organic compounds
2-(4-tert-Butylphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline sesquihydrate
aHubei Key Laboratory of Pollutant Analysis and Reuse Technology, Hubei Normal University, Huangshi 435002, People's Republic of China
*Correspondence e-mail: chunyangzheng@yahoo.com.cn
In the title compound, C23H20N4·1.5H2O, the mean planes of the imidazo[4,5-f][1,10]phenanthroline system and the benzene ring make a dihedral angle of 21.76 (2)°. One water O atom lies on a twofold rotation axis. The organic molecules and water molecules are linked via N—H⋯O, O—H⋯N and O—H⋯O hydrogen bonds. Weak intermolecular C—H⋯N hydrogen bonds and π–π stacking interactions between inversion-related phenanthroline rings complete the three-dimensional hydrogen-bonding network in the The stacking distance is short at 3.513 (2) Å and the perpendicular distance between the rings is 3.355 Å. The three methyl groups are disordered over two positions, with a site-occupancy ratio of 0.875 (14):0.125 (14).
Related literature
For 1,10-phenanthroline derivatives as ligands, see: Cardinaels et al. (2005); Liu et al. (2005). For the crystal structures of 1,10-phenanthroline derivatives, see: Bian et al. (2002); Wu et al. (1998). For aromatic π–π stacking interactions, see: Janiak (2000).
Experimental
Crystal data
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Data collection
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Refinement
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Data collection: SMART (Bruker, 1997); cell SAINT (Bruker, 1999); data reduction: SAINT; 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 and PLATON (Spek, 2009).
Supporting information
10.1107/S1600536809020261/si2177sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809020261/si2177Isup2.hkl
1,10-Phenanthroline-5,6-dione (0.84 g, 0.004 mol) and ammonium acetate (3.1 g, 0.04 mmol) were dissolved in 40 ml of hot glacial acetic acid. While the mixture was stirred, a solution of 4-tert-butylbenzaldehyde (0.65 g, 0.004 mmol) in 10 ml of glacial acetic acid was added dropwise to the mixture. The mixture was heated at 363 K for 3 h and was then poured in 200 ml of water. The solution was neutralized with ammonia to pH=8 and was then cooled to room temperature. The precipitate was filtered off and recrystallized from dillute ethanol solution to give the title compound (I). Crystals suitable for X-ray diffraction were grown by slow evaporation of the EtOH solutions at room temperature.
The methyl groups were found to be disordered over two orientations. The occupancies of the disordered positions C21/C21', C22/C22' and C23/C23' were refined to 0.875 (14)/0.125 (14). Suitable restraints were applied to the C—C distances involving the disordered atoms. The methyl H atoms were constrained to an ideal geometry with C—H distances of 0.96 Å and Uiso(H) = 1.5 Ueq(C), but each group was allowed to rotate freely about its C—C bond. Other H atoms were placed in geometrically idealized positions and constrained to ride on their parent C atoms, with C—H distances of 0.93 to 0.97 Å, and with Uiso(H) = 1.2 Ueq(C). All H atoms on N atoms were positioned geometrically and refined as riding atoms, with N—H = 0.86 Å and Uiso(H) = 1.2 Ueq(N). The H atoms of the waters were located in a Fourier map following isotropic
In the absence of significant effects, Friedel related intensity reflections were averaged.Data collection: SMART (Bruker, 1997); cell
SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); 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) and PLATON (Spek, 2009).Fig. 1. View of the molecular structure of (I), showing the atomic numbering. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are indicated by dashed lines. The three disordered methyl groups were omitted for clarity. | |
Fig. 2. A section of the structure of (I) with intermolecular hydrogen bonds indicated as dashed lines. |
C23H20N4·1.5H2O | Dx = 1.257 Mg m−3 |
Mr = 379.46 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P43212 | Cell parameters from 5405 reflections |
Hall symbol: P4nw 2abw | θ = 2.2–22.5° |
a = 14.809 (4) Å | µ = 0.08 mm−1 |
c = 18.281 (6) Å | T = 298 K |
V = 4009.1 (19) Å3 | Block, yellow |
Z = 8 | 0.16 × 0.13 × 0.10 mm |
F(000) = 1608 |
Bruker SMART CCD area-detector diffractometer | 2508 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.054 |
Graphite monochromator | θmax = 27.5°, θmin = 1.9° |
ϕ and ω scans | h = −19→19 |
46858 measured reflections | k = −19→19 |
2670 independent reflections | l = −23→23 |
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)] = 0.068 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.167 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.28 | w = 1/[σ2(Fo2) + (0.0765P)2 + 0.9688P] where P = (Fo2 + 2Fc2)/3 |
2670 reflections | (Δ/σ)max < 0.001 |
304 parameters | Δρmax = 0.30 e Å−3 |
53 restraints | Δρmin = −0.15 e Å−3 |
C23H20N4·1.5H2O | Z = 8 |
Mr = 379.46 | Mo Kα radiation |
Tetragonal, P43212 | µ = 0.08 mm−1 |
a = 14.809 (4) Å | T = 298 K |
c = 18.281 (6) Å | 0.16 × 0.13 × 0.10 mm |
V = 4009.1 (19) Å3 |
Bruker SMART CCD area-detector diffractometer | 2508 reflections with I > 2σ(I) |
46858 measured reflections | Rint = 0.054 |
2670 independent reflections |
R[F2 > 2σ(F2)] = 0.068 | 53 restraints |
wR(F2) = 0.167 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.28 | Δρmax = 0.30 e Å−3 |
2670 reflections | Δρmin = −0.15 e Å−3 |
304 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) | |
C1 | 0.7310 (2) | 0.4019 (2) | 1.19064 (17) | 0.0436 (7) | |
C2 | 0.6832 (2) | 0.3733 (2) | 1.12626 (16) | 0.0412 (7) | |
C3 | 0.6074 (2) | 0.4156 (2) | 1.10102 (16) | 0.0392 (7) | |
C4 | 0.5709 (2) | 0.4934 (2) | 1.13671 (16) | 0.0399 (7) | |
C5 | 0.6151 (2) | 0.5242 (2) | 1.20079 (17) | 0.0424 (7) | |
C6 | 0.6959 (2) | 0.4778 (2) | 1.22760 (17) | 0.0453 (8) | |
N1 | 0.7345 (2) | 0.5111 (2) | 1.28912 (17) | 0.0593 (9) | |
C7 | 0.8061 (3) | 0.4692 (3) | 1.3142 (2) | 0.0723 (13) | |
H7 | 0.8325 | 0.4915 | 1.3567 | 0.087* | |
C8 | 0.8453 (3) | 0.3944 (4) | 1.2822 (3) | 0.0760 (14) | |
H8 | 0.8961 | 0.3676 | 1.3027 | 0.091* | |
C9 | 0.8074 (3) | 0.3605 (3) | 1.2194 (2) | 0.0623 (10) | |
H9 | 0.8325 | 0.3104 | 1.1965 | 0.075* | |
N2 | 0.5840 (2) | 0.5952 (2) | 1.23928 (16) | 0.0505 (7) | |
C10 | 0.5114 (3) | 0.6373 (3) | 1.2156 (2) | 0.0538 (9) | |
H10 | 0.4901 | 0.6860 | 1.2428 | 0.065* | |
C11 | 0.4647 (3) | 0.6138 (3) | 1.1531 (2) | 0.0569 (9) | |
H11 | 0.4139 | 0.6460 | 1.1385 | 0.068* | |
C12 | 0.4950 (2) | 0.5420 (2) | 1.11298 (19) | 0.0504 (8) | |
H12 | 0.4654 | 0.5254 | 1.0702 | 0.060* | |
C13 | 0.6348 (2) | 0.3069 (2) | 1.02710 (16) | 0.0416 (7) | |
C14 | 0.6341 (2) | 0.2461 (2) | 0.96339 (16) | 0.0426 (7) | |
C15 | 0.5563 (2) | 0.2359 (2) | 0.92178 (18) | 0.0480 (8) | |
H15 | 0.5038 | 0.2657 | 0.9359 | 0.058* | |
C16 | 0.5553 (3) | 0.1825 (2) | 0.85987 (18) | 0.0500 (8) | |
H16 | 0.5020 | 0.1764 | 0.8335 | 0.060* | |
C17 | 0.6319 (3) | 0.1377 (2) | 0.83626 (18) | 0.0510 (9) | |
C18 | 0.7096 (3) | 0.1491 (3) | 0.8774 (2) | 0.0616 (11) | |
H18 | 0.7623 | 0.1202 | 0.8627 | 0.074* | |
C19 | 0.7112 (3) | 0.2021 (3) | 0.93992 (19) | 0.0566 (10) | |
H19 | 0.7646 | 0.2082 | 0.9663 | 0.068* | |
C20 | 0.6326 (3) | 0.0806 (3) | 0.76548 (19) | 0.0646 (11) | |
C21 | 0.5375 (4) | 0.0646 (6) | 0.7367 (4) | 0.110 (3) | 0.875 (14) |
H21A | 0.5404 | 0.0291 | 0.6928 | 0.165* | 0.875 (14) |
H21B | 0.5094 | 0.1216 | 0.7262 | 0.165* | 0.875 (14) |
H21C | 0.5028 | 0.0331 | 0.7729 | 0.165* | 0.875 (14) |
C22 | 0.6769 (8) | −0.0099 (5) | 0.7785 (4) | 0.122 (4) | 0.875 (14) |
H22A | 0.6722 | −0.0460 | 0.7351 | 0.183* | 0.875 (14) |
H22B | 0.6472 | −0.0401 | 0.8182 | 0.183* | 0.875 (14) |
H22C | 0.7394 | −0.0010 | 0.7904 | 0.183* | 0.875 (14) |
C23 | 0.6840 (7) | 0.1327 (6) | 0.7075 (3) | 0.125 (4) | 0.875 (14) |
H23A | 0.7410 | 0.1519 | 0.7269 | 0.188* | 0.875 (14) |
H23B | 0.6495 | 0.1846 | 0.6929 | 0.188* | 0.875 (14) |
H23C | 0.6940 | 0.0945 | 0.6658 | 0.188* | 0.875 (14) |
C21' | 0.565 (3) | 0.003 (3) | 0.765 (3) | 0.13 (2) | 0.125 (14) |
H21D | 0.5711 | −0.0303 | 0.7199 | 0.188* | 0.125 (14) |
H21E | 0.5047 | 0.0268 | 0.7680 | 0.188* | 0.125 (14) |
H21F | 0.5762 | −0.0362 | 0.8054 | 0.188* | 0.125 (14) |
C22' | 0.7261 (17) | 0.040 (4) | 0.752 (3) | 0.099 (17) | 0.125 (14) |
H22D | 0.7216 | −0.0080 | 0.7169 | 0.149* | 0.125 (14) |
H22E | 0.7490 | 0.0154 | 0.7976 | 0.149* | 0.125 (14) |
H22F | 0.7664 | 0.0853 | 0.7347 | 0.149* | 0.125 (14) |
C23' | 0.612 (4) | 0.140 (3) | 0.6995 (18) | 0.12 (2) | 0.125 (14) |
H23D | 0.6390 | 0.1146 | 0.6565 | 0.174* | 0.125 (14) |
H23E | 0.6365 | 0.1996 | 0.7076 | 0.174* | 0.125 (14) |
H23F | 0.5479 | 0.1446 | 0.6929 | 0.174* | 0.125 (14) |
N3 | 0.70020 (19) | 0.30431 (19) | 1.07917 (14) | 0.0433 (6) | |
H3 | 0.734 (2) | 0.2580 (17) | 1.086 (2) | 0.052* | |
N4 | 0.57632 (19) | 0.37297 (18) | 1.03858 (13) | 0.0417 (6) | |
O1 | 0.8076 (2) | 0.1575 (2) | 1.11023 (13) | 0.0661 (9) | |
H1A | 0.852 (2) | 0.159 (4) | 1.0831 (19) | 0.099* | |
H1B | 0.824 (3) | 0.140 (4) | 1.1511 (13) | 0.099* | |
O2 | 0.38586 (17) | 0.38586 (17) | 1.0000 | 0.0487 (8) | |
H2A | 0.4347 (17) | 0.366 (3) | 1.014 (3) | 0.073* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0486 (18) | 0.0470 (18) | 0.0354 (14) | −0.0038 (15) | −0.0049 (13) | 0.0075 (13) |
C2 | 0.0490 (18) | 0.0405 (16) | 0.0341 (14) | −0.0017 (14) | −0.0012 (13) | 0.0037 (12) |
C3 | 0.0475 (17) | 0.0393 (15) | 0.0307 (13) | −0.0020 (13) | −0.0058 (12) | 0.0041 (12) |
C4 | 0.0453 (17) | 0.0405 (16) | 0.0340 (14) | −0.0022 (13) | −0.0008 (13) | 0.0001 (12) |
C5 | 0.0510 (18) | 0.0420 (17) | 0.0342 (14) | −0.0069 (14) | 0.0002 (13) | 0.0027 (12) |
C6 | 0.0514 (18) | 0.0490 (18) | 0.0355 (15) | −0.0111 (15) | −0.0054 (14) | 0.0018 (13) |
N1 | 0.064 (2) | 0.069 (2) | 0.0451 (15) | −0.0063 (17) | −0.0158 (15) | −0.0029 (15) |
C7 | 0.079 (3) | 0.081 (3) | 0.057 (2) | −0.006 (3) | −0.031 (2) | −0.004 (2) |
C8 | 0.069 (3) | 0.086 (3) | 0.072 (3) | 0.010 (3) | −0.031 (2) | 0.002 (3) |
C9 | 0.062 (2) | 0.064 (2) | 0.061 (2) | 0.005 (2) | −0.0200 (19) | −0.0030 (19) |
N2 | 0.0604 (18) | 0.0486 (16) | 0.0425 (14) | −0.0071 (13) | −0.0021 (14) | −0.0057 (13) |
C10 | 0.061 (2) | 0.0452 (18) | 0.0552 (19) | −0.0009 (16) | 0.0023 (18) | −0.0122 (17) |
C11 | 0.060 (2) | 0.048 (2) | 0.062 (2) | 0.0087 (17) | −0.0095 (18) | −0.0069 (17) |
C12 | 0.058 (2) | 0.0471 (18) | 0.0459 (17) | 0.0003 (16) | −0.0133 (16) | −0.0037 (15) |
C13 | 0.0492 (17) | 0.0409 (16) | 0.0347 (14) | 0.0019 (14) | −0.0003 (13) | 0.0050 (13) |
C14 | 0.0523 (18) | 0.0408 (16) | 0.0349 (14) | 0.0042 (14) | −0.0006 (14) | 0.0033 (13) |
C15 | 0.0472 (19) | 0.0515 (19) | 0.0452 (16) | 0.0083 (15) | 0.0009 (15) | −0.0064 (15) |
C16 | 0.058 (2) | 0.051 (2) | 0.0408 (16) | 0.0000 (17) | −0.0041 (16) | −0.0042 (15) |
C17 | 0.073 (2) | 0.0489 (19) | 0.0317 (14) | 0.0097 (17) | 0.0009 (16) | −0.0007 (14) |
C18 | 0.066 (2) | 0.074 (3) | 0.0446 (18) | 0.029 (2) | −0.0004 (18) | −0.0092 (18) |
C19 | 0.056 (2) | 0.069 (2) | 0.0449 (18) | 0.0161 (19) | −0.0064 (16) | −0.0076 (17) |
C20 | 0.090 (3) | 0.069 (3) | 0.0340 (17) | 0.016 (2) | −0.0018 (19) | −0.0102 (18) |
C21 | 0.111 (5) | 0.131 (7) | 0.088 (5) | −0.003 (5) | −0.016 (4) | −0.068 (5) |
C22 | 0.194 (10) | 0.100 (6) | 0.072 (4) | 0.064 (6) | −0.030 (5) | −0.038 (4) |
C23 | 0.169 (9) | 0.162 (8) | 0.044 (3) | −0.053 (7) | 0.024 (4) | −0.020 (4) |
C21' | 0.13 (3) | 0.12 (3) | 0.13 (3) | −0.006 (19) | −0.007 (19) | −0.019 (19) |
C22' | 0.11 (2) | 0.10 (2) | 0.09 (2) | 0.019 (17) | −0.012 (17) | −0.026 (18) |
C23' | 0.13 (3) | 0.11 (3) | 0.11 (2) | 0.003 (19) | −0.011 (19) | −0.014 (18) |
N3 | 0.0484 (16) | 0.0451 (15) | 0.0363 (13) | 0.0073 (12) | −0.0044 (12) | 0.0032 (12) |
N4 | 0.0514 (15) | 0.0418 (14) | 0.0319 (11) | 0.0064 (12) | −0.0039 (12) | −0.0008 (11) |
O1 | 0.0715 (19) | 0.086 (2) | 0.0412 (12) | 0.0343 (17) | 0.0099 (13) | 0.0085 (14) |
O2 | 0.0519 (12) | 0.0519 (12) | 0.0422 (17) | −0.0066 (17) | 0.0024 (11) | −0.0024 (11) |
C1—C9 | 1.390 (5) | C17—C18 | 1.384 (6) |
C1—C6 | 1.411 (5) | C17—C20 | 1.545 (5) |
C1—C2 | 1.437 (4) | C18—C19 | 1.387 (5) |
C2—N3 | 1.360 (4) | C18—H18 | 0.9300 |
C2—C3 | 1.366 (4) | C19—H19 | 0.9300 |
C3—N4 | 1.383 (4) | C20—C22 | 1.511 (6) |
C3—C4 | 1.431 (5) | C20—C23 | 1.516 (6) |
C4—C12 | 1.403 (5) | C20—C21 | 1.522 (6) |
C4—C5 | 1.418 (4) | C20—C21' | 1.524 (10) |
C5—N2 | 1.346 (4) | C20—C23' | 1.527 (10) |
C5—C6 | 1.465 (5) | C20—C22' | 1.532 (10) |
C6—N1 | 1.354 (4) | C21—H21A | 0.9600 |
N1—C7 | 1.312 (6) | C21—H21B | 0.9600 |
C7—C8 | 1.381 (7) | C21—H21C | 0.9600 |
C7—H7 | 0.9300 | C22—H22A | 0.9600 |
C8—C9 | 1.372 (6) | C22—H22B | 0.9600 |
C8—H8 | 0.9300 | C22—H22C | 0.9600 |
C9—H9 | 0.9300 | C23—H23A | 0.9600 |
N2—C10 | 1.316 (5) | C23—H23B | 0.9600 |
C10—C11 | 1.382 (5) | C23—H23C | 0.9600 |
C10—H10 | 0.9300 | C21'—H21D | 0.9600 |
C11—C12 | 1.367 (5) | C21'—H21E | 0.9600 |
C11—H11 | 0.9300 | C21'—H21F | 0.9600 |
C12—H12 | 0.9300 | C22'—H22D | 0.9600 |
C13—N4 | 1.323 (4) | C22'—H22E | 0.9600 |
C13—N3 | 1.359 (4) | C22'—H22F | 0.9600 |
C13—C14 | 1.472 (4) | C23'—H23D | 0.9600 |
C14—C19 | 1.383 (5) | C23'—H23E | 0.9600 |
C14—C15 | 1.389 (5) | C23'—H23F | 0.9600 |
C15—C16 | 1.381 (5) | N3—H3 | 0.86 (3) |
C15—H15 | 0.9300 | O1—H1A | 0.83 (3) |
C16—C17 | 1.383 (5) | O1—H1B | 0.83 (3) |
C16—H16 | 0.9300 | O2—H2A | 0.82 (3) |
C9—C1—C6 | 118.0 (3) | C19—C18—H18 | 119.0 |
C9—C1—C2 | 125.5 (3) | C14—C19—C18 | 120.5 (4) |
C6—C1—C2 | 116.4 (3) | C14—C19—H19 | 119.7 |
N3—C2—C3 | 106.4 (3) | C18—C19—H19 | 119.7 |
N3—C2—C1 | 130.4 (3) | C22—C20—C23 | 110.0 (5) |
C3—C2—C1 | 123.2 (3) | C22—C20—C21 | 108.5 (5) |
C2—C3—N4 | 110.1 (3) | C23—C20—C21 | 107.6 (5) |
C2—C3—C4 | 121.7 (3) | C23—C20—C21' | 135 (2) |
N4—C3—C4 | 128.2 (3) | C22—C20—C23' | 136.5 (19) |
C12—C4—C5 | 117.4 (3) | C21'—C20—C23' | 107.3 (10) |
C12—C4—C3 | 125.1 (3) | C21—C20—C22' | 136.1 (18) |
C5—C4—C3 | 117.5 (3) | C21'—C20—C22' | 107.1 (9) |
N2—C5—C4 | 121.7 (3) | C23'—C20—C22' | 106.7 (9) |
N2—C5—C6 | 118.1 (3) | C22—C20—C17 | 110.9 (3) |
C4—C5—C6 | 120.2 (3) | C23—C20—C17 | 108.1 (4) |
N1—C6—C1 | 122.2 (3) | C21—C20—C17 | 111.7 (4) |
N1—C6—C5 | 116.9 (3) | C21'—C20—C17 | 115 (2) |
C1—C6—C5 | 121.0 (3) | C23'—C20—C17 | 110.1 (19) |
C7—N1—C6 | 117.4 (4) | C22'—C20—C17 | 110.7 (17) |
N1—C7—C8 | 124.8 (4) | C20—C21—H21A | 109.5 |
N1—C7—H7 | 117.6 | C20—C21—H21B | 109.5 |
C8—C7—H7 | 117.6 | C20—C21—H21C | 109.5 |
C9—C8—C7 | 118.5 (4) | C20—C22—H22A | 109.5 |
C9—C8—H8 | 120.8 | C20—C22—H22B | 109.5 |
C7—C8—H8 | 120.8 | C20—C22—H22C | 109.5 |
C8—C9—C1 | 119.2 (4) | C20—C23—H23A | 109.5 |
C8—C9—H9 | 120.4 | C20—C23—H23B | 109.5 |
C1—C9—H9 | 120.4 | C20—C23—H23C | 109.5 |
C10—N2—C5 | 118.5 (3) | C20—C21'—H21D | 109.5 |
N2—C10—C11 | 124.2 (3) | C20—C21'—H21E | 109.5 |
N2—C10—H10 | 117.9 | H21D—C21'—H21E | 109.5 |
C11—C10—H10 | 117.9 | C20—C21'—H21F | 109.5 |
C12—C11—C10 | 118.4 (4) | H21D—C21'—H21F | 109.5 |
C12—C11—H11 | 120.8 | H21E—C21'—H21F | 109.5 |
C10—C11—H11 | 120.8 | C20—C22'—H22D | 109.5 |
C11—C12—C4 | 119.7 (3) | C20—C22'—H22E | 109.5 |
C11—C12—H12 | 120.1 | H22D—C22'—H22E | 109.5 |
C4—C12—H12 | 120.1 | C20—C22'—H22F | 109.5 |
N4—C13—N3 | 112.1 (3) | H22D—C22'—H22F | 109.5 |
N4—C13—C14 | 125.0 (3) | H22E—C22'—H22F | 109.5 |
N3—C13—C14 | 122.8 (3) | C20—C23'—H23D | 109.5 |
C19—C14—C15 | 117.7 (3) | C20—C23'—H23E | 109.5 |
C19—C14—C13 | 121.8 (3) | H23D—C23'—H23E | 109.5 |
C15—C14—C13 | 120.4 (3) | C20—C23'—H23F | 109.5 |
C16—C15—C14 | 121.3 (3) | H23D—C23'—H23F | 109.5 |
C16—C15—H15 | 119.4 | H23E—C23'—H23F | 109.5 |
C14—C15—H15 | 119.4 | C13—N3—C2 | 106.9 (3) |
C15—C16—C17 | 121.5 (3) | C13—N3—H3 | 123 (3) |
C15—C16—H16 | 119.3 | C2—N3—H3 | 128 (3) |
C17—C16—H16 | 119.3 | C13—N4—C3 | 104.5 (3) |
C16—C17—C18 | 117.0 (3) | C13—N4—H2A | 124.9 (13) |
C16—C17—C20 | 121.9 (4) | C3—N4—H2A | 121.2 (13) |
C18—C17—C20 | 121.1 (3) | H3—O1—H1A | 107 (4) |
C17—C18—C19 | 122.1 (4) | H3—O1—H1B | 128 (4) |
C17—C18—H18 | 119.0 | H1A—O1—H1B | 109 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···N1i | 0.83 (3) | 2.45 (3) | 3.193 (5) | 151 (5) |
O1—H1A···N2i | 0.83 (3) | 2.19 (4) | 2.853 (4) | 137 (5) |
O1—H1B···O2ii | 0.83 (3) | 2.07 (2) | 2.878 (3) | 168 (5) |
O2—H2A···N4 | 0.82 (3) | 2.15 (2) | 2.914 (4) | 156 (5) |
N3—H3···O1 | 0.86 (3) | 1.90 (3) | 2.754 (4) | 176 (4) |
C12—H12···N4iii | 0.93 | 2.53 | 3.346 (4) | 147 |
Symmetry codes: (i) −y+3/2, x−1/2, z−1/4; (ii) y+1/2, −x+1/2, z+1/4; (iii) y, x, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C23H20N4·1.5H2O |
Mr | 379.46 |
Crystal system, space group | Tetragonal, P43212 |
Temperature (K) | 298 |
a, c (Å) | 14.809 (4), 18.281 (6) |
V (Å3) | 4009.1 (19) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.16 × 0.13 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 46858, 2670, 2508 |
Rint | 0.054 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.068, 0.167, 1.28 |
No. of reflections | 2670 |
No. of parameters | 304 |
No. of restraints | 53 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.30, −0.15 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···N1i | 0.83 (3) | 2.45 (3) | 3.193 (5) | 151 (5) |
O1—H1A···N2i | 0.83 (3) | 2.19 (4) | 2.853 (4) | 137 (5) |
O1—H1B···O2ii | 0.83 (3) | 2.065 (16) | 2.878 (3) | 168 (5) |
O2—H2A···N4 | 0.82 (3) | 2.15 (2) | 2.914 (4) | 156 (5) |
N3—H3···O1 | 0.86 (3) | 1.90 (3) | 2.754 (4) | 176 (4) |
C12—H12···N4iii | 0.93 | 2.53 | 3.346 (4) | 146.9 |
Symmetry codes: (i) −y+3/2, x−1/2, z−1/4; (ii) y+1/2, −x+1/2, z+1/4; (iii) y, x, −z+2. |
Acknowledgements
The authors are grateful to the Postgraduate Programme of Hubei Normal University for financial support under grant No. 2008D53.
References
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1,10-Phenanthroline and its derivatives are commonly used as ligands in metal complexes (Bian et al. 2002; Cardinaels et al. 2005; Liu et al. 2005; Wu et al. 1998). We report here the structure of the title compound (I) (Fig. 1), which was synthesized from [4,5-f]1,10-phenanthroline. The mean plane of the [4,5-f]1,10-phenanthroline moiety and the benzene ring (C14 - C19) make a dihedral angle of 21.76 (2) °. The water oxygen atom O2 occupies a twofold rotation axis, generating a symmetric four-centre hydrogen bond system that link two imidazo groups and two water molecules O1 via O—H···N and O—H···O bonds (Fig. 2). The other water molecules O1 link the two phenanthroline N-atoms through bifurcated O—H···N hydrogen bonds (Table 1). Intermolecular C—H···N hydrogen bonds and π—π stacking interactions (Janiak, 2000) between inversion related phenanthroline rings complete the hydrogen bonding network in the crystal structure. The short stacking distance Cgi—Cgj is 3.513 (2) Å, the perpendicular distance between the rings is 3.355 Å, and the dihedral angle between the rings is 2.48 °. Cg is the centroid of ring (N2, C5, C4, C12, C11, C10), a symmetry code for Cgj was given as (1 - y, 1 - x, 5/2 - z. The three methyl groups are disordered over two positions, with a site occupancy ratio of ca 7:1.