Crystal structure of 4-(6-bromo-4-oxo-4H-chromen-3-yl)-2-methyl-amino-3-nitro-pyrano[3,2-c]chromen-5(4H)-one chloro-form monosolvate.

In the title compound, C22H13BrN2O7·CHCl3, the pyran ring adopts a shallow sofa conformation with the C atom bearing the bromo-chromene system as the flap [deviation = 0.291 (3) Å]. The dihedral angle between the pyran fused-ring system (all atoms; r.m.s. deviation = 0.032 Å) and the bromo-chromene ring system (r.m.s. deviation = 0.027 Å) is 87.56 (9)°. An intra-molecular N-H⋯O hydrogen bond closes an S(6) ring. The Cl atoms of the solvent mol-ecule are disordered over two sets of sites in a 0.515 (6):0.485 (6) ratio. In the crystal, inversion dimers linked by pairs of N-H⋯O hydrogen bonds generate R 2 (2)(12) loops. The packing also features C-H⋯O and very weak π-π [centroid-centroid separation = 3.960 (2) Å] inter-actions, which link the dimers into a three-dimensional network.

Related literature

For background to chromene derivatives, see: Ercole et al. (2009 ▸); Geen et al. (1996 ▸) Khan et al. (2010 ▸); Raj et al. (2010 ▸). For a related structure, see: Raja et al. (2015 ▸).

Experimental

Crystal data

C22H13BrN2O7·CHCl3

M = 616.62

Triclinic,

a = 9.8816 (2) Å

b = 11.9237 (3) Å

c = 12.0616 (3) Å

α = 80.804 (1)°

β = 68.422 (1)°

γ = 70.735 (1)°

V = 1246.36 (5) Å3

Z = 2

Mo Kα radiation

μ = 2.02 mm−1

T = 293 K

0.35 × 0.30 × 0.25 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▸) T min = 0.539, T max = 0.632

17277 measured reflections

4389 independent reflections

3672 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.120

S = 1.04

4389 reflections

353 parameters

114 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.63 e Å−3

Δρmin = −0.53 e Å−3

Data collection: APEX2 (Bruker, 2008 ▸); cell refinement: SAINT (Bruker, 2008 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015014553/hb7473sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015014553/hb7473Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015014553/hb7473Isup3.cml

Click here for additional data file.

S . DOI: 10.1107/S2056989015014553/hb7473fig1.tif

The mol­ecular structure of the title mol­ecule, with displacement ellipsoids drawn at 30% probability level. The intra­molecular hydrogen bond, which generates an S(6) ring motif, is shown as a dashed line.

Click here for additional data file.

. DOI: 10.1107/S2056989015014553/hb7473fig2.tif

Packing diagram showing the chain motif (12) along the [100] direction.

CCDC reference: 1416576

Additional supporting information: crystallographic information; 3D view; checkCIF report

C22H13BrN2O7·CHCl3	Z = 2
Mr = 616.62	F(000) = 616
Triclinic, P1	Dx = 1.643 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.8816 (2) Å	Cell parameters from 3672 reflections
b = 11.9237 (3) Å	θ = 1.8–25.0°
c = 12.0616 (3) Å	µ = 2.02 mm−1
α = 80.804 (1)°	T = 293 K
β = 68.422 (1)°	Colourless, block
γ = 70.735 (1)°	0.35 × 0.30 × 0.25 mm
V = 1246.36 (5) Å3

Bruker SMART APEXII CCD diffractometer	4389 independent reflections
Radiation source: fine-focus sealed tube	3672 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
ω and φ scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −11→10
Tmin = 0.539, Tmax = 0.632	k = −14→14
17277 measured reflections	l = −14→14

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0626P)2 + 1.1978P] where P = (Fo2 + 2Fc2)/3
4389 reflections	(Δ/σ)max < 0.001
353 parameters	Δρmax = 0.63 e Å−3
114 restraints	Δρmin = −0.53 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.6175 (4)	0.6474 (3)	0.0736 (4)	0.0442 (9)
C2	0.5491 (5)	0.6922 (3)	−0.1038 (3)	0.0447 (9)
C3	0.5920 (6)	0.7284 (4)	−0.2223 (4)	0.0592 (11)
H3	0.6853	0.7436	−0.2601	0.071*
C4	0.4958 (6)	0.7418 (5)	−0.2839 (4)	0.0678 (13)
H4	0.5237	0.7667	−0.3640	0.081*
C5	0.3578 (6)	0.7189 (5)	−0.2288 (4)	0.0675 (13)
H5	0.2936	0.7283	−0.2721	0.081*
C6	0.3140 (5)	0.6820 (4)	−0.1098 (4)	0.0545 (11)
H6	0.2211	0.6660	−0.0732	0.065*
C7	0.4101 (4)	0.6691 (3)	−0.0449 (3)	0.0402 (8)
C8	0.3759 (4)	0.6353 (3)	0.0800 (3)	0.0351 (8)
C9	0.4701 (4)	0.6296 (3)	0.1389 (3)	0.0355 (8)
C10	0.4260 (4)	0.6090 (3)	0.2719 (3)	0.0341 (8)
H10	0.5132	0.5529	0.2910	0.041*
C11	0.2968 (4)	0.5549 (3)	0.3146 (3)	0.0362 (8)
C12	0.2024 (4)	0.5667 (3)	0.2490 (3)	0.0395 (8)
C13	−0.0189 (6)	0.5523 (5)	0.2111 (5)	0.0758 (16)
H13A	−0.1049	0.5241	0.2563	0.114*
H13B	0.0393	0.5076	0.1405	0.114*
H13C	−0.0538	0.6349	0.1888	0.114*
C14	0.3830 (4)	0.7256 (3)	0.3303 (3)	0.0344 (8)
C15	0.4574 (4)	0.7360 (3)	0.3991 (3)	0.0415 (8)
H15	0.5365	0.6704	0.4080	0.050*
C16	0.3129 (4)	0.9334 (3)	0.4428 (3)	0.0406 (8)
C17	0.2842 (5)	1.0337 (4)	0.5026 (4)	0.0530 (10)
H17	0.3397	1.0319	0.5509	0.064*
C18	0.1736 (5)	1.1350 (4)	0.4898 (4)	0.0528 (10)
H18	0.1529	1.2026	0.5296	0.063*
C19	0.0923 (4)	1.1360 (3)	0.4165 (3)	0.0423 (9)
C20	0.1176 (4)	1.0372 (3)	0.3593 (3)	0.0396 (8)
H20	0.0607	1.0391	0.3120	0.047*
C21	0.2297 (4)	0.9331 (3)	0.3724 (3)	0.0362 (8)
C22	0.2577 (4)	0.8247 (3)	0.3136 (3)	0.0368 (8)
N1	0.2703 (4)	0.4975 (3)	0.4251 (3)	0.0405 (7)
N2	0.0763 (4)	0.5375 (3)	0.2832 (3)	0.0519 (9)
H2	0.0471	0.5069	0.3543	0.062*
O1	0.7135 (3)	0.6371 (3)	0.1160 (3)	0.0648 (9)
O2	0.6502 (3)	0.6786 (3)	−0.0456 (2)	0.0533 (7)
O3	0.2394 (3)	0.6112 (2)	0.1340 (2)	0.0408 (6)
O4	0.3527 (3)	0.4944 (2)	0.4837 (2)	0.0506 (7)
O5	0.1646 (3)	0.4491 (3)	0.4673 (3)	0.0514 (7)
O6	0.1798 (3)	0.8194 (2)	0.2569 (3)	0.0525 (7)
O7	0.4263 (3)	0.8351 (2)	0.4569 (2)	0.0498 (7)
Br1	−0.05894 (5)	1.27713 (4)	0.39770 (4)	0.05830 (19)
C23	0.7698 (6)	0.9052 (8)	0.0829 (5)	0.146 (3)
H23A	0.7777	0.8283	0.0580	0.175*	0.515 (6)
H23B	0.7592	0.8259	0.1122	0.175*	0.485 (6)
Cl1	0.9143 (5)	0.8826 (4)	0.1496 (4)	0.1075 (15)	0.515 (6)
Cl2	0.5958 (5)	0.9568 (5)	0.1863 (5)	0.140 (2)	0.515 (6)
Cl3	0.8013 (6)	0.9975 (5)	−0.0393 (3)	0.131 (2)	0.515 (6)
Cl1'	0.8251 (14)	0.9193 (11)	0.1864 (7)	0.260 (6)	0.485 (6)
Cl2'	0.5804 (9)	0.9669 (10)	0.0975 (13)	0.317 (8)	0.485 (6)
Cl3'	0.8819 (8)	0.8620 (7)	−0.0529 (4)	0.174 (3)	0.485 (6)

	U11	U22	U33	U12	U13	U23
C1	0.043 (2)	0.044 (2)	0.046 (2)	−0.0120 (17)	−0.0174 (18)	0.0013 (17)
C2	0.052 (2)	0.040 (2)	0.042 (2)	−0.0108 (18)	−0.0176 (18)	−0.0028 (16)
C3	0.067 (3)	0.062 (3)	0.044 (2)	−0.019 (2)	−0.014 (2)	−0.001 (2)
C4	0.087 (4)	0.071 (3)	0.044 (3)	−0.020 (3)	−0.027 (3)	0.003 (2)
C5	0.086 (4)	0.074 (3)	0.055 (3)	−0.018 (3)	−0.046 (3)	0.001 (2)
C6	0.065 (3)	0.058 (3)	0.052 (3)	−0.017 (2)	−0.034 (2)	−0.001 (2)
C7	0.051 (2)	0.0308 (18)	0.041 (2)	−0.0077 (16)	−0.0213 (18)	−0.0040 (15)
C8	0.0380 (19)	0.0290 (17)	0.041 (2)	−0.0087 (15)	−0.0175 (16)	−0.0025 (14)
C9	0.0356 (19)	0.0303 (17)	0.042 (2)	−0.0076 (15)	−0.0170 (16)	−0.0012 (14)
C10	0.0339 (18)	0.0322 (17)	0.0410 (19)	−0.0075 (14)	−0.0215 (15)	0.0021 (14)
C11	0.0377 (19)	0.0330 (18)	0.041 (2)	−0.0105 (15)	−0.0187 (16)	0.0043 (15)
C12	0.041 (2)	0.0343 (18)	0.049 (2)	−0.0137 (16)	−0.0212 (17)	0.0053 (16)
C13	0.066 (3)	0.096 (4)	0.094 (4)	−0.045 (3)	−0.055 (3)	0.032 (3)
C14	0.0360 (19)	0.0353 (18)	0.0355 (18)	−0.0116 (15)	−0.0174 (15)	0.0042 (14)
C15	0.045 (2)	0.0393 (19)	0.045 (2)	−0.0096 (17)	−0.0255 (18)	0.0016 (16)
C16	0.045 (2)	0.043 (2)	0.038 (2)	−0.0138 (17)	−0.0176 (17)	−0.0001 (16)
C17	0.061 (3)	0.058 (3)	0.051 (2)	−0.018 (2)	−0.028 (2)	−0.010 (2)
C18	0.061 (3)	0.046 (2)	0.053 (2)	−0.019 (2)	−0.014 (2)	−0.0124 (19)
C19	0.041 (2)	0.0357 (19)	0.044 (2)	−0.0124 (16)	−0.0075 (17)	−0.0007 (16)
C20	0.039 (2)	0.039 (2)	0.041 (2)	−0.0134 (16)	−0.0146 (16)	0.0035 (16)
C21	0.0376 (19)	0.0354 (18)	0.0376 (19)	−0.0126 (15)	−0.0144 (16)	0.0011 (15)
C22	0.039 (2)	0.0373 (19)	0.0399 (19)	−0.0118 (16)	−0.0210 (16)	0.0021 (15)
N1	0.0407 (18)	0.0347 (16)	0.0451 (18)	−0.0081 (14)	−0.0186 (15)	0.0046 (13)
N2	0.048 (2)	0.062 (2)	0.059 (2)	−0.0286 (17)	−0.0291 (17)	0.0172 (17)
O1	0.0446 (17)	0.098 (3)	0.0627 (19)	−0.0300 (17)	−0.0268 (15)	0.0082 (17)
O2	0.0475 (16)	0.0693 (19)	0.0447 (16)	−0.0225 (14)	−0.0151 (13)	0.0028 (14)
O3	0.0430 (15)	0.0440 (14)	0.0461 (15)	−0.0173 (12)	−0.0265 (12)	0.0064 (11)
O4	0.0554 (17)	0.0539 (17)	0.0505 (16)	−0.0164 (14)	−0.0336 (14)	0.0148 (13)
O5	0.0497 (16)	0.0521 (16)	0.0548 (17)	−0.0239 (14)	−0.0188 (13)	0.0133 (13)
O6	0.0569 (17)	0.0432 (15)	0.0710 (19)	−0.0030 (13)	−0.0450 (16)	−0.0083 (13)
O7	0.0592 (18)	0.0485 (16)	0.0545 (17)	−0.0080 (13)	−0.0388 (14)	−0.0067 (13)
Br1	0.0560 (3)	0.0359 (2)	0.0753 (3)	−0.00750 (19)	−0.0191 (2)	−0.00208 (19)
C23	0.127 (7)	0.178 (8)	0.117 (6)	−0.035 (6)	−0.027 (5)	−0.024 (6)
Cl1	0.125 (3)	0.100 (3)	0.118 (4)	−0.038 (2)	−0.061 (3)	−0.005 (2)
Cl2	0.107 (3)	0.123 (4)	0.134 (4)	−0.031 (3)	0.019 (3)	−0.002 (3)
Cl3	0.157 (4)	0.152 (5)	0.084 (2)	−0.078 (3)	−0.028 (2)	0.028 (2)
Cl1'	0.426 (17)	0.233 (10)	0.126 (5)	−0.091 (11)	−0.083 (8)	−0.056 (6)
Cl2'	0.257 (11)	0.154 (7)	0.425 (19)	0.054 (7)	−0.078 (12)	−0.041 (11)
Cl3'	0.214 (7)	0.215 (8)	0.098 (3)	−0.102 (6)	−0.032 (4)	0.009 (4)

C1—O1	1.199 (5)	C14—C15	1.337 (5)
C1—O2	1.370 (5)	C14—C22	1.453 (5)
C1—C9	1.446 (5)	C15—O7	1.358 (5)
C2—C3	1.374 (6)	C15—H15	0.9300
C2—O2	1.374 (5)	C16—O7	1.367 (5)
C2—C7	1.391 (6)	C16—C21	1.383 (5)
C3—C4	1.365 (7)	C16—C17	1.390 (6)
C3—H3	0.9300	C17—C18	1.368 (6)
C4—C5	1.377 (7)	C17—H17	0.9300
C4—H4	0.9300	C18—C19	1.392 (6)
C5—C6	1.381 (7)	C18—H18	0.9300
C5—H5	0.9300	C19—C20	1.366 (5)
C6—C7	1.397 (5)	C19—Br1	1.893 (4)
C6—H6	0.9300	C20—C21	1.397 (5)
C7—C8	1.437 (5)	C20—H20	0.9300
C8—C9	1.344 (5)	C21—C22	1.470 (5)
C8—O3	1.369 (4)	C22—O6	1.223 (4)
C9—C10	1.501 (5)	N1—O4	1.248 (4)
C10—C11	1.505 (5)	N1—O5	1.264 (4)
C10—C14	1.521 (5)	N2—H2	0.8600
C10—H10	0.9800	C23—Cl1'	1.587 (7)
C11—N1	1.372 (5)	C23—Cl3'	1.653 (6)
C11—C12	1.391 (5)	C23—Cl3	1.688 (7)
C12—N2	1.307 (5)	C23—Cl2	1.691 (6)
C12—O3	1.364 (4)	C23—Cl2'	1.721 (7)
C13—N2	1.454 (5)	C23—Cl1	1.812 (6)
C13—H13A	0.9600	C23—H23A	0.9800
C13—H13B	0.9600	C23—H23B	0.9800
C13—H13C	0.9600
O1—C1—O2	117.3 (4)	C18—C17—H17	120.3
O1—C1—C9	124.9 (4)	C16—C17—H17	120.3
O2—C1—C9	117.8 (3)	C17—C18—C19	119.4 (4)
C3—C2—O2	117.1 (4)	C17—C18—H18	120.3
C3—C2—C7	121.8 (4)	C19—C18—H18	120.3
O2—C2—C7	121.1 (3)	C20—C19—C18	121.6 (4)
C4—C3—C2	119.0 (5)	C20—C19—Br1	119.3 (3)
C4—C3—H3	120.5	C18—C19—Br1	119.1 (3)
C2—C3—H3	120.5	C19—C20—C21	119.5 (3)
C3—C4—C5	120.9 (4)	C19—C20—H20	120.3
C3—C4—H4	119.6	C21—C20—H20	120.3
C5—C4—H4	119.6	C16—C21—C20	118.8 (3)
C4—C5—C6	120.5 (4)	C16—C21—C22	120.5 (3)
C4—C5—H5	119.8	C20—C21—C22	120.7 (3)
C6—C5—H5	119.8	O6—C22—C14	123.5 (3)
C5—C6—C7	119.6 (4)	O6—C22—C21	122.1 (3)
C5—C6—H6	120.2	C14—C22—C21	114.4 (3)
C7—C6—H6	120.2	O4—N1—O5	120.4 (3)
C2—C7—C6	118.3 (4)	O4—N1—C11	118.6 (3)
C2—C7—C8	116.7 (3)	O5—N1—C11	120.9 (3)
C6—C7—C8	125.0 (4)	C12—N2—C13	125.5 (4)
C9—C8—O3	122.9 (3)	C12—N2—H2	117.3
C9—C8—C7	122.3 (3)	C13—N2—H2	117.3
O3—C8—C7	114.8 (3)	C1—O2—C2	122.3 (3)
C8—C9—C1	119.5 (3)	C12—O3—C8	119.7 (3)
C8—C9—C10	122.2 (3)	C15—O7—C16	118.5 (3)
C1—C9—C10	118.3 (3)	Cl1'—C23—Cl3'	125.6 (5)
C9—C10—C11	108.5 (3)	Cl1'—C23—Cl3	117.6 (7)
C9—C10—C14	109.8 (3)	Cl3'—C23—Cl3	55.4 (3)
C11—C10—C14	112.0 (3)	Cl1'—C23—Cl2	82.4 (5)
C9—C10—H10	108.8	Cl3'—C23—Cl2	151.9 (5)
C11—C10—H10	108.8	Cl3—C23—Cl2	112.8 (5)
C14—C10—H10	108.8	Cl1'—C23—Cl2'	118.9 (5)
N1—C11—C12	120.7 (3)	Cl3'—C23—Cl2'	114.1 (5)
N1—C11—C10	117.0 (3)	Cl3—C23—Cl2'	85.0 (6)
C12—C11—C10	122.3 (3)	Cl2—C23—Cl2'	38.2 (5)
N2—C12—O3	112.1 (3)	Cl1'—C23—Cl1	27.2 (4)
N2—C12—C11	127.7 (3)	Cl3'—C23—Cl1	99.0 (4)
O3—C12—C11	120.3 (3)	Cl3—C23—Cl1	109.5 (5)
N2—C13—H13A	109.5	Cl2—C23—Cl1	109.1 (4)
N2—C13—H13B	109.5	Cl2'—C23—Cl1	146.1 (5)
H13A—C13—H13B	109.5	Cl1'—C23—H23A	123.7
N2—C13—H13C	109.5	Cl3'—C23—H23A	60.5
H13A—C13—H13C	109.5	Cl3—C23—H23A	108.4
H13B—C13—H13C	109.5	Cl2—C23—H23A	108.4
C15—C14—C22	120.1 (3)	Cl2'—C23—H23A	94.7
C15—C14—C10	120.2 (3)	Cl1—C23—H23A	108.4
C22—C14—C10	119.6 (3)	Cl1'—C23—H23B	93.9
C14—C15—O7	124.9 (3)	Cl3'—C23—H23B	93.9
C14—C15—H15	117.6	Cl3—C23—H23B	144.5
O7—C15—H15	117.6	Cl2—C23—H23B	85.5
O7—C16—C21	121.5 (3)	Cl2'—C23—H23B	93.9
O7—C16—C17	117.2 (3)	Cl1—C23—H23B	90.9
C21—C16—C17	121.4 (4)	H23A—C23—H23B	36.2
C18—C17—C16	119.4 (4)
O2—C2—C3—C4	179.3 (4)	C10—C14—C15—O7	−178.8 (3)
C7—C2—C3—C4	−0.1 (7)	O7—C16—C17—C18	178.9 (4)
C2—C3—C4—C5	−0.4 (7)	C21—C16—C17—C18	−1.4 (6)
C3—C4—C5—C6	0.1 (8)	C16—C17—C18—C19	−0.3 (7)
C4—C5—C6—C7	0.6 (7)	C17—C18—C19—C20	1.7 (6)
C3—C2—C7—C6	0.7 (6)	C17—C18—C19—Br1	−179.2 (3)
O2—C2—C7—C6	−178.5 (3)	C18—C19—C20—C21	−1.3 (6)
C3—C2—C7—C8	−178.1 (4)	Br1—C19—C20—C21	179.6 (3)
O2—C2—C7—C8	2.6 (5)	O7—C16—C21—C20	−178.6 (3)
C5—C6—C7—C2	−1.0 (6)	C17—C16—C21—C20	1.7 (6)
C5—C6—C7—C8	177.8 (4)	O7—C16—C21—C22	2.1 (5)
C2—C7—C8—C9	1.9 (5)	C17—C16—C21—C22	−177.5 (4)
C6—C7—C8—C9	−176.9 (4)	C19—C20—C21—C16	−0.4 (5)
C2—C7—C8—O3	−178.9 (3)	C19—C20—C21—C22	178.9 (3)
C6—C7—C8—O3	2.3 (5)	C15—C14—C22—O6	−176.2 (4)
O3—C8—C9—C1	175.2 (3)	C10—C14—C22—O6	2.2 (6)
C7—C8—C9—C1	−5.7 (5)	C15—C14—C22—C21	3.0 (5)
O3—C8—C9—C10	−6.7 (5)	C10—C14—C22—C21	−178.7 (3)
C7—C8—C9—C10	172.4 (3)	C16—C21—C22—O6	175.4 (4)
O1—C1—C9—C8	−175.3 (4)	C20—C21—C22—O6	−3.9 (6)
O2—C1—C9—C8	4.9 (5)	C16—C21—C22—C14	−3.8 (5)
O1—C1—C9—C10	6.6 (6)	C20—C21—C22—C14	176.9 (3)
O2—C1—C9—C10	−173.2 (3)	C12—C11—N1—O4	−176.3 (3)
C8—C9—C10—C11	19.9 (4)	C10—C11—N1—O4	0.6 (5)
C1—C9—C10—C11	−162.0 (3)	C12—C11—N1—O5	3.5 (5)
C8—C9—C10—C14	−102.7 (4)	C10—C11—N1—O5	−179.6 (3)
C1—C9—C10—C14	75.4 (4)	O3—C12—N2—C13	−1.6 (6)
C9—C10—C11—N1	161.2 (3)	C11—C12—N2—C13	179.6 (4)
C14—C10—C11—N1	−77.5 (4)	O1—C1—O2—C2	179.6 (4)
C9—C10—C11—C12	−22.0 (5)	C9—C1—O2—C2	−0.5 (5)
C14—C10—C11—C12	99.3 (4)	C3—C2—O2—C1	177.5 (4)
N1—C11—C12—N2	6.3 (6)	C7—C2—O2—C1	−3.2 (6)
C10—C11—C12—N2	−170.4 (4)	N2—C12—O3—C8	−173.6 (3)
N1—C11—C12—O3	−172.3 (3)	C11—C12—O3—C8	5.3 (5)
C10—C11—C12—O3	11.0 (5)	C9—C8—O3—C12	−7.5 (5)
C9—C10—C14—C15	−121.8 (4)	C7—C8—O3—C12	173.3 (3)
C11—C10—C14—C15	117.6 (4)	C14—C15—O7—C16	−1.5 (6)
C9—C10—C14—C22	59.9 (4)	C21—C16—O7—C15	0.6 (5)
C11—C10—C14—C22	−60.7 (4)	C17—C16—O7—C15	−179.7 (4)
C22—C14—C15—O7	−0.4 (6)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O5	0.86	2.00	2.622 (5)	128
N2—H2···O5i	0.86	2.37	3.063 (5)	138
C4—H4···O7ii	0.93	2.59	3.383 (6)	144
C15—H15···O4iii	0.93	2.36	3.221 (4)	153

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N2H2O5	0.86	2.00	2.622(5)	128
N2H2O5i	0.86	2.37	3.063(5)	138
C4H4O7ii	0.93	2.59	3.383(6)	144
C15H15O4iii	0.93	2.36	3.221(4)	153

Symmetry codes: (i) ; (ii) ; (iii) .