3-{[Bis(pyridin-2-ylmeth­yl)amino]­meth­yl}-2-hy­droxy-5-methyl­benz­aldehyde

Wang, R.-X.; Gao, D.-Z.; Ye, F.; Wu, Y.-F.; Zhu, D.-R.

doi:10.1107/S1600536812019940

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Pages o1672-o1673

doi:10.1107/S1600536812019940

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3-{[Bis(pyridin-2-ylmethyl)amino]methyl}-2-hydroxy-5-methylbenzaldehyde

Ruo-Xu Wang,^a Da-Zhi Gao,^a Fan Ye,^a Yan-Fei Wu ^a and Dun-Ru Zhu ^a ^*

^aCollege of Chemistry and Chemical Engineering, State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: zhudr@njut.edu.cn

(Received 20 April 2012; accepted 3 May 2012; online 12 May 2012)

In the title compound, C₂₁H₂₁N₃O₂, the pyridine rings and the benzene ring lie in a propeller arrangement around the central tertiary amine N atom. The dihedral angles formed by the benzene ring with the pyridine rings are 61.0 (3) and 49.6 (3)°, while the dihedral angle between the pyridine rings is 69.7 (3)°. The molecular conformation is stabilized by intramolecular bifurcated O—H⋯N hydrogen bonds. In the crystal, inversion dimers are formed via pairs of C—H⋯N hydrogen bonds.

Related literature

For general background to unsymmetric phenolate compounds, see: Lambert et al. (1997 ); Dubois, Xiang et al. (2003 ); Dubois, Caspar et al. (2003 ); Carlsson et al. (2004 ). For the syntheses and structures of related compounds, see: Chirakul et al. (2000 ); Abe et al. (2006 ); Bortoluzzi et al. (2007 ); Koval, Huisman, Stassen, Gamez, Lutz, Spek & Reedijk (2004 ); Koval, Huisman, Stassen, Gamez, Lutz, Spek, Pursche et al. (2004 ); Koval et al. (2007 ); Zhu et al. (2007 ). For the synthesis of the title compound, see: Lambert et al. (1997); Koval et al. (2003 ).

Experimental

Crystal data

C₂₁H₂₁N₃O₂
M_r = 347.41
Triclinic, $[P \overline 1]$
a = 8.479 (3) Å
b = 9.007 (3) Å
c = 12.734 (4) Å
α = 107.565 (4)°
β = 94.068 (4)°
γ = 99.092 (4)°
V = 908.2 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 K
0.16 × 0.12 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.987, T_max = 0.993
6434 measured reflections
3159 independent reflections
2612 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.117
S = 1.06
3159 reflections
240 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1B⋯N2	0.94 (3)	2.53 (3)	3.219 (2)	130 (2)
O1—H1B⋯N3	0.94 (3)	1.95 (3)	2.790 (2)	148 (2)
C3—H3A⋯N2ⁱ	0.93	2.59	3.390 (3)	145
Symmetry code: (i) -x+1, -y+1, -z+2.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812019940/rz2747sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812019940/rz2747Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812019940/rz2747Isup3.cml

checkCIF report

Comment top

Unsymmetrical phenolate based "end-off" compartmental ligands which contain two adjacent, but dissimilar coordination sites, are important chelating agents to synthetic model complexes for metalloenzymes such as phosphatase, urease, superoxide dismutase, catalase, tyrosinase, nuclease, etc (Lambert et al., 1997; Dubois, Xiang et al., 2003; Dubois, Caspar et al., 2003; Carlsson et al., 2004). The title compound (HL) is a key precursor to the unsymmetrical ligands (Chirakul et al., 2000; Abe et al., 2006). Up to now, different kinds of interesting model complexes with HL and its derivatives have been reported (Lambert et al., 1997; Koval et al., 2003; Koval, Huisman, Stassen, Gamez, Lutz, Spek & Reedijk, 2004; Koval, Huisman, Stassen, Gamez, Lutz, Spek, Pursche et al., 2004; Koval et al., 2007), however, the crystal structure of the HL itself is still unknown to us. Recently, in the synthesis of HL derivatives (Zhu et al., 2007), we unexpectedly obtained single crystals of HL, and its crystal structure is reported herein.

The X-ray analysis of the title compound (Fig. 1) indicated that two pyridyne rings and the substituted phenyl ring lie in a propeller arrangement around the central tertiary amine N3 atom. The dihedral angles between the phenyl ring and two pyridyne rings are 61.0 (3)° and 49.6 (3)°, respectively, while the dihedral angle between two pyridyne rings is 69.7 (3)°. These angles are larger than those found in the ligand L of the related complexes [Cu₂L(µ-NO₃)(NO₃)₂].CH₃CN, [Cu(HL)Br₂].0.5H₂O, [Mn(HL)Cl₂], (Koval, Huisman, Stassen, Gamez, Lutz, Spek & Reedijk, 2004) and [Co₂L₂](ClO₄)₂.0.7CH₃OH, [Co₂L₂](BF₄)₂.CH₃OH, [Mn₂L₂](BF₄)₂.C₄H₁₀O (Koval, Huisman, Stassen, Gamez, Lutz, Spek, Pursche et al., 2004). The dihedral angle between the phenyl ring and the C18/C21/O2 plane through the aldehyde group is 10.5 (3)°. All bond lengths and angles are normal (Bortoluzzi et al., 2007). An intramolecular bifurcate O—H···N hydrogen bond (Table 1) stabilizes the molecular conformation. In the crystal structure (Fig. 2), centrosymmetrically related molecules are linked by pairs of C—H···N hydrogen bonds into dimers.

Related literature top

For general background to unsymmetric phenolate compounds, see: Lambert et al. (1997); Dubois, Xiang et al. (2003); Dubois, Caspar et al. (2003);Carlsson et al. (2004). For the syntheses and structures of related compounds, see: Chirakul et al. (2000); Abe et al. (2006); Bortoluzzi et al. (2007); Koval, Huisman, Stassen, Gamez, Lutz, Spek & Reedijk (2004); Koval, Huisman, Stassen, Gamez, Lutz, Spek, Pursche et al. (2004); Koval et al. (2007); Zhu et al. (2007). For the synthesis of the title compound, see: Lambert et al. (1997); Koval et al. (2003).

Experimental top

The title compound was synthesized following the method reported by Lambert et al. (1997) and Koval et al. (2003). Diffraction quality crystals were obtained by slow evaporation of an acetone solution.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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).

Figures top

	Fig. 1. The molecular structure of the title compound showing displacement ellipsoids drawn at the 30% probability level. Intramolecular hydrogen bonds are drawn as dashed lines.
	Fig. 2. Partial crystal packing of the title compound showing the formation of a dimer through hydrogen bonds (dashed lines). Symmetry code: (i) 1-x, 1-y, 2-z.

3-{[Bis(pyridin-2-ylmethyl)amino]methyl}-2-hydroxy-5-methylbenzaldehyde top

Crystal data top

C₂₁H₂₁N₃O₂	Z = 2
M_r = 347.41	F(000) = 368
Triclinic, P1	D_x = 1.270 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.479 (3) Å	Cell parameters from 285 reflections
b = 9.007 (3) Å	θ = 1.7–26.9°
c = 12.734 (4) Å	µ = 0.08 mm⁻¹
α = 107.565 (4)°	T = 296 K
β = 94.068 (4)°	Prism, colourless
γ = 99.092 (4)°	0.16 × 0.12 × 0.08 mm
V = 908.2 (5) Å³

Data collection top

Bruker APEXII CCD diffractometer	3159 independent reflections
Radiation source: fine-focus sealed tube	2612 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −10→9
T_min = 0.987, T_max = 0.993	k = −10→9
6434 measured reflections	l = −15→15

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.117	w = 1/[σ²(F_o²) + (0.0586P)² + 0.1506P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.002
3159 reflections	Δρ_max = 0.28 e Å⁻³
240 parameters	Δρ_min = −0.13 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.015 (4)

Crystal data top

C₂₁H₂₁N₃O₂	γ = 99.092 (4)°
M_r = 347.41	V = 908.2 (5) Å³
Triclinic, P1	Z = 2
a = 8.479 (3) Å	Mo Kα radiation
b = 9.007 (3) Å	µ = 0.08 mm⁻¹
c = 12.734 (4) Å	T = 296 K
α = 107.565 (4)°	0.16 × 0.12 × 0.08 mm
β = 94.068 (4)°

Data collection top

Bruker APEXII CCD diffractometer	3159 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2612 reflections with I > 2σ(I)
T_min = 0.987, T_max = 0.993	R_int = 0.016
6434 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.28 e Å⁻³
3159 reflections	Δρ_min = −0.13 e Å⁻³
240 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	U_iso*/U_eq
O1	0.30347 (14)	0.24261 (15)	0.70069 (11)	0.0612 (4)
O2	0.2793 (2)	0.4303 (2)	0.45307 (13)	0.0963 (5)
N1	0.08654 (17)	0.36504 (16)	1.11217 (10)	0.0500 (3)
N2	0.44036 (16)	0.04369 (16)	0.84649 (12)	0.0556 (4)
N3	0.13178 (14)	0.13408 (13)	0.85047 (9)	0.0373 (3)
C1	0.1725 (2)	0.4744 (2)	1.20326 (14)	0.0619 (5)
H1A	0.1422	0.4755	1.2722	0.074*
C2	0.3018 (2)	0.5841 (2)	1.20004 (17)	0.0672 (5)
H2A	0.3586	0.6568	1.2652	0.081*
C3	0.3457 (2)	0.5845 (2)	1.09924 (19)	0.0677 (5)
H3A	0.4331	0.6578	1.0944	0.081*
C4	0.2591 (2)	0.47535 (19)	1.00495 (15)	0.0544 (4)
H4A	0.2865	0.4747	0.9354	0.065*
C5	0.13093 (17)	0.36626 (16)	1.01410 (12)	0.0386 (3)
C6	0.5620 (2)	−0.0253 (2)	0.80858 (17)	0.0649 (5)
H6A	0.6501	0.0376	0.7938	0.078*
C7	0.5662 (2)	−0.1817 (2)	0.79005 (16)	0.0644 (5)
H7A	0.6543	−0.2242	0.7636	0.077*
C8	0.4367 (3)	−0.2741 (2)	0.81160 (18)	0.0719 (6)
H8A	0.4350	−0.3813	0.8001	0.086*
C9	0.3086 (2)	−0.2069 (2)	0.85051 (16)	0.0599 (5)
H9A	0.2190	−0.2683	0.8648	0.072*
C10	0.31508 (17)	−0.04723 (17)	0.86807 (12)	0.0400 (3)
C11	0.03455 (17)	0.24405 (18)	0.91278 (12)	0.0414 (3)
H11A	−0.0550	0.1841	0.9350	0.050*
H11B	−0.0093	0.2971	0.8647	0.050*
C12	0.18157 (18)	0.03443 (18)	0.91383 (12)	0.0433 (4)
H12A	0.0896	−0.0450	0.9134	0.052*
H12B	0.2170	0.0996	0.9903	0.052*
C13	0.04151 (18)	0.03472 (17)	0.74274 (12)	0.0426 (4)
H13A	−0.0639	−0.0127	0.7545	0.051*
H13B	0.0976	−0.0504	0.7096	0.051*
C14	0.02146 (18)	0.12748 (17)	0.66384 (11)	0.0417 (4)
C15	−0.1264 (2)	0.11424 (19)	0.60476 (12)	0.0488 (4)
H15A	−0.2157	0.0511	0.6179	0.059*
C16	−0.1472 (2)	0.1916 (2)	0.52628 (13)	0.0540 (4)
C17	−0.0125 (2)	0.28009 (19)	0.50600 (13)	0.0548 (4)
H17A	−0.0229	0.3306	0.4527	0.066*
C18	0.1394 (2)	0.29671 (18)	0.56266 (12)	0.0496 (4)
C19	0.15547 (19)	0.22339 (18)	0.64412 (12)	0.0447 (4)
C20	−0.3128 (3)	0.1731 (3)	0.46591 (17)	0.0776 (6)
H20A	−0.3064	0.2332	0.4151	0.116*
H20B	−0.3843	0.2111	0.5187	0.116*
H20C	−0.3529	0.0631	0.4256	0.116*
C21	0.2815 (3)	0.3831 (2)	0.53231 (16)	0.0656 (5)
H21A	0.3792	0.4027	0.5768	0.079*
H1B	0.286 (3)	0.207 (3)	0.762 (2)	0.088 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0500 (7)	0.0767 (9)	0.0618 (8)	0.0016 (6)	−0.0033 (6)	0.0369 (7)
O2	0.1206 (13)	0.1079 (12)	0.0805 (10)	0.0155 (10)	0.0190 (9)	0.0608 (10)
N1	0.0583 (8)	0.0525 (8)	0.0402 (7)	0.0139 (6)	0.0080 (6)	0.0143 (6)
N2	0.0447 (8)	0.0503 (8)	0.0726 (9)	0.0084 (6)	0.0122 (7)	0.0196 (7)
N3	0.0409 (7)	0.0406 (7)	0.0325 (6)	0.0132 (5)	0.0043 (5)	0.0118 (5)
C1	0.0779 (13)	0.0663 (12)	0.0402 (9)	0.0278 (10)	0.0011 (8)	0.0092 (8)
C2	0.0591 (12)	0.0548 (11)	0.0687 (13)	0.0207 (9)	−0.0150 (9)	−0.0082 (9)
C3	0.0483 (10)	0.0476 (10)	0.0942 (15)	0.0050 (8)	0.0077 (10)	0.0055 (10)
C4	0.0536 (10)	0.0487 (9)	0.0611 (10)	0.0094 (8)	0.0163 (8)	0.0157 (8)
C5	0.0392 (8)	0.0392 (8)	0.0411 (8)	0.0155 (6)	0.0067 (6)	0.0139 (6)
C6	0.0413 (9)	0.0742 (12)	0.0825 (13)	0.0128 (9)	0.0133 (9)	0.0277 (10)
C7	0.0553 (11)	0.0843 (14)	0.0662 (11)	0.0374 (10)	0.0134 (9)	0.0288 (10)
C8	0.0888 (14)	0.0615 (11)	0.0865 (14)	0.0411 (11)	0.0302 (12)	0.0363 (11)
C9	0.0681 (12)	0.0514 (10)	0.0752 (12)	0.0212 (9)	0.0267 (9)	0.0330 (9)
C10	0.0412 (8)	0.0450 (8)	0.0369 (7)	0.0104 (6)	0.0020 (6)	0.0172 (6)
C11	0.0396 (8)	0.0472 (8)	0.0389 (8)	0.0139 (6)	0.0059 (6)	0.0126 (6)
C12	0.0486 (9)	0.0467 (8)	0.0413 (8)	0.0146 (7)	0.0100 (7)	0.0199 (7)
C13	0.0441 (8)	0.0422 (8)	0.0390 (8)	0.0079 (6)	0.0039 (6)	0.0094 (6)
C14	0.0466 (9)	0.0431 (8)	0.0316 (7)	0.0126 (7)	0.0018 (6)	0.0050 (6)
C15	0.0493 (9)	0.0521 (9)	0.0389 (8)	0.0147 (7)	0.0011 (7)	0.0042 (7)
C16	0.0635 (11)	0.0561 (10)	0.0374 (8)	0.0255 (8)	−0.0058 (7)	0.0032 (7)
C17	0.0792 (13)	0.0498 (9)	0.0364 (8)	0.0240 (9)	−0.0012 (8)	0.0114 (7)
C18	0.0666 (11)	0.0433 (8)	0.0389 (8)	0.0148 (8)	0.0045 (7)	0.0112 (7)
C19	0.0494 (9)	0.0458 (8)	0.0369 (8)	0.0111 (7)	0.0004 (6)	0.0102 (7)
C20	0.0765 (14)	0.0919 (15)	0.0607 (12)	0.0335 (12)	−0.0152 (10)	0.0153 (11)
C21	0.0856 (14)	0.0608 (11)	0.0568 (11)	0.0146 (10)	0.0119 (10)	0.0272 (9)

Geometric parameters (Å, º) top

O1—C19	1.3607 (19)	C9—C10	1.378 (2)
O1—H1B	0.94 (2)	C9—H9A	0.9300
O2—C21	1.207 (2)	C10—C12	1.503 (2)
N1—C5	1.3324 (19)	C11—H11A	0.9700
N1—C1	1.346 (2)	C11—H11B	0.9700
N2—C6	1.332 (2)	C12—H12A	0.9700
N2—C10	1.333 (2)	C12—H12B	0.9700
N3—C12	1.4640 (18)	C13—C14	1.505 (2)
N3—C13	1.4704 (19)	C13—H13A	0.9700
N3—C11	1.4719 (18)	C13—H13B	0.9700
C1—C2	1.367 (3)	C14—C15	1.384 (2)
C1—H1A	0.9300	C14—C19	1.401 (2)
C2—C3	1.363 (3)	C15—C16	1.396 (2)
C2—H2A	0.9300	C15—H15A	0.9300
C3—C4	1.372 (3)	C16—C17	1.372 (3)
C3—H3A	0.9300	C16—C20	1.512 (2)
C4—C5	1.382 (2)	C17—C18	1.394 (2)
C4—H4A	0.9300	C17—H17A	0.9300
C5—C11	1.501 (2)	C18—C19	1.397 (2)
C6—C7	1.364 (3)	C18—C21	1.469 (3)
C6—H6A	0.9300	C20—H20A	0.9600
C7—C8	1.365 (3)	C20—H20B	0.9600
C7—H7A	0.9300	C20—H20C	0.9600
C8—C9	1.376 (3)	C21—H21A	0.9300
C8—H8A	0.9300

C19—O1—H1B	106.1 (14)	H11A—C11—H11B	107.9
C5—N1—C1	117.31 (15)	N3—C12—C10	112.76 (11)
C6—N2—C10	117.32 (15)	N3—C12—H12A	109.0
C12—N3—C13	110.23 (11)	C10—C12—H12A	109.0
C12—N3—C11	111.29 (11)	N3—C12—H12B	109.0
C13—N3—C11	110.37 (11)	C10—C12—H12B	109.0
N1—C1—C2	123.62 (17)	H12A—C12—H12B	107.8
N1—C1—H1A	118.2	N3—C13—C14	112.35 (12)
C2—C1—H1A	118.2	N3—C13—H13A	109.1
C3—C2—C1	118.53 (17)	C14—C13—H13A	109.1
C3—C2—H2A	120.7	N3—C13—H13B	109.1
C1—C2—H2A	120.7	C14—C13—H13B	109.1
C2—C3—C4	119.06 (18)	H13A—C13—H13B	107.9
C2—C3—H3A	120.5	C15—C14—C19	118.35 (14)
C4—C3—H3A	120.5	C15—C14—C13	121.45 (14)
C3—C4—C5	119.49 (17)	C19—C14—C13	120.11 (13)
C3—C4—H4A	120.3	C14—C15—C16	122.85 (16)
C5—C4—H4A	120.3	C14—C15—H15A	118.6
N1—C5—C4	121.98 (14)	C16—C15—H15A	118.6
N1—C5—C11	117.07 (13)	C17—C16—C15	117.36 (15)
C4—C5—C11	120.95 (13)	C17—C16—C20	122.75 (17)
N2—C6—C7	124.44 (17)	C15—C16—C20	119.87 (18)
N2—C6—H6A	117.8	C16—C17—C18	122.13 (15)
C7—C6—H6A	117.8	C16—C17—H17A	118.9
C6—C7—C8	117.75 (16)	C18—C17—H17A	118.9
C6—C7—H7A	121.1	C17—C18—C19	119.25 (16)
C8—C7—H7A	121.1	C17—C18—C21	120.01 (15)
C7—C8—C9	119.36 (17)	C19—C18—C21	120.66 (16)
C7—C8—H8A	120.3	O1—C19—C18	118.99 (15)
C9—C8—H8A	120.3	O1—C19—C14	121.01 (13)
C8—C9—C10	119.11 (17)	C18—C19—C14	119.96 (15)
C8—C9—H9A	120.4	C16—C20—H20A	109.5
C10—C9—H9A	120.4	C16—C20—H20B	109.5
N2—C10—C9	122.01 (14)	H20A—C20—H20B	109.5
N2—C10—C12	116.25 (13)	C16—C20—H20C	109.5
C9—C10—C12	121.74 (14)	H20A—C20—H20C	109.5
N3—C11—C5	112.23 (12)	H20B—C20—H20C	109.5
N3—C11—H11A	109.2	O2—C21—C18	124.0 (2)
C5—C11—H11A	109.2	O2—C21—H21A	118.0
N3—C11—H11B	109.2	C18—C21—H21A	118.0
C5—C11—H11B	109.2

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···N2	0.94 (3)	2.53 (3)	3.219 (2)	130 (2)
O1—H1B···N3	0.94 (3)	1.95 (3)	2.790 (2)	148 (2)
C3—H3A···N2ⁱ	0.93	2.59	3.390 (3)	145

Symmetry code: (i) −x+1, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	C₂₁H₂₁N₃O₂
M_r	347.41
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	8.479 (3), 9.007 (3), 12.734 (4)
α, β, γ (°)	107.565 (4), 94.068 (4), 99.092 (4)
V (Å³)	908.2 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.16 × 0.12 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.987, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	6434, 3159, 2612
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.117, 1.06
No. of reflections	3159
No. of parameters	240
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.13

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

O1—C19	1.3607 (19)	N2—C10	1.333 (2)
O2—C21	1.207 (2)	N3—C12	1.4640 (18)
N1—C5	1.3324 (19)	N3—C13	1.4704 (19)
N1—C1	1.346 (2)	N3—C11	1.4719 (18)
N2—C6	1.332 (2)

C19—O1—H1B	106.1 (14)	C13—N3—C11	110.37 (11)
C12—N3—C13	110.23 (11)	O2—C21—C18	124.0 (2)
C12—N3—C11	111.29 (11)	O2—C21—H21A	118.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···N2	0.94 (3)	2.53 (3)	3.219 (2)	130 (2)
O1—H1B···N3	0.94 (3)	1.95 (3)	2.790 (2)	148 (2)
C3—H3A···N2ⁱ	0.9300	2.5900	3.390 (3)	145.00

Symmetry code: (i) −x+1, −y+1, −z+2.

Acknowledgements

This work was supported financially by the National Natural Science Foundation of China (grant No. 21171093) and the State Key Laboratory of Materials-Oriented Chemical Engineering (grant No. KL11-03).

References

Abe, A. M. M., Helaja, J. & Koskinen, A. M. P. (2006). Org. Lett. 8, 4537–4540. Web of Science CrossRef PubMed CAS Google Scholar
Bortoluzzi, A. J., Neves, A. & Rey, N. A. (2007). Acta Cryst. C63, o84–o86. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Carlsson, H., Haukka, M., Bousseksou, A., Latour, J.-M. & Nordlander, E. (2004). Inorg. Chem. 43, 8252–8262. Web of Science CSD CrossRef PubMed CAS Google Scholar
Chirakul, P., Hampton, P. D. & Bencze, Z. (2000). J. Org. Chem. 65, 8297–8300. Web of Science CrossRef PubMed CAS Google Scholar
Dubois, L., Caspar, R., Jacquamet, L., Petit, P. E., Charlot, M. F., Baffert, C., Collomb, M. N., Deronzier, A. & Latour, J. M. (2003). Inorg. Chem. 42, 4817–4827. Web of Science CrossRef PubMed CAS Google Scholar
Dubois, L., Xiang, D. F., Tan, X. S., Pécaut, J., Jones, P., Baudron, S., Le Pape, L., Latour, J. M., Baffert, C., Chardon-Noblat, S., Collomb, M. N. & Deronzier, A. (2003). Inorg. Chem. 42, 750–760. Web of Science CSD CrossRef PubMed CAS Google Scholar
Koval, I. A., Akhideno, H., Tanase, S., Belle, C., Duboc, C., Saint-Aman, E., Gamez, P., Tooke, D. M., Spek, A. L., Pierre, J.-L. & Reedijk, J. (2007). New J. Chem. 31, 512–518. Web of Science CSD CrossRef CAS Google Scholar
Koval, I. A., Huisman, M., Stassen, A. F., Gamez, P., Lutz, M., Spek, A. L., Pursche, D., Krebs, B. & Reedijk, J. (2004). Inorg. Chim. Acta, 357, 294–300. Web of Science CSD CrossRef CAS Google Scholar
Koval, I. A., Huisman, M., Stassen, A. F., Gamez, P., Lutz, M., Spek, A. L. & Reedijk, J. (2004). Eur. J. Inorg. Chem. pp. 591–600. Web of Science CSD CrossRef Google Scholar
Koval, I. A., Pursche, D., Stassen, A. F., Gamez, P., Krebs, B. & Reedijk, J. (2003). Eur. J. Inorg. Chem. pp. 1669–1674. Web of Science CSD CrossRef Google Scholar
Lambert, E., Chabut, B., Chardon-Noblat, S., Deronzier, A., Chottard, G., Bousseksou, A., Tuchagues, J.-P., Laugier, J., Bardet, M. & Latour, J.-M. (1997). J. Am. Chem. Soc. 119, 9424–9437. CSD CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhu, D., Yan, J., Shen, K. & Shen, X. (2007). Faming Zhuanli Shenqing Gongkai Shuomingshu, CN Patent 101029020A. Google Scholar