Di-2-pyridyl ketone N⁴,N⁴-(butane-1,4-diyl)thiosemicarbazone

The title compound, C₁₆H₁₇N₅S, is in the thione form and crystallizes with two independent mol­ecules in the asymmetric unit. In both mol­ecules, the penta­methyl­ene­imine five-membered ring adopts an envelope conformation, and in one of the molecules this ring shows positional disorder. The thione S and hydrazine N atoms are in the Z configuration with respect to the C-N bond.

S1. Comment

A great number of studies have been devoted to the search for derivatives of thiosemicarbazides, which have been used as drugs and have the ability to form complexes (Petering & van Giessen, 1965). Thiosemicarbazones of α-N-heterocyclic carbaldehydes act as tridentate ligands. The biological activity of the thiosemicarbazone depends on the parent aldehyde or ketone (Padhye & Kauffman, 1985; Liberta & West, 1992; Lukevics et al., 1995). Among thousands of screened compounds (Klayman et al., 1979), 2-acetylpyridine thiosemicarbazones were the first compounds reported as potent antimalarial agents. Among these, the 2-acetylpyridine thiosemicarbazones of the highest activity are those having the N⁴ atom disubstituted or as part of the ring system.

As part of our studies of thiosemicarbazones and their metal complexes (Usman et al., 2002), we have now prepared the title quadridentate N₃S compound, (I), and analysed its crystal structure. Compound (I) was prepared (Ali & Livingstone, 1974; Campbell, 1975; Livingstone, 1965) by adopting the procedures reported by Scovill (1991). Thiosemicarbazones are reported to exhibit thione-thiol tautomerism in solution. However, the absence of a peak at ca δ 4.0 p.p.m. in the ¹H NMR spectrum of (I) indicates that the compound exists as a thione in solution. This fact is supported by the crystallographic data. \sch

There are two crystallographically independent molecules, A and B, in the asymmetric unit of (I), with bond lengths and angles which agree with each other. The values are within normal ranges (Allen et al., 1987). Molecules A and B are related by a local pseudo-twofold rotation axis (Fig. 1). Both molecules show an E configuration about the C6—N3 and C12—N4 bonds relative to the N3—N4 bond. The S and the hydrazine N3 atoms in both molecules are in the Z configuration with respect to the C12—N4 bond. A similar conformation was observed in di-2-pyridylketone thiosemicarbazone (Duan et al., 1996), where the N⁴ position is unsubstituted.

The C12—S1 and C12—N4 bond distances in both molecules are typical of the C═S double bond and the C—N single bond, respectively (Table 1). The comparison of the N3—N4 bond distance [1.361 (3) Å in molecule A and 1.354 (4) Å in molecule B] with the corresponding distance in di-2-pyridylketone thiosemicarbazone (1.371 Å) is indicative of a single bond and suggests the thione form of (I).

In both molecules of (I), the pentamethyleneimine five-membered ring (N5/C13—C16) is out of planarity and tends towards an envelope conformation. In molecule A, atom C14 deviates by 0.410 (5) Å from the N5/C13/C15/C16 plane. In molecule B, this ring shows disorder, so that in the major and minor configurations, atoms C14B and C14C deviate in opposite directions by 0.382 (2) and 0.543 (2) Å, respectively, from the N5/C13/C15/C16 plane.

In both molecules A and B, the relative configurations of the two pyridyl rings with respect to the planar thiosemicarbazone [S1/N3/N4/C6/C12] are conditioned by the sp²-hybridized C6 atom [average bond angle subtended at C6 is 120.0° in molecule A and 119.8° in molecule B]. The dihedral angles between the thiosemicarbazone and the two pyridyl rings are relatively small [35.8 (1) and 22.7 (2)° in molecule A, and 21.7 (2) and 22.7 (2)° in molecule B], due to a resonance effect between the π systems.

An intramolecular N4—H4···N2 hydrogen bond forms a six-membered N2—C7—C6—N3—N4—H4 ring in both molecules of (I) (Fig. 1 and Table 2). In the packing, the molecules are stacked into molecular columns parallel to the b direction.

S2. Experimental

Compound (I) was prepared by refluxing a methanolic solution of di-2-pyridyl ketone (0.184 g, 1 mmol) with pyrrolidine-1-thiocarboxylic acid hydrazide (0.145 g, 1 mmol) and glacial acetic acid (3 drops) for 3 h. The needle-shaped yellow crystals which separated on cooling were filtered and washed with ethanol. Single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of a methanolic solution. Elemental anaylsis, found (calculated): C 62.10 (62.71), H 5.56 (5.50), N 22.43 (22.49)%.

S3. Refinement

H atoms were geometrically fixed and treated as riding atoms on the parent C and N atoms, with C—H distances in the range 0.93–0.97 Å, N—H = 0.86 Å and U_iso(H) = 1.2U_eq(C, N).

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Figures

Fig. 1. The two independent molecules of (I), with 50% probability displacement ellipsoids and the atom-numbering scheme. H atoms are shown as small spheres of arbitrary radii and dashed lines denote the intramolecular N—H···N interactions.

Di-2-pyridyl ketone N⁴,N⁴-(butane-1,4-diyl)thiosemicarbazone

Crystal data

C16H17N5S	Z = 4
Mr = 311.41	F(000) = 656
Triclinic, P1	Dx = 1.329 Mg m^−3
a = 9.0068 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.2034 (8) Å	Cell parameters from 2342 reflections
c = 15.8750 (12) Å	θ = 2.6–28.3°
α = 103.753 (2)°	µ = 0.21 mm^−1
β = 90.361 (2)°	T = 293 K
γ = 90.392 (1)°	Block, orange
V = 1555.9 (2) Å^3	0.5 × 0.4 × 0.3 mm

Data collection

Siemens SMART CCD area-detector diffractometer	7299 independent reflections
Radiation source: fine-focus sealed tube	4123 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
Detector resolution: 8.33 pixels mm^-1	θmax = 28.3°, θmin = 2.6°
ω scans	h = −12→12
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −14→12
Tmin = 0.901, Tmax = 0.939	l = −21→17
9895 measured reflections

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)] = 0.076	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.170	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0522P)^2 + 1.3792P] where P = (Fo^2 + 2Fc^2)/3
7299 reflections	(Δ/σ)max < 0.001
407 parameters	Δρmax = 0.29 e Å^−3
2 restraints	Δρmin = −0.26 e Å^−3

Special details

Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 5 cm and the detector swing angle was -35°. Crystal decay was monitored by repeating 50 initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible.

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

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

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1A	0.24904 (11)	0.13556 (8)	0.49540 (7)	0.0486 (3)
C4A	−0.0523 (4)	0.3447 (3)	0.3265 (2)	0.0446 (9)
H4AA	−0.0639	0.3004	0.3687	0.053*
N2A	0.3176 (3)	0.6097 (2)	0.50737 (18)	0.0385 (7)
N3A	0.1811 (3)	0.3692 (2)	0.44349 (17)	0.0341 (6)
N4A	0.2692 (3)	0.3802 (2)	0.51489 (17)	0.0375 (7)
H4AB	0.3031	0.4512	0.5416	0.045*
N5A	0.3875 (3)	0.3041 (3)	0.61600 (18)	0.0434 (7)
C3A	−0.1393 (4)	0.3179 (4)	0.2524 (2)	0.0543 (10)
H3AB	−0.2106	0.2557	0.2442	0.065*
C2A	−0.1192 (5)	0.3842 (4)	0.1915 (3)	0.0596 (12)
H2AB	−0.1773	0.3690	0.1414	0.071*
C1A	−0.0112 (6)	0.4739 (4)	0.2061 (2)	0.0618 (12)
H1AA	0.0039	0.5173	0.1636	0.074*
N1A	0.0742 (4)	0.5029 (3)	0.27790 (19)	0.0505 (8)
C5A	0.0518 (4)	0.4376 (3)	0.3372 (2)	0.0352 (8)
C6A	0.1492 (3)	0.4663 (3)	0.41616 (19)	0.0294 (7)
C7A	0.1956 (4)	0.5944 (3)	0.4556 (2)	0.0315 (7)
C8A	0.1147 (4)	0.6943 (3)	0.4439 (2)	0.0384 (8)
H8AA	0.0306	0.6825	0.4085	0.046*
C9A	0.1607 (4)	0.8114 (3)	0.4853 (2)	0.0454 (9)
H9AA	0.1069	0.8793	0.4789	0.054*
C10A	0.2864 (4)	0.8266 (3)	0.5359 (3)	0.0499 (10)
H10A	0.3208	0.9048	0.5632	0.060*
C11A	0.3599 (4)	0.7244 (3)	0.5453 (2)	0.0476 (9)
H11A	0.4446	0.7353	0.5802	0.057*
C12A	0.3042 (4)	0.2780 (3)	0.5444 (2)	0.0360 (8)
C13A	0.4499 (5)	0.2082 (4)	0.6547 (3)	0.0559 (11)
H13A	0.5022	0.1471	0.6118	0.067*
H13B	0.3726	0.1676	0.6802	0.067*
C14A	0.5544 (6)	0.2780 (5)	0.7228 (3)	0.0854 (16)
H14A	0.5562	0.2419	0.7727	0.103*
H14B	0.6542	0.2771	0.7001	0.103*
C15A	0.4983 (7)	0.4042 (5)	0.7474 (3)	0.0895 (17)
H15A	0.5787	0.4620	0.7682	0.107*
H15B	0.4246	0.4122	0.7926	0.107*
C16A	0.4300 (5)	0.4276 (4)	0.6658 (2)	0.0532 (10)
H16A	0.3439	0.4801	0.6790	0.064*
H16B	0.5012	0.4654	0.6344	0.064*
S1B	0.77432 (12)	0.32572 (9)	0.94732 (7)	0.0497 (3)
C4B	0.4791 (4)	0.1999 (3)	1.1507 (2)	0.0413 (8)
H4BA	0.4942	0.2435	1.1084	0.050*
N2B	0.8171 (3)	−0.1209 (3)	1.00160 (18)	0.0400 (7)
N3B	0.7010 (3)	0.1248 (2)	1.03527 (18)	0.0367 (7)
N4B	0.7913 (3)	0.0941 (2)	0.96568 (17)	0.0380 (7)
H4BB	0.8257	0.0207	0.9502	0.046*
N5B	0.9116 (3)	0.1327 (3)	0.85051 (18)	0.0405 (7)
C3B	0.3826 (4)	0.2426 (3)	1.2177 (2)	0.0467 (9)
H3BB	0.3317	0.3155	1.2212	0.056*
C2B	0.3621 (4)	0.1763 (3)	1.2796 (2)	0.0463 (9)
H2BB	0.2958	0.2021	1.3248	0.056*
C1B	0.4427 (4)	0.0712 (4)	1.2722 (2)	0.0499 (10)
H1BA	0.4307	0.0275	1.3147	0.060*
N1B	0.5370 (3)	0.0273 (3)	1.20830 (18)	0.0446 (7)
C5B	0.5534 (3)	0.0910 (3)	1.1472 (2)	0.0319 (7)
C6B	0.6564 (3)	0.0404 (3)	1.0736 (2)	0.0322 (7)
C7B	0.6931 (4)	−0.0921 (3)	1.0489 (2)	0.0333 (7)
C8B	0.6039 (4)	−0.1824 (3)	1.0684 (2)	0.0424 (9)
H8BA	0.5169	−0.1614	1.0996	0.051*
C9B	0.6442 (5)	−0.3035 (3)	1.0415 (3)	0.0542 (10)
H9BA	0.5851	−0.3652	1.0543	0.065*
C10B	0.7730 (5)	−0.3323 (4)	0.9955 (3)	0.0581 (11)
H10B	0.8040	−0.4134	0.9779	0.070*
C11B	0.8545 (4)	−0.2387 (4)	0.9763 (3)	0.0511 (10)
H11B	0.9404	−0.2585	0.9439	0.061*
C12B	0.8283 (4)	0.1793 (3)	0.9196 (2)	0.0370 (8)
C13B	0.9658 (5)	0.2058 (4)	0.7913 (3)	0.0556 (11)
H13E	1.0576	0.2469	0.8118	0.067*	0.684 (19)
H13F	0.8939	0.2652	0.7836	0.067*	0.684 (19)
H13C	1.0161	0.2786	0.8231	0.067*	0.316 (19)
H13D	0.8857	0.2290	0.7585	0.067*	0.316 (19)
C14B	1.082 (2)	0.1260 (16)	0.7404 (14)	0.060 (6)	0.316 (19)
H14C	1.0848	0.1375	0.6818	0.072*	0.316 (19)
H14D	1.1784	0.1464	0.7673	0.072*	0.316 (19)
C14C	0.9950 (15)	0.1081 (7)	0.7086 (5)	0.068 (3)	0.684 (19)
H14E	0.9056	0.0897	0.6734	0.082*	0.684 (19)
H14F	1.0722	0.1348	0.6747	0.082*	0.684 (19)
C15B	1.0426 (6)	0.0006 (5)	0.7391 (3)	0.0831 (16)
H15E	1.0259	−0.0758	0.6975	0.100*	0.684 (19)
H15F	1.1471	0.0101	0.7514	0.100*	0.684 (19)
H15C	1.1353	−0.0409	0.7400	0.100*	0.316 (19)
H15D	0.9862	−0.0421	0.6894	0.100*	0.316 (19)
C16B	0.9585 (4)	0.0040 (3)	0.8218 (2)	0.0444 (9)
H16C	0.8732	−0.0511	0.8108	0.053*
H16D	1.0220	−0.0188	0.8649	0.053*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1A	0.0605 (6)	0.0325 (5)	0.0564 (6)	−0.0019 (4)	−0.0033 (5)	0.0180 (4)
C4A	0.046 (2)	0.048 (2)	0.039 (2)	−0.0014 (18)	−0.0016 (17)	0.0105 (17)
N2A	0.0368 (16)	0.0331 (16)	0.0455 (17)	−0.0001 (13)	−0.0029 (14)	0.0092 (13)
N3A	0.0367 (15)	0.0336 (15)	0.0325 (15)	0.0021 (12)	0.0003 (13)	0.0088 (12)
N4A	0.0453 (17)	0.0283 (15)	0.0385 (17)	−0.0008 (13)	−0.0077 (14)	0.0076 (12)
N5A	0.0503 (18)	0.0438 (18)	0.0402 (17)	0.0058 (15)	−0.0058 (15)	0.0181 (14)
C3A	0.053 (2)	0.057 (3)	0.046 (2)	−0.004 (2)	−0.007 (2)	−0.002 (2)
C2A	0.073 (3)	0.058 (3)	0.039 (2)	0.022 (2)	−0.015 (2)	−0.005 (2)
C1A	0.109 (4)	0.048 (2)	0.031 (2)	0.014 (3)	−0.006 (2)	0.0131 (18)
N1A	0.082 (2)	0.0373 (17)	0.0339 (17)	−0.0005 (16)	−0.0012 (16)	0.0121 (14)
C5A	0.045 (2)	0.0279 (17)	0.0310 (18)	0.0071 (15)	0.0022 (15)	0.0034 (14)
C6A	0.0325 (17)	0.0266 (16)	0.0291 (17)	0.0032 (13)	0.0047 (14)	0.0065 (13)
C7A	0.0352 (18)	0.0316 (17)	0.0293 (17)	−0.0005 (14)	0.0081 (15)	0.0101 (14)
C8A	0.0401 (19)	0.0342 (19)	0.041 (2)	0.0019 (16)	−0.0010 (16)	0.0098 (16)
C9A	0.056 (2)	0.0306 (19)	0.052 (2)	0.0052 (17)	0.0042 (19)	0.0148 (17)
C10A	0.058 (2)	0.033 (2)	0.058 (2)	−0.0122 (18)	−0.001 (2)	0.0073 (18)
C11A	0.044 (2)	0.045 (2)	0.052 (2)	−0.0104 (18)	−0.0087 (18)	0.0069 (18)
C12A	0.0358 (19)	0.0343 (19)	0.041 (2)	0.0047 (15)	0.0067 (16)	0.0159 (15)
C13A	0.058 (3)	0.060 (3)	0.060 (3)	0.007 (2)	−0.007 (2)	0.035 (2)
C14A	0.096 (4)	0.096 (4)	0.078 (4)	−0.006 (3)	−0.030 (3)	0.049 (3)
C15A	0.125 (5)	0.085 (4)	0.058 (3)	0.002 (3)	−0.032 (3)	0.017 (3)
C16A	0.062 (3)	0.054 (2)	0.042 (2)	0.001 (2)	−0.0055 (19)	0.0096 (19)
S1B	0.0603 (6)	0.0350 (5)	0.0567 (6)	0.0043 (5)	0.0055 (5)	0.0165 (4)
C4B	0.052 (2)	0.037 (2)	0.0355 (19)	0.0021 (17)	−0.0028 (17)	0.0084 (16)
N2B	0.0353 (16)	0.0376 (17)	0.0463 (18)	0.0050 (13)	0.0001 (14)	0.0085 (14)
N3B	0.0386 (16)	0.0330 (15)	0.0382 (16)	0.0012 (13)	0.0022 (13)	0.0082 (13)
N4B	0.0437 (17)	0.0304 (15)	0.0405 (17)	0.0050 (13)	0.0088 (14)	0.0094 (13)
N5B	0.0457 (18)	0.0381 (17)	0.0398 (17)	−0.0005 (14)	0.0072 (14)	0.0132 (13)
C3B	0.050 (2)	0.043 (2)	0.042 (2)	0.0112 (18)	−0.0012 (18)	−0.0003 (17)
C2B	0.043 (2)	0.051 (2)	0.039 (2)	0.0023 (18)	0.0043 (17)	−0.0013 (18)
C1B	0.060 (3)	0.055 (2)	0.035 (2)	0.007 (2)	0.0118 (19)	0.0104 (18)
N1B	0.0533 (19)	0.0472 (18)	0.0350 (16)	0.0094 (15)	0.0054 (15)	0.0125 (14)
C5B	0.0325 (17)	0.0349 (18)	0.0272 (17)	−0.0026 (14)	−0.0038 (14)	0.0056 (14)
C6B	0.0328 (18)	0.0357 (18)	0.0291 (17)	−0.0009 (14)	−0.0038 (14)	0.0098 (14)
C7B	0.0392 (19)	0.0343 (18)	0.0266 (17)	−0.0006 (15)	−0.0078 (15)	0.0077 (14)
C8B	0.049 (2)	0.040 (2)	0.039 (2)	−0.0006 (17)	−0.0004 (17)	0.0105 (16)
C9B	0.072 (3)	0.038 (2)	0.056 (3)	−0.010 (2)	−0.002 (2)	0.0176 (19)
C10B	0.074 (3)	0.032 (2)	0.067 (3)	0.010 (2)	−0.001 (2)	0.0083 (19)
C11B	0.048 (2)	0.045 (2)	0.059 (3)	0.0108 (19)	0.0033 (19)	0.0101 (19)
C12B	0.0351 (19)	0.0364 (19)	0.041 (2)	−0.0031 (15)	−0.0024 (16)	0.0124 (16)
C13B	0.057 (3)	0.064 (3)	0.056 (3)	0.002 (2)	0.013 (2)	0.035 (2)
C14B	0.044 (10)	0.093 (12)	0.053 (11)	0.024 (8)	0.019 (8)	0.039 (9)
C14C	0.068 (7)	0.095 (6)	0.053 (5)	0.018 (5)	0.014 (4)	0.038 (4)
C15B	0.111 (4)	0.078 (4)	0.059 (3)	0.016 (3)	0.037 (3)	0.011 (3)
C16B	0.049 (2)	0.041 (2)	0.041 (2)	−0.0039 (17)	0.0036 (17)	0.0056 (17)

Geometric parameters (Å, º)

S1A—C12A	1.671 (4)	N2B—C7B	1.348 (4)
C4A—C5A	1.376 (5)	N3B—C6B	1.303 (4)
C4A—C3A	1.379 (5)	N3B—N4B	1.354 (4)
C4A—H4AA	0.9300	N4B—C12B	1.375 (4)
N2A—C11A	1.335 (4)	N4B—H4BB	0.8600
N2A—C7A	1.353 (4)	N5B—C12B	1.335 (4)
N3A—C6A	1.297 (4)	N5B—C13B	1.469 (4)
N3A—N4A	1.361 (3)	N5B—C16B	1.471 (4)
N4A—C12A	1.374 (4)	C3B—C2B	1.377 (5)
N4A—H4AB	0.8600	C3B—H3BB	0.9300
N5A—C12A	1.330 (4)	C2B—C1B	1.370 (5)
N5A—C16A	1.468 (5)	C2B—H2BB	0.9300
N5A—C13A	1.471 (4)	C1B—N1B	1.331 (4)
C3A—C2A	1.364 (6)	C1B—H1BA	0.9300
C3A—H3AB	0.9300	N1B—C5B	1.343 (4)
C2A—C1A	1.372 (6)	C5B—C6B	1.501 (4)
C2A—H2AB	0.9300	C6B—C7B	1.482 (4)
C1A—N1A	1.344 (5)	C7B—C8B	1.381 (5)
C1A—H1AA	0.9300	C8B—C9B	1.374 (5)
N1A—C5A	1.338 (4)	C8B—H8BA	0.9300
C5A—C6A	1.496 (4)	C9B—C10B	1.373 (6)
C6A—C7A	1.479 (4)	C9B—H9BA	0.9300
C7A—C8A	1.388 (4)	C10B—C11B	1.370 (5)
C8A—C9A	1.380 (5)	C10B—H10B	0.9300
C8A—H8AA	0.9300	C11B—H11B	0.9300
C9A—C10A	1.370 (5)	C13B—C14B	1.489 (14)
C9A—H9AA	0.9300	C13B—C14C	1.522 (7)
C10A—C11A	1.365 (5)	C13B—H13E	0.9599
C10A—H10A	0.9300	C13B—H13F	0.9599
C11A—H11A	0.9300	C13B—H13C	0.9598
C13A—C14A	1.498 (6)	C13B—H13D	0.9601
C13A—H13A	0.9700	C14B—C15B	1.440 (18)
C13A—H13B	0.9700	C14B—H13E	1.5635
C14A—C15A	1.468 (7)	C14B—H14C	0.9700
C14A—H14A	0.9700	C14B—H14D	0.9700
C14A—H14B	0.9700	C14B—H15F	1.4767
C15A—C16A	1.509 (5)	C14C—C15B	1.466 (7)
C15A—H15A	0.9700	C14C—H14E	0.9700
C15A—H15B	0.9700	C14C—H14F	0.9700
C16A—H16A	0.9700	C15B—C16B	1.512 (5)
C16A—H16B	0.9700	C15B—H15E	0.9598
S1B—C12B	1.670 (3)	C15B—H15F	0.9600
C4B—C3B	1.375 (5)	C15B—H15C	0.9601
C4B—C5B	1.385 (4)	C15B—H15D	0.9599
C4B—H4BA	0.9300	C16B—H16C	0.9700
N2B—C11B	1.331 (4)	C16B—H16D	0.9700
C5A—C4A—C3A	119.3 (3)	C4B—C5B—C6B	120.3 (3)
C5A—C4A—H4AA	120.4	N3B—C6B—C7B	126.7 (3)
C3A—C4A—H4AA	120.4	N3B—C6B—C5B	111.9 (3)
C11A—N2A—C7A	117.8 (3)	C7B—C6B—C5B	121.3 (3)
C6A—N3A—N4A	119.4 (3)	N2B—C7B—C8B	121.1 (3)
N3A—N4A—C12A	120.0 (3)	N2B—C7B—C6B	115.6 (3)
N3A—N4A—H4AB	120.0	C8B—C7B—C6B	123.2 (3)
C12A—N4A—H4AB	120.0	C9B—C8B—C7B	119.6 (4)
C12A—N5A—C16A	126.0 (3)	C9B—C8B—H8BA	120.2
C12A—N5A—C13A	122.5 (3)	C7B—C8B—H8BA	120.2
C16A—N5A—C13A	111.5 (3)	C10B—C9B—C8B	119.2 (4)
C2A—C3A—C4A	119.0 (4)	C10B—C9B—H9BA	120.4
C2A—C3A—H3AB	120.5	C8B—C9B—H9BA	120.4
C4A—C3A—H3AB	120.5	C11B—C10B—C9B	118.3 (4)
C3A—C2A—C1A	118.3 (4)	C11B—C10B—H10B	120.8
C3A—C2A—H2AB	120.8	C9B—C10B—H10B	120.8
C1A—C2A—H2AB	120.8	N2B—C11B—C10B	123.4 (4)
N1A—C1A—C2A	124.1 (4)	N2B—C11B—H11B	118.3
N1A—C1A—H1AA	118.0	C10B—C11B—H11B	118.3
C2A—C1A—H1AA	118.0	N5B—C12B—N4B	112.9 (3)
C5A—N1A—C1A	116.6 (3)	N5B—C12B—S1B	123.7 (2)
N1A—C5A—C4A	122.7 (3)	N4B—C12B—S1B	123.4 (3)
N1A—C5A—C6A	117.2 (3)	N5B—C13B—C14B	103.2 (6)
C4A—C5A—C6A	120.1 (3)	N5B—C13B—C14C	102.5 (4)
N3A—C6A—C7A	127.1 (3)	C14B—C13B—C14C	35.6 (7)
N3A—C6A—C5A	112.4 (3)	N5B—C13B—H13E	111.3
C7A—C6A—C5A	120.5 (3)	C14B—C13B—H13E	75.9
N2A—C7A—C8A	121.3 (3)	C14C—C13B—H13E	109.0
N2A—C7A—C6A	116.6 (3)	N5B—C13B—H13F	111.3
C8A—C7A—C6A	122.0 (3)	C14B—C13B—H13F	139.2
C9A—C8A—C7A	119.2 (3)	C14C—C13B—H13F	113.2
C9A—C8A—H8AA	120.4	H13E—C13B—H13F	109.4
C7A—C8A—H8AA	120.4	N5B—C13B—H13C	110.5
C10A—C9A—C8A	119.3 (3)	C14B—C13B—H13C	106.4
C10A—C9A—H9AA	120.3	C14C—C13B—H13C	135.7
C8A—C9A—H9AA	120.3	H13E—C13B—H13C	31.4
C11A—C10A—C9A	118.5 (3)	H13F—C13B—H13C	81.5
C11A—C10A—H10A	120.8	N5B—C13B—H13D	111.2
C9A—C10A—H10A	120.8	C14B—C13B—H13D	116.2
N2A—C11A—C10A	123.9 (3)	C14C—C13B—H13D	84.3
N2A—C11A—H11A	118.0	H13E—C13B—H13D	131.0
C10A—C11A—H11A	118.0	H13F—C13B—H13D	30.3
N5A—C12A—N4A	112.9 (3)	H13C—C13B—H13D	109.1
N5A—C12A—S1A	123.3 (2)	C15B—C14B—C13B	107.3 (10)
N4A—C12A—S1A	123.7 (3)	C15B—C14B—H13E	130.5
N5A—C13A—C14A	103.4 (3)	C13B—C14B—H13E	36.6
N5A—C13A—H13A	111.1	C15B—C14B—H14C	110.2
C14A—C13A—H13A	111.1	C13B—C14B—H14C	110.2
N5A—C13A—H13B	111.1	H13E—C14B—H14C	114.3
C14A—C13A—H13B	111.1	C15B—C14B—H14D	110.2
H13A—C13A—H13B	109.0	C13B—C14B—H14D	110.2
C15A—C14A—C13A	106.1 (4)	H13E—C14B—H14D	75.0
C15A—C14A—H14A	110.5	H14C—C14B—H14D	108.5
C13A—C14A—H14A	110.5	C15B—C14B—H15F	38.4
C15A—C14A—H14B	110.5	C13B—C14B—H15F	130.9
C13A—C14A—H14B	110.5	H13E—C14B—H15F	127.6
H14A—C14A—H14B	108.7	H14C—C14B—H15F	114.8
C14A—C15A—C16A	105.5 (4)	H14D—C14B—H15F	73.0
C14A—C15A—H15A	110.6	C15B—C14C—C13B	104.3 (5)
C16A—C15A—H15A	110.6	C15B—C14C—H14E	110.9
C14A—C15A—H15B	110.6	C13B—C14C—H14E	110.9
C16A—C15A—H15B	110.6	C15B—C14C—H14F	110.9
H15A—C15A—H15B	108.8	C13B—C14C—H14F	110.9
N5A—C16A—C15A	103.3 (3)	H14E—C14C—H14F	108.9
N5A—C16A—H16A	111.1	C14B—C15B—C14C	36.9 (7)
C15A—C16A—H16A	111.1	C14B—C15B—C16B	106.5 (7)
N5A—C16A—H16B	111.1	C14C—C15B—C16B	106.5 (4)
C15A—C16A—H16B	111.1	C14B—C15B—H15E	138.7
H16A—C16A—H16B	109.1	C14C—C15B—H15E	113.4
C3B—C4B—C5B	119.1 (3)	C16B—C15B—H15E	111.0
C3B—C4B—H4BA	120.5	C14B—C15B—H15F	72.9
C5B—C4B—H4BA	120.5	C14C—C15B—H15F	107.3
C11B—N2B—C7B	118.3 (3)	C16B—C15B—H15F	110.0
C6B—N3B—N4B	119.7 (3)	H15E—C15B—H15F	108.6
N3B—N4B—C12B	120.4 (3)	C14B—C15B—H15C	105.5
N3B—N4B—H4BB	119.8	C14C—C15B—H15C	134.6
C12B—N4B—H4BB	119.8	C16B—C15B—H15C	110.0
C12B—N5B—C13B	123.2 (3)	H15E—C15B—H15C	77.3
C12B—N5B—C16B	125.9 (3)	H15F—C15B—H15C	34.3
C13B—N5B—C16B	111.0 (3)	C14B—C15B—H15D	115.4
C4B—C3B—C2B	119.4 (3)	C14C—C15B—H15D	82.1
C4B—C3B—H3BB	120.3	C16B—C15B—H15D	110.7
C2B—C3B—H3BB	120.3	H15E—C15B—H15D	33.8
C1B—C2B—C3B	117.7 (3)	H15F—C15B—H15D	133.2
C1B—C2B—H2BB	121.2	H15C—C15B—H15D	108.5
C3B—C2B—H2BB	121.2	N5B—C16B—C15B	103.8 (3)
N1B—C1B—C2B	124.5 (3)	N5B—C16B—H16C	111.0
N1B—C1B—H1BA	117.7	C15B—C16B—H16C	111.0
C2B—C1B—H1BA	117.7	N5B—C16B—H16D	111.0
C1B—N1B—C5B	117.3 (3)	C15B—C16B—H16D	111.0
N1B—C5B—C4B	122.0 (3)	H16C—C16B—H16D	109.0
N1B—C5B—C6B	117.7 (3)
C6A—N3A—N4A—C12A	−179.8 (3)	C1B—N1B—C5B—C4B	1.7 (5)
C5A—C4A—C3A—C2A	0.3 (6)	C1B—N1B—C5B—C6B	−178.4 (3)
C4A—C3A—C2A—C1A	1.0 (6)	C3B—C4B—C5B—N1B	−1.7 (5)
C3A—C2A—C1A—N1A	−1.7 (6)	C3B—C4B—C5B—C6B	178.4 (3)
C2A—C1A—N1A—C5A	1.1 (6)	N4B—N3B—C6B—C7B	−0.5 (5)
C1A—N1A—C5A—C4A	0.3 (5)	N4B—N3B—C6B—C5B	−178.0 (3)
C1A—N1A—C5A—C6A	178.1 (3)	N1B—C5B—C6B—N3B	−159.1 (3)
C3A—C4A—C5A—N1A	−0.9 (5)	C4B—C5B—C6B—N3B	20.8 (4)
C3A—C4A—C5A—C6A	−178.8 (3)	N1B—C5B—C6B—C7B	23.2 (4)
N4A—N3A—C6A—C7A	−1.7 (5)	C4B—C5B—C6B—C7B	−156.9 (3)
N4A—N3A—C6A—C5A	179.9 (3)	C11B—N2B—C7B—C8B	−2.2 (5)
N1A—C5A—C6A—N3A	−144.6 (3)	C11B—N2B—C7B—C6B	−178.9 (3)
C4A—C5A—C6A—N3A	33.4 (4)	N3B—C6B—C7B—N2B	22.0 (5)
N1A—C5A—C6A—C7A	36.9 (4)	C5B—C6B—C7B—N2B	−160.7 (3)
C4A—C5A—C6A—C7A	−145.2 (3)	N3B—C6B—C7B—C8B	−154.7 (3)
C11A—N2A—C7A—C8A	−1.5 (5)	C5B—C6B—C7B—C8B	22.6 (5)
C11A—N2A—C7A—C6A	−178.6 (3)	N2B—C7B—C8B—C9B	2.0 (5)
N3A—C6A—C7A—N2A	22.3 (5)	C6B—C7B—C8B—C9B	178.5 (3)
C5A—C6A—C7A—N2A	−159.4 (3)	C7B—C8B—C9B—C10B	−0.1 (6)
N3A—C6A—C7A—C8A	−154.7 (3)	C8B—C9B—C10B—C11B	−1.6 (6)
C5A—C6A—C7A—C8A	23.6 (4)	C7B—N2B—C11B—C10B	0.4 (6)
N2A—C7A—C8A—C9A	0.5 (5)	C9B—C10B—C11B—N2B	1.6 (6)
C6A—C7A—C8A—C9A	177.4 (3)	C13B—N5B—C12B—N4B	−179.7 (3)
C7A—C8A—C9A—C10A	1.1 (5)	C16B—N5B—C12B—N4B	1.8 (5)
C8A—C9A—C10A—C11A	−1.7 (6)	C13B—N5B—C12B—S1B	0.4 (5)
C7A—N2A—C11A—C10A	1.0 (5)	C16B—N5B—C12B—S1B	−178.1 (3)
C9A—C10A—C11A—N2A	0.7 (6)	N3B—N4B—C12B—N5B	−176.7 (3)
C16A—N5A—C12A—N4A	5.4 (5)	N3B—N4B—C12B—S1B	3.1 (4)
C13A—N5A—C12A—N4A	−174.2 (3)	C12B—N5B—C13B—C14B	165.9 (11)
C16A—N5A—C12A—S1A	−175.0 (3)	C16B—N5B—C13B—C14B	−15.4 (12)
C13A—N5A—C12A—S1A	5.4 (5)	C12B—N5B—C13B—C14C	−157.5 (6)
N3A—N4A—C12A—N5A	−178.2 (3)	C16B—N5B—C13B—C14C	21.2 (7)
N3A—N4A—C12A—S1A	2.2 (4)	N5B—C13B—C14B—C15B	27.1 (17)
C12A—N5A—C13A—C14A	170.5 (4)	C14C—C13B—C14B—C15B	−66.0 (15)
C16A—N5A—C13A—C14A	−9.2 (4)	N5B—C13B—C14C—C15B	−33.0 (9)
N5A—C13A—C14A—C15A	25.8 (5)	C14B—C13B—C14C—C15B	62.2 (11)
C13A—C14A—C15A—C16A	−32.9 (6)	C13B—C14B—C15B—C14C	66.8 (12)
C12A—N5A—C16A—C15A	170.0 (4)	C13B—C14B—C15B—C16B	−28.9 (17)
C13A—N5A—C16A—C15A	−10.4 (5)	C13B—C14C—C15B—C14B	−62.4 (10)
C14A—C15A—C16A—N5A	26.3 (5)	C13B—C14C—C15B—C16B	33.3 (9)
C6B—N3B—N4B—C12B	174.0 (3)	C12B—N5B—C16B—C15B	177.2 (4)
C5B—C4B—C3B—C2B	0.0 (5)	C13B—N5B—C16B—C15B	−1.4 (4)
C4B—C3B—C2B—C1B	1.5 (5)	C14B—C15B—C16B—N5B	18.5 (12)
C3B—C2B—C1B—N1B	−1.5 (6)	C14C—C15B—C16B—N5B	−20.1 (7)
C2B—C1B—N1B—C5B	−0.1 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4A—H4AB···N2A	0.86	1.98	2.636 (3)	132
N4B—H4BB···N2B	0.86	1.95	2.616 (3)	133
C2B—H2BB···N3A^i	0.93	2.55	3.395 (4)	152

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