Tris(1H-benzimidazol-2-yl­meth­yl)­amine–solvent adducts

The tris­(1H-benzimidazol-2-yl­meth­yl)­amine (ntb) mol­ecule crystallizes in different solvent systems, resulting in two kinds of adduct, namely the monohydrate, C₂₄H₂₁N₇·H₂O or ntb·H₂O, (I), and the acetonitrile–methanol–water (1/0.5/1.5) solvate, C₂₄H₂₁N₇·C₂H₃N·0.5CH₄O·1.5H₂O or ntb·1.5H₂O·0.5MeOH·MeCN, (II). In both cases, ntb adopts a tripodal mode to form hydrogen bonds with a solvent water mol­ecule via two N—H...O and one O—H...N hydrogen bond. In (I), the ntb·H₂O adduct is further assembled into a two-dimensional network by N—H...N and O—H...N hydrogen bonds, while in (II), a double-stranded one-dimensional chain structure is assembled via N—H...O and O—H...O hydrogen bonds, with the acetonitrile mol­ecules located inside the cavities of the chain structure.

S1. Comment

The tripodal compound tris(2-benzimidazolylmethyl)amine (ntb) is a versatile ligand which possesses three imine N atoms and three amine NH groups. The three imine N atoms can act as coodination donors to form various metal complexes (Moon et al., 2002; Su, Kang, Mu et al., 1998), while the three amine NH groups are potential hydrogen-bond donors (Su, Kang, Liu et al., 1998; Su et al., 2000). Since the three benzimidazolyl (Bim) arms can rotate freely about methylene (–CH₂–) groups, and the three imine N atoms can also behave as hydrogen-bond acceptors, ntb is a good candidate for formation of hydrogen-bonded adducts via specific steric intermolecular recognition. We have been interested in assembly of supramolecular aggregates with ntb-related compounds, and we report here two kinds of ntb–solvent adducts formed via multiple hydrogen bonds. The adduct (I) has been reported previously (Zhou et al., 1999), but the reported structure was not fully determined or refined as no allowance was made for any of the H atoms in the structure. We have redetermined the structure and located all H atoms. The crystal structural analyses of the adducts C₂₄H₂₁N₇·H₂O, ntb·H₂O, (I), and C₂₄H₂₁N₇·1.5(H₂O)·0.5(CH₄O)·C₂H₃N), ntb·1.5(H₂O)·0.5(MeOH)·MeCN, (II), revealed that the recognition of water molecule by ntb is specific in both adducts, but the extension of the hydrogen bonds are different depending on inclusion of different solvent molecules.

Our structure determination of (I) shows that all imine and amine groups of ntb and the water molecules are involved in hydrogen-bond formation (Table 1). The ntb molecule takes on a tripodal mode, with two NH groups and one imine N atom directed towards the water molecule, which is held by forming two D···A-type N—H···O and one A···D-type N···H—O hydrogen bonds, as shown in Fig. 1. Such a hydrogen-bonding environment is specific for recognition of the water molecule because of its tetrahedral hydrogen-bonding geometry. The remaining H atom of the water molecule forms an O—H···N hydrogen bond with one `outside' imine N atom belonging to a neighbouring ntb molecule. In addition, there is one more imine N atom and one NH group of a neighbouring ntb molecule, which form N—H···N hydrogen bonds resulting in a two-dimensional network parallel to (10–1), as depicted in Fig. 2.

When ntb crystallized in the hydrated MeOH/MeCN solution, the adduct ntb·1.5(H₂O)·0.5(MeOH)·MeCN, (II), was obtained. In this compound, all imine and amine groups of ntb are involved in hydrogen bonding (Table 2). Our structure determination shows that the water molecule was recognized by ntb in exactly the same way as in (I) (details are in Table 2). As in (I), there are two D···A-type N—H···O and one A···D-type N···H—O hydrogen bonds, as shown in Fig. 3. The ntb molecule takes on the same tripodal conformation in both (I) and (II), with one imine N atom and two NH groups pointing `inside' and leaving two imine N atoms and one NH group directed `outside' of the ntb-H₂O moiety.

The analysis of (II) was slightly complicated by disorder. The methanol molecule (O3/C4 in Fig. 3) lies adjacent to an inversion centre with the methyl C atom at such a short intermolecular distance [2.298 (7) Å from C4 at (2 − x, −y, −z)] that it can be present with an occupancy of no more than 0.5. Occupancy refinement showed unequivocally that while methanol atom C4 is only present with 0.5 occupancy, the O-atom site has unit occupancy, implying that this site (labelled as O2 and O3 in Fig. 3) must contain a 0.5-occupancy water molecule (O2) as well as the 0.5-occupancy methanol atom O3.

One of the two outside imine N atom forms an N···H—O hydrogen bond with the 0.5-occupancy methanol/water site (Fig. 3). Water molecule O1 forms its fourth O—H···O hydrogen bond with a neighbouring 0.5-occupancy methanol/water site, thus generating a one-dimensional ntb·(H₂O)···(MeOH/H₂O)···ntb·(H₂O)···(MeOH/H₂O) chain, as depicted in Fig. 4. Since there remains one outside imine N atom and one outside NH group for each ntb molecule, two such one-dimensional chains are connected by the formation of N—H···N hydrogen bonds to result in a double-stranded chain along the a axis (Fig. 4). The acetonitrile molecules are located inside the cavities of such double-stranded chains, with only van der Waals contacts to the hydrogen-bonded chains.

The difference between (I) and (II) is that there is in (II) an additional site equally occupied by methanol and water O atoms, which disrupts the direct hydrogen bonding of the `enclosed' water molecule to a neighbouring ntb molecule as in (I).

S2. Experimental

ntb was prepared from the condensation reaction between nitrilotriacetate and 1,2-diaminobenzene in diethylene glycol (yield 85%). Single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation from 98% methanol solution at room tempearture. The single-crystal of (II) was obtained by slow evaporation from 98% methanol/acetonitrile solution at room temperature.

S3. Refinement

All H atoms, except those on O– and N atoms involved in hydrogen-bond formation, were included as riding atoms. The O– and N-bound H atoms were located in difference Fourier maps and refined with isotropic displacement parameters [for the OH group in (II), U_iso(H) = 1.5U_eq(O)]. In (II) (as noted in the Comment section), the methanol O atom was found to share a site with a water O atom. The site occupancy refinement of the methyl C atom indicated an occupancy of 1/2, while that of the O atom was close to unity. The water (O2) and methanol (O3) O atoms were then assigned occupancies of 0.5 and constrained to lie at the same site. Only one H atom could be located at the O2/O3 site, and this was assigned unit occupancy. The missing 0.5-occupancy water H atom is presumably disordered. Difference maps showed that the H atoms of the methanol and acetonitrile methyl groups in (II) were diffuse, and these were allowed for as six H-atom sites with appropriate occupancy. C-bound H atoms were treated as riding, with C—H distances of 0.93–0.97 Å and Uiso(H) values set at 1.5 (methyl H atoms) and 1.2 (other H atoms) times U_eq(C).

Computing details

Data collection: SMART (Siemens, 1993) for (I); CAD-4 EXPRESS (Enraf–Nonius, 1994) for (II). Cell refinement: SAINT (Siemens, 1995) for (I); CAD-4 EXPRESS for (II). Data reduction: SAINT for (I); XCAD4 (Harms & Wocadlo, 1995) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A view of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen bonds.
	Fig. 2. A view of the hydrogen-bonded two-dimensional network in (I) in the (101) plane. Dashed lines indicate hydrogen bonds. [Symmetry codes: (i) −1/2 + x, 1/2 − y, 1/2 + z; (ii) 1/2 − x, −1/2 + y, 1/2 − z; (iii) 1 − x, −y, 1 − z; (iv) 1 − x, 1 − y, 1 − z.]
	Fig. 3. A view of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen bonds. Atoms O2 and O3 were constrained to share the same site.
	Fig. 4. A view of the hydrogen-bonded chain structure in (II), along the a axis. Dashed lines indicate hydrogen bonds and guest MeCN molecules are in space filling mode. [Symmetry code: (i) x − 1, y, z.]

(I) tris(1H-benzimidazol-2-ylmethyl)amine monohydrate

Crystal data

C24H21N7·H2O	F(000) = 896
Mr = 425.49	Dx = 1.261 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7855 reflections
a = 9.9731 (6) Å	θ = 4.2–26.3°
b = 12.3273 (7) Å	µ = 0.08 mm^−1
c = 18.2323 (11) Å	T = 293 K
β = 91.508 (1)°	Block, colorless
V = 2240.7 (2) Å^3	0.28 × 0.2 × 0.18 mm
Z = 4

Data collection

Bruker SMART 1K CCD diffractometer	6455 independent reflections
Radiation source: fine-focus sealed tube	4526 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
ϕ and ω scans	θmax = 30.0°, θmin = 4.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→14
Tmin = 0.873, Tmax = 1.000	k = −16→17
15554 measured reflections	l = −24→25

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.115	w = 1/[σ^2(Fo^2) + (0.0637P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
6455 reflections	Δρmax = 0.20 e Å^−3
310 parameters	Δρmin = −0.16 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0042 (11)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.63260 (8)	0.41576 (6)	0.13152 (4)	0.03462 (18)
N11	0.80183 (9)	0.33068 (7)	0.24444 (5)	0.0417 (2)
N13	0.73681 (9)	0.45544 (7)	0.32475 (5)	0.0431 (2)
N21	0.83170 (9)	0.34272 (7)	0.03248 (5)	0.0410 (2)
N23	0.81665 (8)	0.50075 (7)	−0.02644 (5)	0.0387 (2)
N33	0.47316 (8)	0.21656 (7)	0.13303 (5)	0.0395 (2)
N31	0.29342 (9)	0.30999 (8)	0.09342 (5)	0.0416 (2)
C1	0.60385 (10)	0.44366 (9)	0.20748 (5)	0.0406 (2)
H1A	0.5226	0.4068	0.2217	0.049*
H1B	0.5883	0.5211	0.2110	0.049*
C12	0.71609 (10)	0.41264 (8)	0.25909 (5)	0.0371 (2)
C14	0.84133 (12)	0.39439 (9)	0.35607 (6)	0.0453 (3)
C15	0.90344 (15)	0.40110 (12)	0.42565 (7)	0.0634 (4)
H15	0.8744	0.4504	0.4604	0.076*
C16	1.00875 (16)	0.33226 (13)	0.44067 (8)	0.0743 (4)
H16	1.0511	0.3350	0.4867	0.089*
C17	1.05402 (16)	0.25861 (12)	0.38920 (9)	0.0709 (4)
H17	1.1269	0.2145	0.4013	0.085*
C18	0.99338 (13)	0.24921 (10)	0.32035 (8)	0.0575 (3)
H18	1.0234	0.2000	0.2858	0.069*
C19	0.88477 (11)	0.31771 (8)	0.30587 (6)	0.0435 (2)
C2	0.72401 (10)	0.49399 (8)	0.09909 (6)	0.0388 (2)
H2A	0.7923	0.5147	0.1353	0.047*
H2B	0.6745	0.5587	0.0847	0.047*
C22	0.78937 (9)	0.44718 (8)	0.03367 (5)	0.0352 (2)
C24	0.88181 (10)	0.42593 (9)	−0.07038 (5)	0.0390 (2)
C25	0.93140 (12)	0.43728 (11)	−0.14071 (6)	0.0538 (3)
H25	0.9244	0.5026	−0.1661	0.065*
C26	0.99128 (14)	0.34770 (13)	−0.17113 (7)	0.0642 (4)
H26	1.0254	0.3529	−0.2180	0.077*
C27	1.00189 (14)	0.25018 (12)	−0.13365 (7)	0.0655 (4)
H27	1.0444	0.1921	−0.1559	0.079*
C28	0.95170 (13)	0.23636 (10)	−0.06465 (7)	0.0573 (3)
H28	0.9577	0.1704	−0.0400	0.069*
C29	0.89165 (10)	0.32649 (8)	−0.03408 (6)	0.0404 (2)
C3	0.51076 (10)	0.40531 (8)	0.08606 (6)	0.0400 (2)
H3A	0.5351	0.3995	0.0351	0.048*
H3B	0.4572	0.4704	0.0911	0.048*
C32	0.42790 (10)	0.30895 (8)	0.10574 (5)	0.0362 (2)
C34	0.35888 (10)	0.15160 (8)	0.13862 (5)	0.0382 (2)
C35	0.34504 (12)	0.04587 (9)	0.16376 (6)	0.0482 (3)
H35	0.4190	0.0064	0.1807	0.058*
C36	0.21837 (13)	0.00148 (10)	0.16283 (7)	0.0578 (3)
H36	0.2073	−0.0696	0.1786	0.069*
C37	0.10616 (13)	0.06042 (11)	0.13880 (7)	0.0616 (3)
H37	0.0219	0.0283	0.1397	0.074*
C38	0.11787 (12)	0.16505 (10)	0.11382 (7)	0.0550 (3)
H38	0.0433	0.2044	0.0975	0.066*
C39	0.24604 (10)	0.20945 (9)	0.11398 (6)	0.0401 (2)
O1	0.75169 (8)	0.17648 (6)	0.13143 (4)	0.04413 (19)
H12	0.6596 (17)	0.1839 (12)	0.1325 (8)	0.074 (4)*
H11	0.7672 (14)	0.1097 (13)	0.1413 (7)	0.065 (4)*
H21	0.8074 (14)	0.2859 (12)	0.0667 (8)	0.070 (4)*
H31	0.2491 (13)	0.3664 (10)	0.0721 (7)	0.056 (4)*
H11A	0.7963 (13)	0.2848 (11)	0.2051 (7)	0.059 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0329 (4)	0.0347 (4)	0.0361 (4)	−0.0001 (3)	−0.0003 (3)	0.0020 (3)
N11	0.0453 (5)	0.0381 (5)	0.0413 (5)	0.0022 (4)	−0.0075 (4)	−0.0050 (4)
N13	0.0490 (5)	0.0406 (5)	0.0396 (5)	−0.0072 (4)	0.0011 (4)	−0.0051 (4)
N21	0.0473 (5)	0.0345 (4)	0.0413 (5)	0.0054 (4)	0.0039 (4)	0.0036 (4)
N23	0.0347 (4)	0.0384 (4)	0.0428 (5)	0.0024 (3)	0.0006 (3)	0.0062 (4)
N33	0.0343 (4)	0.0368 (4)	0.0471 (5)	0.0001 (3)	−0.0044 (3)	0.0072 (4)
N31	0.0331 (4)	0.0411 (5)	0.0503 (5)	0.0029 (4)	−0.0045 (4)	0.0108 (4)
C1	0.0390 (5)	0.0434 (6)	0.0396 (5)	0.0038 (4)	0.0035 (4)	−0.0006 (4)
C12	0.0391 (5)	0.0338 (5)	0.0385 (5)	−0.0043 (4)	0.0024 (4)	−0.0008 (4)
C14	0.0521 (6)	0.0431 (6)	0.0404 (6)	−0.0120 (5)	−0.0050 (5)	0.0011 (4)
C15	0.0776 (9)	0.0680 (8)	0.0440 (6)	−0.0171 (7)	−0.0117 (6)	−0.0004 (6)
C16	0.0854 (10)	0.0796 (10)	0.0562 (8)	−0.0187 (8)	−0.0309 (7)	0.0163 (7)
C17	0.0689 (9)	0.0629 (8)	0.0792 (10)	−0.0054 (7)	−0.0317 (7)	0.0201 (7)
C18	0.0562 (7)	0.0453 (6)	0.0698 (8)	0.0000 (5)	−0.0167 (6)	0.0047 (6)
C19	0.0464 (6)	0.0379 (5)	0.0457 (6)	−0.0076 (5)	−0.0102 (4)	0.0042 (4)
C2	0.0381 (5)	0.0332 (5)	0.0453 (5)	−0.0017 (4)	0.0038 (4)	0.0002 (4)
C22	0.0315 (5)	0.0333 (5)	0.0409 (5)	0.0013 (4)	−0.0008 (4)	0.0027 (4)
C24	0.0317 (5)	0.0458 (6)	0.0394 (5)	−0.0001 (4)	−0.0031 (4)	0.0006 (4)
C25	0.0498 (7)	0.0682 (8)	0.0434 (6)	−0.0018 (6)	0.0031 (5)	0.0047 (6)
C26	0.0577 (8)	0.0915 (10)	0.0438 (7)	−0.0010 (7)	0.0084 (6)	−0.0119 (7)
C27	0.0653 (9)	0.0729 (9)	0.0584 (8)	0.0139 (7)	0.0053 (6)	−0.0218 (7)
C28	0.0657 (8)	0.0488 (7)	0.0574 (7)	0.0132 (6)	0.0006 (6)	−0.0093 (5)
C29	0.0383 (5)	0.0425 (6)	0.0404 (5)	0.0032 (4)	−0.0016 (4)	−0.0023 (4)
C3	0.0379 (5)	0.0384 (5)	0.0434 (5)	−0.0003 (4)	−0.0053 (4)	0.0089 (4)
C32	0.0331 (5)	0.0381 (5)	0.0371 (5)	0.0007 (4)	−0.0035 (4)	0.0036 (4)
C34	0.0361 (5)	0.0377 (5)	0.0405 (5)	−0.0007 (4)	−0.0017 (4)	0.0016 (4)
C35	0.0483 (6)	0.0390 (6)	0.0572 (7)	0.0004 (5)	−0.0016 (5)	0.0049 (5)
C36	0.0585 (8)	0.0439 (6)	0.0710 (8)	−0.0101 (6)	0.0033 (6)	0.0069 (6)
C37	0.0453 (7)	0.0643 (8)	0.0750 (9)	−0.0174 (6)	0.0016 (6)	0.0062 (7)
C38	0.0350 (6)	0.0615 (8)	0.0682 (8)	−0.0031 (5)	−0.0039 (5)	0.0088 (6)
C39	0.0358 (5)	0.0422 (5)	0.0421 (5)	0.0002 (4)	−0.0019 (4)	0.0035 (4)
O1	0.0429 (5)	0.0324 (4)	0.0569 (5)	0.0030 (3)	−0.0025 (3)	0.0052 (3)

Geometric parameters (Å, º)

N1—C3	1.4585 (12)	C18—H18	0.93
N1—C2	1.4626 (12)	C2—C22	1.4904 (14)
N1—C1	1.4627 (12)	C2—H2A	0.97
N11—C12	1.3548 (13)	C2—H2B	0.97
N11—C19	1.3841 (13)	C24—C25	1.3935 (14)
N11—H11A	0.913 (14)	C24—C29	1.3952 (15)
N13—C12	1.3195 (13)	C25—C26	1.3787 (18)
N13—C14	1.3957 (14)	C25—H25	0.93
N21—C22	1.3554 (12)	C26—C27	1.386 (2)
N21—C29	1.3814 (13)	C26—H26	0.93
N21—H21	0.973 (15)	C27—C28	1.3767 (19)
N23—C22	1.3142 (12)	C27—H27	0.93
N23—C24	1.3937 (13)	C28—C29	1.3861 (15)
N33—C32	1.3179 (13)	C28—H28	0.93
N33—C34	1.3988 (13)	C3—C32	1.4961 (14)
N31—C32	1.3541 (12)	C3—H3A	0.97
N31—C39	1.3817 (14)	C3—H3B	0.97
N31—H31	0.906 (13)	C34—C35	1.3898 (15)
C1—C12	1.4929 (14)	C34—C39	1.3965 (14)
C1—H1A	0.97	C35—C36	1.3764 (16)
C1—H1B	0.97	C35—H35	0.93
C14—C19	1.3927 (16)	C36—C37	1.3951 (18)
C14—C15	1.3993 (16)	C36—H36	0.93
C15—C16	1.372 (2)	C37—C38	1.3739 (18)
C15—H15	0.93	C37—H37	0.93
C16—C17	1.390 (2)	C38—C39	1.3905 (15)
C16—H16	0.93	C38—H38	0.93
C17—C18	1.3837 (18)	O1—H12	0.924 (17)
C17—H17	0.93	O1—H11	0.856 (15)
C18—C19	1.3932 (16)
C3—N1—C2	110.32 (8)	N23—C22—C2	125.26 (9)
C3—N1—C1	112.19 (8)	N21—C22—C2	121.58 (8)
C2—N1—C1	111.57 (8)	C25—C24—N23	130.14 (10)
C12—N11—C19	107.07 (9)	C25—C24—C29	120.16 (10)
C12—N11—H11A	126.2 (8)	N23—C24—C29	109.69 (9)
C19—N11—H11A	125.9 (8)	C26—C25—C24	117.24 (12)
C12—N13—C14	104.67 (9)	C26—C25—H25	121.4
C22—N21—C29	107.09 (8)	C24—C25—H25	121.4
C22—N21—H21	126.2 (8)	C25—C26—C27	121.66 (11)
C29—N21—H21	125.4 (8)	C25—C26—H26	119.2
C22—N23—C24	104.87 (8)	C27—C26—H26	119.2
C32—N33—C34	104.51 (8)	C28—C27—C26	122.21 (12)
C32—N31—C39	106.91 (8)	C28—C27—H27	118.9
C32—N31—H31	123.2 (8)	C26—C27—H27	118.9
C39—N31—H31	129.7 (8)	C27—C28—C29	116.08 (12)
N1—C1—C12	111.97 (8)	C27—C28—H28	122.0
N1—C1—H1A	109.2	C29—C28—H28	122.0
C12—C1—H1A	109.2	N21—C29—C28	132.13 (10)
N1—C1—H1B	109.2	N21—C29—C24	105.23 (9)
C12—C1—H1B	109.2	C28—C29—C24	122.63 (10)
H1A—C1—H1B	107.9	N1—C3—C32	113.02 (8)
N13—C12—N11	113.10 (9)	N1—C3—H3A	109.0
N13—C12—C1	124.49 (9)	C32—C3—H3A	109.0
N11—C12—C1	122.24 (9)	N1—C3—H3B	109.0
C19—C14—N13	109.81 (9)	C32—C3—H3B	109.0
C19—C14—C15	119.86 (11)	H3A—C3—H3B	107.8
N13—C14—C15	130.32 (11)	N33—C32—N31	113.50 (9)
C16—C15—C14	117.56 (13)	N33—C32—C3	126.22 (9)
C16—C15—H15	121.2	N31—C32—C3	120.24 (9)
C14—C15—H15	121.2	C35—C34—C39	119.93 (10)
C15—C16—C17	121.98 (13)	C35—C34—N33	130.47 (10)
C15—C16—H16	119.0	C39—C34—N33	109.60 (9)
C17—C16—H16	119.0	C36—C35—C34	117.89 (11)
C18—C17—C16	121.69 (13)	C36—C35—H35	121.1
C18—C17—H17	119.2	C34—C35—H35	121.1
C16—C17—H17	119.2	C35—C36—C37	121.69 (11)
C17—C18—C19	116.12 (13)	C35—C36—H36	119.2
C17—C18—H18	121.9	C37—C36—H36	119.2
C19—C18—H18	121.9	C38—C37—C36	121.23 (11)
N11—C19—C14	105.30 (9)	C38—C37—H37	119.4
N11—C19—C18	131.95 (11)	C36—C37—H37	119.4
C14—C19—C18	122.72 (11)	C37—C38—C39	117.07 (11)
N1—C2—C22	111.02 (8)	C37—C38—H38	121.5
N1—C2—H2A	109.4	C39—C38—H38	121.5
C22—C2—H2A	109.4	N31—C39—C38	132.33 (10)
N1—C2—H2B	109.4	N31—C39—C34	105.48 (9)
C22—C2—H2B	109.4	C38—C39—C34	122.18 (10)
H2A—C2—H2B	108.0	H12—O1—H11	105.4 (13)
N23—C22—N21	113.11 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11A···O1	0.913 (14)	1.938 (14)	2.8380 (12)	168.2 (12)
N31—H31···N23^i	0.906 (13)	1.943 (13)	2.8406 (12)	170.4 (11)
N21—H21···O1	0.973 (15)	1.886 (15)	2.8579 (12)	177.3 (13)
O1—H12···N33	0.924 (17)	1.903 (17)	2.8223 (12)	173.4 (13)
O1—H11···N13^ii	0.856 (15)	2.000 (16)	2.8410 (12)	167.0 (13)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+3/2, y−1/2, −z+1/2.

(II) tris(1H-benzimidazol-2-ylmethyl)amine–water–methanol–acetonitrile (1/1.5/0.5/1)

Crystal data

C24H21N7·1.5H2O·0.5CH4O·C2H3N	Z = 2
Mr = 491.58	F(000) = 520
Triclinic, P1	Dx = 1.246 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.778 (4) Å	Cell parameters from 28 reflections
b = 9.995 (2) Å	θ = 4.6–12.6°
c = 14.397 (6) Å	µ = 0.08 mm^−1
α = 103.34 (1)°	T = 293 K
β = 98.16 (1)°	Block, colorless
γ = 102.34 (1)°	0.75 × 0.65 × 0.50 mm
V = 1310.1 (8) Å^3

Data collection

Siemens P4 diffractometer	3752 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.047
Graphite monochromator	θmax = 26.0°, θmin = 2.2°
ω–2θ scans	h = −1→12
Absorption correction: ψ scan (North et al., 1968)	k = −11→11
Tmin = 0.885, Tmax = 0.938	l = −17→17
5999 measured reflections	3 standard reflections every 197 reflections
5066 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.113	w = 1/[σ^2(Fo^2) + (0.0463P)^2 + 0.303P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.001
5066 reflections	Δρmax = 0.15 e Å^−3
358 parameters	Δρmin = −0.17 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.106 (6)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.46775 (14)	0.09622 (13)	0.32640 (9)	0.0410 (3)
N11	0.42220 (16)	0.17957 (16)	0.15069 (10)	0.0476 (4)
N13	0.63075 (14)	0.14835 (15)	0.11873 (10)	0.0463 (3)
N21	0.32256 (17)	0.29001 (17)	0.42981 (12)	0.0522 (4)
N23	0.49937 (16)	0.34372 (14)	0.55785 (10)	0.0489 (4)
N31	0.30286 (16)	−0.27384 (14)	0.31017 (10)	0.0456 (3)
N33	0.20816 (14)	−0.12802 (14)	0.24167 (10)	0.0465 (3)
C1	0.54940 (18)	0.05535 (18)	0.25195 (12)	0.0476 (4)
H1A	0.5157	−0.0463	0.2222	0.057*
H1B	0.6492	0.0757	0.2827	0.057*
C12	0.53723 (17)	0.13091 (17)	0.17470 (11)	0.0427 (4)
C14	0.57116 (17)	0.21022 (17)	0.05195 (11)	0.0449 (4)
C15	0.6204 (2)	0.24917 (19)	−0.02667 (13)	0.0556 (5)
H15	0.7070	0.2357	−0.0411	0.067*
C16	0.5374 (2)	0.3079 (2)	−0.08185 (14)	0.0639 (5)
H16	0.5685	0.3339	−0.1348	0.077*
C17	0.4082 (2)	0.3297 (2)	−0.06126 (14)	0.0660 (5)
H17	0.3550	0.3703	−0.1004	0.079*
C18	0.3574 (2)	0.2924 (2)	0.01587 (14)	0.0590 (5)
H18	0.2712	0.3074	0.0302	0.071*
C19	0.44045 (17)	0.23165 (18)	0.07119 (12)	0.0460 (4)
C2	0.54805 (17)	0.22778 (17)	0.39910 (12)	0.0459 (4)
H2A	0.5872	0.2973	0.3663	0.055*
H2B	0.6272	0.2093	0.4385	0.055*
C22	0.45679 (18)	0.28734 (16)	0.46352 (12)	0.0439 (4)
C24	0.3836 (2)	0.38694 (18)	0.58822 (13)	0.0531 (4)
C25	0.3693 (3)	0.4527 (2)	0.68176 (16)	0.0713 (6)
H25	0.4438	0.4752	0.7353	0.086*
C26	0.2415 (4)	0.4825 (3)	0.6913 (2)	0.0914 (8)
H26	0.2291	0.5274	0.7526	0.110*
C27	0.1298 (3)	0.4477 (3)	0.6123 (2)	0.0962 (9)
H27	0.0442	0.4692	0.6222	0.115*
C28	0.1407 (3)	0.3820 (3)	0.5187 (2)	0.0823 (7)
H28	0.0652	0.3585	0.4658	0.099*
C29	0.2721 (2)	0.35344 (19)	0.50921 (15)	0.0566 (5)
C3	0.42587 (17)	−0.01741 (17)	0.37257 (11)	0.0439 (4)
H3A	0.3921	0.0199	0.4309	0.053*
H3B	0.5086	−0.0511	0.3919	0.053*
C32	0.31146 (17)	−0.13875 (17)	0.30614 (11)	0.0414 (4)
C34	0.12468 (17)	−0.26664 (18)	0.20032 (12)	0.0459 (4)
C35	0.00123 (19)	−0.3188 (2)	0.12913 (14)	0.0590 (5)
H35	−0.0395	−0.2582	0.1007	0.071*
C36	−0.0591 (2)	−0.4622 (2)	0.10184 (15)	0.0685 (6)
H36	−0.1421	−0.4994	0.0541	0.082*
C37	0.0009 (2)	−0.5531 (2)	0.14388 (16)	0.0695 (6)
H37	−0.0428	−0.6501	0.1233	0.083*
C38	0.1231 (2)	−0.5046 (2)	0.21504 (15)	0.0614 (5)
H38	0.1631	−0.5660	0.2430	0.074*
C39	0.18385 (18)	−0.35803 (18)	0.24313 (12)	0.0457 (4)
N4	0.8059 (3)	0.0332 (4)	0.4728 (2)	0.1275 (10)
C5	0.8497 (2)	−0.0232 (3)	0.4118 (2)	0.0844 (7)
C6	0.9041 (3)	−0.0956 (3)	0.3333 (2)	0.1098 (9)
H6A	0.8594	−0.1957	0.3164	0.165*	0.50
H6B	1.0056	−0.0800	0.3528	0.165*	0.50
H6C	0.8840	−0.0599	0.2778	0.165*	0.50
H6D	0.9733	−0.0280	0.3149	0.165*	0.50
H6E	0.8271	−0.1438	0.2785	0.165*	0.50
H6F	0.9486	−0.1638	0.3536	0.165*	0.50
O1	0.16774 (14)	0.13860 (15)	0.23467 (10)	0.0566 (3)
H11	0.076 (3)	0.129 (2)	0.2038 (17)	0.085*
H12	0.180 (2)	0.053 (3)	0.2375 (17)	0.085*
C4	0.9105 (5)	0.0356 (5)	0.0349 (3)	0.0778 (12)	0.50
H4A	0.9761	0.1161	0.0264	0.117*	0.25
H4B	0.8220	0.0143	−0.0108	0.117*	0.25
H4C	0.9505	−0.0450	0.0240	0.117*	0.25
H4D	0.8563	−0.0592	0.0000	0.117*	0.25
H4E	1.0104	0.0426	0.0372	0.117*	0.25
H4F	0.8819	0.1020	0.0024	0.117*	0.25
O2	0.88523 (18)	0.0672 (2)	0.13064 (13)	0.0935 (6)	0.50
H2	0.796 (4)	0.092 (3)	0.123 (2)	0.140*
O3	0.88523 (18)	0.0672 (2)	0.13064 (13)	0.0935 (6)	0.50
H31	0.363 (2)	−0.2983 (19)	0.3538 (14)	0.060 (5)*
H21	0.275 (2)	0.2506 (19)	0.3711 (15)	0.056 (6)*
H11A	0.344 (3)	0.170 (2)	0.1776 (17)	0.087 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0441 (7)	0.0429 (7)	0.0396 (7)	0.0132 (6)	0.0130 (6)	0.0135 (6)
N11	0.0441 (8)	0.0613 (9)	0.0439 (8)	0.0170 (7)	0.0149 (6)	0.0200 (7)
N13	0.0426 (8)	0.0543 (8)	0.0418 (8)	0.0115 (6)	0.0132 (6)	0.0103 (6)
N21	0.0535 (9)	0.0577 (9)	0.0510 (9)	0.0228 (7)	0.0116 (7)	0.0169 (8)
N23	0.0631 (9)	0.0426 (8)	0.0463 (8)	0.0197 (7)	0.0139 (7)	0.0151 (6)
N31	0.0512 (8)	0.0463 (8)	0.0447 (8)	0.0179 (7)	0.0117 (7)	0.0168 (6)
N33	0.0448 (8)	0.0480 (8)	0.0478 (8)	0.0130 (6)	0.0076 (6)	0.0153 (6)
C1	0.0511 (10)	0.0533 (10)	0.0452 (9)	0.0212 (8)	0.0159 (8)	0.0155 (8)
C12	0.0409 (9)	0.0472 (9)	0.0381 (8)	0.0102 (7)	0.0087 (7)	0.0087 (7)
C14	0.0470 (9)	0.0457 (9)	0.0376 (8)	0.0067 (7)	0.0100 (7)	0.0068 (7)
C15	0.0613 (11)	0.0593 (11)	0.0453 (10)	0.0107 (9)	0.0211 (8)	0.0108 (8)
C16	0.0878 (15)	0.0629 (12)	0.0444 (10)	0.0155 (11)	0.0224 (10)	0.0188 (9)
C17	0.0849 (15)	0.0689 (13)	0.0498 (11)	0.0251 (11)	0.0097 (10)	0.0245 (10)
C18	0.0592 (11)	0.0682 (12)	0.0546 (11)	0.0217 (9)	0.0102 (9)	0.0220 (9)
C19	0.0452 (9)	0.0499 (9)	0.0403 (9)	0.0082 (7)	0.0092 (7)	0.0105 (7)
C2	0.0460 (9)	0.0452 (9)	0.0475 (9)	0.0125 (7)	0.0121 (7)	0.0118 (7)
C22	0.0507 (10)	0.0394 (8)	0.0466 (9)	0.0156 (7)	0.0121 (7)	0.0161 (7)
C24	0.0752 (12)	0.0439 (9)	0.0554 (11)	0.0271 (9)	0.0269 (9)	0.0236 (8)
C25	0.1106 (18)	0.0592 (12)	0.0624 (12)	0.0347 (12)	0.0405 (12)	0.0260 (10)
C26	0.140 (2)	0.0820 (16)	0.0933 (19)	0.0582 (17)	0.0766 (19)	0.0437 (15)
C27	0.110 (2)	0.104 (2)	0.124 (2)	0.0666 (17)	0.081 (2)	0.0566 (18)
C28	0.0783 (15)	0.0952 (17)	0.1046 (19)	0.0490 (14)	0.0422 (14)	0.0484 (15)
C29	0.0661 (12)	0.0562 (11)	0.0664 (12)	0.0310 (9)	0.0308 (10)	0.0290 (9)
C3	0.0467 (9)	0.0482 (9)	0.0391 (8)	0.0139 (7)	0.0072 (7)	0.0158 (7)
C32	0.0433 (9)	0.0452 (9)	0.0406 (8)	0.0153 (7)	0.0130 (7)	0.0149 (7)
C34	0.0451 (9)	0.0499 (10)	0.0438 (9)	0.0119 (8)	0.0143 (7)	0.0118 (7)
C35	0.0506 (11)	0.0678 (12)	0.0544 (11)	0.0107 (9)	0.0093 (9)	0.0131 (9)
C36	0.0562 (12)	0.0757 (14)	0.0575 (12)	0.0017 (11)	0.0118 (9)	0.0008 (11)
C37	0.0711 (14)	0.0546 (11)	0.0675 (13)	−0.0028 (10)	0.0237 (11)	−0.0017 (10)
C38	0.0746 (13)	0.0483 (10)	0.0643 (12)	0.0152 (10)	0.0276 (11)	0.0133 (9)
C39	0.0484 (9)	0.0469 (9)	0.0427 (9)	0.0112 (8)	0.0175 (7)	0.0094 (7)
N4	0.0998 (18)	0.204 (3)	0.115 (2)	0.084 (2)	0.0478 (16)	0.058 (2)
C5	0.0633 (14)	0.118 (2)	0.0972 (19)	0.0385 (14)	0.0320 (13)	0.0550 (16)
C6	0.124 (2)	0.121 (2)	0.112 (2)	0.0518 (19)	0.0586 (19)	0.0451 (19)
O1	0.0439 (7)	0.0609 (8)	0.0724 (9)	0.0176 (6)	0.0108 (6)	0.0290 (7)
C4	0.083 (3)	0.081 (3)	0.068 (3)	0.025 (2)	0.020 (2)	0.013 (2)
O2	0.0672 (10)	0.1297 (15)	0.0911 (12)	0.0509 (10)	0.0099 (9)	0.0239 (10)
O3	0.0672 (10)	0.1297 (15)	0.0911 (12)	0.0509 (10)	0.0099 (9)	0.0239 (10)

Geometric parameters (Å, º)

N1—C3	1.458 (2)	C26—C27	1.382 (4)
N1—C2	1.460 (2)	C26—H26	0.93
N1—C1	1.461 (2)	C27—C28	1.385 (4)
N11—C12	1.350 (2)	C27—H27	0.93
N11—C19	1.381 (2)	C28—C29	1.393 (3)
N11—H11A	0.90 (2)	C28—H28	0.93
N13—C12	1.312 (2)	C3—C32	1.489 (2)
N13—C14	1.384 (2)	C3—H3A	0.97
N21—C22	1.341 (2)	C3—H3B	0.97
N21—C29	1.382 (2)	C34—C35	1.383 (2)
N21—H21	0.86 (2)	C34—C39	1.391 (2)
N23—C22	1.312 (2)	C35—C36	1.367 (3)
N23—C24	1.387 (2)	C35—H35	0.93
N31—C32	1.350 (2)	C36—C37	1.384 (3)
N31—C39	1.372 (2)	C36—H36	0.93
N31—H31	0.91 (2)	C37—C38	1.374 (3)
N33—C32	1.311 (2)	C37—H37	0.93
N33—C34	1.392 (2)	C38—C39	1.396 (2)
C1—C12	1.487 (2)	C38—H38	0.93
C1—H1A	0.97	N4—C5	1.121 (3)
C1—H1B	0.97	C5—C6	1.429 (4)
C14—C15	1.394 (2)	C6—H6A	0.96
C14—C19	1.395 (2)	C6—H6B	0.96
C15—C16	1.367 (3)	C6—H6C	0.96
C15—H15	0.93	C6—H6D	0.96
C16—C17	1.388 (3)	C6—H6E	0.96
C16—H16	0.93	C6—H6F	0.96
C17—C18	1.374 (3)	O1—H11	0.91 (2)
C17—H17	0.93	O1—H12	0.90 (2)
C18—C19	1.383 (2)	C4—O2	1.410 (5)
C18—H18	0.93	C4—H4A	0.96
C2—C22	1.489 (2)	C4—H4B	0.96
C2—H2A	0.97	C4—H4C	0.96
C2—H2B	0.97	C4—H4D	0.96
C24—C29	1.382 (3)	C4—H4E	0.96
C24—C25	1.396 (3)	C4—H4F	0.96
C25—C26	1.363 (3)	O2—H2	0.95 (3)
C25—H25	0.93
C3—N1—C2	110.75 (12)	C26—C27—C28	122.5 (2)
C3—N1—C1	111.29 (12)	C26—C27—H27	118.8
C2—N1—C1	110.97 (13)	C28—C27—H27	118.8
C12—N11—C19	107.19 (14)	C27—C28—C29	115.6 (3)
C12—N11—H11A	126.0 (15)	C27—C28—H28	122.2
C19—N11—H11A	126.5 (15)	C29—C28—H28	122.2
C12—N13—C14	104.75 (13)	C24—C29—N21	105.52 (16)
C22—N21—C29	106.70 (16)	C24—C29—C28	122.1 (2)
C22—N21—H21	125.7 (13)	N21—C29—C28	132.4 (2)
C29—N21—H21	127.2 (13)	N1—C3—C32	111.82 (13)
C22—N23—C24	104.78 (15)	N1—C3—H3A	109.3
C32—N31—C39	106.81 (14)	C32—C3—H3A	109.3
C32—N31—H31	123.8 (12)	N1—C3—H3B	109.3
C39—N31—H31	129.3 (12)	C32—C3—H3B	109.3
C32—N33—C34	105.03 (13)	H3A—C3—H3B	107.9
N1—C1—C12	112.74 (13)	N33—C32—N31	113.18 (15)
N1—C1—H1A	109.0	N33—C32—C3	125.39 (14)
C12—C1—H1A	109.0	N31—C32—C3	121.39 (14)
N1—C1—H1B	109.0	C35—C34—C39	120.53 (16)
C12—C1—H1B	109.0	C35—C34—N33	130.48 (16)
H1A—C1—H1B	107.8	C39—C34—N33	109.00 (14)
N13—C12—N11	113.20 (15)	C36—C35—C34	117.99 (19)
N13—C12—C1	124.03 (15)	C36—C35—H35	121.0
N11—C12—C1	122.60 (14)	C34—C35—H35	121.0
N13—C14—C15	130.51 (16)	C35—C36—C37	121.4 (2)
N13—C14—C19	110.08 (14)	C35—C36—H36	119.3
C15—C14—C19	119.41 (16)	C37—C36—H36	119.3
C16—C15—C14	117.92 (18)	C38—C37—C36	122.07 (19)
C16—C15—H15	121.0	C38—C37—H37	119.0
C14—C15—H15	121.0	C36—C37—H37	119.0
C15—C16—C17	122.00 (18)	C37—C38—C39	116.42 (19)
C15—C16—H16	119.0	C37—C38—H38	121.8
C17—C16—H16	119.0	C39—C38—H38	121.8
C18—C17—C16	121.20 (18)	N31—C39—C34	105.99 (14)
C18—C17—H17	119.4	N31—C39—C38	132.37 (17)
C16—C17—H17	119.4	C34—C39—C38	121.64 (17)
C17—C18—C19	116.91 (18)	N4—C5—C6	179.4 (3)
C17—C18—H18	121.5	C5—C6—H6A	109.5
C19—C18—H18	121.5	C5—C6—H6B	109.5
N11—C19—C18	132.67 (16)	H6A—C6—H6B	109.5
N11—C19—C14	104.77 (14)	C5—C6—H6C	109.5
C18—C19—C14	122.56 (16)	H6A—C6—H6C	109.5
N1—C2—C22	111.81 (13)	H6B—C6—H6C	109.5
N1—C2—H2A	109.3	C5—C6—H6D	109.5
C22—C2—H2A	109.3	H6A—C6—H6D	141.1
N1—C2—H2B	109.3	H6B—C6—H6D	56.3
C22—C2—H2B	109.3	H6C—C6—H6D	56.3
H2A—C2—H2B	107.9	C5—C6—H6E	109.5
N23—C22—N21	113.38 (15)	H6A—C6—H6E	56.3
N23—C22—C2	123.84 (15)	H6B—C6—H6E	141.1
N21—C22—C2	122.77 (16)	H6C—C6—H6E	56.3
C29—C24—N23	109.61 (16)	H6D—C6—H6E	109.5
C29—C24—C25	121.04 (19)	C5—C6—H6F	109.5
N23—C24—C25	129.34 (19)	H6A—C6—H6F	56.3
C26—C25—C24	117.1 (2)	H6B—C6—H6F	56.3
C26—C25—H25	121.4	H6C—C6—H6F	141.1
C24—C25—H25	121.4	H6D—C6—H6F	109.5
C25—C26—C27	121.7 (2)	H6E—C6—H6F	109.5
C25—C26—H26	119.2	H11—O1—H12	110 (2)
C27—C26—H26	119.2	C4—O2—H2	104 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21···O1	0.86 (2)	2.03 (2)	2.886 (2)	174.0 (18)
N11—H11A···O1	0.90 (2)	2.01 (2)	2.910 (2)	177 (2)
O1—H12···N33	0.90 (2)	1.90 (2)	2.798 (2)	179 (2)
O2—H2···N13	0.95 (3)	1.82 (3)	2.772 (2)	176 (3)
O1—H11···O2^i	0.91 (2)	1.91 (3)	2.806 (2)	168 (2)
O1—H11···O3^i	0.91 (2)	1.91 (3)	2.806 (2)	168 (2)
N31—H31···N23^ii	0.91 (2)	1.91 (2)	2.826 (2)	176.3 (17)

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y, −z+1.