A synchrotron-radiation study of the lactone form of rhodamine B at 120 K

The structure of the lactone form of rhod­amine B, 3,6-bis­(diethyl­amino)-1′,3′-di­hydro­spiro­[xanthene-9,3′-isobenzo­furan]-1′-one, C₂₈H₃₀N₂O₃, has been determined at 120 K using synchrotron radiation at a wavelength of 0.496 Å. The structure contains two independent rhod­amine B mol­ecules with virtually identical geometry. The xanthene main planes of the mol­ecules are inclined at an angle of 41.6 (2)° to one another. Molecule 2 has a statistically disordered ethyl group, with 71% in one orientation and 29% in a second orientation. The lactone C—O bonds are 1.497 (1) and 1.495 (1) Å. There are no classical hydrogen bonds, but the structure is stabilized by two short C...O interactions. The crystals of the lactone form were produced by a novel hydro­thermal reaction.

S1. Comment

In an attempt to create a new zeolite with rhodamine as the template molecule, purple crystals of up to millimetre sizes have been produced. Two room-temperature X-ray studies in Shanghai and Grenoble have proved that the crystals were of the lactone form of rhodamine B, (I) (refs?). These studies, however, failed to resolve the disorder of one of the ethyl groups, and the present low-temperature study (120 K), using high-resolution synchrotron radiation out to a resolution of 0.58 Å, was carried out in order to resolve this disorder. \sch

The present work shows that the disorder in (I) is a statistical splitting between two orientations [A 71 (1)% and B 29 (1)%; Fig. 1]. All bond distances have been determined with a precision of about 0.002 Å, except for those involving H atoms.

The structure of (I) contains two independent rhodamine B molecules, both having virtually identical geometry with a central planar section and planar groups bonded to C7 and C35. The two major planes of the molecules are perpendicular to each other [89.17 (4)°] in the two molecules. The major central planes of the molecules are inclined to each other at an angle of 41.6 (2)°.

There are no classical hydrogen bonds in the structure, but one weak C—H···O interaction links the two molecules in the asymmetric unit [C44—H44···O2ⁱ 3.096 (2) Å and 123.4 (13)°; symmetry code: (i) 1/2 + x, 1/2 − y, z − 1/2]. The lactone C—O bonds are rather long C—O single bonds: C7—O3 1.4972 (12) and C35—O6 1.4949 (12) Å. All other bonds are normal.

To our knowledge no other structure determination of the lactone form of rhodamine B has been published, although Abrahams et al. (1986) reported a determination of the zwitterionic form in a platinum complex.

S2. Experimental

A hydrothermal method was used to grow large single crystals of the rhodamine B lactone from the sol-gel system of rhodamine B—Na₂O-SiO₂-glycerol-H₂O. The molecular composition of the sol-gel was 0.2 rhodamine B: 0.18 Na₂O: 1.0 Si₂O: 10 glycerol: 40 H₂O. Silica sol (21.4 wt% Si₂O and 0.2 wt% Na₂O) was mixed with an aqueous solution of sodium hydroxide to form a uniform mixture. A homogeneous sol was obtained after vigorous stirring for 1 h at ambient temperature. The sol was then transferred and sealed into a stainless steel autoclave lined with Teflon and heated under autogeneous pressure at 373 K. A gel was formed from the sol after heating for several hours at this temperature. Single crystals of the lactone, (I), with largest dimensions 7.0× 4.0× 1.4 mm, grew under these hydrothermal conditions over 1–2 d. Crystals were easily isolated from the gel and were washed, filtered and dried at 333 K for 2 h.

S3. Refinement

The structural data were collected at the European Synchrotron Radiation Facility in Grenoble at the ID11 beamline (Kvick & Wulff, 1992; Krumrey et al., 1995) using an undulator source. The ethyl group bonded to N4 was statistically disordered. The occupancies of the two orientations were refined, with the constraint that the two orientations together had full occupancy [C55A, C56A 0.711 (6); C55B, C56B 0.289 (6)]. All H atoms, except for a few on the disordered ethyl group, could be located and refined isotropically with an average C—H distance of 0.975 Å.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1990).

Figures

Fig. 1. The molecular structure of (I), with 50% probability displacement ellipsoids. H atoms have been omitted for clarity. The bonds in the minor component of the disordered ethyl group have been illustrated with dashed lines.

3,6-bis(diethylamino)-1',3'-dihydrospiro[xanthene-9,3'-isobenzofuran]-1'-one

Crystal data

C28H30N2O3	Dx = 1.241 Mg m^−3
Mr = 442.54	Melting point: 452 K
Monoclinic, P21/n	Synchrotron radiation, λ = 0.496 Å
a = 16.224 (2) Å	Cell parameters from 512 reflections
b = 15.523 (3) Å	θ = 2.4–25.0°
c = 19.061 (4) Å	µ = 0.05 mm^−1
β = 99.25 (1)°	T = 120 K
V = 4738.0 (15) Å^3	Triangular prism, purple
Z = 8	0.3 × 0.1 × 0.1 mm
F(000) = 1888

Data collection

Bruker SMART CCD area-detector diffractometer with Oxford Cryosystems cooler (Cosier & Glazer, 1986)	13193 reflections with I > 2σ(I)
Radiation source: ID11 at ESRF	Rint = 0.052
Double crystal Si111 monochromator	θmax = 25°, θmin = 2.4°
ϕ scan 0.1° interval	h = −16→27
49459 measured reflections	k = −20→25
21735 independent reflections	l = −32→24

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.151	All H-atom parameters refined
S = 0.88	w = 1/[σ^2(Fo^2) + (0.0878P)^2] where P = (Fo^2 + 2Fc^2)/3
21667 reflections	(Δ/σ)max = 0.001
842 parameters	Δρmax = 0.72 e Å^−3
0 restraints	Δρmin = −0.30 e Å^−3

Special details

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 on F² for ALL reflections except for 68 with very negative F² or flagged by the user for potential systematic errors·The reflections flagged by the user had resolution above 3.5 Å and were affected by the beam stop. Weighted R-factors wR and all 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 observed criterion of F² > σ(F²) is used only for calculating R factor v obs 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	0.24787 (5)	0.13678 (4)	0.13187 (4)	0.02434 (15)
O2	0.46129 (7)	0.05707 (6)	0.41473 (4)	0.0355 (2)
O3	0.38504 (5)	0.08720 (5)	0.30950 (4)	0.02198 (14)
N1	0.32385 (6)	0.42888 (6)	0.13573 (5)	0.02694 (18)
N2	0.14961 (6)	−0.14903 (6)	0.09847 (5)	0.02672 (18)
C1	0.30696 (6)	0.19609 (6)	0.15865 (5)	0.01987 (16)
C2	0.28891 (7)	0.27924 (6)	0.13567 (6)	0.02268 (18)
C3	0.34369 (7)	0.34694 (6)	0.15749 (5)	0.02135 (17)
C4	0.41890 (7)	0.32559 (7)	0.20212 (6)	0.02478 (19)
C5	0.43496 (7)	0.24203 (7)	0.22370 (6)	0.02444 (19)
C6	0.37946 (6)	0.17437 (6)	0.20346 (5)	0.01987 (16)
C7	0.39400 (6)	0.08544 (6)	0.23255 (5)	0.01922 (16)
C8	0.33074 (6)	0.02427 (6)	0.19601 (5)	0.01933 (16)
C9	0.26227 (6)	0.05189 (6)	0.14926 (5)	0.01823 (16)
C10	0.20138 (6)	−0.00384 (6)	0.11672 (5)	0.01917 (16)
C11	0.20728 (6)	−0.09206 (6)	0.13104 (5)	0.02033 (17)
C12	0.27617 (7)	−0.12047 (7)	0.18007 (6)	0.02482 (19)
C13	0.33547 (7)	−0.06343 (7)	0.21086 (6)	0.02393 (19)
C14	0.45600 (7)	0.06168 (6)	0.35112 (5)	0.02318 (18)
C15	0.51810 (7)	0.04180 (7)	0.30617 (5)	0.02221 (18)
C16	0.59976 (7)	0.01376 (7)	0.32504 (7)	0.0281 (2)
C17	0.64385 (8)	−0.00191 (8)	0.27071 (8)	0.0337 (2)
C18	0.60817 (8)	0.00890 (9)	0.20040 (7)	0.0361 (3)
C19	0.52642 (8)	0.03643 (9)	0.18203 (6)	0.0309 (2)
C20	0.48218 (6)	0.05432 (7)	0.23686 (5)	0.02131 (17)
C21	0.38153 (8)	0.50028 (7)	0.15087 (6)	0.0262 (2)
C22	0.37433 (11)	0.54657 (10)	0.21911 (7)	0.0393 (3)
C23	0.23949 (8)	0.45132 (7)	0.10304 (7)	0.0310 (2)
C24	0.22513 (13)	0.44860 (11)	0.02325 (8)	0.0472 (4)
C25	0.07558 (7)	−0.12092 (7)	0.05214 (6)	0.02364 (18)
C26	0.00406 (9)	−0.09828 (11)	0.09028 (9)	0.0411 (3)
C27	0.15402 (8)	−0.24003 (7)	0.11703 (7)	0.0284 (2)
C28	0.21528 (9)	−0.28998 (8)	0.08163 (8)	0.0341 (3)
H2	0.2375 (11)	0.2895 (10)	0.1042 (9)	0.036 (4)*
H4	0.4582 (10)	0.3697 (10)	0.2195 (8)	0.033 (4)*
H5	0.4896 (11)	0.2310 (11)	0.2554 (9)	0.039 (4)*
H10	0.1533 (10)	0.0217 (10)	0.0859 (8)	0.028 (4)*
H12	0.2824 (10)	−0.1798 (11)	0.1934 (8)	0.035 (4)*
H13	0.3840 (11)	−0.0835 (11)	0.2428 (8)	0.035 (4)*
H16	0.6232 (9)	0.0074 (9)	0.3710 (8)	0.022 (3)*
H17	0.7013 (12)	−0.0216 (13)	0.2802 (10)	0.052 (5)*
H18	0.6389 (10)	−0.0037 (11)	0.1616 (8)	0.036 (4)*
H19	0.4960 (10)	0.0490 (10)	0.1337 (8)	0.031 (4)*
H21A	0.3704 (9)	0.5404 (10)	0.1106 (8)	0.027 (4)*
H21B	0.4370 (11)	0.4803 (11)	0.1506 (8)	0.038 (4)*
H22A	0.4117 (12)	0.5948 (12)	0.2239 (9)	0.047 (5)*
H22B	0.3958 (14)	0.5075 (15)	0.2604 (12)	0.069 (6)*
H22C	0.3173 (14)	0.5661 (13)	0.2214 (10)	0.056 (5)*
H23A	0.1964 (10)	0.4151 (11)	0.1188 (8)	0.032 (4)*
H23B	0.2281 (12)	0.5098 (12)	0.1145 (9)	0.047 (5)*
H24A	0.1663 (16)	0.4672 (15)	0.0029 (12)	0.074 (7)*
H24B	0.2656 (13)	0.4836 (14)	0.0022 (10)	0.059 (6)*
H24C	0.2433 (13)	0.3922 (14)	0.0061 (10)	0.056 (5)*
H25A	0.0599 (9)	−0.1678 (10)	0.0180 (7)	0.026 (3)*
H25B	0.0903 (9)	−0.0713 (10)	0.0238 (7)	0.024 (3)*
H26A	−0.0129 (12)	−0.1477 (13)	0.1168 (10)	0.052 (5)*
H26B	0.0178 (13)	−0.0523 (14)	0.1253 (11)	0.057 (5)*
H26C	−0.0481 (13)	−0.0817 (13)	0.0544 (10)	0.055 (5)*
H27A	0.1665 (9)	−0.2446 (9)	0.1687 (8)	0.025 (3)*
H27B	0.0961 (9)	−0.2621 (9)	0.1030 (7)	0.023 (3)*
H28A	0.2706 (13)	−0.2744 (12)	0.0971 (10)	0.050 (5)*
H28B	0.2061 (14)	−0.3498 (15)	0.0856 (11)	0.065 (6)*
H28C	0.2076 (11)	−0.2806 (11)	0.0291 (9)	0.041 (4)*
O4	0.89152 (5)	0.05992 (5)	0.29472 (4)	0.02506 (15)
O5	0.78133 (5)	0.36553 (5)	0.10435 (5)	0.03046 (17)
O6	0.82376 (5)	0.25385 (5)	0.17473 (4)	0.02310 (14)
N3	0.76898 (7)	−0.14295 (6)	0.12409 (6)	0.0311 (2)
N4	1.03973 (10)	0.22853 (9)	0.47905 (6)	0.0455 (3)
C29	0.86332 (6)	0.04375 (6)	0.22430 (5)	0.02019 (17)
C30	0.83306 (7)	−0.03861 (7)	0.20953 (6)	0.02272 (18)
C31	0.80044 (7)	−0.06252 (7)	0.13991 (6)	0.02328 (19)
C32	0.80010 (7)	0.00018 (7)	0.08647 (6)	0.0251 (2)
C33	0.83197 (7)	0.08054 (7)	0.10296 (5)	0.02348 (19)
C34	0.86465 (6)	0.10515 (6)	0.17194 (5)	0.01979 (17)
C35	0.89650 (6)	0.19366 (6)	0.18848 (5)	0.01949 (16)
C36	0.93545 (7)	0.20189 (6)	0.26435 (5)	0.02081 (17)
C37	0.92877 (6)	0.13740 (6)	0.31320 (5)	0.02075 (17)
C38	0.96119 (7)	0.14573 (7)	0.38442 (5)	0.02461 (19)
C39	1.00578 (8)	0.21939 (8)	0.40920 (6)	0.0305 (2)
C40	1.01439 (9)	0.28465 (8)	0.35967 (7)	0.0345 (3)
C41	0.97914 (8)	0.27535 (7)	0.28990 (6)	0.0290 (2)
C42	0.83392 (7)	0.31272 (6)	0.12488 (6)	0.02228 (18)
C43	0.91513 (6)	0.29820 (6)	0.10251 (5)	0.02072 (17)
C44	0.95368 (7)	0.34332 (7)	0.05423 (6)	0.0256 (2)
C45	1.02987 (7)	0.31357 (8)	0.04174 (6)	0.0276 (2)
C46	1.06614 (7)	0.24064 (8)	0.07651 (6)	0.02511 (19)
C47	1.02761 (6)	0.19700 (7)	0.12564 (5)	0.02189 (17)
C48	0.95137 (6)	0.22714 (6)	0.13806 (5)	0.01900 (16)
C49	0.74282 (9)	−0.17049 (9)	0.05106 (7)	0.0377 (3)
C50	0.65406 (11)	−0.14708 (13)	0.02145 (9)	0.0473 (4)
C51	0.75229 (9)	−0.20179 (8)	0.17935 (8)	0.0333 (3)
C52	0.82486 (14)	−0.25968 (12)	0.20684 (15)	0.0621 (5)
C53	1.01690 (11)	0.17007 (12)	0.53301 (7)	0.0447 (3)
C54	1.07329 (11)	0.09322 (13)	0.54627 (9)	0.0479 (4)
C55A	1.10806 (15)	0.29050 (16)	0.50105 (11)	0.0402 (6)	0.711 (6)
C56A	1.0741 (2)	0.3730 (2)	0.52510 (18)	0.0742 (11)	0.711 (6)
C55B	1.0548 (5)	0.3166 (4)	0.5125 (3)	0.052 (2)	0.289 (6)
C56B	1.1428 (6)	0.3232 (13)	0.5181 (8)	0.147 (7)	0.289 (6)
H30	0.8372 (11)	−0.0748 (11)	0.2483 (9)	0.039 (4)*
H32	0.7774 (10)	−0.0114 (10)	0.0362 (8)	0.033 (4)*
H33	0.8310 (9)	0.1217 (10)	0.0633 (8)	0.027 (4)*
H38	0.9559 (10)	0.0981 (10)	0.4148 (8)	0.029 (4)*
H40	1.0451 (12)	0.3370 (12)	0.3732 (9)	0.045 (5)*
H41	0.9822 (12)	0.3205 (12)	0.2582 (9)	0.048 (5)*
H44	0.9287 (11)	0.3920 (11)	0.0304 (9)	0.038 (4)*
H45	1.0594 (10)	0.3439 (11)	0.0086 (8)	0.034 (4)*
H46	1.1168 (10)	0.2197 (10)	0.0643 (8)	0.027 (4)*
H47	1.0521 (9)	0.1460 (9)	0.1513 (7)	0.022 (3)*
H49A	0.7809 (10)	−0.1476 (10)	0.0211 (8)	0.029 (4)*
H49B	0.7456 (12)	−0.2322 (13)	0.0511 (10)	0.049 (5)*
H50A	0.6406 (14)	−0.1707 (16)	−0.0255 (12)	0.072 (6)*
H50B	0.6466 (14)	−0.0844 (15)	0.0165 (11)	0.060 (6)*
H50C	0.6171 (13)	−0.1674 (13)	0.0525 (10)	0.052 (5)*
H51A	0.7340 (10)	−0.1701 (11)	0.2200 (8)	0.036 (4)*
H51B	0.7033 (11)	−0.2367 (11)	0.1602 (8)	0.035 (4)*
H52A	0.877 (2)	−0.222 (2)	0.2272 (15)	0.099 (9)*
H52B	0.8413 (15)	−0.2895 (15)	0.1705 (12)	0.066 (6)*
H52C	0.8099 (18)	−0.3034 (19)	0.2434 (15)	0.096 (8)*
H53A	1.0210 (15)	0.1948 (16)	0.5771 (13)	0.075 (7)*
H53B	0.9587 (12)	0.1527 (11)	0.5224 (9)	0.040 (4)*
H54A	1.0658 (13)	0.0523 (13)	0.5020 (10)	0.053 (5)*
H54B	1.1320 (18)	0.1158 (17)	0.5609 (14)	0.088 (8)*
H54C	1.0600 (17)	0.0624 (18)	0.5882 (14)	0.088 (8)*
H55A	1.1402 (14)	0.3082 (15)	0.4639 (12)	0.030 (5)*	0.711 (6)
H55B	1.1430 (12)	0.2984 (11)	0.5675 (10)	0.012 (4)*	0.711 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0195 (3)	0.0131 (3)	0.0361 (4)	−0.0005 (2)	−0.0088 (3)	0.0002 (3)
O2	0.0462 (6)	0.0375 (5)	0.0211 (3)	0.0110 (4)	0.0003 (4)	−0.0039 (3)
O3	0.0225 (3)	0.0227 (3)	0.0205 (3)	0.0043 (3)	0.0029 (3)	−0.0018 (2)
N1	0.0279 (5)	0.0162 (4)	0.0337 (5)	−0.0063 (3)	−0.0041 (4)	0.0022 (3)
N2	0.0239 (4)	0.0144 (3)	0.0390 (5)	−0.0031 (3)	−0.0037 (4)	0.0018 (3)
C1	0.0167 (4)	0.0155 (4)	0.0258 (4)	−0.0008 (3)	−0.0016 (3)	−0.0019 (3)
C2	0.0199 (4)	0.0162 (4)	0.0293 (5)	−0.0014 (3)	−0.0038 (4)	0.0003 (3)
C3	0.0215 (4)	0.0177 (4)	0.0243 (4)	−0.0035 (3)	0.0019 (4)	−0.0006 (3)
C4	0.0205 (4)	0.0224 (4)	0.0298 (5)	−0.0061 (4)	−0.0009 (4)	−0.0005 (4)
C5	0.0175 (4)	0.0233 (5)	0.0305 (5)	−0.0025 (4)	−0.0025 (4)	0.0001 (4)
C6	0.0161 (4)	0.0179 (4)	0.0246 (4)	0.0007 (3)	0.0003 (3)	−0.0011 (3)
C7	0.0166 (4)	0.0214 (4)	0.0192 (4)	0.0025 (3)	0.0014 (3)	−0.0014 (3)
C8	0.0182 (4)	0.0170 (4)	0.0217 (4)	0.0022 (3)	0.0000 (3)	−0.0013 (3)
C9	0.0177 (4)	0.0141 (4)	0.0222 (4)	0.0019 (3)	0.0010 (3)	−0.0009 (3)
C10	0.0180 (4)	0.0149 (4)	0.0233 (4)	0.0004 (3)	−0.0004 (3)	−0.0003 (3)
C11	0.0207 (4)	0.0152 (4)	0.0248 (4)	−0.0001 (3)	0.0026 (3)	0.0000 (3)
C12	0.0260 (5)	0.0162 (4)	0.0302 (5)	0.0022 (4)	−0.0015 (4)	0.0021 (3)
C13	0.0238 (5)	0.0184 (4)	0.0270 (4)	0.0036 (4)	−0.0036 (4)	0.0006 (3)
C14	0.0256 (5)	0.0184 (4)	0.0239 (4)	0.0042 (4)	−0.0012 (4)	−0.0039 (3)
C15	0.0205 (4)	0.0198 (4)	0.0248 (4)	0.0033 (3)	−0.0009 (4)	−0.0019 (3)
C16	0.0219 (5)	0.0231 (5)	0.0365 (6)	0.0042 (4)	−0.0034 (4)	0.0009 (4)
C17	0.0209 (5)	0.0307 (6)	0.0489 (7)	0.0064 (4)	0.0033 (5)	0.0037 (5)
C18	0.0277 (6)	0.0404 (7)	0.0431 (7)	0.0106 (5)	0.0145 (5)	0.0035 (5)
C19	0.0256 (5)	0.0374 (6)	0.0306 (5)	0.0074 (5)	0.0075 (4)	0.0013 (4)
C20	0.0167 (4)	0.0220 (4)	0.0247 (4)	0.0026 (3)	0.0018 (3)	0.0004 (3)
C21	0.0332 (6)	0.0207 (4)	0.0257 (4)	−0.0116 (4)	0.0077 (4)	−0.0011 (3)
C22	0.0460 (8)	0.0429 (7)	0.0312 (6)	−0.0211 (6)	0.0127 (6)	−0.0125 (5)
C23	0.0315 (6)	0.0172 (4)	0.0410 (6)	−0.0009 (4)	−0.0043 (5)	0.0023 (4)
C24	0.0572 (10)	0.0377 (7)	0.0401 (7)	−0.0096 (7)	−0.0119 (7)	0.0100 (6)
C25	0.0218 (5)	0.0197 (4)	0.0280 (5)	−0.0034 (4)	−0.0004 (4)	−0.0005 (3)
C26	0.0273 (6)	0.0430 (8)	0.0541 (8)	0.0016 (5)	0.0099 (6)	−0.0014 (6)
C27	0.0301 (6)	0.0155 (4)	0.0390 (6)	−0.0037 (4)	0.0035 (5)	0.0039 (4)
C28	0.0354 (7)	0.0204 (5)	0.0458 (7)	−0.0006 (4)	0.0044 (5)	−0.0025 (4)
O4	0.0295 (4)	0.0211 (3)	0.0230 (3)	−0.0047 (3)	−0.0003 (3)	0.0034 (3)
O5	0.0226 (4)	0.0237 (4)	0.0415 (4)	0.0052 (3)	−0.0059 (3)	0.0021 (3)
O6	0.0178 (3)	0.0206 (3)	0.0306 (4)	0.0027 (3)	0.0029 (3)	0.0015 (3)
N3	0.0361 (5)	0.0213 (4)	0.0385 (5)	−0.0098 (4)	0.0144 (4)	−0.0076 (4)
N4	0.0614 (9)	0.0431 (7)	0.0269 (5)	−0.0107 (6)	−0.0080 (5)	−0.0032 (4)
C29	0.0185 (4)	0.0185 (4)	0.0236 (4)	0.0004 (3)	0.0035 (3)	0.0009 (3)
C30	0.0218 (5)	0.0174 (4)	0.0300 (5)	−0.0013 (3)	0.0073 (4)	0.0016 (3)
C31	0.0202 (4)	0.0197 (4)	0.0319 (5)	−0.0026 (3)	0.0101 (4)	−0.0040 (3)
C32	0.0250 (5)	0.0247 (5)	0.0266 (5)	−0.0056 (4)	0.0077 (4)	−0.0043 (4)
C33	0.0249 (5)	0.0230 (4)	0.0232 (4)	−0.0036 (4)	0.0059 (4)	−0.0003 (3)
C34	0.0185 (4)	0.0177 (4)	0.0233 (4)	−0.0016 (3)	0.0036 (3)	0.0007 (3)
C35	0.0165 (4)	0.0169 (4)	0.0247 (4)	0.0005 (3)	0.0021 (3)	0.0022 (3)
C36	0.0206 (4)	0.0188 (4)	0.0226 (4)	0.0003 (3)	0.0021 (3)	0.0002 (3)
C37	0.0192 (4)	0.0189 (4)	0.0239 (4)	0.0012 (3)	0.0028 (3)	−0.0001 (3)
C38	0.0242 (5)	0.0255 (5)	0.0235 (4)	0.0031 (4)	0.0019 (4)	0.0014 (3)
C39	0.0322 (6)	0.0310 (6)	0.0260 (5)	−0.0002 (5)	−0.0020 (4)	−0.0037 (4)
C40	0.0427 (7)	0.0270 (5)	0.0310 (5)	−0.0081 (5)	−0.0026 (5)	−0.0034 (4)
C41	0.0347 (6)	0.0221 (5)	0.0286 (5)	−0.0065 (4)	0.0003 (4)	0.0001 (4)
C42	0.0189 (4)	0.0180 (4)	0.0278 (4)	0.0003 (3)	−0.0028 (4)	−0.0006 (3)
C43	0.0184 (4)	0.0176 (4)	0.0240 (4)	−0.0014 (3)	−0.0030 (3)	0.0028 (3)
C44	0.0263 (5)	0.0217 (4)	0.0267 (5)	−0.0045 (4)	−0.0023 (4)	0.0064 (3)
C45	0.0246 (5)	0.0287 (5)	0.0284 (5)	−0.0082 (4)	0.0012 (4)	0.0067 (4)
C46	0.0167 (4)	0.0307 (5)	0.0271 (5)	−0.0048 (4)	0.0011 (4)	0.0026 (4)
C47	0.0159 (4)	0.0241 (4)	0.0243 (4)	−0.0003 (3)	−0.0010 (3)	0.0028 (3)
C48	0.0160 (4)	0.0177 (4)	0.0219 (4)	−0.0016 (3)	−0.0009 (3)	0.0027 (3)
C49	0.0439 (7)	0.0306 (6)	0.0427 (7)	−0.0122 (5)	0.0192 (6)	−0.0157 (5)
C50	0.0437 (8)	0.0561 (10)	0.0433 (7)	−0.0201 (7)	0.0108 (7)	−0.0145 (7)
C51	0.0320 (6)	0.0201 (5)	0.0502 (7)	−0.0058 (4)	0.0141 (5)	−0.0011 (4)
C52	0.0598 (12)	0.0320 (8)	0.0972 (16)	0.0167 (8)	0.0208 (11)	0.0101 (9)
C53	0.0493 (9)	0.0596 (10)	0.0243 (5)	−0.0041 (7)	0.0029 (6)	−0.0060 (5)
C54	0.0383 (8)	0.0620 (10)	0.0392 (7)	−0.0109 (7)	−0.0059 (6)	0.0137 (7)
C55A	0.0304 (11)	0.0596 (14)	0.0295 (9)	−0.0093 (9)	0.0017 (8)	−0.0153 (8)
C56A	0.0626 (18)	0.070 (2)	0.097 (2)	−0.0186 (14)	0.0332 (16)	−0.0585 (17)
C55B	0.064 (4)	0.039 (3)	0.043 (3)	0.008 (3)	−0.023 (3)	−0.014 (2)
C56B	0.032 (4)	0.29 (2)	0.119 (9)	−0.031 (7)	0.002 (5)	−0.107 (12)

Geometric parameters (Å, º)

O1—C1	1.3674 (12)	C45—C46	1.3935 (17)
O1—C9	1.3696 (12)	C46—C47	1.3837 (15)
O2—C14	1.2038 (13)	C47—C48	1.3781 (14)
O3—C14	1.3484 (13)	C49—C50	1.504 (3)
O3—C7	1.4972 (12)	C51—C52	1.507 (2)
N1—C3	1.3604 (14)	C53—C54	1.500 (3)
N1—C21	1.4494 (14)	C55A—C56B	0.789 (12)
N1—C23	1.4521 (16)	C55A—C55B	1.009 (7)
N2—C11	1.3623 (13)	C55A—C56A	1.495 (4)
N2—C25	1.4393 (15)	C56A—C55B	0.948 (6)
N2—C27	1.4553 (14)	C56A—C56B	1.380 (13)
C1—C2	1.3793 (14)	C55B—C56B	1.419 (12)
C1—C6	1.3797 (14)	C2—H2	0.959 (18)
C2—C3	1.3958 (14)	C4—H4	0.958 (16)
C3—C4	1.4101 (16)	C5—H5	1.004 (18)
C4—C5	1.3731 (16)	C10—H10	0.982 (16)
C5—C6	1.3967 (14)	C12—H12	0.956 (17)
C6—C7	1.4923 (14)	C13—H13	0.966 (17)
C7—C8	1.4868 (14)	C16—H16	0.904 (15)
C7—C20	1.4997 (14)	C17—H17	0.97 (2)
C8—C9	1.3761 (14)	C18—H18	0.976 (16)
C8—C13	1.3901 (14)	C19—H19	0.992 (15)
C9—C10	1.3827 (14)	C21—H21A	0.982 (15)
C10—C11	1.3967 (14)	C21—H21B	0.953 (18)
C11—C12	1.4076 (15)	C22—H22B	1.01 (2)
C12—C13	1.3684 (16)	C22—H22C	0.98 (2)
C14—C15	1.4566 (15)	C22—H22A	0.958 (19)
C15—C20	1.3695 (14)	C23—H23A	0.981 (17)
C15—C16	1.3859 (15)	C23—H23B	0.959 (19)
C16—C17	1.3716 (18)	C24—H24A	1.01 (3)
C17—C18	1.382 (2)	C24—H24B	0.99 (2)
C18—C19	1.3839 (18)	C24—H24C	1.00 (2)
C19—C20	1.3878 (15)	C25—H25A	0.982 (15)
C21—C22	1.5069 (16)	C25—H25B	0.992 (15)
C23—C24	1.502 (2)	C26—H26A	0.98 (2)
C25—C26	1.5066 (18)	C26—H26B	0.98 (2)
C27—C28	1.5032 (19)	C26—H26C	1.03 (2)
O4—C37	1.3666 (13)	C27—H27B	0.996 (15)
O4—C29	1.3698 (13)	C27—H27A	0.976 (15)
O5—C42	1.2024 (13)	C28—H28A	0.93 (2)
O6—C42	1.3474 (13)	C28—H28B	0.95 (2)
O6—C35	1.4949 (12)	C28—H28C	1.000 (17)
N3—C31	1.3641 (14)	C30—H30	0.922 (17)
N3—C51	1.4522 (16)	C32—H32	0.984 (15)
N3—C49	1.4528 (17)	C33—H33	0.988 (15)
N4—C39	1.3641 (16)	C40—H40	0.966 (19)
N4—C53	1.463 (2)	C41—H41	0.932 (18)
N4—C55A	1.477 (3)	C44—H44	0.939 (17)
N4—C55B	1.511 (5)	C45—H45	0.973 (16)
C29—C30	1.3821 (14)	C46—H46	0.947 (14)
C29—C34	1.3826 (13)	C47—H47	0.980 (14)
C30—C31	1.3976 (16)	C49—H49A	0.973 (16)
C31—C32	1.4081 (16)	C49—H49B	0.96 (2)
C32—C33	1.3675 (15)	C50—H50A	0.96 (2)
C33—C34	1.3899 (15)	C50—H50B	0.98 (2)
C34—C35	1.4839 (14)	C50—H50C	0.96 (2)
C35—C36	1.4877 (14)	C51—H51A	1.002 (16)
C35—C48	1.5037 (14)	C51—H51B	0.983 (17)
C36—C37	1.3832 (14)	C52—H52A	1.05 (3)
C36—C41	1.3889 (15)	C52—H52B	0.91 (2)
C37—C38	1.3807 (15)	C52—H52C	1.03 (3)
C38—C39	1.3943 (17)	C53—H53A	0.92 (2)
C39—C40	1.4069 (18)	C53—H53B	0.971 (19)
C40—C41	1.3683 (17)	C54—H54A	1.048 (19)
C42—C43	1.4660 (15)	C54—H54B	1.01 (3)
C43—C48	1.3761 (14)	C54—H54C	0.99 (3)
C43—C44	1.3833 (15)	C55A—H55A	0.98 (2)
C44—C45	1.3757 (17)	C55A—H55B	1.306 (19)
C1—O1—C9	118.39 (8)	C56B—C55B—N4	101.0 (8)
C14—O3—C7	111.27 (8)	C55A—C56B—C56A	82.3 (8)
C3—N1—C21	122.73 (10)	C55A—C56B—C55B	43.8 (5)
C3—N1—C23	121.05 (9)	C56A—C56B—C55B	39.6 (4)
C21—N1—C23	115.83 (9)	C1—C2—H2	118.2 (9)
C11—N2—C25	121.81 (9)	C3—C2—H2	120.6 (9)
C11—N2—C27	121.06 (9)	C3—C4—H4	120.3 (9)
C25—N2—C27	116.55 (9)	C5—C4—H4	119.2 (9)
O1—C1—C2	114.29 (9)	C4—C5—H5	116.6 (10)
O1—C1—C6	122.91 (9)	C6—C5—H5	120.4 (10)
C2—C1—C6	122.79 (9)	C9—C10—H10	117.2 (9)
C1—C2—C3	121.16 (10)	C11—C10—H10	122.4 (9)
N1—C3—C2	120.32 (10)	C13—C12—H12	118.2 (10)
N1—C3—C4	122.89 (9)	C11—C12—H12	121.1 (10)
C2—C3—C4	116.78 (9)	C12—C13—H13	120.5 (10)
C5—C4—C3	120.46 (10)	C8—C13—H13	117.2 (10)
C4—C5—C6	123.00 (10)	C15—C16—H16	121.4 (9)
C1—C6—C5	115.78 (9)	C17—C16—H16	121.6 (9)
C1—C6—C7	121.62 (9)	C16—C17—H17	121.1 (11)
C5—C6—C7	122.44 (9)	C18—C17—H17	117.3 (11)
C8—C7—C6	111.14 (8)	C17—C18—H18	121.7 (9)
C8—C7—O3	107.59 (8)	C19—C18—H18	117.1 (9)
C6—C7—O3	108.22 (7)	C20—C19—H19	114.8 (9)
C8—C7—C20	113.61 (8)	C18—C19—H19	127.5 (9)
C6—C7—C20	114.25 (8)	N1—C21—H21B	109.3 (10)
O3—C7—C20	101.20 (7)	N1—C21—H21A	107.3 (9)
C9—C8—C13	116.70 (9)	H21A—C21—H21B	104.9 (130
C9—C8—C7	121.94 (9)	C21—C22—H22A	108.69 (11)
C13—C8—C7	121.25 (9)	C21—C22—H22B	108.7 (13)
O1—C9—C8	123.02 (9)	C21—C22—H22C	113.0 (11)
O1—C9—C10	114.31 (8)	N1—C23—H23A	113.6 (9)
C8—C9—C10	122.66 (9)	N1—C23—H23B	109.4 (11)
C9—C10—C11	120.28 (9)	C24—C23—H23A	107.0 (9)
N2—C11—C10	121.80 (9)	C24—C23—H23B	104.7 (10)
N2—C11—C12	120.87 (9)	H23A—C23—H23B	107.5 (15)
C10—C11—C12	117.33 (9)	C23—C24—H24A	111.3 (12)
C13—C12—C11	120.69 (10)	C23—C24—H24B	113.1 (11)
C12—C13—C8	122.31 (10)	C23—C24—H24C	110.6 (11)
O2—C14—O3	121.72 (10)	H24A—C24—H24B	109.6 (11)
O2—C14—C15	129.48 (11)	H24B—C24—H24C	95.7 (11)
O3—C14—C15	108.79 (9)	H24A—C24—H24C	115.8 (11)
C20—C15—C16	122.39 (10)	C26—C25—H25A	110.8 (9)
C20—C15—C14	108.06 (9)	C26—C25—H25B	110.7 (8)
C16—C15—C14	129.55 (10)	N2—C25—H25A	106.5 (9)
C17—C16—C15	116.91 (11)	N2—C25—H25B	108.6 (8)
C16—C17—C18	121.52 (11)	H25A—C25—H25B	105.9 (12)
C17—C18—C19	121.18 (11)	C25—C26—H26A	111.2 (12)
C18—C19—C20	117.51 (11)	C25—C26—H26B	113.0 (13)
C15—C20—C19	120.45 (10)	H26A—C26—H26B	105.7 (17)
C15—C20—C7	110.66 (8)	H26A—C26—H26C	105.6 (16)
C19—C20—C7	128.87 (9)	H26B—C26—H26C	110.1 (179
N1—C21—C22	113.54 (10)	C25—C26—H26C	110.6 (11)
N1—C23—C24	114.20 (13)	C28—C27—H27A	111.8 (9)
N2—C25—C26	113.96 (11)	N2—C27—H27A	108.1 (8)
N2—C27—C28	113.69 (10)	N2—C27—H27B	105.2 (8)
C37—O4—C29	118.56 (8)	H27A—C27—H27B	106.2 (12)
C42—O6—C35	111.40 (8)	C28—C27—H27B	111.4 (8)
C31—N3—C51	121.47 (10)	C27—C28—H28C	112.9 (10)
C31—N3—C49	121.50 (10)	C27—C28—H28B	110.3 (14)
C51—N3—C49	116.75 (10)	H28A—C28—H28B	112.8 (18)
C39—N4—C53	120.89 (12)	H28B—C28—H28C	103.1 (16)
C39—N4—C55A	120.79 (13)	H28A—C28—H28C	103.8 (16)
C53—N4—C55A	117.89 (13)	C27—C28—H28A	113.2 (12)
C39—N4—C55B	121.2 (2)	C29—C30—H30	115.0 (11)
C53—N4—C55B	107.9 (3)	C31—C30—H30	124.5 (11)
C55A—N4—C55B	39.5 (3)	C31—C32—H32	122.3 (9)
O4—C29—C30	114.88 (9)	C33—C32—H32	117.2 (9)
O4—C29—C34	122.65 (9)	C32—C33—H33	117.9 (9)
C30—C29—C34	122.46 (9)	C34—C33—H33	120.2 (9)
C29—C30—C31	120.46 (9)	C37—C38—H38	117.9 (9)
N3—C31—C30	121.61 (10)	C39—C38—H38	121.6 (9)
N3—C31—C32	120.99 (10)	C39—C40—H40	121.9 (10)
C30—C31—C32	117.40 (9)	C41—C40—H40	117.7 (10)
C33—C32—C31	120.46 (10)	C48—C47—H47	119.4 (8)
C32—C33—C34	122.74 (10)	N3—C49—H49A	109.8 (9)
C29—C34—C33	116.46 (9)	N3—C49—H49B	106.7 (11)
C29—C34—C35	122.02 (9)	C50—C49—H49A	110.6 (9)
C33—C34—C35	121.49 (9)	C50—C49—H49B	106.5 (12)
C34—C35—C36	111.41 (8)	H49A—C49—H49B	109.3 (15)
C34—C35—O6	107.65 (8)	C49—C50—H50A	108.6 (14)
C36—C35—O6	108.47 (8)	C49—C50—H50B	111.8 (13)
C34—C35—C48	113.95 (8)	C49—C50—H50C	110.1 (12)
C36—C35—C48	112.90 (8)	H50A—C50—H50B	106.4 (19)
O6—C35—C48	101.75 (7)	H50A—C50—H50C	112.2 (18)
C37—C36—C41	116.68 (10)	H50B—C50—H50C	107.7 (18)
C37—C36—C35	121.69 (9)	N3—C51—H51A	111.4 (10)
C41—C36—C35	121.63 (9)	N3—C51—H51B	108.1 (9)
O4—C37—C38	114.75 (9)	C52—C51—H51A	109.6 (9)
O4—C37—C36	122.86 (9)	C52—C51—H51B	109.9 (10)
C38—C37—C36	122.37 (10)	H51A—C51—H51B	103.6 (14)
C37—C38—C39	120.31 (10)	C51—C52—H52A	109.5 (17)
N4—C39—C38	121.48 (11)	C51—C52—H52B	110.3 (15)
N4—C39—C40	120.79 (12)	C36—C41—H41	117.9 (11)
C38—C39—C40	117.73 (10)	C40—C41—H41	119.6 (11)
C41—C40—C39	120.34 (11)	C43—C44—H44	121.5 (11)
C40—C41—C36	122.51 (11)	C45—C44—H44	121.1 (11)
O5—C42—O6	122.08 (10)	C44—C45—H45	120.0 (10)
O5—C42—C43	129.34 (10)	C46—C45—H45	119.2 (10)
O6—C42—C43	108.57 (8)	C45—C46—H46	118.6 (9)
C48—C43—C44	122.03 (10)	C47—C46—H46	120.2 (9)
C48—C43—C42	108.23 (9)	C46—C47—H47	122.8 (8)
C44—C43—C42	129.74 (9)	C51—C52—H52C	111.8 (17)
C45—C44—C43	117.39 (10)	H52A—C52—H52B	104 (2)
C44—C45—C46	120.86 (10)	H52A—C52—H52C	112 (2)
C47—C46—C45	121.15 (10)	H52B—C52—H52C	108 (2)
C48—C47—C46	117.76 (10)	N4—C53—H53A	113.3 (16)
C43—C48—C47	120.78 (9)	N4—C53—H53B	111.9 (11)
C43—C48—C35	109.99 (9)	C54—C53—H53A	103.1 (10)
C47—C48—C35	129.23 (9)	C54—C53—H53B	111.1 (10)
N3—C49—C50	113.76 (11)	H53A—C53—H53B	103.4 (19)
N3—C51—C52	113.64 (13)	C53—C54—H54A	110.0 (11)
N4—C53—C54	113.28 (14)	C53—C54—H54B	107.0 (15)
C56B—C55A—C55B	103.5 (10)	C53—C54—H53C	108.4 (16)
C56B—C55A—N4	172.1 (11)	H54A—C54—H54B	114.5 (9)
C55B—C55A—N4	72.1 (4)	H54A—C54—H54C	110.3 (19)
C56B—C55A—C56A	66.2 (10)	H54B—C54—H54C	105 (2)
C55B—C55A—C56A	38.7 (4)	N4—C55A—H55A	115.9 (13)
N4—C55A—C56A	110.4 (2)	N4—C55A—H55B	121.7 (8)
C55B—C56A—C56B	72.4 (8)	C56A—C55A—H55A	104.3 (14)
C55B—C56A—C55A	41.7 (5)	C56A—C55A—H55B	75.4 (8)
C56B—C56A—C55A	31.5 (5)	H55A—C55A—H55B	118.3 (6)
C56A—C55B—C55A	99.5 (7)	C22—C21—H21A	110.0 (9)
C56A—C55B—C56B	68.0 (9)	C22—C21—H21B	111.4 (9)
C55A—C55B—C56B	32.7 (6)	H22A—C22—H22B	105.1 (17)
C56A—C55B—N4	165.2 (8)	H22A—C22—H22C	110.7 (17)
C55A—C55B—N4	68.4 (3)	H22B—C22—H22C	111.1 (17)