One-pot green synthesis of biologically relevant novel spiro[indolin-2-one-3,4′-pyrano[2,3-c]pyrazoles] and studies on their spectral and X-ray crystallographic behaviors

Syntheses via green route and single-crystal X-ray structural investigations have been carried out for three spiro­[indolin-2-one-3,4′-pyrano[2,3-c]pyrazole] derivatives, 6′-amino-2-oxo-3′-propyl-2′H-spiro­[indoline-3,4′-pyrano[2,3-c]pyrazole]-5′-carbonitrile dimethyl sulfoxide monosolvate (5a), 6′-amino-5-fluoro-2-oxo-3′-propyl-2′H-spiro­[indoline-3,4′-pyrano[2,3-c]pyrazole]-5′-carbonitrile dimethyl sulfoxide monosolvate (5b) and methyl 6′-amino-5-cyano-1-methyl-2-oxo-3′-propyl-2′H-spiro­[indoline-3,4′-pyrano[2,3-c]pyrazole]-3′-carboxylate 0.25 hydrate (5c), respectively. Compounds (5a) and (5b) crystallize in the triclinic space group , whereas compound (5c) crystallizes in the monoclinic space group C2/c. In molecules (5a) and (5b) all the rings are practically flat, while in (5c), the heterocyclic pyran ring adopts a flattened-boat conformation. In (5a) and (5b) the cyanide group is oriented in a (−ap) conformation, while the amino group is oriented in a (+ap) conformation with a pyran ring, but in (5c) both the cyanide and amino groups are oriented in a (−ap) conformation with the pyran ring. In the crystal structure of (5a) and (5b), the molecules are linked by an elaborate system of N—H...O and N—H...N hydrogen bonds to generate a zigzag-like construct. In (5c) molecules are linked by N—H...O hydrogen bonds, thereby generating extended chains. The present communication focuses on the detailed and comparative information about spectral behaviors, single-crystal X-ray crystallographic properties and solid-state supramolecular architectures of these synthesized compounds of potential biological interests.

Computing details

For all compounds, data collection: CrysAlis PRO (Oxford Diffraction,2010); cell refinement: CrysAlis PRO (Oxford Diffraction,2010); data reduction: CrysAlis PRO (Oxford Diffraction,2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek,2009).

(gbbb72) 6'-amino-2-oxo-3'-propyl-2'H-spiro [indoline-3,4'-pyrano[2,3-c]pyrazole]-5'-carboxylate

Crystal data

C19H21N5O3S	Z = 2
Mr = 399.47	F(000) = 420
Triclinic, P1	Dx = 1.301 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.2198 (7) Å	Cell parameters from 2060 reflections
b = 9.7844 (8) Å	θ = 4.2–27.9°
c = 11.7345 (10) Å	µ = 0.19 mm^−1
α = 94.456 (7)°	T = 293 K
β = 103.358 (7)°	Block, white
γ = 95.444 (7)°	0.3 × 0.2 × 0.2 mm
V = 1019.85 (14) Å^3

Data collection

Xcalibur, Sapphire3 diffractometer	4006 independent reflections
Radiation source: fine-focus sealed tube	2912 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
Detector resolution: 16.1049 pixels mm^-1	θmax = 26.0°, θmin = 3.6°
ω Scan scans	h = −11→11
Absorption correction: multi-scan Crys Alis Red	k = −11→12
Tmin = 0.894, Tmax = 1.000	l = −14→14
7141 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.134	w = 1/[σ^2(Fo^2) + (0.060P)^2 + 0.1872P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
4006 reflections	Δρmax = 0.38 e Å^−3
257 parameters	Δρmin = −0.40 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.032 (3)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
N1	0.50691 (19)	−0.2449 (2)	0.29736 (16)	0.0429 (5)
H1	0.4308	−0.3024	0.2986	0.052*
C2	0.5560 (2)	−0.2249 (2)	0.19976 (19)	0.0332 (5)
C3	0.6977 (2)	−0.1157 (2)	0.23548 (17)	0.0290 (4)
C4	0.8055 (2)	0.0125 (3)	0.44728 (19)	0.0438 (6)
H4	0.8804	0.0682	0.4261	0.053*
C5	0.7915 (3)	0.0209 (3)	0.5628 (2)	0.0568 (7)
H5	0.8580	0.0826	0.6198	0.068*
C6	0.6805 (3)	−0.0609 (3)	0.5936 (2)	0.0605 (7)
H6	0.6729	−0.0533	0.6714	0.073*
C7	0.5802 (3)	−0.1539 (3)	0.5123 (2)	0.0545 (7)
H7	0.5057	−0.2098	0.5338	0.065*
C8	0.5945 (2)	−0.1610 (2)	0.39744 (19)	0.0379 (5)
C9	0.7063 (2)	−0.0801 (2)	0.36496 (17)	0.0320 (5)
O10	0.50200 (16)	−0.28188 (16)	0.10130 (13)	0.0439 (4)
C11	0.6771 (2)	0.0040 (2)	0.16102 (17)	0.0304 (5)
C12	0.7681 (2)	0.0471 (2)	0.09113 (17)	0.0312 (5)
O13	0.89131 (15)	−0.01421 (16)	0.07912 (13)	0.0412 (4)
C14	0.9175 (2)	−0.1256 (2)	0.14089 (17)	0.0313 (5)
C15	0.8327 (2)	−0.1785 (2)	0.21374 (16)	0.0290 (4)
C16	0.5507 (2)	0.0751 (2)	0.16136 (18)	0.0362 (5)
N17	0.4467 (2)	0.1297 (2)	0.16132 (19)	0.0590 (6)
N18	0.7553 (2)	0.15478 (19)	0.02748 (16)	0.0427 (5)
H18A	0.8201	0.1752	−0.0126	0.051*
H18B	0.6823	0.2036	0.0266	0.051*
C19	0.9051 (2)	−0.2880 (2)	0.25556 (17)	0.0339 (5)
N20	1.02158 (18)	−0.29325 (19)	0.20509 (15)	0.0374 (4)
H20	1.0829	−0.3545	0.2170	0.045*
N21	1.03284 (18)	−0.19197 (19)	0.13324 (15)	0.0373 (4)
C22	0.8760 (3)	−0.3886 (2)	0.3392 (2)	0.0452 (6)
H22A	0.8358	−0.3419	0.3990	0.054*
H22B	0.9709	−0.4179	0.3784	0.054*
C23	0.7689 (3)	−0.5155 (3)	0.2835 (3)	0.0655 (8)
H23A	0.6743	−0.4871	0.2427	0.079*
H23B	0.8101	−0.5648	0.2256	0.079*
C24	0.7406 (5)	−0.6110 (4)	0.3723 (3)	0.1125 (15)
H24A	0.8325	−0.6454	0.4084	0.169*
H24B	0.6676	−0.6869	0.3336	0.169*
H24C	0.7035	−0.5618	0.4315	0.169*
S100	0.29496 (6)	0.41042 (7)	0.21737 (6)	0.0525 (2)
O100	0.25184 (16)	0.54599 (16)	0.26320 (14)	0.0488 (4)
C100	0.1390 (3)	0.2869 (3)	0.2046 (3)	0.0735 (9)
H10A	0.1249	0.2728	0.2815	0.110*
H10B	0.1559	0.2014	0.1666	0.110*
H10C	0.0510	0.3191	0.1586	0.110*
C200	0.2830 (4)	0.4181 (3)	0.0674 (3)	0.0810 (10)
H20A	0.1862	0.4425	0.0300	0.121*
H20B	0.2966	0.3297	0.0324	0.121*
H20C	0.3597	0.4864	0.0573	0.121*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0359 (9)	0.0429 (11)	0.0536 (12)	−0.0038 (9)	0.0205 (9)	0.0071 (9)
C2	0.0293 (10)	0.0284 (11)	0.0443 (12)	0.0076 (9)	0.0112 (9)	0.0067 (9)
C3	0.0269 (9)	0.0306 (11)	0.0312 (10)	0.0041 (8)	0.0100 (8)	0.0035 (8)
C4	0.0413 (12)	0.0496 (14)	0.0404 (12)	0.0051 (11)	0.0114 (10)	0.0004 (11)
C5	0.0576 (15)	0.0750 (19)	0.0348 (13)	0.0141 (14)	0.0064 (11)	−0.0060 (12)
C6	0.0693 (17)	0.086 (2)	0.0337 (13)	0.0282 (16)	0.0197 (13)	0.0087 (13)
C7	0.0576 (15)	0.0669 (18)	0.0550 (15)	0.0179 (14)	0.0358 (13)	0.0248 (13)
C8	0.0388 (11)	0.0411 (13)	0.0405 (12)	0.0111 (10)	0.0182 (10)	0.0102 (10)
C9	0.0329 (10)	0.0364 (12)	0.0314 (10)	0.0102 (9)	0.0134 (9)	0.0084 (9)
O10	0.0403 (8)	0.0412 (9)	0.0452 (9)	0.0027 (7)	0.0031 (7)	−0.0028 (7)
C11	0.0318 (10)	0.0304 (11)	0.0324 (10)	0.0065 (9)	0.0128 (8)	0.0050 (9)
C12	0.0300 (10)	0.0324 (11)	0.0336 (11)	0.0063 (9)	0.0109 (8)	0.0054 (9)
O13	0.0374 (8)	0.0464 (9)	0.0521 (9)	0.0150 (7)	0.0260 (7)	0.0224 (7)
C14	0.0308 (10)	0.0329 (11)	0.0326 (10)	0.0063 (9)	0.0107 (8)	0.0064 (9)
C15	0.0285 (9)	0.0300 (11)	0.0296 (10)	0.0034 (8)	0.0092 (8)	0.0037 (8)
C16	0.0429 (12)	0.0352 (12)	0.0374 (12)	0.0075 (10)	0.0199 (10)	0.0104 (9)
N17	0.0590 (13)	0.0639 (15)	0.0721 (15)	0.0307 (12)	0.0367 (12)	0.0236 (12)
N18	0.0415 (10)	0.0431 (11)	0.0547 (11)	0.0150 (9)	0.0248 (9)	0.0216 (9)
C19	0.0322 (10)	0.0351 (12)	0.0349 (11)	0.0039 (9)	0.0094 (9)	0.0029 (9)
N20	0.0370 (9)	0.0356 (10)	0.0444 (10)	0.0129 (8)	0.0143 (8)	0.0087 (8)
N21	0.0345 (9)	0.0399 (11)	0.0434 (10)	0.0095 (8)	0.0172 (8)	0.0103 (8)
C22	0.0459 (13)	0.0437 (14)	0.0510 (14)	0.0114 (11)	0.0166 (11)	0.0138 (11)
C23	0.0683 (17)	0.0475 (16)	0.0764 (19)	−0.0031 (14)	0.0087 (15)	0.0186 (14)
C24	0.138 (3)	0.079 (3)	0.107 (3)	−0.038 (3)	0.012 (2)	0.039 (2)
S100	0.0382 (3)	0.0428 (4)	0.0731 (5)	0.0117 (3)	0.0078 (3)	−0.0056 (3)
O100	0.0415 (8)	0.0384 (9)	0.0676 (11)	0.0100 (7)	0.0158 (8)	−0.0035 (8)
C100	0.0678 (18)	0.0466 (17)	0.107 (2)	0.0009 (15)	0.0250 (17)	0.0074 (16)
C200	0.101 (2)	0.066 (2)	0.075 (2)	−0.0089 (19)	0.0340 (18)	−0.0142 (17)

Geometric parameters (Å, º)

N1—C2	1.346 (3)	C16—N17	1.140 (3)
N1—C8	1.411 (3)	N18—H18A	0.8600
N1—H1	0.8600	N18—H18B	0.8600
C2—O10	1.215 (2)	C19—N20	1.344 (2)
C2—C3	1.561 (3)	C19—C22	1.492 (3)
C3—C15	1.503 (3)	N20—N21	1.362 (2)
C3—C9	1.514 (3)	N20—H20	0.8600
C3—C11	1.515 (3)	C22—C23	1.512 (3)
C4—C9	1.374 (3)	C22—H22A	0.9700
C4—C5	1.388 (3)	C22—H22B	0.9700
C4—H4	0.9300	C23—C24	1.502 (4)
C5—C6	1.371 (4)	C23—H23A	0.9700
C5—H5	0.9300	C23—H23B	0.9700
C6—C7	1.375 (4)	C24—H24A	0.9600
C6—H6	0.9300	C24—H24B	0.9600
C7—C8	1.381 (3)	C24—H24C	0.9600
C7—H7	0.9300	S100—O100	1.5148 (16)
C8—C9	1.382 (3)	S100—C200	1.746 (3)
C11—C12	1.364 (3)	S100—C100	1.759 (3)
C11—C16	1.414 (3)	C100—H10A	0.9600
C12—N18	1.337 (3)	C100—H10B	0.9600
C12—O13	1.364 (2)	C100—H10C	0.9600
O13—C14	1.365 (2)	C200—H20A	0.9600
C14—N21	1.314 (3)	C200—H20B	0.9600
C14—C15	1.383 (3)	C200—H20C	0.9600
C15—C19	1.379 (3)
C2—N1—C8	112.36 (17)	C12—N18—H18A	120.0
C2—N1—H1	123.8	C12—N18—H18B	120.0
C8—N1—H1	123.8	H18A—N18—H18B	120.0
O10—C2—N1	126.76 (19)	N20—C19—C15	106.17 (18)
O10—C2—C3	125.47 (18)	N20—C19—C22	121.3 (2)
N1—C2—C3	107.77 (17)	C15—C19—C22	132.54 (19)
C15—C3—C9	113.08 (16)	C19—N20—N21	113.34 (18)
C15—C3—C11	106.88 (15)	C19—N20—H20	123.3
C9—C3—C11	114.99 (16)	N21—N20—H20	123.3
C15—C3—C2	110.21 (16)	C14—N21—N20	102.19 (16)
C9—C3—C2	101.15 (15)	C19—C22—C23	114.9 (2)
C11—C3—C2	110.46 (16)	C19—C22—H22A	108.5
C9—C4—C5	118.5 (2)	C23—C22—H22A	108.5
C9—C4—H4	120.7	C19—C22—H22B	108.5
C5—C4—H4	120.7	C23—C22—H22B	108.5
C6—C5—C4	120.6 (2)	H22A—C22—H22B	107.5
C6—C5—H5	119.7	C24—C23—C22	112.5 (2)
C4—C5—H5	119.7	C24—C23—H23A	109.1
C5—C6—C7	121.6 (2)	C22—C23—H23A	109.1
C5—C6—H6	119.2	C24—C23—H23B	109.1
C7—C6—H6	119.2	C22—C23—H23B	109.1
C6—C7—C8	117.4 (2)	H23A—C23—H23B	107.8
C6—C7—H7	121.3	C23—C24—H24A	109.5
C8—C7—H7	121.3	C23—C24—H24B	109.5
C7—C8—C9	121.7 (2)	H24A—C24—H24B	109.5
C7—C8—N1	129.2 (2)	C23—C24—H24C	109.5
C9—C8—N1	109.08 (18)	H24A—C24—H24C	109.5
C4—C9—C8	120.12 (19)	H24B—C24—H24C	109.5
C4—C9—C3	130.31 (18)	O100—S100—C200	106.60 (14)
C8—C9—C3	109.55 (17)	O100—S100—C100	106.25 (12)
C12—C11—C16	116.98 (19)	C200—S100—C100	97.93 (16)
C12—C11—C3	125.56 (18)	S100—C100—H10A	109.5
C16—C11—C3	117.44 (17)	S100—C100—H10B	109.5
N18—C12—O13	109.63 (17)	H10A—C100—H10B	109.5
N18—C12—C11	126.83 (19)	S100—C100—H10C	109.5
O13—C12—C11	123.52 (19)	H10A—C100—H10C	109.5
C12—O13—C14	115.36 (15)	H10B—C100—H10C	109.5
N21—C14—O13	119.42 (17)	S100—C200—H20A	109.5
N21—C14—C15	114.55 (19)	S100—C200—H20B	109.5
O13—C14—C15	126.03 (18)	H20A—C200—H20B	109.5
C19—C15—C14	103.73 (18)	S100—C200—H20C	109.5
C19—C15—C3	133.64 (19)	H20A—C200—H20C	109.5
C14—C15—C3	122.61 (18)	H20B—C200—H20C	109.5
N17—C16—C11	178.5 (2)
C8—N1—C2—O10	−179.5 (2)	C16—C11—C12—N18	4.0 (3)
C8—N1—C2—C3	1.3 (2)	C3—C11—C12—N18	−177.76 (18)
O10—C2—C3—C15	−61.9 (3)	C16—C11—C12—O13	−177.92 (18)
N1—C2—C3—C15	117.33 (18)	C3—C11—C12—O13	0.3 (3)
O10—C2—C3—C9	178.2 (2)	N18—C12—O13—C14	179.54 (17)
N1—C2—C3—C9	−2.6 (2)	C11—C12—O13—C14	1.2 (3)
O10—C2—C3—C11	56.0 (3)	C12—O13—C14—N21	179.16 (17)
N1—C2—C3—C11	−124.79 (18)	C12—O13—C14—C15	−0.9 (3)
C9—C4—C5—C6	−0.3 (4)	N21—C14—C15—C19	0.6 (2)
C4—C5—C6—C7	0.3 (4)	O13—C14—C15—C19	−179.41 (18)
C5—C6—C7—C8	−0.6 (4)	N21—C14—C15—C3	179.05 (16)
C6—C7—C8—C9	1.1 (4)	O13—C14—C15—C3	−0.9 (3)
C6—C7—C8—N1	−179.2 (2)	C9—C3—C15—C19	52.5 (3)
C2—N1—C8—C7	−179.1 (2)	C11—C3—C15—C19	−180.0 (2)
C2—N1—C8—C9	0.6 (3)	C2—C3—C15—C19	−59.9 (3)
C5—C4—C9—C8	0.8 (3)	C9—C3—C15—C14	−125.5 (2)
C5—C4—C9—C3	−177.4 (2)	C11—C3—C15—C14	2.1 (2)
C7—C8—C9—C4	−1.2 (3)	C2—C3—C15—C14	122.1 (2)
N1—C8—C9—C4	179.0 (2)	C12—C11—C16—N17	132 (8)
C7—C8—C9—C3	177.3 (2)	C3—C11—C16—N17	−46 (9)
N1—C8—C9—C3	−2.4 (2)	C14—C15—C19—N20	−0.9 (2)
C15—C3—C9—C4	63.5 (3)	C3—C15—C19—N20	−179.14 (19)
C11—C3—C9—C4	−59.6 (3)	C14—C15—C19—C22	178.8 (2)
C2—C3—C9—C4	−178.7 (2)	C3—C15—C19—C22	0.6 (4)
C15—C3—C9—C8	−114.85 (19)	C15—C19—N20—N21	1.0 (2)
C11—C3—C9—C8	122.00 (19)	C22—C19—N20—N21	−178.72 (17)
C2—C3—C9—C8	3.0 (2)	O13—C14—N21—N20	180.00 (17)
C15—C3—C11—C12	−1.9 (3)	C15—C14—N21—N20	0.0 (2)
C9—C3—C11—C12	124.5 (2)	C19—N20—N21—C14	−0.7 (2)
C2—C3—C11—C12	−121.8 (2)	N20—C19—C22—C23	−92.8 (3)
C15—C3—C11—C16	176.40 (16)	C15—C19—C22—C23	87.6 (3)
C9—C3—C11—C16	−57.2 (2)	C19—C22—C23—C24	−178.4 (3)
C2—C3—C11—C16	56.5 (2)

(gbbb7-100) 6'-amino-5-fluoro-2-oxo-3'-propyl-2'H-spiro [indoline-3,4'-pyrano[2,3-c]pyrazole]-5'-carboxylate

Crystal data

C19H20FN5O3S	Z = 2
Mr = 417.46	F(000) = 436
Triclinic, P1	Dx = 1.302 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.139 (5) Å	Cell parameters from 2413 reflections
b = 9.877 (5) Å	θ = 4.0–28.0°
c = 12.166 (5) Å	µ = 0.19 mm^−1
α = 91.214 (5)°	T = 293 K
β = 102.681 (5)°	Block, white
γ = 95.862 (5)°	0.3 × 0.2 × 0.2 mm
V = 1064.7 (9) Å^3

Data collection

Xcalibur, Sapphire3 diffractometer	4181 independent reflections
Radiation source: fine-focus sealed tube	3075 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
Detector resolution: 16.1049 pixels mm^-1	θmax = 26.0°, θmin = 3.6°
ω Scan scans	h = −9→11
Absorption correction: multi-scan Crys Alis Red	k = −12→11
Tmin = 0.866, Tmax = 1.000	l = −14→14
7947 measured reflections

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.147	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.061P)^2 + 0.5835P] where P = (Fo^2 + 2Fc^2)/3
4181 reflections	(Δ/σ)max < 0.001
265 parameters	Δρmax = 0.60 e Å^−3
0 restraints	Δρmin = −0.52 e Å^−3

Special details

Experimental. CrysAlisPro, Agilent Technologies, Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET) (compiled Feb 1 2013,16:14:44) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
F1	0.8479 (3)	0.5627 (3)	1.11800 (18)	0.1176 (10)
N1	0.4905 (2)	0.2328 (2)	0.77908 (19)	0.0465 (6)
H1	0.4127	0.1756	0.7780	0.056*
C2	0.5489 (2)	0.2593 (2)	0.6879 (2)	0.0353 (5)
C3	0.6902 (2)	0.3666 (2)	0.72566 (19)	0.0306 (5)
C4	0.7852 (3)	0.4778 (3)	0.9300 (2)	0.0498 (7)
H4	0.8650	0.5338	0.9135	0.060*
C5	0.7563 (4)	0.4769 (4)	1.0373 (3)	0.0670 (9)
C6	0.6414 (4)	0.3964 (4)	1.0646 (3)	0.0691 (9)
H6	0.6273	0.3995	1.1380	0.083*
C7	0.5455 (4)	0.3100 (3)	0.9835 (3)	0.0617 (8)
H7	0.4661	0.2539	1.0007	0.074*
C8	0.5716 (3)	0.3096 (3)	0.8757 (2)	0.0414 (6)
C9	0.6897 (3)	0.3917 (2)	0.84951 (19)	0.0347 (5)
O10	0.50154 (19)	0.20923 (18)	0.59306 (15)	0.0464 (5)
C11	0.6719 (2)	0.4920 (2)	0.65610 (19)	0.0319 (5)
C12	0.7633 (2)	0.5389 (2)	0.5868 (2)	0.0329 (5)
O13	0.88623 (18)	0.47828 (17)	0.57302 (15)	0.0426 (4)
C14	0.9135 (2)	0.3653 (2)	0.63426 (19)	0.0324 (5)
C15	0.8291 (2)	0.3089 (2)	0.70657 (19)	0.0310 (5)
C16	0.5463 (3)	0.5631 (2)	0.6599 (2)	0.0390 (6)
N17	0.4428 (3)	0.6179 (3)	0.6646 (2)	0.0621 (7)
N18	0.7519 (2)	0.6504 (2)	0.52656 (19)	0.0440 (5)
H18A	0.8171	0.6734	0.4872	0.053*
H18B	0.6792	0.6991	0.5272	0.053*
C19	0.9031 (3)	0.1994 (2)	0.7477 (2)	0.0376 (6)
N20	1.0200 (2)	0.1974 (2)	0.69739 (18)	0.0407 (5)
H20	1.0822	0.1368	0.7091	0.049*
N21	1.0304 (2)	0.3004 (2)	0.62628 (18)	0.0395 (5)
C22	0.8744 (3)	0.0946 (3)	0.8299 (2)	0.0523 (7)
H22A	0.8277	0.1357	0.8847	0.063*
H22B	0.9705	0.0685	0.8701	0.063*
C23	0.7755 (5)	−0.0317 (3)	0.7778 (3)	0.0818 (11)
H23A	0.6783	−0.0066	0.7386	0.098*
H23B	0.8212	−0.0732	0.7225	0.098*
C24	0.7522 (7)	−0.1335 (5)	0.8636 (5)	0.139 (2)
H24A	0.8458	−0.1690	0.8945	0.208*
H24B	0.6784	−0.2067	0.8283	0.208*
H24C	0.7174	−0.0901	0.9229	0.208*
S100	0.71055 (7)	0.10743 (7)	0.28977 (7)	0.0545 (2)
O100	0.75793 (19)	−0.02339 (17)	0.24811 (17)	0.0504 (5)
C100	0.8658 (4)	0.2326 (3)	0.3013 (3)	0.0733 (10)
H10A	0.9540	0.2008	0.3471	0.110*
H10B	0.8451	0.3150	0.3354	0.110*
H10C	0.8829	0.2503	0.2275	0.110*
C200	0.7185 (5)	0.0907 (4)	0.4336 (3)	0.0850 (12)
H20A	0.6402	0.0225	0.4434	0.128*
H20B	0.7046	0.1763	0.4667	0.128*
H20C	0.8150	0.0642	0.4698	0.128*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F1	0.1045 (17)	0.180 (3)	0.0547 (13)	−0.0028 (17)	0.0029 (11)	−0.0554 (15)
N1	0.0407 (11)	0.0462 (12)	0.0557 (14)	−0.0077 (10)	0.0232 (10)	0.0021 (11)
C2	0.0319 (12)	0.0331 (12)	0.0425 (14)	0.0061 (10)	0.0107 (10)	0.0045 (11)
C3	0.0320 (11)	0.0320 (12)	0.0304 (12)	0.0031 (9)	0.0124 (9)	0.0018 (9)
C4	0.0467 (15)	0.0622 (18)	0.0391 (15)	0.0035 (13)	0.0080 (12)	−0.0057 (13)
C5	0.066 (2)	0.094 (3)	0.0397 (17)	0.0182 (19)	0.0053 (15)	−0.0149 (17)
C6	0.079 (2)	0.103 (3)	0.0351 (16)	0.031 (2)	0.0226 (16)	0.0064 (17)
C7	0.070 (2)	0.073 (2)	0.0561 (19)	0.0158 (17)	0.0395 (16)	0.0192 (16)
C8	0.0428 (13)	0.0454 (14)	0.0428 (15)	0.0096 (11)	0.0212 (11)	0.0083 (12)
C9	0.0361 (12)	0.0397 (13)	0.0315 (13)	0.0095 (10)	0.0120 (10)	0.0057 (10)
O10	0.0437 (10)	0.0456 (10)	0.0453 (11)	0.0017 (8)	0.0025 (8)	−0.0060 (9)
C11	0.0342 (12)	0.0322 (12)	0.0318 (12)	0.0042 (10)	0.0122 (10)	0.0030 (10)
C12	0.0311 (11)	0.0345 (12)	0.0347 (13)	0.0047 (10)	0.0101 (10)	0.0035 (10)
O13	0.0391 (9)	0.0457 (10)	0.0529 (11)	0.0138 (8)	0.0257 (8)	0.0210 (8)
C14	0.0315 (11)	0.0353 (12)	0.0323 (12)	0.0040 (10)	0.0107 (9)	0.0058 (10)
C15	0.0294 (11)	0.0327 (12)	0.0319 (12)	0.0024 (9)	0.0094 (9)	0.0018 (10)
C16	0.0472 (14)	0.0369 (13)	0.0386 (14)	0.0076 (11)	0.0197 (11)	0.0064 (11)
N17	0.0650 (16)	0.0635 (16)	0.0731 (18)	0.0301 (13)	0.0362 (14)	0.0161 (14)
N18	0.0420 (11)	0.0428 (12)	0.0558 (14)	0.0127 (10)	0.0238 (10)	0.0198 (10)
C19	0.0374 (12)	0.0376 (13)	0.0394 (14)	0.0038 (10)	0.0117 (11)	0.0044 (11)
N20	0.0386 (11)	0.0407 (12)	0.0473 (13)	0.0127 (9)	0.0148 (9)	0.0089 (10)
N21	0.0359 (11)	0.0434 (12)	0.0439 (12)	0.0088 (9)	0.0158 (9)	0.0118 (10)
C22	0.0590 (17)	0.0476 (16)	0.0569 (18)	0.0140 (13)	0.0218 (14)	0.0186 (14)
C23	0.088 (3)	0.061 (2)	0.094 (3)	−0.0043 (19)	0.019 (2)	0.023 (2)
C24	0.176 (5)	0.088 (3)	0.141 (5)	−0.045 (3)	0.034 (4)	0.045 (3)
S100	0.0383 (4)	0.0447 (4)	0.0788 (6)	0.0091 (3)	0.0085 (3)	−0.0102 (4)
O100	0.0448 (10)	0.0390 (10)	0.0700 (13)	0.0099 (8)	0.0168 (9)	−0.0040 (9)
C100	0.0589 (19)	0.0499 (18)	0.108 (3)	−0.0031 (15)	0.0174 (19)	−0.0022 (19)
C200	0.111 (3)	0.068 (2)	0.078 (3)	−0.013 (2)	0.039 (2)	−0.017 (2)

Geometric parameters (Å, º)

F1—C5	1.357 (4)	C16—N17	1.148 (3)
N1—C2	1.352 (3)	N18—H18A	0.8600
N1—C8	1.404 (3)	N18—H18B	0.8600
N1—H1	0.8600	C19—N20	1.344 (3)
C2—O10	1.215 (3)	C19—C22	1.497 (3)
C2—C3	1.563 (3)	N20—N21	1.359 (3)
C3—C15	1.504 (3)	N20—H20	0.8600
C3—C11	1.518 (3)	C22—C23	1.503 (4)
C3—C9	1.523 (3)	C22—H22A	0.9700
C4—C9	1.372 (3)	C22—H22B	0.9700
C4—C5	1.388 (4)	C23—C24	1.499 (5)
C4—H4	0.9300	C23—H23A	0.9700
C5—C6	1.356 (5)	C23—H23B	0.9700
C6—C7	1.380 (5)	C24—H24A	0.9600
C6—H6	0.9300	C24—H24B	0.9600
C7—C8	1.384 (4)	C24—H24C	0.9600
C7—H7	0.9300	S100—O100	1.5155 (19)
C8—C9	1.380 (3)	S100—C200	1.748 (4)
C11—C12	1.367 (3)	S100—C100	1.763 (3)
C11—C16	1.414 (3)	C100—H10A	0.9600
C12—N18	1.335 (3)	C100—H10B	0.9600
C12—O13	1.366 (3)	C100—H10C	0.9600
O13—C14	1.369 (3)	C200—H20A	0.9600
C14—N21	1.320 (3)	C200—H20B	0.9600
C14—C15	1.382 (3)	C200—H20C	0.9600
C15—C19	1.379 (3)
C2—N1—C8	112.2 (2)	C12—N18—H18A	120.0
C2—N1—H1	123.9	C12—N18—H18B	120.0
C8—N1—H1	123.9	H18A—N18—H18B	120.0
O10—C2—N1	126.8 (2)	N20—C19—C15	106.2 (2)
O10—C2—C3	125.4 (2)	N20—C19—C22	121.2 (2)
N1—C2—C3	107.8 (2)	C15—C19—C22	132.6 (2)
C15—C3—C11	107.05 (18)	C19—N20—N21	113.5 (2)
C15—C3—C9	113.97 (19)	C19—N20—H20	123.2
C11—C3—C9	114.10 (18)	N21—N20—H20	123.2
C15—C3—C2	110.29 (18)	C14—N21—N20	102.09 (18)
C11—C3—C2	110.39 (18)	C19—C22—C23	114.7 (3)
C9—C3—C2	100.98 (18)	C19—C22—H22A	108.6
C9—C4—C5	116.4 (3)	C23—C22—H22A	108.6
C9—C4—H4	121.8	C19—C22—H22B	108.6
C5—C4—H4	121.8	C23—C22—H22B	108.6
C6—C5—F1	119.0 (3)	H22A—C22—H22B	107.6
C6—C5—C4	123.5 (3)	C24—C23—C22	112.4 (4)
F1—C5—C4	117.5 (3)	C24—C23—H23A	109.1
C5—C6—C7	120.0 (3)	C22—C23—H23A	109.1
C5—C6—H6	120.0	C24—C23—H23B	109.1
C7—C6—H6	120.0	C22—C23—H23B	109.1
C6—C7—C8	117.6 (3)	H23A—C23—H23B	107.9
C6—C7—H7	121.2	C23—C24—H24A	109.5
C8—C7—H7	121.2	C23—C24—H24B	109.5
C9—C8—C7	121.6 (3)	H24A—C24—H24B	109.5
C9—C8—N1	109.7 (2)	C23—C24—H24C	109.5
C7—C8—N1	128.6 (3)	H24A—C24—H24C	109.5
C4—C9—C8	120.9 (2)	H24B—C24—H24C	109.5
C4—C9—C3	129.9 (2)	O100—S100—C200	106.18 (16)
C8—C9—C3	109.2 (2)	O100—S100—C100	106.52 (14)
C12—C11—C16	117.3 (2)	C200—S100—C100	98.10 (19)
C12—C11—C3	125.5 (2)	S100—C100—H10A	109.5
C16—C11—C3	117.12 (19)	S100—C100—H10B	109.5
N18—C12—O13	109.72 (19)	H10A—C100—H10B	109.5
N18—C12—C11	126.8 (2)	S100—C100—H10C	109.5
O13—C12—C11	123.5 (2)	H10A—C100—H10C	109.5
C12—O13—C14	115.28 (17)	H10B—C100—H10C	109.5
N21—C14—O13	119.33 (19)	S100—C200—H20A	109.5
N21—C14—C15	114.4 (2)	S100—C200—H20B	109.5
O13—C14—C15	126.2 (2)	H20A—C200—H20B	109.5
C19—C15—C14	103.8 (2)	S100—C200—H20C	109.5
C19—C15—C3	133.8 (2)	H20A—C200—H20C	109.5
C14—C15—C3	122.5 (2)	H20B—C200—H20C	109.5
N17—C16—C11	178.1 (3)
C8—N1—C2—O10	−179.3 (2)	C9—C3—C11—C16	−53.6 (3)
C8—N1—C2—C3	1.0 (3)	C2—C3—C11—C16	59.2 (3)
O10—C2—C3—C15	−60.4 (3)	C16—C11—C12—N18	4.2 (4)
N1—C2—C3—C15	119.4 (2)	C3—C11—C12—N18	−178.5 (2)
O10—C2—C3—C11	57.7 (3)	C16—C11—C12—O13	−178.4 (2)
N1—C2—C3—C11	−122.5 (2)	C3—C11—C12—O13	−1.1 (4)
O10—C2—C3—C9	178.7 (2)	N18—C12—O13—C14	177.6 (2)
N1—C2—C3—C9	−1.5 (2)	C11—C12—O13—C14	−0.1 (3)
C9—C4—C5—C6	0.2 (5)	C12—O13—C14—N21	−179.8 (2)
C9—C4—C5—F1	−179.1 (3)	C12—O13—C14—C15	0.2 (3)
F1—C5—C6—C7	179.0 (3)	N21—C14—C15—C19	0.7 (3)
C4—C5—C6—C7	−0.3 (5)	O13—C14—C15—C19	−179.3 (2)
C5—C6—C7—C8	−0.1 (5)	N21—C14—C15—C3	−179.0 (2)
C6—C7—C8—C9	0.4 (4)	O13—C14—C15—C3	1.0 (4)
C6—C7—C8—N1	−179.4 (3)	C11—C3—C15—C19	178.6 (2)
C2—N1—C8—C9	0.0 (3)	C9—C3—C15—C19	51.4 (3)
C2—N1—C8—C7	179.9 (3)	C2—C3—C15—C19	−61.3 (3)
C5—C4—C9—C8	0.2 (4)	C11—C3—C15—C14	−1.9 (3)
C5—C4—C9—C3	−179.3 (3)	C9—C3—C15—C14	−129.0 (2)
C7—C8—C9—C4	−0.5 (4)	C2—C3—C15—C14	118.3 (2)
N1—C8—C9—C4	179.4 (2)	C14—C15—C19—N20	−1.0 (3)
C7—C8—C9—C3	179.1 (2)	C3—C15—C19—N20	178.7 (2)
N1—C8—C9—C3	−1.1 (3)	C14—C15—C19—C22	179.5 (3)
C15—C3—C9—C4	62.8 (3)	C3—C15—C19—C22	−0.9 (5)
C11—C3—C9—C4	−60.6 (3)	C15—C19—N20—N21	1.0 (3)
C2—C3—C9—C4	−179.0 (3)	C22—C19—N20—N21	−179.4 (2)
C15—C3—C9—C8	−116.7 (2)	O13—C14—N21—N20	179.9 (2)
C11—C3—C9—C8	119.9 (2)	C15—C14—N21—N20	−0.1 (3)
C2—C3—C9—C8	1.5 (2)	C19—N20—N21—C14	−0.6 (3)
C15—C3—C11—C12	2.0 (3)	N20—C19—C22—C23	−88.9 (3)
C9—C3—C11—C12	129.1 (2)	C15—C19—C22—C23	90.6 (4)
C2—C3—C11—C12	−118.1 (2)	C19—C22—C23—C24	179.3 (4)
C15—C3—C11—C16	179.3 (2)

(gbbb378) Methyl 6'-amino,5'-cyano-1-methyl-2-oxo-2'H-spiro [indoline-3,4'-pyrano[2,3-c]pyrazole]-3'-carboxylate

Crystal data

C68H52N20O17	F(000) = 1472
Mr = 1421.30	Dx = 1.440 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1907 reflections
a = 7.6155 (6) Å	θ = 3.9–26.9°
b = 27.2024 (12) Å	µ = 0.11 mm^−1
c = 16.0187 (13) Å	T = 293 K
β = 98.988 (8)°	Block, white
V = 3277.7 (4) Å^3	0.3 × 0.2 × 0.2 mm
Z = 2

Data collection

Xcalibur, Sapphire3 diffractometer	2870 independent reflections
Radiation source: fine-focus sealed tube	1803 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
Detector resolution: 16.1049 pixels mm^-1	θmax = 25.0°, θmin = 3.5°
ω Scan scans	h = −9→7
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET) (compiled Feb 1 2013,16:14:44) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −32→31
Tmin = 0.556, Tmax = 1.000	l = −19→15
6064 measured reflections

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.139	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0627P)^2 + 0.2153P] where P = (Fo^2 + 2Fc^2)/3
2870 reflections	(Δ/σ)max < 0.001
242 parameters	Δρmax = 0.20 e Å^−3
0 restraints	Δρmin = −0.22 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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)
N1	−0.1963 (3)	0.08268 (8)	0.48147 (17)	0.0529 (7)
C1	−0.3611 (4)	0.05446 (11)	0.4764 (2)	0.0778 (11)
H1A	−0.4127	0.0598	0.5266	0.117*
H1B	−0.3358	0.0201	0.4712	0.117*
H1C	−0.4431	0.0649	0.4279	0.117*
C2	−0.1825 (4)	0.12454 (9)	0.43802 (19)	0.0448 (7)
C3	0.0100 (3)	0.14503 (8)	0.46383 (16)	0.0368 (6)
C4	0.2528 (4)	0.10567 (10)	0.57846 (18)	0.0497 (8)
H4	0.3393	0.1290	0.5727	0.060*
C5	0.2890 (5)	0.06728 (11)	0.6358 (2)	0.0628 (9)
H5	0.4009	0.0648	0.6684	0.075*
C6	0.1603 (6)	0.03271 (11)	0.6447 (2)	0.0734 (11)
H6	0.1859	0.0077	0.6843	0.088*
C7	−0.0065 (5)	0.03480 (10)	0.5956 (2)	0.0650 (10)
H7	−0.0930	0.0114	0.6012	0.078*
C8	−0.0394 (4)	0.07266 (9)	0.53847 (19)	0.0478 (8)
C9	0.0882 (4)	0.10852 (8)	0.53083 (18)	0.0413 (7)
O10	−0.3009 (3)	0.14337 (7)	0.38778 (14)	0.0576 (6)
C11	0.1088 (3)	0.14525 (8)	0.38775 (16)	0.0396 (7)
C12	0.1572 (3)	0.18595 (9)	0.34838 (17)	0.0422 (7)
O13	0.1237 (2)	0.23291 (6)	0.37209 (11)	0.0473 (5)
C14	0.0518 (3)	0.23634 (9)	0.44520 (17)	0.0403 (7)
C15	0.0003 (3)	0.19761 (8)	0.49119 (16)	0.0373 (6)
C16	0.1607 (4)	0.09975 (10)	0.35688 (18)	0.0489 (8)
N17	0.2063 (4)	0.06348 (9)	0.33073 (19)	0.0780 (10)
N18	0.2433 (3)	0.18685 (8)	0.28187 (15)	0.0605 (7)
H18A	0.2731	0.1598	0.2602	0.073*
H18B	0.2688	0.2145	0.2607	0.073*
C19	−0.0604 (3)	0.22109 (9)	0.55811 (17)	0.0390 (6)
N20	−0.0401 (3)	0.26986 (7)	0.54618 (15)	0.0463 (6)
H20	−0.0681	0.2919	0.5803	0.056*
N21	0.0284 (3)	0.28061 (7)	0.47557 (15)	0.0479 (6)
C22	−0.1409 (3)	0.20457 (10)	0.63042 (18)	0.0458 (7)
O23	−0.1766 (3)	0.23144 (8)	0.68472 (14)	0.0741 (7)
O24	−0.1703 (3)	0.15704 (7)	0.62814 (12)	0.0578 (6)
C25	−0.2494 (5)	0.13709 (13)	0.6968 (2)	0.0824 (12)
H25A	−0.1713	0.1424	0.7491	0.124*
H25B	−0.2686	0.1025	0.6882	0.124*
H25C	−0.3611	0.1531	0.6988	0.124*
O1	0.5000	−0.0191 (4)	0.7500	0.193 (5)	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0594 (15)	0.0374 (13)	0.0684 (19)	−0.0127 (12)	0.0298 (15)	−0.0059 (13)
C1	0.072 (2)	0.0616 (19)	0.109 (3)	−0.0312 (18)	0.044 (2)	−0.018 (2)
C2	0.0539 (18)	0.0326 (15)	0.053 (2)	−0.0036 (14)	0.0232 (16)	−0.0087 (14)
C3	0.0451 (14)	0.0297 (13)	0.0386 (16)	−0.0042 (12)	0.0155 (13)	−0.0006 (12)
C4	0.0660 (19)	0.0417 (16)	0.0437 (19)	0.0073 (14)	0.0153 (16)	0.0022 (14)
C5	0.090 (2)	0.0523 (17)	0.047 (2)	0.0188 (18)	0.0146 (19)	0.0058 (16)
C6	0.126 (3)	0.0440 (18)	0.056 (2)	0.021 (2)	0.031 (3)	0.0149 (17)
C7	0.100 (3)	0.0343 (16)	0.070 (3)	−0.0042 (17)	0.043 (2)	0.0073 (16)
C8	0.071 (2)	0.0273 (13)	0.052 (2)	0.0013 (14)	0.0315 (18)	−0.0023 (13)
C9	0.0554 (17)	0.0306 (13)	0.0424 (17)	0.0027 (13)	0.0218 (15)	−0.0007 (13)
O10	0.0531 (12)	0.0528 (12)	0.0662 (16)	−0.0003 (10)	0.0075 (12)	−0.0064 (11)
C11	0.0496 (15)	0.0339 (13)	0.0373 (17)	−0.0017 (12)	0.0130 (13)	0.0041 (12)
C12	0.0470 (16)	0.0420 (15)	0.0385 (17)	−0.0028 (13)	0.0099 (14)	0.0014 (13)
O13	0.0605 (12)	0.0343 (10)	0.0499 (13)	−0.0026 (9)	0.0171 (10)	0.0090 (9)
C14	0.0418 (15)	0.0333 (14)	0.0454 (18)	−0.0012 (12)	0.0059 (14)	0.0033 (13)
C15	0.0395 (14)	0.0316 (13)	0.0413 (17)	0.0002 (11)	0.0079 (13)	0.0006 (12)
C16	0.0642 (19)	0.0411 (15)	0.0461 (19)	−0.0076 (14)	0.0234 (16)	−0.0007 (14)
N17	0.112 (2)	0.0472 (15)	0.086 (2)	−0.0004 (16)	0.049 (2)	−0.0100 (15)
N18	0.0823 (18)	0.0528 (14)	0.0538 (17)	−0.0112 (13)	0.0332 (15)	0.0042 (13)
C19	0.0398 (14)	0.0336 (13)	0.0433 (17)	0.0025 (12)	0.0060 (13)	−0.0040 (13)
N20	0.0517 (14)	0.0359 (12)	0.0509 (16)	0.0027 (10)	0.0065 (12)	−0.0094 (11)
N21	0.0531 (14)	0.0327 (12)	0.0580 (17)	0.0003 (11)	0.0086 (13)	−0.0008 (12)
C22	0.0463 (16)	0.0464 (16)	0.0455 (19)	0.0071 (13)	0.0096 (15)	−0.0072 (14)
O23	0.0987 (18)	0.0672 (14)	0.0623 (16)	0.0057 (12)	0.0304 (14)	−0.0243 (12)
O24	0.0777 (14)	0.0472 (11)	0.0560 (14)	−0.0025 (10)	0.0342 (12)	−0.0007 (10)
C25	0.104 (3)	0.086 (2)	0.068 (3)	−0.016 (2)	0.047 (2)	0.008 (2)
O1	0.156 (10)	0.200 (11)	0.218 (14)	0.000	0.018 (10)	0.000

Geometric parameters (Å, º)

N1—C2	1.347 (3)	C11—C12	1.353 (3)
N1—C8	1.412 (4)	C11—C16	1.412 (3)
N1—C1	1.463 (3)	C12—N18	1.336 (3)
C1—H1A	0.9600	C12—O13	1.368 (3)
C1—H1B	0.9600	O13—C14	1.372 (3)
C1—H1C	0.9600	C14—N21	1.321 (3)
C2—O10	1.223 (3)	C14—C15	1.377 (3)
C2—C3	1.563 (4)	C15—C19	1.388 (3)
C3—C15	1.501 (3)	C16—N17	1.147 (3)
C3—C9	1.514 (4)	N18—H18A	0.8600
C3—C11	1.529 (3)	N18—H18B	0.8600
C4—C9	1.364 (4)	C19—N20	1.353 (3)
C4—C5	1.389 (4)	C19—C22	1.463 (3)
C4—H4	0.9300	N20—N21	1.349 (3)
C5—C6	1.382 (4)	N20—H20	0.8600
C5—H5	0.9300	C22—O23	1.199 (3)
C6—C7	1.386 (5)	C22—O24	1.312 (3)
C6—H6	0.9300	O24—C25	1.440 (3)
C7—C8	1.375 (4)	C25—H25A	0.9600
C7—H7	0.9300	C25—H25B	0.9600
C8—C9	1.396 (3)	C25—H25C	0.9600
C2—N1—C8	111.7 (2)	C8—C9—C3	108.6 (3)
C2—N1—C1	123.4 (3)	C12—C11—C16	116.3 (2)
C8—N1—C1	124.5 (3)	C12—C11—C3	125.3 (2)
N1—C1—H1A	109.5	C16—C11—C3	118.4 (2)
N1—C1—H1B	109.5	N18—C12—C11	126.1 (2)
H1A—C1—H1B	109.5	N18—C12—O13	109.9 (2)
N1—C1—H1C	109.5	C11—C12—O13	124.0 (2)
H1A—C1—H1C	109.5	C12—O13—C14	114.66 (18)
H1B—C1—H1C	109.5	N21—C14—O13	118.1 (2)
O10—C2—N1	125.8 (3)	N21—C14—C15	115.7 (2)
O10—C2—C3	126.1 (2)	O13—C14—C15	126.1 (2)
N1—C2—C3	108.1 (3)	C14—C15—C19	102.6 (2)
C15—C3—C9	116.7 (2)	C14—C15—C3	122.8 (2)
C15—C3—C11	106.36 (18)	C19—C15—C3	134.6 (2)
C9—C3—C11	112.31 (19)	N17—C16—C11	178.1 (3)
C15—C3—C2	109.28 (19)	C12—N18—H18A	120.0
C9—C3—C2	101.7 (2)	C12—N18—H18B	120.0
C11—C3—C2	110.4 (2)	H18A—N18—H18B	120.0
C9—C4—C5	118.8 (3)	N20—C19—C15	106.4 (2)
C9—C4—H4	120.6	N20—C19—C22	119.0 (2)
C5—C4—H4	120.6	C15—C19—C22	134.5 (2)
C6—C5—C4	120.6 (3)	N21—N20—C19	113.5 (2)
C6—C5—H5	119.7	N21—N20—H20	123.3
C4—C5—H5	119.7	C19—N20—H20	123.3
C5—C6—C7	121.0 (3)	C14—N21—N20	101.7 (2)
C5—C6—H6	119.5	O23—C22—O24	124.3 (2)
C7—C6—H6	119.5	O23—C22—C19	123.9 (3)
C8—C7—C6	117.7 (3)	O24—C22—C19	111.8 (2)
C8—C7—H7	121.2	C22—O24—C25	116.1 (2)
C6—C7—H7	121.2	O24—C25—H25A	109.5
C7—C8—C9	121.7 (3)	O24—C25—H25B	109.5
C7—C8—N1	128.5 (3)	H25A—C25—H25B	109.5
C9—C8—N1	109.8 (2)	O24—C25—H25C	109.5
C4—C9—C8	120.2 (3)	H25A—C25—H25C	109.5
C4—C9—C3	131.2 (2)	H25B—C25—H25C	109.5
C8—N1—C2—O10	−176.0 (2)	C9—C3—C11—C16	41.7 (3)
C1—N1—C2—O10	−2.3 (4)	C2—C3—C11—C16	−71.0 (3)
C8—N1—C2—C3	3.3 (3)	C16—C11—C12—N18	2.4 (4)
C1—N1—C2—C3	177.0 (2)	C3—C11—C12—N18	−179.9 (3)
O10—C2—C3—C15	52.3 (3)	C16—C11—C12—O13	−177.5 (3)
N1—C2—C3—C15	−127.0 (2)	C3—C11—C12—O13	0.2 (4)
O10—C2—C3—C9	176.3 (3)	N18—C12—O13—C14	−173.7 (2)
N1—C2—C3—C9	−3.1 (2)	C11—C12—O13—C14	6.2 (4)
O10—C2—C3—C11	−64.4 (3)	C12—O13—C14—N21	175.0 (2)
N1—C2—C3—C11	116.3 (2)	C12—O13—C14—C15	−5.0 (4)
C9—C4—C5—C6	−0.3 (4)	N21—C14—C15—C19	−0.5 (3)
C4—C5—C6—C7	1.4 (5)	O13—C14—C15—C19	179.4 (2)
C5—C6—C7—C8	−0.6 (5)	N21—C14—C15—C3	177.2 (2)
C6—C7—C8—C9	−1.3 (4)	O13—C14—C15—C3	−2.8 (4)
C6—C7—C8—N1	179.6 (3)	C9—C3—C15—C14	134.3 (3)
C2—N1—C8—C7	176.9 (3)	C11—C3—C15—C14	8.1 (3)
C1—N1—C8—C7	3.3 (4)	C2—C3—C15—C14	−111.1 (3)
C2—N1—C8—C9	−2.2 (3)	C9—C3—C15—C19	−48.8 (4)
C1—N1—C8—C9	−175.8 (2)	C11—C3—C15—C19	−175.0 (3)
C5—C4—C9—C8	−1.5 (4)	C2—C3—C15—C19	65.8 (4)
C5—C4—C9—C3	−179.5 (2)	C14—C15—C19—N20	0.0 (3)
C7—C8—C9—C4	2.4 (4)	C3—C15—C19—N20	−177.4 (3)
N1—C8—C9—C4	−178.4 (2)	C14—C15—C19—C22	177.4 (3)
C7—C8—C9—C3	−179.2 (2)	C3—C15—C19—C22	0.0 (5)
N1—C8—C9—C3	0.0 (3)	C15—C19—N20—N21	0.6 (3)
C15—C3—C9—C4	−61.3 (3)	C22—C19—N20—N21	−177.3 (2)
C11—C3—C9—C4	61.9 (4)	O13—C14—N21—N20	−179.1 (2)
C2—C3—C9—C4	179.9 (3)	C15—C14—N21—N20	0.9 (3)
C15—C3—C9—C8	120.5 (2)	C19—N20—N21—C14	−0.9 (3)
C11—C3—C9—C8	−116.2 (2)	N20—C19—C22—O23	−6.8 (4)
C2—C3—C9—C8	1.8 (2)	C15—C19—C22—O23	176.0 (3)
C15—C3—C11—C12	−7.0 (4)	N20—C19—C22—O24	172.7 (2)
C9—C3—C11—C12	−135.9 (3)	C15—C19—C22—O24	−4.5 (4)
C2—C3—C11—C12	111.4 (3)	O23—C22—O24—C25	−0.5 (4)
C15—C3—C11—C16	170.6 (2)	C19—C22—O24—C25	180.0 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···N17^i	0.93	2.53	3.379 (4)	153
N18—H18A···O10^ii	0.86	2.45	3.058 (3)	128
N18—H18B···O23^iii	0.86	1.99	2.834 (3)	165
N20—H20···O10^iv	0.86	2.13	2.925 (3)	155

Symmetry codes: (i) −x, −y, −z+1; (ii) −x, y, −z+1/2; (iii) x+1/2, −y+1/2, z−1/2; (iv) −x−1/2, −y+1/2, −z+1.