3',6'-Bis(ethyl-amino)-2',7'-dimethyl-2-{2-(E)-[(thio-phen-2-yl)methyl-idene-amino]-eth-yl}spiro-[isoindoline-1,9'-xanthen]-3-one methanol monosolvate.

The title compound, C(33)H(34)N(4)O(2)S·CH(3)OH, was prepared as a spiro-lactam ring formation of rhodamine 6 G dye for comparison with a ring-opened form. The xanthene and spiro-lactam rings are approximately planar [r.m.s. deviations from planarity = 0.122 (3) and 0.072 (6) Å, respectively]. The dihedral angles formed by the spiro-lactam and thio-phene rings with the xanthene ring system are 89.7 (6) and 86.5 (2)°, respectively. The crystal structure features N-H⋯O and C-H⋯O hydrogen bonds.

Related literature

For rhodamine derivatives bearing a n class="Chemical">lactam moiety, see: Tian & Peng (2008 ▶); Wu et al. (2007 ▶); Xi et al. (2011 ▶); Xu et al. (2009 ▶, 2011 ▶); Xu, Guo et al. (2010 ▶); Xu, Zhang et al. (2010 ▶); Zhang et al. (2008 ▶).

Experimental

Crystal data

C33H34N4O2S·CH4O

M = 582.74

Monoclinic,

a = 9.287 (2) Å

b = 9.493 (2) Å

c = 35.754 (8) Å

β = 95.683 (4)°

V = 3136.8 (12) Å3

Z = 4

Mo Kα radiation

μ = 0.14 mm−1

T = 296 K

0.25 × 0.23 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.965, T max = 0.975

15561 measured reflections

5610 independent reflections

3564 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.077

wR(F 2) = 0.250

S = 1.03

5610 reflections

385 parameters

35 restraints

H-atom parameters constrained

Δρmax = 1.10 e Å−3

Δρmin = −0.56 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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812018181/zj2071sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812018181/zj2071Isup2.hkl

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

C33H34N4O2S·CH4O	F(000) = 1240
Mr = 582.74	Dx = 1.234 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.287 (2) Å	Cell parameters from 3316 reflections
b = 9.493 (2) Å	µ = 0.14 mm−1
c = 35.754 (8) Å	T = 296 K
β = 95.683 (4)°	Block, colorless
V = 3136.8 (12) Å3	0.25 × 0.23 × 0.18 mm
Z = 4

Bruker SMART CCD area-detector diffractometer	5610 independent reflections
Radiation source: fine-focus sealed tube	3564 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
phi and ω scans	θmax = 25.2°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −11→11
Tmin = 0.965, Tmax = 0.975	k = −11→11
15561 measured reflections	l = −42→24

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)] = 0.077	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.250	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.1391P)2 + 1.4198P] where P = (Fo2 + 2Fc2)/3
5610 reflections	(Δ/σ)max < 0.001
385 parameters	Δρmax = 1.10 e Å−3
35 restraints	Δρmin = −0.56 e Å−3

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.

	x	y	z	Uiso*/Ueq
N3	0.3532 (3)	0.0575 (4)	0.04285 (10)	0.0731 (9)
H3	0.2884	−0.0001	0.0492	0.088*
C21	0.3228 (4)	0.1405 (5)	0.01026 (12)	0.0769 (12)
H21A	0.3916	0.1190	−0.0076	0.092*
H21B	0.3326	0.2395	0.0168	0.092*
C22	0.1706 (5)	0.1118 (6)	−0.00738 (14)	0.1012 (17)
H22A	0.1629	0.0151	−0.0152	0.152*
H22B	0.1495	0.1720	−0.0288	0.152*
H22C	0.1030	0.1300	0.0107	0.152*
N2	1.2815 (3)	0.4693 (3)	0.07386 (9)	0.0700 (9)
H2	1.3620	0.4874	0.0870	0.084*
C28	1.2508 (6)	0.5386 (6)	0.03806 (16)	0.0947 (15)
H28A	1.3418	0.5698	0.0297	0.114*
H28B	1.2103	0.4692	0.0201	0.114*
C29	1.1596 (11)	0.6506 (11)	0.0368 (3)	0.181 (3)
H29A	1.0626	0.6183	0.0386	0.272*
H29B	1.1637	0.6999	0.0134	0.272*
H29C	1.1881	0.7130	0.0573	0.272*
S1	0.50637 (16)	0.71838 (15)	0.19815 (4)	0.1033 (5)
O1	0.8277 (3)	0.2390 (3)	0.06317 (7)	0.0677 (8)
C16	0.7508 (3)	0.0775 (3)	0.10973 (9)	0.0468 (8)
C33	0.9946 (3)	0.1860 (3)	0.11752 (8)	0.0448 (7)
C14	0.9616 (3)	−0.0529 (3)	0.14470 (9)	0.0437 (7)
C25	0.9593 (3)	0.2555 (3)	0.08435 (9)	0.0493 (8)
C30	1.2295 (3)	0.3048 (4)	0.12193 (9)	0.0508 (8)
N4	0.8638 (3)	0.1385 (3)	0.17287 (7)	0.0463 (6)
C20	0.4841 (4)	0.0657 (4)	0.06497 (10)	0.0577 (9)
C27	1.1875 (3)	0.3756 (3)	0.08784 (9)	0.0516 (8)
C17	0.6351 (4)	−0.0026 (4)	0.11972 (10)	0.0573 (9)
H17	0.6481	−0.0545	0.1419	0.069*
C9	0.9808 (3)	−0.0692 (3)	0.18313 (9)	0.0477 (8)
O2	0.9118 (3)	0.0733 (3)	0.23449 (7)	0.0712 (7)
C23	0.5967 (4)	0.1470 (4)	0.05452 (10)	0.0589 (9)
H23	0.5848	0.1982	0.0322	0.071*
C8	0.9173 (3)	0.0521 (4)	0.20091 (9)	0.0511 (8)
C24	0.7267 (3)	0.1532 (4)	0.07680 (9)	0.0515 (8)
C26	1.0530 (4)	0.3494 (4)	0.06969 (10)	0.0579 (9)
H26	1.0243	0.3954	0.0472	0.070*
C15	0.8912 (3)	0.0887 (3)	0.13460 (8)	0.0436 (7)
C32	1.1319 (3)	0.2136 (3)	0.13547 (9)	0.0502 (8)
H32	1.1592	0.1675	0.1580	0.060*
C12	1.0738 (4)	−0.2726 (4)	0.13768 (12)	0.0616 (10)
H12	1.1052	−0.3431	0.1224	0.074*
C13	1.0076 (3)	−0.1542 (4)	0.12131 (10)	0.0540 (8)
H13	0.9947	−0.1437	0.0953	0.065*
C7	0.7759 (4)	0.2598 (4)	0.17917 (11)	0.0559 (9)
H7A	0.7385	0.2495	0.2034	0.067*
H7B	0.6938	0.2609	0.1602	0.067*
N1	0.7468 (3)	0.5095 (3)	0.18310 (9)	0.0635 (8)
C11	1.0941 (4)	−0.2885 (4)	0.17591 (13)	0.0669 (10)
H11	1.1398	−0.3689	0.1862	0.080*
C5	0.7711 (4)	0.5849 (4)	0.21151 (12)	0.0659 (10)
H5	0.8553	0.5697	0.2273	0.079*
C10	1.0479 (4)	−0.1873 (4)	0.19906 (11)	0.0621 (10)
H10	1.0615	−0.1978	0.2250	0.074*
C3	0.7036 (6)	0.7954 (6)	0.25073 (17)	0.1065 (18)
H3A	0.7857	0.7988	0.2679	0.128*
C4	0.6718 (5)	0.6968 (4)	0.22100 (12)	0.0725 (11)
C6	0.8522 (4)	0.3990 (4)	0.17837 (12)	0.0641 (10)
H6A	0.9303	0.4035	0.1985	0.077*
H6B	0.8930	0.4108	0.1546	0.077*
C1	0.4698 (8)	0.8549 (7)	0.2229 (2)	0.121 (2)
H1	0.3823	0.9031	0.2198	0.145*
C2	0.5783 (10)	0.8903 (7)	0.2483 (2)	0.142 (3)
H2A	0.5750	0.9697	0.2634	0.170*
O3	0.5909 (4)	0.5509 (5)	0.10809 (10)	0.1090 (12)
H3B	0.6220	0.5510	0.1304	0.164*
C34	0.6938 (7)	0.6016 (7)	0.08725 (18)	0.126 (2)
H34A	0.6659	0.6935	0.0779	0.188*
H34B	0.7038	0.5394	0.0665	0.188*
H34C	0.7844	0.6078	0.1026	0.188*
C18	0.5032 (4)	−0.0097 (4)	0.09893 (11)	0.0629 (10)
C19	0.3811 (5)	−0.0949 (6)	0.11157 (15)	0.0973 (16)
H19A	0.4152	−0.1482	0.1335	0.146*
H19B	0.3453	−0.1581	0.0918	0.146*
H19C	0.3048	−0.0331	0.1175	0.146*
C31	1.3756 (4)	0.3270 (5)	0.14240 (12)	0.0770 (12)
H31A	1.3874	0.2660	0.1639	0.116*
H31B	1.3851	0.4233	0.1505	0.116*
H31C	1.4485	0.3060	0.1260	0.116*

	U11	U22	U33	U12	U13	U23
N3	0.0471 (17)	0.087 (2)	0.080 (2)	−0.0115 (16)	−0.0174 (15)	−0.0034 (19)
C21	0.057 (2)	0.093 (3)	0.075 (3)	0.004 (2)	−0.020 (2)	−0.011 (2)
C22	0.058 (3)	0.143 (5)	0.095 (3)	0.007 (3)	−0.027 (2)	−0.024 (3)
N2	0.0590 (18)	0.079 (2)	0.071 (2)	−0.0209 (16)	0.0008 (15)	0.0240 (17)
C28	0.081 (3)	0.088 (3)	0.114 (4)	−0.021 (3)	0.004 (3)	0.040 (3)
C29	0.193 (9)	0.179 (8)	0.170 (8)	−0.020 (7)	0.005 (7)	0.007 (7)
S1	0.1007 (10)	0.0925 (9)	0.1156 (11)	0.0222 (7)	0.0048 (8)	0.0020 (8)
O1	0.0522 (14)	0.0884 (18)	0.0585 (14)	−0.0218 (13)	−0.0145 (11)	0.0252 (13)
C16	0.0396 (16)	0.0493 (18)	0.0501 (18)	−0.0038 (14)	−0.0019 (13)	0.0029 (15)
C33	0.0427 (17)	0.0447 (17)	0.0462 (17)	−0.0008 (13)	0.0002 (13)	0.0029 (14)
C14	0.0352 (15)	0.0459 (17)	0.0492 (18)	−0.0076 (13)	0.0003 (13)	0.0038 (14)
C25	0.0438 (17)	0.0559 (19)	0.0467 (18)	−0.0054 (14)	−0.0028 (14)	0.0044 (15)
C30	0.0428 (17)	0.0556 (19)	0.0527 (19)	−0.0068 (15)	−0.0022 (14)	0.0047 (15)
N4	0.0449 (14)	0.0462 (15)	0.0472 (14)	−0.0008 (12)	0.0013 (11)	0.0020 (12)
C20	0.0448 (18)	0.063 (2)	0.062 (2)	−0.0004 (16)	−0.0102 (15)	−0.0086 (18)
C27	0.0465 (18)	0.0512 (19)	0.058 (2)	−0.0066 (15)	0.0075 (15)	0.0026 (16)
C17	0.0484 (19)	0.061 (2)	0.061 (2)	−0.0095 (16)	−0.0030 (16)	0.0100 (17)
C9	0.0455 (17)	0.0466 (18)	0.0491 (18)	−0.0084 (14)	−0.0049 (14)	0.0044 (15)
O2	0.0900 (19)	0.0758 (17)	0.0470 (14)	−0.0010 (15)	0.0027 (13)	−0.0039 (13)
C23	0.0492 (19)	0.070 (2)	0.055 (2)	−0.0055 (17)	−0.0098 (16)	0.0029 (17)
C8	0.0501 (18)	0.0543 (19)	0.0473 (19)	−0.0087 (15)	−0.0027 (14)	0.0006 (16)
C24	0.0426 (17)	0.061 (2)	0.0496 (18)	−0.0058 (15)	−0.0009 (14)	−0.0006 (16)
C26	0.058 (2)	0.063 (2)	0.0512 (19)	−0.0083 (17)	−0.0012 (16)	0.0146 (17)
C15	0.0397 (16)	0.0460 (17)	0.0442 (16)	−0.0030 (13)	−0.0010 (13)	0.0025 (14)
C32	0.0427 (17)	0.056 (2)	0.0505 (18)	−0.0038 (15)	−0.0026 (14)	0.0101 (15)
C12	0.050 (2)	0.050 (2)	0.085 (3)	0.0005 (16)	0.0104 (19)	−0.0049 (19)
C13	0.0457 (18)	0.056 (2)	0.060 (2)	−0.0050 (15)	0.0064 (15)	−0.0048 (17)
C7	0.0488 (19)	0.053 (2)	0.065 (2)	0.0001 (15)	0.0029 (16)	−0.0059 (16)
N1	0.0647 (19)	0.0474 (16)	0.077 (2)	0.0011 (14)	−0.0005 (16)	−0.0065 (16)
C11	0.057 (2)	0.050 (2)	0.093 (3)	0.0025 (17)	0.004 (2)	0.014 (2)
C5	0.060 (2)	0.063 (2)	0.075 (3)	−0.0038 (18)	0.0062 (19)	0.005 (2)
C10	0.061 (2)	0.058 (2)	0.065 (2)	−0.0041 (18)	−0.0041 (18)	0.0150 (19)
C3	0.093 (3)	0.103 (4)	0.125 (4)	−0.001 (3)	0.018 (3)	−0.066 (3)
C4	0.080 (3)	0.063 (2)	0.077 (3)	−0.003 (2)	0.021 (2)	−0.004 (2)
C6	0.057 (2)	0.053 (2)	0.082 (3)	−0.0007 (17)	0.0056 (18)	−0.0047 (19)
C1	0.120 (5)	0.108 (5)	0.140 (5)	0.032 (4)	0.040 (4)	−0.004 (4)
C2	0.159 (7)	0.115 (5)	0.159 (6)	0.019 (5)	0.053 (5)	−0.055 (5)
O3	0.078 (2)	0.149 (3)	0.097 (2)	−0.047 (2)	−0.0066 (18)	0.023 (2)
C34	0.099 (4)	0.158 (6)	0.121 (5)	−0.034 (4)	0.015 (3)	0.023 (4)
C18	0.0433 (19)	0.067 (2)	0.077 (3)	−0.0107 (17)	−0.0006 (17)	0.003 (2)
C19	0.059 (3)	0.127 (4)	0.103 (3)	−0.034 (3)	−0.007 (2)	0.022 (3)
C31	0.054 (2)	0.097 (3)	0.077 (3)	−0.025 (2)	−0.0080 (19)	0.022 (2)

N3—C20	1.385 (4)	C17—H17	0.9300
N3—C21	1.412 (5)	C9—C10	1.379 (5)
N3—H3	0.8600	C9—C8	1.466 (5)
C21—C22	1.515 (5)	O2—C8	1.223 (4)
C21—H21A	0.9700	C23—C24	1.381 (4)
C21—H21B	0.9700	C23—H23	0.9300
C22—H22A	0.9600	C26—H26	0.9300
C22—H22B	0.9600	C32—H32	0.9300
C22—H22C	0.9600	C12—C11	1.370 (6)
N2—C27	1.375 (4)	C12—C13	1.383 (5)
N2—C28	1.442 (5)	C12—H12	0.9300
N2—H2	0.8600	C13—H13	0.9300
C28—C29	1.357 (10)	C7—C6	1.502 (5)
C28—H28A	0.9700	C7—H7A	0.9700
C28—H28B	0.9700	C7—H7B	0.9700
C29—H29A	0.9600	N1—C5	1.245 (5)
C29—H29B	0.9600	N1—C6	1.456 (5)
C29—H29C	0.9600	C11—C10	1.365 (5)
S1—C1	1.625 (7)	C11—H11	0.9300
S1—C4	1.680 (5)	C5—C4	1.468 (6)
O1—C24	1.368 (4)	C5—H5	0.9300
O1—C25	1.381 (4)	C10—H10	0.9300
C16—C24	1.379 (4)	C3—C4	1.425 (6)
C16—C17	1.392 (4)	C3—C2	1.468 (9)
C16—C15	1.507 (4)	C3—H3A	0.9300
C33—C25	1.368 (4)	C6—H6A	0.9700
C33—C32	1.394 (4)	C6—H6B	0.9700
C33—C15	1.505 (4)	C1—C2	1.330 (9)
C14—C13	1.370 (5)	C1—H1	0.9300
C14—C9	1.377 (4)	C2—H2A	0.9300
C14—C15	1.522 (4)	O3—C34	1.357 (6)
C25—C26	1.384 (5)	O3—H3B	0.8200
C30—C32	1.376 (4)	C34—H34A	0.9600
C30—C27	1.413 (5)	C34—H34B	0.9600
C30—C31	1.492 (5)	C34—H34C	0.9600
N4—C8	1.351 (4)	C18—C19	1.498 (5)
N4—C7	1.442 (4)	C19—H19A	0.9600
N4—C15	1.493 (4)	C19—H19B	0.9600
C20—C23	1.381 (5)	C19—H19C	0.9600
C20—C18	1.405 (5)	C31—H31A	0.9600
C27—C26	1.372 (5)	C31—H31B	0.9600
C17—C18	1.370 (5)	C31—H31C	0.9600
C20—N3—C21	122.1 (3)	C25—C26—H26	119.5
C20—N3—H3	118.9	N4—C15—C33	110.5 (2)
C21—N3—H3	118.9	N4—C15—C16	110.3 (2)
N3—C21—C22	110.2 (4)	C33—C15—C16	110.7 (2)
N3—C21—H21A	109.6	N4—C15—C14	99.8 (2)
C22—C21—H21A	109.6	C33—C15—C14	111.2 (2)
N3—C21—H21B	109.6	C16—C15—C14	113.8 (2)
C22—C21—H21B	109.6	C30—C32—C33	124.1 (3)
H21A—C21—H21B	108.1	C30—C32—H32	117.9
C21—C22—H22A	109.5	C33—C32—H32	117.9
C21—C22—H22B	109.5	C11—C12—C13	121.6 (4)
H22A—C22—H22B	109.5	C11—C12—H12	119.2
C21—C22—H22C	109.5	C13—C12—H12	119.2
H22A—C22—H22C	109.5	C14—C13—C12	117.7 (3)
H22B—C22—H22C	109.5	C14—C13—H13	121.2
C27—N2—C28	122.7 (3)	C12—C13—H13	121.2
C27—N2—H2	118.6	N4—C7—C6	115.1 (3)
C28—N2—H2	118.6	N4—C7—H7A	108.5
C29—C28—N2	117.1 (6)	C6—C7—H7A	108.5
C29—C28—H28A	108.0	N4—C7—H7B	108.5
N2—C28—H28A	108.0	C6—C7—H7B	108.5
C29—C28—H28B	108.0	H7A—C7—H7B	107.5
N2—C28—H28B	108.0	C5—N1—C6	116.0 (3)
H28A—C28—H28B	107.3	C10—C11—C12	120.4 (3)
C28—C29—H29A	109.5	C10—C11—H11	119.8
C28—C29—H29B	109.5	C12—C11—H11	119.8
H29A—C29—H29B	109.5	N1—C5—C4	122.5 (4)
C28—C29—H29C	109.5	N1—C5—H5	118.7
H29A—C29—H29C	109.5	C4—C5—H5	118.7
H29B—C29—H29C	109.5	C11—C10—C9	118.6 (3)
C1—S1—C4	93.6 (3)	C11—C10—H10	120.7
C24—O1—C25	118.2 (2)	C9—C10—H10	120.7
C24—C16—C17	116.1 (3)	C4—C3—C2	104.7 (5)
C24—C16—C15	121.6 (3)	C4—C3—H3A	127.6
C17—C16—C15	122.1 (3)	C2—C3—H3A	127.6
C25—C33—C32	116.0 (3)	C3—C4—C5	124.0 (4)
C25—C33—C15	122.7 (3)	C3—C4—S1	113.3 (4)
C32—C33—C15	121.3 (3)	C5—C4—S1	122.8 (3)
C13—C14—C9	120.9 (3)	N1—C6—C7	107.9 (3)
C13—C14—C15	128.9 (3)	N1—C6—H6A	110.1
C9—C14—C15	110.3 (3)	C7—C6—H6A	110.1
C33—C25—O1	122.9 (3)	N1—C6—H6B	110.1
C33—C25—C26	122.2 (3)	C7—C6—H6B	110.1
O1—C25—C26	114.9 (3)	H6A—C6—H6B	108.4
C32—C30—C27	117.9 (3)	C2—C1—S1	112.8 (5)
C32—C30—C31	121.0 (3)	C2—C1—H1	123.6
C27—C30—C31	121.1 (3)	S1—C1—H1	123.6
C8—N4—C7	122.8 (3)	C1—C2—C3	115.3 (6)
C8—N4—C15	113.9 (3)	C1—C2—H2A	122.3
C7—N4—C15	123.1 (3)	C3—C2—H2A	122.3
C23—C20—N3	121.5 (3)	C34—O3—H3B	109.5
C23—C20—C18	119.0 (3)	O3—C34—H34A	109.5
N3—C20—C18	119.5 (3)	O3—C34—H34B	109.5
C26—C27—N2	121.8 (3)	H34A—C34—H34B	109.5
C26—C27—C30	118.8 (3)	O3—C34—H34C	109.5
N2—C27—C30	119.4 (3)	H34A—C34—H34C	109.5
C18—C17—C16	124.0 (3)	H34B—C34—H34C	109.5
C18—C17—H17	118.0	C17—C18—C20	118.2 (3)
C16—C17—H17	118.0	C17—C18—C19	121.7 (4)
C14—C9—C10	120.8 (3)	C20—C18—C19	120.1 (3)
C14—C9—C8	109.1 (3)	C18—C19—H19A	109.5
C10—C9—C8	130.1 (3)	C18—C19—H19B	109.5
C20—C23—C24	120.7 (3)	H19A—C19—H19B	109.5
C20—C23—H23	119.7	C18—C19—H19C	109.5
C24—C23—H23	119.7	H19A—C19—H19C	109.5
O2—C8—N4	125.5 (3)	H19B—C19—H19C	109.5
O2—C8—C9	127.7 (3)	C30—C31—H31A	109.5
N4—C8—C9	106.8 (3)	C30—C31—H31B	109.5
O1—C24—C16	123.8 (3)	H31A—C31—H31B	109.5
O1—C24—C23	114.3 (3)	C30—C31—H31C	109.5
C16—C24—C23	122.0 (3)	H31A—C31—H31C	109.5
C27—C26—C25	121.0 (3)	H31B—C31—H31C	109.5
C27—C26—H26	119.5
C20—N3—C21—C22	−178.4 (4)	C25—C33—C15—N4	−120.9 (3)
C27—N2—C28—C29	79.0 (7)	C32—C33—C15—N4	57.2 (4)
C32—C33—C25—O1	179.7 (3)	C25—C33—C15—C16	1.7 (4)
C15—C33—C25—O1	−2.1 (5)	C32—C33—C15—C16	179.8 (3)
C32—C33—C25—C26	−1.0 (5)	C25—C33—C15—C14	129.2 (3)
C15—C33—C25—C26	177.2 (3)	C32—C33—C15—C14	−52.7 (4)
C24—O1—C25—C33	2.5 (5)	C24—C16—C15—N4	120.7 (3)
C24—O1—C25—C26	−176.8 (3)	C17—C16—C15—N4	−55.2 (4)
C21—N3—C20—C23	−5.7 (6)	C24—C16—C15—C33	−2.0 (4)
C21—N3—C20—C18	174.1 (4)	C17—C16—C15—C33	−177.9 (3)
C28—N2—C27—C26	−4.7 (6)	C24—C16—C15—C14	−128.1 (3)
C28—N2—C27—C30	175.7 (4)	C17—C16—C15—C14	56.0 (4)
C32—C30—C27—C26	−0.7 (5)	C13—C14—C15—N4	177.2 (3)
C31—C30—C27—C26	178.6 (4)	C9—C14—C15—N4	−4.9 (3)
C32—C30—C27—N2	178.9 (3)	C13—C14—C15—C33	−66.1 (4)
C31—C30—C27—N2	−1.8 (5)	C9—C14—C15—C33	111.7 (3)
C24—C16—C17—C18	0.3 (5)	C13—C14—C15—C16	59.7 (4)
C15—C16—C17—C18	176.4 (3)	C9—C14—C15—C16	−122.4 (3)
C13—C14—C9—C10	0.6 (5)	C27—C30—C32—C33	0.4 (5)
C15—C14—C9—C10	−177.5 (3)	C31—C30—C32—C33	−178.9 (4)
C13—C14—C9—C8	−178.1 (3)	C25—C33—C32—C30	0.4 (5)
C15—C14—C9—C8	3.8 (3)	C15—C33—C32—C30	−177.9 (3)
N3—C20—C23—C24	−179.6 (3)	C9—C14—C13—C12	−0.1 (4)
C18—C20—C23—C24	0.7 (6)	C15—C14—C13—C12	177.6 (3)
C7—N4—C8—O2	−8.3 (5)	C11—C12—C13—C14	−0.5 (5)
C15—N4—C8—O2	177.7 (3)	C8—N4—C7—C6	103.6 (4)
C7—N4—C8—C9	171.4 (3)	C15—N4—C7—C6	−82.9 (4)
C15—N4—C8—C9	−2.6 (3)	C13—C12—C11—C10	0.6 (5)
C14—C9—C8—O2	178.9 (3)	C6—N1—C5—C4	−177.4 (3)
C10—C9—C8—O2	0.3 (6)	C12—C11—C10—C9	−0.1 (5)
C14—C9—C8—N4	−0.8 (3)	C14—C9—C10—C11	−0.5 (5)
C10—C9—C8—N4	−179.4 (3)	C8—C9—C10—C11	177.9 (3)
C25—O1—C24—C16	−2.9 (5)	C2—C3—C4—C5	177.0 (5)
C25—O1—C24—C23	177.7 (3)	C2—C3—C4—S1	−4.4 (6)
C17—C16—C24—O1	178.9 (3)	N1—C5—C4—C3	−172.5 (5)
C15—C16—C24—O1	2.8 (5)	N1—C5—C4—S1	9.0 (6)
C17—C16—C24—C23	−1.7 (5)	C1—S1—C4—C3	2.2 (4)
C15—C16—C24—C23	−177.8 (3)	C1—S1—C4—C5	−179.1 (4)
C20—C23—C24—O1	−179.3 (3)	C5—N1—C6—C7	118.2 (4)
C20—C23—C24—C16	1.2 (6)	N4—C7—C6—N1	176.9 (3)
N2—C27—C26—C25	−179.5 (3)	C4—S1—C1—C2	1.0 (6)
C30—C27—C26—C25	0.1 (5)	S1—C1—C2—C3	−4.0 (9)
C33—C25—C26—C27	0.8 (6)	C4—C3—C2—C1	5.3 (8)
O1—C25—C26—C27	−179.9 (3)	C16—C17—C18—C20	1.5 (6)
C8—N4—C15—C33	−112.6 (3)	C16—C17—C18—C19	−178.4 (4)
C7—N4—C15—C33	73.4 (3)	C23—C20—C18—C17	−2.0 (5)
C8—N4—C15—C16	124.6 (3)	N3—C20—C18—C17	178.2 (3)
C7—N4—C15—C16	−49.4 (4)	C23—C20—C18—C19	178.0 (4)
C8—N4—C15—C14	4.6 (3)	N3—C20—C18—C19	−1.8 (6)
C7—N4—C15—C14	−169.5 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O3i	0.86	2.27	3.108	166
C5—H5···O2ii	0.93	2.44	3.360	170

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O3i	0.86	2.27	3.108	166
C5—H5⋯O2ii	0.93	2.44	3.360	170

Symmetry codes: (i) ; (ii) .