organic compounds
2-Methylbenzimidazolium thiocyanate–2-methylbenzimidazole (1/1)
aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: khaledi@siswa.um.edu.my
In the 8H9N2+·SCN−·C8H8N2, the three components are linked by intermolecular N—H⋯N and N—H⋯S hydrogen bonds into infinite chains along the c axis.
of the title compound, CRelated literature
For related structures, see: Bhattacharya et al. (2004); Ding et al. (2004); Huang et al. (2006). For applications of benzimidazole derivatives in crystal engineering, see: Cai et al. (2002). For the biological properties of benzimidazole derivatives, see: Refaat (2010); Ansari & Lal (2009).
Experimental
Crystal data
|
Refinement
|
Data collection: APEX2 (Bruker, 2007); cell 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: X-SEED (Barbour, 2001); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010).
Supporting information
https://doi.org/10.1107/S1600536810031181/pv2314sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810031181/pv2314Isup2.hkl
An ethanolic solution (12 ml) of 2-methylbenzimidazole (9 mmol, 1.2 g) was added to an aqueous solution (10 ml) of FeCl3 (3 mmol) followed by addition of an aqueous solution (10 ml) of KSCN (9 mmol). The mixture was heated in a water bath for 15 min. The resulting precipitates were filtered off, washed with ethanol (50%) and recrystallized from ethanol whereupon the pale yellow crystals of the title compound were obtained unexpectedly.
The C-bound hydrogen atoms were placed at calculated positions (C—H 0.95 - 0.98 Å) and were treated as riding on their parent atoms with Uiso(H) set to 1.2–1.5 Ueq(C). The N-bound hydrogen atoms were located in a difference Fourier map and were refined with a distance restraint of N—H 0.88 (2) Å.
Benzimidazole derivatives are biologically active compounds (Refaat, 2010; Ansari & Lal, 2009). Their applications in crystal-engineering have been reported (Cai et al., 2002). The crystal structures of several compounds similar to the title compound have been publsihed (Bhattacharya et al., 2004; Ding et al., 2004; Huang et al., 2006. In this article, the preparation and
of the title compound is presented.The
of the title compound contains a 2-methylbenzimidazolium cation, a thiocyante anion and a molecule of 2-methylbenzimidazole (Fig. 1). In the the three moieties are linked by intramolecular N—H···N and N—H···S hydrogen bondings into infinite one-dimensional chains (Tab. 1 & Fig. 2).For related structures, see: Bhattacharya et al. (2004); Ding et al. (2004); Huang et al. (2006). For applications of benzimidazole derivatives in crystal engineering, see: Cai et al. (2002). For the biological properties of benzimidazole derivatives, see: Refaat (2010); Ansari & Lal (2009).
Data collection: APEX2 (Bruker, 2007); cell
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: X-SEED (Barbour, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).C8H9N2+·SCN−·C8H8N2 | F(000) = 680 |
Mr = 323.42 | Dx = 1.321 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 1739 reflections |
a = 11.0952 (7) Å | θ = 2.3–25.1° |
b = 6.9664 (4) Å | µ = 0.21 mm−1 |
c = 21.4195 (13) Å | T = 100 K |
β = 100.745 (1)° | Plate, yellow |
V = 1626.56 (17) Å3 | 0.25 × 0.25 × 0.06 mm |
Z = 4 |
Bruker APEXII CCD diffractometer | 3193 independent reflections |
Radiation source: fine-focus sealed tube | 2427 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
φ and ω scans | θmax = 26.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→13 |
Tmin = 0.950, Tmax = 0.988 | k = −7→8 |
8812 measured reflections | l = −26→26 |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.093 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.035P)2 + 0.6349P] where P = (Fo2 + 2Fc2)/3 |
3193 reflections | (Δ/σ)max < 0.001 |
222 parameters | Δρmax = 0.20 e Å−3 |
3 restraints | Δρmin = −0.28 e Å−3 |
C8H9N2+·SCN−·C8H8N2 | V = 1626.56 (17) Å3 |
Mr = 323.42 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.0952 (7) Å | µ = 0.21 mm−1 |
b = 6.9664 (4) Å | T = 100 K |
c = 21.4195 (13) Å | 0.25 × 0.25 × 0.06 mm |
β = 100.745 (1)° |
Bruker APEXII CCD diffractometer | 3193 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2427 reflections with I > 2σ(I) |
Tmin = 0.950, Tmax = 0.988 | Rint = 0.037 |
8812 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 3 restraints |
wR(F2) = 0.093 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.20 e Å−3 |
3193 reflections | Δρmin = −0.28 e Å−3 |
222 parameters |
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 | ||
N1 | 0.76009 (14) | 0.1676 (2) | 0.43464 (7) | 0.0183 (4) | |
H1N | 0.7853 (18) | 0.196 (3) | 0.4761 (8) | 0.033 (6)* | |
N2 | 0.76652 (13) | 0.1089 (2) | 0.33548 (7) | 0.0169 (3) | |
H2N | 0.7976 (19) | 0.090 (3) | 0.2999 (8) | 0.038 (7)* | |
C1 | 0.96598 (16) | 0.1988 (3) | 0.40543 (9) | 0.0233 (4) | |
H1A | 1.0105 | 0.0784 | 0.4165 | 0.035* | |
H1B | 0.9851 | 0.2889 | 0.4410 | 0.035* | |
H1C | 0.9908 | 0.2546 | 0.3678 | 0.035* | |
C2 | 0.83267 (16) | 0.1602 (3) | 0.39179 (8) | 0.0174 (4) | |
C3 | 0.64561 (16) | 0.0800 (3) | 0.34260 (9) | 0.0170 (4) | |
C4 | 0.54091 (16) | 0.0242 (3) | 0.29996 (9) | 0.0198 (4) | |
H4 | 0.5429 | −0.0024 | 0.2567 | 0.024* | |
C5 | 0.43398 (17) | 0.0096 (3) | 0.32393 (10) | 0.0244 (5) | |
H5 | 0.3608 | −0.0290 | 0.2963 | 0.029* | |
C6 | 0.43008 (17) | 0.0498 (3) | 0.38747 (10) | 0.0262 (5) | |
H6 | 0.3545 | 0.0381 | 0.4019 | 0.031* | |
C7 | 0.53387 (17) | 0.1064 (3) | 0.42968 (10) | 0.0227 (4) | |
H7 | 0.5317 | 0.1352 | 0.4728 | 0.027* | |
C8 | 0.64148 (16) | 0.1190 (3) | 0.40569 (9) | 0.0173 (4) | |
N3 | 0.49936 (14) | 0.4693 (2) | 0.66246 (7) | 0.0179 (3) | |
H3N | 0.5709 (14) | 0.483 (3) | 0.6527 (9) | 0.022 (5)* | |
N4 | 0.36143 (13) | 0.4455 (2) | 0.72545 (7) | 0.0175 (3) | |
C9 | 0.57509 (16) | 0.5348 (3) | 0.77709 (9) | 0.0236 (4) | |
H9A | 0.5377 | 0.5843 | 0.8119 | 0.035* | |
H9B | 0.6283 | 0.6334 | 0.7640 | 0.035* | |
H9C | 0.6239 | 0.4205 | 0.7915 | 0.035* | |
C10 | 0.47689 (16) | 0.4834 (3) | 0.72223 (9) | 0.0174 (4) | |
C11 | 0.39134 (16) | 0.4178 (3) | 0.62290 (9) | 0.0173 (4) | |
C12 | 0.36142 (17) | 0.3839 (3) | 0.55802 (9) | 0.0212 (4) | |
H12 | 0.4209 | 0.3944 | 0.5315 | 0.025* | |
C13 | 0.24092 (18) | 0.3343 (3) | 0.53365 (9) | 0.0235 (4) | |
H13 | 0.2171 | 0.3092 | 0.4895 | 0.028* | |
C14 | 0.15347 (18) | 0.3204 (3) | 0.57299 (9) | 0.0239 (4) | |
H14 | 0.0715 | 0.2865 | 0.5549 | 0.029* | |
C15 | 0.18384 (16) | 0.3548 (3) | 0.63752 (9) | 0.0204 (4) | |
H15 | 0.1240 | 0.3455 | 0.6638 | 0.024* | |
C16 | 0.30494 (16) | 0.4037 (3) | 0.66294 (8) | 0.0167 (4) | |
S1 | 0.79070 (4) | 0.52630 (8) | 0.64995 (2) | 0.02656 (15) | |
N5 | 0.83250 (16) | 0.2375 (3) | 0.56491 (8) | 0.0283 (4) | |
C17 | 0.81466 (16) | 0.3567 (3) | 0.60007 (9) | 0.0208 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0217 (8) | 0.0189 (9) | 0.0143 (8) | 0.0006 (7) | 0.0030 (6) | −0.0004 (7) |
N2 | 0.0162 (8) | 0.0193 (9) | 0.0156 (8) | 0.0004 (6) | 0.0041 (6) | −0.0006 (7) |
C1 | 0.0184 (10) | 0.0266 (12) | 0.0237 (10) | 0.0000 (8) | 0.0006 (8) | −0.0034 (9) |
C2 | 0.0200 (9) | 0.0152 (10) | 0.0169 (9) | 0.0024 (7) | 0.0029 (7) | 0.0009 (8) |
C3 | 0.0186 (9) | 0.0132 (10) | 0.0198 (10) | 0.0019 (7) | 0.0051 (7) | 0.0022 (8) |
C4 | 0.0197 (9) | 0.0175 (10) | 0.0210 (10) | 0.0005 (8) | 0.0008 (7) | 0.0007 (9) |
C5 | 0.0181 (9) | 0.0196 (11) | 0.0343 (12) | −0.0004 (8) | 0.0016 (8) | 0.0046 (9) |
C6 | 0.0213 (10) | 0.0226 (11) | 0.0380 (12) | 0.0022 (8) | 0.0145 (9) | 0.0068 (10) |
C7 | 0.0283 (11) | 0.0180 (11) | 0.0248 (10) | 0.0030 (8) | 0.0125 (8) | 0.0040 (9) |
C8 | 0.0197 (9) | 0.0115 (10) | 0.0207 (10) | 0.0015 (7) | 0.0043 (7) | 0.0028 (8) |
N3 | 0.0143 (8) | 0.0202 (9) | 0.0205 (8) | 0.0002 (7) | 0.0063 (6) | 0.0005 (7) |
N4 | 0.0178 (8) | 0.0181 (9) | 0.0165 (8) | −0.0002 (6) | 0.0031 (6) | 0.0013 (7) |
C9 | 0.0197 (10) | 0.0262 (11) | 0.0242 (10) | −0.0011 (8) | 0.0021 (8) | −0.0001 (9) |
C10 | 0.0180 (9) | 0.0149 (10) | 0.0193 (9) | 0.0001 (7) | 0.0032 (7) | −0.0002 (8) |
C11 | 0.0192 (9) | 0.0131 (10) | 0.0193 (9) | 0.0011 (7) | 0.0027 (7) | 0.0009 (8) |
C12 | 0.0291 (10) | 0.0159 (10) | 0.0201 (10) | 0.0016 (8) | 0.0083 (8) | 0.0022 (8) |
C13 | 0.0328 (11) | 0.0177 (11) | 0.0177 (10) | −0.0005 (9) | −0.0011 (8) | 0.0000 (9) |
C14 | 0.0230 (10) | 0.0202 (11) | 0.0258 (11) | −0.0027 (8) | −0.0018 (8) | 0.0027 (9) |
C15 | 0.0182 (9) | 0.0188 (11) | 0.0240 (10) | −0.0017 (8) | 0.0032 (8) | 0.0029 (9) |
C16 | 0.0213 (9) | 0.0126 (9) | 0.0159 (9) | 0.0023 (7) | 0.0025 (7) | 0.0027 (8) |
S1 | 0.0226 (3) | 0.0293 (3) | 0.0296 (3) | −0.0040 (2) | 0.0095 (2) | −0.0066 (2) |
N5 | 0.0336 (10) | 0.0324 (11) | 0.0184 (9) | 0.0026 (8) | 0.0033 (7) | −0.0006 (8) |
C17 | 0.0166 (9) | 0.0285 (12) | 0.0165 (9) | −0.0007 (8) | 0.0010 (7) | 0.0060 (9) |
N1—C2 | 1.330 (2) | N3—C11 | 1.380 (2) |
N1—C8 | 1.388 (2) | N3—H3N | 0.862 (15) |
N1—H1N | 0.901 (15) | N4—C10 | 1.322 (2) |
N2—C2 | 1.338 (2) | N4—C16 | 1.399 (2) |
N2—C3 | 1.393 (2) | C9—C10 | 1.489 (2) |
N2—H2N | 0.902 (15) | C9—H9A | 0.9800 |
C1—C2 | 1.478 (2) | C9—H9B | 0.9800 |
C1—H1A | 0.9800 | C9—H9C | 0.9800 |
C1—H1B | 0.9800 | C11—C12 | 1.387 (3) |
C1—H1C | 0.9800 | C11—C16 | 1.404 (3) |
C3—C8 | 1.387 (2) | C12—C13 | 1.385 (3) |
C3—C4 | 1.392 (2) | C12—H12 | 0.9500 |
C4—C5 | 1.381 (3) | C13—C14 | 1.402 (3) |
C4—H4 | 0.9500 | C13—H13 | 0.9500 |
C5—C6 | 1.398 (3) | C14—C15 | 1.381 (3) |
C5—H5 | 0.9500 | C14—H14 | 0.9500 |
C6—C7 | 1.382 (3) | C15—C16 | 1.395 (2) |
C6—H6 | 0.9500 | C15—H15 | 0.9500 |
C7—C8 | 1.388 (3) | S1—C17 | 1.647 (2) |
C7—H7 | 0.9500 | N5—C17 | 1.163 (2) |
N3—C10 | 1.353 (2) | ||
C2—N1—C8 | 109.14 (15) | C10—N3—C11 | 107.93 (15) |
C2—N1—H1N | 124.9 (13) | C10—N3—H3N | 124.1 (13) |
C8—N1—H1N | 125.9 (13) | C11—N3—H3N | 127.8 (13) |
C2—N2—C3 | 108.51 (15) | C10—N4—C16 | 104.90 (15) |
C2—N2—H2N | 124.6 (14) | C10—C9—H9A | 109.5 |
C3—N2—H2N | 126.8 (14) | C10—C9—H9B | 109.5 |
C2—C1—H1A | 109.5 | H9A—C9—H9B | 109.5 |
C2—C1—H1B | 109.5 | C10—C9—H9C | 109.5 |
H1A—C1—H1B | 109.5 | H9A—C9—H9C | 109.5 |
C2—C1—H1C | 109.5 | H9B—C9—H9C | 109.5 |
H1A—C1—H1C | 109.5 | N4—C10—N3 | 112.71 (15) |
H1B—C1—H1C | 109.5 | N4—C10—C9 | 125.46 (17) |
N1—C2—N2 | 109.35 (15) | N3—C10—C9 | 121.82 (16) |
N1—C2—C1 | 124.67 (16) | N3—C11—C12 | 132.64 (17) |
N2—C2—C1 | 125.96 (17) | N3—C11—C16 | 104.88 (16) |
C8—C3—C4 | 121.23 (17) | C12—C11—C16 | 122.48 (17) |
C8—C3—N2 | 106.61 (15) | C13—C12—C11 | 116.98 (17) |
C4—C3—N2 | 132.17 (17) | C13—C12—H12 | 121.5 |
C5—C4—C3 | 116.49 (18) | C11—C12—H12 | 121.5 |
C5—C4—H4 | 121.8 | C12—C13—C14 | 121.20 (18) |
C3—C4—H4 | 121.8 | C12—C13—H13 | 119.4 |
C4—C5—C6 | 122.11 (18) | C14—C13—H13 | 119.4 |
C4—C5—H5 | 118.9 | C15—C14—C13 | 121.49 (18) |
C6—C5—H5 | 118.9 | C15—C14—H14 | 119.3 |
C7—C6—C5 | 121.38 (18) | C13—C14—H14 | 119.3 |
C7—C6—H6 | 119.3 | C14—C15—C16 | 118.08 (17) |
C5—C6—H6 | 119.3 | C14—C15—H15 | 121.0 |
C6—C7—C8 | 116.43 (18) | C16—C15—H15 | 121.0 |
C6—C7—H7 | 121.8 | C15—C16—N4 | 130.66 (17) |
C8—C7—H7 | 121.8 | C15—C16—C11 | 119.76 (17) |
C3—C8—C7 | 122.36 (17) | N4—C16—C11 | 109.58 (15) |
C3—C8—N1 | 106.39 (15) | N5—C17—S1 | 179.47 (18) |
C7—C8—N1 | 131.25 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···N5 | 0.90 (2) | 1.90 (2) | 2.799 (2) | 176 (2) |
N2—H2N···N4i | 0.90 (2) | 1.88 (2) | 2.781 (2) | 179 (2) |
N3—H3N···S1 | 0.86 (2) | 2.47 (2) | 3.317 (2) | 168 (2) |
Symmetry code: (i) x+1/2, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C8H9N2+·SCN−·C8H8N2 |
Mr | 323.42 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 100 |
a, b, c (Å) | 11.0952 (7), 6.9664 (4), 21.4195 (13) |
β (°) | 100.745 (1) |
V (Å3) | 1626.56 (17) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.21 |
Crystal size (mm) | 0.25 × 0.25 × 0.06 |
Data collection | |
Diffractometer | Bruker APEXII CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.950, 0.988 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8812, 3193, 2427 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.093, 1.03 |
No. of reflections | 3193 |
No. of parameters | 222 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.20, −0.28 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), X-SEED (Barbour, 2001), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···N5 | 0.90 (2) | 1.90 (2) | 2.799 (2) | 176 (2) |
N2—H2N···N4i | 0.90 (2) | 1.88 (2) | 2.781 (2) | 179 (2) |
N3—H3N···S1 | 0.86 (2) | 2.47 (2) | 3.317 (2) | 168 (2) |
Symmetry code: (i) x+1/2, −y+1/2, z−1/2. |
Acknowledgements
The authors thank the University of Malaya for funding this study (FRGS grant FP009/2008 C).
References
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Benzimidazole derivatives are biologically active compounds (Refaat, 2010; Ansari & Lal, 2009). Their applications in crystal-engineering have been reported (Cai et al., 2002). The crystal structures of several compounds similar to the title compound have been publsihed (Bhattacharya et al., 2004; Ding et al., 2004; Huang et al., 2006. In this article, the preparation and crystal structure of the title compound is presented.
The asymmetric unit of the title compound contains a 2-methylbenzimidazolium cation, a thiocyante anion and a molecule of 2-methylbenzimidazole (Fig. 1). In the crystal structure, the three moieties are linked by intramolecular N—H···N and N—H···S hydrogen bondings into infinite one-dimensional chains (Tab. 1 & Fig. 2).