The tris(1
H-benzimidazol-2-ylmethyl)amine (ntb) molecule crystallizes in different solvent systems, resulting in two kinds of adduct, namely the monohydrate, C
24H
21N
7·H
2O or ntb·H
2O, (I), and the acetonitrile–methanol–water (1/0.5/1.5) solvate, C
24H
21N
7·C
2H
3N·0.5CH
4O·1.5H
2O or ntb·1.5H
2O·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·H
2O 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.
Supporting information
CCDC references: 285654; 285655
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.
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), Uiso(H) = 1.5Ueq(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 Ueq(C).
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.
(I) tris(1
H-benzimidazol-2-ylmethyl)amine monohydrate
top
Crystal data top
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) Å3 | 0.28 × 0.2 × 0.18 mm |
Z = 4 | |
Data collection top
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 top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.040 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.115 | w = 1/[σ2(Fo2) + (0.0637P)2] where P = (Fo2 + 2Fc2)/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+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0042 (11) |
Crystal data top
C24H21N7·H2O | V = 2240.7 (2) Å3 |
Mr = 425.49 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.9731 (6) Å | µ = 0.08 mm−1 |
b = 12.3273 (7) Å | T = 293 K |
c = 18.2323 (11) Å | 0.28 × 0.2 × 0.18 mm |
β = 91.508 (1)° | |
Data collection top
Bruker SMART 1K CCD diffractometer | 6455 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4526 reflections with I > 2σ(I) |
Tmin = 0.873, Tmax = 1.000 | Rint = 0.019 |
15554 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.115 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.20 e Å−3 |
6455 reflections | Δρmin = −0.16 e Å−3 |
310 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 | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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) top
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···N23i | 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···N13ii | 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(1
H-benzimidazol-2-ylmethyl)amine–water–methanol–acetonitrile (1/1.5/0.5/1)
top
Crystal data top
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) Å3 | |
Data collection top
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 top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.045 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.113 | w = 1/[σ2(Fo2) + (0.0463P)2 + 0.303P] where P = (Fo2 + 2Fc2)/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+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.106 (6) |
Crystal data top
C24H21N7·1.5H2O·0.5CH4O·C2H3N | γ = 102.34 (1)° |
Mr = 491.58 | V = 1310.1 (8) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.778 (4) Å | Mo Kα radiation |
b = 9.995 (2) Å | µ = 0.08 mm−1 |
c = 14.397 (6) Å | T = 293 K |
α = 103.34 (1)° | 0.75 × 0.65 × 0.50 mm |
β = 98.16 (1)° | |
Data collection top
Siemens P4 diffractometer | 3752 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.047 |
Tmin = 0.885, Tmax = 0.938 | 3 standard reflections every 197 reflections |
5999 measured reflections | intensity decay: none |
5066 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.15 e Å−3 |
5066 reflections | Δρmin = −0.17 e Å−3 |
358 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 | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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) top
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···O2i | 0.91 (2) | 1.91 (3) | 2.806 (2) | 168 (2) |
O1—H11···O3i | 0.91 (2) | 1.91 (3) | 2.806 (2) | 168 (2) |
N31—H31···N23ii | 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. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C24H21N7·H2O | C24H21N7·1.5H2O·0.5CH4O·C2H3N |
Mr | 425.49 | 491.58 |
Crystal system, space group | Monoclinic, P21/n | Triclinic, P1 |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 9.9731 (6), 12.3273 (7), 18.2323 (11) | 9.778 (4), 9.995 (2), 14.397 (6) |
α, β, γ (°) | 90, 91.508 (1), 90 | 103.34 (1), 98.16 (1), 102.34 (1) |
V (Å3) | 2240.7 (2) | 1310.1 (8) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.08 |
Crystal size (mm) | 0.28 × 0.2 × 0.18 | 0.75 × 0.65 × 0.50 |
|
Data collection |
Diffractometer | Bruker SMART 1K CCD diffractometer | Siemens P4 diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.873, 1.000 | 0.885, 0.938 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15554, 6455, 4526 | 5999, 5066, 3752 |
Rint | 0.019 | 0.047 |
(sin θ/λ)max (Å−1) | 0.704 | 0.617 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.115, 1.03 | 0.045, 0.113, 1.01 |
No. of reflections | 6455 | 5066 |
No. of parameters | 310 | 358 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.20, −0.16 | 0.15, −0.17 |
Hydrogen-bond geometry (Å, º) for (I) top
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···N23i | 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···N13ii | 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. |
Hydrogen-bond geometry (Å, º) for (II) top
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···O2i | 0.91 (2) | 1.91 (3) | 2.806 (2) | 168 (2) |
O1—H11···O3i | 0.91 (2) | 1.91 (3) | 2.806 (2) | 168 (2) |
N31—H31···N23ii | 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. |
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).