 (6) | 0.0017 (4) | 0.0007 (4) | −0.0010 (5) |
C1 | 0.0249 (6) | 0.0252 (6) | 0.0178 (6) | −0.0029 (5) | 0.0022 (5) | 0.0003 (5) |
C2 | 0.0240 (6) | 0.0233 (6) | 0.0209 (7) | −0.0025 (5) | 0.0012 (6) | 0.0026 (5) |
C3 | 0.0316 (7) | 0.0282 (7) | 0.0193 (7) | −0.0032 (6) | 0.0030 (5) | −0.0011 (5) |
C4 | 0.0299 (7) | 0.0274 (7) | 0.0268 (7) | 0.0015 (5) | 0.0081 (6) | −0.0009 (6) |
C5 | 0.0260 (7) | 0.0315 (7) | 0.0281 (7) | 0.0037 (6) | 0.0017 (6) | 0.0022 (6) |
C6 | 0.0262 (6) | 0.0319 (7) | 0.0224 (8) | 0.0003 (5) | −0.0016 (5) | −0.0005 (6) |
C7 | 0.0241 (6) | 0.0250 (7) | 0.0193 (7) | −0.0016 (5) | 0.0035 (6) | 0.0004 (5) |
C8 | 0.0255 (7) | 0.0255 (7) | 0.0205 (7) | 0.0008 (5) | 0.0008 (5) | 0.0014 (5) |
C9 | 0.0247 (6) | 0.0264 (7) | 0.0204 (7) | −0.0004 (5) | −0.0001 (5) | 0.0020 (6) |
C10 | 0.0304 (7) | 0.0236 (7) | 0.0193 (7) | −0.0002 (5) | 0.0023 (5) | 0.0015 (6) |
C11 | 0.0265 (7) | 0.0280 (7) | 0.0238 (7) | 0.0028 (5) | 0.0033 (5) | 0.0019 (6) |
C12 | 0.0259 (7) | 0.0362 (8) | 0.0258 (8) | 0.0018 (5) | −0.0037 (6) | −0.0014 (6) |
C13 | 0.0303 (7) | 0.0314 (7) | 0.0215 (7) | −0.0001 (6) | −0.0013 (5) | −0.0030 (6) |
C14 | 0.0336 (7) | 0.0308 (8) | 0.0291 (8) | −0.0019 (5) | −0.0021 (6) | −0.0070 (6) |
C15 | 0.0282 (8) | 0.0531 (10) | 0.0428 (11) | 0.0092 (7) | −0.0067 (7) | −0.0144 (8) |
O1—C10 | 1.3651 (18) | C6—C7 | 1.3942 (19) |
O1—C14 | 1.4345 (18) | C6—H6 | 0.96 |
O2—C11 | 1.3606 (18) | C8—C9 | 1.401 (2) |
O2—C15 | 1.4319 (19) | C8—C13 | 1.389 (2) |
N1—C1 | 1.357 (2) | C9—C10 | 1.380 (2) |
N1—C2 | 1.3820 (17) | C9—H9 | 0.96 |
N1—H1 | 0.903 (19) | C10—C11 | 1.412 (2) |
N2—C1 | 1.331 (2) | C11—C12 | 1.383 (2) |
N2—C7 | 1.3943 (19) | C12—C13 | 1.391 (2) |
C1—C8 | 1.4633 (19) | C12—H12 | 0.96 |
C2—C3 | 1.391 (2) | C13—H13 | 0.96 |
C2—C7 | 1.401 (2) | C14—H14a | 0.96 |
C3—C4 | 1.381 (2) | C14—H14b | 0.96 |
C3—H3 | 0.96 | C14—H14c | 0.96 |
C4—C5 | 1.402 (3) | C15—H15a | 0.96 |
C4—H4 | 0.96 | C15—H15b | 0.96 |
C5—C6 | 1.391 (2) | C15—H15c | 0.96 |
C5—H5 | 0.96 | ||
C10—O1—C14 | 116.79 (11) | C9—C8—C13 | 119.67 (12) |
C11—O2—C15 | 116.86 (13) | C8—C9—C10 | 120.42 (13) |
C1—N1—C2 | 107.09 (13) | C8—C9—H9 | 119.7897 |
C1—N1—H1 | 128.4 (11) | C10—C9—H9 | 119.7883 |
C2—N1—H1 | 124.4 (11) | O1—C10—C9 | 124.92 (13) |
C1—N2—C7 | 104.62 (14) | O1—C10—C11 | 115.50 (12) |
N1—C1—N2 | 113.01 (12) | C9—C10—C11 | 119.59 (15) |
N1—C1—C8 | 123.04 (13) | O2—C11—C10 | 115.09 (14) |
N2—C1—C8 | 123.95 (15) | O2—C11—C12 | 125.08 (13) |
N1—C2—C3 | 132.21 (16) | C10—C11—C12 | 119.83 (13) |
N1—C2—C7 | 105.55 (13) | C11—C12—C13 | 120.32 (13) |
C3—C2—C7 | 122.23 (13) | C11—C12—H12 | 119.839 |
C2—C3—C4 | 116.80 (16) | C13—C12—H12 | 119.8382 |
C2—C3—H3 | 121.5999 | C8—C13—C12 | 120.14 (15) |
C4—C3—H3 | 121.5996 | C8—C13—H13 | 119.9308 |
C3—C4—C5 | 121.72 (15) | C12—C13—H13 | 119.9316 |
C3—C4—H4 | 119.1383 | O1—C14—H14a | 109.4704 |
C5—C4—H4 | 119.138 | O1—C14—H14b | 109.4712 |
C4—C5—C6 | 121.28 (14) | O1—C14—H14c | 109.4714 |
C4—C5—H5 | 119.362 | H14a—C14—H14b | 109.4712 |
C6—C5—H5 | 119.3623 | H14a—C14—H14c | 109.471 |
C5—C6—C7 | 117.42 (16) | H14b—C14—H14c | 109.4722 |
C5—C6—H6 | 121.2877 | O2—C15—H15a | 109.4714 |
C7—C6—H6 | 121.2879 | O2—C15—H15b | 109.4715 |
N2—C7—C2 | 109.72 (12) | O2—C15—H15c | 109.4712 |
N2—C7—C6 | 129.76 (16) | H15a—C15—H15b | 109.4715 |
C2—C7—C6 | 120.52 (14) | H15a—C15—H15c | 109.4712 |
C1—C8—C9 | 118.71 (12) | H15b—C15—H15c | 109.4705 |
C1—C8—C13 | 121.59 (14) | ||
C9—C10—O1—C14 | −7.8 (2) | N1—C1—C8—C9 | −154.38 (14) |
C10—C11—O2—C15 | −174.97 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14c···O2i | 0.96 | 2.49 | 3.224 (2) | 133 |
C15—H15b···O1ii | 0.96 | 2.50 | 3.372 (2) | 151 |
N1—H1···N2iii | 0.903 (19) | 2.01 (2) | 2.887 (2) | 164.6 (16) |
Symmetry codes: (i) x+1/2, −y+2, z; (ii) −x+1/2, y, z−1/2; (iii) −x+3/2, y, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C15H14N2O2 |
Mr | 254.3 |
Crystal system, space group | Orthorhombic, Pca21 |
Temperature (K) | 120 |
a, b, c (Å) | 9.2274 (8), 15.0109 (9), 9.2681 (3) |
V (Å3) | 1283.74 (14) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 0.72 |
Crystal size (mm) | 0.40 × 0.21 × 0.09 |
Data collection | |
Diffractometer | Agilent Xcalibur diffractometer with an Atlas (Gemini ultra Cu) detector |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2010) |
Tmin, Tmax | 0.75, 1 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 12506, 1982, 1919 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.598 |
Refinement | |
R[F > 3σ(F)], wR(F), S | 0.026, 0.072, 1.46 |
No. of reflections | 1982 |
No. of parameters | 174 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.08, −0.11 |
Computer programs: CrysAlis PRO (Agilent, 2010), SIR2002 (Burla et al., 2003), JANA2006 (Petříček et al., 2006), DIAMOND (Brandenburg & Putz, 2005).
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14c···O2i | 0.96 | 2.49 | 3.224 (2) | 133 |
C15—H15b···O1ii | 0.96 | 2.50 | 3.372 (2) | 151 |
N1—H1···N2iii | 0.903 (19) | 2.01 (2) | 2.887 (2) | 164.6 (16) |
Symmetry codes: (i) x+1/2, −y+2, z; (ii) −x+1/2, y, z−1/2; (iii) −x+3/2, y, z−1/2. |
Acknowledgements
We acknowledge Golestan University and the Islamic Azad University, Qaemshahr, for partial support of this work, the Institutional Research Plan No. AVOZ10100521 of the Institute of Physics and the Praemium Academiae Project of the Academy of Sciences of the Czech Republic.
References
Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Burla, M. C., Camalli, M., Carrozzini, B., Cascarano, G. L., Giacovazzo, C., Polidori, G. & Spagna, R. (2003). J. Appl. Cryst. 36, 1103. CrossRef IUCr Journals Google Scholar
Khalaji, A. D., Jian, F., Xiao, H. & Harrison, W. T. A. (2008). Acta Cryst. E64, o1093. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kia, R., Fun, H.-K. & Kargar, H. (2008). Acta Cryst. E64, o2406. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kia, R., Fun, H.-K. & Kargar, H. (2009). Acta Cryst. E65, o338–o339. Web of Science CSD CrossRef IUCr Journals Google Scholar
Petříček, V., Dušek, M. & Palatinus, L. (2006). JANA2006. Institute of Physics, Praha, Czech Republic. Google Scholar
Rashid, N., Tahir, M. K., Kanwal, S., Yusof, N. M. & Yamin, B. M. (2007). Acta Cryst. E63, o1402–o1403. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
As part of our ongoing studies of imidazoline derivatives (Khalaji et al., 2008), we now report the synthesis and structure of the title compound, (I).
The dihedral angle between the N1/N2/C1—C7 and C8—C13 aromatic ring planes in (I) is 26.47 (6)°, which is comparable with related structures (Khalaji et al., 2008; Kia et al., 2008, 2009; Rashid et al., 2007). Atoms C14 and C15 in (I) are displaced from the mean plane of the C8—C13 ring by 0.1134 (17) Å and 0.1756 (18) Å, respectively.
In the crystal of (I), an N—H···N hydrogen bond links the molecules into chains propagating in [001] direction (Fig. 2). There are no aromatic π-π stacking interactions in (I) as the closest centroid-centroid separation of aromatic rings is 4.419 (1) Å, which contrasts with the situation in 2-(4-fluorophenyl)-1H-benzimidazole (Rashid et al., 2007) in which both N—H···N and π-π stacking help to establish the packing. The crystal structure of (I) is further stabilized by weak C—H···O interactions.