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In the title compound, C22H18N4·2H2O, the organic fragment lies across a centre of inversion in the P21/n space group. The water mol­ecules form C(2)-type hydrogen-bonded chains which are linked to the 1,4-bis­(1H-benzimidazol-1-yl­methyl)­benzene mol­ecules through O—H...N hydrogen bonds, forming sheets reinforced by π–π stacking inter­actions between the aromatic rings within the layers.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108002175/gd3187sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108002175/gd3187Isup2.hkl
Contains datablock I

CCDC reference: 682822

Comment top

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 ππ 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 ππ 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 ππ 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 ππ 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).

Related literature top

For related literature, see: Berends & Stephan (1984); Cai et al. (2004); Chen et al. (2003, 2005, 2006, 2007); Infantes & Motherwell (2002); Lü, Pan, He, Cai, Kang & Su (2006); Lü, Qiao, He, Pan, Kang & Su (2006); Li et al. (2007); Liu et al. (2007); Su et al. (1998, 2001, 2002, 2003); Wahon et al. (1994); Zhang, Guo, Yang, Lu, Tong & Su (2007); Zhang, Guo, Yang, Wang, Liu, Kang & Su (2007); Zheng et al. (2005, 2007).

Experimental top

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.

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The molecular structure and crystallographic numbering scheme for (I). Displacement ellipsoids are shown at the 30% probability level. Solvent water molecules have been omitted for clarity. Unlabelled atoms are related to labelled atoms by the symmetry code (1 - x, -y, 1 - z).
[Figure 2] Fig. 2. A view of the two-dimensional layers, showing hydrogen bonds and ππ interactions as dashed lines.
1,4-bis(benzimidazol-1-ylmethyl)benzene dihydrate top
Crystal data top
C22H18N4·2H2OF(000) = 396
Mr = 374.44Dx = 1.305 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 7740 reflections
a = 5.4040 (2) Åθ = 3.1–28°
b = 10.7114 (4) ŵ = 0.09 mm1
c = 16.5003 (5) ÅT = 150 K
β = 94.079 (3)°Block, colourless
V = 952.69 (6) Å30.25 × 0.20 × 0.18 mm
Z = 2
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer
2275 independent reflections
Radiation source: fine-focus sealed tube1412 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
ϕ and ω scansθmax = 28.0°, θmin = 3.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 77
Tmin = 0.964, Tmax = 0.985k = 1414
7740 measured reflectionsl = 2117
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.120Only 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 parametersΔρmax = 0.53 e Å3
6 restraintsΔρmin = 0.31 e Å3
Crystal data top
C22H18N4·2H2OV = 952.69 (6) Å3
Mr = 374.44Z = 2
Monoclinic, P21/nMo Kα radiation
a = 5.4040 (2) ŵ = 0.09 mm1
b = 10.7114 (4) ÅT = 150 K
c = 16.5003 (5) Å0.25 × 0.20 × 0.18 mm
β = 94.079 (3)°
Data collection top
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 = 0.985Rint = 0.027
7740 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0436 restraints
wR(F2) = 0.120Only H-atom coordinates refined
S = 1.03Δρmax = 0.53 e Å3
2275 reflectionsΔρmin = 0.31 e Å3
127 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
xyzUiso*/UeqOcc. (<1)
N10.2344 (2)0.68189 (11)0.67908 (7)0.0291 (3)
N20.2076 (2)0.63342 (11)0.81060 (7)0.0353 (3)
C10.3129 (3)0.67456 (14)0.59626 (8)0.0342 (4)
H1A0.48770.64650.59790.041*
H1B0.30330.75860.57130.041*
C20.3247 (3)0.61432 (14)0.74455 (8)0.0344 (4)
H20.46040.55830.74270.041*
C30.0251 (3)0.71987 (13)0.78666 (8)0.0301 (3)
C40.1576 (3)0.77382 (15)0.83115 (9)0.0379 (4)
H40.17070.75370.88680.046*
C50.3181 (3)0.85728 (15)0.79147 (10)0.0429 (4)
H50.44380.89540.82040.052*
C60.3005 (3)0.88723 (14)0.70959 (10)0.0397 (4)
H60.41440.94530.68440.048*
C70.1221 (3)0.83471 (13)0.66454 (9)0.0326 (4)
H70.10980.85520.60890.039*
C80.0380 (3)0.75078 (12)0.70446 (8)0.0277 (3)
C90.1527 (3)0.58523 (13)0.54475 (8)0.0284 (3)
C100.0533 (3)0.62584 (14)0.49686 (8)0.0331 (4)
H100.09130.71240.49420.040*
C110.2037 (3)0.45811 (14)0.54686 (8)0.0330 (4)
H110.34440.42840.57890.040*
O10.2470 (3)0.52830 (15)0.97150 (7)0.0822 (5)
H1E0.24710.55610.92190.123*
H1D0.11490.52110.99550.123*0.50
H1C0.39220.51090.99370.123*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0278 (7)0.0323 (7)0.0271 (6)0.0028 (5)0.0012 (5)0.0040 (5)
N20.0386 (8)0.0354 (7)0.0310 (7)0.0074 (6)0.0028 (6)0.0014 (5)
C10.0332 (8)0.0407 (9)0.0294 (8)0.0068 (7)0.0082 (6)0.0043 (6)
C20.0325 (9)0.0342 (8)0.0357 (9)0.0022 (7)0.0039 (7)0.0012 (6)
C30.0319 (8)0.0305 (7)0.0276 (7)0.0093 (7)0.0004 (6)0.0028 (6)
C40.0406 (10)0.0430 (9)0.0311 (8)0.0143 (8)0.0093 (7)0.0091 (7)
C50.0365 (9)0.0419 (10)0.0516 (10)0.0062 (8)0.0114 (8)0.0184 (8)
C60.0361 (9)0.0312 (8)0.0515 (10)0.0004 (7)0.0005 (7)0.0099 (7)
C70.0371 (9)0.0286 (8)0.0315 (8)0.0053 (7)0.0016 (6)0.0013 (6)
C80.0287 (8)0.0274 (7)0.0273 (7)0.0071 (7)0.0032 (6)0.0051 (6)
C90.0302 (8)0.0330 (8)0.0229 (7)0.0021 (6)0.0085 (6)0.0020 (6)
C100.0416 (9)0.0299 (8)0.0280 (7)0.0034 (7)0.0042 (7)0.0006 (6)
C110.0323 (9)0.0388 (9)0.0277 (7)0.0076 (7)0.0003 (6)0.0023 (6)
O10.1175 (13)0.0926 (11)0.0346 (7)0.0164 (9)0.0081 (7)0.0086 (7)
Geometric parameters (Å, º) top
N1—C21.3616 (18)C5—H50.9500
N1—C81.3821 (17)C6—C71.379 (2)
N1—C11.4614 (17)C6—H60.9500
N2—C21.3144 (17)C7—C81.382 (2)
N2—C31.3895 (19)C7—H70.9500
C1—C91.5107 (19)C9—C101.389 (2)
C1—H1A0.9900C9—C111.389 (2)
C1—H1B0.9900C10—C11i1.380 (2)
C2—H20.9500C10—H100.9500
C3—C41.397 (2)C11—C10i1.380 (2)
C3—C81.4028 (19)C11—H110.9500
C4—C51.378 (2)O1—H1E0.8718
C4—H40.9500O1—H1D0.8436
C5—C61.398 (2)O1—H1C0.8625
C2—N1—C8106.43 (11)C7—C6—C5121.71 (16)
C2—N1—C1127.02 (12)C7—C6—H6119.1
C8—N1—C1126.31 (12)C5—C6—H6119.1
C2—N2—C3104.00 (12)C6—C7—C8116.53 (14)
N1—C1—C9111.56 (11)C6—C7—H7121.7
N1—C1—H1A109.3C8—C7—H7121.7
C9—C1—H1A109.3C7—C8—N1132.16 (13)
N1—C1—H1B109.3C7—C8—C3122.83 (13)
C9—C1—H1B109.3N1—C8—C3105.01 (12)
H1A—C1—H1B108.0C10—C9—C11118.09 (13)
N2—C2—N1114.13 (14)C10—C9—C1121.73 (13)
N2—C2—H2122.9C11—C9—C1120.13 (14)
N1—C2—H2122.9C11i—C10—C9120.77 (13)
N2—C3—C4129.81 (13)C11i—C10—H10119.6
N2—C3—C8110.43 (12)C9—C10—H10119.6
C4—C3—C8119.75 (14)C10i—C11—C9121.13 (14)
C5—C4—C3117.60 (14)C10i—C11—H11119.4
C5—C4—H4121.2C9—C11—H11119.4
C3—C4—H4121.2H1E—O1—H1D121.9
C4—C5—C6121.59 (15)H1E—O1—H1C114.3
C4—C5—H5119.2H1D—O1—H1C123.8
C6—C5—H5119.2
Symmetry code: (i) x, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1C···O1ii0.862.042.892 (3)171.1
O1—H1D···O1iii0.842.132.955 (4)164.5
O1—H1E···N20.872.012.8778 (17)172.4
Symmetry codes: (ii) x+1, y+1, z+2; (iii) x, y+1, z+2.

Experimental details

Crystal data
Chemical formulaC22H18N4·2H2O
Mr374.44
Crystal system, space groupMonoclinic, P21/n
Temperature (K)150
a, b, c (Å)5.4040 (2), 10.7114 (4), 16.5003 (5)
β (°) 94.079 (3)
V3)952.69 (6)
Z2
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.25 × 0.20 × 0.18
Data collection
DiffractometerBruker SMART 1K CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.964, 0.985
No. of measured, independent and
observed [I > 2σ(I)] reflections
7740, 2275, 1412
Rint0.027
(sin θ/λ)max1)0.661
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.120, 1.03
No. of reflections2275
No. of parameters127
No. of restraints6
H-atom treatmentOnly H-atom coordinates refined
Δρmax, Δρmin (e Å3)0.53, 0.31

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1C···O1i0.862.042.892 (3)171.1
O1—H1D···O1ii0.842.132.955 (4)164.5
O1—H1E···N20.872.012.8778 (17)172.4
Symmetry codes: (i) x+1, y+1, z+2; (ii) x, y+1, z+2.
 

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