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The title compound (H2L), C27H28N4O2, is an asymmetric binucleating ligand with well defined soft (N3O-donor) and hard (NO2-donor) sides. H2L was designed as a ligand for the preparation of heterodinuclear mixed-valence MIII/MII complexes which are models for heterobimetallic active sites of enzymes, principally calcineurin. The mol­ecular structure of H2L shows a spatial pre-organization of the donor groups for coordination. This conformation is stabilized by bifurcated intra- and inter­molecular O—H...N hydrogen bonds involving both phenol groups. The inter­molecular hydrogen bonds link mol­ecules of H2L into chains running parallel to the crystallographic c axis.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106050517/bm3018sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106050517/bm3018Isup2.hkl
Contains datablock I

CCDC reference: 638312

Comment top

Many enzymes contain bimetallic cores within their catalytic sites and can be classified as either homobinuclear [e.g. catechol oxidase, with its CuIICuII centre (Klabunde et al., 1998)] or heterobinuclear [e.g. kbPAP, with its FeIIIZnII centre (Sträter et al., 1995)] metalloenzymes, depending on the nature of the metals present. Recent X-ray crystallographic studies have indicated that, even for homobinuclear sites, the two metal centres usually reside in chemically different environments, an asymmetry that may also involve the coordination numbers and the geometry of the metal centres (Belle & Pierre, 2003). Calcineurin, a phosphatase found predominantly in neural tissues, constitutes an interesting example of total asymmetry in heterobinuclear sites: the metal, coordination number, donor and geometry all exhibit asymmetry. This enzyme contains an FeIIIZnII bimetallic core in its active centre, which comprises an octahedral FeIII nucleus coordinated by one O atom from Asp90, one N atom from His92, an O-bridging carboxylate from Asp118 and three water molecules. Three water molecules, one of them acting as an exogenous bridge, complete the Fe coordination sphere. On the other hand, the ZnII centre shows a distorted trigonal–bipyramidal geometry formed by three O atoms from Asp118, Asn150 and the bridging water molecule, and two N atoms from His199 and His281 (Kissinger et al., 1995).

In recent years, the study of models based on simple dinuclear metal complexes has become an important tool to gain insight into the biological functions of such bimetallic cores. In this context, the design of binucleating ligands capable of providing asymmetric dinuclear complexes is a subject of great interest. It is convenient to classify binucleating ligands by the bridging groups that are used for assembling the two metal ions in close proximity (Gavrilova & Bosnich, 2004). Our research group has long experience in the development of asymmetric binucleating ligands containing alkoxide (Rossi et al., 2005) and phenoxide (Mitić et al., 2006) bridging units, which have been used in the synthesis of numerous bimetallic complexes. Here, we report the structure of a new phenoxide-based binucleating hexadentate ligand, H2L, (I), which presents donor, geometry and coordination-number asymmetries, thereby constituting a versatile precursor to synthetic models for the active sites of asymmetric metalloenzymes, with a special focus on calcineurin. It should be emphasized that H2L possesses a softer N3O-donor side, defined by the tertiary amine, both pyridine rings and the bridging phenolate group, capable of accommodating divalent metal ions, and a harder NO2-donor side, comprising the secondary amine and the terminal and bridging phenol moieties, which binds preferentially to trivalent cations. This represents a convenient strategy for the attainment of mixed-valence heterobimetallic systems.

The structure of H2L is shown in Fig. 1, and selected bond lengths and angles are given in Table 1. The bond distances and angles for the aromatic and heteroaromatic rings are not significantly different from those found in similar compounds containing these groups (Example references?). An interesting trend in the three-dimensional arrangement of the molecule is that H2L shows a self-induced spatial pre-organization of the donor groups for coordination: with the exception of atom N32, all donor atoms point towards the bridging atom O1. The respective O20···O1 and N42···O1 distances are 3.622 (3) and 3.310 (4) Å, which are very similar to the values observed for a hydroxo-bridged FeIIIZnII complex [3.950 (8) and 3.354 (8) Å, respectively] of the asymmetric ligand 2-bis[{(2-pyridylmethyl)aminomethyl}-6-{(2-hydroxybenzyl)-(2-pyridylmethyl)}-aminomethyl]-4-methylphenol (Neves et al., 2006).

The molecular conformation is influenced by intra- and intermolecular hydrogen bonds involving both phenol groups (Table 2). Within each molecule, the N1—H1N donor interacts with the acceptors O1 [N···O = 2.896 (3) Å] and O20 [N···O = 2.662 (3) Å], although the latter only achieves a less favourable five-membered ring. The bridging phenol acts as an acceptor in the N1—H1N···O1 interaction, and as a donor in a second bifurcated hydrogen bond involving the interactions O1—H1O···N4 [moderate, O···N = 2.758 (3) Å] and O1—H1O···N42 [weak, O···N = 3.309 (4) Å]. It is interesting to note that the shorter component of this bifurcated hydrogen bond is associated with a narrower angle [N4—C3—C13 = 112.7 (2)°] compared with N1—C2—C11 [116.1 (2)°].

The title ligand has a direct linkage between the terminal phenolic ring and the secondary amine, allowing the formation of a more rigid five-membered chelate during the complexation process. The constriction induced in the complexes by going from a six-membered to a five-membered ring can give rise to modified spectroscopic and electrochemical properties. This was observed by Neves et al. (1992) for a mononuclear MnIII complex with the ligand N,N'-bis(2-hydroxybenzyl)-N,N'-bis(2-methylpyridy1)ethylenediamine. As far as we know, there is only one previous example in the literature of a phenoxide-bridging ligand with such a structural feature (Campbell et al., 1993).

Moderate intermolecular hydrogen bonds (Table 2) of the type O20—H20O···N1i [2.814 (3) Å; symmetry code: (i) x, 1/2 - y, z - 1/2] link the molecules of H2L into zigzag chains (Fig. 2) which run parallel to the crystallographic c axis.

Related literature top

For related literature, see: Belle & Pierre (2003); Campbell et al. (1993); Gavrilova & Bosnich (2004); Kissinger et al. (1995); Klabunde et al. (1998); Mitić et al. (2006); Neves et al. (1992, 2006); Rossi et al. (2005); Sträter et al. (1995); Uozumi et al. (1998).

Experimental top

H2L was synthesized from the precursor compound 3-[N,N-di(2-pyridylmethyl)aminomethyl]-5-methylsalicylaldehyde (bpmamff), which was prepared as described by Uozumi et al. (1998) by nucleophilic substitution of bis(2-pyridylmethyl)amine in 3-chloromethyl-5-methylsalicylaldehyde.

A methanolic solution (Volume?) of 2-aminophenol (0.32 g, 2.9 mmol) was added dropwise to a stirred solution of bpmamff (1.0 g, 2.9 mmol) in methanol–tetrahydrofuran (1:1) (Volume?) and the mixture was left to react for 30 min. A strong orange colour appeared progressively due to the formation of the Schiff base. Reduction of the imine was performed by the addition, in portions, of NaBH4 (0.11 g, 2.9 mmol) in an ice bath. The pH of the medium was then carefully adjusted to 6.0–7.0 with 4M HCl, and the solvent was evaporated to half of its initial volume. The solution was then filtered to eliminate any undesirable precipitate. After a few hours, crystals of (I) suitable for X-ray determination were isolated by filtration, washed with small amounts of cold methanol and diethyl ether, and dried in vacuo (yield 0.56 g, 44%; m.p. 416 K). Analysis, found: C 73.56, H 6.33, N 12.55%; calculated for C27H28N4O2: C 73.61, H 6.41, N 12.72%.

Refinement top

The phenol hydroxyl H atoms were found from ΔF maps and were then refined as part of rigid rotating groups, with O—H fixed at 0.82 Å and Uiso(H) = 1.5Ueq(O). The amine H atom was found in a ΔF map and thereafter refined freely with N—H restrained to 0.86 (1) Å. The remaining H atoms were added in their geometrically calculated positions and refined with C—H = 0.93 Å (0.96 Å for methyl groups) and Uiso(H) = 1.2Ueq(C), with the H atoms on C5 being treated as an idealized methyl group equally disordered over two orientations separated by a rotation of 60°. The slightly high displacement parameters observed for atoms N42, C43, C44, C45 and C46 indicate possible disorder of this aromatic ring, but the ΔF peaks near C45 and C46 are small, and no valid disorder model could be developed. We therefore accepted the ordered model with high U values.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: SET4 in CAD-4 EXPRESS; data reduction: HELENA (Spek, 1996); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of H2L, with the atom-labelling scheme. Displacement ellipsoids are drawn at the 40% probability level. Only those H atoms involved in intramolecular hydrogen bonds (drawn as dashed lines) are shown.
[Figure 2] Fig. 2. A view of H2L, showing the hydrogen-bonding network. Intermolecular hydrogen bonds are drawn as dashed lines.
2-[N,N-Bis(2-pyridylmethyl)aminomethyl]-6-[N-(2-hydroxyanilino)methyl]- 4-methylphenol top
Crystal data top
C27H28N4O2F(000) = 936
Mr = 440.53Dx = 1.233 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 12.651 (1) ÅCell parameters from 25 reflections
b = 21.071 (5) Åθ = 6.7–13.7°
c = 9.262 (1) ŵ = 0.08 mm1
β = 106.09 (1)°T = 293 K
V = 2372.2 (7) Å3Irregular block, pale yellow
Z = 40.46 × 0.30 × 0.23 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer
Rint = 0.039
Radiation source: fine-focus sealed tubeθmax = 25.1°, θmin = 1.7°
Graphite monochromatorh = 150
ω/2θ scansk = 025
4338 measured reflectionsl = 1011
4142 independent reflections3 standard reflections every 200 reflections
2138 reflections with I > 2σ(I) intensity decay: 1%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.053H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.155 w = 1/[σ2(Fo2) + (0.056P)2 + 0.792P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
4142 reflectionsΔρmax = 0.23 e Å3
305 parametersΔρmin = 0.18 e Å3
1 restraintExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0072 (11)
Crystal data top
C27H28N4O2V = 2372.2 (7) Å3
Mr = 440.53Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.651 (1) ŵ = 0.08 mm1
b = 21.071 (5) ÅT = 293 K
c = 9.262 (1) Å0.46 × 0.30 × 0.23 mm
β = 106.09 (1)°
Data collection top
Enraf–Nonius CAD-4
diffractometer
Rint = 0.039
4338 measured reflections3 standard reflections every 200 reflections
4142 independent reflections intensity decay: 1%
2138 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0531 restraint
wR(F2) = 0.155H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 0.23 e Å3
4142 reflectionsΔρmin = 0.18 e Å3
305 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
O10.68229 (18)0.12805 (9)0.7041 (3)0.0599 (6)
H1O0.73700.12340.67410.090*
O200.47861 (18)0.24240 (11)0.5095 (2)0.0643 (7)
H20O0.47000.25850.42640.096*
N10.4876 (2)0.18120 (13)0.7641 (3)0.0509 (7)
H1N0.5396 (17)0.1931 (13)0.728 (3)0.050 (9)*
N40.84061 (19)0.05914 (12)0.6194 (3)0.0485 (7)
N321.1004 (3)0.03344 (17)0.8827 (4)0.0802 (10)
N420.8029 (3)0.17139 (15)0.4450 (3)0.0786 (10)
C20.5232 (3)0.12487 (15)0.8595 (3)0.0553 (9)
H2A0.46490.11340.90400.066*
H2B0.58690.13650.94090.066*
C30.7420 (2)0.02186 (15)0.5442 (3)0.0506 (8)
H3A0.76440.02050.52410.061*
H3B0.70590.04150.44850.061*
C50.4781 (3)0.10945 (16)0.7337 (4)0.0635 (10)
H5A0.42610.10520.79140.076*0.50
H5B0.53360.13960.78140.076*0.50
H5C0.44080.12390.63430.076*0.50
H5D0.50760.14060.68000.076*0.50
H5E0.40000.10620.69000.076*0.50
H5F0.49290.12190.83710.076*0.50
C110.5522 (2)0.06693 (14)0.7822 (3)0.0448 (7)
C120.6327 (2)0.07022 (14)0.7071 (3)0.0450 (7)
C130.6613 (2)0.01699 (14)0.6364 (3)0.0432 (7)
C140.6101 (2)0.04015 (14)0.6476 (3)0.0466 (8)
H140.62960.07590.60190.056*
C150.5310 (2)0.04600 (14)0.7243 (3)0.0461 (8)
C160.5027 (2)0.00816 (15)0.7886 (3)0.0491 (8)
H160.44830.00540.83830.059*
C210.3899 (2)0.17803 (14)0.6457 (3)0.0464 (8)
C220.3845 (3)0.21213 (14)0.5142 (4)0.0491 (8)
C230.2884 (3)0.21430 (17)0.3998 (4)0.0674 (10)
H230.28600.23680.31260.081*
C240.1961 (3)0.18349 (19)0.4132 (5)0.0793 (12)
H240.13140.18510.33530.095*
C250.1997 (3)0.15053 (19)0.5411 (5)0.0778 (12)
H250.13670.13030.55080.093*
C260.2960 (3)0.14690 (16)0.6563 (4)0.0624 (9)
H260.29780.12330.74180.075*
C300.9078 (3)0.02456 (16)0.7502 (4)0.0624 (9)
H30A0.93550.01400.71620.075*
H30B0.86190.01240.81380.075*
C311.0032 (3)0.06306 (19)0.8409 (4)0.0625 (9)
C331.1866 (4)0.0661 (3)0.9666 (5)0.0963 (15)
H331.25460.04600.99590.116*
C341.1802 (5)0.1264 (3)1.0107 (5)0.1101 (18)
H341.24210.14671.07080.132*
C351.0820 (5)0.1573 (3)0.9664 (6)0.1223 (18)
H351.07580.19960.99210.147*
C360.9915 (4)0.1240 (2)0.8817 (5)0.0980 (14)
H360.92280.14330.85280.118*
C400.9037 (3)0.07305 (17)0.5122 (4)0.0631 (10)
H40A0.91150.03430.45940.076*
H40B0.97690.08700.56730.076*
C410.8518 (2)0.12308 (15)0.3990 (4)0.0515 (8)
C430.7592 (4)0.21651 (18)0.3444 (4)0.0839 (13)
H430.72330.25000.37630.101*
C440.7633 (4)0.2172 (2)0.2025 (5)0.0857 (13)
H440.73540.25100.13870.103*
C450.8102 (4)0.1662 (3)0.1551 (5)0.120 (2)
H450.81280.16400.05580.144*
C460.8540 (4)0.1176 (2)0.2534 (4)0.0937 (14)
H460.88430.08200.22090.112*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0582 (15)0.0454 (13)0.0839 (17)0.0073 (11)0.0330 (13)0.0076 (12)
O200.0640 (15)0.0663 (16)0.0620 (15)0.0166 (13)0.0164 (12)0.0110 (13)
N10.0566 (18)0.0493 (17)0.0515 (16)0.0032 (14)0.0228 (15)0.0017 (13)
N40.0370 (14)0.0532 (17)0.0562 (16)0.0011 (12)0.0143 (12)0.0144 (13)
N320.054 (2)0.106 (3)0.073 (2)0.004 (2)0.0055 (17)0.0227 (19)
N420.116 (3)0.066 (2)0.0558 (18)0.029 (2)0.0274 (18)0.0058 (16)
C20.067 (2)0.057 (2)0.0443 (18)0.0028 (18)0.0195 (16)0.0025 (16)
C30.0479 (18)0.051 (2)0.0542 (19)0.0041 (15)0.0157 (15)0.0006 (16)
C50.064 (2)0.058 (2)0.069 (2)0.0074 (18)0.0175 (18)0.0088 (18)
C110.0478 (17)0.0488 (19)0.0374 (16)0.0009 (15)0.0109 (14)0.0007 (14)
C120.0453 (17)0.0416 (19)0.0465 (18)0.0011 (15)0.0099 (15)0.0036 (14)
C130.0393 (16)0.0444 (18)0.0438 (17)0.0001 (14)0.0083 (14)0.0002 (14)
C140.0466 (18)0.0432 (18)0.0465 (18)0.0022 (15)0.0067 (15)0.0010 (15)
C150.0430 (17)0.0474 (19)0.0437 (18)0.0014 (15)0.0049 (14)0.0078 (15)
C160.0481 (18)0.061 (2)0.0399 (18)0.0017 (16)0.0154 (14)0.0089 (16)
C210.0523 (19)0.0404 (18)0.0518 (19)0.0007 (15)0.0230 (17)0.0083 (15)
C220.051 (2)0.0395 (18)0.058 (2)0.0013 (15)0.0166 (17)0.0009 (16)
C230.071 (3)0.060 (2)0.067 (2)0.001 (2)0.011 (2)0.0083 (19)
C240.056 (2)0.076 (3)0.098 (3)0.004 (2)0.008 (2)0.002 (2)
C250.054 (2)0.073 (3)0.113 (3)0.016 (2)0.034 (2)0.011 (3)
C260.062 (2)0.062 (2)0.072 (2)0.0066 (18)0.033 (2)0.0007 (18)
C300.0482 (19)0.064 (2)0.074 (2)0.0049 (18)0.0151 (18)0.0206 (19)
C310.054 (2)0.074 (3)0.059 (2)0.001 (2)0.0147 (18)0.0169 (19)
C330.057 (3)0.149 (5)0.074 (3)0.010 (3)0.004 (2)0.028 (3)
C340.099 (4)0.148 (5)0.077 (3)0.044 (4)0.015 (3)0.002 (4)
C350.133 (5)0.107 (4)0.124 (4)0.026 (4)0.030 (4)0.031 (3)
C360.078 (3)0.088 (3)0.124 (4)0.007 (3)0.022 (3)0.020 (3)
C400.050 (2)0.069 (2)0.078 (2)0.0114 (18)0.0309 (18)0.0161 (19)
C410.0492 (19)0.050 (2)0.062 (2)0.0010 (16)0.0270 (17)0.0074 (17)
C430.129 (4)0.054 (2)0.066 (3)0.024 (2)0.024 (3)0.000 (2)
C440.119 (4)0.073 (3)0.075 (3)0.017 (3)0.044 (3)0.025 (2)
C450.155 (5)0.155 (5)0.071 (3)0.075 (4)0.063 (3)0.042 (3)
C460.111 (3)0.108 (4)0.075 (3)0.053 (3)0.047 (3)0.007 (3)
Geometric parameters (Å, º) top
O1—C121.374 (3)C16—H160.9300
O1—H1O0.8200C21—C261.384 (4)
O20—C221.362 (3)C21—C221.399 (4)
O20—H20O0.8200C22—C231.374 (4)
N1—C211.408 (4)C23—C241.371 (5)
N1—C21.474 (4)C23—H230.9300
N1—H1N0.86 (1)C24—C251.363 (5)
N4—C401.465 (4)C24—H240.9300
N4—C301.466 (4)C25—C261.382 (5)
N4—C31.475 (4)C25—H250.9300
N32—C311.337 (4)C26—H260.9300
N32—C331.341 (5)C30—C311.503 (5)
N42—C411.322 (4)C30—H30A0.9700
N42—C431.338 (4)C30—H30B0.9700
C2—C111.511 (4)C31—C361.357 (5)
C2—H2A0.9700C33—C341.342 (7)
C2—H2B0.9700C33—H330.9300
C3—C131.505 (4)C34—C351.362 (7)
C3—H3A0.9700C34—H340.9300
C3—H3B0.9700C35—C361.386 (6)
C5—C151.509 (4)C35—H350.9300
C5—H5A0.9600C36—H360.9300
C5—H5B0.9600C40—C411.504 (4)
C5—H5C0.9600C40—H40A0.9700
C5—H5D0.9600C40—H40B0.9700
C5—H5E0.9600C41—C461.362 (5)
C5—H5F0.9600C43—C441.330 (5)
C11—C121.385 (4)C43—H430.9300
C11—C161.396 (4)C44—C451.358 (6)
C12—C131.396 (4)C44—H440.9300
C13—C141.384 (4)C45—C461.379 (5)
C14—C151.384 (4)C45—H450.9300
C14—H140.9300C46—H460.9300
C15—C161.380 (4)
C12—O1—H1O109.5C26—C21—C22118.0 (3)
C22—O20—H20O109.5C26—C21—N1123.5 (3)
C21—N1—C2119.0 (3)C22—C21—N1118.3 (3)
C21—N1—H1N108 (2)O20—C22—C23123.6 (3)
C2—N1—H1N109 (2)O20—C22—C21115.9 (3)
C40—N4—C30111.0 (2)C23—C22—C21120.5 (3)
C40—N4—C3109.6 (2)C24—C23—C22120.5 (4)
C30—N4—C3110.2 (2)C24—C23—H23119.7
C31—N32—C33117.6 (4)C22—C23—H23119.7
C41—N42—C43117.5 (3)C25—C24—C23119.7 (4)
N1—C2—C11116.1 (2)C25—C24—H24120.2
N1—C2—H2A108.3C23—C24—H24120.2
C11—C2—H2A108.3C24—C25—C26120.6 (3)
N1—C2—H2B108.3C24—C25—H25119.7
C11—C2—H2B108.3C26—C25—H25119.7
H2A—C2—H2B107.4C25—C26—C21120.6 (3)
N4—C3—C13112.7 (2)C25—C26—H26119.7
N4—C3—H3A109.0C21—C26—H26119.7
C13—C3—H3A109.0N4—C30—C31112.7 (3)
N4—C3—H3B109.0N4—C30—H30A109.1
C13—C3—H3B109.0C31—C30—H30A109.1
H3A—C3—H3B107.8N4—C30—H30B109.1
C15—C5—H5A109.5C31—C30—H30B109.1
C15—C5—H5B109.5H30A—C30—H30B107.8
H5A—C5—H5B109.5N32—C31—C36121.5 (4)
C15—C5—H5C109.5N32—C31—C30116.2 (4)
H5A—C5—H5C109.5C36—C31—C30122.2 (4)
H5B—C5—H5C109.5N32—C33—C34123.7 (5)
C15—C5—H5D109.5N32—C33—H33118.2
H5A—C5—H5D141.1C34—C33—H33118.2
H5B—C5—H5D56.3C33—C34—C35119.2 (5)
H5C—C5—H5D56.3C33—C34—H34120.4
C15—C5—H5E109.5C35—C34—H34120.4
H5A—C5—H5E56.3C34—C35—C36117.9 (6)
H5B—C5—H5E141.1C34—C35—H35121.0
H5C—C5—H5E56.3C36—C35—H35121.0
H5D—C5—H5E109.5C31—C36—C35120.0 (5)
C15—C5—H5F109.5C31—C36—H36120.0
H5A—C5—H5F56.3C35—C36—H36120.0
H5B—C5—H5F56.3N4—C40—C41113.4 (2)
H5C—C5—H5F141.1N4—C40—H40A108.9
H5D—C5—H5F109.5C41—C40—H40A108.9
H5E—C5—H5F109.5N4—C40—H40B108.9
C12—C11—C16117.8 (3)C41—C40—H40B108.9
C12—C11—C2120.4 (3)H40A—C40—H40B107.7
C16—C11—C2121.7 (3)N42—C41—C46121.6 (3)
O1—C12—C11117.2 (3)N42—C41—C40117.9 (3)
O1—C12—C13121.6 (3)C46—C41—C40120.5 (3)
C11—C12—C13121.2 (3)C44—C43—N42125.0 (4)
C14—C13—C12118.4 (3)C44—C43—H43117.5
C14—C13—C3120.4 (3)N42—C43—H43117.5
C12—C13—C3121.1 (3)C43—C44—C45116.8 (4)
C15—C14—C13122.4 (3)C43—C44—H44121.6
C15—C14—H14118.8C45—C44—H44121.6
C13—C14—H14118.8C44—C45—C46120.3 (4)
C16—C15—C14117.4 (3)C44—C45—H45119.8
C16—C15—C5122.4 (3)C46—C45—H45119.8
C14—C15—C5120.3 (3)C41—C46—C45118.5 (4)
C15—C16—C11122.8 (3)C41—C46—H46120.8
C15—C16—H16118.6C45—C46—H46120.8
C11—C16—H16118.6
C21—N1—C2—C1163.9 (4)C21—C22—C23—C240.5 (5)
C40—N4—C3—C13168.3 (2)C22—C23—C24—C250.1 (6)
C30—N4—C3—C1369.2 (3)C23—C24—C25—C261.2 (6)
N1—C2—C11—C1257.2 (4)C24—C25—C26—C211.7 (6)
N1—C2—C11—C16125.3 (3)C22—C21—C26—C251.1 (5)
C16—C11—C12—O1178.8 (3)N1—C21—C26—C25173.9 (3)
C2—C11—C12—O11.2 (4)C40—N4—C30—C3164.4 (4)
C16—C11—C12—C131.8 (4)C3—N4—C30—C31174.0 (3)
C2—C11—C12—C13179.4 (3)C33—N32—C31—C360.1 (5)
O1—C12—C13—C14178.2 (3)C33—N32—C31—C30178.5 (3)
C11—C12—C13—C142.4 (4)N4—C30—C31—N32134.2 (3)
O1—C12—C13—C34.5 (4)N4—C30—C31—C3647.4 (5)
C11—C12—C13—C3174.9 (3)C31—N32—C33—C340.3 (6)
N4—C3—C13—C14137.2 (3)N32—C33—C34—C351.5 (8)
N4—C3—C13—C1245.5 (4)C33—C34—C35—C362.4 (8)
C12—C13—C14—C150.9 (4)N32—C31—C36—C351.2 (7)
C3—C13—C14—C15176.4 (3)C30—C31—C36—C35179.5 (4)
C13—C14—C15—C161.1 (4)C34—C35—C36—C312.3 (8)
C13—C14—C15—C5179.8 (3)C30—N4—C40—C41164.0 (3)
C14—C15—C16—C111.7 (4)C3—N4—C40—C4174.0 (4)
C5—C15—C16—C11179.2 (3)C43—N42—C41—C462.7 (6)
C12—C11—C16—C150.3 (4)C43—N42—C41—C40178.4 (3)
C2—C11—C16—C15177.2 (3)N4—C40—C41—N4237.6 (4)
C2—N1—C21—C2639.0 (4)N4—C40—C41—C46141.3 (4)
C2—N1—C21—C22146.0 (3)C41—N42—C43—C441.5 (7)
C26—C21—C22—O20179.4 (3)N42—C43—C44—C453.8 (7)
N1—C21—C22—O204.2 (4)C43—C44—C45—C462.0 (8)
C26—C21—C22—C230.0 (4)N42—C41—C46—C454.3 (7)
N1—C21—C22—C23175.3 (3)C40—C41—C46—C45176.8 (4)
O20—C22—C23—C24178.9 (3)C44—C45—C46—C411.9 (8)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O10.86 (1)2.32 (2)2.896 (3)124 (2)
N1—H1N···O200.86 (1)2.22 (3)2.662 (3)113 (2)
O1—H1O···N40.822.042.758 (3)145
O1—H1O···N420.822.683.309 (4)134
O20—H20O···N1i0.822.032.813 (3)160
Symmetry code: (i) x, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC27H28N4O2
Mr440.53
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)12.651 (1), 21.071 (5), 9.262 (1)
β (°) 106.09 (1)
V3)2372.2 (7)
Z4
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.46 × 0.30 × 0.23
Data collection
DiffractometerEnraf–Nonius CAD-4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
4338, 4142, 2138
Rint0.039
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.053, 0.155, 1.02
No. of reflections4142
No. of parameters305
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.23, 0.18

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), SET4 in CAD-4 EXPRESS, HELENA (Spek, 1996), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97.

Selected geometric parameters (Å, º) top
O1—C121.374 (3)N4—C401.465 (4)
O20—C221.362 (3)N4—C301.466 (4)
N1—C211.408 (4)N4—C31.475 (4)
N1—C21.474 (4)C2—C111.511 (4)
C21—N1—C2119.0 (3)C30—N4—C3110.2 (2)
C40—N4—C30111.0 (2)N1—C2—C11116.1 (2)
C40—N4—C3109.6 (2)N4—C3—C13112.7 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O10.86 (1)2.32 (2)2.896 (3)124 (2)
N1—H1N···O200.86 (1)2.22 (3)2.662 (3)113 (2)
O1—H1O···N40.822.042.758 (3)145
O1—H1O···N420.822.683.309 (4)134
O20—H20O···N1i0.822.032.813 (3)160
Symmetry code: (i) x, y+1/2, z1/2.
 

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