Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807033612/xu2292sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807033612/xu2292Isup2.hkl |
CCDC reference: 657743
To phenylenediamine (3.67 g, 0.034 mol) in propylene glycol (50 ml) was added 4-hydroxybenzoic acid (4.69 g, 0.034 mol), and the solution refluxed for 24 h and then cooled to room temperature. Ice cold water (50 ml) was then added to force the precipitation of a brown solid which was collected and dissolved in hot methanol. The solution is filtered over activated carbon and the filtrate was allowed to evaporate slowly to give single crystals (yield 6.15 g, 86%).
H atoms on C and O atoms were placed in idealized positions, and refined in riding mode with Uiso(H) = 1.2Ueq(C) or Uiso(O). H atom on N atom was located in a difference Fourier map and refined isotropically.
The ligands containing benzimidazolyl substituent(s), which could provide hydrogen bond donor NH groups and π-π stacking interaction, have being extensively investigated now (Cai, Chen et al., 2003). As a part of the structural studies of benzimidazolyl series (Cai et al., 2002; Cai, Su et al. 2003) here we report the synthesis and structure of the title compound.
Fig. 1 shows an ORTEP diagram of the compound together with the atom numbering scheme. The benzimidazolyl ring is almost coplanar to phenol ring with 8.11 (1)° of dihedral angle in the molecule. The dihedral angle between two perpendicular sheet-like molecules is 86.19 (6)° in the crystal structure, which are connected by hydrogen bondings N—H···O [O···N 2.856 (1) Å, H···O 2.012 (2) Å, N—H···O 158.8 (1)° [symmetry code: x - 1/2,-y + 1/2,z + 1/2] and O—H···N [O···N 2.652 (1) Å, H···O 1.843 (1) Å, O—H···N 173.5 (2)° [symmetry code: x - 1/2,-y + 1/2,z - 1/2] to form an infinite wave-like two-dimensional layer, while the three-dimensional network structure is constructed by face-to-face π-π stacking interaction, the shortest distance between benzimidazole ring and phenol ring is 3.554 Å.
For general background, see Cai, Chen et al. (2003). For related structures, see Cai, Su et al. (2003); Su et al. (2002).
For related literature, see: Cai (2002).
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.
Fig. 1. The structure of title molecule. The atom-numbering scheme is shown at the 30% probability level. | |
Fig. 2. A view of the molecular network parallel to (101) |
C13H10N2O | F(000) = 440 |
Mr = 210.23 | Dx = 1.298 Mg m−3 |
Monoclinic, P21/n | Melting point: 508 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 7.1679 (3) Å | Cell parameters from 5172 reflections |
b = 15.1517 (6) Å | θ = 2.4–27.5° |
c = 9.9079 (4) Å | µ = 0.09 mm−1 |
β = 90.556 (2)° | T = 298 K |
V = 1076.01 (8) Å3 | Block, colourless |
Z = 4 | 0.22 × 0.17 × 0.13 mm |
Bruker SMART CCD area-detector diffractometer | 2092 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.019 |
Graphite monochromator | θmax = 27.5°, θmin = 2.4° |
φ and ω scans | h = −9→9 |
10089 measured reflections | k = −19→15 |
2464 independent reflections | l = −12→12 |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.103 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0496P)2 + 0.1927P] where P = (Fo2 + 2Fc2)/3 |
2464 reflections | (Δ/σ)max < 0.001 |
149 parameters | Δρmax = 0.16 e Å−3 |
1 restraint | Δρmin = −0.17 e Å−3 |
C13H10N2O | V = 1076.01 (8) Å3 |
Mr = 210.23 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.1679 (3) Å | µ = 0.09 mm−1 |
b = 15.1517 (6) Å | T = 298 K |
c = 9.9079 (4) Å | 0.22 × 0.17 × 0.13 mm |
β = 90.556 (2)° |
Bruker SMART CCD area-detector diffractometer | 2092 reflections with I > 2σ(I) |
10089 measured reflections | Rint = 0.019 |
2464 independent reflections |
R[F2 > 2σ(F2)] = 0.037 | 1 restraint |
wR(F2) = 0.103 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.16 e Å−3 |
2464 reflections | Δρmin = −0.17 e Å−3 |
149 parameters |
Experimental. The assigned structure was substantiated by EA and MS data. Elemental analysis calculated for C13H10N2O: C, 74.27; H, 4.79; N, 13.33; found: C, 73.98; H, 4.87; N, 13.28. FAB-MS m/z (%): 211(M++1, 68), 210(M+, 100). |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.12380 (10) | 0.35627 (6) | 0.15835 (9) | 0.0498 (2) | |
H1A | 0.0185 | 0.3760 | 0.1462 | 0.075* | |
N2 | 0.29490 (13) | 0.06719 (6) | 0.61996 (10) | 0.0455 (2) | |
N1 | −0.01358 (12) | 0.06759 (6) | 0.63364 (10) | 0.0406 (2) | |
C1 | 0.24064 (16) | 0.00742 (8) | 0.71879 (12) | 0.0460 (3) | |
C2 | 0.3466 (2) | −0.04686 (10) | 0.80335 (16) | 0.0646 (4) | |
H2 | 0.4761 | −0.0477 | 0.7984 | 0.078* | |
C3 | 0.2541 (2) | −0.09910 (10) | 0.89419 (16) | 0.0691 (4) | |
H3 | 0.3225 | −0.1360 | 0.9511 | 0.083* | |
C4 | 0.0615 (2) | −0.09817 (9) | 0.90314 (14) | 0.0614 (4) | |
H4 | 0.0036 | −0.1344 | 0.9659 | 0.074* | |
C5 | −0.04601 (19) | −0.04497 (9) | 0.82150 (13) | 0.0522 (3) | |
H5 | −0.1754 | −0.0442 | 0.8278 | 0.063* | |
C6 | 0.04717 (15) | 0.00766 (7) | 0.72905 (11) | 0.0412 (3) | |
C7 | 0.13874 (14) | 0.10192 (7) | 0.57169 (11) | 0.0381 (2) | |
C8 | 0.12968 (14) | 0.16878 (7) | 0.46561 (10) | 0.0381 (2) | |
C9 | 0.29061 (15) | 0.19137 (8) | 0.39541 (12) | 0.0448 (3) | |
H9 | 0.4029 | 0.1639 | 0.4175 | 0.054* | |
C10 | 0.28632 (15) | 0.25331 (8) | 0.29430 (12) | 0.0467 (3) | |
H10 | 0.3953 | 0.2671 | 0.2487 | 0.056* | |
C11 | 0.12059 (15) | 0.29563 (8) | 0.25943 (11) | 0.0407 (3) | |
C12 | −0.04087 (15) | 0.27377 (8) | 0.32846 (12) | 0.0446 (3) | |
H12 | −0.1528 | 0.3016 | 0.3065 | 0.054* | |
C13 | −0.03603 (15) | 0.21105 (8) | 0.42931 (11) | 0.0435 (3) | |
H13 | −0.1455 | 0.1967 | 0.4739 | 0.052* | |
H1 | −0.1306 (13) | 0.0848 (9) | 0.6208 (13) | 0.052* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0285 (4) | 0.0655 (6) | 0.0555 (5) | 0.0017 (4) | 0.0022 (3) | 0.0137 (4) |
N2 | 0.0315 (5) | 0.0487 (5) | 0.0563 (6) | 0.0007 (4) | −0.0027 (4) | 0.0007 (4) |
N1 | 0.0295 (5) | 0.0450 (5) | 0.0473 (5) | 0.0007 (4) | −0.0001 (4) | −0.0024 (4) |
C1 | 0.0390 (6) | 0.0444 (6) | 0.0546 (7) | 0.0011 (5) | −0.0036 (5) | −0.0013 (5) |
C2 | 0.0470 (7) | 0.0663 (9) | 0.0804 (10) | 0.0077 (6) | −0.0102 (7) | 0.0127 (7) |
C3 | 0.0730 (10) | 0.0614 (9) | 0.0727 (9) | 0.0062 (7) | −0.0139 (8) | 0.0164 (7) |
C4 | 0.0737 (9) | 0.0539 (8) | 0.0567 (7) | −0.0047 (7) | 0.0002 (7) | 0.0068 (6) |
C5 | 0.0504 (7) | 0.0523 (7) | 0.0540 (7) | −0.0044 (5) | 0.0037 (5) | −0.0011 (6) |
C6 | 0.0399 (6) | 0.0391 (5) | 0.0445 (6) | 0.0003 (4) | −0.0018 (4) | −0.0066 (4) |
C7 | 0.0302 (5) | 0.0402 (6) | 0.0438 (5) | −0.0007 (4) | −0.0012 (4) | −0.0090 (4) |
C8 | 0.0320 (5) | 0.0418 (6) | 0.0405 (5) | −0.0017 (4) | −0.0009 (4) | −0.0065 (4) |
C9 | 0.0281 (5) | 0.0536 (7) | 0.0525 (6) | 0.0035 (4) | −0.0005 (4) | −0.0002 (5) |
C10 | 0.0272 (5) | 0.0599 (7) | 0.0532 (6) | −0.0010 (5) | 0.0049 (4) | 0.0041 (5) |
C11 | 0.0309 (5) | 0.0489 (6) | 0.0422 (6) | −0.0023 (4) | −0.0010 (4) | −0.0020 (5) |
C12 | 0.0269 (5) | 0.0573 (7) | 0.0497 (6) | 0.0031 (5) | 0.0001 (4) | 0.0025 (5) |
C13 | 0.0284 (5) | 0.0554 (7) | 0.0467 (6) | −0.0011 (4) | 0.0036 (4) | −0.0002 (5) |
O1—C11 | 1.3595 (14) | C4—H4 | 0.9300 |
O1—H1A | 0.8200 | C5—C6 | 1.3902 (17) |
N2—C7 | 1.3221 (14) | C5—H5 | 0.9300 |
N2—C1 | 1.3920 (15) | C7—C8 | 1.4609 (16) |
N1—C7 | 1.3610 (14) | C8—C13 | 1.3935 (15) |
N1—C6 | 1.3784 (15) | C8—C9 | 1.3953 (15) |
N1—H1 | 0.886 (8) | C9—C10 | 1.3728 (17) |
C1—C6 | 1.3915 (16) | C9—H9 | 0.9300 |
C1—C2 | 1.3939 (18) | C10—C11 | 1.3906 (15) |
C2—C3 | 1.374 (2) | C10—H10 | 0.9300 |
C2—H2 | 0.9300 | C11—C12 | 1.3901 (15) |
C3—C4 | 1.384 (2) | C12—C13 | 1.3792 (16) |
C3—H3 | 0.9300 | C12—H12 | 0.9300 |
C4—C5 | 1.3733 (19) | C13—H13 | 0.9300 |
C11—O1—H1A | 109.5 | C5—C6—C1 | 122.15 (11) |
C7—N2—C1 | 105.79 (9) | N2—C7—N1 | 111.40 (10) |
C7—N1—C6 | 108.16 (9) | N2—C7—C8 | 124.60 (10) |
C7—N1—H1 | 125.8 (9) | N1—C7—C8 | 124.00 (9) |
C6—N1—H1 | 125.8 (9) | C13—C8—C9 | 117.74 (11) |
C6—C1—N2 | 109.58 (10) | C13—C8—C7 | 122.42 (10) |
C6—C1—C2 | 119.69 (12) | C9—C8—C7 | 119.83 (10) |
N2—C1—C2 | 130.72 (12) | C10—C9—C8 | 121.24 (10) |
C3—C2—C1 | 118.03 (13) | C10—C9—H9 | 119.4 |
C3—C2—H2 | 121.0 | C8—C9—H9 | 119.4 |
C1—C2—H2 | 121.0 | C9—C10—C11 | 120.63 (10) |
C2—C3—C4 | 121.61 (13) | C9—C10—H10 | 119.7 |
C2—C3—H3 | 119.2 | C11—C10—H10 | 119.7 |
C4—C3—H3 | 119.2 | O1—C11—C12 | 122.93 (10) |
C5—C4—C3 | 121.50 (14) | O1—C11—C10 | 118.30 (10) |
C5—C4—H4 | 119.2 | C12—C11—C10 | 118.76 (11) |
C3—C4—H4 | 119.2 | C13—C12—C11 | 120.36 (10) |
C4—C5—C6 | 117.02 (13) | C13—C12—H12 | 119.8 |
C4—C5—H5 | 121.5 | C11—C12—H12 | 119.8 |
C6—C5—H5 | 121.5 | C12—C13—C8 | 121.27 (10) |
N1—C6—C5 | 132.78 (11) | C12—C13—H13 | 119.4 |
N1—C6—C1 | 105.07 (10) | C8—C13—H13 | 119.4 |
C7—N2—C1—C6 | −0.36 (13) | C6—N1—C7—N2 | 0.72 (12) |
C7—N2—C1—C2 | −179.12 (14) | C6—N1—C7—C8 | −179.15 (9) |
C6—C1—C2—C3 | 0.4 (2) | N2—C7—C8—C13 | −172.12 (11) |
N2—C1—C2—C3 | 179.05 (13) | N1—C7—C8—C13 | 7.74 (16) |
C1—C2—C3—C4 | −0.4 (2) | N2—C7—C8—C9 | 8.78 (16) |
C2—C3—C4—C5 | 0.0 (2) | N1—C7—C8—C9 | −171.36 (10) |
C3—C4—C5—C6 | 0.3 (2) | C13—C8—C9—C10 | 0.21 (17) |
C7—N1—C6—C5 | 178.88 (12) | C7—C8—C9—C10 | 179.36 (11) |
C7—N1—C6—C1 | −0.89 (12) | C8—C9—C10—C11 | 0.26 (19) |
C4—C5—C6—N1 | −179.96 (12) | C9—C10—C11—O1 | −179.84 (11) |
C4—C5—C6—C1 | −0.23 (18) | C9—C10—C11—C12 | −0.28 (18) |
N2—C1—C6—N1 | 0.77 (13) | O1—C11—C12—C13 | 179.35 (11) |
C2—C1—C6—N1 | 179.70 (12) | C10—C11—C12—C13 | −0.18 (18) |
N2—C1—C6—C5 | −179.02 (10) | C11—C12—C13—C8 | 0.67 (18) |
C2—C1—C6—C5 | −0.10 (18) | C9—C8—C13—C12 | −0.68 (17) |
C1—N2—C7—N1 | −0.22 (12) | C7—C8—C13—C12 | −179.80 (10) |
C1—N2—C7—C8 | 179.65 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···N2i | 0.82 | 1.84 | 2.6515 (12) | 174 |
N1—H1···O1ii | 0.89 (1) | 2.01 (1) | 2.8564 (12) | 159 (1) |
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) x−1/2, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C13H10N2O |
Mr | 210.23 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 7.1679 (3), 15.1517 (6), 9.9079 (4) |
β (°) | 90.556 (2) |
V (Å3) | 1076.01 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.22 × 0.17 × 0.13 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10089, 2464, 2092 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.103, 1.04 |
No. of reflections | 2464 |
No. of parameters | 149 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.16, −0.17 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···N2i | 0.82 | 1.84 | 2.6515 (12) | 174 |
N1—H1···O1ii | 0.886 (8) | 2.012 (9) | 2.8564 (12) | 158.8 (12) |
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) x−1/2, −y+1/2, z+1/2. |
The ligands containing benzimidazolyl substituent(s), which could provide hydrogen bond donor NH groups and π-π stacking interaction, have being extensively investigated now (Cai, Chen et al., 2003). As a part of the structural studies of benzimidazolyl series (Cai et al., 2002; Cai, Su et al. 2003) here we report the synthesis and structure of the title compound.
Fig. 1 shows an ORTEP diagram of the compound together with the atom numbering scheme. The benzimidazolyl ring is almost coplanar to phenol ring with 8.11 (1)° of dihedral angle in the molecule. The dihedral angle between two perpendicular sheet-like molecules is 86.19 (6)° in the crystal structure, which are connected by hydrogen bondings N—H···O [O···N 2.856 (1) Å, H···O 2.012 (2) Å, N—H···O 158.8 (1)° [symmetry code: x - 1/2,-y + 1/2,z + 1/2] and O—H···N [O···N 2.652 (1) Å, H···O 1.843 (1) Å, O—H···N 173.5 (2)° [symmetry code: x - 1/2,-y + 1/2,z - 1/2] to form an infinite wave-like two-dimensional layer, while the three-dimensional network structure is constructed by face-to-face π-π stacking interaction, the shortest distance between benzimidazole ring and phenol ring is 3.554 Å.