Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108002175/gd3187sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108002175/gd3187Isup2.hkl |
CCDC reference: 682822
The title compound was prepared according the literature method of Su et al. (2003). Single crystals were grown from an ethanol solution over several days at room temperature.
Water H atoms were located in the electronic map and refined isotropically, with O—H distances restrained to about 0.86 (s.u.?) Å. Because the crystallographically imposed inversion centre is located in the middle of two adjacent water molecules, the H atom which forms the O—H···O hydrogen bond is required by symmetry to be distributed over two positions with half occupancy. All other H atoms were placed in calculated positions and included in the refinement in the riding-model approximation, with C—H distances in the range 0.95–0.99 Å [Please check added text], and with Uiso(H) = 1.5Ueq(O) for water H atoms or 1.2Ueq(C) for all other H atoms.
Data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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).
C22H18N4·2H2O | F(000) = 396 |
Mr = 374.44 | Dx = 1.305 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 7740 reflections |
a = 5.4040 (2) Å | θ = 3.1–28° |
b = 10.7114 (4) Å | µ = 0.09 mm−1 |
c = 16.5003 (5) Å | T = 150 K |
β = 94.079 (3)° | Block, colourless |
V = 952.69 (6) Å3 | 0.25 × 0.20 × 0.18 mm |
Z = 2 |
Bruker SMART 1K CCD area-detector diffractometer | 2275 independent reflections |
Radiation source: fine-focus sealed tube | 1412 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
ϕ and ω scans | θmax = 28.0°, θmin = 3.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −7→7 |
Tmin = 0.964, Tmax = 0.985 | k = −14→14 |
7740 measured reflections | l = −21→17 |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.120 | Only H-atom coordinates refined |
S = 1.03 | w = 1/[σ2(Fo2) + (0.068P)2] where P = (Fo2 + 2Fc2)/3 |
2275 reflections | (Δ/σ)max = 0.001 |
127 parameters | Δρmax = 0.53 e Å−3 |
6 restraints | Δρmin = −0.31 e Å−3 |
C22H18N4·2H2O | V = 952.69 (6) Å3 |
Mr = 374.44 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.4040 (2) Å | µ = 0.09 mm−1 |
b = 10.7114 (4) Å | T = 150 K |
c = 16.5003 (5) Å | 0.25 × 0.20 × 0.18 mm |
β = 94.079 (3)° |
Bruker SMART 1K CCD area-detector diffractometer | 2275 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1412 reflections with I > 2σ(I) |
Tmin = 0.964, Tmax = 0.985 | Rint = 0.027 |
7740 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 6 restraints |
wR(F2) = 0.120 | Only H-atom coordinates refined |
S = 1.03 | Δρmax = 0.53 e Å−3 |
2275 reflections | Δρmin = −0.31 e Å−3 |
127 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 | Occ. (<1) | |
N1 | 0.2344 (2) | 0.68189 (11) | 0.67908 (7) | 0.0291 (3) | |
N2 | 0.2076 (2) | 0.63342 (11) | 0.81060 (7) | 0.0353 (3) | |
C1 | 0.3129 (3) | 0.67456 (14) | 0.59626 (8) | 0.0342 (4) | |
H1A | 0.4877 | 0.6465 | 0.5979 | 0.041* | |
H1B | 0.3033 | 0.7586 | 0.5713 | 0.041* | |
C2 | 0.3247 (3) | 0.61432 (14) | 0.74455 (8) | 0.0344 (4) | |
H2 | 0.4604 | 0.5583 | 0.7427 | 0.041* | |
C3 | 0.0251 (3) | 0.71987 (13) | 0.78666 (8) | 0.0301 (3) | |
C4 | −0.1576 (3) | 0.77382 (15) | 0.83115 (9) | 0.0379 (4) | |
H4 | −0.1707 | 0.7537 | 0.8868 | 0.046* | |
C5 | −0.3181 (3) | 0.85728 (15) | 0.79147 (10) | 0.0429 (4) | |
H5 | −0.4438 | 0.8954 | 0.8204 | 0.052* | |
C6 | −0.3005 (3) | 0.88723 (14) | 0.70959 (10) | 0.0397 (4) | |
H6 | −0.4144 | 0.9453 | 0.6844 | 0.048* | |
C7 | −0.1221 (3) | 0.83471 (13) | 0.66454 (9) | 0.0326 (4) | |
H7 | −0.1098 | 0.8552 | 0.6089 | 0.039* | |
C8 | 0.0380 (3) | 0.75078 (12) | 0.70446 (8) | 0.0277 (3) | |
C9 | 0.1527 (3) | 0.58523 (13) | 0.54475 (8) | 0.0284 (3) | |
C10 | −0.0533 (3) | 0.62584 (14) | 0.49686 (8) | 0.0331 (4) | |
H10 | −0.0913 | 0.7124 | 0.4942 | 0.040* | |
C11 | 0.2037 (3) | 0.45811 (14) | 0.54686 (8) | 0.0330 (4) | |
H11 | 0.3444 | 0.4284 | 0.5789 | 0.040* | |
O1 | 0.2470 (3) | 0.52830 (15) | 0.97150 (7) | 0.0822 (5) | |
H1E | 0.2471 | 0.5561 | 0.9219 | 0.123* | |
H1D | 0.1149 | 0.5211 | 0.9955 | 0.123* | 0.50 |
H1C | 0.3922 | 0.5109 | 0.9937 | 0.123* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0278 (7) | 0.0323 (7) | 0.0271 (6) | −0.0028 (5) | 0.0012 (5) | −0.0040 (5) |
N2 | 0.0386 (8) | 0.0354 (7) | 0.0310 (7) | −0.0074 (6) | −0.0028 (6) | 0.0014 (5) |
C1 | 0.0332 (8) | 0.0407 (9) | 0.0294 (8) | −0.0068 (7) | 0.0082 (6) | −0.0043 (6) |
C2 | 0.0325 (9) | 0.0342 (8) | 0.0357 (9) | −0.0022 (7) | −0.0039 (7) | −0.0012 (6) |
C3 | 0.0319 (8) | 0.0305 (7) | 0.0276 (7) | −0.0093 (7) | −0.0004 (6) | −0.0028 (6) |
C4 | 0.0406 (10) | 0.0430 (9) | 0.0311 (8) | −0.0143 (8) | 0.0093 (7) | −0.0091 (7) |
C5 | 0.0365 (9) | 0.0419 (10) | 0.0516 (10) | −0.0062 (8) | 0.0114 (8) | −0.0184 (8) |
C6 | 0.0361 (9) | 0.0312 (8) | 0.0515 (10) | −0.0004 (7) | 0.0005 (7) | −0.0099 (7) |
C7 | 0.0371 (9) | 0.0286 (8) | 0.0315 (8) | −0.0053 (7) | −0.0016 (6) | −0.0013 (6) |
C8 | 0.0287 (8) | 0.0274 (7) | 0.0273 (7) | −0.0071 (7) | 0.0032 (6) | −0.0051 (6) |
C9 | 0.0302 (8) | 0.0330 (8) | 0.0229 (7) | −0.0021 (6) | 0.0085 (6) | −0.0020 (6) |
C10 | 0.0416 (9) | 0.0299 (8) | 0.0280 (7) | 0.0034 (7) | 0.0042 (7) | −0.0006 (6) |
C11 | 0.0323 (9) | 0.0388 (9) | 0.0277 (7) | 0.0076 (7) | −0.0003 (6) | −0.0023 (6) |
O1 | 0.1175 (13) | 0.0926 (11) | 0.0346 (7) | 0.0164 (9) | −0.0081 (7) | 0.0086 (7) |
N1—C2 | 1.3616 (18) | C5—H5 | 0.9500 |
N1—C8 | 1.3821 (17) | C6—C7 | 1.379 (2) |
N1—C1 | 1.4614 (17) | C6—H6 | 0.9500 |
N2—C2 | 1.3144 (17) | C7—C8 | 1.382 (2) |
N2—C3 | 1.3895 (19) | C7—H7 | 0.9500 |
C1—C9 | 1.5107 (19) | C9—C10 | 1.389 (2) |
C1—H1A | 0.9900 | C9—C11 | 1.389 (2) |
C1—H1B | 0.9900 | C10—C11i | 1.380 (2) |
C2—H2 | 0.9500 | C10—H10 | 0.9500 |
C3—C4 | 1.397 (2) | C11—C10i | 1.380 (2) |
C3—C8 | 1.4028 (19) | C11—H11 | 0.9500 |
C4—C5 | 1.378 (2) | O1—H1E | 0.8718 |
C4—H4 | 0.9500 | O1—H1D | 0.8436 |
C5—C6 | 1.398 (2) | O1—H1C | 0.8625 |
C2—N1—C8 | 106.43 (11) | C7—C6—C5 | 121.71 (16) |
C2—N1—C1 | 127.02 (12) | C7—C6—H6 | 119.1 |
C8—N1—C1 | 126.31 (12) | C5—C6—H6 | 119.1 |
C2—N2—C3 | 104.00 (12) | C6—C7—C8 | 116.53 (14) |
N1—C1—C9 | 111.56 (11) | C6—C7—H7 | 121.7 |
N1—C1—H1A | 109.3 | C8—C7—H7 | 121.7 |
C9—C1—H1A | 109.3 | C7—C8—N1 | 132.16 (13) |
N1—C1—H1B | 109.3 | C7—C8—C3 | 122.83 (13) |
C9—C1—H1B | 109.3 | N1—C8—C3 | 105.01 (12) |
H1A—C1—H1B | 108.0 | C10—C9—C11 | 118.09 (13) |
N2—C2—N1 | 114.13 (14) | C10—C9—C1 | 121.73 (13) |
N2—C2—H2 | 122.9 | C11—C9—C1 | 120.13 (14) |
N1—C2—H2 | 122.9 | C11i—C10—C9 | 120.77 (13) |
N2—C3—C4 | 129.81 (13) | C11i—C10—H10 | 119.6 |
N2—C3—C8 | 110.43 (12) | C9—C10—H10 | 119.6 |
C4—C3—C8 | 119.75 (14) | C10i—C11—C9 | 121.13 (14) |
C5—C4—C3 | 117.60 (14) | C10i—C11—H11 | 119.4 |
C5—C4—H4 | 121.2 | C9—C11—H11 | 119.4 |
C3—C4—H4 | 121.2 | H1E—O1—H1D | 121.9 |
C4—C5—C6 | 121.59 (15) | H1E—O1—H1C | 114.3 |
C4—C5—H5 | 119.2 | H1D—O1—H1C | 123.8 |
C6—C5—H5 | 119.2 |
Symmetry code: (i) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1C···O1ii | 0.86 | 2.04 | 2.892 (3) | 171.1 |
O1—H1D···O1iii | 0.84 | 2.13 | 2.955 (4) | 164.5 |
O1—H1E···N2 | 0.87 | 2.01 | 2.8778 (17) | 172.4 |
Symmetry codes: (ii) −x+1, −y+1, −z+2; (iii) −x, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C22H18N4·2H2O |
Mr | 374.44 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 150 |
a, b, c (Å) | 5.4040 (2), 10.7114 (4), 16.5003 (5) |
β (°) | 94.079 (3) |
V (Å3) | 952.69 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.25 × 0.20 × 0.18 |
Data collection | |
Diffractometer | Bruker SMART 1K CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.964, 0.985 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7740, 2275, 1412 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.120, 1.03 |
No. of reflections | 2275 |
No. of parameters | 127 |
No. of restraints | 6 |
H-atom treatment | Only H-atom coordinates refined |
Δρmax, Δρmin (e Å−3) | 0.53, −0.31 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1C···O1i | 0.86 | 2.04 | 2.892 (3) | 171.1 |
O1—H1D···O1ii | 0.84 | 2.13 | 2.955 (4) | 164.5 |
O1—H1E···N2 | 0.87 | 2.01 | 2.8778 (17) | 172.4 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x, −y+1, −z+2. |
Benzimidazole-based organic ligands have been widely used in supramolecular coordination chemistry to generate various discrete and one- to three-dimensional coordination architectures (Wahon et al., 1994; Berends & Stephan, 1984; Su et al., 2002, 2003; Zhang, Guo, Yang, Lu et al., 2007 [Reference was originally ambiguous - please confirm]; Zheng et al., 2007; Chen et al., 2007). Bis-benzimidazole ligands, with two benzimidazole groups connected by an organic spacer at the 1-positions, can take either trans or cis conformations (Liu et al., 2007; Lü, Pan et al., 2006 [Reference was originally ambiguous - please confirm]). Besides acting as coordination donors, the imino N atoms of the two benzimidazole groups can also act as hydrogen-bond acceptors (Zheng et al., 2005). Here, we describe the title dihydrated compound, (I), which forms a hydrogen-bonded layer structure in the crystal structure displaying π–π interactions between the aromatic groups.
The organic component (Fig. 1) lies across an inversion centre, so that the asymmetric unit consists of one-half of an organic component and one water molecule. The organic molecule adopts the trans conformation, with the two benzimidazole arms arranged up and down on the two sides of the central benzene ring, showing a dihedral angle of 75.5° [with each other?] (Fig. 1). The imino N atoms of the two benzimidazole arms form O—H···N hydrogen bonds with the water molecules (Table 1; Li et al., 2007). Furthermore, the three aromatic rings are stacked in a parallel fashion, displaying π–π interactions (Chen et al., 2003; Zhang, Guo, Yang, Wang et al., 2007). Therefore, the crystal packing of the organic molecules is directed by these intermolecular interactions (Su et al., 1998, 2001; Chen et al., 2005, 2006).
One H atom of the water component is disordered over two sites, due to the presence of inversion centres relating pairs of adjacent water molecules. The water molecules are linked through O—H···O hydrogen bonds (Table 1). Each water molecule is involved in three hydrogen bonds, one of which links the molecular components via an O—H···N hydrogen bond, while the other two, involving the disordered H atom, link pairs of the water molecules. The water molecules alone are hydrogen bonded into zigzag chains along [100]. Since every two water molecules form the unit cell repeat unit of the chain, the one-dimensional water chain can be described as a C(2) chain (Infantes & Motherwell, 2002). The zigzag arrangement of the water chain is directed by the intrinsic angles of the hydrogen bonds around the water molecule. The organic molecules are connected through the O—H···N hydrogen bonds to water chains on both sides to generate two-dimensional layers parallel to (010).
The C22H18N4 molecule is composed of three aromatic rings and adopts the trans conformation. The whole molecule is non-planar. The organic molecules overlap each other in the a [direction? text missing] and π–π interactions are formed between adjacent aromatic rings (Fig. 2). The centroid-to-centroid distance between the phenyl ring and the imidazole ring of an adjacent benzimidazole ring system at (-1 + x, y, z) is 3.9796 (9) Å, with an interplanar angle of 0.4 (2)°, and this interaction reinforces the hydrogen-bonded sheet.
In the ac plane, the water chains and organic arrays are aligned alternately via O—H···N hydrogen bonds to give a two-dimensional layer (Fig. 2). The layers display a weaving feature due to the trans conformation of the organic molecules. Therefore, the overall crystal packing is sustained by offset stacking of the two-dimensional layers in the b direction.
The title compound crystallizes in a slightly different way to the previously reported compound 1,4-bis(1H-benzotriazole-1-ylmethyl)benzene (Cai et al., 2004). These two compounds have rather similar molecular structures but with a modest difference between their five-membered N-heterocyclic rings. In addition, the title compound is a dihydrate, while the previously reported one is a tetrahydrate. 1,4-Bis(1H-benzotriazole-1-ylmethyl)benzene has two free N atoms to act as potential hydrogen-bond donors, although only one N atom is involved in hydrogen bonding, quite similar to the present compound. Nevertheless, 1,4-bis(1H-benzotriazole-1-ylmethyl)benzene crystallizes as a tetrahydrate adduct with the water molecules forming a one-dimensional O—H···O hydrogen-bonded tape, while in (I) the dihydrate crystallizes with the water molecules forming a C(2)-type hydrogen-bonded chain. In both cases, the organic molecules are connected by the water chain or tape in essentially the same way through O—H···N hydrogen bonds to generate similar two-dimensional layers. These results indicate that similar organic molecules can display similar intermolecular interactions, which play important roles in directing molecular arrangement and crystal packing.
In summary, co-crystallization of the non-planar linear organic molecule, 1,4-bis(benzimidazol-1-ylmethyl)benzene, and water affords a layered structure which is consolidated by cooperative O—H···O and O—H···N hydrogen bonds and π–π interactions. This is an example of the synergistic effect of different supramolecular interactions in the direction of the crystal packing, which is of significance to crystal engineering (Su et al., 1998, 2001; Lü, Qiao et al., 2006).