Evidence for stereoelectronic effects in the N—C—N group of 8,10,12-tri­aza-1-azonia­tetra­cyclo[8.3.1.1^8,12.0^2,7]penta­decane 4-nitro­phenolate 4-nitro­phenol monosolvate from the protonation of aminal (2R,7R)-1,8,10,12-tetra­aza­tetra­cyclo[8.3.1.1^8,12.0^2,7]penta­decane: X-ray and natural bond orbital analysis

The title mol­ecular salt, C₁₁H₂₁N₄⁺·C₆H₄NO₃⁻·C₆H₅NO₃, (II), crystallizes with two independent three-component aggregates in the asymmetric unit. In the cations, the cyclo­hexane rings fused to the cage aza­adamantane systems both adopt a chair conformation. In the crystal structure, the aggregates are connected by C—H...O hydrogen bonds, forming a supra­molecular unit enclosing an R₄⁴(24) ring motif. These units are linked via C—H...O and C—H...N hydrogen bonds, forming a three-dimensional network. Even hydrogen-bond formation to one of the N atoms is enough to induce structural stereoelectronic effects in the normal donor→acceptor direction. The C—N bond distances provide structural evidence for a strong anomeric effect. The structure also displays O—H...O and N—H...O hydrogen bonding. Geometric optimization and natural bond orbital (NBO) analysis of (II) were undertaken by utilizing DFT/B3LYP with the 6-31+G(d,p) basis set. NBO second-order perturbation theory calculations indicate donor–acceptor inter­actions between nitro­gen lone pairs and the anti­bonding orbital of the C—C and C—N bonds for the protonated polyamine, in agreement with the occurrence of bond-length and bond-angle changes within the aminal cage structure.

Computing details

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: SHELXL2014 (Sheldrick, 2015); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

8,10,12-Triaza-1-azoniatetracyclo[8.3.1.1^8,12.0^2,7]pentadecane 4-nitrophenolate 4-nitrophenol monosolvate

Crystal data

C11H21N4^+·C6H4NO3^−·C6H5NO3	F(000) = 1032
Mr = 486.53	Dx = 1.343 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 6.2201 (6) Å	Cell parameters from 10933 reflections
b = 22.964 (2) Å	θ = 3.4–25.9°
c = 16.8626 (16) Å	µ = 0.10 mm^−1
β = 92.879 (8)°	T = 173 K
V = 2405.6 (4) Å^3	Plate, yellow
Z = 4	0.27 × 0.22 × 0.11 mm

Data collection

Stoe IPDS II two-circle diffractometer	6220 reflections with I > 2σ(I)
Radiation source: Genix 3D IµS microfocus X-ray source	Rint = 0.038
ω scans	θmax = 25.6°, θmin = 3.4°
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2001)	h = −7→7
Tmin = 0.944, Tmax = 0.970	k = −26→27
12586 measured reflections	l = −16→20
8218 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)] = 0.044	w = 1/[σ^2(Fo^2) + (0.060P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.107	(Δ/σ)max < 0.001
S = 0.94	Δρmax = 0.17 e Å^−3
8218 reflections	Δρmin = −0.21 e Å^−3
647 parameters	Absolute structure: Flack x parameter determined using 2249 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: −0.9 (10)

Special details

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

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

	x	y	z	Uiso*/Ueq
N1	0.7231 (5)	0.76571 (16)	0.9399 (2)	0.0298 (8)
N2	1.1649 (4)	0.72911 (16)	0.9478 (2)	0.0247 (8)
N3	0.8431 (5)	0.66606 (17)	0.9222 (2)	0.0272 (8)
H3	0.811 (8)	0.627 (3)	0.927 (4)	0.063 (18)*
N4	0.9398 (5)	0.73696 (18)	0.8260 (2)	0.0322 (9)
C1	0.8648 (5)	0.78687 (18)	1.0059 (2)	0.0287 (8)
H1	0.8347	0.7620	1.0527	0.034*
C2	1.1070 (6)	0.78085 (17)	0.9933 (3)	0.0277 (9)
H2	1.1472	0.8152	0.9608	0.033*
C3	1.2284 (6)	0.7873 (2)	1.0724 (3)	0.0395 (10)
H3B	1.3844	0.7818	1.0659	0.047*
H3C	1.1796	0.7575	1.1099	0.047*
C4	1.1867 (8)	0.8484 (3)	1.1050 (4)	0.0545 (15)
H4A	1.2559	0.8517	1.1590	0.065*
H4B	1.2545	0.8775	1.0709	0.065*
C5	0.9496 (8)	0.8624 (2)	1.1087 (3)	0.0536 (14)
H5A	0.9334	0.9041	1.1221	0.064*
H5B	0.8888	0.8393	1.1518	0.064*
C6	0.8215 (7)	0.8497 (2)	1.0307 (3)	0.0419 (12)
H6A	0.6658	0.8552	1.0379	0.050*
H6B	0.8655	0.8769	0.9889	0.050*
C7	1.1560 (6)	0.7400 (2)	0.8630 (3)	0.0294 (10)
H7A	1.2481	0.7112	0.8373	0.035*
H7B	1.2161	0.7792	0.8534	0.035*
C8	0.7856 (6)	0.7783 (2)	0.8596 (3)	0.0343 (11)
H8A	0.8499	0.8177	0.8592	0.041*
H8B	0.6539	0.7792	0.8241	0.041*
C9	0.6672 (6)	0.70603 (19)	0.9480 (3)	0.0299 (10)
H9A	0.5334	0.6980	0.9156	0.036*
H9B	0.6387	0.6980	1.0042	0.036*
C10	1.0617 (6)	0.67514 (18)	0.9663 (3)	0.0275 (9)
H10A	1.0416	0.6738	1.0241	0.033*
H10B	1.1580	0.6426	0.9532	0.033*
C11	0.8652 (7)	0.6779 (2)	0.8351 (3)	0.0347 (11)
H11A	0.9693	0.6503	0.8131	0.042*
H11B	0.7245	0.6727	0.8058	0.042*
N21	0.0853 (10)	0.3926 (3)	0.6506 (3)	0.0650 (15)
O21	0.2755 (5)	0.56016 (14)	0.8783 (2)	0.0340 (8)
H21	0.419 (9)	0.560 (3)	0.893 (3)	0.054 (15)*
O22	0.2293 (9)	0.3595 (3)	0.6318 (4)	0.099 (2)
O23	−0.0995 (8)	0.3900 (3)	0.6218 (3)	0.0927 (18)
C21	0.2347 (6)	0.51935 (19)	0.8242 (3)	0.0289 (10)
C22	0.0252 (7)	0.5146 (2)	0.7908 (3)	0.0348 (11)
H22	−0.0841	0.5400	0.8076	0.042*
C23	−0.0229 (7)	0.4735 (2)	0.7339 (3)	0.0390 (12)
H23	−0.1648	0.4706	0.7107	0.047*
C24	0.1355 (8)	0.4364 (2)	0.7107 (3)	0.0405 (12)
C25	0.3430 (8)	0.4395 (2)	0.7430 (3)	0.0398 (12)
H25	0.4502	0.4135	0.7260	0.048*
C26	0.3928 (7)	0.4807 (2)	0.7999 (3)	0.0331 (11)
H26	0.5351	0.4830	0.8230	0.040*
N31	0.8656 (7)	0.4095 (2)	1.1831 (3)	0.0433 (11)
O31	0.6592 (5)	0.56054 (14)	0.9352 (2)	0.0331 (7)
O32	0.7276 (7)	0.37614 (18)	1.2066 (3)	0.0559 (10)
O33	1.0507 (6)	0.41117 (19)	1.2132 (3)	0.0597 (11)
C31	0.7077 (7)	0.52352 (19)	0.9923 (3)	0.0302 (10)
C32	0.5536 (7)	0.4843 (2)	1.0218 (3)	0.0344 (11)
H32	0.4111	0.4840	0.9987	0.041*
C33	0.6069 (7)	0.4473 (2)	1.0826 (3)	0.0349 (11)
H33	0.5018	0.4214	1.1014	0.042*
C34	0.8126 (7)	0.4472 (2)	1.1170 (3)	0.0347 (11)
C35	0.9691 (7)	0.4840 (2)	1.0886 (3)	0.0342 (11)
H35	1.1112	0.4833	1.1119	0.041*
C36	0.9186 (6)	0.5209 (2)	1.0276 (3)	0.0342 (11)
H36	1.0272	0.5454	1.0082	0.041*
N1A	0.2438 (5)	0.23971 (15)	0.4399 (2)	0.0258 (8)
N2A	0.6609 (4)	0.29117 (16)	0.4552 (2)	0.0261 (8)
N4A	0.4377 (5)	0.27791 (18)	0.3291 (2)	0.0321 (9)
N3A	0.3343 (5)	0.34582 (16)	0.4274 (2)	0.0264 (8)
C1A	0.4121 (5)	0.20952 (17)	0.4880 (2)	0.0269 (8)
H1A	0.4738	0.1797	0.4523	0.032*
C2A	0.5992 (5)	0.24895 (18)	0.5150 (3)	0.0280 (10)
H2A	0.5494	0.2720	0.5609	0.034*
C3A	0.7870 (6)	0.2114 (2)	0.5473 (3)	0.0387 (10)
H3A1	0.8371	0.1859	0.5047	0.046*
H3A2	0.9084	0.2367	0.5657	0.046*
C4A	0.7147 (7)	0.1745 (3)	0.6160 (3)	0.0453 (13)
H4A1	0.8333	0.1480	0.6337	0.054*
H4A2	0.6842	0.2003	0.6611	0.054*
C5A	0.5169 (7)	0.1389 (2)	0.5943 (3)	0.0428 (11)
H5A1	0.4682	0.1191	0.6423	0.051*
H5A2	0.5538	0.1085	0.5555	0.051*
C6A	0.3343 (6)	0.1762 (2)	0.5586 (3)	0.0347 (10)
H6A1	0.2111	0.1511	0.5415	0.042*
H6A2	0.2852	0.2038	0.5990	0.042*
C7A	0.1905 (5)	0.29833 (18)	0.4614 (3)	0.0264 (9)
H7A1	0.1991	0.3014	0.5200	0.032*
H7A2	0.0394	0.3061	0.4431	0.032*
C8A	0.6512 (6)	0.2730 (2)	0.3711 (3)	0.0328 (11)
H8A1	0.6992	0.2320	0.3683	0.039*
H8A2	0.7547	0.2970	0.3425	0.039*
C9A	0.2786 (6)	0.2360 (2)	0.3552 (3)	0.0315 (10)
H9A1	0.1402	0.2429	0.3252	0.038*
H9A2	0.3272	0.1962	0.3427	0.038*
C10A	0.5600 (6)	0.34641 (19)	0.4639 (3)	0.0278 (10)
H10C	0.6449	0.3768	0.4379	0.033*
H10D	0.5563	0.3561	0.5210	0.033*
C11A	0.3545 (7)	0.3354 (2)	0.3401 (3)	0.0342 (11)
H11C	0.2119	0.3393	0.3118	0.041*
H11D	0.4527	0.3645	0.3183	0.041*
N21A	−0.4123 (8)	0.6241 (2)	0.1464 (3)	0.0542 (13)
O21A	−0.2318 (5)	0.45706 (14)	0.3764 (2)	0.0339 (7)
O22A	−0.2682 (8)	0.6576 (2)	0.1291 (3)	0.0799 (15)
O23A	−0.5939 (7)	0.6252 (2)	0.1142 (3)	0.0763 (14)
C21A	−0.2713 (6)	0.49818 (19)	0.3222 (3)	0.0272 (9)
C22A	−0.1133 (6)	0.5371 (2)	0.2992 (3)	0.0311 (10)
H22A	0.0279	0.5348	0.3232	0.037*
C23A	−0.1595 (7)	0.5783 (2)	0.2424 (3)	0.0363 (11)
H23A	−0.0520	0.6050	0.2274	0.044*
C24A	−0.3652 (8)	0.5808 (2)	0.2071 (3)	0.0360 (11)
C25A	−0.5245 (7)	0.5435 (2)	0.2289 (3)	0.0373 (11)
H25A	−0.6651	0.5462	0.2045	0.045*
C26A	−0.4783 (6)	0.5020 (2)	0.2866 (3)	0.0335 (11)
H26A	−0.5876	0.4761	0.3021	0.040*
N31A	0.3632 (8)	0.6054 (2)	0.6795 (3)	0.0476 (12)
O31A	0.1472 (5)	0.45273 (14)	0.4355 (2)	0.0334 (7)
O32A	0.5466 (7)	0.60263 (19)	0.7114 (3)	0.0608 (11)
O33A	0.2261 (7)	0.63961 (18)	0.7021 (3)	0.0593 (11)
C31A	0.1982 (6)	0.48961 (19)	0.4917 (3)	0.0282 (10)
C32A	0.4079 (7)	0.4921 (2)	0.5263 (3)	0.0361 (11)
H32A	0.5153	0.4672	0.5069	0.043*
C33A	0.4622 (7)	0.5296 (2)	0.5877 (3)	0.0391 (12)
H33A	0.6044	0.5299	0.6110	0.047*
C34A	0.3072 (7)	0.5670 (2)	0.6151 (3)	0.0335 (11)
C35A	0.0989 (7)	0.5677 (2)	0.5811 (3)	0.0356 (11)
H35A	−0.0058	0.5939	0.5994	0.043*
C36A	0.0477 (7)	0.5293 (2)	0.5201 (3)	0.0339 (11)
H36A	−0.0941	0.5297	0.4964	0.041*
H3A	0.269 (6)	0.384 (2)	0.434 (3)	0.028 (11)*
H21A	−0.058 (13)	0.461 (5)	0.408 (5)	0.14 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0226 (15)	0.0328 (19)	0.034 (2)	0.0021 (13)	−0.0017 (13)	0.0079 (17)
N2	0.0226 (14)	0.0250 (17)	0.027 (2)	−0.0019 (13)	0.0004 (13)	−0.0028 (16)
N3	0.0268 (16)	0.027 (2)	0.027 (2)	−0.0017 (14)	−0.0025 (14)	0.0013 (17)
N4	0.0328 (17)	0.039 (2)	0.025 (2)	−0.0029 (16)	−0.0015 (15)	0.0045 (19)
C1	0.0269 (16)	0.029 (2)	0.031 (2)	0.0040 (15)	0.0046 (14)	0.0023 (18)
C2	0.0292 (18)	0.0223 (19)	0.032 (2)	−0.0027 (14)	0.0054 (15)	−0.0044 (18)
C3	0.037 (2)	0.043 (2)	0.038 (2)	−0.0050 (18)	−0.0030 (17)	−0.014 (2)
C4	0.062 (3)	0.052 (3)	0.049 (3)	−0.015 (2)	0.003 (2)	−0.025 (3)
C5	0.065 (3)	0.040 (3)	0.058 (3)	−0.001 (2)	0.021 (3)	−0.019 (3)
C6	0.045 (2)	0.032 (2)	0.050 (3)	0.0049 (18)	0.014 (2)	0.002 (2)
C7	0.0278 (19)	0.034 (2)	0.026 (2)	−0.0025 (17)	0.0027 (16)	0.001 (2)
C8	0.031 (2)	0.039 (3)	0.033 (3)	0.0028 (18)	−0.0013 (17)	0.016 (2)
C9	0.0233 (17)	0.032 (2)	0.034 (2)	−0.0018 (15)	0.0020 (15)	0.006 (2)
C10	0.0231 (18)	0.026 (2)	0.033 (3)	0.0021 (15)	−0.0023 (16)	0.001 (2)
C11	0.037 (2)	0.043 (3)	0.024 (2)	−0.0095 (19)	−0.0049 (18)	−0.004 (2)
N21	0.088 (4)	0.067 (4)	0.040 (3)	−0.026 (3)	0.002 (3)	−0.018 (3)
O21	0.0355 (17)	0.0281 (17)	0.038 (2)	0.0000 (13)	0.0005 (14)	−0.0077 (16)
O22	0.114 (4)	0.103 (4)	0.080 (4)	−0.012 (3)	0.018 (3)	−0.065 (4)
O23	0.100 (3)	0.103 (4)	0.072 (4)	−0.034 (3)	−0.029 (3)	−0.034 (3)
C21	0.031 (2)	0.023 (2)	0.032 (3)	−0.0025 (16)	0.0011 (18)	0.005 (2)
C22	0.033 (2)	0.027 (2)	0.044 (3)	−0.0019 (18)	−0.002 (2)	0.004 (2)
C23	0.037 (2)	0.039 (3)	0.040 (3)	−0.011 (2)	−0.007 (2)	0.008 (3)
C24	0.058 (3)	0.037 (3)	0.027 (3)	−0.016 (2)	0.003 (2)	−0.009 (2)
C25	0.042 (3)	0.042 (3)	0.036 (3)	−0.007 (2)	0.012 (2)	−0.011 (3)
C26	0.034 (2)	0.030 (2)	0.036 (3)	−0.0029 (18)	0.0064 (19)	−0.003 (2)
N31	0.066 (3)	0.034 (3)	0.030 (3)	0.020 (2)	0.000 (2)	−0.005 (2)
O31	0.0344 (15)	0.0339 (17)	0.0304 (19)	−0.0086 (12)	−0.0049 (13)	0.0020 (16)
O32	0.088 (3)	0.039 (2)	0.041 (2)	0.005 (2)	0.011 (2)	0.009 (2)
O33	0.071 (2)	0.061 (3)	0.046 (3)	0.028 (2)	−0.0137 (19)	0.004 (2)
C31	0.038 (2)	0.022 (2)	0.031 (3)	−0.0023 (16)	−0.0002 (19)	−0.004 (2)
C32	0.031 (2)	0.038 (3)	0.035 (3)	−0.0057 (19)	0.0052 (19)	0.002 (2)
C33	0.044 (2)	0.026 (2)	0.035 (3)	−0.0038 (19)	0.008 (2)	0.001 (2)
C34	0.044 (2)	0.028 (2)	0.031 (3)	0.0071 (19)	0.000 (2)	−0.003 (2)
C35	0.033 (2)	0.037 (3)	0.032 (3)	0.0070 (18)	−0.0057 (18)	−0.003 (2)
C36	0.029 (2)	0.034 (3)	0.040 (3)	−0.0061 (17)	0.0022 (19)	−0.004 (2)
N1A	0.0247 (15)	0.0237 (17)	0.029 (2)	0.0009 (12)	−0.0024 (13)	−0.0021 (16)
N2A	0.0218 (14)	0.0281 (19)	0.028 (2)	−0.0005 (13)	0.0001 (13)	0.0061 (17)
N4A	0.0318 (17)	0.038 (2)	0.027 (2)	0.0066 (15)	0.0003 (15)	0.0014 (19)
N3A	0.0257 (15)	0.0242 (19)	0.029 (2)	0.0063 (13)	−0.0032 (14)	0.0011 (17)
C1A	0.0252 (16)	0.0271 (19)	0.028 (2)	0.0016 (14)	−0.0012 (14)	0.0033 (18)
C2A	0.0229 (17)	0.031 (2)	0.031 (2)	0.0022 (13)	0.0010 (15)	0.0044 (18)
C3A	0.0267 (18)	0.045 (2)	0.044 (3)	0.0069 (17)	−0.0033 (16)	0.015 (2)
C4A	0.036 (2)	0.055 (3)	0.044 (3)	0.008 (2)	−0.0031 (19)	0.021 (3)
C5A	0.046 (2)	0.044 (3)	0.038 (3)	0.008 (2)	0.0036 (19)	0.019 (2)
C6A	0.0327 (19)	0.034 (2)	0.037 (3)	−0.0043 (16)	−0.0001 (17)	0.010 (2)
C7A	0.0200 (15)	0.027 (2)	0.032 (2)	0.0007 (14)	−0.0002 (14)	−0.0001 (18)
C8A	0.0275 (19)	0.039 (3)	0.032 (3)	0.0062 (17)	0.0069 (17)	0.006 (2)
C9A	0.033 (2)	0.033 (2)	0.027 (3)	0.0037 (18)	−0.0054 (17)	−0.003 (2)
C10A	0.0222 (18)	0.024 (2)	0.036 (3)	−0.0031 (15)	−0.0040 (16)	0.001 (2)
C11A	0.031 (2)	0.038 (3)	0.033 (3)	0.0060 (18)	−0.0002 (19)	0.007 (2)
N21A	0.071 (3)	0.055 (3)	0.036 (3)	0.017 (2)	−0.003 (2)	0.014 (3)
O21A	0.0352 (15)	0.0298 (17)	0.036 (2)	−0.0016 (13)	−0.0022 (14)	0.0073 (16)
O22A	0.095 (3)	0.081 (4)	0.064 (3)	0.003 (3)	0.004 (2)	0.046 (3)
O23A	0.081 (3)	0.086 (4)	0.059 (3)	0.023 (3)	−0.023 (2)	0.021 (3)
C21A	0.033 (2)	0.022 (2)	0.027 (3)	0.0034 (16)	0.0019 (17)	0.000 (2)
C22A	0.028 (2)	0.032 (2)	0.033 (3)	0.0015 (18)	0.0001 (18)	0.002 (2)
C23A	0.039 (2)	0.034 (3)	0.037 (3)	−0.0008 (19)	0.006 (2)	0.001 (2)
C24A	0.045 (2)	0.035 (3)	0.027 (3)	0.011 (2)	−0.002 (2)	0.000 (2)
C25A	0.040 (2)	0.037 (3)	0.034 (3)	0.010 (2)	−0.011 (2)	−0.006 (2)
C26A	0.028 (2)	0.032 (3)	0.040 (3)	−0.0020 (18)	−0.0001 (18)	−0.008 (2)
N31A	0.078 (3)	0.033 (3)	0.033 (3)	−0.020 (2)	0.010 (2)	−0.001 (2)
O31A	0.0372 (15)	0.0299 (17)	0.0325 (19)	0.0071 (13)	−0.0051 (13)	−0.0039 (16)
O32A	0.074 (3)	0.059 (3)	0.048 (3)	−0.033 (2)	−0.013 (2)	−0.005 (2)
O33A	0.099 (3)	0.036 (2)	0.043 (3)	−0.011 (2)	0.014 (2)	−0.012 (2)
C31A	0.032 (2)	0.027 (2)	0.026 (2)	−0.0006 (16)	−0.0001 (17)	0.005 (2)
C32A	0.034 (2)	0.034 (3)	0.039 (3)	0.0018 (18)	0.0012 (19)	0.000 (2)
C33A	0.038 (2)	0.038 (3)	0.040 (3)	−0.006 (2)	−0.003 (2)	0.005 (3)
C34A	0.051 (3)	0.030 (2)	0.020 (3)	−0.012 (2)	0.003 (2)	0.000 (2)
C35A	0.041 (2)	0.033 (3)	0.034 (3)	0.0012 (19)	0.006 (2)	−0.002 (2)
C36A	0.034 (2)	0.030 (2)	0.037 (3)	0.0016 (18)	−0.0044 (19)	−0.002 (2)

Geometric parameters (Å, º)

N1—C9	1.422 (6)	N1A—C9A	1.457 (6)
N1—C8	1.456 (6)	N1A—C1A	1.466 (5)
N1—C1	1.467 (5)	N2A—C10A	1.426 (5)
N2—C10	1.437 (5)	N2A—C2A	1.464 (5)
N2—C7	1.450 (6)	N2A—C8A	1.476 (6)
N2—C2	1.469 (5)	N4A—C11A	1.433 (6)
N3—C11	1.508 (6)	N4A—C9A	1.463 (6)
N3—C9	1.509 (5)	N4A—C8A	1.477 (5)
N3—C10	1.530 (5)	N3A—C11A	1.503 (6)
N3—H3	0.93 (7)	N3A—C10A	1.504 (5)
N4—C11	1.444 (6)	N3A—C7A	1.539 (5)
N4—C7	1.455 (5)	N3A—H3A	0.98 (5)
N4—C8	1.482 (6)	C1A—C6A	1.514 (6)
C1—C6	1.530 (6)	C1A—C2A	1.526 (5)
C1—C2	1.538 (5)	C1A—H1A	1.0000
C1—H1	1.0000	C2A—C3A	1.530 (5)
C2—C3	1.506 (6)	C2A—H2A	1.0000
C2—H2	1.0000	C3A—C4A	1.522 (7)
C3—C4	1.534 (7)	C3A—H3A1	0.9900
C3—H3B	0.9900	C3A—H3A2	0.9900
C3—H3C	0.9900	C4A—C5A	1.508 (7)
C4—C5	1.514 (7)	C4A—H4A1	0.9900
C4—H4A	0.9900	C4A—H4A2	0.9900
C4—H4B	0.9900	C5A—C6A	1.523 (6)
C5—C6	1.531 (8)	C5A—H5A1	0.9900
C5—H5A	0.9900	C5A—H5A2	0.9900
C5—H5B	0.9900	C6A—H6A1	0.9900
C6—H6A	0.9900	C6A—H6A2	0.9900
C6—H6B	0.9900	C7A—H7A1	0.9900
C7—H7A	0.9900	C7A—H7A2	0.9900
C7—H7B	0.9900	C8A—H8A1	0.9900
C8—H8A	0.9900	C8A—H8A2	0.9900
C8—H8B	0.9900	C9A—H9A1	0.9900
C9—H9A	0.9900	C9A—H9A2	0.9900
C9—H9B	0.9900	C10A—H10C	0.9900
C10—H10A	0.9900	C10A—H10D	0.9900
C10—H10B	0.9900	C11A—H11C	0.9900
C11—H11A	0.9900	C11A—H11D	0.9900
C11—H11B	0.9900	N21A—O22A	1.227 (7)
N21—O23	1.226 (6)	N21A—O23A	1.229 (6)
N21—O22	1.227 (8)	N21A—C24A	1.448 (7)
N21—C24	1.452 (7)	O21A—C21A	1.329 (6)
O21—C21	1.324 (6)	O21A—H21A	1.18 (9)
O21—H21	0.91 (6)	C21A—C26A	1.396 (6)
C21—C22	1.398 (6)	C21A—C22A	1.397 (6)
C21—C26	1.401 (6)	C22A—C23A	1.367 (7)
C22—C23	1.367 (7)	C22A—H22A	0.9500
C22—H22	0.9500	C23A—C24A	1.385 (7)
C23—C24	1.374 (7)	C23A—H23A	0.9500
C23—H23	0.9500	C24A—C25A	1.373 (7)
C24—C25	1.377 (7)	C25A—C26A	1.381 (7)
C25—C26	1.372 (7)	C25A—H25A	0.9500
C25—H25	0.9500	C26A—H26A	0.9500
C26—H26	0.9500	N31A—O33A	1.234 (6)
N31—O32	1.230 (6)	N31A—O32A	1.239 (6)
N31—O33	1.235 (6)	N31A—C34A	1.428 (7)
N31—C34	1.437 (7)	O31A—C31A	1.298 (6)
O31—C31	1.308 (6)	O31A—H21A	1.35 (9)
C31—C36	1.415 (6)	C31A—C32A	1.404 (6)
C31—C32	1.423 (6)	C31A—C36A	1.408 (6)
C32—C33	1.359 (7)	C32A—C33A	1.375 (7)
C32—H32	0.9500	C32A—H32A	0.9500
C33—C34	1.378 (7)	C33A—C34A	1.388 (7)
C33—H33	0.9500	C33A—H33A	0.9500
C34—C35	1.392 (7)	C34A—C35A	1.391 (6)
C35—C36	1.356 (7)	C35A—C36A	1.379 (7)
C35—H35	0.9500	C35A—H35A	0.9500
C36—H36	0.9500	C36A—H36A	0.9500
N1A—C7A	1.437 (5)
C9—N1—C8	111.0 (4)	C7A—N1A—C1A	118.1 (3)
C9—N1—C1	112.7 (3)	C9A—N1A—C1A	112.2 (3)
C8—N1—C1	117.5 (3)	C10A—N2A—C2A	112.7 (3)
C10—N2—C7	111.6 (3)	C10A—N2A—C8A	110.7 (4)
C10—N2—C2	117.4 (3)	C2A—N2A—C8A	118.4 (4)
C7—N2—C2	112.1 (3)	C11A—N4A—C9A	108.2 (3)
C11—N3—C9	105.9 (3)	C11A—N4A—C8A	109.2 (4)
C11—N3—C10	109.0 (3)	C9A—N4A—C8A	114.3 (3)
C9—N3—C10	114.6 (3)	C11A—N3A—C10A	106.2 (3)
C11—N3—H3	107 (4)	C11A—N3A—C7A	109.3 (3)
C9—N3—H3	114 (3)	C10A—N3A—C7A	113.7 (3)
C10—N3—H3	106 (3)	C11A—N3A—H3A	108 (3)
C11—N4—C7	107.2 (4)	C10A—N3A—H3A	109 (2)
C11—N4—C8	110.1 (3)	C7A—N3A—H3A	110 (2)
C7—N4—C8	114.0 (4)	N1A—C1A—C6A	115.2 (3)
N1—C1—C6	114.4 (3)	N1A—C1A—C2A	113.4 (3)
N1—C1—C2	114.9 (3)	C6A—C1A—C2A	109.6 (3)
C6—C1—C2	108.0 (3)	N1A—C1A—H1A	106.0
N1—C1—H1	106.3	C6A—C1A—H1A	106.0
C6—C1—H1	106.3	C2A—C1A—H1A	106.0
C2—C1—H1	106.3	N2A—C2A—C1A	114.2 (3)
N2—C2—C3	114.6 (3)	N2A—C2A—C3A	113.4 (3)
N2—C2—C1	114.4 (3)	C1A—C2A—C3A	109.2 (3)
C3—C2—C1	108.7 (3)	N2A—C2A—H2A	106.5
N2—C2—H2	106.2	C1A—C2A—H2A	106.5
C3—C2—H2	106.2	C3A—C2A—H2A	106.5
C1—C2—H2	106.2	C4A—C3A—C2A	109.6 (3)
C2—C3—C4	108.7 (4)	C4A—C3A—H3A1	109.8
C2—C3—H3B	109.9	C2A—C3A—H3A1	109.8
C4—C3—H3B	109.9	C4A—C3A—H3A2	109.8
C2—C3—H3C	109.9	C2A—C3A—H3A2	109.8
C4—C3—H3C	109.9	H3A1—C3A—H3A2	108.2
H3B—C3—H3C	108.3	C5A—C4A—C3A	112.7 (4)
C5—C4—C3	113.1 (4)	C5A—C4A—H4A1	109.1
C5—C4—H4A	109.0	C3A—C4A—H4A1	109.1
C3—C4—H4A	109.0	C5A—C4A—H4A2	109.1
C5—C4—H4B	109.0	C3A—C4A—H4A2	109.1
C3—C4—H4B	109.0	H4A1—C4A—H4A2	107.8
H4A—C4—H4B	107.8	C4A—C5A—C6A	112.0 (4)
C4—C5—C6	112.9 (4)	C4A—C5A—H5A1	109.2
C4—C5—H5A	109.0	C6A—C5A—H5A1	109.2
C6—C5—H5A	109.0	C4A—C5A—H5A2	109.2
C4—C5—H5B	109.0	C6A—C5A—H5A2	109.2
C6—C5—H5B	109.0	H5A1—C5A—H5A2	107.9
H5A—C5—H5B	107.8	C1A—C6A—C5A	109.5 (3)
C1—C6—C5	108.9 (4)	C1A—C6A—H6A1	109.8
C1—C6—H6A	109.9	C5A—C6A—H6A1	109.8
C5—C6—H6A	109.9	C1A—C6A—H6A2	109.8
C1—C6—H6B	109.9	C5A—C6A—H6A2	109.8
C5—C6—H6B	109.9	H6A1—C6A—H6A2	108.2
H6A—C6—H6B	108.3	N1A—C7A—N3A	115.1 (3)
N2—C7—N4	113.8 (3)	N1A—C7A—H7A1	108.5
N2—C7—H7A	108.8	N3A—C7A—H7A1	108.5
N4—C7—H7A	108.8	N1A—C7A—H7A2	108.5
N2—C7—H7B	108.8	N3A—C7A—H7A2	108.5
N4—C7—H7B	108.8	H7A1—C7A—H7A2	107.5
H7A—C7—H7B	107.7	N2A—C8A—N4A	115.5 (3)
N1—C8—N4	115.9 (4)	N2A—C8A—H8A1	108.4
N1—C8—H8A	108.3	N4A—C8A—H8A1	108.4
N4—C8—H8A	108.3	N2A—C8A—H8A2	108.4
N1—C8—H8B	108.3	N4A—C8A—H8A2	108.4
N4—C8—H8B	108.3	H8A1—C8A—H8A2	107.5
H8A—C8—H8B	107.4	N1A—C9A—N4A	113.1 (4)
N1—C9—N3	112.0 (3)	N1A—C9A—H9A1	109.0
N1—C9—H9A	109.2	N4A—C9A—H9A1	109.0
N3—C9—H9A	109.2	N1A—C9A—H9A2	109.0
N1—C9—H9B	109.2	N4A—C9A—H9A2	109.0
N3—C9—H9B	109.2	H9A1—C9A—H9A2	107.8
H9A—C9—H9B	107.9	N2A—C10A—N3A	110.9 (3)
N2—C10—N3	114.1 (3)	N2A—C10A—H10C	109.5
N2—C10—H10A	108.7	N3A—C10A—H10C	109.5
N3—C10—H10A	108.7	N2A—C10A—H10D	109.5
N2—C10—H10B	108.7	N3A—C10A—H10D	109.5
N3—C10—H10B	108.7	H10C—C10A—H10D	108.0
H10A—C10—H10B	107.6	N4A—C11A—N3A	108.8 (4)
N4—C11—N3	108.5 (4)	N4A—C11A—H11C	109.9
N4—C11—H11A	110.0	N3A—C11A—H11C	109.9
N3—C11—H11A	110.0	N4A—C11A—H11D	109.9
N4—C11—H11B	110.0	N3A—C11A—H11D	109.9
N3—C11—H11B	110.0	H11C—C11A—H11D	108.3
H11A—C11—H11B	108.4	O22A—N21A—O23A	123.3 (5)
O23—N21—O22	123.3 (6)	O22A—N21A—C24A	118.4 (5)
O23—N21—C24	118.3 (6)	O23A—N21A—C24A	118.4 (5)
O22—N21—C24	118.3 (5)	C21A—O21A—H21A	113 (5)
C21—O21—H21	109 (4)	O21A—C21A—C26A	118.4 (4)
O21—C21—C22	118.4 (4)	O21A—C21A—C22A	122.5 (4)
O21—C21—C26	122.4 (4)	C26A—C21A—C22A	119.1 (4)
C22—C21—C26	119.1 (4)	C23A—C22A—C21A	120.7 (4)
C23—C22—C21	120.2 (4)	C23A—C22A—H22A	119.6
C23—C22—H22	119.9	C21A—C22A—H22A	119.6
C21—C22—H22	119.9	C22A—C23A—C24A	119.1 (5)
C22—C23—C24	119.5 (4)	C22A—C23A—H23A	120.5
C22—C23—H23	120.3	C24A—C23A—H23A	120.5
C24—C23—H23	120.3	C25A—C24A—C23A	121.5 (5)
C23—C24—C25	121.8 (5)	C25A—C24A—N21A	119.7 (5)
C23—C24—N21	119.8 (5)	C23A—C24A—N21A	118.8 (5)
C25—C24—N21	118.4 (5)	C24A—C25A—C26A	119.4 (4)
C26—C25—C24	119.1 (5)	C24A—C25A—H25A	120.3
C26—C25—H25	120.4	C26A—C25A—H25A	120.3
C24—C25—H25	120.4	C25A—C26A—C21A	120.1 (4)
C25—C26—C21	120.3 (4)	C25A—C26A—H26A	120.0
C25—C26—H26	119.9	C21A—C26A—H26A	120.0
C21—C26—H26	119.9	O33A—N31A—O32A	122.3 (5)
O32—N31—O33	122.6 (5)	O33A—N31A—C34A	118.8 (5)
O32—N31—C34	119.2 (4)	O32A—N31A—C34A	118.8 (5)
O33—N31—C34	118.2 (5)	C31A—O31A—H21A	111 (4)
O31—C31—C36	120.8 (4)	O31A—C31A—C32A	121.2 (4)
O31—C31—C32	122.3 (4)	O31A—C31A—C36A	121.9 (4)
C36—C31—C32	116.9 (4)	C32A—C31A—C36A	116.9 (4)
C33—C32—C31	121.1 (4)	C33A—C32A—C31A	121.7 (4)
C33—C32—H32	119.5	C33A—C32A—H32A	119.1
C31—C32—H32	119.5	C31A—C32A—H32A	119.1
C32—C33—C34	120.3 (4)	C32A—C33A—C34A	119.4 (5)
C32—C33—H33	119.8	C32A—C33A—H33A	120.3
C34—C33—H33	119.8	C34A—C33A—H33A	120.3
C33—C34—C35	120.3 (5)	C33A—C34A—C35A	121.1 (5)
C33—C34—N31	120.0 (4)	C33A—C34A—N31A	119.3 (5)
C35—C34—N31	119.7 (4)	C35A—C34A—N31A	119.6 (5)
C36—C35—C34	120.1 (4)	C36A—C35A—C34A	118.5 (4)
C36—C35—H35	120.0	C36A—C35A—H35A	120.8
C34—C35—H35	120.0	C34A—C35A—H35A	120.8
C35—C36—C31	121.3 (4)	C35A—C36A—C31A	122.3 (4)
C35—C36—H36	119.3	C35A—C36A—H36A	118.8
C31—C36—H36	119.3	C31A—C36A—H36A	118.8
C7A—N1A—C9A	110.4 (4)
C9—N1—C1—C6	−143.5 (4)	C7A—N1A—C1A—C6A	89.1 (4)
C8—N1—C1—C6	85.5 (4)	C9A—N1A—C1A—C6A	−140.8 (4)
C9—N1—C1—C2	90.7 (4)	C7A—N1A—C1A—C2A	−38.3 (5)
C8—N1—C1—C2	−40.4 (5)	C9A—N1A—C1A—C2A	91.9 (4)
C10—N2—C2—C3	83.7 (4)	C10A—N2A—C2A—C1A	94.6 (4)
C7—N2—C2—C3	−145.2 (3)	C8A—N2A—C2A—C1A	−36.8 (4)
C10—N2—C2—C1	−42.8 (5)	C10A—N2A—C2A—C3A	−139.5 (4)
C7—N2—C2—C1	88.3 (4)	C8A—N2A—C2A—C3A	89.2 (4)
N1—C1—C2—N2	−34.2 (5)	N1A—C1A—C2A—N2A	−38.8 (4)
C6—C1—C2—N2	−163.2 (4)	C6A—C1A—C2A—N2A	−169.0 (3)
N1—C1—C2—C3	−163.6 (4)	N1A—C1A—C2A—C3A	−166.9 (3)
C6—C1—C2—C3	67.3 (4)	C6A—C1A—C2A—C3A	62.9 (4)
N2—C2—C3—C4	168.5 (4)	N2A—C2A—C3A—C4A	172.9 (4)
C1—C2—C3—C4	−62.2 (5)	C1A—C2A—C3A—C4A	−58.5 (5)
C2—C3—C4—C5	53.8 (6)	C2A—C3A—C4A—C5A	54.1 (6)
C3—C4—C5—C6	−49.9 (7)	C3A—C4A—C5A—C6A	−53.0 (6)
N1—C1—C6—C5	169.7 (3)	N1A—C1A—C6A—C5A	170.2 (4)
C2—C1—C6—C5	−61.0 (4)	C2A—C1A—C6A—C5A	−60.5 (5)
C4—C5—C6—C1	53.1 (6)	C4A—C5A—C6A—C1A	55.4 (5)
C10—N2—C7—N4	53.2 (5)	C9A—N1A—C7A—N3A	−46.1 (4)
C2—N2—C7—N4	−80.9 (4)	C1A—N1A—C7A—N3A	84.9 (4)
C11—N4—C7—N2	−63.6 (5)	C11A—N3A—C7A—N1A	48.4 (4)
C8—N4—C7—N2	58.5 (5)	C10A—N3A—C7A—N1A	−70.1 (5)
C9—N1—C8—N4	−47.2 (5)	C10A—N2A—C8A—N4A	−48.4 (5)
C1—N1—C8—N4	84.6 (5)	C2A—N2A—C8A—N4A	83.8 (4)
C11—N4—C8—N1	50.6 (5)	C11A—N4A—C8A—N2A	51.7 (5)
C7—N4—C8—N1	−69.9 (5)	C9A—N4A—C8A—N2A	−69.7 (5)
C8—N1—C9—N3	53.7 (5)	C7A—N1A—C9A—N4A	53.9 (4)
C1—N1—C9—N3	−80.5 (4)	C1A—N1A—C9A—N4A	−80.1 (4)
C11—N3—C9—N1	−63.0 (4)	C11A—N4A—C9A—N1A	−64.6 (5)
C10—N3—C9—N1	57.3 (5)	C8A—N4A—C9A—N1A	57.3 (5)
C7—N2—C10—N3	−45.6 (4)	C2A—N2A—C10A—N3A	−81.1 (4)
C2—N2—C10—N3	85.8 (5)	C8A—N2A—C10A—N3A	54.0 (4)
C11—N3—C10—N2	49.2 (5)	C11A—N3A—C10A—N2A	−63.4 (4)
C9—N3—C10—N2	−69.3 (5)	C7A—N3A—C10A—N2A	56.8 (5)
C7—N4—C11—N3	65.5 (4)	C9A—N4A—C11A—N3A	64.9 (4)
C8—N4—C11—N3	−59.0 (4)	C8A—N4A—C11A—N3A	−60.1 (4)
C9—N3—C11—N4	64.9 (4)	C10A—N3A—C11A—N4A	66.4 (4)
C10—N3—C11—N4	−58.9 (4)	C7A—N3A—C11A—N4A	−56.7 (4)
O21—C21—C22—C23	179.2 (4)	O21A—C21A—C22A—C23A	179.2 (4)
C26—C21—C22—C23	−1.4 (7)	C26A—C21A—C22A—C23A	−0.2 (7)
C21—C22—C23—C24	0.9 (7)	C21A—C22A—C23A—C24A	−0.7 (7)
C22—C23—C24—C25	−0.2 (8)	C22A—C23A—C24A—C25A	1.3 (7)
C22—C23—C24—N21	179.8 (5)	C22A—C23A—C24A—N21A	−179.3 (5)
O23—N21—C24—C23	0.2 (8)	O22A—N21A—C24A—C25A	178.7 (5)
O22—N21—C24—C23	−179.0 (6)	O23A—N21A—C24A—C25A	−2.1 (8)
O23—N21—C24—C25	−179.7 (6)	O22A—N21A—C24A—C23A	−0.8 (8)
O22—N21—C24—C25	1.0 (8)	O23A—N21A—C24A—C23A	178.5 (5)
C23—C24—C25—C26	0.1 (8)	C23A—C24A—C25A—C26A	−0.9 (7)
N21—C24—C25—C26	−180.0 (5)	N21A—C24A—C25A—C26A	179.7 (5)
C24—C25—C26—C21	−0.6 (7)	C24A—C25A—C26A—C21A	−0.1 (7)
O21—C21—C26—C25	−179.3 (4)	O21A—C21A—C26A—C25A	−178.8 (4)
C22—C21—C26—C25	1.3 (7)	C22A—C21A—C26A—C25A	0.6 (7)
O31—C31—C32—C33	−178.3 (4)	O31A—C31A—C32A—C33A	−177.8 (5)
C36—C31—C32—C33	1.7 (7)	C36A—C31A—C32A—C33A	2.9 (7)
C31—C32—C33—C34	0.1 (7)	C31A—C32A—C33A—C34A	−1.4 (7)
C32—C33—C34—C35	−1.5 (7)	C32A—C33A—C34A—C35A	−0.7 (7)
C32—C33—C34—N31	177.7 (5)	C32A—C33A—C34A—N31A	179.2 (5)
O32—N31—C34—C33	2.5 (7)	O33A—N31A—C34A—C33A	178.1 (4)
O33—N31—C34—C33	−178.9 (4)	O32A—N31A—C34A—C33A	−3.0 (7)
O32—N31—C34—C35	−178.3 (4)	O33A—N31A—C34A—C35A	−2.0 (7)
O33—N31—C34—C35	0.2 (7)	O32A—N31A—C34A—C35A	176.9 (5)
C33—C34—C35—C36	1.0 (7)	C33A—C34A—C35A—C36A	1.2 (7)
N31—C34—C35—C36	−178.2 (4)	N31A—C34A—C35A—C36A	−178.7 (4)
C34—C35—C36—C31	0.9 (7)	C34A—C35A—C36A—C31A	0.4 (7)
O31—C31—C36—C35	177.8 (4)	O31A—C31A—C36A—C35A	178.3 (4)
C32—C31—C36—C35	−2.2 (7)	C32A—C31A—C36A—C35A	−2.5 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O21—H21···O31	0.91 (6)	1.62 (6)	2.527 (5)	169 (5)
O21A—H21A···O31A	1.18 (9)	1.35 (9)	2.515 (4)	166 (9)
N3—H3···O31	0.93 (7)	1.80 (6)	2.693 (5)	161 (5)
N3A—H3A···O31A	0.98 (5)	1.74 (5)	2.723 (5)	174 (4)
C11—H11B···O32A	0.99	2.48	3.294 (7)	139
C7A—H7A1···O22	0.99	2.31	3.197 (8)	149
C9—H9A···N2^i	0.99	2.49	3.169 (5)	126
C10A—H10C···O21A^ii	0.99	2.27	3.241 (5)	167
C11—H11A···O33A^ii	0.99	2.53	3.369 (7)	142
C8A—H8A1···O33A^iii	0.99	2.49	3.404 (6)	154
C9A—H9A2···O32A^iii	0.99	2.48	3.456 (6)	170
C8—H8A···O33^iv	0.99	2.56	3.461 (6)	151
C9—H9B···O22A^v	0.99	2.35	3.256 (7)	152
C10—H10B···O21^ii	0.99	2.41	3.338 (5)	156

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