Opipramol dipicrate.

In the crystal structure of the title compound, C(23)H(31)N(3)O(2+)·2C(6)H(2)N(3)O(7) (-), {systematic name: 1-[3-(5H-dibenz[b,f]azepin-5-yl)prop-yl]-4-(2-hy-droxy-eth-yl)piperazine-1,4-diium bis-(2,4,6-trinitro-phrenolate)} the piperazine group in the opipramol dication is protonated at both N atoms. Each picrate anion inter-acts with the protonated N atom in the cation through a bifurcated N-H⋯O hydrogen bond, forming an R(2) (1)(6) ring motif. In the cation, the dihedral angle between the mean planes of the two benzene rings is 50.81 (8) Å. Inter-molecular O-H⋯O and weak C-H⋯O hydrogen bonds, and weak π-ring and π-π stacking inter-actions dominate the crystal packing.

Related literature

For the use of opipramol in the treatment of anxiety disorder, see: Moller et al. (2001 ▶). For its use in the preparation of amine derivatives, see: Shriner et al. (1980 ▶). For crystal engineering research, see: Desiraju et al. (1989 ▶). For related structures, see: Bindya et al. (2007 ▶); Jasinski et al. (2010 ▶); Yathirajan et al. (2007 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C23H31N3O2+·2C6H2N3O7 −

M = 821.72

Triclinic,

a = 7.3838 (8) Å

b = 12.0400 (13) Å

c = 22.074 (2) Å

α = 74.821 (1)°

β = 84.355 (2)°

γ = 73.866 (2)°

V = 1818.6 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.12 mm−1

T = 100 K

0.55 × 0.50 × 0.14 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.937, T max = 0.983

10692 measured reflections

10692 independent reflections

7831 reflections with I > 2σ(I)

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.123

S = 0.98

10692 reflections

669 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.64 e Å−3

Δρmin = −0.39 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: SHELXTL (Sheldrick, 2008 ▶); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810026565/xu2786sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810026565/xu2786Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C23H31N3O2+·2C6H2N3O7−	Z = 2
Mr = 821.72	F(000) = 856
Triclinic, P1	Dx = 1.501 Mg m−3
Hall symbol: -p 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3838 (8) Å	Cell parameters from 5178 reflections
b = 12.0400 (13) Å	θ = 2.9–30.4°
c = 22.074 (2) Å	µ = 0.12 mm−1
α = 74.821 (1)°	T = 100 K
β = 84.355 (2)°	Plate, yellow
γ = 73.866 (2)°	0.55 × 0.50 × 0.14 mm
V = 1818.6 (3) Å3

Bruker APEXII CCD diffractometer	10692 independent reflections
Radiation source: fine-focus sealed tube	7831 reflections with I > 2σ(I)
graphite	Rint = 0.0000
ω scans	θmax = 31.1°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −10→10
Tmin = 0.937, Tmax = 0.983	k = −16→17
10692 measured reflections	l = 0→30

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ2(Fo2) + (0.0431P)2 + 1.3196P] where P = (Fo2 + 2Fc2)/3
10692 reflections	(Δ/σ)max < 0.001
669 parameters	Δρmax = 0.64 e Å−3
0 restraints	Δρmin = −0.39 e Å−3

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

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 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
N1	1.02455 (17)	0.60675 (11)	0.37838 (6)	0.0151 (2)
N1A	0.8758 (2)	0.06526 (12)	0.19787 (7)	0.0288 (3)
N1B	0.49985 (18)	0.35440 (11)	0.34309 (6)	0.0191 (2)
N2	0.83911 (17)	0.63062 (11)	0.26315 (5)	0.0154 (2)
N2A	0.36714 (18)	−0.11954 (11)	0.30334 (6)	0.0201 (3)
N2B	0.0123 (2)	0.16475 (12)	0.46259 (7)	0.0240 (3)
N3	0.65920 (18)	0.69770 (11)	0.08383 (6)	0.0183 (2)
N3A	0.2539 (2)	0.30858 (12)	0.23707 (7)	0.0296 (3)
N3B	0.6228 (2)	−0.07470 (12)	0.40742 (6)	0.0262 (3)
O1	1.32600 (16)	0.50804 (10)	0.47765 (5)	0.0238 (2)
H1C	1.3355	0.4665	0.4528	0.036*
O1A	0.73234 (15)	−0.13584 (9)	0.23643 (5)	0.0225 (2)
O1B	0.13483 (17)	0.36702 (10)	0.41214 (6)	0.0335 (3)
O2A	0.45142 (16)	−0.22069 (9)	0.29802 (6)	0.0243 (2)
O2B	−0.12159 (18)	0.22565 (14)	0.43026 (7)	0.0439 (4)
O3A	0.23060 (17)	−0.10226 (11)	0.33974 (6)	0.0309 (3)
O3B	−0.00152 (19)	0.10754 (10)	0.51708 (6)	0.0302 (3)
O4A	0.0937 (2)	0.31534 (12)	0.25984 (7)	0.0451 (4)
O4B	0.5803 (2)	−0.16385 (10)	0.44083 (6)	0.0363 (3)
O5A	0.3147 (2)	0.39677 (10)	0.21386 (6)	0.0366 (3)
O5B	0.76309 (19)	−0.07890 (11)	0.37238 (6)	0.0350 (3)
O6A	0.9082 (2)	0.14690 (14)	0.15701 (10)	0.0721 (6)
O6B	0.64141 (15)	0.33702 (10)	0.30921 (5)	0.0240 (2)
O7A	0.99987 (19)	−0.02019 (13)	0.22406 (7)	0.0419 (3)
O7B	0.40979 (18)	0.45584 (10)	0.34673 (6)	0.0327 (3)
C1	1.2578 (2)	0.63008 (14)	0.44618 (8)	0.0226 (3)
C1A	0.6250 (2)	−0.03839 (12)	0.24106 (7)	0.0169 (3)
C1B	0.2478 (2)	0.27017 (12)	0.40804 (7)	0.0188 (3)
C2	1.0532 (2)	0.65724 (14)	0.43134 (7)	0.0201 (3)
C2A	0.4357 (2)	−0.01908 (12)	0.26842 (7)	0.0174 (3)
C2B	0.2017 (2)	0.15826 (13)	0.43494 (7)	0.0180 (3)
C3	0.8236 (2)	0.60313 (13)	0.37804 (7)	0.0158 (3)
C3A	0.3154 (2)	0.09238 (13)	0.26613 (7)	0.0203 (3)
C3B	0.3198 (2)	0.04765 (13)	0.43780 (7)	0.0203 (3)
C4	0.7918 (2)	0.55480 (12)	0.32445 (6)	0.0157 (3)
C4A	0.3782 (2)	0.19229 (13)	0.23820 (7)	0.0223 (3)
C4B	0.4978 (2)	0.04110 (12)	0.40896 (7)	0.0196 (3)
C5	1.0750 (2)	0.68021 (13)	0.31640 (7)	0.0173 (3)
C5A	0.5629 (2)	0.18292 (13)	0.21535 (7)	0.0224 (3)
C5B	0.5537 (2)	0.14175 (13)	0.37891 (7)	0.0180 (3)
C6	1.0402 (2)	0.63363 (13)	0.26278 (7)	0.0181 (3)
C6A	0.6808 (2)	0.07208 (13)	0.21871 (7)	0.0202 (3)
C6B	0.4335 (2)	0.25296 (12)	0.37819 (7)	0.0170 (3)
C7	0.8042 (2)	0.58956 (14)	0.20786 (7)	0.0208 (3)
C8	0.5958 (2)	0.61594 (14)	0.19562 (7)	0.0199 (3)
C9	0.5705 (2)	0.61345 (14)	0.12799 (7)	0.0217 (3)
C10	0.7251 (2)	0.67135 (13)	0.02498 (7)	0.0196 (3)
C11	0.6288 (3)	0.61785 (14)	−0.00504 (7)	0.0252 (3)
C12	0.7035 (3)	0.58299 (15)	−0.05966 (8)	0.0309 (4)
C13	0.8755 (3)	0.60076 (16)	−0.08394 (8)	0.0327 (4)
C14	0.9697 (3)	0.65574 (15)	−0.05503 (8)	0.0296 (4)
C15	0.8954 (2)	0.69466 (14)	−0.00106 (7)	0.0229 (3)
C16	0.9953 (2)	0.75994 (16)	0.02502 (8)	0.0280 (3)
C17	0.9182 (3)	0.84618 (16)	0.05467 (8)	0.0284 (4)
C18	0.7192 (2)	0.89186 (14)	0.07048 (7)	0.0228 (3)
C19	0.6521 (3)	1.01141 (15)	0.07358 (8)	0.0312 (4)
C20	0.4661 (3)	1.05952 (16)	0.08865 (8)	0.0359 (4)
C21	0.3421 (3)	0.98862 (17)	0.10155 (8)	0.0345 (4)
C22	0.4037 (2)	0.87034 (16)	0.09885 (7)	0.0264 (3)
C23	0.5914 (2)	0.82097 (13)	0.08345 (7)	0.0198 (3)
H1	1.096 (3)	0.5306 (18)	0.3834 (9)	0.027 (5)*
H2	0.769 (3)	0.7069 (19)	0.2581 (9)	0.032 (5)*
H1A	1.334 (3)	0.6519 (17)	0.4086 (9)	0.029 (5)*
H1B	1.265 (3)	0.6790 (17)	0.4736 (9)	0.028 (5)*
H2A	1.000 (3)	0.7399 (18)	0.4188 (9)	0.028 (5)*
H2B	0.984 (2)	0.6202 (16)	0.4667 (9)	0.019 (4)*
H3A	0.748 (2)	0.6818 (15)	0.3746 (8)	0.014 (4)*
H3B	0.797 (2)	0.5526 (16)	0.4172 (8)	0.018 (4)*
H3C	0.192 (3)	0.0976 (17)	0.2851 (9)	0.027 (5)*
H3D	0.280 (3)	−0.0219 (17)	0.4569 (9)	0.025 (5)*
H4A	0.871 (2)	0.4727 (15)	0.3266 (8)	0.014 (4)*
H4B	0.660 (3)	0.5557 (15)	0.3244 (8)	0.018 (4)*
H5A	1.205 (3)	0.6769 (16)	0.3158 (8)	0.020 (4)*
H5B	0.995 (3)	0.7623 (16)	0.3130 (8)	0.022 (5)*
H5C	0.608 (3)	0.2514 (18)	0.1990 (9)	0.031 (5)*
H5D	0.670 (3)	0.1386 (17)	0.3592 (9)	0.029 (5)*
H6A	1.064 (3)	0.6881 (17)	0.2241 (9)	0.028 (5)*
H6B	1.119 (3)	0.5537 (17)	0.2650 (8)	0.023 (5)*
H7A	0.868 (3)	0.5037 (18)	0.2157 (9)	0.028 (5)*
H7B	0.865 (3)	0.6356 (16)	0.1722 (9)	0.021 (4)*
H8A	0.530 (2)	0.6955 (15)	0.2024 (8)	0.015 (4)*
H8B	0.537 (2)	0.5596 (16)	0.2237 (8)	0.019 (4)*
H9A	0.637 (3)	0.5335 (17)	0.1205 (8)	0.023 (5)*
H9B	0.430 (3)	0.6262 (17)	0.1206 (9)	0.029 (5)*
H11	0.513 (3)	0.6024 (18)	0.0116 (10)	0.033 (5)*
H12	0.632 (3)	0.5471 (19)	−0.0806 (10)	0.038 (6)*
H13	0.932 (3)	0.5741 (19)	−0.1207 (10)	0.038 (6)*
H14	1.085 (3)	0.6724 (17)	−0.0727 (9)	0.030 (5)*
H16	1.129 (3)	0.746 (2)	0.0137 (10)	0.044 (6)*
H17	0.998 (3)	0.8897 (18)	0.0633 (10)	0.036 (6)*
H19	0.740 (3)	1.0580 (18)	0.0661 (10)	0.034 (5)*
H20	0.426 (3)	1.1418 (19)	0.0917 (10)	0.040 (6)*
H21	0.213 (3)	1.023 (2)	0.1115 (11)	0.045 (6)*
H22	0.313 (3)	0.8197 (17)	0.1082 (9)	0.029 (5)*

	U11	U22	U33	U12	U13	U23
N1	0.0133 (6)	0.0123 (5)	0.0194 (6)	−0.0018 (4)	−0.0006 (4)	−0.0052 (4)
N1A	0.0266 (7)	0.0211 (6)	0.0364 (8)	−0.0088 (6)	0.0042 (6)	−0.0022 (6)
N1B	0.0171 (6)	0.0173 (6)	0.0237 (6)	−0.0042 (5)	0.0011 (5)	−0.0073 (5)
N2	0.0164 (6)	0.0132 (5)	0.0158 (5)	−0.0026 (5)	−0.0005 (4)	−0.0032 (4)
N2A	0.0165 (6)	0.0203 (6)	0.0246 (6)	−0.0040 (5)	−0.0010 (5)	−0.0083 (5)
N2B	0.0241 (7)	0.0248 (7)	0.0272 (7)	−0.0115 (6)	0.0024 (5)	−0.0092 (5)
N3	0.0225 (6)	0.0187 (6)	0.0144 (5)	−0.0071 (5)	0.0001 (5)	−0.0036 (5)
N3A	0.0403 (9)	0.0184 (6)	0.0229 (7)	0.0090 (6)	−0.0089 (6)	−0.0073 (5)
N3B	0.0341 (8)	0.0167 (6)	0.0246 (7)	0.0057 (6)	−0.0132 (6)	−0.0082 (5)
O1	0.0223 (6)	0.0215 (5)	0.0244 (5)	0.0004 (4)	−0.0065 (4)	−0.0047 (4)
O1A	0.0192 (5)	0.0133 (5)	0.0306 (6)	−0.0006 (4)	0.0033 (4)	−0.0030 (4)
O1B	0.0281 (6)	0.0145 (5)	0.0456 (7)	0.0017 (5)	0.0160 (5)	−0.0005 (5)
O2A	0.0216 (6)	0.0166 (5)	0.0340 (6)	−0.0045 (4)	0.0040 (5)	−0.0071 (5)
O2B	0.0188 (6)	0.0655 (10)	0.0417 (8)	−0.0087 (6)	−0.0041 (5)	−0.0047 (7)
O3A	0.0267 (6)	0.0318 (6)	0.0347 (7)	−0.0081 (5)	0.0110 (5)	−0.0126 (5)
O3B	0.0439 (7)	0.0259 (6)	0.0256 (6)	−0.0174 (5)	0.0102 (5)	−0.0098 (5)
O4A	0.0434 (8)	0.0295 (7)	0.0431 (8)	0.0164 (6)	0.0061 (6)	−0.0060 (6)
O4B	0.0476 (8)	0.0139 (5)	0.0443 (8)	−0.0005 (5)	−0.0108 (6)	−0.0065 (5)
O5A	0.0537 (9)	0.0153 (5)	0.0377 (7)	0.0023 (5)	−0.0136 (6)	−0.0090 (5)
O5B	0.0374 (7)	0.0278 (6)	0.0285 (6)	0.0135 (5)	−0.0034 (5)	−0.0101 (5)
O6A	0.0530 (10)	0.0301 (8)	0.1039 (15)	−0.0083 (7)	0.0356 (10)	0.0170 (9)
O6B	0.0191 (5)	0.0256 (6)	0.0279 (6)	−0.0064 (4)	0.0065 (4)	−0.0094 (5)
O7A	0.0241 (7)	0.0411 (8)	0.0543 (9)	−0.0092 (6)	−0.0031 (6)	0.0005 (7)
O7B	0.0311 (7)	0.0154 (5)	0.0498 (8)	−0.0068 (5)	0.0170 (6)	−0.0109 (5)
C1	0.0212 (8)	0.0202 (7)	0.0256 (8)	−0.0051 (6)	−0.0080 (6)	−0.0018 (6)
C1A	0.0175 (7)	0.0139 (6)	0.0171 (6)	−0.0010 (5)	−0.0033 (5)	−0.0022 (5)
C1B	0.0182 (7)	0.0141 (6)	0.0218 (7)	−0.0019 (5)	−0.0004 (5)	−0.0031 (5)
C2	0.0185 (7)	0.0190 (7)	0.0239 (7)	0.0002 (6)	−0.0065 (6)	−0.0103 (6)
C2A	0.0166 (7)	0.0159 (6)	0.0193 (6)	−0.0018 (5)	−0.0034 (5)	−0.0052 (5)
C2B	0.0180 (7)	0.0176 (6)	0.0186 (6)	−0.0057 (5)	−0.0017 (5)	−0.0034 (5)
C3	0.0123 (6)	0.0174 (6)	0.0173 (6)	−0.0030 (5)	0.0003 (5)	−0.0049 (5)
C3A	0.0182 (7)	0.0214 (7)	0.0198 (7)	0.0021 (6)	−0.0060 (5)	−0.0081 (6)
C3B	0.0285 (8)	0.0149 (6)	0.0187 (7)	−0.0060 (6)	−0.0052 (6)	−0.0042 (5)
C4	0.0173 (7)	0.0137 (6)	0.0165 (6)	−0.0053 (5)	−0.0012 (5)	−0.0028 (5)
C4A	0.0294 (8)	0.0146 (6)	0.0193 (7)	0.0042 (6)	−0.0072 (6)	−0.0061 (5)
C4B	0.0243 (8)	0.0128 (6)	0.0200 (7)	0.0020 (5)	−0.0073 (6)	−0.0060 (5)
C5	0.0144 (7)	0.0142 (6)	0.0222 (7)	−0.0039 (5)	−0.0003 (5)	−0.0021 (5)
C5A	0.0325 (9)	0.0144 (6)	0.0193 (7)	−0.0041 (6)	−0.0043 (6)	−0.0032 (5)
C5B	0.0162 (7)	0.0188 (7)	0.0186 (6)	0.0000 (5)	−0.0041 (5)	−0.0075 (5)
C6	0.0147 (7)	0.0178 (7)	0.0192 (7)	−0.0024 (5)	0.0007 (5)	−0.0026 (5)
C6A	0.0223 (7)	0.0162 (6)	0.0208 (7)	−0.0041 (6)	−0.0015 (6)	−0.0029 (5)
C6B	0.0176 (7)	0.0143 (6)	0.0192 (6)	−0.0036 (5)	−0.0011 (5)	−0.0044 (5)
C7	0.0246 (8)	0.0203 (7)	0.0162 (6)	0.0002 (6)	−0.0034 (6)	−0.0078 (6)
C8	0.0246 (8)	0.0210 (7)	0.0149 (6)	−0.0085 (6)	−0.0005 (5)	−0.0031 (5)
C9	0.0275 (8)	0.0239 (7)	0.0164 (6)	−0.0115 (6)	−0.0009 (6)	−0.0046 (6)
C10	0.0237 (7)	0.0167 (6)	0.0155 (6)	−0.0027 (6)	−0.0013 (5)	−0.0011 (5)
C11	0.0337 (9)	0.0235 (8)	0.0191 (7)	−0.0096 (7)	−0.0014 (6)	−0.0041 (6)
C12	0.0503 (11)	0.0242 (8)	0.0189 (7)	−0.0099 (8)	−0.0037 (7)	−0.0052 (6)
C13	0.0464 (11)	0.0259 (8)	0.0182 (7)	0.0012 (8)	0.0028 (7)	−0.0051 (6)
C14	0.0295 (9)	0.0263 (8)	0.0232 (8)	0.0008 (7)	0.0052 (7)	0.0000 (6)
C15	0.0220 (8)	0.0211 (7)	0.0200 (7)	−0.0004 (6)	−0.0022 (6)	−0.0001 (6)
C16	0.0195 (8)	0.0325 (9)	0.0283 (8)	−0.0076 (7)	−0.0019 (6)	0.0000 (7)
C17	0.0286 (9)	0.0300 (8)	0.0290 (8)	−0.0148 (7)	−0.0065 (7)	−0.0017 (7)
C18	0.0314 (8)	0.0204 (7)	0.0168 (7)	−0.0077 (6)	−0.0052 (6)	−0.0021 (6)
C19	0.0537 (12)	0.0206 (8)	0.0207 (8)	−0.0128 (8)	−0.0081 (7)	−0.0019 (6)
C20	0.0590 (13)	0.0199 (8)	0.0207 (8)	0.0056 (8)	−0.0101 (8)	−0.0046 (6)
C21	0.0375 (10)	0.0329 (9)	0.0219 (8)	0.0107 (8)	−0.0051 (7)	−0.0073 (7)
C22	0.0242 (8)	0.0307 (8)	0.0197 (7)	−0.0003 (7)	−0.0041 (6)	−0.0046 (6)
C23	0.0258 (8)	0.0186 (7)	0.0134 (6)	−0.0029 (6)	−0.0049 (5)	−0.0027 (5)

N1—C5	1.4973 (18)	C3B—C4B	1.394 (2)
N1—C3	1.4973 (18)	C3B—H3D	0.944 (19)
N1—C2	1.5077 (18)	C4—H4A	0.992 (17)
N1—H1	0.91 (2)	C4—H4B	0.970 (18)
N1A—O6A	1.2087 (19)	C4A—C5A	1.391 (2)
N1A—O7A	1.2250 (19)	C4B—C5B	1.372 (2)
N1A—C6A	1.455 (2)	C5—C6	1.506 (2)
N1B—O6B	1.2256 (16)	C5—H5A	0.947 (19)
N1B—O7B	1.2370 (16)	C5—H5B	0.988 (18)
N1B—C6B	1.4473 (18)	C5A—C6A	1.364 (2)
N2—C4	1.4913 (18)	C5A—H5C	0.95 (2)
N2—C6	1.4944 (19)	C5B—C6B	1.383 (2)
N2—C7	1.4996 (18)	C5B—H5D	0.92 (2)
N2—H2	0.90 (2)	C6—H6A	0.97 (2)
N2A—O3A	1.2316 (16)	C6—H6B	0.968 (19)
N2A—O2A	1.2344 (16)	C7—C8	1.519 (2)
N2A—C2A	1.4451 (19)	C7—H7A	0.99 (2)
N2B—O2B	1.2189 (19)	C7—H7B	0.983 (18)
N2B—O3B	1.2298 (18)	C8—C9	1.532 (2)
N2B—C2B	1.460 (2)	C8—H8A	0.989 (17)
N3—C10	1.4250 (18)	C8—H8B	0.960 (18)
N3—C23	1.4264 (19)	C9—H9A	1.000 (18)
N3—C9	1.4609 (19)	C9—H9B	1.03 (2)
N3A—O4A	1.229 (2)	C10—C11	1.389 (2)
N3A—O5A	1.235 (2)	C10—C15	1.400 (2)
N3A—C4A	1.4408 (19)	C11—C12	1.393 (2)
N3B—O5B	1.2277 (19)	C11—H11	0.95 (2)
N3B—O4B	1.2334 (19)	C12—C13	1.379 (3)
N3B—C4B	1.4493 (19)	C12—H12	0.98 (2)
O1—C1	1.4207 (18)	C13—C14	1.377 (3)
O1—H1C	0.8200	C13—H13	0.97 (2)
O1A—C1A	1.2431 (17)	C14—C15	1.400 (2)
O1B—C1B	1.2504 (18)	C14—H14	0.95 (2)
C1—C2	1.505 (2)	C15—C16	1.462 (2)
C1—H1A	0.97 (2)	C16—C17	1.336 (3)
C1—H1B	0.96 (2)	C16—H16	0.97 (2)
C1A—C2A	1.449 (2)	C17—C18	1.461 (2)
C1A—C6A	1.450 (2)	C17—H17	0.95 (2)
C1B—C2B	1.442 (2)	C18—C23	1.403 (2)
C1B—C6B	1.447 (2)	C18—C19	1.404 (2)
C2—H2A	0.94 (2)	C19—C20	1.379 (3)
C2—H2B	0.965 (18)	C19—H19	0.95 (2)
C2A—C3A	1.379 (2)	C20—C21	1.380 (3)
C2B—C3B	1.364 (2)	C20—H20	0.97 (2)
C3—C4	1.5114 (19)	C21—C22	1.385 (3)
C3—H3A	0.944 (17)	C21—H21	0.95 (2)
C3—H3B	0.956 (18)	C22—C23	1.395 (2)
C3A—C4A	1.381 (2)	C22—H22	1.00 (2)
C3A—H3C	0.960 (19)
C5—N1—C3	109.19 (11)	N1—C5—H5A	108.6 (11)
C5—N1—C2	110.78 (11)	C6—C5—H5A	108.5 (11)
C3—N1—C2	110.41 (11)	N1—C5—H5B	106.6 (10)
C5—N1—H1	109.1 (12)	C6—C5—H5B	110.4 (11)
C3—N1—H1	106.7 (12)	H5A—C5—H5B	111.4 (15)
C2—N1—H1	110.5 (12)	C6A—C5A—C4A	118.59 (14)
O6A—N1A—O7A	123.06 (16)	C6A—C5A—H5C	120.0 (12)
O6A—N1A—C6A	118.13 (15)	C4A—C5A—H5C	121.4 (12)
O7A—N1A—C6A	118.74 (13)	C4B—C5B—C6B	119.73 (14)
O6B—N1B—O7B	122.01 (13)	C4B—C5B—H5D	122.4 (12)
O6B—N1B—C6B	118.63 (12)	C6B—C5B—H5D	117.8 (12)
O7B—N1B—C6B	119.32 (12)	N2—C6—C5	111.06 (12)
C4—N2—C6	109.13 (11)	N2—C6—H6A	107.4 (12)
C4—N2—C7	112.96 (11)	C5—C6—H6A	107.9 (12)
C6—N2—C7	110.53 (11)	N2—C6—H6B	108.0 (11)
C4—N2—H2	110.9 (13)	C5—C6—H6B	111.3 (11)
C6—N2—H2	106.2 (13)	H6A—C6—H6B	111.0 (16)
C7—N2—H2	106.9 (13)	C5A—C6A—C1A	124.68 (15)
O3A—N2A—O2A	121.74 (13)	C5A—C6A—N1A	117.16 (14)
O3A—N2A—C2A	118.85 (12)	C1A—C6A—N1A	118.16 (13)
O2A—N2A—C2A	119.34 (12)	C5B—C6B—C1B	123.28 (13)
O2B—N2B—O3B	124.29 (15)	C5B—C6B—N1B	116.20 (13)
O2B—N2B—C2B	118.14 (13)	C1B—C6B—N1B	120.47 (12)
O3B—N2B—C2B	117.58 (14)	N2—C7—C8	112.82 (12)
C10—N3—C23	116.26 (11)	N2—C7—H7A	107.2 (11)
C10—N3—C9	117.10 (12)	C8—C7—H7A	112.1 (11)
C23—N3—C9	118.09 (12)	N2—C7—H7B	104.2 (11)
O4A—N3A—O5A	123.17 (14)	C8—C7—H7B	109.4 (11)
O4A—N3A—C4A	118.62 (15)	H7A—C7—H7B	110.9 (15)
O5A—N3A—C4A	118.21 (15)	C7—C8—C9	109.79 (13)
O5B—N3B—O4B	123.64 (14)	C7—C8—H8A	109.1 (10)
O5B—N3B—C4B	118.44 (14)	C9—C8—H8A	109.9 (10)
O4B—N3B—C4B	117.91 (15)	C7—C8—H8B	112.2 (11)
C1—O1—H1C	109.5	C9—C8—H8B	108.8 (11)
O1—C1—C2	110.26 (13)	H8A—C8—H8B	107.1 (14)
O1—C1—H1A	111.6 (12)	N3—C9—C8	110.31 (12)
C2—C1—H1A	111.5 (12)	N3—C9—H9A	105.3 (10)
O1—C1—H1B	109.2 (12)	C8—C9—H9A	110.6 (11)
C2—C1—H1B	106.8 (12)	N3—C9—H9B	114.5 (11)
H1A—C1—H1B	107.3 (16)	C8—C9—H9B	109.6 (11)
O1A—C1A—C2A	126.28 (13)	H9A—C9—H9B	106.4 (15)
O1A—C1A—C6A	121.87 (14)	C11—C10—C15	119.85 (14)
C2A—C1A—C6A	111.85 (12)	C11—C10—N3	121.27 (14)
O1B—C1B—C2B	121.18 (14)	C15—C10—N3	118.80 (14)
O1B—C1B—C6B	127.15 (14)	C10—C11—C12	120.62 (17)
C2B—C1B—C6B	111.66 (12)	C10—C11—H11	120.9 (12)
C1—C2—N1	112.61 (12)	C12—C11—H11	118.4 (13)
C1—C2—H2A	110.8 (12)	C13—C12—C11	119.76 (17)
N1—C2—H2A	106.4 (12)	C13—C12—H12	121.0 (12)
C1—C2—H2B	110.7 (11)	C11—C12—H12	119.2 (12)
N1—C2—H2B	104.6 (11)	C14—C13—C12	119.82 (16)
H2A—C2—H2B	111.4 (16)	C14—C13—H13	119.3 (13)
C3A—C2A—N2A	116.23 (13)	C12—C13—H13	120.9 (13)
C3A—C2A—C1A	123.64 (14)	C13—C14—C15	121.58 (17)
N2A—C2A—C1A	120.05 (12)	C13—C14—H14	120.5 (12)
C3B—C2B—C1B	125.93 (14)	C15—C14—H14	117.8 (12)
C3B—C2B—N2B	117.41 (13)	C10—C15—C14	118.24 (16)
C1B—C2B—N2B	116.65 (13)	C10—C15—C16	122.62 (14)
N1—C3—C4	111.05 (11)	C14—C15—C16	119.13 (16)
N1—C3—H3A	107.0 (10)	C17—C16—C15	126.76 (16)
C4—C3—H3A	111.2 (10)	C17—C16—H16	118.1 (13)
N1—C3—H3B	107.5 (11)	C15—C16—H16	114.5 (13)
C4—C3—H3B	109.9 (11)	C16—C17—C18	127.92 (16)
H3A—C3—H3B	110.0 (14)	C16—C17—H17	117.6 (13)
C2A—C3A—C4A	119.18 (15)	C18—C17—H17	114.2 (13)
C2A—C3A—H3C	118.5 (11)	C23—C18—C19	118.16 (16)
C4A—C3A—H3C	122.3 (11)	C23—C18—C17	122.83 (14)
C2B—C3B—C4B	117.56 (14)	C19—C18—C17	119.01 (16)
C2B—C3B—H3D	121.2 (11)	C20—C19—C18	121.74 (18)
C4B—C3B—H3D	121.2 (11)	C20—C19—H19	120.6 (13)
N2—C4—C3	110.39 (11)	C18—C19—H19	117.6 (13)
N2—C4—H4A	106.7 (10)	C19—C20—C21	119.48 (17)
C3—C4—H4A	112.7 (10)	C19—C20—H20	119.4 (13)
N2—C4—H4B	108.1 (10)	C21—C20—H20	121.1 (13)
C3—C4—H4B	109.6 (10)	C20—C21—C22	120.24 (18)
H4A—C4—H4B	109.3 (14)	C20—C21—H21	119.0 (14)
C3A—C4A—C5A	121.45 (14)	C22—C21—H21	120.7 (14)
C3A—C4A—N3A	119.11 (15)	C21—C22—C23	120.70 (17)
C5A—C4A—N3A	119.27 (15)	C21—C22—H22	119.7 (11)
C5B—C4B—C3B	121.63 (13)	C23—C22—H22	119.6 (11)
C5B—C4B—N3B	119.06 (14)	C22—C23—C18	119.68 (15)
C3B—C4B—N3B	119.21 (14)	C22—C23—N3	121.32 (14)
N1—C5—C6	111.44 (12)	C18—C23—N3	118.92 (14)
O1—C1—C2—N1	−73.47 (17)	O6A—N1A—C6A—C5A	−30.2 (2)
C5—N1—C2—C1	−75.95 (15)	O7A—N1A—C6A—C5A	146.94 (16)
C3—N1—C2—C1	162.96 (13)	O6A—N1A—C6A—C1A	149.37 (18)
O3A—N2A—C2A—C3A	−16.0 (2)	O7A—N1A—C6A—C1A	−33.4 (2)
O2A—N2A—C2A—C3A	167.07 (13)	C4B—C5B—C6B—C1B	0.1 (2)
O3A—N2A—C2A—C1A	160.72 (14)	C4B—C5B—C6B—N1B	−177.32 (13)
O2A—N2A—C2A—C1A	−16.2 (2)	O1B—C1B—C6B—C5B	176.23 (16)
O1A—C1A—C2A—C3A	−172.63 (14)	C2B—C1B—C6B—C5B	−3.3 (2)
C6A—C1A—C2A—C3A	7.6 (2)	O1B—C1B—C6B—N1B	−6.4 (2)
O1A—C1A—C2A—N2A	10.9 (2)	C2B—C1B—C6B—N1B	174.07 (12)
C6A—C1A—C2A—N2A	−168.85 (12)	O6B—N1B—C6B—C5B	10.6 (2)
O1B—C1B—C2B—C3B	−174.15 (15)	O7B—N1B—C6B—C5B	−171.39 (14)
C6B—C1B—C2B—C3B	5.4 (2)	O6B—N1B—C6B—C1B	−166.93 (13)
O1B—C1B—C2B—N2B	4.6 (2)	O7B—N1B—C6B—C1B	11.1 (2)
C6B—C1B—C2B—N2B	−175.85 (12)	C4—N2—C7—C8	72.88 (16)
O2B—N2B—C2B—C3B	−127.14 (16)	C6—N2—C7—C8	−164.52 (12)
O3B—N2B—C2B—C3B	52.44 (19)	N2—C7—C8—C9	160.20 (12)
O2B—N2B—C2B—C1B	54.0 (2)	C10—N3—C9—C8	152.17 (13)
O3B—N2B—C2B—C1B	−126.42 (15)	C23—N3—C9—C8	−61.06 (17)
C5—N1—C3—C4	56.93 (14)	C7—C8—C9—N3	−56.46 (17)
C2—N1—C3—C4	178.96 (12)	C23—N3—C10—C11	−111.87 (16)
N2A—C2A—C3A—C4A	174.47 (13)	C9—N3—C10—C11	35.5 (2)
C1A—C2A—C3A—C4A	−2.1 (2)	C23—N3—C10—C15	71.41 (18)
C1B—C2B—C3B—C4B	−4.1 (2)	C9—N3—C10—C15	−141.22 (14)
N2B—C2B—C3B—C4B	177.17 (13)	C15—C10—C11—C12	2.4 (2)
C6—N2—C4—C3	58.56 (15)	N3—C10—C11—C12	−174.26 (14)
C7—N2—C4—C3	−178.06 (12)	C10—C11—C12—C13	0.6 (3)
N1—C3—C4—N2	−59.29 (15)	C11—C12—C13—C14	−1.8 (3)
C2A—C3A—C4A—C5A	−3.5 (2)	C12—C13—C14—C15	0.0 (3)
C2A—C3A—C4A—N3A	−178.66 (13)	C11—C10—C15—C14	−4.1 (2)
O4A—N3A—C4A—C3A	−1.6 (2)	N3—C10—C15—C14	172.67 (14)
O5A—N3A—C4A—C3A	177.50 (14)	C11—C10—C15—C16	174.51 (15)
O4A—N3A—C4A—C5A	−176.91 (15)	N3—C10—C15—C16	−8.7 (2)
O5A—N3A—C4A—C5A	2.2 (2)	C13—C14—C15—C10	2.9 (2)
C2B—C3B—C4B—C5B	0.2 (2)	C13—C14—C15—C16	−175.71 (16)
C2B—C3B—C4B—N3B	−176.01 (13)	C10—C15—C16—C17	−31.2 (3)
O5B—N3B—C4B—C5B	−9.7 (2)	C14—C15—C16—C17	147.44 (18)
O4B—N3B—C4B—C5B	171.44 (14)	C15—C16—C17—C18	3.0 (3)
O5B—N3B—C4B—C3B	166.71 (14)	C16—C17—C18—C23	30.6 (3)
O4B—N3B—C4B—C3B	−12.2 (2)	C16—C17—C18—C19	−150.09 (18)
C3—N1—C5—C6	−56.04 (15)	C23—C18—C19—C20	−0.2 (2)
C2—N1—C5—C6	−177.86 (12)	C17—C18—C19—C20	−179.58 (16)
C3A—C4A—C5A—C6A	2.6 (2)	C18—C19—C20—C21	0.5 (3)
N3A—C4A—C5A—C6A	177.78 (14)	C19—C20—C21—C22	−0.5 (3)
C3B—C4B—C5B—C6B	1.6 (2)	C20—C21—C22—C23	0.3 (2)
N3B—C4B—C5B—C6B	177.86 (13)	C21—C22—C23—C18	−0.1 (2)
C4—N2—C6—C5	−57.85 (15)	C21—C22—C23—N3	176.53 (14)
C7—N2—C6—C5	177.35 (12)	C19—C18—C23—C22	0.0 (2)
N1—C5—C6—N2	57.52 (15)	C17—C18—C23—C22	179.34 (15)
C4A—C5A—C6A—C1A	4.0 (2)	C19—C18—C23—N3	−176.67 (13)
C4A—C5A—C6A—N1A	−176.42 (14)	C17—C18—C23—N3	2.7 (2)
O1A—C1A—C6A—C5A	171.60 (15)	C10—N3—C23—C22	116.62 (16)
C2A—C1A—C6A—C5A	−8.7 (2)	C9—N3—C23—C22	−30.4 (2)
O1A—C1A—C6A—N1A	−8.0 (2)	C10—N3—C23—C18	−66.76 (18)
C2A—C1A—C6A—N1A	171.77 (13)	C9—N3—C23—C18	146.20 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1Bi	0.91 (2)	1.85 (2)	2.6901 (16)	152.6 (18)
N1—H1···O7Bi	0.91 (2)	2.383 (19)	3.0466 (17)	130.0 (16)
N2—H2···O1Aii	0.90 (2)	1.78 (2)	2.6204 (16)	154.6 (19)
N2—H2···O2Aii	0.90 (2)	2.43 (2)	3.0711 (16)	128.2 (16)
O1—H1C···O1Bi	0.82	2.50	3.1600 (19)	138
O1—H1C···O7Bi	0.82	2.38	3.0841 (18)	144
C2—H2A···O5Bii	0.94 (2)	2.43 (2)	3.3130 (19)	155.7 (16)
C2—H2A···O3Biii	0.94 (2)	2.60 (2)	3.2350 (19)	125.4 (15)
C3—H3B···O1iv	0.956 (18)	2.410 (18)	3.3250 (18)	160.0 (14)
C3B—H3D···O3Bv	0.944 (19)	2.503 (19)	3.318 (2)	144.7 (15)
C4—H4B···O2Aii	0.970 (18)	2.648 (17)	3.1064 (18)	109.3 (12)
C5—H5A···O2Avi	0.947 (19)	2.418 (19)	3.2683 (18)	149.3 (14)
C5—H5B···O1Aii	0.988 (18)	2.523 (18)	3.1842 (18)	124.1 (13)
C5—H5B···O5Bii	0.988 (18)	2.714 (18)	3.5844 (19)	147.2 (14)
C6—H6B···O5Ai	0.968 (19)	2.492 (19)	3.3728 (19)	151.2 (15)
C7—H7A···O4Ai	0.99 (2)	2.44 (2)	3.371 (2)	158.0 (16)
C8—H8A···O2Aii	0.989 (17)	2.521 (17)	3.2870 (19)	134.1 (13)
C14—H14···O6Avii	0.95 (2)	2.47 (2)	3.085 (2)	122.0 (15)

Y—X···Cg	X···Cg	Y···Cg	X···Perp
C1A-O1A···Cg3i	3.5674 (13)	3.6471 (17)	3.494
N3A-O4A···Cg9ii	3.8172 (17)	3.8173 (17)	-3.357
N3B-O4B···Cg9iii	3.4320 (15)	3.9391 (15)	3.288

	CgX···CgY	CgX···Perp	CgY···Perp
Cg2···Cg2i	3.8038 (11)	-3.5589 (7)	-3.5590 (7)
Cg3···Cg3i	3.7164 (10)	-3.6624 (7)	-3.6623 (7)
Cg8···Cg9ii	3.9558 (10)	-3.2475 (6)	3.3731 (6)
Cg9···Cg8ii	3.9557 (10)	3.3730 (6)	-3.2475 (6)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1Bi	0.91 (2)	1.85 (2)	2.6901 (16)	152.6 (18)
N1—H1⋯O7Bi	0.91 (2)	2.383 (19)	3.0466 (17)	130.0 (16)
N2—H2⋯O1Aii	0.90 (2)	1.78 (2)	2.6204 (16)	154.6 (19)
N2—H2⋯O2Aii	0.90 (2)	2.43 (2)	3.0711 (16)	128.2 (16)
O1—H1C⋯O1Bi	0.82	2.50	3.1600 (19)	138
O1—H1C⋯O7Bi	0.82	2.38	3.0841 (18)	144

Symmetry codes: (i) ; (ii) .

Table 2

Y—X⋯Cg π ring inter­actions (Å)

Cg3 and Cg9 are the centroids of the C10–C15 and C1A–C6A rings, respectively. CgX⋯Perp and CgY⋯Perp are the perpendicular distances between atoms X and Y and the ring centroid.

Y—X⋯Cg	X⋯Cg	Y⋯Cg	X⋯Perp
C1A—O1A⋯Cg3i	3.5674 (13)	3.6471 (17)	3.494
N3A—O4A⋯Cg9	3.8172 (17)	3.8173 (17)	−3.357
N3B—O4B⋯Cg9ii	3.4320 (15)	3.9391 (15)	3.288

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

Table 3

Cg⋯Cg π stacking inter­actions (Å)

Cg2, Cg3, Cg8 and Cg9 are the centroids of the C10–C15, C18–C23, C1A–C6A and C1B–C6B rings, respectively. CgX⋯Perp and CgY⋯Perp are the perpendicular distances between the ring centroid and the other ring.

	CgX⋯CgY	CgX⋯Perp	CgY⋯Perp
Cg2⋯Cg2i	3.8038 (11)	−3.5589 (7)	−3.5590 (7)
Cg3⋯Cg3i	3.7164 (10)	−3.6624 (7)	−3.6623 (7)
Cg8⋯Cg9	3.9558 (10)	−3.2475 (6)	3.3731 (6)

Symmetry code: (i) 2 − x, 1 − y, −z.