3′,6′-Bis(ethyl­amino)-2′,7′-dimethyl-2-{[2-[(E)-3,4-methyl­enedioxy­benzyl­idene­amino]eth­yl}spiro­[isoindoline-1,9′-xanthen]-3-one

Xu, Z.-H.; Wang, H.-S.; Tao, L.-T.; Wang, H.-W.

doi:10.1107/S1600536809025872

organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1876

doi:10.1107/S1600536809025872

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3′,6′-Bis(ethylamino)-2′,7′-dimethyl-2-{[2-[(E)-3,4-methylenedioxybenzylideneamino]ethyl}spiro[isoindoline-1,9′-xanthen]-3-one

Zhi-Hong Xu,^a ^* Hong-Sheng Wang,^a Lian-Ting Tao ^a and Hong-Wei Wang ^b

^aCollege of Chemistry and Chemical Engineering, Xuchang University, Xuchang, Henan Province 461000, People's Republic of China, and ^bInstitute of Traditional Chinese Materia Medica, Chengde Medical College, Chengde 067000, People's Republic of China
^*Correspondence e-mail: xuzhihong1980@yahoo.cn

(Received 24 June 2009; accepted 3 July 2009; online 15 July 2009)

The title compound, C₃₆H₃₆N₄O₄, was prepared as a spirolactam ring formation of the rhodamine dye for comparison with a ring-opened form. The xanthene ring system is approximately planar [r.m.s. deviations from planarity = 0.023 (9) Å for the xanthene ring]. The dihedral angles formed by the spirolactam and 1,3-benzodioxole rings with the xanthene ring system are 86.8 (1) and 74.3 (1)°, respectively.

Related literature

Rhodamine dyes are one of the most widely used fluorophores for labeling and sensing biomolecules, see: Ko et al. (2006 ); Wu et al. (2007 ). For the structures of rhodamine derivatives bearing a lactam unit, see: Kwon et al. (2006 ); Wu et al. (2007); Zhang et al. (2008 ); Deng et al. (2009 ); Tian & Peng (2008 ).

Experimental

Crystal data

C₃₆H₃₆N₄O₄
M_r = 588.69
Triclinic, $[P \overline 1]$
a = 9.561 (4) Å
b = 12.262 (5) Å
c = 13.005 (6) Å
α = 93.623 (8)°
β = 92.078 (8)°
γ = 92.827 (7)°
V = 1518.5 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.35 × 0.32 × 0.27 mm

Data collection

Bruker SMART CCD area detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.971, T_max = 0.977
8102 measured reflections
5606 independent reflections
3838 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.069
S = 1.83
5606 reflections
409 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: SMART (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/S1600536809025872/at2829sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809025872/at2829Isup2.hkl

checkCIF report

Comment top

Among many fluorescent compounds, rhodamine dyes are known to have excellent photophysical properties, and they are one of the most widely used fluorophores for labeling and sensing biomolecules (Ko et al., 2006; Wu et al., 2007). There are a few single-crystal reports about rhodamine derivatives bearing a lactam moiety (Kwon et al., 2006; Wu et al., 2007; Zhang et al., 2008; Tian et al., 2008; Deng et al., 2009). Detailed information on their molecular and crystal structures is necessary to understand their photophysical and photochemical properties.

In agreement with other reported models, (Wu et al., 2007; Zhang et al., 2008; Tian et al., 2008;) the main skeleton of the molecule is formed by the xanthene ring and the spirolactam-ring. As shown in Figure 1, The atoms of the xanthene ring or the spirolactam-ring are both nearly planar and are almost perpendicular to each other. The dihedral angle between the xanthene mean planes and the spirolactamring fragment is 86.8°. The dihedral angle between the xanthene mean planes and the 1,3-benzodioxole ring is 74.3°.

Related literature top

Rhodamine dyes are one of the most widely used fluorophores for labeling and sensing biomolecules, see: Ko et al. (2006); Wu et al. (2007). For the structures of rhodamine derivatives bearing a lactam unit, see: Kwon et al. (2006); Wu et al. (2007); Zhang et al. (2008); Deng et al. (2009); Tian & Peng (2008).

Experimental top

A portion of the N-(rhodamine-6 G)lactam-ethylenediamine (228 mg, 0.5 mmol) and 3,4-methylenedioxy-benzaldehyde (90 mg, 0.6 mmol) were mixed in fresh distilled acetonitrile (50 ml). The reaction solution was refluxed for 24 h under N₂ atmosphere, the reslulting solution was evaporated to 10 ml and allowed to stand at room temperature overnight. The precipitate which appeared next day was filtered and the crude product was purified by recrystallization from acetonitrile to give 264.6 mg of the title compound in 90% yield. Single crystals suitable for X-ray measurements were obtained from acetonitrile solution by slow evaporation at room temperature.

Computing details top

Data collection: SMART (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, with displacement ellipsoids drawn at 30% probability level.

3',6'-Bis(ethylamino)-2',7'-dimethyl-2-{[2-[(E)-3,4- methylenedioxybenzylideneamino]ethyl}spiro[isoindoline-1,9'-xanthen]-3-one top

Crystal data top

C₃₆H₃₆N₄O₄	Z = 2
M_r = 588.69	F(000) = 624
Triclinic, P1	D_x = 1.287 Mg m⁻³
a = 9.561 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.262 (5) Å	Cell parameters from 2059 reflections
c = 13.005 (6) Å	θ = 2.6–25.8°
α = 93.623 (8)°	µ = 0.09 mm⁻¹
β = 92.078 (8)°	T = 296 K
γ = 92.827 (7)°	Block, colorless
V = 1518.5 (12) Å³	0.35 × 0.32 × 0.27 mm

Data collection top

Bruker SMART CCD area detector diffractometer	5606 independent reflections
Radiation source: fine-focus sealed tube	3838 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ϕ and ω scans	θ_max = 25.5°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.971, T_max = 0.977	k = −13→14
8102 measured reflections	l = −13→15

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 1.83	w = 1/[σ²(F_o²)]
5606 reflections	(Δ/σ)_max < 0.001
409 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₃₆H₃₆N₄O₄	γ = 92.827 (7)°
M_r = 588.69	V = 1518.5 (12) Å³
Triclinic, P1	Z = 2
a = 9.561 (4) Å	Mo Kα radiation
b = 12.262 (5) Å	µ = 0.09 mm⁻¹
c = 13.005 (6) Å	T = 296 K
α = 93.623 (8)°	0.35 × 0.32 × 0.27 mm
β = 92.078 (8)°

Data collection top

Bruker SMART CCD area detector diffractometer	5606 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3838 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.977	R_int = 0.016
8102 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 1.83	Δρ_max = 0.18 e Å⁻³
5606 reflections	Δρ_min = −0.25 e Å⁻³
409 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
C1	1.0868 (2)	1.00378 (15)	−0.21394 (16)	0.0673 (7)
H1A	1.0771	1.0680	−0.1692	0.101*
H1B	1.0286	1.0075	−0.2752	0.101*
H1C	1.1828	0.9996	−0.2323	0.101*
C2	1.0422 (2)	0.90267 (15)	−0.15876 (15)	0.0498 (6)
H2A	0.9451	0.9067	−0.1404	0.060*
H2B	1.0499	0.8378	−0.2044	0.060*
C3	1.1025 (2)	0.81736 (15)	0.00388 (15)	0.0366 (5)
C4	1.1834 (2)	0.82230 (15)	0.09733 (15)	0.0384 (5)
C5	1.15344 (19)	0.74560 (14)	0.16730 (14)	0.0384 (5)
H5	1.2072	0.7484	0.2285	0.046*
C6	1.04600 (19)	0.66337 (14)	0.15110 (14)	0.0317 (5)
C7	0.97058 (19)	0.66070 (14)	0.05864 (14)	0.0333 (5)
C8	0.99800 (19)	0.73535 (14)	−0.01517 (14)	0.0373 (5)
H8	0.9462	0.7303	−0.0774	0.045*
C9	1.2989 (2)	0.91013 (15)	0.11943 (16)	0.0585 (6)
H9A	1.2585	0.9796	0.1321	0.088*
H9B	1.3576	0.9130	0.0612	0.088*
H9C	1.3540	0.8936	0.1791	0.088*
C10	1.01167 (19)	0.58503 (14)	0.23360 (14)	0.0329 (5)
C11	0.89724 (18)	0.50054 (14)	0.19301 (14)	0.0312 (5)
C12	0.82788 (19)	0.50651 (14)	0.09922 (15)	0.0335 (5)
C13	0.71638 (19)	0.43470 (14)	0.06531 (15)	0.0382 (5)
H13	0.6713	0.4423	0.0018	0.046*
C14	0.6722 (2)	0.35141 (15)	0.12629 (15)	0.0371 (5)
C15	0.7419 (2)	0.34181 (15)	0.22286 (15)	0.0381 (5)
C16	0.85157 (19)	0.41539 (14)	0.25314 (14)	0.0381 (5)
H16	0.8976	0.4083	0.3164	0.046*
C17	0.6979 (2)	0.25228 (15)	0.29171 (16)	0.0565 (6)
H17A	0.7611	0.2543	0.3509	0.085*
H17B	0.6999	0.1824	0.2542	0.085*
H17C	0.6046	0.2633	0.3137	0.085*
C18	0.4790 (2)	0.28637 (16)	−0.00008 (17)	0.0574 (6)
H18A	0.5399	0.2817	−0.0581	0.069*
H18B	0.4365	0.3566	0.0010	0.069*
C19	0.3653 (2)	0.19525 (17)	−0.01317 (19)	0.0815 (8)
H19A	0.4075	0.1257	−0.0159	0.122*
H19B	0.3116	0.2023	−0.0760	0.122*
H19C	0.3049	0.2001	0.0441	0.122*
C20	1.14037 (19)	0.53312 (14)	0.27722 (14)	0.0320 (5)
C21	1.2363 (2)	0.47156 (14)	0.22513 (15)	0.0426 (5)
H21	1.2253	0.4545	0.1545	0.051*
C22	1.3490 (2)	0.43615 (15)	0.28146 (17)	0.0507 (6)
H22	1.4161	0.3964	0.2478	0.061*
C23	1.3639 (2)	0.45904 (16)	0.38774 (17)	0.0503 (6)
H23	1.4399	0.4338	0.4243	0.060*
C24	1.2665 (2)	0.51889 (15)	0.43903 (15)	0.0445 (5)
H24	1.2754	0.5340	0.5100	0.053*
C25	1.15530 (19)	0.55590 (14)	0.38242 (14)	0.0332 (5)
C26	1.0429 (2)	0.62796 (15)	0.41636 (16)	0.0363 (5)
C27	0.86305 (19)	0.72948 (14)	0.32757 (15)	0.0435 (5)
H27A	0.8826	0.7745	0.2706	0.052*
H27B	0.8758	0.7761	0.3906	0.052*
C28	0.7120 (2)	0.68842 (16)	0.31699 (18)	0.0617 (7)
H28A	0.6937	0.6478	0.2510	0.074*
H28B	0.6904	0.6404	0.3714	0.074*
C29	0.5234 (2)	0.77978 (17)	0.38177 (17)	0.0555 (6)
H29	0.5086	0.7161	0.4160	0.067*
C30	0.4246 (2)	0.86726 (16)	0.39934 (16)	0.0446 (5)
C31	0.3017 (2)	0.84294 (16)	0.44650 (16)	0.0523 (6)
H31	0.2865	0.7731	0.4692	0.063*
C32	0.1989 (2)	0.91831 (17)	0.46180 (17)	0.0558 (6)
H32	0.1159	0.9008	0.4936	0.067*
C33	0.2274 (2)	1.01850 (17)	0.42755 (17)	0.0503 (6)
C34	0.3508 (2)	1.04583 (17)	0.38140 (17)	0.0491 (6)
C35	0.4526 (2)	0.97297 (16)	0.36598 (16)	0.0510 (6)
H35	0.5359	0.9920	0.3352	0.061*
C36	0.2187 (2)	1.19285 (17)	0.38506 (19)	0.0656 (7)
H36A	0.2343	1.2557	0.4340	0.079*
H36B	0.1657	1.2152	0.3256	0.079*
N1	0.96564 (15)	0.64561 (11)	0.32967 (11)	0.0345 (4)
N4	0.62548 (19)	0.78474 (14)	0.32444 (15)	0.0602 (5)
N2	1.1293 (2)	0.89507 (15)	−0.06710 (14)	0.0502 (5)
O2	0.86117 (13)	0.58540 (10)	0.03119 (9)	0.0419 (4)
N3	0.56092 (19)	0.27858 (15)	0.09466 (16)	0.0523 (5)
O4	1.02493 (14)	0.66716 (10)	0.50372 (10)	0.0505 (4)
O5	0.34971 (16)	1.15342 (11)	0.35415 (14)	0.0777 (5)
O6	0.14296 (15)	1.10722 (12)	0.43125 (13)	0.0706 (5)
H3N	0.542 (2)	0.2270 (15)	0.1319 (15)	0.061 (8)*
H2N	1.183 (2)	0.9440 (15)	−0.0491 (15)	0.057 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0826 (19)	0.0578 (15)	0.0642 (17)	−0.0007 (13)	−0.0017 (14)	0.0310 (13)
C2	0.0529 (15)	0.0500 (13)	0.0481 (14)	0.0009 (11)	−0.0011 (12)	0.0188 (12)
C3	0.0382 (12)	0.0331 (11)	0.0402 (13)	0.0051 (10)	0.0070 (10)	0.0088 (10)
C4	0.0409 (13)	0.0360 (12)	0.0385 (13)	−0.0013 (10)	0.0005 (10)	0.0051 (10)
C5	0.0401 (13)	0.0424 (12)	0.0325 (12)	0.0044 (10)	−0.0059 (10)	0.0037 (10)
C6	0.0332 (11)	0.0316 (11)	0.0309 (12)	0.0044 (9)	0.0010 (9)	0.0049 (9)
C7	0.0339 (12)	0.0315 (11)	0.0350 (12)	0.0006 (10)	0.0021 (10)	0.0059 (10)
C8	0.0384 (12)	0.0409 (12)	0.0331 (12)	0.0024 (10)	−0.0029 (9)	0.0082 (10)
C9	0.0613 (16)	0.0547 (14)	0.0579 (15)	−0.0132 (12)	−0.0068 (12)	0.0092 (12)
C10	0.0357 (12)	0.0355 (11)	0.0283 (11)	0.0048 (10)	0.0024 (9)	0.0050 (9)
C11	0.0341 (12)	0.0310 (11)	0.0292 (11)	0.0049 (9)	0.0038 (9)	0.0037 (9)
C12	0.0328 (12)	0.0328 (11)	0.0359 (12)	0.0016 (9)	0.0051 (10)	0.0081 (10)
C13	0.0371 (12)	0.0413 (12)	0.0364 (12)	0.0001 (10)	−0.0019 (10)	0.0072 (10)
C14	0.0320 (12)	0.0347 (12)	0.0451 (13)	0.0025 (10)	0.0063 (10)	0.0022 (11)
C15	0.0386 (12)	0.0358 (12)	0.0416 (13)	0.0032 (10)	0.0099 (10)	0.0087 (11)
C16	0.0428 (13)	0.0399 (12)	0.0332 (12)	0.0069 (10)	0.0030 (10)	0.0094 (10)
C17	0.0577 (15)	0.0544 (14)	0.0592 (16)	−0.0044 (12)	0.0067 (12)	0.0218 (13)
C18	0.0439 (14)	0.0501 (14)	0.0772 (18)	−0.0020 (12)	−0.0104 (13)	0.0071 (13)
C19	0.0530 (16)	0.0713 (17)	0.116 (2)	−0.0197 (14)	−0.0203 (15)	0.0078 (16)
C20	0.0331 (11)	0.0314 (11)	0.0320 (12)	0.0027 (9)	0.0007 (9)	0.0059 (9)
C21	0.0434 (13)	0.0459 (13)	0.0393 (13)	0.0090 (11)	0.0005 (11)	0.0042 (11)
C22	0.0435 (14)	0.0530 (14)	0.0571 (16)	0.0172 (11)	0.0045 (12)	0.0016 (12)
C23	0.0416 (13)	0.0510 (14)	0.0588 (16)	0.0122 (11)	−0.0117 (12)	0.0073 (12)
C24	0.0492 (14)	0.0470 (13)	0.0370 (13)	0.0040 (11)	−0.0079 (11)	0.0058 (11)
C25	0.0361 (12)	0.0316 (11)	0.0321 (12)	0.0000 (9)	−0.0002 (10)	0.0066 (9)
C26	0.0401 (13)	0.0342 (12)	0.0346 (13)	−0.0024 (10)	0.0028 (10)	0.0058 (10)
C27	0.0482 (14)	0.0399 (12)	0.0443 (13)	0.0117 (11)	0.0080 (11)	0.0056 (10)
C28	0.0477 (15)	0.0549 (15)	0.0834 (19)	0.0167 (12)	0.0039 (13)	−0.0004 (13)
C29	0.0504 (15)	0.0536 (14)	0.0631 (17)	0.0079 (12)	−0.0034 (13)	0.0074 (13)
C30	0.0440 (14)	0.0455 (13)	0.0439 (14)	0.0069 (11)	−0.0032 (11)	−0.0007 (11)
C31	0.0527 (15)	0.0509 (14)	0.0539 (15)	0.0005 (12)	0.0080 (12)	0.0064 (12)
C32	0.0485 (15)	0.0524 (15)	0.0676 (17)	0.0009 (12)	0.0174 (13)	0.0056 (13)
C33	0.0404 (14)	0.0482 (14)	0.0617 (16)	0.0082 (12)	0.0063 (12)	−0.0073 (12)
C34	0.0462 (15)	0.0432 (14)	0.0579 (16)	0.0008 (12)	0.0061 (12)	0.0008 (12)
C35	0.0411 (14)	0.0562 (15)	0.0562 (15)	0.0040 (12)	0.0075 (11)	0.0027 (12)
C36	0.0593 (17)	0.0528 (15)	0.087 (2)	0.0119 (13)	0.0100 (14)	0.0092 (14)
N1	0.0379 (10)	0.0356 (9)	0.0309 (10)	0.0095 (8)	0.0021 (8)	0.0032 (8)
N4	0.0460 (12)	0.0657 (13)	0.0716 (15)	0.0197 (10)	0.0092 (11)	0.0086 (11)
N2	0.0550 (13)	0.0457 (13)	0.0504 (13)	−0.0078 (11)	−0.0064 (10)	0.0197 (11)
O2	0.0443 (9)	0.0436 (8)	0.0374 (8)	−0.0103 (7)	−0.0093 (7)	0.0154 (7)
N3	0.0471 (12)	0.0488 (13)	0.0613 (14)	−0.0095 (10)	0.0016 (10)	0.0159 (12)
O4	0.0631 (10)	0.0582 (9)	0.0303 (8)	0.0083 (8)	0.0046 (7)	−0.0029 (7)
O5	0.0602 (11)	0.0485 (10)	0.1288 (16)	0.0102 (9)	0.0299 (11)	0.0207 (10)
O6	0.0518 (10)	0.0517 (10)	0.1091 (15)	0.0076 (8)	0.0208 (10)	−0.0020 (10)

Geometric parameters (Å, º) top

C1—C2	1.522 (2)	C19—H19A	0.9600
C1—H1A	0.9600	C19—H19B	0.9600
C1—H1B	0.9600	C19—H19C	0.9600
C1—H1C	0.9600	C20—C25	1.380 (2)
C2—N2	1.440 (2)	C20—C21	1.385 (2)
C2—H2A	0.9700	C21—C22	1.384 (3)
C2—H2B	0.9700	C21—H21	0.9300
C3—C8	1.386 (2)	C22—C23	1.394 (3)
C3—N2	1.389 (2)	C22—H22	0.9300
C3—C4	1.413 (3)	C23—C24	1.379 (3)
C4—C5	1.377 (2)	C23—H23	0.9300
C4—C9	1.511 (2)	C24—C25	1.382 (2)
C5—C6	1.404 (2)	C24—H24	0.9300
C5—H5	0.9300	C25—C26	1.486 (2)
C6—C7	1.377 (2)	C26—O4	1.227 (2)
C6—C10	1.519 (2)	C26—N1	1.360 (2)
C7—O2	1.3821 (19)	C27—N1	1.456 (2)
C7—C8	1.391 (2)	C27—C28	1.504 (2)
C8—H8	0.9300	C27—H27A	0.9700
C9—H9A	0.9600	C27—H27B	0.9700
C9—H9B	0.9600	C28—N4	1.475 (2)
C9—H9C	0.9600	C28—H28A	0.9700
C10—N1	1.504 (2)	C28—H28B	0.9700
C10—C20	1.521 (2)	C29—N4	1.251 (2)
C10—C11	1.525 (2)	C29—C30	1.476 (3)
C11—C12	1.375 (2)	C29—H29	0.9300
C11—C16	1.405 (2)	C30—C31	1.373 (2)
C12—O2	1.3850 (19)	C30—C35	1.409 (2)
C12—C13	1.389 (2)	C31—C32	1.393 (3)
C13—C14	1.391 (2)	C31—H31	0.9300
C13—H13	0.9300	C32—C33	1.351 (2)
C14—N3	1.388 (2)	C32—H32	0.9300
C14—C15	1.415 (3)	C33—C34	1.380 (2)
C15—C16	1.378 (2)	C33—O6	1.386 (2)
C15—C17	1.513 (2)	C34—C35	1.365 (3)
C16—H16	0.9300	C34—O5	1.388 (2)
C17—H17A	0.9600	C35—H35	0.9300
C17—H17B	0.9600	C36—O6	1.423 (2)
C17—H17C	0.9600	C36—O5	1.427 (2)
C18—N3	1.447 (3)	C36—H36A	0.9700
C18—C19	1.517 (2)	C36—H36B	0.9700
C18—H18A	0.9700	N2—H2N	0.790 (17)
C18—H18B	0.9700	N3—H3N	0.836 (17)

C2—C1—H1A	109.5	H19A—C19—H19C	109.5
C2—C1—H1B	109.5	H19B—C19—H19C	109.5
H1A—C1—H1B	109.5	C25—C20—C21	120.81 (18)
C2—C1—H1C	109.5	C25—C20—C10	110.72 (16)
H1A—C1—H1C	109.5	C21—C20—C10	128.47 (18)
H1B—C1—H1C	109.5	C22—C21—C20	117.94 (19)
N2—C2—C1	110.27 (17)	C22—C21—H21	121.0
N2—C2—H2A	109.6	C20—C21—H21	121.0
C1—C2—H2A	109.6	C21—C22—C23	121.21 (19)
N2—C2—H2B	109.6	C21—C22—H22	119.4
C1—C2—H2B	109.6	C23—C22—H22	119.4
H2A—C2—H2B	108.1	C24—C23—C22	120.3 (2)
C8—C3—N2	121.31 (19)	C24—C23—H23	119.8
C8—C3—C4	119.48 (17)	C22—C23—H23	119.8
N2—C3—C4	119.21 (18)	C23—C24—C25	118.43 (19)
C5—C4—C3	118.24 (18)	C23—C24—H24	120.8
C5—C4—C9	121.26 (18)	C25—C24—H24	120.8
C3—C4—C9	120.50 (17)	C20—C25—C24	121.28 (18)
C4—C5—C6	123.46 (18)	C20—C25—C26	109.15 (17)
C4—C5—H5	118.3	C24—C25—C26	129.45 (19)
C6—C5—H5	118.3	O4—C26—N1	126.31 (19)
C7—C6—C5	116.48 (16)	O4—C26—C25	127.68 (19)
C7—C6—C10	122.18 (17)	N1—C26—C25	105.97 (17)
C5—C6—C10	121.29 (17)	N1—C27—C28	115.78 (15)
C6—C7—O2	123.60 (16)	N1—C27—H27A	108.3
C6—C7—C8	122.26 (18)	C28—C27—H27A	108.3
O2—C7—C8	114.13 (17)	N1—C27—H27B	108.3
C3—C8—C7	120.05 (18)	C28—C27—H27B	108.3
C3—C8—H8	120.0	H27A—C27—H27B	107.4
C7—C8—H8	120.0	N4—C28—C27	107.44 (16)
C4—C9—H9A	109.5	N4—C28—H28A	110.2
C4—C9—H9B	109.5	C27—C28—H28A	110.2
H9A—C9—H9B	109.5	N4—C28—H28B	110.2
C4—C9—H9C	109.5	C27—C28—H28B	110.2
H9A—C9—H9C	109.5	H28A—C28—H28B	108.5
H9B—C9—H9C	109.5	N4—C29—C30	125.0 (2)
N1—C10—C6	111.05 (14)	N4—C29—H29	117.5
N1—C10—C20	99.76 (14)	C30—C29—H29	117.5
C6—C10—C20	112.95 (15)	C31—C30—C35	120.1 (2)
N1—C10—C11	109.94 (14)	C31—C30—C29	118.63 (19)
C6—C10—C11	110.04 (15)	C35—C30—C29	121.19 (19)
C20—C10—C11	112.71 (14)	C30—C31—C32	122.9 (2)
C12—C11—C16	116.36 (17)	C30—C31—H31	118.6
C12—C11—C10	122.45 (16)	C32—C31—H31	118.6
C16—C11—C10	121.10 (17)	C33—C32—C31	115.79 (19)
C11—C12—O2	123.13 (17)	C33—C32—H32	122.1
C11—C12—C13	122.70 (17)	C31—C32—H32	122.1
O2—C12—C13	114.16 (17)	C32—C33—C34	122.6 (2)
C12—C13—C14	120.03 (19)	C32—C33—O6	127.6 (2)
C12—C13—H13	120.0	C34—C33—O6	109.75 (19)
C14—C13—H13	120.0	C35—C34—C33	122.3 (2)
N3—C14—C13	121.38 (19)	C35—C34—O5	128.24 (19)
N3—C14—C15	119.65 (18)	C33—C34—O5	109.46 (19)
C13—C14—C15	118.97 (18)	C34—C35—C30	116.26 (19)
C16—C15—C14	118.74 (17)	C34—C35—H35	121.9
C16—C15—C17	120.40 (19)	C30—C35—H35	121.9
C14—C15—C17	120.86 (18)	O6—C36—O5	108.36 (16)
C15—C16—C11	123.19 (18)	O6—C36—H36A	110.0
C15—C16—H16	118.4	O5—C36—H36A	110.0
C11—C16—H16	118.4	O6—C36—H36B	110.0
C15—C17—H17A	109.5	O5—C36—H36B	110.0
C15—C17—H17B	109.5	H36A—C36—H36B	108.4
H17A—C17—H17B	109.5	C26—N1—C27	122.31 (16)
C15—C17—H17C	109.5	C26—N1—C10	114.23 (15)
H17A—C17—H17C	109.5	C27—N1—C10	122.72 (15)
H17B—C17—H17C	109.5	C29—N4—C28	116.83 (19)
N3—C18—C19	110.73 (17)	C3—N2—C2	122.46 (19)
N3—C18—H18A	109.5	C3—N2—H2N	116.6 (15)
C19—C18—H18A	109.5	C2—N2—H2N	119.4 (15)
N3—C18—H18B	109.5	C7—O2—C12	118.22 (14)
C19—C18—H18B	109.5	C14—N3—C18	123.18 (18)
H18A—C18—H18B	108.1	C14—N3—H3N	117.7 (15)
C18—C19—H19A	109.5	C18—N3—H3N	119.1 (15)
C18—C19—H19B	109.5	C34—O5—C36	106.19 (15)
H19A—C19—H19B	109.5	C33—O6—C36	106.24 (16)
C18—C19—H19C	109.5

C8—C3—C4—C5	−1.0 (3)	C10—C20—C25—C24	−178.84 (15)
N2—C3—C4—C5	178.93 (17)	C21—C20—C25—C26	176.84 (15)
C8—C3—C4—C9	179.32 (17)	C10—C20—C25—C26	−2.4 (2)
N2—C3—C4—C9	−0.7 (3)	C23—C24—C25—C20	0.6 (3)
C3—C4—C5—C6	−0.6 (3)	C23—C24—C25—C26	−174.98 (17)
C9—C4—C5—C6	179.08 (17)	C20—C25—C26—O4	−178.01 (18)
C4—C5—C6—C7	1.2 (3)	C24—C25—C26—O4	−2.0 (3)
C4—C5—C6—C10	−176.25 (17)	C20—C25—C26—N1	−0.2 (2)
C5—C6—C7—O2	−179.61 (15)	C24—C25—C26—N1	175.78 (18)
C10—C6—C7—O2	−2.2 (3)	N1—C27—C28—N4	175.74 (17)
C5—C6—C7—C8	−0.3 (3)	N4—C29—C30—C31	166.7 (2)
C10—C6—C7—C8	177.18 (16)	N4—C29—C30—C35	−11.4 (4)
N2—C3—C8—C7	−178.01 (17)	C35—C30—C31—C32	1.4 (3)
C4—C3—C8—C7	1.9 (3)	C29—C30—C31—C32	−176.7 (2)
C6—C7—C8—C3	−1.3 (3)	C30—C31—C32—C33	−0.3 (3)
O2—C7—C8—C3	178.12 (15)	C31—C32—C33—C34	−0.8 (3)
C7—C6—C10—N1	−115.91 (19)	C31—C32—C33—O6	178.7 (2)
C5—C6—C10—N1	61.4 (2)	C32—C33—C34—C35	0.8 (4)
C7—C6—C10—C20	132.98 (18)	O6—C33—C34—C35	−178.8 (2)
C5—C6—C10—C20	−49.7 (2)	C32—C33—C34—O5	179.7 (2)
C7—C6—C10—C11	6.1 (2)	O6—C33—C34—O5	0.1 (3)
C5—C6—C10—C11	−176.62 (16)	C33—C34—C35—C30	0.4 (3)
N1—C10—C11—C12	115.71 (19)	O5—C34—C35—C30	−178.4 (2)
C6—C10—C11—C12	−6.9 (2)	C31—C30—C35—C34	−1.4 (3)
C20—C10—C11—C12	−133.97 (18)	C29—C30—C35—C34	176.7 (2)
N1—C10—C11—C16	−60.5 (2)	O4—C26—N1—C27	10.4 (3)
C6—C10—C11—C16	176.87 (15)	C25—C26—N1—C27	−167.46 (14)
C20—C10—C11—C16	49.8 (2)	O4—C26—N1—C10	−179.26 (17)
C16—C11—C12—O2	−179.68 (15)	C25—C26—N1—C10	2.92 (19)
C10—C11—C12—O2	3.9 (3)	C28—C27—N1—C26	−110.2 (2)
C16—C11—C12—C13	1.5 (3)	C28—C27—N1—C10	80.2 (2)
C10—C11—C12—C13	−174.94 (16)	C6—C10—N1—C26	−123.48 (17)
C11—C12—C13—C14	−1.1 (3)	C20—C10—N1—C26	−4.13 (18)
O2—C12—C13—C14	179.95 (15)	C11—C10—N1—C26	114.50 (17)
C12—C13—C14—N3	179.83 (17)	C6—C10—N1—C27	46.8 (2)
C12—C13—C14—C15	0.4 (3)	C20—C10—N1—C27	166.20 (14)
N3—C14—C15—C16	−179.57 (17)	C11—C10—N1—C27	−75.17 (19)
C13—C14—C15—C16	−0.1 (3)	C30—C29—N4—C28	−179.9 (2)
N3—C14—C15—C17	0.7 (3)	C27—C28—N4—C29	−133.9 (2)
C13—C14—C15—C17	−179.81 (16)	C8—C3—N2—C2	6.7 (3)
C14—C15—C16—C11	0.5 (3)	C4—C3—N2—C2	−173.21 (19)
C17—C15—C16—C11	−179.76 (16)	C1—C2—N2—C3	172.91 (18)
C12—C11—C16—C15	−1.2 (3)	C6—C7—O2—C12	−1.7 (2)
C10—C11—C16—C15	175.26 (17)	C8—C7—O2—C12	178.86 (15)
N1—C10—C20—C25	3.82 (18)	C11—C12—O2—C7	0.9 (2)
C6—C10—C20—C25	121.76 (17)	C13—C12—O2—C7	179.80 (15)
C11—C10—C20—C25	−112.75 (17)	C13—C14—N3—C18	−3.1 (3)
N1—C10—C20—C21	−175.41 (17)	C15—C14—N3—C18	176.40 (19)
C6—C10—C20—C21	−57.5 (2)	C19—C18—N3—C14	179.95 (18)
C11—C10—C20—C21	68.0 (2)	C35—C34—O5—C36	178.7 (2)
C25—C20—C21—C22	−1.6 (3)	C33—C34—O5—C36	−0.2 (3)
C10—C20—C21—C22	177.57 (17)	O6—C36—O5—C34	0.2 (3)
C20—C21—C22—C23	1.7 (3)	C32—C33—O6—C36	−179.5 (2)
C21—C22—C23—C24	−0.7 (3)	C34—C33—O6—C36	0.0 (3)
C22—C23—C24—C25	−0.5 (3)	O5—C36—O6—C33	−0.2 (2)
C21—C20—C25—C24	0.5 (3)

Experimental details

Crystal data
Chemical formula	C₃₆H₃₆N₄O₄
M_r	588.69
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	9.561 (4), 12.262 (5), 13.005 (6)
α, β, γ (°)	93.623 (8), 92.078 (8), 92.827 (7)
V (Å³)	1518.5 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.35 × 0.32 × 0.27

Data collection
Diffractometer	Bruker SMART CCD area detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.971, 0.977
No. of measured, independent and observed [I > 2σ(I)] reflections	8102, 5606, 3838
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.069, 1.83
No. of reflections	5606
No. of parameters	409
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.25

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

Acknowledgements

The authors thank the Xuchang University for financial support.

References

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