3′,6′-Bis(diethyl­amino)-2-(2-hydroxy­ethyl­amino)spiro­[isoindoline-1,9′-xanthen]-3-one

Abstract

In the title mol­ecule, C₃₀H₃₆N₄O₃, the dihedral angle between the planes of the xanthene and spiro­lactam rings systems is 88.69 (4)°. Both C atoms of one of the ethyl groups are disordered over two sites with occupancies 0.72 (2)/0.28 (2). The conformation of the mol­ecule may be influenced by two intra­molecular hydrogen bonds.

Related literature

For related literature, see: Zhang et al. (2007 ▶); Wu et al. (2007 ▶); Bae & Tae 2007 ▶).

Experimental

Crystal data

• C₃₀H₃₆N₄O₃

• M _r = 500.63

• Monoclinic,

• a = 12.269 (4) Å

• b = 12.203 (4) Å

• c = 18.458 (6) Å

• β = 108.127 (5)°

• V = 2626.4 (15) ų

• Z = 4

• Mo Kα radiation

• μ = 0.08 mm⁻¹

• T = 298 (2) K

• 0.58 × 0.25 × 0.25 mm

Data collection

• Bruker SMART APEXII diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.849, T _max = 0.900 (expected range = 0.924–0.979)

• 17363 measured reflections

• 4620 independent reflections

• 2841 reflections with I > 2σ(I)

• R _int = 0.064

Refinement

• R[F ² > 2σ(F ²)] = 0.050

• wR(F ²) = 0.129

• S = 1.00

• 4620 reflections

• 359 parameters

• 13 restraints

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

• Δρ_max = 0.21 e Å⁻³

• Δρ_min = −0.20 e Å⁻³

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: PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3O⋯O2	1.00 (4)	1.79 (4)	2.780 (3)	172 (4)
N4—H1N⋯O2	0.96 (3)	2.45 (2)	2.828 (3)	103 (2)

supplementary crystallographic information

Comment

Rhodamine dyes are molecules used extensively as fluorescent labeling reagents and dye laser sources because of their excellent photophysical properties, such as long absorption and emission wavelengths elongated to visible region, high fluorescence quantum yield, and large absorption coefficient. (Zhang et al., 2007; Wu et al., 2007; Bae & Tae, 2007). Detailed information on their molecular and crystal structures is necessary to understand their photophysical and photochemical properties. As part of our own work on rhodamine derivatives, we report here the synthesis and crystal structure of the title compound (I).

As shown in Fig.1, the xanthene ring is close to planar with an r.m.s. deviation of 0.089 (9) Å. The lactam moiety of the molecule is oriented nearly orthogonal to the xanthene moiety i.e. the dihedral angle between the planes of the xanthene and the spirolactam rings systems is 88.69 (4)°.

Experimental

Sodium borohydride (15.2 mg, 0.4 mmol) was slowly added to a solution of compound 3',6'-Bis(diethylamino)-2-(2-oxoethylideneamino)spiro [isoindoline-1,9'-xanthen]-3-one (150 mg, 0.3 mmol) in ethanol (20 ml). The reaction mixture was stirred for 2 h at room temperature and solvent was totally removed under reduced pressure. The crude product was dissolved in CH₂Cl₂ (20 ml) and 3 ml of an aqueous solution of K₂CO₃ was added. The organic layer was dried over MgSO₄. After filtration, the solvent was removed under reduced pressure. The residue was placed on a silica gel column (200–300 mesh). The column was eluted with a mixture (2:1, v/v) of petroleum spirit/ethyl acetate, to give 136 mg of the title compound (90%). Crystals were grown by dissolving the compound in CH₂Cl₂ and slowly diffusing n-hexane into the solution.

Refinement

H atoms bonded to Catoms were positioned geometrically (C—H = 0.93–0.97 Å) and refined as riding, with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C). The positional parameters of the H atoms bonded to N and O were refined independently with U_iso(H) = 1.5U_eq(N,O).

Figures

Fig. 1.

The molecular structure of (I), showing the atom-numbering scheme and displacement ellipsoids at the 30% probability level. H atoms bonded to C atoms have been omitted and the disorder is not shown.

Crystal data

C30H36N4O3	F000 = 1072
Mr = 500.63	Dx = 1.266 Mg m−3
Monoclinic, P21/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3630 reflections
a = 12.269 (4) Å	θ = 2.0–25.0º
b = 12.203 (4) Å	µ = 0.08 mm−1
c = 18.458 (6) Å	T = 298 (2) K
β = 108.127 (5)º	Block, white
V = 2626.4 (15) Å3	0.58 × 0.25 × 0.25 mm
Z = 4

Data collection

Bruker SMART APEXII diffractometer	4620 independent reflections
Radiation source: fine-focus sealed tube	2841 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.064
T = 298(2) K	θmax = 25.0º
φ and ω scans	θmin = 2.0º
Absorption correction: multi-scan(SADABS; Bruker, 2005)	h = −14→14
Tmin = 0.849, Tmax = 0.900	k = −14→14
17363 measured reflections	l = −21→21

Refinement

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)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.129	w = 1/[σ2(Fo2) + (0.0755P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max = 0.002
4620 reflections	Δρmax = 0.21 e Å−3
359 parameters	Δρmin = −0.20 e Å−3
13 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: 0.026 (4)

Special details

Experimental. 1H NMR (CDCl3, 400MHz, Me4Si): δ 7.91 (d, 1H, J=6.4 Hz, C6H4), 7.52-7.47 (m, 2H, C6H4), 7.15 (d, 1H, J= 6.4 Hz), 6.41 (m, 4H, Xanthene-H), 6.26 (dd, 2H, J= 8.8 Hz, J= 2.4 Hz, Xanthene-H), 4.65 (t, 1H, J= 7.2 Hz, NH), 4.45 (t, 1H, J= 6.0 Hz, OH), 3.36-3.31 (m, 10H, CH2O, CH2), 2.46-2.45 (m, 2H, CH2N), 1.16 (t, 12H, J=6.8 Hz, CH3); 13C NMR (CDCl3, 100MHz, Me4Si): δ 168.31, 164.31, 153.97, 151.59, 149.05, 133.17, 129.99, 128.51, 123.08, 124.20, 107.97, 105.29, 97.98, 66.39, 58.76, 52.83, 44.51, 12.75. HRMS(ESI): calcd for C30H36N4O3 [M+Na]+ 523.2685; found 523.2671.

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 > 2σ(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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.02779 (11)	0.63551 (12)	0.15665 (9)	0.0590 (5)
O2	−0.40178 (12)	0.91274 (15)	0.13067 (9)	0.0670 (5)
O3	−0.34132 (15)	0.9162 (2)	0.28884 (13)	0.0941 (7)
H3O	−0.370 (3)	0.915 (3)	0.232 (2)	0.141*
N1	0.31949 (16)	0.86643 (19)	0.30367 (13)	0.0770 (7)
N2	−0.19898 (16)	0.38340 (17)	−0.02009 (11)	0.0620 (5)
N3	−0.22666 (13)	0.83188 (15)	0.15192 (9)	0.0443 (4)
N4	−0.23247 (17)	0.76085 (17)	0.20976 (11)	0.0570 (5)
H1N	−0.313 (2)	0.749 (2)	0.2013 (14)	0.085*
C1	0.05554 (16)	0.74041 (19)	0.18219 (11)	0.0459 (5)
C2	0.16682 (17)	0.7528 (2)	0.22812 (12)	0.0551 (6)
H2A	0.2155	0.6925	0.2386	0.066*
C3	0.20776 (17)	0.8541 (2)	0.25922 (13)	0.0525 (6)
C4	0.13007 (17)	0.94070 (19)	0.24316 (12)	0.0488 (6)
H4A	0.1530	1.0093	0.2643	0.059*
C5	0.02040 (17)	0.92561 (18)	0.19652 (12)	0.0468 (5)
H5A	−0.0292	0.9853	0.1863	0.056*
C6	−0.02056 (15)	0.82580 (18)	0.16369 (11)	0.0407 (5)
C7	−0.14135 (15)	0.81057 (17)	0.11196 (11)	0.0417 (5)
C8	−0.15672 (16)	0.69727 (18)	0.07841 (11)	0.0439 (5)
C9	−0.25529 (17)	0.6667 (2)	0.02086 (13)	0.0570 (6)
H9A	−0.3130	0.7186	0.0030	0.068*
C10	−0.27173 (19)	0.5653 (2)	−0.01066 (13)	0.0593 (6)
H10A	−0.3398	0.5491	−0.0487	0.071*
C11	−0.18663 (17)	0.48494 (19)	0.01373 (12)	0.0501 (6)
C12	−0.08854 (17)	0.51411 (19)	0.07132 (12)	0.0494 (6)
H12A	−0.0307	0.4626	0.0898	0.059*
C13	−0.07482 (16)	0.61794 (18)	0.10178 (11)	0.0436 (5)
C14	0.4083 (4)	0.7842 (6)	0.2970 (4)	0.062 (2)	0.720 (17)
H14A	0.3815	0.7481	0.2478	0.074*	0.720 (17)
H14B	0.4792	0.8221	0.3002	0.074*	0.720 (17)
C15	0.4301 (7)	0.7010 (7)	0.3586 (4)	0.099 (2)	0.720 (17)
H15A	0.4863	0.6496	0.3533	0.149*	0.720 (17)
H15B	0.3601	0.6631	0.3550	0.149*	0.720 (17)
H15C	0.4580	0.7367	0.4072	0.149*	0.720 (17)
C14A	0.3796 (13)	0.7676 (16)	0.3463 (9)	0.074 (7)	0.280 (17)
H14C	0.4289	0.7869	0.3969	0.088*	0.280 (17)
H14D	0.3254	0.7120	0.3505	0.088*	0.280 (17)
C15A	0.4469 (17)	0.731 (2)	0.2969 (13)	0.111 (7)	0.280 (17)
H15D	0.4904	0.6668	0.3187	0.166*	0.280 (17)
H15E	0.4983	0.7881	0.2928	0.166*	0.280 (17)
H15F	0.3959	0.7135	0.2472	0.166*	0.280 (17)
C16	0.3656 (2)	0.9732 (2)	0.33183 (16)	0.0739 (8)
H16A	0.4332	0.9633	0.3757	0.089*
H16B	0.3092	1.0128	0.3485	0.089*
C17	0.3969 (2)	1.0400 (3)	0.27363 (18)	0.0852 (9)
H17A	0.4269	1.1094	0.2953	0.128*
H17B	0.3299	1.0517	0.2305	0.128*
H17C	0.4539	1.0020	0.2576	0.128*
C18	−0.3044 (2)	0.3522 (2)	−0.07672 (14)	0.0690 (7)
H18A	−0.2890	0.2907	−0.1054	0.083*
H18B	−0.3301	0.4127	−0.1120	0.083*
C19	−0.3997 (2)	0.3211 (3)	−0.04619 (17)	0.0877 (9)
H19A	−0.4665	0.3023	−0.0877	0.132*
H19B	−0.4170	0.3817	−0.0185	0.132*
H19C	−0.3766	0.2592	−0.0127	0.132*
C20	−0.1110 (2)	0.2997 (2)	0.00744 (14)	0.0665 (7)
H20A	−0.0363	0.3339	0.0183	0.080*
H20B	−0.1183	0.2465	−0.0328	0.080*
C21	−0.1165 (2)	0.2407 (2)	0.07736 (15)	0.0744 (8)
H21A	−0.0561	0.1874	0.0921	0.112*
H21B	−0.1893	0.2047	0.0668	0.112*
H21C	−0.1075	0.2924	0.1180	0.112*
C22	−0.34216 (19)	1.0120 (2)	−0.00789 (14)	0.0593 (6)
H22A	−0.4118	1.0420	−0.0078	0.071*
C23	−0.2949 (2)	1.0373 (2)	−0.06426 (14)	0.0654 (7)
H23A	−0.3340	1.0832	−0.1041	0.078*
C24	−0.1899 (2)	0.9951 (2)	−0.06186 (14)	0.0692 (7)
H24A	−0.1574	1.0154	−0.0991	0.083*
C25	−0.13217 (19)	0.9237 (2)	−0.00578 (13)	0.0571 (6)
H25A	−0.0617	0.8949	−0.0051	0.068*
C26	−0.18049 (16)	0.89571 (18)	0.04935 (12)	0.0455 (5)
C27	−0.28307 (16)	0.94066 (18)	0.04841 (12)	0.0482 (6)
C28	−0.31390 (17)	0.89661 (19)	0.11342 (12)	0.0499 (6)
C29	−0.1807 (2)	0.8051 (3)	0.28589 (13)	0.0694 (8)
H29A	−0.0986	0.8101	0.2953	0.083*
H29B	−0.1933	0.7534	0.3224	0.083*
C30	−0.2233 (2)	0.9153 (3)	0.30112 (16)	0.0804 (9)
H30A	−0.1842	0.9361	0.3535	0.097*
H30B	−0.2048	0.9693	0.2682	0.097*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0457 (8)	0.0423 (10)	0.0714 (10)	0.0041 (7)	−0.0072 (7)	−0.0086 (8)
O2	0.0416 (8)	0.0841 (14)	0.0751 (11)	0.0098 (8)	0.0178 (8)	0.0037 (9)
O3	0.0625 (11)	0.143 (2)	0.0822 (13)	0.0030 (11)	0.0306 (10)	−0.0282 (13)
N1	0.0511 (11)	0.0595 (16)	0.0937 (16)	0.0007 (10)	−0.0163 (11)	−0.0167 (13)
N2	0.0701 (12)	0.0476 (13)	0.0588 (13)	−0.0039 (10)	0.0065 (10)	−0.0138 (10)
N3	0.0412 (9)	0.0439 (11)	0.0479 (10)	0.0031 (8)	0.0141 (7)	0.0043 (9)
N4	0.0620 (11)	0.0576 (14)	0.0535 (12)	0.0019 (10)	0.0211 (10)	0.0056 (10)
C1	0.0424 (11)	0.0430 (15)	0.0490 (13)	−0.0023 (10)	0.0093 (9)	−0.0057 (10)
C2	0.0467 (12)	0.0491 (16)	0.0587 (14)	0.0057 (11)	0.0009 (10)	−0.0040 (12)
C3	0.0426 (11)	0.0570 (17)	0.0505 (13)	−0.0034 (11)	0.0039 (9)	−0.0047 (11)
C4	0.0479 (12)	0.0478 (15)	0.0502 (13)	−0.0037 (10)	0.0146 (10)	−0.0092 (11)
C5	0.0431 (11)	0.0436 (15)	0.0547 (13)	0.0025 (10)	0.0167 (10)	−0.0038 (11)
C6	0.0376 (10)	0.0411 (14)	0.0427 (11)	0.0011 (9)	0.0115 (8)	0.0000 (10)
C7	0.0368 (10)	0.0389 (14)	0.0484 (12)	−0.0003 (9)	0.0117 (9)	−0.0015 (10)
C8	0.0395 (10)	0.0429 (14)	0.0467 (12)	0.0005 (10)	0.0097 (9)	−0.0005 (10)
C9	0.0465 (12)	0.0463 (16)	0.0650 (15)	0.0033 (11)	−0.0019 (10)	−0.0006 (12)
C10	0.0540 (13)	0.0500 (16)	0.0581 (15)	−0.0037 (12)	−0.0055 (11)	−0.0046 (12)
C11	0.0545 (13)	0.0475 (15)	0.0454 (13)	−0.0040 (11)	0.0115 (10)	−0.0019 (11)
C12	0.0487 (12)	0.0407 (15)	0.0538 (14)	0.0038 (10)	0.0086 (10)	−0.0014 (11)
C13	0.0382 (10)	0.0451 (14)	0.0430 (12)	−0.0011 (10)	0.0061 (9)	−0.0005 (10)
C14	0.039 (2)	0.073 (4)	0.067 (3)	−0.001 (2)	0.007 (2)	−0.008 (3)
C15	0.116 (4)	0.091 (5)	0.083 (4)	0.042 (4)	0.021 (3)	0.013 (3)
C14A	0.058 (8)	0.085 (14)	0.068 (9)	−0.009 (8)	0.006 (6)	−0.020 (7)
C15A	0.089 (11)	0.114 (16)	0.137 (16)	0.022 (9)	0.046 (10)	−0.030 (12)
C16	0.0539 (13)	0.074 (2)	0.0739 (18)	−0.0028 (13)	−0.0099 (13)	−0.0210 (16)
C17	0.0611 (16)	0.084 (2)	0.109 (2)	−0.0023 (15)	0.0243 (16)	−0.0150 (19)
C18	0.0865 (17)	0.0548 (18)	0.0527 (15)	−0.0111 (14)	0.0029 (13)	−0.0077 (12)
C19	0.0829 (18)	0.075 (2)	0.092 (2)	−0.0107 (16)	0.0089 (16)	0.0116 (17)
C20	0.0777 (16)	0.0508 (17)	0.0700 (17)	−0.0048 (13)	0.0216 (13)	−0.0173 (13)
C21	0.0750 (17)	0.071 (2)	0.0689 (17)	−0.0050 (14)	0.0101 (13)	−0.0033 (15)
C22	0.0542 (13)	0.0487 (16)	0.0643 (16)	0.0053 (11)	0.0026 (12)	0.0008 (13)
C23	0.0765 (17)	0.0556 (17)	0.0541 (15)	−0.0006 (13)	0.0058 (13)	0.0085 (13)
C24	0.0820 (17)	0.071 (2)	0.0526 (15)	−0.0097 (15)	0.0179 (13)	0.0046 (14)
C25	0.0563 (13)	0.0583 (17)	0.0585 (15)	0.0003 (12)	0.0206 (11)	0.0047 (13)
C26	0.0426 (11)	0.0405 (14)	0.0485 (13)	−0.0011 (9)	0.0069 (9)	−0.0037 (10)
C27	0.0421 (11)	0.0428 (14)	0.0529 (14)	−0.0006 (10)	0.0048 (9)	0.0013 (11)
C28	0.0363 (11)	0.0513 (15)	0.0580 (14)	0.0023 (10)	0.0086 (10)	−0.0027 (11)
C29	0.0540 (13)	0.103 (2)	0.0488 (15)	0.0018 (14)	0.0126 (11)	0.0089 (15)
C30	0.0612 (15)	0.114 (3)	0.0668 (17)	−0.0129 (16)	0.0209 (13)	−0.0303 (17)

Geometric parameters (Å, °)

O1—C13	1.365 (2)	C15—H15B	0.9600
O1—C1	1.370 (3)	C15—H15C	0.9600
O2—C28	1.231 (2)	C14A—C15A	1.48 (4)
O3—C30	1.394 (3)	C14A—H14C	0.9700
O3—H3O	0.99 (4)	C14A—H14D	0.9700
N1—C3	1.369 (3)	C15A—H15D	0.9600
N1—C16	1.450 (3)	C15A—H15E	0.9600
N1—C14A	1.50 (2)	C15A—H15F	0.9600
N1—C14	1.514 (8)	C16—C17	1.491 (4)
N2—C11	1.374 (3)	C16—H16A	0.9700
N2—C18	1.438 (3)	C16—H16B	0.9700
N2—C20	1.457 (3)	C17—H17A	0.9600
N3—C28	1.342 (3)	C17—H17B	0.9600
N3—N4	1.394 (2)	C17—H17C	0.9600
N3—C7	1.479 (2)	C18—C19	1.496 (4)
N4—C29	1.454 (3)	C18—H18A	0.9700
N4—H1N	0.96 (3)	C18—H18B	0.9700
C1—C6	1.370 (3)	C19—H19A	0.9600
C1—C2	1.373 (3)	C19—H19B	0.9600
C2—C3	1.389 (3)	C19—H19C	0.9600
C2—H2A	0.9300	C20—C21	1.497 (4)
C3—C4	1.392 (3)	C20—H20A	0.9700
C4—C5	1.365 (3)	C20—H20B	0.9700
C4—H4A	0.9300	C21—H21A	0.9600
C5—C6	1.383 (3)	C21—H21B	0.9600
C5—H5A	0.9300	C21—H21C	0.9600
C6—C7	1.504 (3)	C22—C23	1.375 (3)
C7—C8	1.503 (3)	C22—C27	1.376 (3)
C7—C26	1.517 (3)	C22—H22A	0.9300
C8—C13	1.365 (3)	C23—C24	1.375 (3)
C8—C9	1.389 (3)	C23—H23A	0.9300
C9—C10	1.355 (3)	C24—C25	1.370 (3)
C9—H9A	0.9300	C24—H24A	0.9300
C10—C11	1.401 (3)	C25—C26	1.371 (3)
C10—H10A	0.9300	C25—H25A	0.9300
C11—C12	1.382 (3)	C26—C27	1.368 (3)
C12—C13	1.375 (3)	C27—C28	1.468 (3)
C12—H12A	0.9300	C29—C30	1.501 (4)
C14—C15	1.485 (13)	C29—H29A	0.9700
C14—H14A	0.9700	C29—H29B	0.9700
C14—H14B	0.9700	C30—H30A	0.9700
C15—H15A	0.9600	C30—H30B	0.9700
C13—O1—C1	118.37 (16)	H14C—C14A—H14D	109.3
C30—O3—H3O	101 (2)	C14A—C15A—H15D	109.5
C3—N1—C16	121.3 (2)	C14A—C15A—H15E	109.5
C3—N1—C14A	117.6 (5)	H15D—C15A—H15E	109.5
C16—N1—C14A	117.4 (4)	C14A—C15A—H15F	109.5
C3—N1—C14	119.3 (2)	H15D—C15A—H15F	109.5
C16—N1—C14	114.5 (2)	H15E—C15A—H15F	109.5
C14A—N1—C14	42.5 (6)	N1—C16—C17	113.1 (2)
C11—N2—C18	121.1 (2)	N1—C16—H16A	109.0
C11—N2—C20	120.56 (19)	C17—C16—H16A	109.0
C18—N2—C20	117.9 (2)	N1—C16—H16B	109.0
C28—N3—N4	123.30 (17)	C17—C16—H16B	109.0
C28—N3—C7	114.26 (17)	H16A—C16—H16B	107.8
N4—N3—C7	119.03 (16)	C16—C17—H17A	109.5
N3—N4—C29	113.5 (2)	C16—C17—H17B	109.5
N3—N4—H1N	105.4 (16)	H17A—C17—H17B	109.5
C29—N4—H1N	109.4 (15)	C16—C17—H17C	109.5
C6—C1—O1	123.23 (17)	H17A—C17—H17C	109.5
C6—C1—C2	122.7 (2)	H17B—C17—H17C	109.5
O1—C1—C2	114.11 (19)	N2—C18—C19	115.1 (2)
C1—C2—C3	121.0 (2)	N2—C18—H18A	108.5
C1—C2—H2A	119.5	C19—C18—H18A	108.5
C3—C2—H2A	119.5	N2—C18—H18B	108.5
N1—C3—C2	120.7 (2)	C19—C18—H18B	108.5
N1—C3—C4	122.4 (2)	H18A—C18—H18B	107.5
C2—C3—C4	116.86 (19)	C18—C19—H19A	109.5
C5—C4—C3	120.5 (2)	C18—C19—H19B	109.5
C5—C4—H4A	119.8	H19A—C19—H19B	109.5
C3—C4—H4A	119.8	C18—C19—H19C	109.5
C4—C5—C6	123.2 (2)	H19A—C19—H19C	109.5
C4—C5—H5A	118.4	H19B—C19—H19C	109.5
C6—C5—H5A	118.4	N2—C20—C21	114.2 (2)
C1—C6—C5	115.73 (18)	N2—C20—H20A	108.7
C1—C6—C7	121.66 (19)	C21—C20—H20A	108.7
C5—C6—C7	122.61 (18)	N2—C20—H20B	108.7
N3—C7—C8	110.47 (16)	C21—C20—H20B	108.7
N3—C7—C6	111.84 (16)	H20A—C20—H20B	107.6
C8—C7—C6	110.36 (16)	C20—C21—H21A	109.5
N3—C7—C26	98.86 (15)	C20—C21—H21B	109.5
C8—C7—C26	110.30 (17)	H21A—C21—H21B	109.5
C6—C7—C26	114.52 (17)	C20—C21—H21C	109.5
C13—C8—C9	115.6 (2)	H21A—C21—H21C	109.5
C13—C8—C7	122.46 (18)	H21B—C21—H21C	109.5
C9—C8—C7	121.98 (19)	C23—C22—C27	117.8 (2)
C10—C9—C8	123.4 (2)	C23—C22—H22A	121.1
C10—C9—H9A	118.3	C27—C22—H22A	121.1
C8—C9—H9A	118.3	C24—C23—C22	120.2 (2)
C9—C10—C11	120.3 (2)	C24—C23—H23A	119.9
C9—C10—H10A	119.8	C22—C23—H23A	119.9
C11—C10—H10A	119.8	C25—C24—C23	121.5 (2)
N2—C11—C12	121.9 (2)	C25—C24—H24A	119.3
N2—C11—C10	121.3 (2)	C23—C24—H24A	119.3
C12—C11—C10	116.8 (2)	C24—C25—C26	118.6 (2)
C13—C12—C11	121.2 (2)	C24—C25—H25A	120.7
C13—C12—H12A	119.4	C26—C25—H25A	120.7
C11—C12—H12A	119.4	C27—C26—C25	119.9 (2)
O1—C13—C8	122.78 (19)	C27—C26—C7	110.87 (18)
O1—C13—C12	114.55 (18)	C25—C26—C7	128.97 (19)
C8—C13—C12	122.67 (19)	C26—C27—C22	122.0 (2)
C15—C14—N1	110.7 (7)	C26—C27—C28	108.24 (18)
C15—C14—H14A	109.5	C22—C27—C28	129.8 (2)
N1—C14—H14A	109.5	O2—C28—N3	125.1 (2)
C15—C14—H14B	109.5	O2—C28—C27	128.5 (2)
N1—C14—H14B	109.5	N3—C28—C27	106.41 (17)
H14A—C14—H14B	108.1	N4—C29—C30	116.2 (2)
C14—C15—H15A	109.5	N4—C29—H29A	108.2
C14—C15—H15B	109.5	C30—C29—H29A	108.2
H15A—C15—H15B	109.5	N4—C29—H29B	108.2
C14—C15—H15C	109.5	C30—C29—H29B	108.2
H15A—C15—H15C	109.5	H29A—C29—H29B	107.4
H15B—C15—H15C	109.5	O3—C30—C29	112.4 (2)
C15A—C14A—N1	101.4 (18)	O3—C30—H30A	109.1
C15A—C14A—H14C	111.5	C29—C30—H30A	109.1
N1—C14A—H14C	111.5	O3—C30—H30B	109.1
C15A—C14A—H14D	111.5	C29—C30—H30B	109.1
N1—C14A—H14D	111.5	H30A—C30—H30B	107.9
C28—N3—N4—C29	−98.3 (2)	N2—C11—C12—C13	176.4 (2)
C7—N3—N4—C29	103.7 (2)	C10—C11—C12—C13	−1.3 (3)
C13—O1—C1—C6	9.6 (3)	C1—O1—C13—C8	−8.6 (3)
C13—O1—C1—C2	−170.31 (18)	C1—O1—C13—C12	170.74 (18)
C6—C1—C2—C3	0.7 (4)	C9—C8—C13—O1	178.64 (18)
O1—C1—C2—C3	−179.3 (2)	C7—C8—C13—O1	−0.8 (3)
C16—N1—C3—C2	175.4 (2)	C9—C8—C13—C12	−0.6 (3)
C14A—N1—C3—C2	−27.0 (8)	C7—C8—C13—C12	179.92 (19)
C14—N1—C3—C2	21.6 (5)	C11—C12—C13—O1	−178.19 (19)
C16—N1—C3—C4	−4.9 (4)	C11—C12—C13—C8	1.1 (3)
C14A—N1—C3—C4	152.7 (8)	C3—N1—C14—C15	−98.4 (4)
C14—N1—C3—C4	−158.7 (4)	C16—N1—C14—C15	106.1 (4)
C1—C2—C3—N1	−178.6 (2)	C14A—N1—C14—C15	1.5 (7)
C1—C2—C3—C4	1.6 (3)	C3—N1—C14A—C15A	100.1 (9)
N1—C3—C4—C5	177.9 (2)	C16—N1—C14A—C15A	−101.4 (9)
C2—C3—C4—C5	−2.4 (3)	C14—N1—C14A—C15A	−4.3 (8)
C3—C4—C5—C6	0.9 (3)	C3—N1—C16—C17	−79.7 (3)
O1—C1—C6—C5	177.82 (18)	C14A—N1—C16—C17	122.7 (8)
C2—C1—C6—C5	−2.2 (3)	C14—N1—C16—C17	75.3 (4)
O1—C1—C6—C7	−1.2 (3)	C11—N2—C18—C19	−77.1 (3)
C2—C1—C6—C7	178.74 (19)	C20—N2—C18—C19	95.2 (3)
C4—C5—C6—C1	1.5 (3)	C11—N2—C20—C21	79.8 (3)
C4—C5—C6—C7	−179.54 (19)	C18—N2—C20—C21	−92.5 (3)
C28—N3—C7—C8	−103.7 (2)	C27—C22—C23—C24	−2.3 (4)
N4—N3—C7—C8	56.2 (2)	C22—C23—C24—C25	2.8 (4)
C28—N3—C7—C6	132.94 (19)	C23—C24—C25—C26	−0.9 (4)
N4—N3—C7—C6	−67.2 (2)	C24—C25—C26—C27	−1.4 (4)
C28—N3—C7—C26	11.9 (2)	C24—C25—C26—C7	172.8 (2)
N4—N3—C7—C26	171.83 (17)	N3—C7—C26—C27	−9.7 (2)
C1—C6—C7—N3	116.1 (2)	C8—C7—C26—C27	106.1 (2)
C5—C6—C7—N3	−62.9 (3)	C6—C7—C26—C27	−128.69 (19)
C1—C6—C7—C8	−7.3 (3)	N3—C7—C26—C25	175.7 (2)
C5—C6—C7—C8	173.74 (18)	C8—C7—C26—C25	−68.6 (3)
C1—C6—C7—C26	−132.5 (2)	C6—C7—C26—C25	56.6 (3)
C5—C6—C7—C26	48.6 (3)	C25—C26—C27—C22	1.8 (3)
N3—C7—C8—C13	−115.9 (2)	C7—C26—C27—C22	−173.42 (19)
C6—C7—C8—C13	8.3 (3)	C25—C26—C27—C28	−179.9 (2)
C26—C7—C8—C13	135.9 (2)	C7—C26—C27—C28	4.9 (2)
N3—C7—C8—C9	64.7 (3)	C23—C22—C27—C26	0.1 (3)
C6—C7—C8—C9	−171.09 (18)	C23—C22—C27—C28	−177.8 (2)
C26—C7—C8—C9	−43.6 (3)	N4—N3—C28—O2	10.5 (3)
C13—C8—C9—C10	0.5 (3)	C7—N3—C28—O2	169.5 (2)
C7—C8—C9—C10	179.9 (2)	N4—N3—C28—C27	−168.71 (18)
C8—C9—C10—C11	−0.8 (4)	C7—N3—C28—C27	−9.8 (2)
C18—N2—C11—C12	176.2 (2)	C26—C27—C28—O2	−176.5 (2)
C20—N2—C11—C12	4.1 (3)	C22—C27—C28—O2	1.7 (4)
C18—N2—C11—C10	−6.1 (3)	C26—C27—C28—N3	2.8 (2)
C20—N2—C11—C10	−178.3 (2)	C22—C27—C28—N3	−179.1 (2)
C9—C10—C11—N2	−176.6 (2)	N3—N4—C29—C30	53.9 (3)
C9—C10—C11—C12	1.2 (4)	N4—C29—C30—O3	57.8 (3)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O2	1.00 (4)	1.79 (4)	2.780 (3)	172 (4)
N4—H1N···O2	0.96 (3)	2.45 (2)	2.828 (3)	103 (2)