4-[Bis(3-phenyl-1H-pyrazol-1-yl)meth­yl]benzene-1,2-diol

Blasberg, F.; Lerner, H.-W.; Bolte, M.

doi:10.1107/S1600536811037949

organic compounds

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Volume 67| Part 10| October 2011| Page o2741

https://doi.org/10.1107/S1600536811037949

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4-[Bis(3-phenyl-1H-pyrazol-1-yl)methyl]benzene-1,2-diol

Florian Blasberg,^a Hans-Wolfram Lerner ^a and Michael Bolte ^a ^*

^aInstitut für Anorganische Chemie, J. W. Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt/Main, Germany
^*Correspondence e-mail: bolte@chemie.uni-frankfurt.de

(Received 14 September 2011; accepted 16 September 2011; online 30 September 2011)

The title compound, C₂₅H₂₀N₄O₂, is a ditopic ortho-hydroquinone-based bis(pyrazol-1-yl)methane ligand. The dihedral angles between the planes of the pyrazole rings and their attached phenyl rings are 17.4 (3) and 5.9 (4)°. The pyrazole rings make a dihedral angle of 87.84 (16)°. One of the two hydroxy groups forms an intramolecular hydrogen bond to the other hydroxy group, whereas the second is involved in an intermolecular O—H⋯N hydrogen bond. As a result of these intermolecular hydrogen bonds, helical chains running along the b axis are formed.

Related literature

For the synthesis, structural characterization and coordination behavior of ditopic ortho-hydroquinone-based bis(pyrazol-1-yl)methane ligands, see: Blasberg et al. (2011 ).

Experimental

Crystal data

C₂₅H₂₀N₄O₂
M_r = 408.45
Monoclinic, P 2₁ /n
a = 13.493 (3) Å
b = 5.6288 (11) Å
c = 26.309 (5) Å
β = 100.87 (3)°
V = 1962.3 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 173 K
0.40 × 0.15 × 0.10 mm

Data collection

Stoe IPDS II two-circle diffractometer
16343 measured reflections
3450 independent reflections
1434 reflections with I > 2σ(I)
R_int = 0.111

Refinement

R[F² > 2σ(F²)] = 0.069
wR(F²) = 0.121
S = 0.82
3450 reflections
282 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O23—H23⋯O24	0.84	2.21	2.646 (5)	113
O24—H24⋯N12ⁱ	0.84	2.08	2.853 (5)	153
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: X-AREA (Stoe & Cie, 2001 ); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811037949/ez2261sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811037949/ez2261Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811037949/ez2261Isup3.cml

checkCIF report

Comment top

Very recently we have reported on the synthesis, structural characterization, and coordination behavior of ditopic ortho-hydroquinone-based bis(pyrazol-1-yl)methane ligands (Blasberg et al., 2011). In this report, we have already noted ortho-(OH)₂C₆H₃-4-CH(3-Phpz)₂, but metric parameters will be discussed here. The bis(pyrazol-1-yl)methane derivative (I) was prepared in a three-step one-pot procedure as shown in Fig. 1.

The dihedral angles between the planes of the pyrazol rings and the attached phenyl rings are 20.9 (3)° and 5.9 (4)°. One of the two hydroxy groups forms an intramolecular hydrogen bond to the other hydroxy group, whereas the second one is involved in an intermolecular O—H···N hydrogen bond. As a result of these intermolecular hydrogen bonds, helical chains running along the b axis are formed.

Related literature top

For the synthesis, structural characterization and coordination behavior of ditopic ortho-hydroquinone-based bis(pyrazol-1-yl)methane ligands, see: Blasberg et al. (2011).

Experimental top

Neat 3-phenylpyrazole (2.00 g, 13.87 mmol) was added to NaH (0.33 g, 13.87 mmol) suspended in THF (60 ml) at r.t. After 30 min SOCl₂ (0.50 ml, 0.83 g, 6.94 mmol) was added in one portion and the resulting mixture stirred at r.t. for 5 min. After 3,4-dihydroxybenzaldehyde (0.96 g, 6.94 mmol) and pyridine (5.60 ml, 4.78 g, 60.40 mmol) were added, the reaction mixture was kept at reflux temperature for 16 h. H₂O (50 ml) was added and the aqueous phase extracted into CH₂Cl₂ (3×50 ml). The combined organic extracts were washed with brine, dried (MgSO₄), filtered, and the filtrate was evaporated to dryness in vacuo. The crude product was purified by column chromatography (silica gel; CHCl₃/EtOAc 1:1) and all product-containing fractions were concentrated by rotary evaporation at 40°C to ca. half of the original volume. Upon cooling to r.t. colorless crystals of the title compound precipitated, which were isolated by filtration and washed with Et₂O. Yield: 1.53 g (54%). Single crystals suitable for X-ray diffraction were obtained by repeatedly dissolving the compound in refluxing MeCN and letting the clear colorless solution cool to room temperature. After three cycles needles of sufficient size were obtained. R</f = 0.63 (silica gel, CHCl₃/EtOAc 1:1). ¹H NMR (400.1 MHz, d₆-DMSO) δ = 6.48 (dd, ³J_HH = 8.3, ⁴J_HH = 2.0, 1 H; HQ—H6), 6.66 (d, ⁴J_HH = 2.0, 1 H; HQ—H2), 6.76 (d, ³J_HH = 8.3, 1 H; HQ—H5), 6.84 (d, ³J_HH = 2.5, 2 H; pz-H4), 7.31 (m, 2 H; Ph—H4), 7.41 (m, 4 H; Ph—H3), 7.82 (m, 4 H; Ph—H2), 7.91 (s, 1H, CH), 7.94 (d, ³J_HH = 2.5, 2 H; pz-H5), 9.15 (bs, 2 H; OH). ¹³C NMR (100.6 MHz, d₆-DMSO) δ = 76.7 (Cpz₂), 103.5 (pz-C4), 114.4 (HQ—C2), 115.5 (HQ—C5), 118.2 (HQ—C6), 125.3 (Ph—C2), 127.2 (HQ—C1), 127.8 (Ph—C4), 128.7 (Ph—C3), 131.9 (pz-C5), 132.8 (Ph—C1), 145.3, 146.1 (HQ—C3,4), 151.0 (pz-C3). ESI-MS: m/z (%) 263 (67) [M—Phpz]^-, 408 (100) [M—H]^-. Anal. Calcd (%) for C₂₅H₂₀N₄O₂ (408.45): C 73.51, H 4.94, N 13.72. Found: C 73.22, H 4.86, N 13.67.

Structure description top

For the synthesis, structural characterization and coordination behavior of ditopic ortho-hydroquinone-based bis(pyrazol-1-yl)methane ligands, see: Blasberg et al. (2011).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Synthesis and numbering scheme of ortho-hydroquinone-based bis(pyrazol-1-yl)methane ligand (I). (a) (i) NaH, THF, 30 min; (ii) SOCl₂, THF, 5 min; (iii) 3,4-dihydroxybenzaldehyde, pyridine, THF, reflux, over night.
	Fig. 2. Perspective view of the title compound with displacement ellipsoids drawn at the 50% probability level.

4-[Bis(3-phenyl-1H-pyrazol-1-yl)methyl]benzene-1,2-diol top

Crystal data top

C₂₅H₂₀N₄O₂	F(000) = 856
M_r = 408.45	D_x = 1.383 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2882 reflections
a = 13.493 (3) Å	θ = 3.7–25.8°
b = 5.6288 (11) Å	µ = 0.09 mm⁻¹
c = 26.309 (5) Å	T = 173 K
β = 100.87 (3)°	Needle, colourless
V = 1962.3 (7) Å³	0.40 × 0.15 × 0.10 mm
Z = 4

Data collection top

Stoe IPDS II two-circle diffractometer	1434 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.111
Graphite monochromator	θ_max = 25.0°, θ_min = 3.7°
ω scans	h = −16→16
16343 measured reflections	k = −6→6
3450 independent reflections	l = −31→31

Refinement top

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)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.121	H-atom parameters constrained
S = 0.82	w = 1/[σ²(F_o²) + (0.003P)²] where P = (F_o² + 2F_c²)/3
3450 reflections	(Δ/σ)_max < 0.001
282 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₂₅H₂₀N₄O₂	V = 1962.3 (7) Å³
M_r = 408.45	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 13.493 (3) Å	µ = 0.09 mm⁻¹
b = 5.6288 (11) Å	T = 173 K
c = 26.309 (5) Å	0.40 × 0.15 × 0.10 mm
β = 100.87 (3)°

Data collection top

Stoe IPDS II two-circle diffractometer	1434 reflections with I > 2σ(I)
16343 measured reflections	R_int = 0.111
3450 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.069	0 restraints
wR(F²) = 0.121	H-atom parameters constrained
S = 0.82	Δρ_max = 0.22 e Å⁻³
3450 reflections	Δρ_min = −0.27 e Å⁻³
282 parameters

Special details top

Experimental. ;

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	U_iso*/U_eq
N1	0.6081 (3)	0.2494 (7)	0.30782 (15)	0.0162 (10)
C1	0.5052 (4)	0.2507 (9)	0.31608 (19)	0.0199 (12)
H1	0.4873	0.0847	0.3245	0.024*
N2	0.6784 (3)	0.1200 (7)	0.34051 (15)	0.0181 (9)
C3	0.7672 (4)	0.1933 (8)	0.33129 (19)	0.0189 (12)
C4	0.7529 (4)	0.3725 (8)	0.29212 (19)	0.0216 (12)
H4	0.8037	0.4530	0.2782	0.026*
C5	0.6523 (4)	0.4033 (9)	0.27902 (19)	0.0224 (12)
H5	0.6184	0.5127	0.2542	0.027*
N11	0.4994 (3)	0.4008 (7)	0.36107 (14)	0.0171 (9)
N12	0.4236 (3)	0.3584 (6)	0.38778 (15)	0.0165 (10)
C13	0.4318 (4)	0.5389 (8)	0.42204 (18)	0.0171 (12)
C14	0.5103 (4)	0.6909 (8)	0.4161 (2)	0.0214 (12)
H14	0.5308	0.8302	0.4356	0.026*
C15	0.5517 (4)	0.6011 (9)	0.37699 (19)	0.0239 (12)
H15	0.6064	0.6659	0.3635	0.029*
C21	0.4313 (4)	0.3296 (8)	0.26841 (19)	0.0179 (12)
C22	0.4107 (4)	0.1733 (8)	0.22619 (19)	0.0209 (12)
H22	0.4464	0.0273	0.2272	0.025*
C23	0.3402 (4)	0.2291 (9)	0.1838 (2)	0.0214 (12)
O23	0.3195 (3)	0.0753 (6)	0.14321 (13)	0.0287 (9)
H23	0.2640	0.1116	0.1245	0.043*
C24	0.2880 (4)	0.4488 (8)	0.18097 (19)	0.0168 (11)
O24	0.2181 (3)	0.4800 (6)	0.13669 (13)	0.0237 (9)
H24	0.1816	0.5976	0.1402	0.036*
C25	0.3102 (4)	0.6034 (8)	0.22209 (18)	0.0196 (12)
H25	0.2768	0.7525	0.2206	0.024*
C26	0.3800 (4)	0.5442 (8)	0.26527 (19)	0.0193 (12)
H26	0.3935	0.6523	0.2935	0.023*
C31	0.8626 (4)	0.0957 (8)	0.36075 (19)	0.0190 (11)
C32	0.9534 (4)	0.2161 (8)	0.3623 (2)	0.0238 (13)
H32	0.9540	0.3577	0.3427	0.029*
C33	1.0414 (4)	0.1348 (9)	0.3913 (2)	0.0312 (14)
H33	1.1021	0.2212	0.3919	0.037*
C34	1.0433 (4)	−0.0750 (10)	0.4203 (2)	0.0317 (14)
H34	1.1042	−0.1318	0.4409	0.038*
C35	0.9530 (5)	−0.1962 (9)	0.4177 (2)	0.0332 (15)
H35	0.9531	−0.3406	0.4364	0.040*
C36	0.8634 (4)	−0.1155 (9)	0.38900 (19)	0.0249 (13)
H36	0.8027	−0.2021	0.3884	0.030*
C41	0.3634 (4)	0.5541 (8)	0.45945 (19)	0.0176 (12)
C42	0.3673 (4)	0.7591 (9)	0.4918 (2)	0.0263 (13)
H42	0.4139	0.8830	0.4891	0.032*
C43	0.3040 (4)	0.7773 (9)	0.5268 (2)	0.0272 (14)
H43	0.3078	0.9133	0.5485	0.033*
C44	0.2345 (4)	0.6001 (9)	0.53102 (19)	0.0239 (12)
H44	0.1905	0.6154	0.5551	0.029*
C45	0.2296 (4)	0.4007 (9)	0.49981 (19)	0.0248 (12)
H45	0.1820	0.2790	0.5023	0.030*
C46	0.2950 (4)	0.3786 (8)	0.46467 (19)	0.0223 (12)
H46	0.2922	0.2396	0.4440	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.019 (3)	0.014 (2)	0.016 (2)	−0.0032 (19)	0.0029 (19)	0.0009 (17)
C1	0.019 (3)	0.021 (3)	0.021 (3)	−0.001 (2)	0.006 (2)	−0.003 (2)
N2	0.019 (2)	0.017 (2)	0.019 (2)	−0.0002 (19)	0.0042 (19)	−0.0018 (18)
C3	0.019 (3)	0.016 (2)	0.022 (3)	0.000 (2)	0.005 (2)	−0.004 (2)
C4	0.016 (3)	0.026 (3)	0.025 (3)	−0.002 (2)	0.010 (2)	0.001 (2)
C5	0.031 (3)	0.018 (3)	0.019 (3)	−0.003 (2)	0.004 (2)	0.004 (2)
N11	0.019 (2)	0.019 (2)	0.016 (2)	−0.005 (2)	0.0077 (19)	−0.0038 (18)
N12	0.021 (3)	0.014 (2)	0.014 (2)	0.0026 (18)	0.0023 (19)	−0.0035 (17)
C13	0.018 (3)	0.019 (3)	0.013 (3)	−0.002 (2)	0.000 (2)	0.002 (2)
C14	0.022 (3)	0.019 (3)	0.023 (3)	−0.005 (2)	0.004 (2)	−0.012 (2)
C15	0.020 (3)	0.022 (3)	0.027 (3)	−0.006 (2)	−0.001 (2)	0.002 (2)
C21	0.015 (3)	0.023 (3)	0.018 (3)	−0.002 (2)	0.008 (2)	0.000 (2)
C22	0.027 (3)	0.015 (2)	0.021 (3)	−0.002 (2)	0.006 (3)	−0.006 (2)
C23	0.021 (3)	0.020 (3)	0.024 (3)	−0.005 (2)	0.005 (2)	−0.009 (2)
O23	0.032 (2)	0.024 (2)	0.025 (2)	0.0058 (18)	−0.0061 (18)	−0.0090 (17)
C24	0.009 (3)	0.020 (3)	0.023 (3)	0.005 (2)	0.005 (2)	0.002 (2)
O24	0.026 (2)	0.0201 (19)	0.022 (2)	0.0082 (16)	−0.0056 (17)	−0.0014 (14)
C25	0.018 (3)	0.016 (2)	0.024 (3)	0.002 (2)	0.000 (2)	0.001 (2)
C26	0.020 (3)	0.017 (3)	0.024 (3)	−0.002 (2)	0.011 (2)	−0.008 (2)
C31	0.020 (3)	0.020 (2)	0.018 (3)	−0.005 (2)	0.008 (2)	−0.007 (2)
C32	0.025 (3)	0.021 (3)	0.025 (3)	−0.010 (2)	0.004 (3)	0.005 (2)
C33	0.020 (3)	0.036 (3)	0.038 (4)	−0.007 (3)	0.008 (3)	0.000 (3)
C34	0.022 (3)	0.037 (3)	0.034 (3)	0.012 (3)	0.002 (3)	0.006 (3)
C35	0.034 (4)	0.027 (3)	0.039 (4)	0.003 (3)	0.007 (3)	0.012 (3)
C36	0.024 (3)	0.020 (3)	0.029 (3)	−0.002 (2)	0.003 (3)	−0.001 (2)
C41	0.020 (3)	0.014 (3)	0.019 (3)	−0.001 (2)	0.001 (2)	−0.002 (2)
C42	0.032 (3)	0.022 (3)	0.027 (3)	−0.001 (3)	0.008 (3)	−0.002 (2)
C43	0.032 (4)	0.025 (3)	0.027 (3)	0.001 (3)	0.012 (3)	−0.010 (2)
C44	0.030 (3)	0.026 (3)	0.017 (3)	0.002 (3)	0.008 (2)	−0.002 (2)
C45	0.026 (3)	0.028 (3)	0.022 (3)	−0.006 (3)	0.010 (2)	0.003 (3)
C46	0.027 (3)	0.016 (2)	0.024 (3)	−0.005 (2)	0.003 (2)	−0.006 (2)

Geometric parameters (Å, º) top

N1—C5	1.360 (6)	C24—C25	1.377 (7)
N1—N2	1.364 (5)	O24—H24	0.8400
N1—C1	1.445 (7)	C25—C26	1.373 (7)
C1—N11	1.468 (6)	C25—H25	0.9500
C1—C21	1.515 (6)	C26—H26	0.9500
C1—H1	1.0000	C31—C32	1.394 (7)
N2—C3	1.333 (7)	C31—C36	1.401 (7)
C3—C4	1.429 (7)	C32—C33	1.364 (7)
C3—C31	1.477 (7)	C32—H32	0.9500
C4—C5	1.348 (7)	C33—C34	1.403 (7)
C4—H4	0.9500	C33—H33	0.9500
C5—H5	0.9500	C34—C35	1.387 (8)
N11—C15	1.354 (6)	C34—H34	0.9500
N11—N12	1.367 (6)	C35—C36	1.376 (7)
N12—C13	1.349 (6)	C35—H35	0.9500
C13—C14	1.392 (7)	C36—H36	0.9500
C13—C41	1.473 (7)	C41—C46	1.376 (7)
C14—C15	1.358 (7)	C41—C42	1.430 (7)
C14—H14	0.9500	C42—C43	1.373 (7)
C15—H15	0.9500	C42—H42	0.9500
C21—C26	1.386 (6)	C43—C44	1.388 (7)
C21—C22	1.403 (6)	C43—H43	0.9500
C22—C23	1.360 (7)	C44—C45	1.385 (7)
C22—H22	0.9500	C44—H44	0.9500
C23—O23	1.362 (6)	C45—C46	1.398 (8)
C23—C24	1.418 (6)	C45—H45	0.9500
O23—H23	0.8400	C46—H46	0.9500
C24—O24	1.365 (6)

C5—N1—N2	111.4 (4)	C25—C24—C23	118.6 (4)
C5—N1—C1	128.0 (4)	C24—O24—H24	109.5
N2—N1—C1	118.7 (4)	C26—C25—C24	120.7 (5)
N1—C1—N11	108.8 (4)	C26—C25—H25	119.7
N1—C1—C21	112.2 (4)	C24—C25—H25	119.7
N11—C1—C21	111.8 (4)	C25—C26—C21	121.2 (4)
N1—C1—H1	107.9	C25—C26—H26	119.4
N11—C1—H1	107.9	C21—C26—H26	119.4
C21—C1—H1	107.9	C32—C31—C36	118.6 (5)
C3—N2—N1	105.2 (4)	C32—C31—C3	120.5 (4)
N2—C3—C4	110.2 (5)	C36—C31—C3	120.8 (5)
N2—C3—C31	120.9 (4)	C33—C32—C31	121.4 (5)
C4—C3—C31	128.8 (5)	C33—C32—H32	119.3
C5—C4—C3	105.5 (5)	C31—C32—H32	119.3
C5—C4—H4	127.2	C32—C33—C34	120.7 (5)
C3—C4—H4	127.2	C32—C33—H33	119.6
C4—C5—N1	107.6 (4)	C34—C33—H33	119.6
C4—C5—H5	126.2	C35—C34—C33	117.5 (5)
N1—C5—H5	126.2	C35—C34—H34	121.3
C15—N11—N12	112.5 (4)	C33—C34—H34	121.3
C15—N11—C1	128.7 (4)	C36—C35—C34	122.6 (5)
N12—N11—C1	118.2 (4)	C36—C35—H35	118.7
C13—N12—N11	103.7 (4)	C34—C35—H35	118.7
N12—C13—C14	110.9 (5)	C35—C36—C31	119.2 (5)
N12—C13—C41	120.5 (4)	C35—C36—H36	120.4
C14—C13—C41	128.7 (4)	C31—C36—H36	120.4
C15—C14—C13	106.7 (4)	C46—C41—C42	118.1 (5)
C15—C14—H14	126.7	C46—C41—C13	122.8 (4)
C13—C14—H14	126.7	C42—C41—C13	119.1 (5)
N11—C15—C14	106.2 (5)	C43—C42—C41	120.1 (5)
N11—C15—H15	126.9	C43—C42—H42	119.9
C14—C15—H15	126.9	C41—C42—H42	119.9
C26—C21—C22	118.5 (5)	C42—C43—C44	121.0 (5)
C26—C21—C1	123.3 (4)	C42—C43—H43	119.5
C22—C21—C1	118.2 (4)	C44—C43—H43	119.5
C23—C22—C21	120.5 (5)	C45—C44—C43	119.5 (5)
C23—C22—H22	119.7	C45—C44—H44	120.3
C21—C22—H22	119.7	C43—C44—H44	120.3
C22—C23—O23	120.3 (5)	C44—C45—C46	119.9 (5)
C22—C23—C24	120.6 (4)	C44—C45—H45	120.0
O23—C23—C24	119.1 (4)	C46—C45—H45	120.0
C23—O23—H23	109.5	C41—C46—C45	121.4 (5)
O24—C24—C25	127.0 (4)	C41—C46—H46	119.3
O24—C24—C23	114.4 (4)	C45—C46—H46	119.3

C5—N1—C1—N11	−88.4 (5)	C22—C23—C24—O24	−178.9 (5)
N2—N1—C1—N11	74.6 (5)	O23—C23—C24—O24	1.8 (7)
C5—N1—C1—C21	35.9 (6)	C22—C23—C24—C25	−0.2 (8)
N2—N1—C1—C21	−161.0 (4)	O23—C23—C24—C25	−179.6 (5)
C5—N1—N2—C3	−0.7 (5)	O24—C24—C25—C26	177.4 (5)
C1—N1—N2—C3	−166.4 (4)	C23—C24—C25—C26	−1.1 (8)
N1—N2—C3—C4	0.1 (5)	C24—C25—C26—C21	1.0 (8)
N1—N2—C3—C31	178.5 (4)	C22—C21—C26—C25	0.4 (8)
N2—C3—C4—C5	0.6 (6)	C1—C21—C26—C25	−176.9 (5)
C31—C3—C4—C5	−177.7 (5)	N2—C3—C31—C32	−161.3 (5)
C3—C4—C5—N1	−1.0 (6)	C4—C3—C31—C32	16.8 (8)
N2—N1—C5—C4	1.1 (5)	N2—C3—C31—C36	16.7 (7)
C1—N1—C5—C4	165.2 (4)	C4—C3—C31—C36	−165.2 (5)
N1—C1—N11—C15	34.3 (6)	C36—C31—C32—C33	−1.3 (8)
C21—C1—N11—C15	−90.2 (6)	C3—C31—C32—C33	176.8 (5)
N1—C1—N11—N12	−155.2 (4)	C31—C32—C33—C34	0.6 (9)
C21—C1—N11—N12	80.2 (5)	C32—C33—C34—C35	0.7 (9)
C15—N11—N12—C13	−1.2 (5)	C33—C34—C35—C36	−1.4 (9)
C1—N11—N12—C13	−173.1 (4)	C34—C35—C36—C31	0.7 (9)
N11—N12—C13—C14	0.7 (5)	C32—C31—C36—C35	0.6 (8)
N11—N12—C13—C41	−178.6 (4)	C3—C31—C36—C35	−177.4 (5)
N12—C13—C14—C15	0.0 (6)	N12—C13—C41—C46	5.9 (7)
C41—C13—C14—C15	179.3 (5)	C14—C13—C41—C46	−173.3 (5)
N12—N11—C15—C14	1.2 (5)	N12—C13—C41—C42	−173.9 (4)
C1—N11—C15—C14	172.1 (5)	C14—C13—C41—C42	6.8 (8)
C13—C14—C15—N11	−0.7 (5)	C46—C41—C42—C43	−0.1 (8)
N1—C1—C21—C26	−110.4 (6)	C13—C41—C42—C43	179.7 (5)
N11—C1—C21—C26	12.2 (7)	C41—C42—C43—C44	−0.8 (8)
N1—C1—C21—C22	72.2 (6)	C42—C43—C44—C45	0.7 (8)
N11—C1—C21—C22	−165.1 (5)	C43—C44—C45—C46	0.4 (8)
C26—C21—C22—C23	−1.7 (8)	C42—C41—C46—C45	1.2 (7)
C1—C21—C22—C23	175.8 (5)	C13—C41—C46—C45	−178.6 (5)
C21—C22—C23—O23	−179.1 (5)	C44—C45—C46—C41	−1.4 (8)
C21—C22—C23—C24	1.6 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O23—H23···O24	0.84	2.21	2.646 (5)	113
O24—H24···N12ⁱ	0.84	2.08	2.853 (5)	153

Symmetry code: (i) −x+1/2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₅H₂₀N₄O₂
M_r	408.45
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	13.493 (3), 5.6288 (11), 26.309 (5)
β (°)	100.87 (3)
V (Å³)	1962.3 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.40 × 0.15 × 0.10

Data collection
Diffractometer	Stoe IPDS II two-circle
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	16343, 3450, 1434
R_int	0.111
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.069, 0.121, 0.82
No. of reflections	3450
No. of parameters	282
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.27

Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), XP (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O23—H23···O24	0.84	2.21	2.646 (5)	112.8
O24—H24···N12ⁱ	0.84	2.08	2.853 (5)	153.3

Symmetry code: (i) −x+1/2, y+1/2, −z+1/2.

References

Blasberg, F., Bolte, M., Wagner, M. & Lerner, H.-W. (2011). J. Organomet. Chem. doi:10.1016/j.jorganchem.2011.08.002. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2001). X-AREA. Stoe & Cie, Darmstadt, Germany. Google Scholar

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Volume 67| Part 10| October 2011| Page o2741

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