Novel hydrazone derivatives of 7-hydroxy-3′,3′-dimethyl-3′H-spiro[chromene-2,1′-isobenzofuran]-8-carbaldehyde

The structures of new oxaindane spiro­pyrans derived from 7-hy­droxy-3′,3′-dimethyl-3′H-spiro­[chromene-2,1′-isobenzofuran]-8-carbaldehyde (SP1), namely N-benzyl-2-[(7-hy­droxy-3′,3′-dimethyl-3′H-spiro­[chromene-2,1′-isobenzofuran]-8-yl)­methyl­idene]hydrazinecarbothio­amide, C₂₇H₂₅N₃O₃S, (I), at 120 (2) K, and N′-[(7-hy­droxy-3′,3′-dimethyl-3′H-spiro­[chro­mene-2,1′-isobenzofuran]-8-yl)methyl­idene]-4-methyl­benzo­hydrazide acetone monosolvate, C₂₇H₂₄N₂O₄·C₃H₆O, (II), at 100 (2) K, are reported. The photochromically active C_spiro—O bond length in (I) is close to that in the parent compound (SP1), and in (II) it is shorter. In (I), centrosymmetric pairs of mol­ecules are bound by two equivalent N—H...S hydrogen bonds, forming an eight-membered ring with two donors and two acceptors.

S1. Comment

The design and synthesis of multifunctional molecules, combining in their structure several active moieties, sensitive towards different external influences have attracted significant interest recently. One such example is photomagnetoactive substances capable of switching their magnetic properties under light irradiation. A promising development strategy in this direction is the synthesis of mono- or polynuclear transition or f-block metal complexes with photochromic organic molecules functionalized with chelate-forming centres. Heterocyclic spiropyrans of different series are perspective substances which can possess photochromic properties as a result of reversible opening–closing reactions of the pyran ring under the effect of light (Bertleson, 1971; Durr, 1990; Minkin, 2004). This work extends our efforts in obtaining chelatofore functionalized spiropyrans (Bulanov et al., 2002, 2003, 2008, 2009).

We present here the crystal structure of two novel hydrazone derivatives of the previously reported (Bulanov et al., 2009) spiropyran of the 2-oxaindane series, 7-hydroxy-8-formyl-3',3'-dimethylspiro[3H-benzopyran-3,1'-[2]oxaindane] (hereafter referred to as SP1). Compound (I), N-benzyl-2-[(7-hydroxy-3',3'-dimethyl-3'H-spiro[chromene-2,1'-ιsobenzofuran]-8-yl)methylene]hydrazinecarbothioamide, was obtained by condensation reaction with N-benzylhydrazinecarbothioamide, and compound (II), N'-[(7-hydroxy-3',3'-dimethyl-3'H-spiro[chromene-2,1'-ιsobenzofuran]-8-yl)methylene]-4-methylbenzohydrazide acetone solvate, with 4-methyl benzohydrazide. The atom-numbering schemes for (I) and (II) are shown in Figs. 1 and 2, respectively, and selected geometric parameters are given in Table 1.

Both compounds crystallize in the closed spiroform. The main features of the spiropyran moiety structure of both compounds are similar to those of the mother spiropyran, SP1, and other derivatives studied so far. 2H-Chromene and oxaindane fragments are nearly orthogonal to each other [the angle between least-squares planes is 83.1 (2)° in (I) and 83.91 (13)° in (II)]. Pyran and oxaindane rings joined at the spirocentre C2 are substantially non-planar. The oxaindane moiety is in the `envelope' conformation with the O2' atom at the apex, going out of the least-squares plane defined by the other non-H atoms of this fragment, C1', C2, C3A, C4'–C7', C7A (due to bending along the C2···C1' line), by 0.247 (3) Å in (I) and 0.238 (2) Å in (II). The extent of the pyran ring distortion in both compounds is rather close [similar?]. From the least-squares plane defined by ten non-H atoms of the benzopyran moieties, the most significant deviation is found for the C2 spiroatom [-0.234 (4) Å in (I) and -0.241 (2) Å in (II)] and O1 [0.155 (3) Å in (I) and 0.160 (2) Å in (II)]. The pyran ring is bent in such a way that the O2' atom of the oxaindane moiety is closer to the plane of the pyran ring. This conformation favours the conjugation between the lone pair of the O2' atom and the antibonding σ orbital of the C2—O1 bond in the pyran ring, analogous to benzoxazinone (Bulanov et al., 2008) and other series (Minkin, 2004) of spiropyrans.

In both compounds strong intramolecular hydrogen bonds between neighbouring 7-OH and azomethine nitrogen atoms (O2—H2···N1) are observed; their geometric parameters can be found in Tables 2 and 3. One more intramolecular hydrogen bond is present in (I) between the thioamide hydrogen and hydrazone nitrogen atoms, N3—H3N···N1, which is involved in stabilization of the nearly planar configuration of the thiosemicarbazone moiety.

Of special interest in spiropyran molecules is the length of the C_spiro—O bond in the pyran ring (C2—O1 in the structures reported here), which is involved in the opening–closing of the pyran ring reaction. For comparison, some geometric parameters of SP1, taken from Bulanov et al. (2009), are presented in Table 1. It can be seen that in (I) this bond is nearly the same as in the mother compound (SP1) whereas in (II) this bond is noticeably shorter, close to the shortest interatomic distance observed for 2-oxaindane series spiropyrans (Bulanov et al., 2009). Thus it can be proposed that functionalization of the mother spiropyran (SP1) with chelatofore groups in the case of the benzocarbohydrazide (II) derivative can suppress its photochromic properties, while the thiosemicarbazone derivative (I) is not expected to perform worse then SP1.

From the data in Table 1 it is also seen that loosening of the active bond correlates rather well with shortening of the C8A—O1 and C2—O2' bonds, indicating their negative conjugation.

In crystals of (I) centrosymmetrically bound complementary pairs of molecules are formed by two equivalent intermolecular hydrogen bonds, N2—H2N ··· S1ⁱ and S1···H2Nⁱ—N2ⁱ [symmetry code: (i) -x + 1, -y, -z ]. Thus, an eight-membered ring involving two donors and two acceptors is observed (see Fig. 3 and Table 2). In the same dimers short intermolecular contacts, C9—H9··· S1ⁱ and S1···H9ⁱ—C9ⁱ, are also observed.

In the crystal structure of (II), a molecule of solvent (acetone) interacts with the hydrazone molecule by an intermolecular hydrogen bond (N2—H2N···O1S), a short contact (C27—H27···O1S, 0.30 Å less than the van der Waals sum) and a C—H···π interaction of the C3S—H3SC group with the aromatic system (C3A/C4'–C7'/C7A) of the oxaindane moiety [H3SC···centroid distance = 2.68 Å, C3S···centroid = 3.634 (3)Å and C3S—H3SC···centroid = 165°]. The acetone solvent molecule is also linked with another hydrazone molecule by a strong C—H···O hydrogen bond (C3S—H3SB···O3ⁱⁱ; see Table 3 for details). Between hydrazone molecules, C—H···π interactions with near to optimal characteristics are observed between the C7'—H7' group and the C22–C27 ring at (x-1/2, -y+1/2, z-1/2) [H7'···centroid distance = 2.80 Å, C7'···centroid = 3.715 (3) Å and C7'—H7'···centroid = 163°].

Related literature

For related literature, see: Bertleson (1971); Bulanov et al. (2002, 2003, 2008, 2009); Durr (1990); Minkin (2004).

S2. Experimental

Hydrazones (I) and (II) were obtained by a similar procedure. To 0.01 M solution of 7-hydroxy-8-formyl-3',3'-dimethylspiro[3H-benzopyran-3,1'-[2]oxaindane] (SP1) in ethanol, a hot 0.01 M ethanol solution of the corresponding hydrazide was added. After 15 min of reflux the solid matter started to precipitate. The solution was cooled to room temperature and left for 1 h. The precipitated crystalline solid [red in the case of (I) and yellow in the case of (II)] was filtered off and washed twice with hot petroleum ether. The yields were 52% (I), 60% (II), and melting points 463 K (I), 436 K (II).

Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of the benzene solution. In the case of (II) a mixed benzene:acetone (1:1) solution was employed for crystal growth.

S3. Refinement

The H atoms of NH and OH groups were found in difference Fourier maps and were refined in isotropic approximation with constrained N—H and O—H distances (0.90 and 0.85 Å, respectively) with U_iso(H) = 1.2U_eq of the respective parent atom. The H(C) atom positions were calculated and refined in isotropic approximation in riding model with U_iso(H) = 1.2U_eq(C) for aromatic, and 1.5 U_eq(Ci), for methyl groups.

To improve the refinement results, several reflections [one in the case of (I) and seven in the case of (II)] with too high values of δ(F²)/e.s.d. and with F_o² < F_c² were deleted from the refinement, because an account for extinction was unsuccessful .

Computing details

Data collection: SMART (Bruker, 1998) for (I); APEX2 (Bruker, 2005) for (II). Cell refinement: SAINT-Plus (Bruker, 1998) for (I); SAINT (Bruker, 2005) for (II). Data reduction: SAINT-Plus (Bruker, 1998) for (I); SAINT (Bruker, 2005) for (II). For both compounds, program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. The crystal structure of (I), with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The crystal structure of (II), with displacement ellipsoids drawn at the 50% probability level.
	Fig. 3. Inter- and intramolecular hydrogen bonds in (I) [symmetry code: (i) -x + 1, -y, -z].

(I) 1-benzyl-3-({7'-hydroxy-3,3-dimethylspiro[2-benzofuran-1,2'-chromene]-8'- ylmethylidene}amino)thiourea

Crystal data

C27H25N3O3S	Z = 2
Mr = 471.56	F(000) = 496
Triclinic, P1	Dx = 1.332 Mg m^−3
Hall symbol: -P 1	Melting point: 463 K
a = 8.4023 (14) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.4893 (15) Å	Cell parameters from 209 reflections
c = 15.210 (3) Å	θ = 3–26°
α = 87.020 (4)°	µ = 0.17 mm^−1
β = 83.192 (4)°	T = 120 K
γ = 77.714 (4)°	Plate, colourless
V = 1176.1 (3) Å^3	0.45 × 0.30 × 0.25 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer	4139 independent reflections
Radiation source: fine-focus sealed tube	2089 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.075
ω scans at different fixed ϕ positions	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −9→9
Tmin = 0.941, Tmax = 0.958	k = −11→11
9676 measured reflections	l = −18→18

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)] = 0.059	H-atom parameters constrained
wR(F^2) = 0.139	w = 1/[σ^2(Fo^2) + (0.0261P)^2 + 0.5P] where P = (Fo^2 + 2Fc^2)/3
S = 1.15	(Δ/σ)max = 0.001
4139 reflections	Δρmax = 0.51 e Å^−3
307 parameters	Δρmin = −0.35 e Å^−3
0 restraints

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 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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.31128 (15)	0.99624 (12)	0.11254 (8)	0.0411 (3)
O1	0.9734 (3)	0.5947 (3)	−0.17649 (17)	0.0287 (7)
O2	0.7080 (3)	0.3682 (3)	0.06789 (18)	0.0359 (7)
O2'	0.9499 (3)	0.5664 (3)	−0.32594 (18)	0.0318 (7)
C1'	0.8703 (5)	0.7070 (4)	−0.3621 (3)	0.0320 (11)
C2	1.0612 (5)	0.5831 (4)	−0.2652 (3)	0.0291 (10)
C3	1.1998 (5)	0.4556 (4)	−0.2711 (3)	0.0327 (11)
C3A	1.0943 (5)	0.7301 (4)	−0.2885 (3)	0.0292 (10)
C4	1.2000 (5)	0.3419 (4)	−0.2161 (3)	0.0328 (11)
C4'	1.2103 (5)	0.7961 (4)	−0.2588 (3)	0.0327 (11)
C4A	1.0728 (5)	0.3437 (4)	−0.1437 (3)	0.0285 (10)
C5	1.0578 (5)	0.2238 (4)	−0.0867 (3)	0.0350 (11)
C5'	1.2124 (5)	0.9362 (5)	−0.2867 (3)	0.0371 (11)
C6	0.9364 (5)	0.2336 (4)	−0.0166 (3)	0.0322 (11)
C6'	1.0995 (5)	1.0108 (5)	−0.3413 (3)	0.0370 (11)
C7	0.8266 (5)	0.3632 (4)	−0.0009 (3)	0.0277 (10)
C7'	0.9841 (5)	0.9445 (4)	−0.3708 (3)	0.0348 (11)
C7A	0.9841 (5)	0.8030 (4)	−0.3424 (3)	0.0287 (10)
C8	0.8364 (5)	0.4862 (4)	−0.0559 (3)	0.0252 (9)
C8'	0.8627 (5)	0.6929 (4)	−0.4599 (3)	0.0372 (11)
C8A	0.9612 (5)	0.4711 (4)	−0.1269 (3)	0.0257 (10)
C9'	0.6991 (5)	0.7499 (4)	−0.3121 (3)	0.0363 (11)
C9	0.7292 (5)	0.6255 (4)	−0.0392 (3)	0.0286 (10)
C21	0.4120 (5)	0.8246 (4)	0.1042 (3)	0.0265 (10)
C22	0.2594 (5)	0.7355 (4)	0.2381 (3)	0.0316 (10)
C23	0.3249 (5)	0.7451 (4)	0.3249 (3)	0.0259 (10)
C24	0.2780 (5)	0.6644 (4)	0.3977 (3)	0.0348 (11)
C25	0.3288 (5)	0.6775 (5)	0.4794 (3)	0.0423 (12)
C26	0.4291 (5)	0.7729 (5)	0.4891 (3)	0.0395 (12)
C27	0.4767 (5)	0.8532 (4)	0.4171 (3)	0.0334 (11)
C28	0.4250 (5)	0.8405 (4)	0.3356 (3)	0.0302 (10)
N1	0.6157 (4)	0.6456 (3)	0.0265 (2)	0.0278 (8)
N2	0.5294 (4)	0.7864 (3)	0.0366 (2)	0.0312 (9)
N3	0.3853 (4)	0.7181 (3)	0.1623 (2)	0.0283 (8)
H2	0.6431	0.4498	0.0750	0.043*
H2N	0.5524	0.8544	−0.0035	0.037*
H3	1.2901	0.4555	−0.3151	0.039*
H3N	0.4491	0.6298	0.1537	0.034*
H4	1.2852	0.2586	−0.2247	0.039*
H4'	1.2859	0.7459	−0.2203	0.039*
H5	1.1330	0.1345	−0.0969	0.042*
H5'	1.2922	0.9825	−0.2684	0.044*
H6	0.9281	0.1516	0.0208	0.039*
H6'	1.1013	1.1081	−0.3588	0.044*
H7'	0.9077	0.9942	−0.4090	0.042*
H8A	0.9741	0.6651	−0.4900	0.056*
H8B	0.8081	0.7855	−0.4848	0.056*
H8C	0.8009	0.6189	−0.4685	0.056*
H9	0.7431	0.7048	−0.0779	0.034*
H9A	0.7083	0.7578	−0.2490	0.055*
H9B	0.6361	0.6764	−0.3196	0.055*
H22A	0.2041	0.6528	0.2416	0.038*
H22B	0.1761	0.8242	0.2284	0.038*
H24	0.2095	0.5986	0.3915	0.042*
H25	0.2952	0.6212	0.5288	0.051*
H26	0.4645	0.7826	0.5451	0.047*
H27	0.5460	0.9184	0.4234	0.040*
H28	0.4583	0.8975	0.2864	0.036*
H9C	0.6430	0.8431	−0.3355	0.055*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0518 (8)	0.0281 (6)	0.0389 (8)	−0.0061 (5)	0.0067 (6)	0.0045 (5)
O1	0.0323 (17)	0.0222 (16)	0.0313 (18)	−0.0053 (12)	−0.0039 (13)	0.0017 (13)
O2'	0.0353 (17)	0.0281 (17)	0.0326 (18)	−0.0060 (13)	−0.0086 (14)	0.0032 (13)
O2	0.0355 (18)	0.0287 (17)	0.042 (2)	−0.0045 (13)	−0.0055 (15)	0.0097 (14)
C1'	0.036 (3)	0.026 (2)	0.032 (3)	−0.001 (2)	−0.008 (2)	0.0031 (19)
C2	0.032 (3)	0.032 (3)	0.022 (3)	−0.007 (2)	−0.001 (2)	0.0005 (19)
C21	0.032 (2)	0.029 (2)	0.022 (2)	−0.0107 (19)	−0.009 (2)	0.0039 (19)
C22	0.033 (3)	0.038 (3)	0.027 (3)	−0.015 (2)	−0.004 (2)	0.003 (2)
C23	0.028 (2)	0.025 (2)	0.026 (2)	−0.0078 (19)	−0.0060 (19)	0.0021 (18)
C24	0.035 (3)	0.037 (3)	0.036 (3)	−0.017 (2)	−0.005 (2)	0.010 (2)
C25	0.047 (3)	0.055 (3)	0.028 (3)	−0.019 (2)	−0.005 (2)	0.010 (2)
C26	0.039 (3)	0.055 (3)	0.028 (3)	−0.016 (2)	−0.009 (2)	−0.002 (2)
C27	0.027 (2)	0.038 (3)	0.038 (3)	−0.012 (2)	−0.007 (2)	−0.007 (2)
C28	0.030 (2)	0.027 (2)	0.033 (3)	−0.0061 (19)	−0.001 (2)	0.0045 (19)
C3	0.031 (3)	0.033 (3)	0.033 (3)	−0.003 (2)	−0.007 (2)	−0.003 (2)
C3A	0.032 (3)	0.030 (2)	0.024 (3)	−0.007 (2)	0.004 (2)	0.0020 (19)
C4'	0.035 (3)	0.034 (3)	0.029 (3)	−0.007 (2)	−0.004 (2)	0.003 (2)
C4	0.036 (3)	0.030 (3)	0.033 (3)	−0.002 (2)	−0.010 (2)	0.001 (2)
C4A	0.029 (2)	0.029 (2)	0.030 (3)	−0.0051 (19)	−0.014 (2)	−0.003 (2)
C5	0.040 (3)	0.025 (2)	0.044 (3)	−0.007 (2)	−0.018 (2)	0.002 (2)
C5'	0.044 (3)	0.040 (3)	0.031 (3)	−0.021 (2)	−0.002 (2)	−0.001 (2)
C6	0.034 (3)	0.028 (3)	0.036 (3)	−0.009 (2)	−0.011 (2)	0.011 (2)
C6'	0.043 (3)	0.030 (3)	0.035 (3)	−0.006 (2)	0.005 (2)	0.006 (2)
C7	0.028 (2)	0.032 (3)	0.025 (3)	−0.008 (2)	−0.008 (2)	0.0003 (19)
C7'	0.032 (3)	0.035 (3)	0.035 (3)	−0.005 (2)	0.000 (2)	0.007 (2)
C7A	0.025 (2)	0.031 (3)	0.029 (3)	−0.0053 (19)	0.001 (2)	0.003 (2)
C8	0.028 (2)	0.025 (2)	0.026 (3)	−0.0095 (18)	−0.0104 (19)	−0.0006 (18)
C8'	0.040 (3)	0.040 (3)	0.031 (3)	−0.006 (2)	−0.006 (2)	0.003 (2)
C8A	0.030 (2)	0.025 (2)	0.026 (3)	−0.0093 (19)	−0.015 (2)	0.0043 (19)
C9'	0.037 (3)	0.031 (3)	0.039 (3)	−0.006 (2)	−0.004 (2)	0.004 (2)
C9	0.038 (3)	0.022 (2)	0.027 (3)	−0.0062 (19)	−0.011 (2)	0.0073 (18)
N1	0.030 (2)	0.027 (2)	0.027 (2)	−0.0063 (16)	−0.0050 (17)	−0.0016 (15)
N2	0.041 (2)	0.025 (2)	0.025 (2)	−0.0051 (17)	0.0025 (17)	0.0027 (15)
N3	0.034 (2)	0.027 (2)	0.025 (2)	−0.0070 (16)	−0.0059 (16)	0.0028 (16)

Geometric parameters (Å, º)

O1—C2	1.456 (4)	C8'—H8A	0.9800
O1—C8A	1.377 (4)	C8'—H8B	0.9800
O2'—C1'	1.471 (4)	C8'—H8C	0.9800
O2'—C2	1.428 (5)	C8A—C4A	1.378 (5)
O2—C7	1.352 (4)	C8A—C8	1.404 (5)
O2—H2	0.8500	C9—C8	1.448 (5)
S1—C21	1.672 (4)	C9—H9	0.9500
C1'—C8'	1.511 (5)	C9'—H9A	0.9800
C1'—C9'	1.530 (5)	C9'—H9B	0.9800
C2—C3A	1.496 (5)	C9'—H9C	0.9800
C3—C2	1.488 (5)	C22—C23	1.503 (5)
C3—H3	0.9500	C22—H22A	0.9900
C3A—C4'	1.394 (6)	C22—H22B	0.9900
C3A—C7A	1.362 (5)	C23—C24	1.381 (5)
C4—C3	1.331 (5)	C23—C28	1.388 (5)
C4'—C5'	1.377 (5)	C24—C25	1.380 (6)
C4—H4	0.9500	C24—H24	0.9500
C4'—H4'	0.9500	C25—C26	1.385 (6)
C4A—C4	1.440 (5)	C25—H25	0.9500
C5—C4A	1.413 (5)	C26—C27	1.371 (5)
C5'—C6'	1.390 (5)	C26—H26	0.9500
C5—H5	0.9500	C27—C28	1.381 (5)
C5'—H5'	0.9500	C27—H27	0.9500
C6—C5	1.377 (5)	C28—H28	0.9500
C6'—C7'	1.389 (6)	N1—C9	1.288 (5)
C6—H6	0.9500	N2—C21	1.344 (5)
C6'—H6'	0.9500	N2—H2N	0.9000
C7—C6	1.385 (5)	N2—N1	1.384 (4)
C7'—C7A	1.389 (5)	N3—C21	1.345 (5)
C7'—H7'	0.9500	N3—C22	1.460 (5)
C7A—C1'	1.517 (6)	N3—H3N	0.9000
C8—C7	1.411 (5)
O1—C2—C3	111.3 (3)	C7A—C3A—C4'	120.9 (4)
O1—C2—C3A	105.2 (3)	C7A—C7'—C6'	117.7 (4)
O1—C8A—C4A	121.0 (4)	C7A—C7'—H7'	121.2
O1—C8A—C8	116.0 (3)	C8'—C1'—C7A	113.5 (3)
O2'—C1'—C7A	102.0 (3)	C8'—C1'—C9'	111.5 (3)
O2'—C1'—C8'	108.5 (3)	C8—C9—H9	118.9
O2'—C1'—C9'	108.0 (3)	C8A—C4A—C4	118.3 (4)
O2'—C2—C3	108.4 (3)	C8A—C4A—C5	117.7 (4)
O2'—C2—C3A	103.4 (3)	C8A—C8—C7	117.2 (4)
O2'—C2—O1	108.4 (3)	C8A—C8—C9	120.0 (4)
O2—C7—C6	118.2 (4)	C8A—O1—C2	119.4 (3)
O2—C7—C8	120.9 (4)	C9—N1—N2	115.5 (3)
C1'—C8'—H8A	109.5	C21—N2—H2N	119.0
C1'—C8'—H8B	109.5	C21—N2—N1	122.1 (3)
C1'—C8'—H8C	109.5	C21—N3—C22	124.6 (3)
C1'—C9'—H9A	109.5	C21—N3—H3N	117.7
C1'—C9'—H9B	109.5	C22—N3—H3N	117.7
C1'—C9'—H9C	109.5	C23—C22—H22A	108.8
C2—C3—H3	119.3	C23—C22—H22B	108.8
C2—O2'—C1'	111.0 (3)	C23—C24—H24	119.4
C3—C2—C3A	119.4 (4)	C23—C28—H28	119.8
C3—C4—C4A	120.8 (4)	C24—C23—C22	120.2 (4)
C3—C4—H4	119.6	C24—C23—C28	118.3 (4)
C3A—C4'—H4'	120.9	C24—C25—C26	119.8 (4)
C3A—C7A—C1'	109.6 (3)	C24—C25—H25	120.1
C3A—C7A—C7'	121.7 (4)	C25—C24—C23	121.2 (4)
C4—C3—C2	121.4 (4)	C25—C24—H24	119.4
C4—C3—H3	119.3	C25—C26—H26	120.3
C4'—C3A—C2	128.8 (4)	C26—C25—H25	120.1
C4'—C5'—C6'	121.0 (4)	C26—C27—C28	120.7 (4)
C4'—C5'—H5'	119.5	C26—C27—H27	119.6
C4A—C4—H4	119.6	C27—C26—C25	119.4 (4)
C4A—C5—H5	119.4	C27—C26—H26	120.3
C4A—C8A—C8	123.0 (4)	C27—C28—C23	120.5 (4)
C5'—C4'—C3A	118.1 (4)	C27—C28—H28	119.8
C5'—C4'—H4'	120.9	C28—C23—C22	121.4 (4)
C5—C4A—C4	124.0 (4)	C28—C27—H27	119.6
C5—C6—C7	119.9 (4)	H8A—C8'—H8B	109.5
C5'—C6'—H6'	119.7	H8A—C8'—H8C	109.5
C5—C6—H6	120.1	H8B—C8'—H8C	109.5
C6—C5—C4A	121.3 (4)	H9A—C9'—H9B	109.5
C6—C5—H5	119.4	H9A—C9'—H9C	109.5
C6'—C5'—H5'	119.5	H9B—C9'—H9C	109.5
C6—C7—C8	121.0 (4)	H22A—C22—H22B	107.7
C6'—C7'—H7'	121.2	N1—C9—C8	122.3 (4)
C7'—C6'—C5'	120.7 (4)	N1—C9—H9	118.9
C7'—C6'—H6'	119.7	N1—N2—H2N	118.9
C7—C6—H6	120.1	N2—C21—N3	115.9 (4)
C7'—C7A—C1'	128.7 (4)	N2—C21—S1	119.9 (3)
C7—C8—C9	122.7 (4)	N3—C21—S1	124.2 (3)
C7—O2—H2	115.0	N3—C22—C23	113.7 (3)
C7A—C1'—C9'	112.7 (3)	N3—C22—H22A	108.8
C7A—C3A—C2	110.2 (4)	N3—C22—H22B	108.8
O1—C2—C3A—C4'	75.6 (5)	C6—C5—C4A—C8A	−0.2 (6)
O1—C2—C3A—C7A	−100.6 (4)	C6'—C7'—C7A—C1'	178.3 (4)
O1—C8A—C4A—C4	−1.7 (5)	C6'—C7'—C7A—C3A	−0.8 (6)
O1—C8A—C4A—C5	176.4 (3)	C7—C6—C5—C4A	−0.3 (6)
O1—C8A—C8—C7	−176.6 (3)	C7'—C7A—C1'—C8'	54.6 (6)
O1—C8A—C8—C9	0.5 (5)	C7'—C7A—C1'—C9'	−73.4 (5)
O2'—C2—C3A—C4'	−170.8 (4)	C7'—C7A—C1'—O2'	171.1 (4)
O2'—C2—C3A—C7A	13.1 (4)	C7A—C3A—C4'—C5'	−1.2 (6)
O2—C7—C6—C5	179.3 (4)	C8—C7—C6—C5	0.2 (6)
C1'—O2'—C2—C3	−147.4 (3)	C8—C8A—C4A—C4	−177.4 (4)
C1'—O2'—C2—C3A	−19.7 (4)	C8—C8A—C4A—C5	0.7 (6)
C1'—O2'—C2—O1	91.6 (3)	C8A—C4A—C4—C3	−7.0 (6)
C2—C3A—C4'—C5'	−177.0 (4)	C8A—C8—C7—C6	0.2 (6)
C2—C3A—C7A—C1'	−1.9 (5)	C8A—C8—C7—O2	−178.8 (3)
C2—C3A—C7A—C7'	177.4 (4)	C8A—O1—C2—C3	−32.9 (5)
C2—O1—C8A—C4A	23.0 (5)	C8A—O1—C2—C3A	−163.6 (3)
C2—O1—C8A—C8	−161.0 (3)	C8A—O1—C2—O2'	86.3 (4)
C2—O2'—C1'—C7A	18.4 (4)	C9—C8—C7—C6	−176.8 (4)
C2—O2'—C1'—C8'	138.5 (3)	C9—C8—C7—O2	4.2 (6)
C2—O2'—C1'—C9'	−100.4 (4)	C21—N2—N1—C9	−177.3 (4)
C3—C2—C3A—C4'	−50.3 (6)	C21—N3—C22—C23	−102.3 (4)
C3—C2—C3A—C7A	133.6 (4)	C22—C23—C24—C25	−176.2 (4)
C3A—C4'—C5'—C6'	1.5 (6)	C22—C23—C28—C27	176.5 (4)
C3A—C7A—C1'—C8'	−126.2 (4)	C22—N3—C21—N2	−177.5 (3)
C3A—C7A—C1'—C9'	105.8 (4)	C22—N3—C21—S1	3.2 (5)
C3A—C7A—C1'—O2'	−9.6 (4)	C23—C24—C25—C26	−0.1 (7)
C4—C3—C2—C3A	147.4 (4)	C24—C23—C28—C27	0.3 (6)
C4—C3—C2—O1	24.5 (5)	C24—C25—C26—C27	−0.1 (7)
C4—C3—C2—O2'	−94.6 (4)	C25—C26—C27—C28	0.4 (6)
C4'—C3A—C7A—C1'	−178.4 (4)	C26—C27—C28—C23	−0.5 (6)
C4'—C3A—C7A—C7'	0.9 (6)	C28—C23—C24—C25	0.0 (6)
C4'—C5'—C6'—C7'	−1.5 (6)	N1—C9—C8—C7	−1.2 (6)
C4A—C4—C3—C2	−5.7 (6)	N1—C9—C8—C8A	−178.2 (4)
C4A—C8A—C8—C7	−0.7 (6)	N1—N2—C21—N3	1.1 (5)
C4A—C8A—C8—C9	176.5 (4)	N1—N2—C21—S1	−179.6 (3)
C5—C4A—C4—C3	175.0 (4)	N2—N1—C9—C8	176.5 (3)
C5'—C6'—C7'—C7A	1.1 (6)	N3—C22—C23—C24	−133.1 (4)
C6—C5—C4A—C4	177.8 (4)	N3—C22—C23—C28	50.8 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···N1	0.90	2.27	2.668 (5)	107
O2—H2···N1	0.85	1.94	2.646 (4)	140
N2—H2N···S1^i	0.90	2.46	3.341 (4)	165
C9—H9···S1^i	0.95	2.81	3.660 (4)	150

Symmetry code: (i) −x+1, −y+2, −z.

(II) N'-{7'-hydroxy-3,3-dimethyl-3H-spiro[2-benzofuran-1,2'- chromene]-8'-ylmethylidene}-4-methylbenzohydrazide acetone monosolvate

Crystal data

C27H24N2O4·C3H6O	F(000) = 1056
Mr = 498.56	Dx = 1.272 Mg m^−3
Monoclinic, P21/n	Melting point: 436 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 8.591 (2) Å	Cell parameters from 294 reflections
b = 17.272 (5) Å	θ = 3–25°
c = 17.569 (5) Å	µ = 0.09 mm^−1
β = 93.265 (5)°	T = 100 K
V = 2602.6 (12) Å^3	Plate, colourless
Z = 4	0.60 × 0.40 × 0.20 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	4568 independent reflections
Radiation source: fine-focus sealed tube	2752 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.092
ω scans	θmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −10→10
Tmin = 0.959, Tmax = 0.983	k = −20→20
20745 measured reflections	l = −20→20

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)] = 0.048	H-atom parameters constrained
wR(F^2) = 0.096	w = 1/[σ^2(Fo^2) + (0.0096P)^2 + 1.950P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.021
4568 reflections	Δρmax = 0.23 e Å^−3
339 parameters	Δρmin = −0.22 e Å^−3
0 restraints

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 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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.79594 (19)	0.38448 (9)	0.11316 (9)	0.0223 (4)
O2'	0.7757 (2)	0.39769 (10)	−0.01990 (9)	0.0280 (4)
O2	0.9620 (2)	0.58048 (10)	0.29126 (9)	0.0291 (4)
O3	1.3701 (2)	0.51923 (10)	0.34654 (10)	0.0335 (5)
C1'	0.8818 (3)	0.34356 (15)	−0.05476 (14)	0.0259 (6)
C2	0.7058 (3)	0.36367 (14)	0.04398 (14)	0.0240 (6)
C3	0.5414 (3)	0.39191 (15)	0.04512 (14)	0.0272 (6)
C3A	0.7319 (3)	0.27829 (14)	0.03436 (13)	0.0222 (6)
C4	0.5057 (3)	0.45318 (15)	0.08634 (14)	0.0279 (7)
C4'	0.6724 (3)	0.21732 (14)	0.07420 (14)	0.0246 (6)
C4A	0.6233 (3)	0.49039 (14)	0.13647 (14)	0.0233 (6)
C5	0.5995 (3)	0.55781 (15)	0.17806 (15)	0.0290 (7)
C5'	0.7151 (3)	0.14235 (14)	0.05466 (14)	0.0252 (6)
C6	0.7129 (3)	0.58699 (15)	0.22889 (15)	0.0303 (7)
C6'	0.8196 (3)	0.13090 (15)	−0.00183 (14)	0.0288 (7)
C7	0.8554 (3)	0.55007 (14)	0.23977 (14)	0.0256 (6)
C7'	0.8815 (3)	0.19302 (14)	−0.04020 (14)	0.0268 (6)
C7A	0.8352 (3)	0.26684 (14)	−0.02115 (13)	0.0218 (6)
C8'	0.8481 (3)	0.34860 (15)	−0.13980 (14)	0.0297 (7)
C8	0.8860 (3)	0.48182 (14)	0.19841 (14)	0.0224 (6)
C8A	0.7668 (3)	0.45362 (13)	0.14786 (14)	0.0221 (6)
C9	1.0337 (3)	0.44133 (14)	0.20700 (14)	0.0227 (6)
C9'	1.0509 (3)	0.36602 (16)	−0.03179 (16)	0.0353 (7)
C21	1.3939 (3)	0.46069 (14)	0.30987 (14)	0.0246 (6)
C22	1.5450 (3)	0.41764 (14)	0.31922 (13)	0.0223 (6)
C23	1.6538 (3)	0.44426 (15)	0.37477 (14)	0.0281 (7)
C24	1.7919 (3)	0.40520 (15)	0.39095 (14)	0.0287 (6)
C25	1.8262 (3)	0.33786 (15)	0.35180 (14)	0.0276 (6)
C26	1.7188 (3)	0.31255 (15)	0.29538 (14)	0.0307 (7)
C27	1.5799 (3)	0.35107 (14)	0.27829 (14)	0.0259 (6)
C28	1.9766 (3)	0.29511 (17)	0.37014 (16)	0.0374 (7)
H2	1.0453	0.5539	0.2909	0.035*
H2N	1.2963	0.3867	0.2333	0.029*
H3	0.4613	0.3656	0.0159	0.033*
H4	0.4022	0.4728	0.0830	0.033*
H4'	0.6040	0.2262	0.1139	0.029*
H5	0.5028	0.5843	0.1712	0.035*
H5'	0.6728	0.0992	0.0799	0.030*
H6	0.6930	0.6328	0.2567	0.036*
H6'	0.8492	0.0797	−0.0144	0.035*
H7'	0.9537	0.1850	−0.0785	0.032*
H8A	0.7407	0.3320	−0.1525	0.044*
H8B	0.9203	0.3149	−0.1656	0.044*
H8C	0.8615	0.4022	−0.1566	0.044*
H9	1.0506	0.3956	0.1786	0.027*
H9A	1.0664	0.3655	0.0239	0.053*
H9B	1.0721	0.4180	−0.0509	0.053*
H9C	1.1220	0.3288	−0.0537	0.053*
H23	1.6327	0.4902	0.4021	0.034*
H24	1.8643	0.4245	0.4292	0.034*
H26	1.7413	0.2672	0.2675	0.037*
H27	1.5089	0.3324	0.2391	0.031*
H28A	1.9607	0.2397	0.3606	0.056*
H28B	2.0095	0.3032	0.4239	0.056*
H28C	2.0572	0.3146	0.3378	0.056*
N1	1.1417 (3)	0.46797 (12)	0.25351 (11)	0.0247 (5)
N2	1.2823 (2)	0.43020 (11)	0.26018 (11)	0.0240 (5)
O1S	1.2860 (2)	0.28980 (11)	0.15979 (11)	0.0393 (5)
C1S	1.2132 (3)	0.23218 (15)	0.13813 (14)	0.0266 (6)
C2S	1.2607 (3)	0.18452 (16)	0.07321 (15)	0.0332 (7)
H2SA	1.3399	0.2124	0.0459	0.050*
H2SB	1.1697	0.1744	0.0384	0.050*
H2SC	1.3041	0.1353	0.0924	0.050*
C3S	1.0682 (3)	0.20773 (16)	0.17455 (15)	0.0356 (7)
H3SA	1.0534	0.2400	0.2194	0.053*
H3SB	1.0776	0.1534	0.1901	0.053*
H3SC	0.9785	0.2137	0.1380	0.053*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0210 (10)	0.0188 (9)	0.0271 (10)	0.0046 (8)	0.0007 (8)	−0.0015 (8)
O2'	0.0270 (11)	0.0260 (10)	0.0316 (10)	0.0041 (9)	0.0072 (8)	0.0065 (8)
O2	0.0294 (11)	0.0247 (10)	0.0338 (11)	−0.0004 (9)	0.0079 (9)	−0.0052 (8)
O3	0.0341 (12)	0.0228 (10)	0.0433 (12)	0.0009 (9)	0.0007 (9)	−0.0107 (9)
C1'	0.0225 (16)	0.0265 (14)	0.0290 (15)	0.0054 (12)	0.0054 (12)	0.0033 (12)
C2	0.0214 (15)	0.0279 (14)	0.0226 (14)	−0.0009 (12)	0.0003 (11)	0.0017 (11)
C3	0.0188 (15)	0.0308 (16)	0.0321 (15)	0.0021 (13)	0.0018 (12)	0.0054 (13)
C3A	0.0214 (15)	0.0235 (14)	0.0213 (14)	0.0015 (12)	−0.0020 (11)	0.0020 (11)
C4'	0.0187 (15)	0.0318 (15)	0.0230 (14)	−0.0003 (13)	−0.0010 (11)	0.0036 (12)
C4	0.0202 (16)	0.0300 (16)	0.0338 (16)	0.0089 (13)	0.0058 (12)	0.0111 (13)
C4A	0.0224 (16)	0.0220 (14)	0.0260 (15)	0.0041 (12)	0.0073 (12)	0.0056 (11)
C5'	0.0262 (16)	0.0226 (14)	0.0267 (15)	−0.0025 (12)	−0.0009 (12)	0.0049 (11)
C5	0.0265 (17)	0.0250 (15)	0.0368 (16)	0.0086 (13)	0.0133 (13)	0.0075 (13)
C6'	0.0312 (18)	0.0254 (15)	0.0295 (15)	0.0036 (13)	−0.0018 (13)	0.0017 (12)
C6	0.0357 (19)	0.0181 (14)	0.0388 (17)	0.0045 (13)	0.0165 (14)	0.0025 (13)
C7'	0.0244 (17)	0.0296 (16)	0.0267 (15)	0.0060 (13)	0.0043 (12)	0.0014 (12)
C7	0.0292 (17)	0.0203 (14)	0.0283 (15)	−0.0019 (13)	0.0101 (13)	0.0042 (12)
C7A	0.0198 (15)	0.0256 (14)	0.0197 (13)	−0.0014 (12)	−0.0021 (11)	0.0039 (11)
C8	0.0240 (16)	0.0181 (13)	0.0258 (14)	0.0024 (12)	0.0092 (12)	0.0035 (11)
C8'	0.0271 (17)	0.0320 (16)	0.0304 (15)	0.0016 (13)	0.0060 (12)	0.0094 (12)
C8A	0.0255 (16)	0.0186 (13)	0.0232 (14)	0.0040 (12)	0.0089 (12)	0.0025 (11)
C9'	0.0242 (17)	0.0372 (17)	0.0447 (18)	−0.0003 (14)	0.0037 (13)	0.0084 (14)
C9	0.0262 (16)	0.0179 (13)	0.0247 (14)	0.0018 (12)	0.0061 (12)	0.0019 (11)
C21	0.0281 (17)	0.0195 (14)	0.0264 (15)	−0.0036 (12)	0.0035 (12)	0.0016 (12)
C22	0.0232 (16)	0.0234 (14)	0.0205 (14)	−0.0043 (12)	0.0030 (11)	0.0028 (11)
C23	0.0308 (18)	0.0241 (14)	0.0293 (15)	−0.0047 (13)	0.0025 (13)	−0.0031 (12)
C24	0.0292 (17)	0.0303 (16)	0.0260 (15)	−0.0043 (13)	−0.0031 (12)	0.0000 (12)
C25	0.0266 (17)	0.0294 (15)	0.0266 (15)	−0.0004 (13)	0.0013 (12)	0.0049 (12)
C26	0.0352 (18)	0.0284 (16)	0.0284 (16)	0.0036 (14)	0.0000 (13)	−0.0039 (12)
C27	0.0285 (17)	0.0250 (14)	0.0239 (14)	−0.0013 (13)	−0.0009 (12)	−0.0025 (12)
C28	0.0325 (19)	0.0418 (18)	0.0369 (17)	0.0088 (15)	−0.0054 (13)	0.0002 (14)
N1	0.0238 (13)	0.0223 (12)	0.0283 (13)	−0.0010 (11)	0.0049 (10)	0.0022 (10)
N2	0.0224 (14)	0.0196 (11)	0.0300 (12)	0.0022 (10)	0.0009 (10)	−0.0044 (10)
O1S	0.0349 (13)	0.0329 (11)	0.0498 (13)	−0.0106 (10)	−0.0017 (9)	−0.0116 (10)
C1S	0.0215 (16)	0.0272 (15)	0.0304 (15)	0.0040 (13)	−0.0045 (12)	0.0024 (12)
C2S	0.0232 (17)	0.0381 (17)	0.0386 (17)	0.0006 (14)	0.0059 (13)	−0.0030 (13)
C3S	0.0321 (18)	0.0388 (17)	0.0366 (17)	−0.0031 (15)	0.0076 (13)	−0.0032 (14)

Geometric parameters (Å, º)

C1'—C8'	1.508 (3)	C5—C4A	1.396 (3)
C1'—C9'	1.535 (4)	C5'—C6'	1.390 (3)
C1S—C2S	1.483 (3)	C5—H5	0.9500
C1S—C3S	1.493 (3)	C5'—H5'	0.9500
C2—C3A	1.503 (3)	C6—C5	1.379 (4)
C21—C22	1.496 (4)	C6'—C7'	1.389 (3)
C22—C23	1.391 (3)	C6—H6	0.9500
C22—C27	1.398 (3)	C6'—H6'	0.9500
C23—C24	1.381 (4)	C7—C6	1.384 (4)
C23—H23	0.9500	C7'—C7A	1.382 (3)
C24—C25	1.391 (4)	C7'—H7'	0.9500
C24—H24	0.9500	C7A—C1'	1.514 (3)
C25—C26	1.386 (4)	C8—C7	1.417 (3)
C25—C28	1.506 (4)	C8'—H8A	0.9800
C26—C27	1.384 (4)	C8'—H8B	0.9800
C26—H26	0.9500	C8'—H8C	0.9800
C27—H27	0.9500	C8A—C4A	1.391 (3)
C28—H28A	0.9800	C8A—C8	1.404 (4)
C28—H28B	0.9800	C9—C8	1.449 (3)
C28—H28C	0.9800	C9—H9	0.9500
C2S—H2SA	0.9800	C9'—H9A	0.9800
C2S—H2SB	0.9800	C9'—H9B	0.9800
C2S—H2SC	0.9800	C9'—H9C	0.9800
C3—C2	1.495 (4)	N1—C9	1.286 (3)
C3—H3	0.9500	N2—C21	1.365 (3)
C3A—C4'	1.379 (3)	N2—H2N	0.9000
C3A—C7A	1.370 (3)	N2—N1	1.372 (3)
C3S—H3SA	0.9800	O1—C2	1.449 (3)
C3S—H3SB	0.9800	O1—C8A	1.370 (3)
C3S—H3SC	0.9800	O1S—C1S	1.224 (3)
C4—C3	1.328 (3)	O2'—C1'	1.464 (3)
C4'—C5'	1.394 (3)	O2'—C2	1.429 (3)
C4—H4	0.9500	O2—C7	1.356 (3)
C4'—H4'	0.9500	O2—H2	0.8500
C4A—C4	1.452 (4)	O3—C21	1.222 (3)
C1'—C8'—H8A	109.5	C6—C5—H5	119.2
C1'—C8'—H8B	109.5	C6'—C5'—H5'	120.1
C1'—C8'—H8C	109.5	C6—C7—C8	120.0 (3)
C1'—C9'—H9A	109.5	C6'—C7'—H7'	120.9
C1'—C9'—H9B	109.5	C7'—C6'—C5'	121.2 (2)
C1'—C9'—H9C	109.5	C7'—C6'—H6'	119.4
C1S—C2S—H2SA	109.5	C7—C6—H6	119.7
C1S—C2S—H2SB	109.5	C7'—C7A—C1'	128.8 (2)
C1S—C2S—H2SC	109.5	C7—C8—C9	122.3 (2)
C1S—C3S—H3SA	109.5	C7—O2—H2	108.8
C1S—C3S—H3SB	109.5	C7A—C1'—C9'	112.7 (2)
C1S—C3S—H3SC	109.5	C7A—C3A—C2	109.2 (2)
C2—C3—H3	119.5	C7A—C3A—C4'	121.7 (2)
C2—O2'—C1'	111.43 (17)	C7A—C7'—C6'	118.1 (2)
C21—N2—H2N	123.2	C7A—C7'—H7'	120.9
C21—N2—N1	117.0 (2)	C8'—C1'—C7A	113.4 (2)
C22—C23—H23	119.4	C8'—C1'—C9'	111.8 (2)
C22—C27—H27	120.3	C8—C9—H9	120.4
C23—C22—C21	117.2 (2)	C8A—C4A—C4	117.7 (2)
C23—C22—C27	118.5 (3)	C8A—C4A—C5	117.4 (3)
C23—C24—C25	120.7 (3)	C8A—C8—C7	117.6 (2)
C23—C24—H24	119.6	C8A—C8—C9	120.1 (2)
C24—C23—C22	121.2 (2)	C8A—O1—C2	119.13 (19)
C24—C23—H23	119.4	C9—N1—N2	118.9 (2)
C24—C25—C28	120.5 (2)	H28A—C28—H28B	109.5
C25—C24—H24	119.6	H28A—C28—H28C	109.5
C25—C26—H26	118.9	H28B—C28—H28C	109.5
C25—C28—H28A	109.5	H2SA—C2S—H2SB	109.5
C25—C28—H28B	109.5	H2SA—C2S—H2SC	109.5
C25—C28—H28C	109.5	H2SB—C2S—H2SC	109.5
C26—C25—C24	117.8 (3)	H3SA—C3S—H3SB	109.5
C26—C25—C28	121.7 (2)	H3SA—C3S—H3SC	109.5
C26—C27—C22	119.4 (2)	H3SB—C3S—H3SC	109.5
C26—C27—H27	120.3	H8A—C8'—H8B	109.5
C27—C22—C21	124.2 (2)	H8A—C8'—H8C	109.5
C27—C26—C25	122.3 (2)	H8B—C8'—H8C	109.5
C27—C26—H26	118.9	H9A—C9'—H9B	109.5
C2S—C1S—C3S	116.5 (2)	H9A—C9'—H9C	109.5
C3—C2—C3A	118.0 (2)	H9B—C9'—H9C	109.5
C3—C4—C4A	120.6 (3)	N1—C9—C8	119.3 (2)
C3—C4—H4	119.7	N1—C9—H9	120.4
C3A—C4'—C5'	118.3 (2)	N1—N2—H2N	119.7
C3A—C4'—H4'	120.9	N2—C21—C22	116.9 (2)
C3A—C7A—C1'	110.4 (2)	O1—C2—C3	111.6 (2)
C3A—C7A—C7'	120.8 (2)	O1—C2—C3A	105.2 (2)
C4—C3—C2	121.0 (3)	O1—C8A—C4A	121.1 (2)
C4—C3—H3	119.5	O1—C8A—C8	116.0 (2)
C4'—C3A—C2	129.1 (2)	O1S—C1S—C2S	122.1 (2)
C4'—C5'—H5'	120.1	O1S—C1S—C3S	121.4 (2)
C4A—C4—H4	119.7	O2'—C1'—C7A	102.18 (19)
C4A—C5—H5	119.2	O2'—C1'—C8'	106.8 (2)
C4A—C8A—C8	122.8 (2)	O2'—C1'—C9'	109.3 (2)
C5'—C4'—H4'	120.9	O2'—C2—C3	108.4 (2)
C5—C4A—C4	124.7 (3)	O2'—C2—C3A	104.06 (19)
C5—C6—C7	120.5 (3)	O2'—C2—O1	109.17 (19)
C5'—C6'—H6'	119.4	O2—C7—C6	118.2 (2)
C5—C6—H6	119.7	O2—C7—C8	121.8 (2)
C6'—C5'—C4'	119.9 (2)	O3—C21—C22	121.6 (2)
C6—C5—C4A	121.7 (3)	O3—C21—N2	121.6 (3)
C1'—O2'—C2—C3	−143.4 (2)	C6—C5—C4A—C4	175.2 (2)
C1'—O2'—C2—C3A	−17.1 (3)	C6—C5—C4A—C8A	−0.4 (4)
C1'—O2'—C2—O1	94.8 (2)	C6'—C7'—C7A—C1'	−178.7 (3)
C2—C3A—C4'—C5'	−179.7 (3)	C6'—C7'—C7A—C3A	0.4 (4)
C2—C3A—C7A—C1'	−1.9 (3)	C7—C6—C5—C4A	0.5 (4)
C2—C3A—C7A—C7'	178.8 (2)	C7'—C7A—C1'—C8'	56.6 (4)
C2—O1—C8A—C4A	23.4 (3)	C7'—C7A—C1'—C9'	−71.7 (3)
C2—O1—C8A—C8	−160.3 (2)	C7'—C7A—C1'—O2'	171.1 (3)
C2—O2'—C1'—C7A	15.8 (3)	C7A—C3A—C4'—C5'	−2.5 (4)
C2—O2'—C1'—C8'	135.0 (2)	C8—C7—C6—C5	0.1 (4)
C2—O2'—C1'—C9'	−103.9 (2)	C8—C8A—C4A—C4	−176.2 (2)
C21—C22—C23—C24	175.6 (2)	C8—C8A—C4A—C5	−0.4 (4)
C21—C22—C27—C26	−175.3 (2)	C8A—C4A—C4—C3	−8.8 (4)
C21—N2—N1—C9	179.6 (2)	C8A—C8—C7—C6	−0.8 (3)
C22—C23—C24—C25	0.1 (4)	C8A—C8—C7—O2	178.3 (2)
C23—C22—C27—C26	1.7 (4)	C8A—O1—C2—C3	−34.9 (3)
C23—C24—C25—C26	1.2 (4)	C8A—O1—C2—C3A	−163.9 (2)
C23—C24—C25—C28	−179.5 (2)	C8A—O1—C2—O2'	84.9 (2)
C24—C25—C26—C27	−1.1 (4)	C9—C8—C7—C6	179.3 (2)
C25—C26—C27—C22	−0.4 (4)	C9—C8—C7—O2	−1.5 (4)
C27—C22—C23—C24	−1.6 (4)	N1—C9—C8—C7	−0.2 (4)
C28—C25—C26—C27	179.6 (2)	N1—C9—C8—C8A	180.0 (2)
C3—C2—C3A—C4'	−51.0 (4)	N1—N2—C21—C22	177.7 (2)
C3—C2—C3A—C7A	131.5 (2)	N1—N2—C21—O3	−0.3 (3)
C3A—C4'—C5'—C6'	2.3 (4)	N2—C21—C22—C23	−174.2 (2)
C3A—C7A—C1'—C8'	−122.6 (2)	N2—C21—C22—C27	2.8 (4)
C3A—C7A—C1'—C9'	109.1 (3)	N2—N1—C9—C8	−178.7 (2)
C3A—C7A—C1'—O2'	−8.1 (3)	O1—C2—C3A—C4'	74.1 (3)
C4—C3—C2—C3A	148.1 (2)	O1—C2—C3A—C7A	−103.3 (2)
C4—C3—C2—O1	26.1 (3)	O1—C8A—C4A—C4	−0.2 (3)
C4—C3—C2—O2'	−94.1 (3)	O1—C8A—C4A—C5	175.6 (2)
C4'—C3A—C7A—C1'	−179.6 (2)	O1—C8A—C8—C7	−175.3 (2)
C4'—C3A—C7A—C7'	1.2 (4)	O1—C8A—C8—C9	4.6 (3)
C4'—C5'—C6'—C7'	−0.8 (4)	O2'—C2—C3A—C4'	−171.1 (2)
C4A—C4—C3—C2	−5.3 (4)	O2'—C2—C3A—C7A	11.4 (3)
C4A—C8A—C8—C7	0.9 (3)	O2—C7—C6—C5	−179.0 (2)
C4A—C8A—C8—C9	−179.2 (2)	O3—C21—C22—C23	3.8 (4)
C5—C4A—C4—C3	175.6 (2)	O3—C21—C22—C27	−179.1 (2)
C5'—C6'—C7'—C7A	−0.6 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O1S	0.90	2.11	3.000 (3)	169
O2—H2···N1	0.85	1.84	2.591 (3)	147
C27—H27···O1S	0.95	2.42	3.351 (3)	167
C3S—H3SB···O3^i	0.98	2.45	3.323 (3)	148

Symmetry code: (i) −x+5/2, y−1/2, −z+1/2.