Mechanochemical synthesis and X-ray structural characterization of three 3-nitro­phenol cocrystals with three aminal cage aza­adamantanes: the role of the stereoelectronic effect on inter­molecular hydrogen-bonding patterns

The structures of the cocrystalline adducts of 3-nitro­phenol (3-NP) with 1,3,5,7-tetra­aza­tri­cyclo­[3.3.1.1^3,7]decane [HMTA, (1)] as the 2:1:1 hydrate, 2C₆H₅NO₃·C₆H₁₂N₄·H₂O, (1a), with 1,3,6,8-tetra­aza­tri­cyclo­[4.3.1.1^3,8]undecane [TATU (2)] as the 2:1 cocrystal, 2C₆H₅NO₃·C₇H₁₄N₄, (2a), and with 1,3,6,8-tetra­aza­tri­cyclo­[4.4.1.1^3,8]dodecane [TATD, (3)] as the 2:1 cocrystal, 2C₆H₅NO₃·C₈H₁₆N₄, (3a), are reported. In the binary crystals (2a) and (3a), the 3-nitro­phenol mol­ecules are linked via O—H...N hydrogen bonds into aminal cage aza­adamantanes. In (1a), the structure is stabilized by O—H...N and O—H...O hydrogen bonds, and generates ternary cocrystals. There are C—H...O hydrogen bonds present in all three cocrystals, and in (1a), there are also C—H...O and C—H...π inter­actions present. The presence of an ethyl­ene bridge in the structures of (2) and (3) defines the formation of a hydrogen-bonded motif in the supra­molecular architectures of (2a) and (3a). The differences in the C—N bond lengths of the aminal cage structures, as a result of hyperconjugative inter­actions and electron delocalization, were analysed. These three cocrystals were obtained by the solvent-free assisted grinding method. Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation from a mixture of hexa­nes.

Computing details

For all structures, data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008). Program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015) for (1a), (2a); SHELXL2014 (Sheldrick, 2015) for (3a). For all structures, molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008). Software used to prepare material for publication: SHELXL for (1a), (3a); SHELXL2018 (Sheldrick, 2015) for (2a).

3-Nitrophenol–1,3,5,7-tetraazatricyclo[3.3.1.1^3,7]decane–water (2:1:1) (1a)

Crystal data

2C6H5NO3·C6H12N4·H2O	F(000) = 920
Mr = 436.43	Dx = 1.427 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.6765 (6) Å	Cell parameters from 8615 reflections
b = 28.819 (3) Å	θ = 2.4–25.5°
c = 6.8163 (4) Å	µ = 0.11 mm^−1
β = 104.395 (5)°	T = 173 K
V = 2031.5 (2) Å^3	Block, colourless
Z = 4	0.26 × 0.25 × 0.23 mm

Data collection

Stoe IPDS II two-circle diffractometer	3024 reflections with I > 2σ(I)
Radiation source: Genix 3D IµS microfocus X-ray source	Rint = 0.030
ω scans	θmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2001)	h = −12→12
Tmin = 0.678, Tmax = 1.000	k = −32→34
8615 measured reflections	l = −8→8
3559 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.057	w = 1/[σ^2(Fo^2) + (0.0402P)^2 + 1.5429P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.136	(Δ/σ)max < 0.001
S = 1.24	Δρmax = 0.19 e Å^−3
3559 reflections	Δρmin = −0.19 e Å^−3
297 parameters	Extinction correction: SHELXL2018 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0076 (14)
Primary atom site location: structure-invariant direct methods

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
N1	0.5573 (2)	0.67919 (7)	0.7511 (4)	0.0366 (5)
N2	0.4781 (2)	0.60884 (7)	0.5599 (3)	0.0327 (5)
N3	0.33305 (19)	0.65519 (7)	0.7072 (3)	0.0332 (5)
N4	0.5062 (2)	0.61043 (7)	0.9282 (3)	0.0331 (5)
C1	0.5915 (3)	0.65086 (10)	0.9378 (4)	0.0401 (7)
H1A	0.681983	0.640054	0.959915	0.048*
H1B	0.586100	0.670411	1.054823	0.048*
C2	0.5156 (3)	0.58242 (9)	0.7514 (4)	0.0322 (6)
H2A	0.458936	0.554902	0.741831	0.039*
H2B	0.605653	0.571291	0.771096	0.039*
C3	0.3720 (2)	0.62791 (9)	0.8928 (4)	0.0359 (6)
H3A	0.312399	0.601265	0.884507	0.043*
H3B	0.364706	0.647336	1.009225	0.043*
C4	0.5646 (3)	0.64920 (10)	0.5797 (4)	0.0382 (7)
H4A	0.541298	0.667554	0.453018	0.046*
H4B	0.654635	0.638251	0.598163	0.046*
C5	0.4215 (2)	0.69446 (9)	0.7219 (5)	0.0373 (6)
H5A	0.414552	0.714399	0.836998	0.045*
H5B	0.395893	0.713233	0.596619	0.045*
C6	0.3447 (3)	0.62584 (10)	0.5374 (4)	0.0384 (7)
H6A	0.317536	0.643770	0.410031	0.046*
H6B	0.285698	0.598956	0.527655	0.046*
O1	0.67092 (17)	0.76454 (7)	0.7865 (3)	0.0385 (5)
H1	0.651 (3)	0.7352 (13)	0.787 (5)	0.055 (10)*
N11	1.1070 (2)	0.70433 (8)	1.0448 (3)	0.0353 (5)
O11	1.0675 (2)	0.66478 (7)	1.0085 (4)	0.0513 (6)
O12	1.22130 (18)	0.71336 (7)	1.1252 (4)	0.0513 (6)
C11	0.8000 (2)	0.76995 (9)	0.8651 (4)	0.0285 (5)
C12	0.8856 (2)	0.73314 (8)	0.9132 (4)	0.0286 (5)
H12	0.856114	0.701995	0.892213	0.034*
C13	1.0151 (2)	0.74298 (9)	0.9928 (4)	0.0290 (6)
C14	1.0635 (2)	0.78777 (9)	1.0261 (4)	0.0338 (6)
H14	1.152891	0.793388	1.082108	0.041*
C15	0.9763 (3)	0.82382 (9)	0.9747 (4)	0.0346 (6)
H15	1.006319	0.854908	0.994883	0.042*
C16	0.8464 (2)	0.81552 (9)	0.8945 (4)	0.0322 (6)
H16	0.788122	0.840830	0.859155	0.039*
O2	0.7877 (2)	0.50228 (8)	0.3853 (3)	0.0440 (5)
H2	0.716 (4)	0.5208 (14)	0.345 (6)	0.072 (12)*
C21	0.8154 (2)	0.48511 (9)	0.2156 (4)	0.0318 (6)
N21	1.0827 (2)	0.41888 (8)	0.0861 (4)	0.0424 (6)
O21	1.1452 (2)	0.40915 (8)	0.2579 (4)	0.0583 (6)
O22	1.1177 (2)	0.40958 (8)	−0.0674 (4)	0.0554 (6)
C22	0.9311 (2)	0.46097 (9)	0.2370 (4)	0.0336 (6)
H22	0.988755	0.456605	0.366383	0.040*
C23	0.9595 (2)	0.44357 (8)	0.0639 (4)	0.0329 (6)
C24	0.8798 (3)	0.44897 (9)	−0.1276 (4)	0.0354 (6)
H24	0.902966	0.436865	−0.243325	0.043*
C25	0.7648 (3)	0.47265 (9)	−0.1451 (4)	0.0356 (6)
H25	0.707599	0.476886	−0.274972	0.043*
C26	0.7322 (2)	0.49024 (8)	0.0246 (4)	0.0314 (6)
H26	0.652246	0.505971	0.010350	0.038*
O1W	0.5718 (2)	0.55333 (8)	0.2806 (3)	0.0446 (5)
H1WA	0.536 (5)	0.5697 (17)	0.356 (8)	0.104 (17)*
H1WB	0.558 (4)	0.5722 (16)	0.165 (8)	0.098 (15)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0253 (11)	0.0278 (11)	0.0552 (15)	0.0004 (9)	0.0070 (10)	0.0017 (10)
N2	0.0364 (12)	0.0321 (12)	0.0299 (12)	0.0056 (9)	0.0087 (9)	0.0007 (9)
N3	0.0241 (11)	0.0283 (11)	0.0467 (13)	0.0025 (9)	0.0075 (9)	0.0030 (10)
N4	0.0338 (12)	0.0310 (11)	0.0350 (12)	0.0066 (9)	0.0094 (9)	0.0021 (9)
C1	0.0293 (13)	0.0375 (15)	0.0474 (17)	0.0020 (11)	−0.0017 (12)	−0.0074 (13)
C2	0.0349 (14)	0.0260 (13)	0.0361 (14)	0.0038 (11)	0.0095 (11)	0.0015 (11)
C3	0.0336 (14)	0.0325 (14)	0.0448 (16)	0.0028 (11)	0.0157 (12)	0.0005 (12)
C4	0.0348 (14)	0.0378 (15)	0.0471 (17)	0.0044 (12)	0.0196 (12)	0.0100 (13)
C5	0.0292 (14)	0.0248 (13)	0.0578 (18)	0.0036 (11)	0.0107 (12)	0.0028 (12)
C6	0.0310 (14)	0.0368 (14)	0.0419 (16)	0.0005 (11)	−0.0014 (11)	−0.0006 (12)
O1	0.0287 (10)	0.0300 (10)	0.0527 (12)	−0.0047 (8)	0.0023 (8)	0.0034 (9)
N11	0.0332 (12)	0.0336 (12)	0.0403 (13)	−0.0012 (10)	0.0117 (10)	−0.0003 (10)
O11	0.0469 (12)	0.0291 (11)	0.0753 (16)	0.0001 (9)	0.0103 (11)	−0.0006 (10)
O12	0.0274 (10)	0.0466 (12)	0.0761 (16)	0.0010 (9)	0.0058 (10)	−0.0008 (11)
C11	0.0275 (13)	0.0297 (13)	0.0297 (13)	−0.0043 (10)	0.0097 (10)	−0.0011 (10)
C12	0.0333 (13)	0.0258 (12)	0.0282 (13)	−0.0069 (10)	0.0104 (10)	−0.0009 (10)
C13	0.0276 (13)	0.0287 (13)	0.0322 (14)	−0.0009 (10)	0.0106 (10)	−0.0005 (10)
C14	0.0281 (13)	0.0341 (14)	0.0393 (15)	−0.0064 (11)	0.0088 (11)	−0.0038 (11)
C15	0.0381 (15)	0.0276 (13)	0.0404 (15)	−0.0078 (11)	0.0140 (12)	−0.0045 (11)
C16	0.0354 (14)	0.0268 (13)	0.0366 (15)	−0.0021 (11)	0.0132 (11)	−0.0007 (11)
O2	0.0449 (12)	0.0533 (13)	0.0325 (11)	0.0168 (10)	0.0074 (9)	0.0002 (9)
C21	0.0325 (13)	0.0279 (13)	0.0352 (14)	0.0011 (11)	0.0089 (11)	0.0008 (11)
N21	0.0312 (12)	0.0274 (12)	0.0700 (18)	−0.0008 (10)	0.0149 (13)	−0.0004 (12)
O21	0.0364 (11)	0.0552 (14)	0.0786 (17)	0.0150 (10)	0.0055 (11)	0.0075 (12)
O22	0.0455 (12)	0.0463 (13)	0.0844 (17)	0.0045 (10)	0.0347 (12)	−0.0059 (12)
C22	0.0289 (13)	0.0288 (13)	0.0407 (15)	−0.0018 (11)	0.0042 (11)	0.0039 (11)
C23	0.0277 (13)	0.0214 (12)	0.0510 (17)	−0.0010 (10)	0.0124 (11)	0.0000 (11)
C24	0.0377 (14)	0.0300 (14)	0.0405 (15)	−0.0017 (11)	0.0134 (12)	−0.0047 (11)
C25	0.0359 (14)	0.0329 (14)	0.0364 (15)	−0.0009 (11)	0.0057 (11)	0.0006 (11)
C26	0.0294 (13)	0.0261 (13)	0.0383 (15)	0.0038 (10)	0.0074 (11)	0.0036 (11)
O1W	0.0502 (12)	0.0507 (13)	0.0350 (11)	0.0204 (10)	0.0147 (10)	0.0040 (10)

Geometric parameters (Å, º)

N1—C4	1.471 (4)	N11—C13	1.469 (3)
N1—C1	1.479 (4)	C11—C12	1.385 (4)
N1—C5	1.481 (3)	C11—C16	1.400 (4)
N2—C4	1.470 (3)	C12—C13	1.383 (3)
N2—C2	1.478 (3)	C12—H12	0.9500
N2—C6	1.478 (3)	C13—C14	1.388 (4)
N3—C3	1.459 (3)	C14—C15	1.381 (4)
N3—C5	1.461 (3)	C14—H14	0.9500
N3—C6	1.464 (4)	C15—C16	1.379 (4)
N4—C1	1.470 (4)	C15—H15	0.9500
N4—C2	1.474 (3)	C16—H16	0.9500
N4—C3	1.481 (3)	O2—C21	1.357 (3)
C1—H1A	0.9900	O2—H2	0.92 (4)
C1—H1B	0.9900	C21—C26	1.389 (4)
C2—H2A	0.9900	C21—C22	1.394 (4)
C2—H2B	0.9900	N21—O22	1.225 (3)
C3—H3A	0.9900	N21—O21	1.227 (3)
C3—H3B	0.9900	N21—C23	1.470 (3)
C4—H4A	0.9900	C22—C23	1.383 (4)
C4—H4B	0.9900	C22—H22	0.9500
C5—H5A	0.9900	C23—C24	1.378 (4)
C5—H5B	0.9900	C24—C25	1.384 (4)
C6—H6A	0.9900	C24—H24	0.9500
C6—H6B	0.9900	C25—C26	1.384 (4)
O1—C11	1.358 (3)	C25—H25	0.9500
O1—H1	0.87 (4)	C26—H26	0.9500
N11—O11	1.219 (3)	O1W—H1WA	0.85 (5)
N11—O12	1.234 (3)	O1W—H1WB	0.94 (5)
C4—N1—C1	108.0 (2)	H6A—C6—H6B	107.9
C4—N1—C5	108.1 (2)	C11—O1—H1	109 (2)
C1—N1—C5	107.7 (2)	O11—N11—O12	122.8 (2)
C4—N2—C2	107.5 (2)	O11—N11—C13	118.9 (2)
C4—N2—C6	108.3 (2)	O12—N11—C13	118.3 (2)
C2—N2—C6	107.8 (2)	O1—C11—C12	123.4 (2)
C3—N3—C5	108.5 (2)	O1—C11—C16	116.9 (2)
C3—N3—C6	108.2 (2)	C12—C11—C16	119.7 (2)
C5—N3—C6	108.7 (2)	C13—C12—C11	118.1 (2)
C1—N4—C2	107.7 (2)	C13—C12—H12	120.9
C1—N4—C3	107.5 (2)	C11—C12—H12	120.9
C2—N4—C3	108.2 (2)	C12—C13—C14	123.4 (2)
N4—C1—N1	112.4 (2)	C12—C13—N11	118.8 (2)
N4—C1—H1A	109.1	C14—C13—N11	117.8 (2)
N1—C1—H1A	109.1	C15—C14—C13	117.3 (2)
N4—C1—H1B	109.1	C15—C14—H14	121.4
N1—C1—H1B	109.1	C13—C14—H14	121.4
H1A—C1—H1B	107.9	C16—C15—C14	121.2 (2)
N4—C2—N2	112.4 (2)	C16—C15—H15	119.4
N4—C2—H2A	109.1	C14—C15—H15	119.4
N2—C2—H2A	109.1	C15—C16—C11	120.3 (2)
N4—C2—H2B	109.1	C15—C16—H16	119.9
N2—C2—H2B	109.1	C11—C16—H16	119.9
H2A—C2—H2B	107.9	C21—O2—H2	107 (2)
N3—C3—N4	112.3 (2)	O2—C21—C26	122.4 (2)
N3—C3—H3A	109.1	O2—C21—C22	117.9 (2)
N4—C3—H3A	109.1	C26—C21—C22	119.7 (2)
N3—C3—H3B	109.1	O22—N21—O21	123.8 (3)
N4—C3—H3B	109.1	O22—N21—C23	118.2 (3)
H3A—C3—H3B	107.9	O21—N21—C23	118.0 (3)
N2—C4—N1	112.5 (2)	C23—C22—C21	117.9 (2)
N2—C4—H4A	109.1	C23—C22—H22	121.0
N1—C4—H4A	109.1	C21—C22—H22	121.0
N2—C4—H4B	109.1	C24—C23—C22	123.5 (2)
N1—C4—H4B	109.1	C24—C23—N21	118.6 (3)
H4A—C4—H4B	107.8	C22—C23—N21	117.9 (2)
N3—C5—N1	111.9 (2)	C23—C24—C25	117.6 (3)
N3—C5—H5A	109.2	C23—C24—H24	121.2
N1—C5—H5A	109.2	C25—C24—H24	121.2
N3—C5—H5B	109.2	C24—C25—C26	120.7 (2)
N1—C5—H5B	109.2	C24—C25—H25	119.7
H5A—C5—H5B	107.9	C26—C25—H25	119.7
N3—C6—N2	112.2 (2)	C25—C26—C21	120.6 (2)
N3—C6—H6A	109.2	C25—C26—H26	119.7
N2—C6—H6A	109.2	C21—C26—H26	119.7
N3—C6—H6B	109.2	H1WA—O1W—H1WB	101 (4)
N2—C6—H6B	109.2
C2—N4—C1—N1	58.2 (3)	C11—C12—C13—C14	−0.2 (4)
C3—N4—C1—N1	−58.2 (3)	C11—C12—C13—N11	179.9 (2)
C4—N1—C1—N4	−58.1 (3)	O11—N11—C13—C12	3.1 (4)
C5—N1—C1—N4	58.4 (3)	O12—N11—C13—C12	−176.4 (2)
C1—N4—C2—N2	−58.9 (3)	O11—N11—C13—C14	−176.8 (2)
C3—N4—C2—N2	57.1 (3)	O12—N11—C13—C14	3.7 (4)
C4—N2—C2—N4	59.0 (3)	C12—C13—C14—C15	−0.5 (4)
C6—N2—C2—N4	−57.5 (3)	N11—C13—C14—C15	179.4 (2)
C5—N3—C3—N4	−59.0 (3)	C13—C14—C15—C16	0.4 (4)
C6—N3—C3—N4	58.8 (3)	C14—C15—C16—C11	0.5 (4)
C1—N4—C3—N3	58.3 (3)	O1—C11—C16—C15	179.7 (2)
C2—N4—C3—N3	−57.7 (3)	C12—C11—C16—C15	−1.2 (4)
C2—N2—C4—N1	−58.7 (3)	O2—C21—C22—C23	−179.8 (2)
C6—N2—C4—N1	57.4 (3)	C26—C21—C22—C23	1.0 (4)
C1—N1—C4—N2	58.4 (3)	C21—C22—C23—C24	0.2 (4)
C5—N1—C4—N2	−57.9 (3)	C21—C22—C23—N21	178.9 (2)
C3—N3—C5—N1	58.9 (3)	O22—N21—C23—C24	9.7 (3)
C6—N3—C5—N1	−58.6 (3)	O21—N21—C23—C24	−171.0 (2)
C4—N1—C5—N3	58.2 (3)	O22—N21—C23—C22	−169.1 (2)
C1—N1—C5—N3	−58.2 (3)	O21—N21—C23—C22	10.2 (3)
C3—N3—C6—N2	−59.5 (3)	C22—C23—C24—C25	−0.8 (4)
C5—N3—C6—N2	58.2 (3)	N21—C23—C24—C25	−179.5 (2)
C4—N2—C6—N3	−57.3 (3)	C23—C24—C25—C26	0.2 (4)
C2—N2—C6—N3	58.7 (3)	C24—C25—C26—C21	1.1 (4)
O1—C11—C12—C13	−179.9 (2)	O2—C21—C26—C25	179.2 (2)
C16—C11—C12—C13	1.0 (4)	C22—C21—C26—C25	−1.7 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.87 (4)	1.89 (4)	2.727 (3)	162 (3)
O2—H2···O1W	0.92 (4)	1.76 (4)	2.677 (3)	175 (4)
O1W—H1WA···N2	0.85 (5)	2.00 (5)	2.852 (3)	172 (5)
O1W—H1WB···N4^i	0.94 (5)	1.92 (5)	2.852 (3)	173 (4)
C1—H1A···O22^ii	0.99	2.53	3.476 (3)	161
C1—H1B···O1^iii	0.99	2.47	3.363 (3)	149
C4—H4B···O21^ii	0.99	2.52	3.457 (3)	158
C14—H14···N3^iv	0.95	2.41	3.278 (3)	152

Symmetry codes: (i) x, y, z−1; (ii) −x+2, −y+1, −z+1; (iii) x, −y+3/2, z+1/2; (iv) x+1, −y+3/2, z+1/2.

3-Nitrophenol–1,3,6,8-tetraazatricyclo[4.3.1.1^3,8]undecane (2:1) (2a)

Crystal data

C7H14N4·2C6H5NO3	F(000) = 456
Mr = 432.44	Dx = 1.413 Mg m^−3
Monoclinic, Cm	Mo Kα radiation, λ = 0.71073 Å
a = 7.2053 (7) Å	Cell parameters from 8351 reflections
b = 25.253 (2) Å	θ = 3.4–27.8°
c = 6.5134 (6) Å	µ = 0.11 mm^−1
β = 120.939 (6)°	T = 173 K
V = 1016.52 (17) Å^3	Plate, yellow
Z = 2	0.23 × 0.17 × 0.08 mm

Data collection

Stoe IPDS II two-circle diffractometer	2119 reflections with I > 2σ(I)
Radiation source: Genix 3D IµS microfocus X-ray source	Rint = 0.036
ω scans	θmax = 27.6°, θmin = 3.4°
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2001)	h = −9→9
Tmin = 0.529, Tmax = 1.000	k = −32→32
8351 measured reflections	l = −8→8
2401 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.039	w = 1/[σ^2(Fo^2) + (0.0567P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.094	(Δ/σ)max < 0.001
S = 1.05	Δρmax = 0.17 e Å^−3
2401 reflections	Δρmin = −0.19 e Å^−3
149 parameters	Absolute structure: Flack x determined using 883 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
2 restraints	Absolute structure parameter: −1.8 (10)
Primary atom site location: structure-invariant direct methods

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	Occ. (<1)
O1	0.5286 (3)	0.16364 (8)	0.7582 (3)	0.0347 (5)
H1	0.530 (6)	0.1304 (15)	0.718 (6)	0.042 (9)*
O2	0.5119 (4)	0.37561 (9)	0.3797 (4)	0.0585 (7)
O3	0.5330 (4)	0.35709 (9)	0.7134 (4)	0.0495 (6)
N1	0.5539 (4)	0.05764 (9)	0.7291 (4)	0.0322 (5)
N2	0.8694 (6)	0.000000	1.0000 (6)	0.0405 (8)
N3	0.5526 (6)	0.000000	1.0384 (6)	0.0380 (8)
N11	0.5176 (4)	0.34371 (9)	0.5246 (4)	0.0361 (6)
C1	0.7924 (5)	0.04855 (11)	0.8566 (6)	0.0392 (7)
H1A	0.837407	0.047695	0.736394	0.047*
H1B	0.865436	0.079135	0.963243	0.047*
C2	0.4302 (6)	0.03087 (11)	0.4979 (5)	0.0403 (7)
H2A	0.486413	0.042928	0.395508	0.048*
H2B	0.278114	0.042929	0.421294	0.048*
C3	0.4749 (5)	0.04851 (11)	0.8952 (5)	0.0376 (7)
H3A	0.517924	0.079087	1.005633	0.045*
H3B	0.314779	0.047512	0.801087	0.045*
C4	0.7891 (8)	0.000000	1.1659 (7)	0.0430 (10)
H4A	0.844458	−0.031708	1.269749	0.052*	0.5
H4B	0.844459	0.031708	1.269750	0.052*	0.5
C11	0.5156 (4)	0.19734 (10)	0.5904 (4)	0.0246 (5)
C12	0.5266 (4)	0.25136 (11)	0.6409 (4)	0.0258 (5)
H12	0.546383	0.263450	0.788997	0.031*
C13	0.5077 (4)	0.28686 (10)	0.4689 (4)	0.0267 (5)
C14	0.4793 (4)	0.27170 (11)	0.2496 (4)	0.0301 (6)
H14	0.466071	0.297122	0.135315	0.036*
C15	0.4711 (4)	0.21778 (11)	0.2049 (4)	0.0298 (5)
H15	0.453845	0.205983	0.057549	0.036*
C16	0.4876 (4)	0.18075 (10)	0.3706 (4)	0.0276 (5)
H16	0.479787	0.144038	0.335216	0.033*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0577 (13)	0.0219 (9)	0.0310 (9)	0.0006 (9)	0.0274 (9)	0.0025 (7)
O2	0.0795 (19)	0.0290 (12)	0.0552 (14)	−0.0007 (11)	0.0261 (13)	0.0148 (10)
O3	0.0660 (15)	0.0305 (11)	0.0626 (14)	−0.0020 (10)	0.0405 (12)	−0.0109 (11)
N1	0.0488 (14)	0.0221 (10)	0.0312 (11)	0.0011 (10)	0.0245 (10)	0.0017 (9)
N2	0.043 (2)	0.0312 (17)	0.0422 (19)	0.000	0.0187 (16)	0.000
N3	0.067 (2)	0.0230 (15)	0.0340 (16)	0.000	0.0327 (17)	0.000
N11	0.0346 (13)	0.0232 (11)	0.0461 (15)	0.0018 (9)	0.0175 (11)	0.0030 (10)
C1	0.0489 (17)	0.0279 (14)	0.0464 (16)	−0.0057 (12)	0.0284 (14)	−0.0011 (11)
C2	0.0609 (19)	0.0271 (15)	0.0302 (13)	0.0047 (12)	0.0215 (13)	0.0031 (10)
C3	0.059 (2)	0.0246 (13)	0.0409 (15)	0.0027 (12)	0.0343 (15)	0.0000 (11)
C4	0.066 (3)	0.028 (2)	0.0284 (18)	0.000	0.0198 (19)	0.000
C11	0.0256 (12)	0.0249 (12)	0.0232 (11)	0.0006 (10)	0.0123 (9)	0.0015 (9)
C12	0.0263 (12)	0.0261 (12)	0.0237 (11)	0.0009 (10)	0.0120 (9)	−0.0003 (9)
C13	0.0249 (12)	0.0230 (12)	0.0289 (11)	0.0010 (9)	0.0114 (10)	0.0015 (9)
C14	0.0286 (13)	0.0333 (13)	0.0266 (12)	0.0024 (11)	0.0129 (10)	0.0076 (10)
C15	0.0275 (13)	0.0381 (14)	0.0234 (11)	0.0004 (11)	0.0127 (10)	−0.0002 (10)
C16	0.0308 (13)	0.0245 (12)	0.0279 (12)	−0.0002 (10)	0.0154 (11)	−0.0039 (10)

Geometric parameters (Å, º)

O1—C11	1.350 (3)	C2—H2A	0.9900
O1—H1	0.88 (4)	C2—H2B	0.9900
O2—N11	1.225 (3)	C3—H3A	0.9900
O3—N11	1.224 (3)	C3—H3B	0.9900
N1—C2	1.463 (4)	C4—H4A	0.9900
N1—C3	1.477 (3)	C4—H4B	0.9900
N1—C1	1.493 (4)	C11—C12	1.396 (3)
N2—C4	1.465 (5)	C11—C16	1.403 (3)
N2—C1^i	1.466 (3)	C12—C13	1.386 (3)
N2—C1	1.466 (3)	C12—H12	0.9500
N3—C4	1.462 (6)	C13—C14	1.388 (4)
N3—C3^i	1.465 (3)	C14—C15	1.387 (4)
N3—C3	1.465 (3)	C14—H14	0.9500
N11—C13	1.474 (3)	C15—C16	1.386 (4)
C1—H1A	0.9900	C15—H15	0.9500
C1—H1B	0.9900	C16—H16	0.9500
C2—C2^i	1.559 (6)
C11—O1—H1	111 (2)	N3—C3—H3B	108.4
C2—N1—C3	114.9 (2)	N1—C3—H3B	108.4
C2—N1—C1	114.8 (2)	H3A—C3—H3B	107.5
C3—N1—C1	109.6 (2)	N3—C4—N2	111.6 (3)
C4—N2—C1^i	107.8 (2)	N3—C4—H4A	109.3
C4—N2—C1	107.8 (2)	N2—C4—H4A	109.3
C1^i—N2—C1	113.4 (3)	N3—C4—H4B	109.3
C4—N3—C3^i	108.3 (2)	N2—C4—H4B	109.3
C4—N3—C3	108.3 (2)	H4A—C4—H4B	108.0
C3^i—N3—C3	113.5 (3)	O1—C11—C12	117.0 (2)
O3—N11—O2	122.8 (3)	O1—C11—C16	123.5 (2)
O3—N11—C13	119.0 (2)	C12—C11—C16	119.5 (2)
O2—N11—C13	118.2 (2)	C13—C12—C11	118.1 (2)
N2—C1—N1	115.7 (2)	C13—C12—H12	120.9
N2—C1—H1A	108.4	C11—C12—H12	120.9
N1—C1—H1A	108.4	C12—C13—C14	123.7 (2)
N2—C1—H1B	108.4	C12—C13—N11	117.3 (2)
N1—C1—H1B	108.4	C14—C13—N11	119.0 (2)
H1A—C1—H1B	107.4	C15—C14—C13	117.0 (2)
N1—C2—C2^i	117.53 (13)	C15—C14—H14	121.5
N1—C2—H2A	107.9	C13—C14—H14	121.5
C2^i—C2—H2A	107.9	C16—C15—C14	121.4 (2)
N1—C2—H2B	107.9	C16—C15—H15	119.3
C2^i—C2—H2B	107.9	C14—C15—H15	119.3
H2A—C2—H2B	107.2	C15—C16—C11	120.2 (2)
N3—C3—N1	115.6 (2)	C15—C16—H16	119.9
N3—C3—H3A	108.4	C11—C16—H16	119.9
N1—C3—H3A	108.4
C4—N2—C1—N1	−54.3 (3)	O1—C11—C12—C13	−178.3 (2)
C1^i—N2—C1—N1	65.0 (4)	C16—C11—C12—C13	0.4 (3)
C2—N1—C1—N2	−84.3 (3)	C11—C12—C13—C14	−0.2 (4)
C3—N1—C1—N2	46.9 (3)	C11—C12—C13—N11	179.4 (2)
C3—N1—C2—C2^i	−64.1 (2)	O3—N11—C13—C12	−2.9 (3)
C1—N1—C2—C2^i	64.4 (2)	O2—N11—C13—C12	176.5 (3)
C4—N3—C3—N1	54.7 (3)	O3—N11—C13—C14	176.8 (3)
C3^i—N3—C3—N1	−65.6 (4)	O2—N11—C13—C14	−3.9 (4)
C2—N1—C3—N3	84.2 (3)	C12—C13—C14—C15	−0.4 (4)
C1—N1—C3—N3	−46.8 (3)	N11—C13—C14—C15	180.0 (2)
C3^i—N3—C4—N2	61.73 (19)	C13—C14—C15—C16	0.9 (4)
C3—N3—C4—N2	−61.73 (19)	C14—C15—C16—C11	−0.7 (4)
C1^i—N2—C4—N3	−61.4 (2)	O1—C11—C16—C15	178.6 (3)
C1—N2—C4—N3	61.4 (2)	C12—C11—C16—C15	0.1 (3)

Symmetry code: (i) x, −y, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.88 (4)	1.84 (4)	2.696 (3)	162 (3)
C4—H4A···O2^ii	0.99	2.56	3.476 (3)	154
C4—H4B···O2^iii	0.99	2.56	3.476 (3)	154
C15—H15···O1^iv	0.95	2.51	3.427 (3)	161

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

3-Nitrophenol–1,3,6,8-tetraazatricyclo[4.4.1.1^3,8]dodecane (2:1) (3a)

Crystal data

C8H16N4·2C6H5NO3	F(000) = 944
Mr = 446.47	Dx = 1.421 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 26.159 (3) Å	Cell parameters from 11125 reflections
b = 6.4931 (4) Å	θ = 3.5–25.8°
c = 12.8070 (14) Å	µ = 0.11 mm^−1
β = 106.338 (8)°	T = 173 K
V = 2087.5 (4) Å^3	Plate, yellow
Z = 4	0.26 × 0.24 × 0.09 mm

Data collection

Stoe IPDS II two-circle diffractometer	3297 reflections with I > 2σ(I)
Radiation source: Genix 3D IµS microfocus X-ray source	Rint = 0.027
ω scans	θmax = 25.6°, θmin = 3.5°
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2001)	h = −31→31
Tmin = 0.582, Tmax = 1.000	k = −7→7
11125 measured reflections	l = −15→15
3505 independent reflections

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0416P)^2 + 1.2092P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.036	(Δ/σ)max < 0.001
wR(F^2) = 0.087	Δρmax = 0.14 e Å^−3
S = 1.08	Δρmin = −0.15 e Å^−3
3505 reflections	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
298 parameters	Extinction coefficient: 0.0087 (10)
2 restraints	Absolute structure: Flack x determined using 1329 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.2 (9)
Hydrogen site location: mixed

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
N1	0.44528 (9)	0.2931 (4)	0.4785 (2)	0.0231 (5)
N2	0.55900 (10)	0.3302 (3)	0.5346 (2)	0.0244 (5)
N3	0.50770 (10)	0.0032 (4)	0.4661 (2)	0.0252 (5)
N4	0.49760 (9)	0.3696 (4)	0.3449 (2)	0.0247 (5)
C1	0.47168 (12)	0.4020 (5)	0.5808 (3)	0.0337 (7)
H1A	0.4651	0.3234	0.6419	0.040*
H1B	0.4545	0.5383	0.5791	0.040*
C2	0.53212 (12)	0.4353 (5)	0.6047 (3)	0.0370 (8)
H2A	0.5386	0.5850	0.6008	0.044*
H2B	0.5491	0.3915	0.6806	0.044*
C3	0.45716 (12)	0.0699 (4)	0.4817 (3)	0.0272 (6)
H3A	0.4553	0.0166	0.5530	0.033*
H3B	0.4283	0.0022	0.4252	0.033*
C4	0.45002 (11)	0.4014 (4)	0.3795 (2)	0.0264 (6)
H4A	0.4190	0.3613	0.3185	0.032*
H4B	0.4468	0.5510	0.3914	0.032*
C5	0.55491 (12)	0.1024 (4)	0.5363 (3)	0.0305 (7)
H5A	0.5863	0.0452	0.5177	0.037*
H5B	0.5578	0.0605	0.6121	0.037*
C6	0.54774 (12)	0.4195 (5)	0.4247 (3)	0.0300 (7)
H6A	0.5496	0.5712	0.4327	0.036*
H6B	0.5769	0.3776	0.3940	0.036*
C7	0.50771 (14)	−0.0199 (5)	0.3531 (3)	0.0351 (7)
H7A	0.4801	−0.1218	0.3180	0.042*
H7B	0.5426	−0.0771	0.3516	0.042*
C8	0.49764 (13)	0.1784 (5)	0.2851 (2)	0.0306 (7)
H8A	0.5252	0.1892	0.2461	0.037*
H8B	0.4628	0.1655	0.2296	0.037*
N11	0.15684 (11)	0.4297 (6)	0.3322 (2)	0.0422 (8)
O11	0.33946 (9)	0.2081 (4)	0.4343 (2)	0.0402 (6)
H11	0.3734 (18)	0.252 (7)	0.449 (3)	0.048 (11)*
O12	0.14277 (10)	0.2493 (5)	0.3334 (2)	0.0594 (8)
O13	0.12521 (9)	0.5734 (5)	0.2996 (2)	0.0596 (8)
C11	0.30418 (11)	0.3667 (5)	0.4201 (2)	0.0267 (6)
C12	0.25005 (12)	0.3201 (5)	0.3832 (2)	0.0308 (7)
H12	0.2383	0.1823	0.3668	0.037*
C13	0.21382 (11)	0.4798 (6)	0.3711 (2)	0.0310 (7)
C14	0.22866 (13)	0.6835 (6)	0.3947 (3)	0.0355 (8)
H14	0.2028	0.7896	0.3859	0.043*
C15	0.28227 (14)	0.7260 (5)	0.4311 (3)	0.0358 (7)
H15	0.2936	0.8642	0.4477	0.043*
C16	0.32020 (12)	0.5711 (5)	0.4442 (3)	0.0316 (7)
H16	0.3570	0.6039	0.4696	0.038*
N21	0.84474 (10)	0.5845 (5)	0.6896 (2)	0.0377 (7)
O21	0.66682 (9)	0.3172 (3)	0.6068 (2)	0.0402 (7)
H21	0.635 (2)	0.344 (7)	0.582 (4)	0.061 (14)*
O22	0.86017 (10)	0.4093 (4)	0.6811 (3)	0.0532 (8)
O23	0.87489 (10)	0.7320 (5)	0.7172 (3)	0.0589 (8)
C21	0.69850 (11)	0.4855 (4)	0.6209 (2)	0.0258 (6)
C22	0.75329 (11)	0.4526 (5)	0.6475 (3)	0.0281 (7)
H22	0.7674	0.3168	0.6548	0.034*
C23	0.78669 (12)	0.6217 (5)	0.6629 (2)	0.0274 (6)
C24	0.76851 (13)	0.8228 (5)	0.6538 (3)	0.0322 (7)
H24	0.7925	0.9360	0.6656	0.039*
C25	0.71378 (13)	0.8522 (5)	0.6266 (3)	0.0319 (7)
H25	0.6999	0.9883	0.6186	0.038*
C26	0.67895 (12)	0.6860 (5)	0.6109 (2)	0.0274 (7)
H26	0.6416	0.7093	0.5932	0.033*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0177 (11)	0.0254 (12)	0.0264 (12)	0.0001 (9)	0.0063 (10)	0.0009 (10)
N2	0.0196 (11)	0.0234 (12)	0.0282 (13)	0.0034 (10)	0.0035 (9)	−0.0021 (10)
N3	0.0234 (11)	0.0203 (11)	0.0318 (13)	0.0001 (9)	0.0074 (10)	0.0028 (10)
N4	0.0224 (11)	0.0237 (12)	0.0267 (12)	0.0002 (9)	0.0051 (9)	0.0059 (10)
C1	0.0282 (15)	0.0410 (18)	0.0323 (17)	0.0010 (14)	0.0091 (13)	−0.0085 (14)
C2	0.0280 (15)	0.049 (2)	0.0329 (17)	−0.0013 (14)	0.0065 (13)	−0.0157 (15)
C3	0.0233 (14)	0.0270 (14)	0.0329 (15)	0.0012 (12)	0.0106 (12)	0.0100 (13)
C4	0.0228 (13)	0.0239 (14)	0.0301 (15)	0.0042 (11)	0.0034 (12)	0.0055 (12)
C5	0.0225 (13)	0.0243 (15)	0.0391 (17)	0.0031 (12)	−0.0005 (12)	0.0061 (13)
C6	0.0231 (14)	0.0289 (15)	0.0358 (17)	−0.0049 (11)	0.0048 (12)	0.0068 (13)
C7	0.0417 (18)	0.0287 (16)	0.0390 (18)	−0.0035 (13)	0.0178 (15)	−0.0049 (13)
C8	0.0297 (15)	0.0364 (18)	0.0252 (15)	0.0032 (12)	0.0069 (12)	0.0012 (12)
N11	0.0211 (13)	0.076 (2)	0.0289 (14)	−0.0010 (14)	0.0055 (11)	−0.0050 (14)
O11	0.0204 (11)	0.0334 (12)	0.0642 (17)	−0.0017 (10)	0.0076 (11)	−0.0007 (11)
O12	0.0291 (13)	0.084 (2)	0.0609 (18)	−0.0197 (14)	0.0050 (12)	−0.0018 (15)
O13	0.0238 (13)	0.095 (2)	0.0580 (18)	0.0156 (14)	0.0078 (12)	−0.0007 (16)
C11	0.0220 (14)	0.0308 (15)	0.0266 (15)	0.0019 (11)	0.0054 (12)	0.0014 (12)
C12	0.0258 (15)	0.0383 (18)	0.0288 (16)	−0.0042 (13)	0.0084 (12)	−0.0022 (13)
C13	0.0203 (14)	0.052 (2)	0.0208 (15)	0.0022 (14)	0.0062 (12)	−0.0016 (13)
C14	0.0275 (15)	0.049 (2)	0.0308 (17)	0.0090 (14)	0.0097 (13)	−0.0038 (15)
C15	0.0384 (17)	0.0337 (18)	0.0357 (18)	0.0006 (14)	0.0113 (14)	−0.0048 (14)
C16	0.0227 (14)	0.0407 (19)	0.0301 (16)	−0.0035 (13)	0.0052 (12)	−0.0029 (14)
N21	0.0237 (13)	0.0477 (18)	0.0387 (15)	−0.0027 (13)	0.0039 (11)	0.0018 (14)
O21	0.0184 (11)	0.0252 (12)	0.0715 (18)	0.0016 (9)	0.0036 (12)	−0.0019 (11)
O22	0.0256 (12)	0.0537 (17)	0.073 (2)	0.0081 (12)	0.0027 (12)	0.0022 (14)
O23	0.0296 (13)	0.0651 (18)	0.077 (2)	−0.0200 (13)	0.0070 (13)	−0.0159 (16)
C21	0.0238 (14)	0.0236 (15)	0.0273 (16)	0.0030 (12)	0.0030 (11)	−0.0006 (12)
C22	0.0249 (15)	0.0262 (16)	0.0310 (15)	0.0056 (12)	0.0043 (12)	0.0002 (12)
C23	0.0221 (14)	0.0343 (16)	0.0227 (14)	−0.0029 (12)	0.0014 (11)	−0.0012 (12)
C24	0.0380 (18)	0.0298 (17)	0.0303 (15)	−0.0084 (13)	0.0120 (14)	−0.0043 (13)
C25	0.0427 (18)	0.0228 (14)	0.0301 (16)	0.0049 (13)	0.0101 (14)	−0.0001 (12)
C26	0.0259 (15)	0.0279 (16)	0.0282 (15)	0.0077 (12)	0.0074 (12)	0.0029 (12)

Geometric parameters (Å, º)

N1—C1	1.478 (4)	N11—O12	1.229 (5)
N1—C3	1.481 (4)	N11—O13	1.239 (4)
N1—C4	1.484 (4)	N11—C13	1.469 (4)
N2—C2	1.457 (4)	O11—C11	1.360 (4)
N2—C6	1.473 (4)	O11—H11	0.90 (5)
N2—C5	1.484 (4)	C11—C12	1.394 (4)
N3—C7	1.455 (4)	C11—C16	1.400 (4)
N3—C3	1.457 (4)	C12—C13	1.384 (5)
N3—C5	1.457 (4)	C12—H12	0.9500
N4—C4	1.449 (4)	C13—C14	1.388 (5)
N4—C6	1.455 (4)	C14—C15	1.376 (5)
N4—C8	1.459 (4)	C14—H14	0.9500
C1—C2	1.539 (4)	C15—C16	1.389 (5)
C1—H1A	0.9900	C15—H15	0.9500
C1—H1B	0.9900	C16—H16	0.9500
C2—H2A	0.9900	N21—O22	1.222 (4)
C2—H2B	0.9900	N21—O23	1.228 (4)
C3—H3A	0.9900	N21—C23	1.480 (4)
C3—H3B	0.9900	O21—C21	1.353 (4)
C4—H4A	0.9900	O21—H21	0.83 (5)
C4—H4B	0.9900	C21—C26	1.391 (4)
C5—H5A	0.9900	C21—C22	1.393 (4)
C5—H5B	0.9900	C22—C23	1.383 (4)
C6—H6A	0.9900	C22—H22	0.9500
C6—H6B	0.9900	C23—C24	1.383 (4)
C7—C8	1.535 (5)	C24—C25	1.388 (5)
C7—H7A	0.9900	C24—H24	0.9500
C7—H7B	0.9900	C25—C26	1.390 (4)
C8—H8A	0.9900	C25—H25	0.9500
C8—H8B	0.9900	C26—H26	0.9500
C1—N1—C3	113.7 (2)	C8—C7—H7B	108.4
C1—N1—C4	113.6 (2)	H7A—C7—H7B	107.5
C3—N1—C4	114.8 (2)	N4—C8—C7	116.2 (3)
C2—N2—C6	113.8 (2)	N4—C8—H8A	108.2
C2—N2—C5	114.1 (3)	C7—C8—H8A	108.2
C6—N2—C5	114.2 (2)	N4—C8—H8B	108.2
C7—N3—C3	114.9 (2)	C7—C8—H8B	108.2
C7—N3—C5	115.0 (2)	H8A—C8—H8B	107.4
C3—N3—C5	115.3 (3)	O12—N11—O13	123.2 (3)
C4—N4—C6	115.8 (2)	O12—N11—C13	119.1 (3)
C4—N4—C8	114.2 (2)	O13—N11—C13	117.7 (3)
C6—N4—C8	115.1 (2)	C11—O11—H11	112 (3)
N1—C1—C2	116.2 (3)	O11—C11—C12	117.9 (3)
N1—C1—H1A	108.2	O11—C11—C16	122.6 (3)
C2—C1—H1A	108.2	C12—C11—C16	119.5 (3)
N1—C1—H1B	108.2	C13—C12—C11	118.3 (3)
C2—C1—H1B	108.2	C13—C12—H12	120.9
H1A—C1—H1B	107.4	C11—C12—H12	120.9
N2—C2—C1	117.3 (3)	C12—C13—C14	123.3 (3)
N2—C2—H2A	108.0	C12—C13—N11	118.0 (3)
C1—C2—H2A	108.0	C14—C13—N11	118.7 (3)
N2—C2—H2B	108.0	C15—C14—C13	117.5 (3)
C1—C2—H2B	108.0	C15—C14—H14	121.3
H2A—C2—H2B	107.2	C13—C14—H14	121.3
N3—C3—N1	118.6 (2)	C14—C15—C16	121.4 (3)
N3—C3—H3A	107.7	C14—C15—H15	119.3
N1—C3—H3A	107.7	C16—C15—H15	119.3
N3—C3—H3B	107.7	C15—C16—C11	120.0 (3)
N1—C3—H3B	107.7	C15—C16—H16	120.0
H3A—C3—H3B	107.1	C11—C16—H16	120.0
N4—C4—N1	118.6 (2)	O22—N21—O23	123.4 (3)
N4—C4—H4A	107.7	O22—N21—C23	118.4 (3)
N1—C4—H4A	107.7	O23—N21—C23	118.2 (3)
N4—C4—H4B	107.7	C21—O21—H21	113 (3)
N1—C4—H4B	107.7	O21—C21—C26	123.2 (3)
H4A—C4—H4B	107.1	O21—C21—C22	117.3 (3)
N3—C5—N2	118.9 (2)	C26—C21—C22	119.5 (3)
N3—C5—H5A	107.6	C23—C22—C21	118.6 (3)
N2—C5—H5A	107.6	C23—C22—H22	120.7
N3—C5—H5B	107.6	C21—C22—H22	120.7
N2—C5—H5B	107.6	C22—C23—C24	123.3 (3)
H5A—C5—H5B	107.0	C22—C23—N21	118.0 (3)
N4—C6—N2	118.8 (2)	C24—C23—N21	118.7 (3)
N4—C6—H6A	107.6	C23—C24—C25	117.2 (3)
N2—C6—H6A	107.6	C23—C24—H24	121.4
N4—C6—H6B	107.6	C25—C24—H24	121.4
N2—C6—H6B	107.6	C24—C25—C26	121.1 (3)
H6A—C6—H6B	107.0	C24—C25—H25	119.4
N3—C7—C8	115.4 (3)	C26—C25—H25	119.4
N3—C7—H7A	108.4	C25—C26—C21	120.3 (3)
C8—C7—H7A	108.4	C25—C26—H26	119.9
N3—C7—H7B	108.4	C21—C26—H26	119.9
C3—N1—C1—C2	72.9 (4)	C16—C11—C12—C13	0.4 (5)
C4—N1—C1—C2	−60.8 (4)	C11—C12—C13—C14	−0.5 (5)
C6—N2—C2—C1	73.0 (4)	C11—C12—C13—N11	180.0 (3)
C5—N2—C2—C1	−60.6 (4)	O12—N11—C13—C12	15.0 (4)
N1—C1—C2—N2	−9.3 (5)	O13—N11—C13—C12	−165.0 (3)
C7—N3—C3—N1	−85.0 (3)	O12—N11—C13—C14	−164.5 (3)
C5—N3—C3—N1	52.3 (4)	O13—N11—C13—C14	15.5 (4)
C1—N1—C3—N3	−79.7 (3)	C12—C13—C14—C15	0.4 (5)
C4—N1—C3—N3	53.5 (3)	N11—C13—C14—C15	179.9 (3)
C6—N4—C4—N1	−57.2 (3)	C13—C14—C15—C16	−0.2 (5)
C8—N4—C4—N1	80.0 (3)	C14—C15—C16—C11	0.1 (5)
C1—N1—C4—N4	84.3 (3)	O11—C11—C16—C15	−178.1 (3)
C3—N1—C4—N4	−48.9 (3)	C12—C11—C16—C15	−0.2 (5)
C7—N3—C5—N2	80.1 (4)	O21—C21—C22—C23	−179.7 (3)
C3—N3—C5—N2	−57.2 (4)	C26—C21—C22—C23	−0.1 (4)
C2—N2—C5—N3	84.1 (4)	C21—C22—C23—C24	0.2 (5)
C6—N2—C5—N3	−49.2 (4)	C21—C22—C23—N21	−179.2 (3)
C4—N4—C6—N2	51.8 (3)	O22—N21—C23—C22	10.5 (5)
C8—N4—C6—N2	−85.1 (3)	O23—N21—C23—C22	−170.7 (3)
C2—N2—C6—N4	−79.0 (3)	O22—N21—C23—C24	−168.9 (3)
C5—N2—C6—N4	54.5 (4)	O23—N21—C23—C24	9.9 (5)
C3—N3—C7—C8	63.2 (3)	C22—C23—C24—C25	−0.6 (5)
C5—N3—C7—C8	−74.3 (3)	N21—C23—C24—C25	178.8 (3)
C4—N4—C8—C7	−75.2 (3)	C23—C24—C25—C26	0.9 (5)
C6—N4—C8—C7	62.4 (4)	C24—C25—C26—C21	−0.8 (5)
N3—C7—C8—N4	9.3 (4)	O21—C21—C26—C25	179.9 (3)
O11—C11—C12—C13	178.4 (3)	C22—C21—C26—C25	0.4 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11···N1	0.90 (5)	1.83 (5)	2.722 (3)	170 (4)
O21—H21···N2	0.83 (5)	1.90 (5)	2.711 (3)	164 (5)
C15—H15···O11^i	0.95	2.56	3.465 (4)	158
C25—H25···O21^i	0.95	2.29	3.243 (4)	178

Symmetry code: (i) x, y+1, z.