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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

N-(1,10-Phenanthrolin-5-yl)-4-(2-pyridyl)­benzamide monohydrate

aDepartment of Chemistry, Faculty of Science, Kyushu University, Hakozaki 6-10-1, Higashi-ku, Fukuoka 812-8581, Japan
*Correspondence e-mail: ksakai@chem.kyushu-univ.jp

(Received 18 August 2008; accepted 17 September 2008; online 20 September 2008)

In the title mol­ecule, C24H16N4O·H2O, the benzene ring of the 1,10-phenanthroline group and that of the 2-phenyl­pyridine group are respectively twisted by 67.9 (1) and 15.3 (3)° from the carbamoyl group defined by the plane of the O=C—N group of atoms. The water mol­ecule is hydrogen bonded to one of the phenanthroline N atoms. In the crystal structure, significant ππ stacking inter­actions occur, with centroid-to-centroid separations in the range 3.567–3.681 (2) Å.

Related literature

For background information, see: Ozawa & Sakai (2007[Ozawa, H. & Sakai, K. (2007). Chem. Lett. 36, 920-921.]); Ozawa et al. (2006[Ozawa, H., Haga, M. & Sakai, K. (2006). J. Am. Chem. Soc. 128, 4926-927.], 2007[Ozawa, H., Yokoyama, Y., Haga, M. & Sakai, K. (2007). Dalton Trans. pp. 1197-1206.]); Sakai & Ozawa (2007[Sakai, K. & Ozawa, H. (2007). Coord. Chem. Rev. 251, 2753-2766.]).

[Scheme 1]

Experimental

Crystal data
  • C24H16N4O·H2O

  • Mr = 394.42

  • Triclinic, [P \overline 1]

  • a = 8.226 (2) Å

  • b = 9.357 (3) Å

  • c = 13.849 (4) Å

  • α = 73.638 (3)°

  • β = 82.883 (4)°

  • γ = 64.695 (3)°

  • V = 924.7 (5) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.09 mm−1

  • T = 296 (2) K

  • 0.13 × 0.05 × 0.05 mm

Data collection
  • Bruker SMART APEX CCD-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.992, Tmax = 0.995

  • 8821 measured reflections

  • 3222 independent reflections

  • 2284 reflections with I > 2σ(I)

  • Rint = 0.036

Refinement
  • R[F2 > 2σ(F2)] = 0.047

  • wR(F2) = 0.114

  • S = 1.03

  • 3222 reflections

  • 279 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.30 e Å−3

  • Δρmin = −0.23 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O2—H1S⋯N2 0.92 (4) 2.01 (4) 2.905 (2) 163 (3)

Data collection: APEX2 (Bruker, 2006[Bruker (2006). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2004[Bruker (2004). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: KENX (Sakai, 2004[Sakai, K. (2004). KENX. Kyushu University, Japan.]); software used to prepare material for publication: SHELXL97, TEXSAN (Molecular Structure Corporation, 2001[Molecular Structure Corporation (2001). TEXSAN. MSC, The Woodlands, Texas, USA.]), KENX and ORTEPII (Johnson, 1976[Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.]).

Supporting information


Comment top

Interest has been focused on the development of photo-hydrogen-evolving molecular devices, which not only serve as a photosensitizing molecule but also as an H2-evolving catalyst (Ozawa et al., 2006, 2007; Ozawa & Sakai, 2007; Sakai & Ozawa, 2007). One of the most important findings in these studies is that the visible light-induced reduction of water by edta (a sacrificial electron donor) into molecular hydrogen can be driven by a condensation product of [Ru(bpy)2(5-amino-phen)]2+ and PtCl2(4,4'-dicarboxy-bpy) (bpy = 2,2'-bipyridine; phen = 1,10-phenanthroline) with a quantum efficiency of ca 0.01. N-(1,10-phenanthrolin-5-yl)-4-carbamoyl-4'-carboxy-2,2'-bipyridine, which is considered a structural analog of the title compound (I), is employed as a bridging spacer connecting the two different metal centers (Ozawa et al., 2006). In order to improve the quantum efficiency in the light-driven H2 formation, efforts have been made to clarify the mechanism of this photoinduced process and also to develop the more highly efficient photo-hydrogen-evolving molecular devices. The new bridging spacer (I) was prepared to evaluate the change in photocatalytic efficiency upon replacing the bpy attached to the PtII center with a phenylpyridinate ligand. We have already succeeded in preparing and testing the corresponding RuII/PtII complex but, unfortunately, the compound was found to be ineffective towards the edta-based reduction of H2O into H2, which will be separately reported elsewhere in a future publication.

The molecular structure of (I) is shown in Fig. 1. The water is hydrogen bonded to one of the nitrogen atoms of the phen moiety (Table 1). The phen moiety is slightly deformed from an ideal planar geometry, presumably due to the ππ stacking interactions formed in the crystal, as discussed below. The C1–C3 and the C8–C10 groups of atoms are shifted from the central benzene plane of phen, defined with atoms C4–C7, C11 and C12, in such a manner that the C1–C3 and the C8–C10 units are shifted to opposite sides of the benzene plane. The two pyridyl planes within phen, i.e., the planes defined with atoms N1 and C1–C5 and atoms N2 and C6–C10, are declined with respect to the central benzene plane by 3.7 (1) and 2.5 (1)°, respectively. The carbamoyl group defined by the plane of atoms C13, O1, and N3 is twisted with regard to the benzene ring of phen at an angle of 67.9 (1)°. The carbamoyl plane is also declined by 15.3 (3)° with respect to the benzene plane of the phenylpyridine moiety defined with atoms C14–C19. The dihedral angle between the plane defined with atoms C14–C19 and that with atoms N4 and C20–C24 is 5.6 (2)°, which corresponds to the dihedral angle of the two aromatic rings within the phenylpyridine moiety. In the best plane calculations carried out for the above-mentioned five aromatic rings, the 6-atom r.m.s. deviations are in the range of 0.003–0.015 Å, revealing that all these rings have an essentially planar geometry.

As shown in Fig. 2, the phen moiety has a π-stack to the adjacent phen moieties to give a one-dimensional stack in the crystal. As shown in Fig. 3, one is considered as a strong stack with almost full overlap of the phen moieties, while the other as a relatively weak stack based on the partial overlap of the phen moieties. The interplanar separations between the two aromatic systems for the former and the latter geometries are 3.52 (2) and 3.43 (2) Å, respectively. On the other hand, the phenylpyridine moiety forms a π-stack dimer with the interplanar separation 3.48 (11) Å.

Related literature top

For background information, see: Ozawa & Sakai (2007); Ozawa et al. (2006, 2007); Sakai & Ozawa (2007).

Experimental top

A suspension of 4-(2-pyridyl)benzoic acid.0.5H2O (0.25 g, 1.2 mmol) in 10 ml of thionyl chloride was refluxed for 3 h. The resulting solution was evaporated to dryness and the residue was dried in vacuo to give 4-(2-pyridyl)benzoil chloride. This was dissolved in 20 ml of anhydrous CH2Cl2. To a solution of 5-amino-1,10-phenanthroline (0.20 g, 1.0 mmol) and triethylamine (0.5 ml) in a 1:1 mixture of anhydrous CH2Cl2 and anhydrous acetonitrile (100 ml) under cooling in an ice bath was added the former solution under Ar over 30 min. After stirring for 3 days at room temperature, the solution was evaporated to dryness. The residue was washed with aqueous 5% NaHCO3 solution (20 ml), and collected by filtration. The crude product was recrystallized from ethanol. Yield: 0.29 g (72%). Analysis calculated for C24H16N4O.1.5H2O: C, 71.45; H, 4.75; N; 13.89. Found: C, 71.30; H, 4.52; N, 13.90. 1H NMR (300.53 MHz, dmso-d6), p.p.m.: δ 10.75 (s, 1H), 9.14 (d, 1H, J = 4.24 Hz), 9.08 (d, 1H, J = 4.24 Hz), 8.73 (d, 1H, J = 4.96 Hz), 8.53 (t, 2H, J = 9.11 Hz), 8.32–8.23 (m, 4H), 8.15 (s, 1H), 8.12 (d, 1H, J = 6.97 Hz), 7.98–7.92 (m, 1H), 7.83–7.76 (m, 2H), 7.45–7.41 (m, 1H). ESI-TOF MS (positive ion, methanol): m/z 376.96 [M - 1.5H2O + H+]+. A good quality single-crystal was prepared by slow evaporation of a N,N-dimethylformamide (DMF) solution as follows. Compound (I) was dissolved in a minimum amount of DMF and the solution was left for several days at room temperature, during which the solution gradually reduced its volume to give crystals suitable for X-ray diffraction analysis.

Refinement top

Hydrogen atoms, except for those of a water molecule, were placed in their idealized positions (aromatic C—H = 0.93 Å and N—H = 0.86 Å), and included in the refinement in a riding-model approximation with Uiso(H) = 1.2Ueq(C and N). Hydrogen atoms of a water molecule were refined isotropically. In the final difference Fourier map, the highest peak was located 0.63 Å from atom H3. The deepest hole was located 0.38 Å from atom H3.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: KENX (Sakai, 2004); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), TEXSAN (Molecular Structure Corporation, 2001), KENX (Sakai, 2004) and ORTEPII (Johnson, 1976).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A view showing the manner how the aromatic moieties are stacked in the crystal. Water molecules are omitted for clarity.
[Figure 3] Fig. 3. View showing the manner in whch the phen moieties of two symmetry related molecules are stacked, showing a view perpendicular to the planes stacked to each other. Only the labeled atoms are involved in the mean-plane calculations carried out to determine the interplanar separation between the two planes stacked with two different interactions within a one dimensional column. H atoms have been omitted for clarity. [Symmetry codes: (i) 1 - x, 1 - y, 1 - z; (ii) 2 - x, 1 - y, 1 - z].
[Figure 4] Fig. 4. View showing the manner in whch the phen moieties of two symmetry related molecules are stacked, showing a view perpendicular to the planes stacked to each other. Only the labeled atoms are involved in the mean-plane calculations carried out to determine the interplanar separation between the two planes stacked with two different interactions within a one dimensional column. H atoms have been omitted for clarity. [Symmetry codes: (i) 1 - x, 1 - y, 1 - z; (ii) 2 - x, 1 - y, 1 - z].
N-(1,10-Phenanthrolin-5-yl)-4-(2-pyridyl)benzamide monohydrate top
Crystal data top
C24H16N4O·H2OZ = 2
Mr = 394.42F(000) = 412
Triclinic, P1? # Insert any comments here.
Hall symbol: -P 1Dx = 1.417 Mg m3
a = 8.226 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.357 (3) ÅCell parameters from 7706 reflections
c = 13.849 (4) Åθ = 2.5–25.0°
α = 73.638 (3)°µ = 0.09 mm1
β = 82.883 (4)°T = 296 K
γ = 64.695 (3)°Cube, yellow
V = 924.7 (5) Å30.13 × 0.05 × 0.05 mm
Data collection top
Bruker SMART APEX CCD-detector
diffractometer
3222 independent reflections
Radiation source: rotating anode with a mirror focusing unit2284 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
ϕ and ω scansθmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 99
Tmin = 0.992, Tmax = 0.995k = 1111
8821 measured reflectionsl = 1616
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0447P)2 + 0.4023P]
where P = (Fo2 + 2Fc2)/3
3222 reflections(Δ/σ)max < 0.001
279 parametersΔρmax = 0.30 e Å3
0 restraintsΔρmin = 0.23 e Å3
Crystal data top
C24H16N4O·H2Oγ = 64.695 (3)°
Mr = 394.42V = 924.7 (5) Å3
Triclinic, P1Z = 2
a = 8.226 (2) ÅMo Kα radiation
b = 9.357 (3) ŵ = 0.09 mm1
c = 13.849 (4) ÅT = 296 K
α = 73.638 (3)°0.13 × 0.05 × 0.05 mm
β = 82.883 (4)°
Data collection top
Bruker SMART APEX CCD-detector
diffractometer
3222 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2284 reflections with I > 2σ(I)
Tmin = 0.992, Tmax = 0.995Rint = 0.037
8821 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.114H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.30 e Å3
3222 reflectionsΔρmin = 0.23 e Å3
279 parameters
Special details top

Experimental. The first 50 frames were rescanned at the end of data collection to evaluate any possible decay phenomenon. Since it was judged to be negligible, no decay correction was applied to the data.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.6321 (2)0.64738 (18)0.79108 (12)0.0325 (4)
O20.8041 (2)0.0010 (2)0.48055 (13)0.0320 (4)
N10.9204 (2)0.3157 (2)0.44978 (14)0.0227 (4)
N20.7555 (2)0.2000 (2)0.61822 (14)0.0240 (4)
N30.4357 (2)0.7537 (2)0.66380 (13)0.0234 (4)
H30.33110.82310.64040.028*
N40.1196 (2)1.2126 (2)1.05472 (14)0.0283 (5)
C10.9942 (3)0.3743 (3)0.36656 (17)0.0261 (5)
H11.08060.30020.33400.031*
C20.9506 (3)0.5398 (3)0.32478 (17)0.0269 (5)
H21.00480.57490.26540.032*
C30.8266 (3)0.6497 (3)0.37276 (17)0.0242 (5)
H3A0.79570.76100.34660.029*
C40.7459 (3)0.5937 (2)0.46189 (16)0.0202 (5)
C50.7961 (3)0.4238 (2)0.49721 (16)0.0194 (5)
C60.7149 (3)0.3620 (2)0.58924 (16)0.0196 (5)
C70.5959 (3)0.4720 (2)0.64404 (16)0.0203 (5)
C80.5206 (3)0.4072 (3)0.73217 (17)0.0251 (5)
H80.44210.47540.77080.030*
C90.5626 (3)0.2438 (3)0.76114 (18)0.0281 (5)
H90.51370.19910.81970.034*
C100.6796 (3)0.1450 (3)0.70180 (18)0.0274 (5)
H100.70610.03380.72190.033*
C110.6237 (3)0.7014 (2)0.51907 (17)0.0222 (5)
H110.59140.81330.49520.027*
C120.5542 (3)0.6440 (2)0.60716 (16)0.0207 (5)
C130.4863 (3)0.7494 (3)0.75393 (17)0.0235 (5)
C140.3587 (3)0.8709 (2)0.80803 (16)0.0214 (5)
C150.1777 (3)0.9621 (2)0.78548 (17)0.0226 (5)
H150.12890.95000.73280.027*
C160.0692 (3)1.0709 (3)0.84065 (17)0.0241 (5)
H160.05191.13090.82450.029*
C170.1378 (3)1.0925 (2)0.92009 (16)0.0214 (5)
C180.3183 (3)0.9973 (3)0.94320 (18)0.0273 (5)
H180.36661.00690.99710.033*
C190.4274 (3)0.8894 (3)0.88841 (17)0.0267 (5)
H190.54820.82820.90520.032*
C200.0297 (3)1.2124 (3)0.97979 (17)0.0222 (5)
C210.1468 (3)1.3208 (3)0.95877 (18)0.0271 (5)
H210.20651.31840.90690.033*
C220.2342 (3)1.4330 (3)1.01517 (18)0.0303 (6)
H220.35351.50641.00210.036*
C230.1423 (3)1.4343 (3)1.09085 (18)0.0297 (6)
H230.19721.50921.12970.036*
C240.0327 (3)1.3224 (3)1.10773 (18)0.0303 (6)
H240.09441.32321.15930.036*
H1S0.809 (4)0.067 (4)0.518 (3)0.093 (12)*
H2S0.900 (4)0.092 (4)0.494 (2)0.068 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0266 (9)0.0314 (9)0.0339 (10)0.0004 (8)0.0089 (8)0.0150 (8)
O20.0348 (10)0.0202 (9)0.0357 (11)0.0016 (8)0.0115 (8)0.0102 (8)
N10.0229 (10)0.0218 (10)0.0218 (11)0.0049 (8)0.0011 (8)0.0096 (8)
N20.0272 (10)0.0207 (10)0.0235 (11)0.0087 (8)0.0050 (9)0.0045 (8)
N30.0183 (10)0.0242 (10)0.0249 (11)0.0022 (8)0.0025 (8)0.0116 (8)
N40.0317 (11)0.0307 (11)0.0263 (12)0.0140 (9)0.0018 (9)0.0120 (9)
C10.0248 (13)0.0314 (13)0.0209 (14)0.0075 (10)0.0008 (10)0.0119 (11)
C20.0279 (13)0.0325 (13)0.0200 (13)0.0125 (11)0.0026 (10)0.0053 (11)
C30.0281 (13)0.0208 (11)0.0229 (14)0.0099 (10)0.0055 (10)0.0023 (10)
C40.0189 (11)0.0209 (11)0.0202 (13)0.0064 (9)0.0050 (9)0.0053 (9)
C50.0180 (11)0.0190 (11)0.0209 (13)0.0050 (9)0.0048 (9)0.0067 (10)
C60.0187 (11)0.0182 (11)0.0217 (13)0.0063 (9)0.0051 (9)0.0047 (9)
C70.0164 (11)0.0234 (11)0.0212 (13)0.0064 (9)0.0038 (9)0.0073 (10)
C80.0225 (12)0.0290 (12)0.0258 (14)0.0102 (10)0.0024 (10)0.0118 (10)
C90.0304 (13)0.0328 (13)0.0237 (14)0.0166 (11)0.0003 (11)0.0055 (11)
C100.0322 (13)0.0213 (11)0.0286 (15)0.0124 (10)0.0048 (11)0.0020 (11)
C110.0218 (12)0.0152 (11)0.0265 (14)0.0039 (9)0.0060 (10)0.0044 (10)
C120.0177 (11)0.0211 (11)0.0222 (13)0.0047 (9)0.0041 (10)0.0075 (10)
C130.0222 (12)0.0225 (12)0.0250 (14)0.0074 (10)0.0051 (10)0.0055 (10)
C140.0232 (12)0.0179 (11)0.0233 (13)0.0092 (9)0.0014 (10)0.0050 (10)
C150.0267 (12)0.0220 (11)0.0202 (13)0.0104 (10)0.0020 (10)0.0057 (10)
C160.0215 (12)0.0219 (11)0.0285 (14)0.0074 (10)0.0022 (10)0.0073 (10)
C170.0248 (12)0.0184 (11)0.0224 (13)0.0109 (10)0.0004 (10)0.0043 (10)
C180.0289 (13)0.0304 (13)0.0271 (14)0.0120 (11)0.0042 (11)0.0127 (11)
C190.0225 (12)0.0265 (12)0.0315 (15)0.0072 (10)0.0026 (10)0.0117 (11)
C200.0262 (12)0.0219 (11)0.0224 (13)0.0150 (10)0.0027 (10)0.0046 (10)
C210.0278 (13)0.0270 (12)0.0281 (14)0.0121 (10)0.0003 (11)0.0081 (11)
C220.0257 (13)0.0285 (13)0.0364 (15)0.0103 (10)0.0059 (11)0.0116 (11)
C230.0321 (14)0.0325 (13)0.0310 (15)0.0168 (11)0.0106 (11)0.0166 (11)
C240.0373 (15)0.0349 (14)0.0257 (14)0.0188 (12)0.0028 (11)0.0133 (11)
Geometric parameters (Å, º) top
O1—C131.229 (2)C9—C101.388 (3)
O2—H1S0.92 (4)C9—H90.9300
O2—H2S0.88 (3)C10—H100.9300
N1—C11.324 (3)C11—C121.351 (3)
N1—C51.351 (3)C11—H110.9300
N2—C101.325 (3)C13—C141.490 (3)
N2—C61.352 (3)C14—C151.386 (3)
N3—C131.349 (3)C14—C191.392 (3)
N3—C121.424 (3)C15—C161.381 (3)
N3—H30.8600C15—H150.9300
N4—C241.331 (3)C16—C171.395 (3)
N4—C201.347 (3)C16—H160.9300
C1—C21.391 (3)C17—C181.388 (3)
C1—H10.9300C17—C201.490 (3)
C2—C31.363 (3)C18—C191.375 (3)
C2—H20.9300C18—H180.9300
C3—C41.403 (3)C19—H190.9300
C3—H3A0.9300C20—C211.378 (3)
C4—C51.410 (3)C21—C221.381 (3)
C4—C111.428 (3)C21—H210.9300
C5—C61.452 (3)C22—C231.372 (3)
C6—C71.410 (3)C22—H220.9300
C7—C81.400 (3)C23—C241.371 (3)
C7—C121.441 (3)C23—H230.9300
C8—C91.362 (3)C24—H240.9300
C8—H80.9300
H1S—O2—H2S109 (3)C11—C12—N3120.22 (19)
C1—N1—C5117.71 (19)C11—C12—C7120.60 (19)
C10—N2—C6117.68 (19)N3—C12—C7119.2 (2)
C13—N3—C12120.42 (17)O1—C13—N3121.2 (2)
C13—N3—H3119.8O1—C13—C14120.86 (19)
C12—N3—H3119.8N3—C13—C14117.90 (18)
C24—N4—C20117.8 (2)C15—C14—C19118.5 (2)
N1—C1—C2124.1 (2)C15—C14—C13124.69 (19)
N1—C1—H1118.0C19—C14—C13116.80 (19)
C2—C1—H1118.0C16—C15—C14120.5 (2)
C3—C2—C1118.5 (2)C16—C15—H15119.7
C3—C2—H2120.7C14—C15—H15119.7
C1—C2—H2120.7C15—C16—C17121.3 (2)
C2—C3—C4119.6 (2)C15—C16—H16119.3
C2—C3—H3A120.2C17—C16—H16119.3
C4—C3—H3A120.2C18—C17—C16117.4 (2)
C3—C4—C5117.66 (19)C18—C17—C20118.70 (19)
C3—C4—C11122.32 (19)C16—C17—C20123.92 (19)
C5—C4—C11119.9 (2)C19—C18—C17121.7 (2)
N1—C5—C4122.4 (2)C19—C18—H18119.2
N1—C5—C6118.61 (18)C17—C18—H18119.2
C4—C5—C6119.02 (19)C18—C19—C14120.5 (2)
N2—C6—C7122.6 (2)C18—C19—H19119.7
N2—C6—C5118.13 (19)C14—C19—H19119.7
C7—C6—C5119.30 (19)N4—C20—C21121.5 (2)
C8—C7—C6117.37 (19)N4—C20—C17114.92 (19)
C8—C7—C12122.94 (19)C21—C20—C17123.5 (2)
C6—C7—C12119.7 (2)C20—C21—C22119.6 (2)
C9—C8—C7119.7 (2)C20—C21—H21120.2
C9—C8—H8120.1C22—C21—H21120.2
C7—C8—H8120.1C23—C22—C21118.9 (2)
C8—C9—C10118.9 (2)C23—C22—H22120.6
C8—C9—H9120.6C21—C22—H22120.6
C10—C9—H9120.6C24—C23—C22118.2 (2)
N2—C10—C9123.8 (2)C24—C23—H23120.9
N2—C10—H10118.1C22—C23—H23120.9
C9—C10—H10118.1N4—C24—C23124.0 (2)
C12—C11—C4121.33 (19)N4—C24—H24118.0
C12—C11—H11119.3C23—C24—H24118.0
C4—C11—H11119.3
C5—N1—C1—C20.5 (3)C8—C7—C12—C11176.69 (19)
N1—C1—C2—C31.2 (3)C6—C7—C12—C112.1 (3)
C1—C2—C3—C40.4 (3)C8—C7—C12—N32.0 (3)
C2—C3—C4—C50.9 (3)C6—C7—C12—N3179.23 (17)
C2—C3—C4—C11175.97 (19)C12—N3—C13—O12.9 (3)
C1—N1—C5—C40.9 (3)C12—N3—C13—C14178.02 (19)
C1—N1—C5—C6179.31 (17)O1—C13—C14—C15163.3 (2)
C3—C4—C5—N11.6 (3)N3—C13—C14—C1515.8 (3)
C11—C4—C5—N1175.33 (18)O1—C13—C14—C1915.0 (3)
C3—C4—C5—C6179.97 (17)N3—C13—C14—C19165.89 (19)
C11—C4—C5—C63.1 (3)C19—C14—C15—C161.1 (3)
C10—N2—C6—C70.3 (3)C13—C14—C15—C16179.4 (2)
C10—N2—C6—C5179.43 (18)C14—C15—C16—C170.1 (3)
N1—C5—C6—N26.0 (3)C15—C16—C17—C181.6 (3)
C4—C5—C6—N2175.59 (17)C15—C16—C17—C20177.5 (2)
N1—C5—C6—C7174.89 (18)C16—C17—C18—C192.0 (3)
C4—C5—C6—C73.6 (3)C20—C17—C18—C19177.2 (2)
N2—C6—C7—C80.8 (3)C17—C18—C19—C140.8 (4)
C5—C6—C7—C8179.88 (17)C15—C14—C19—C180.8 (3)
N2—C6—C7—C12178.05 (18)C13—C14—C19—C18179.2 (2)
C5—C6—C7—C121.1 (3)C24—N4—C20—C210.6 (3)
C6—C7—C8—C90.5 (3)C24—N4—C20—C17176.9 (2)
C12—C7—C8—C9178.31 (19)C18—C17—C20—N42.1 (3)
C7—C8—C9—C100.2 (3)C16—C17—C20—N4178.8 (2)
C6—N2—C10—C90.5 (3)C18—C17—C20—C21175.3 (2)
C8—C9—C10—N20.8 (3)C16—C17—C20—C213.8 (3)
C3—C4—C11—C12176.79 (19)N4—C20—C21—C220.3 (3)
C5—C4—C11—C120.0 (3)C17—C20—C21—C22177.0 (2)
C4—C11—C12—N3178.66 (18)C20—C21—C22—C230.4 (3)
C4—C11—C12—C72.6 (3)C21—C22—C23—C240.7 (3)
C13—N3—C12—C11112.9 (2)C20—N4—C24—C230.3 (3)
C13—N3—C12—C768.4 (3)C22—C23—C24—N40.4 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H1S···N20.92 (4)2.01 (4)2.905 (2)163 (3)

Experimental details

Crystal data
Chemical formulaC24H16N4O·H2O
Mr394.42
Crystal system, space groupTriclinic, P1
Temperature (K)296
a, b, c (Å)8.226 (2), 9.357 (3), 13.849 (4)
α, β, γ (°)73.638 (3), 82.883 (4), 64.695 (3)
V3)924.7 (5)
Z2
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.13 × 0.05 × 0.05
Data collection
DiffractometerBruker SMART APEX CCD-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.992, 0.995
No. of measured, independent and
observed [I > 2σ(I)] reflections
8821, 3222, 2284
Rint0.037
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.114, 1.04
No. of reflections3222
No. of parameters279
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.30, 0.23

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), TEXSAN (Molecular Structure Corporation, 2001), KENX (Sakai, 2004) and ORTEPII (Johnson, 1976).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H1S···N20.92 (4)2.01 (4)2.905 (2)163 (3)
 

Acknowledgements

This work was in part supported by a Grant-in-Aid for Scientific Research (A) (No. 17205008), a Grant-in-Aid for Specially Promoted Research (No. 18002016), and a Grant-in-Aid for the Global COE Program (`Science for Future Molecular Systems') from the Ministry of Education, Culture, Sports, Science and Technology of Japan.

References

First citationBruker (2004). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationBruker (2006). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationJohnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.  Google Scholar
First citationMolecular Structure Corporation (2001). TEXSAN. MSC, The Woodlands, Texas, USA.  Google Scholar
First citationOzawa, H., Haga, M. & Sakai, K. (2006). J. Am. Chem. Soc. 128, 4926–927.  Web of Science CrossRef PubMed CAS Google Scholar
First citationOzawa, H. & Sakai, K. (2007). Chem. Lett. 36, 920–921.  Web of Science CrossRef CAS Google Scholar
First citationOzawa, H., Yokoyama, Y., Haga, M. & Sakai, K. (2007). Dalton Trans. pp. 1197–1206.  Web of Science CrossRef Google Scholar
First citationSakai, K. (2004). KENX. Kyushu University, Japan.  Google Scholar
First citationSakai, K. & Ozawa, H. (2007). Coord. Chem. Rev. 251, 2753–2766.  Web of Science CrossRef CAS Google Scholar
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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