Models for potential dendritic nitric oxide donors: crystal structures of two 2-nitro­anilino precursors and nitric oxide-release behavior of the nitro­sated derivatives

Two mol­ecular precursors to dendrimeric materials that could serve as slow and sustained NO-releasing therapeutic agents have been synthesized and characterized. N¹,N⁴-Bis(2-nitro­phen­yl)butane-1,4-di­amine, C₁₆H₁₈N₄O₄, (I), crystallizes in a lattice with equal populations of two mol­ecules of different conformations, both of which possess inversion symmetry through the central C—C bond. One mol­ecule has exclusively anti conformations along the butyl chain, while the other has a gauche conformation of the substituents on the first C—C bond. N²,N²-Bis­[2-(2-nitroanilino)­eth­yl]-N¹-(2-nitro­phen­yl)ethane-1,2-di­amine, C₂₄H₂₇N₇O₆, (II), crystallizes with one unique mol­ecule in the asymmetric unit. Neighboring pairs of mol­ecules are linked into dimers via N—H...O amine–nitro hydrogen bonds. The dimers are assembled into layers that stack in an A–B–A–B sequence such that the repeat distance in the stacking direction is over 46 Å. Mol­ecular NO-release agents N¹,N⁴-bis­(2-nitro­phen­yl)-N¹,N⁴-di­nitroso­butane-1,4-di­amine, C₁₆H₁₆N₆O₆, (III), and N¹-(2-nitro­phen­yl)-N²,N²-bis­{2-[(2-nitro­phen­yl)(nitroso)amino]­eth­yl}-N¹-nitroso­ethane-1,2-di­amine, C₂₄H₂₄N₁₀O₉, (IV), were prepared via treatment of (I) and (II), respectively, with NaNO₂ and acetic acid. The release of NO from solid-phase samples of (III) and (IV) suspended in phosphate buffer was monitored spectroscopically over a period of 21 days. Although (IV) released a greater amount of NO, as expected due to it having three NO moieties for every two in (III), the (IV):(III) ratio of the rate and extent of NO release was significantly less than 1.5:1, suggesting that some combination of electronic, chemical, and/or steric factors may be affecting the release process.

Computing details

For both structures, data collection: APEX3 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXS97 (Sheldrick 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: CrystalMaker (Palmer, 2014); software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015).

N¹,N⁴-Bis(2-nitrophenyl)butane-1,4-diamine (C16H18N4O4)

Crystal data

C16H18N4O4	F(000) = 348
Mr = 330.34	Dx = 1.466 Mg m^−3
Triclinic, P1	Melting point: 426 K
a = 6.7032 (4) Å	Cu Kα radiation, λ = 1.54178 Å
b = 8.1646 (5) Å	Cell parameters from 8641 reflections
c = 15.1177 (9) Å	θ = 3.0–69.8°
α = 81.099 (2)°	µ = 0.90 mm^−1
β = 79.555 (2)°	T = 120 K
γ = 67.488 (2)°	Plate, orange
V = 748.34 (8) Å^3	0.08 × 0.07 × 0.03 mm
Z = 2

Data collection

Bruker APEXII CCD diffractometer	2595 independent reflections
Radiation source: ImuS	2314 reflections with I > 2σ(I)
Multi-layer optics monochromator	Rint = 0.027
φ and ω scans	θmax = 69.9°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→8
Tmin = 0.689, Tmax = 0.753	k = −9→9
2595 measured reflections	l = 0→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)] = 0.043	Hydrogen site location: mixed
wR(F^2) = 0.138	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0905P)^2 + 0.1858P] where P = (Fo^2 + 2Fc^2)/3
2595 reflections	(Δ/σ)max < 0.001
226 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.34 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. Refined as a 2-component twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.3995 (2)	0.39294 (16)	0.06812 (8)	0.0234 (3)
O2	0.4336 (2)	0.18683 (17)	0.17903 (9)	0.0328 (4)
N1	0.2731 (2)	0.72853 (19)	0.09832 (10)	0.0184 (3)
N2	0.3819 (2)	0.34646 (18)	0.15066 (10)	0.0193 (3)
C1	0.2477 (3)	0.9133 (2)	0.06805 (11)	0.0197 (4)
H1A	0.358057	0.915574	0.015071	0.024*
H1B	0.275780	0.966550	0.116822	0.024*
C2	0.0214 (3)	1.0264 (2)	0.04247 (11)	0.0189 (4)
H2A	−0.089810	1.014268	0.093221	0.023*
H2B	0.006300	1.153139	0.032834	0.023*
C3	0.2460 (3)	0.6631 (2)	0.18512 (11)	0.0170 (4)
C4	0.3000 (3)	0.4780 (2)	0.21374 (11)	0.0175 (4)
C5	0.2769 (3)	0.4156 (2)	0.30547 (12)	0.0200 (4)
H5	0.315419	0.291392	0.322189	0.024*
C6	0.1996 (3)	0.5310 (2)	0.37113 (11)	0.0212 (4)
H6	0.185322	0.487901	0.433117	0.025*
C7	0.1418 (3)	0.7143 (2)	0.34535 (11)	0.0204 (4)
H7	0.088022	0.795481	0.390472	0.025*
C8	0.1618 (3)	0.7780 (2)	0.25606 (11)	0.0192 (4)
H8	0.117980	0.902940	0.240922	0.023*
H1N	0.335 (4)	0.649 (3)	0.0588 (15)	0.031 (6)*
O11	0.7626 (2)	0.35662 (16)	0.43988 (8)	0.0264 (3)
O12	0.9038 (3)	0.15051 (17)	0.34842 (9)	0.0364 (4)
N11	0.6419 (2)	0.69358 (19)	0.37783 (10)	0.0191 (3)
N12	0.8198 (2)	0.30994 (19)	0.36156 (10)	0.0213 (3)
C11	0.5565 (3)	0.8826 (2)	0.39118 (11)	0.0202 (4)
H11A	0.407060	0.939507	0.374695	0.024*
H11B	0.649339	0.941833	0.352011	0.024*
C12	0.5537 (3)	0.9028 (2)	0.48948 (11)	0.0208 (4)
H12A	0.705134	0.854587	0.503870	0.025*
H12B	0.473649	0.832488	0.528306	0.025*
C13	0.7037 (3)	0.6276 (2)	0.29682 (11)	0.0172 (4)
C14	0.7889 (3)	0.4419 (2)	0.28573 (11)	0.0178 (4)
C15	0.8498 (3)	0.3795 (2)	0.19956 (12)	0.0204 (4)
H15	0.905061	0.255025	0.194199	0.024*
C16	0.8301 (3)	0.4963 (2)	0.12335 (12)	0.0214 (4)
H16	0.870755	0.453865	0.065180	0.026*
C17	0.7489 (3)	0.6794 (2)	0.13241 (12)	0.0202 (4)
H17	0.736216	0.761044	0.079733	0.024*
C18	0.6876 (3)	0.7431 (2)	0.21577 (11)	0.0188 (4)
H18	0.632815	0.868101	0.219405	0.023*
H11N	0.641 (4)	0.619 (3)	0.4231 (17)	0.039 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0346 (7)	0.0198 (6)	0.0138 (6)	−0.0083 (5)	−0.0017 (5)	−0.0023 (5)
O2	0.0529 (9)	0.0136 (6)	0.0270 (7)	−0.0071 (6)	−0.0057 (6)	−0.0007 (5)
N1	0.0244 (7)	0.0135 (7)	0.0155 (7)	−0.0047 (6)	−0.0036 (6)	−0.0012 (6)
N2	0.0248 (7)	0.0134 (7)	0.0187 (8)	−0.0056 (6)	−0.0039 (6)	−0.0005 (6)
C1	0.0263 (9)	0.0148 (8)	0.0184 (8)	−0.0079 (7)	−0.0041 (7)	0.0000 (6)
C2	0.0251 (9)	0.0133 (8)	0.0161 (8)	−0.0052 (7)	−0.0024 (6)	−0.0001 (6)
C3	0.0175 (8)	0.0164 (8)	0.0168 (8)	−0.0048 (7)	−0.0051 (6)	−0.0009 (6)
C4	0.0193 (8)	0.0167 (8)	0.0161 (9)	−0.0051 (7)	−0.0030 (6)	−0.0035 (7)
C5	0.0238 (8)	0.0169 (8)	0.0190 (9)	−0.0069 (7)	−0.0055 (7)	0.0011 (7)
C6	0.0251 (9)	0.0243 (9)	0.0146 (8)	−0.0093 (7)	−0.0047 (7)	0.0003 (7)
C7	0.0210 (8)	0.0214 (9)	0.0190 (9)	−0.0064 (7)	−0.0025 (6)	−0.0059 (7)
C8	0.0210 (8)	0.0162 (8)	0.0198 (9)	−0.0050 (7)	−0.0027 (7)	−0.0045 (7)
O11	0.0447 (8)	0.0199 (6)	0.0150 (6)	−0.0119 (6)	−0.0040 (5)	−0.0026 (5)
O12	0.0613 (10)	0.0126 (6)	0.0270 (8)	−0.0057 (6)	−0.0022 (7)	−0.0024 (5)
N11	0.0270 (8)	0.0153 (7)	0.0148 (7)	−0.0074 (6)	−0.0017 (6)	−0.0030 (6)
N12	0.0299 (8)	0.0147 (7)	0.0189 (8)	−0.0075 (6)	−0.0027 (6)	−0.0029 (6)
C11	0.0264 (9)	0.0152 (8)	0.0190 (9)	−0.0066 (7)	−0.0024 (7)	−0.0042 (7)
C12	0.0278 (9)	0.0161 (9)	0.0182 (9)	−0.0077 (7)	−0.0005 (7)	−0.0043 (7)
C13	0.0170 (8)	0.0173 (8)	0.0177 (8)	−0.0060 (7)	−0.0018 (6)	−0.0037 (7)
C14	0.0212 (8)	0.0160 (8)	0.0165 (9)	−0.0067 (7)	−0.0030 (6)	−0.0019 (7)
C15	0.0227 (8)	0.0178 (8)	0.0206 (9)	−0.0065 (7)	−0.0008 (7)	−0.0067 (7)
C16	0.0227 (8)	0.0253 (9)	0.0173 (9)	−0.0087 (7)	−0.0022 (7)	−0.0057 (7)
C17	0.0204 (8)	0.0234 (9)	0.0175 (9)	−0.0090 (7)	−0.0034 (6)	−0.0002 (7)
C18	0.0216 (8)	0.0153 (8)	0.0197 (9)	−0.0065 (7)	−0.0041 (6)	−0.0015 (7)

Geometric parameters (Å, º)

O1—N2	1.2448 (18)	O11—N12	1.2480 (19)
O2—N2	1.2400 (19)	O12—N12	1.2365 (19)
N1—C3	1.346 (2)	N11—C13	1.346 (2)
N1—C1	1.460 (2)	N11—C11	1.459 (2)
N1—H1N	0.88 (2)	N11—H11N	0.84 (2)
N2—C4	1.428 (2)	N12—C14	1.432 (2)
C1—C2	1.527 (2)	C11—C12	1.516 (2)
C1—H1A	0.9900	C11—H11A	0.9900
C1—H1B	0.9900	C11—H11B	0.9900
C2—C2^i	1.523 (3)	C12—C12^ii	1.528 (3)
C2—H2A	0.9900	C12—H12A	0.9900
C2—H2B	0.9900	C12—H12B	0.9900
C3—C8	1.426 (2)	C13—C18	1.420 (2)
C3—C4	1.428 (2)	C13—C14	1.426 (2)
C4—C5	1.404 (2)	C14—C15	1.406 (2)
C5—C6	1.368 (2)	C15—C16	1.369 (2)
C5—H5	0.9500	C15—H15	0.9500
C6—C7	1.404 (2)	C16—C17	1.401 (2)
C6—H6	0.9500	C16—H16	0.9500
C7—C8	1.371 (2)	C17—C18	1.371 (2)
C7—H7	0.9500	C17—H17	0.9500
C8—H8	0.9500	C18—H18	0.9500
C3—N1—C1	124.99 (14)	C13—N11—C11	124.79 (15)
C3—N1—H1N	115.9 (14)	C13—N11—H11N	115.9 (17)
C1—N1—H1N	118.0 (14)	C11—N11—H11N	119.0 (17)
O2—N2—O1	120.78 (14)	O12—N12—O11	120.77 (14)
O2—N2—C4	119.36 (14)	O12—N12—C14	119.34 (14)
O1—N2—C4	119.86 (14)	O11—N12—C14	119.88 (14)
N1—C1—C2	113.07 (14)	N11—C11—C12	109.10 (14)
N1—C1—H1A	109.0	N11—C11—H11A	109.9
C2—C1—H1A	109.0	C12—C11—H11A	109.9
N1—C1—H1B	109.0	N11—C11—H11B	109.9
C2—C1—H1B	109.0	C12—C11—H11B	109.9
H1A—C1—H1B	107.8	H11A—C11—H11B	108.3
C2^i—C2—C1	112.72 (17)	C11—C12—C12^ii	112.04 (18)
C2^i—C2—H2A	109.0	C11—C12—H12A	109.2
C1—C2—H2A	109.0	C12^ii—C12—H12A	109.2
C2^i—C2—H2B	109.0	C11—C12—H12B	109.2
C1—C2—H2B	109.0	C12^ii—C12—H12B	109.2
H2A—C2—H2B	107.8	H12A—C12—H12B	107.9
N1—C3—C8	121.09 (15)	N11—C13—C18	120.68 (15)
N1—C3—C4	123.83 (15)	N11—C13—C14	123.62 (15)
C8—C3—C4	115.07 (15)	C18—C13—C14	115.70 (15)
C5—C4—C3	121.72 (15)	C15—C14—C13	121.51 (16)
C5—C4—N2	116.48 (15)	C15—C14—N12	116.71 (15)
C3—C4—N2	121.80 (15)	C13—C14—N12	121.77 (15)
C6—C5—C4	120.95 (16)	C16—C15—C14	120.61 (16)
C6—C5—H5	119.5	C16—C15—H15	119.7
C4—C5—H5	119.5	C14—C15—H15	119.7
C5—C6—C7	118.87 (16)	C15—C16—C17	118.99 (15)
C5—C6—H6	120.6	C15—C16—H16	120.5
C7—C6—H6	120.6	C17—C16—H16	120.5
C8—C7—C6	121.04 (16)	C18—C17—C16	121.31 (16)
C8—C7—H7	119.5	C18—C17—H17	119.3
C6—C7—H7	119.5	C16—C17—H17	119.3
C7—C8—C3	122.31 (16)	C17—C18—C13	121.87 (16)
C7—C8—H8	118.8	C17—C18—H18	119.1
C3—C8—H8	118.8	C13—C18—H18	119.1
C4—C3—N1—C1	−171.20 (15)	C3—N1—C1—C2	−95.43 (19)
C14—C13—N11—C11	179.27 (15)	C13—N11—C11—C12	−167.33 (15)
C8—C3—N1—C1	8.0 (2)	N1—C1—C2—C2^i	−68.4 (2)
C18—C13—N11—C11	−0.4 (2)	N11—C11—C12—C12^ii	−174.65 (17)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1	0.88 (2)	1.95 (2)	2.6273 (18)	132.2 (19)
N1—H1N···O1^iii	0.88 (2)	2.34 (2)	3.0388 (19)	136.8 (19)
C8—H8···O12^iv	0.95	2.60	3.256 (2)	127
N11—H11N···O11	0.84 (2)	1.97 (2)	2.6221 (19)	133 (2)
C12—H12B···O11^v	0.99	2.55	3.470 (2)	155
C18—H18···O2^vi	0.95	2.46	3.366 (2)	159

Symmetry codes: (iii) −x+1, −y+1, −z; (iv) x−1, y+1, z; (v) −x+1, −y+1, −z+1; (vi) x, y+1, z.

N¹-(2-Nitrophenyl)-N²,N²-bis[2-[(2-nitroanilino)ethyl]ethane-1,2-diamine (C24H27N7O6)

Crystal data

C24H27N7O6	Dx = 1.436 Mg m^−3
Mr = 509.52	Melting point: 376 K
Orthorhombic, Pbca	Cu Kα radiation, λ = 1.54178 Å
a = 7.5749 (2) Å	Cell parameters from 9785 reflections
b = 13.4138 (4) Å	θ = 3.8–70.0°
c = 46.3793 (14) Å	µ = 0.89 mm^−1
V = 4712.5 (2) Å^3	T = 120 K
Z = 8	Triangular prism, yellow
F(000) = 2144	0.21 × 0.13 × 0.06 mm

Data collection

Bruker APEXII CCD diffractometer	4413 independent reflections
Radiation source: ImuS	4182 reflections with I > 2σ(I)
Multi-layer optics monochromator	Rint = 0.026
φ and ω scans	θmax = 70.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→8
Tmin = 0.655, Tmax = 0.753	k = −16→16
50384 measured reflections	l = −55→56

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)] = 0.031	Hydrogen site location: difference Fourier map
wR(F^2) = 0.079	All H-atom parameters refined
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0343P)^2 + 2.0708P] where P = (Fo^2 + 2Fc^2)/3
4413 reflections	(Δ/σ)max = 0.001
442 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.24 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.10378 (12)	1.08863 (7)	−0.01246 (2)	0.0308 (2)
O2	0.30627 (13)	1.14180 (7)	−0.04137 (2)	0.0323 (2)
O3	0.78758 (13)	0.54020 (7)	0.12028 (2)	0.0343 (2)
O4	0.84429 (12)	0.46457 (6)	0.16032 (2)	0.0306 (2)
O5	0.29091 (12)	1.04871 (6)	0.14961 (2)	0.0296 (2)
O6	0.39256 (12)	1.11208 (7)	0.18916 (2)	0.0375 (2)
N1	0.18245 (12)	0.84159 (7)	0.09745 (2)	0.0173 (2)
N2	0.17842 (14)	1.04263 (7)	0.04110 (2)	0.0236 (2)
N3	0.25888 (14)	1.11500 (7)	−0.01723 (2)	0.0230 (2)
N4	0.58206 (13)	0.69789 (8)	0.11960 (2)	0.0216 (2)
N5	0.77672 (13)	0.53401 (7)	0.14699 (2)	0.0242 (2)
N6	0.06877 (13)	0.89790 (7)	0.15092 (2)	0.0188 (2)
N7	0.30044 (13)	1.05048 (7)	0.17636 (2)	0.0253 (2)
C1	0.20183 (16)	0.88416 (8)	0.06863 (2)	0.0199 (2)
C2	0.13671 (18)	0.99193 (9)	0.06804 (3)	0.0255 (3)
C3	0.34148 (16)	1.07529 (8)	0.03378 (2)	0.0203 (2)
C4	0.38489 (16)	1.11365 (8)	0.00601 (2)	0.0206 (2)
C5	0.55501 (17)	1.14786 (9)	−0.00052 (3)	0.0258 (3)
C6	0.68709 (18)	1.14413 (9)	0.01954 (3)	0.0308 (3)
C7	0.64809 (18)	1.10657 (9)	0.04694 (3)	0.0300 (3)
C8	0.48243 (17)	1.07365 (9)	0.05396 (3)	0.0254 (3)
C9	0.29142 (15)	0.75279 (8)	0.10129 (2)	0.0194 (2)
C10	0.48761 (16)	0.77778 (9)	0.10495 (2)	0.0225 (2)
C11	0.58330 (14)	0.68520 (8)	0.14861 (2)	0.0179 (2)
C12	0.68072 (14)	0.60927 (8)	0.16288 (2)	0.0194 (2)
C13	0.68717 (16)	0.60277 (9)	0.19294 (3)	0.0232 (3)
C14	0.59608 (17)	0.66913 (9)	0.20977 (3)	0.0253 (3)
C15	0.49346 (16)	0.74231 (9)	0.19626 (3)	0.0238 (2)
C16	0.48690 (15)	0.75010 (8)	0.16682 (2)	0.0204 (2)
C17	−0.00235 (15)	0.82235 (9)	0.10512 (2)	0.0196 (2)
C18	−0.02435 (16)	0.81483 (8)	0.13772 (2)	0.0198 (2)
C19	0.08961 (14)	0.90749 (8)	0.17968 (2)	0.0180 (2)
C20	0.20124 (15)	0.97899 (8)	0.19303 (3)	0.0214 (2)
C21	0.21675 (17)	0.98492 (10)	0.22306 (3)	0.0291 (3)
C22	0.12409 (18)	0.92142 (11)	0.24059 (3)	0.0322 (3)
C23	0.01299 (17)	0.85070 (10)	0.22796 (3)	0.0274 (3)
C24	−0.00427 (15)	0.84361 (9)	0.19865 (2)	0.0214 (2)
H2N	0.103 (2)	1.0378 (12)	0.0267 (3)	0.036 (4)*
H4N	0.648 (2)	0.6565 (12)	0.1101 (3)	0.031 (4)*
H6N	0.139 (2)	0.9301 (11)	0.1401 (3)	0.025 (4)*
H1A	0.1409 (18)	0.8448 (10)	0.0537 (3)	0.025 (3)*
H1B	0.3274 (18)	0.8833 (9)	0.0637 (3)	0.017 (3)*
H2A	0.005 (2)	0.9948 (11)	0.0697 (3)	0.032 (4)*
H2B	0.1903 (19)	1.0281 (11)	0.0848 (3)	0.028 (4)*
H5	0.572 (2)	1.1733 (11)	−0.0196 (3)	0.030 (4)*
H6	0.804 (2)	1.1655 (12)	0.0147 (3)	0.037 (4)*
H7	0.740 (2)	1.1021 (11)	0.0615 (3)	0.034 (4)*
H8	0.461 (2)	1.0464 (11)	0.0726 (3)	0.031 (4)*
H9A	0.2767 (18)	0.7064 (10)	0.0854 (3)	0.025 (3)*
H9B	0.2520 (17)	0.7198 (9)	0.1188 (3)	0.017 (3)*
H10A	0.5474 (18)	0.7857 (10)	0.0861 (3)	0.024 (3)*
H10B	0.5010 (18)	0.8401 (11)	0.1163 (3)	0.026 (4)*
H13	0.758 (2)	0.5507 (11)	0.2014 (3)	0.032 (4)*
H14	0.600 (2)	0.6643 (11)	0.2305 (3)	0.033 (4)*
H15	0.4245 (19)	0.7886 (11)	0.2077 (3)	0.027 (4)*
H16	0.4179 (19)	0.7999 (11)	0.1586 (3)	0.025 (3)*
H17A	−0.0486 (18)	0.7592 (10)	0.0961 (3)	0.022 (3)*
H17B	−0.0755 (18)	0.8780 (10)	0.0982 (3)	0.020 (3)*
H18A	0.0214 (18)	0.7488 (10)	0.1453 (3)	0.022 (3)*
H18B	−0.1512 (18)	0.8185 (10)	0.1423 (3)	0.021 (3)*
H21	0.293 (2)	1.0352 (12)	0.2308 (3)	0.040 (4)*
H22	0.134 (2)	0.9250 (13)	0.2619 (4)	0.046 (5)*
H23	−0.054 (2)	0.8052 (11)	0.2402 (3)	0.031 (4)*
H24	−0.0815 (19)	0.7948 (11)	0.1908 (3)	0.023 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0283 (5)	0.0345 (5)	0.0297 (5)	−0.0039 (4)	−0.0047 (4)	0.0102 (4)
O2	0.0478 (6)	0.0311 (5)	0.0180 (4)	0.0027 (4)	0.0064 (4)	0.0050 (3)
O3	0.0355 (5)	0.0365 (5)	0.0308 (5)	0.0114 (4)	0.0050 (4)	−0.0041 (4)
O4	0.0252 (5)	0.0192 (4)	0.0475 (5)	0.0049 (4)	−0.0046 (4)	0.0028 (4)
O5	0.0262 (5)	0.0261 (4)	0.0365 (5)	−0.0055 (4)	−0.0007 (4)	0.0064 (4)
O6	0.0272 (5)	0.0276 (5)	0.0577 (6)	−0.0077 (4)	−0.0061 (4)	−0.0115 (4)
N1	0.0196 (5)	0.0178 (4)	0.0147 (4)	−0.0002 (4)	0.0014 (3)	0.0024 (3)
N2	0.0258 (5)	0.0236 (5)	0.0214 (5)	0.0018 (4)	0.0019 (4)	0.0073 (4)
N3	0.0326 (6)	0.0171 (5)	0.0194 (5)	0.0022 (4)	0.0022 (4)	0.0020 (4)
N4	0.0201 (5)	0.0245 (5)	0.0201 (5)	0.0025 (4)	0.0011 (4)	0.0015 (4)
N5	0.0184 (5)	0.0209 (5)	0.0332 (6)	0.0010 (4)	−0.0006 (4)	−0.0006 (4)
N6	0.0197 (5)	0.0191 (5)	0.0178 (5)	−0.0046 (4)	0.0030 (4)	0.0001 (4)
N7	0.0173 (5)	0.0191 (5)	0.0395 (6)	0.0006 (4)	−0.0029 (4)	−0.0036 (4)
C1	0.0249 (6)	0.0199 (6)	0.0149 (5)	0.0019 (5)	0.0022 (4)	0.0012 (4)
C2	0.0326 (7)	0.0214 (6)	0.0225 (6)	0.0047 (5)	0.0080 (5)	0.0054 (5)
C3	0.0260 (6)	0.0135 (5)	0.0214 (5)	0.0041 (4)	0.0020 (5)	−0.0008 (4)
C4	0.0263 (6)	0.0153 (5)	0.0201 (5)	0.0014 (4)	0.0025 (5)	−0.0016 (4)
C5	0.0312 (7)	0.0179 (6)	0.0283 (6)	−0.0006 (5)	0.0099 (5)	−0.0039 (5)
C6	0.0251 (6)	0.0221 (6)	0.0451 (8)	−0.0017 (5)	0.0056 (6)	−0.0095 (5)
C7	0.0296 (7)	0.0231 (6)	0.0372 (7)	0.0047 (5)	−0.0082 (6)	−0.0098 (5)
C8	0.0329 (7)	0.0204 (6)	0.0229 (6)	0.0051 (5)	−0.0027 (5)	−0.0029 (5)
C9	0.0222 (6)	0.0170 (5)	0.0189 (5)	−0.0012 (4)	−0.0015 (4)	0.0013 (4)
C10	0.0221 (6)	0.0247 (6)	0.0208 (6)	−0.0024 (5)	−0.0001 (5)	0.0061 (5)
C11	0.0136 (5)	0.0176 (5)	0.0226 (5)	−0.0041 (4)	−0.0006 (4)	0.0013 (4)
C12	0.0151 (5)	0.0172 (5)	0.0260 (6)	−0.0015 (4)	0.0000 (4)	0.0005 (4)
C13	0.0208 (6)	0.0205 (6)	0.0281 (6)	−0.0033 (5)	−0.0037 (5)	0.0062 (5)
C14	0.0277 (6)	0.0279 (6)	0.0201 (6)	−0.0047 (5)	−0.0020 (5)	0.0023 (5)
C15	0.0226 (6)	0.0240 (6)	0.0248 (6)	−0.0012 (5)	0.0010 (5)	−0.0043 (5)
C16	0.0185 (5)	0.0175 (5)	0.0252 (6)	0.0004 (4)	−0.0022 (4)	0.0007 (4)
C17	0.0192 (6)	0.0211 (6)	0.0184 (5)	−0.0022 (5)	−0.0008 (4)	0.0008 (4)
C18	0.0208 (6)	0.0199 (6)	0.0188 (5)	−0.0040 (5)	0.0018 (4)	−0.0006 (4)
C19	0.0156 (5)	0.0183 (5)	0.0200 (5)	0.0046 (4)	0.0008 (4)	−0.0009 (4)
C20	0.0166 (5)	0.0195 (5)	0.0281 (6)	0.0042 (4)	−0.0012 (4)	−0.0031 (4)
C21	0.0240 (6)	0.0323 (7)	0.0310 (7)	0.0065 (5)	−0.0076 (5)	−0.0109 (5)
C22	0.0327 (7)	0.0442 (8)	0.0198 (6)	0.0097 (6)	−0.0039 (5)	−0.0051 (5)
C23	0.0285 (7)	0.0331 (7)	0.0206 (6)	0.0071 (5)	0.0034 (5)	0.0029 (5)
C24	0.0212 (6)	0.0225 (6)	0.0205 (5)	0.0017 (5)	0.0021 (4)	0.0000 (4)

Geometric parameters (Å, º)

O1—N3	1.2467 (14)	C7—C8	1.3695 (19)
O2—N3	1.2294 (13)	C7—H7	0.970 (16)
O3—N5	1.2444 (13)	C8—H8	0.953 (15)
O4—N5	1.2296 (13)	C9—C10	1.5328 (16)
O5—N7	1.2432 (14)	C9—H9A	0.972 (14)
O6—N7	1.2337 (14)	C9—H9B	0.973 (13)
N1—C9	1.4602 (14)	C10—H10A	0.993 (14)
N1—C1	1.4608 (13)	C10—H10B	0.993 (14)
N1—C17	1.4672 (14)	C11—C16	1.4157 (16)
N2—C3	1.3539 (16)	C11—C12	1.4212 (16)
N2—C2	1.4571 (14)	C12—C13	1.3978 (16)
N2—H2N	0.884 (17)	C13—C14	1.3702 (18)
N3—C4	1.4400 (15)	C13—H13	0.963 (16)
N4—C11	1.3563 (14)	C14—C15	1.4000 (17)
N4—C10	1.4566 (15)	C14—H14	0.962 (15)
N4—H4N	0.868 (16)	C15—C16	1.3703 (16)
N5—C12	1.4460 (15)	C15—H15	0.970 (15)
N6—C19	1.3493 (14)	C16—H16	0.930 (15)
N6—C18	1.4539 (14)	C17—C18	1.5245 (15)
N6—H6N	0.849 (15)	C17—H17A	1.008 (14)
N7—C20	1.4427 (16)	C17—H17B	0.982 (14)
C1—C2	1.5276 (16)	C18—H18A	1.014 (14)
C1—H1A	0.987 (14)	C18—H18B	0.985 (14)
C1—H1B	0.978 (13)	C19—C24	1.4192 (16)
C2—H2A	0.999 (16)	C19—C20	1.4206 (16)
C2—H2B	1.004 (15)	C20—C21	1.4002 (17)
C3—C8	1.4200 (17)	C21—C22	1.371 (2)
C3—C4	1.4253 (16)	C21—H21	0.956 (17)
C4—C5	1.4011 (17)	C22—C23	1.397 (2)
C5—C6	1.367 (2)	C22—H22	0.994 (17)
C5—H5	0.958 (15)	C23—C24	1.3690 (16)
C6—C7	1.399 (2)	C23—H23	0.977 (15)
C6—H6	0.955 (17)	C24—H24	0.950 (15)
C9—N1—C1	111.96 (9)	H9A—C9—H9B	107.9 (11)
C9—N1—C17	111.48 (9)	N4—C10—C9	111.53 (9)
C1—N1—C17	112.73 (9)	N4—C10—H10A	105.4 (8)
C3—N2—C2	124.33 (11)	C9—C10—H10A	111.6 (8)
C3—N2—H2N	115.2 (10)	N4—C10—H10B	108.8 (8)
C2—N2—H2N	118.3 (10)	C9—C10—H10B	110.0 (8)
O2—N3—O1	121.32 (10)	H10A—C10—H10B	109.3 (11)
O2—N3—C4	119.46 (10)	N4—C11—C16	120.73 (10)
O1—N3—C4	119.22 (9)	N4—C11—C12	123.74 (10)
C11—N4—C10	123.95 (10)	C16—C11—C12	115.52 (10)
C11—N4—H4N	114.8 (10)	C13—C12—C11	121.82 (11)
C10—N4—H4N	121.1 (10)	C13—C12—N5	116.56 (10)
O4—N5—O3	121.58 (10)	C11—C12—N5	121.62 (10)
O4—N5—C12	118.82 (10)	C14—C13—C12	120.66 (11)
O3—N5—C12	119.60 (10)	C14—C13—H13	121.2 (9)
C19—N6—C18	123.09 (9)	C12—C13—H13	118.1 (9)
C19—N6—H6N	117.6 (10)	C13—C14—C15	118.71 (11)
C18—N6—H6N	116.4 (10)	C13—C14—H14	120.5 (9)
O6—N7—O5	121.72 (11)	C15—C14—H14	120.7 (9)
O6—N7—C20	118.82 (11)	C16—C15—C14	121.29 (11)
O5—N7—C20	119.46 (9)	C16—C15—H15	118.6 (8)
N1—C1—C2	110.72 (9)	C14—C15—H15	120.1 (8)
N1—C1—H1A	112.8 (8)	C15—C16—C11	121.92 (11)
C2—C1—H1A	110.0 (8)	C15—C16—H16	118.9 (9)
N1—C1—H1B	107.9 (7)	C11—C16—H16	119.1 (9)
C2—C1—H1B	108.7 (8)	N1—C17—C18	110.88 (9)
H1A—C1—H1B	106.5 (11)	N1—C17—H17A	112.3 (8)
N2—C2—C1	112.77 (10)	C18—C17—H17A	108.6 (7)
N2—C2—H2A	105.3 (8)	N1—C17—H17B	109.0 (8)
C1—C2—H2A	110.9 (9)	C18—C17—H17B	108.1 (7)
N2—C2—H2B	110.6 (8)	H17A—C17—H17B	107.9 (10)
C1—C2—H2B	108.2 (8)	N6—C18—C17	108.29 (9)
H2A—C2—H2B	108.9 (12)	N6—C18—H18A	110.9 (8)
N2—C3—C8	121.04 (11)	C17—C18—H18A	111.4 (7)
N2—C3—C4	123.65 (11)	N6—C18—H18B	110.1 (8)
C8—C3—C4	115.31 (11)	C17—C18—H18B	108.5 (8)
C5—C4—C3	121.73 (11)	H18A—C18—H18B	107.6 (11)
C5—C4—N3	116.34 (10)	N6—C19—C24	119.78 (10)
C3—C4—N3	121.87 (10)	N6—C19—C20	124.39 (10)
C6—C5—C4	120.92 (12)	C24—C19—C20	115.83 (10)
C6—C5—H5	122.9 (9)	C21—C20—C19	121.46 (11)
C4—C5—H5	116.2 (9)	C21—C20—N7	116.84 (11)
C5—C6—C7	118.49 (12)	C19—C20—N7	121.69 (10)
C5—C6—H6	120.5 (9)	C22—C21—C20	120.79 (12)
C7—C6—H6	121.0 (9)	C22—C21—H21	121.6 (9)
C8—C7—C6	121.70 (12)	C20—C21—H21	117.6 (9)
C8—C7—H7	118.1 (9)	C21—C22—C23	118.79 (12)
C6—C7—H7	120.2 (9)	C21—C22—H22	121.4 (10)
C7—C8—C3	121.84 (12)	C23—C22—H22	119.8 (10)
C7—C8—H8	119.7 (9)	C24—C23—C22	121.41 (12)
C3—C8—H8	118.5 (9)	C24—C23—H23	118.8 (9)
N1—C9—C10	112.53 (9)	C22—C23—H23	119.8 (9)
N1—C9—H9A	111.4 (8)	C23—C24—C19	121.72 (11)
C10—C9—H9A	109.6 (8)	C23—C24—H24	119.1 (8)
N1—C9—H9B	107.5 (8)	C19—C24—H24	119.2 (8)
C10—C9—H9B	107.7 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O1	0.884 (17)	1.939 (16)	2.6214 (13)	132.9 (14)
N2—H2N···O1^i	0.884 (17)	2.399 (16)	3.0715 (14)	133.1 (13)
N4—H4N···O3	0.868 (16)	1.942 (16)	2.6265 (13)	134.7 (13)
N6—H6N···O5	0.849 (15)	2.013 (15)	2.6320 (13)	129.1 (12)
C10—H10A···O2^ii	0.993 (14)	2.543 (14)	3.5068 (14)	163.6 (11)
C18—H18B···O4^iii	0.985 (14)	2.584 (14)	3.3177 (15)	131.3 (10)

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