Chloro­bis­(thio­urea-κS)copper(I) bis(4,5-di­aza­fluoren-9-one) mono­hydrate

The title compound, [CuCl(CH₄N₂S)₂]·2C₁₁H₆N₂O·H₂O, consists of mol­ecules of a Cu^I–thio­urea complex, free 4,5-di­aza­fluoren-9-one (dafone) and crystalline water. The planar complex mol­ecule has trigonal coordination geometry around the Cu^I atom. The dafone and water mol­ecules, which are hydrogen bonded to the Cu^I complex, are approximately coplanar with this complex. The crystal displays a sheet structure and π–π stacking is observed between neighbouring sheets.

S1. Comment

The structural study of transition metal complexes containing sulfur coordination is helpful for catalysis (Stiefel & Matsumoto, 1996) and medicinal chemistry (Jurisson et al., 1993). As a ligand containing an S atom, thiourea is an interesting reagent, having several possible modes of bonding to a metal ion.

A thiourea–Cu^I complex has been reported previously (Spofford & Amma, 1970) in which the thiourea acted as a bridging ligand, the S atoms bonding to neighbouring Cu^I atoms forming a spiral structure. Recently, during an investigation of the coordination ability of 4,5-diazafluoren-9-one (dafone), a new thiourea–Cu^I complex, (I), in which thiourea displays a different coordination mode from that reported, was obtained in our laboratory.

The molecular structure of (I) is illustrated in Fig. 1. Selected geometric parameters and hydrogen-bonding geometry are listed in Tables 1 and 2, respectively. The asymmetric unit consists of molecules of the Cu^I complex, free dafone and crystalline water. The Cu^I atom lies in a planar trigonal coordination environment, with a deviation of 0.0456 (9) Å from the plane formed by atoms Cl, S1 and S2. Two monodentate thiourea molecules coordinate to the Cu^I atom through their S atoms, with normal Cu—S distances of 2.2084 (10) and 2.2158 (10) Å. A Cl atom coordinates to the Cu^I atom with a distance of 2.2429 (10) Å, which is much shorter than the distances of 2.828 (5) and 3.164 (4) Å found in the Cu^I complex cited above (Spofford & Amma, 1970). Intramolecular hydrogen bonding between the chlorine and amine groups stabilizes the planar structure of the Cu^I complex.

The dafone and water molecules link the Cu^I complex through hydrogen bonds, as shown in Fig. 1. Both dafone and the water O atom are approximately coplanar with the Cu^I complex, the maximum atomic deviation from the mean plane of the complex being 0.858 (6) Å for O1. The planar dafone molecule is structurally similar to phenanthroline (phen), but the carbonyl bridge in dafone distorts the bipyridine portion. The average bond angle of 126.7 (3)° for N6—C12—C13 and N5—C13—C12 resulted in a longer N5···N6 separation of 3.075 (4) Å, while the average bond angle of 126.6 (3)° for N8—C23—C24 and N7—C24—C23 resulted in a similar N7···N8 separation of 3.066 (4) Å. The N···N separations in the present structure are in agreement with the values of 3.055 and 3.064 Å found in the reported structures containing free dafone (Fun et al., 1995; Luo et al., 2002), but much longer than N···N distance of 2.724 Å in free phen (Nishigaki et al., 1978). The longer N···N separation in dafone reduces overlap of the nitrogen–metal orbitals (Henderson et al., 1984) and results in a weaker chelating ability of dafone than phen. In fact, several complex structures with uncoordinated dafone (Menon et al., 1994; Chen, 1998; Kulkarni et al., 2001), dafone coordinated as a monodentate ligand (Lu et al., 1996) or dafone as an asymmetric chelate (i.e. one normal bond and another much longer bond) (Menon & Rajasekharan, 1998; Balagopalakrishna et al., 1992) have been reported previously. Structures with dafone symmetrically chelating to a metal ion have also been reported. It is interesting that significantly shorter N···N distances of 2.850 and 2.806 Å were found in the symmetrically chelating structures (Xiong et al., 1996; Menon & Rajasekharan, 1997). These facts imply that the structure of dafone is rather flexible and the distortion of the bipyridine portion in dafone may be self-adjusting when dafone chelates a metal ion.

With the aid of hydrogen bonds between dafone, water and thiourea, the asymmetric units link to each other to form planar chains. The chains self-assemble to form a two-dimensional sheet structure, as shown in Fig. 2. The centrosymmetric N—H···S hydrogen-bonded dimer observed in the present structure has also been found in both a free thiourea structure (Truter, 1967) and a thiourea complex (Johnson & Steed, 1998).

Between the neighboring sheets, the dafone rings are approximately parallel [dihedral angle 1.13 (10)°] and partially overlap each other, as shown in Fig. 3. Atoms of the N6A-pyridine ring deviate from the mean plane of the N7-dafone molecule with relatively shorter distances ranging from 3.354 (4) Å (C8A) to 3.455 (4) Å (C11A), which suggests the existence of aromatic π–π-stacking interactions between neighbouring dafone molecules.

S2. Experimental

Dafone was prepared according to a reported method (Henderson et al., 1984). An aqueous solution (15 ml) containing CuCl₂·2H₂O (0.85 g, 0.5 mmol) was mixed with an aqueous solution (15 ml) containing thiourea (0.076 g, 1 mmol) at room temperature. Thiourea reduced Cu^II to Cu^I (Perrin, 1970) and a large amount of white precipitate of a Cu^I compound appeared. Dafone (0.182 g, 1 mmol) was introduced in to the solution involving the precipitate. The solution was refluxed for about 2 h until the white precipitate had completely disappeared. Then the yellow solution was filtered and the filtrate kept in a thermostat with 338 K. Yellow crystals of the title compound were obtained after 2 d. Analysis (Carlo-Erba 1160 instrument) calculated for C₂₄H₂₂ClCuN₈O₃S₂: C 45.50, H 3.48, N 17.60%; found: C 45.12, H 3.41, N 17.14%.

S3. Refinement

H atoms were placed on calculated positions with C—H distances of 0.93 Å, N—H distances of 0.86 Å and O—H distances of 0.85 Å (Nardelli, 1999). All H atoms were included in the final cycles of least-squares refinement; water H atoms with fixed coordinates and U_iso values of 0.08 Ų, while the other H atom were refined as riding on their parent non-H atoms with U_iso values 1.2 times the U_eq values of the parent atoms.

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1985); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The structure of (I) shown with 30% probability displacement ellipsoids. Dashed lines show hydrogen bonds between the complex and dafone molecules.
	Fig. 2. A view of the sheet structure in (I) assembled by planar supramolecular chains.
	Fig. 3. A view showing the aromatic π–π interactions between neighbouring dafone molecules. [Symmetry code: (i) x, y, -1 + z.]

Bis(thiourea)chlorocopper(I) di(4,5-Diazafluoren-9-one) monohydrate

Crystal data

[CuCl(CH4N2S)2]·2C11H6N2O·H2O	Z = 2
Mr = 633.64	F(000) = 648
Triclinic, P1	Dx = 1.549 Mg m^−3
a = 8.3016 (9) Å	Mo Kα radiation, λ = 0.71069 Å
b = 11.8473 (18) Å	Cell parameters from 25 reflections
c = 14.3024 (9) Å	θ = 4.6–9.9°
α = 93.896 (8)°	µ = 1.10 mm^−1
β = 99.206 (7)°	T = 298 K
γ = 100.562 (10)°	Prism, yellow
V = 1358.1 (3) Å^3	0.44 × 0.40 × 0.38 mm

Data collection

Rigaku AFC-7S diffractometer	3411 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.031
Graphite monochromator	θmax = 26°, θmin = 2.2°
ω/2θ scans	h = −10→10
Absorption correction: ψ scan (North et al., 1968)	k = 0→14
Tmin = 0.617, Tmax = 0.659	l = −17→17
5608 measured reflections	3 standard reflections every 100 reflections
5336 independent reflections	intensity decay: 0.5%

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.132	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0711P)^2 + 0.5579P] where P = (Fo^2 + 2Fc^2)/3
5336 reflections	(Δ/σ)max < 0.001
352 parameters	Δρmax = 0.81 e Å^−3
0 restraints	Δρmin = −0.57 e Å^−3

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.

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
Cu	0.80725 (6)	0.64355 (4)	0.73924 (3)	0.05318 (16)
Cl	0.71265 (16)	0.80875 (9)	0.74969 (8)	0.0766 (4)
S1	0.81548 (14)	0.52762 (8)	0.85440 (6)	0.0580 (3)
S2	0.91653 (15)	0.58813 (8)	0.61706 (7)	0.0638 (3)
O1	0.4098 (4)	0.8012 (3)	1.41964 (19)	0.0775 (9)
O2	0.8428 (4)	1.0801 (2)	0.09320 (17)	0.0645 (7)
O3	0.8123 (5)	0.3155 (3)	1.0905 (3)	0.1016 (12)
N1	0.7090 (4)	0.5148 (3)	1.0171 (2)	0.0632 (9)
H1	0.6616	0.5372	1.0622	0.076*
H2	0.7488	0.4528	1.0197	0.076*
N2	0.6598 (4)	0.6695 (2)	0.9410 (2)	0.0536 (8)
H3	0.6126	0.6910	0.9866	0.064*
H4	0.6668	0.7098	0.8936	0.064*
N3	0.9863 (4)	0.6710 (3)	0.4602 (2)	0.0585 (8)
H5	0.9877	0.7199	0.4184	0.070*
H6	1.0306	0.6115	0.4530	0.070*
N4	0.8496 (4)	0.7787 (2)	0.5446 (2)	0.0530 (7)
H7	0.8518	0.8270	0.5023	0.064*
H8	0.8035	0.7904	0.5932	0.064*
N5	0.6202 (4)	0.5686 (2)	1.2035 (2)	0.0522 (7)
N6	0.5164 (4)	0.7722 (2)	1.10323 (19)	0.0489 (7)
N7	0.9693 (4)	0.7860 (2)	0.2849 (2)	0.0487 (7)
N8	0.8257 (4)	0.9575 (2)	0.40162 (18)	0.0467 (7)
C1	0.7209 (4)	0.5755 (3)	0.9439 (2)	0.0463 (8)
C2	0.9165 (4)	0.6872 (3)	0.5350 (2)	0.0458 (8)
C3	0.6497 (5)	0.4873 (3)	1.2611 (3)	0.0636 (10)
H9	0.6947	0.4271	1.2378	0.076*
C4	0.6174 (6)	0.4874 (4)	1.3535 (3)	0.0693 (11)
H10	0.6383	0.4276	1.3897	0.083*
C5	0.5542 (5)	0.5766 (3)	1.3909 (3)	0.0598 (10)
H11	0.5332	0.5798	1.4529	0.072*
C6	0.5234 (4)	0.6606 (3)	1.3330 (2)	0.0467 (8)
C7	0.4534 (5)	0.7664 (3)	1.3487 (2)	0.0502 (8)
C8	0.4481 (4)	0.8204 (3)	1.2574 (2)	0.0443 (7)
C9	0.3956 (5)	0.9174 (3)	1.2298 (3)	0.0537 (9)
H12	0.3561	0.9652	1.2713	0.064*
C10	0.4037 (5)	0.9415 (3)	1.1371 (3)	0.0566 (9)
H13	0.3698	1.0070	1.1150	0.068*
C11	0.4622 (5)	0.8681 (3)	1.0778 (3)	0.0547 (9)
H14	0.4644	0.8860	1.0156	0.066*
C12	0.5072 (4)	0.7514 (3)	1.1928 (2)	0.0410 (7)
C13	0.5567 (4)	0.6525 (3)	1.2409 (2)	0.0432 (7)
C14	1.0171 (5)	0.7214 (3)	0.2175 (3)	0.0548 (9)
H15	1.0484	0.6529	0.2339	0.066*
C15	1.0234 (5)	0.7489 (3)	0.1261 (3)	0.0571 (9)
H16	1.0580	0.7001	0.0831	0.069*
C16	0.9776 (4)	0.8499 (3)	0.0988 (2)	0.0521 (9)
H17	0.9805	0.8711	0.0375	0.063*
C17	0.9275 (4)	0.9177 (3)	0.1661 (2)	0.0429 (7)
C18	0.8631 (4)	1.0265 (3)	0.1619 (2)	0.0478 (8)
C19	0.8199 (4)	1.0528 (3)	0.2574 (2)	0.0441 (7)
C20	0.7457 (5)	1.1368 (3)	0.2923 (3)	0.0545 (9)
H18	0.7193	1.1955	0.2564	0.065*
C21	0.7116 (5)	1.1302 (3)	0.3841 (3)	0.0572 (9)
H19	0.6608	1.1848	0.4112	0.069*
C22	0.7543 (5)	1.0412 (3)	0.4347 (2)	0.0560 (9)
H20	0.7318	1.0394	0.4963	0.067*
C23	0.8561 (4)	0.9658 (3)	0.3138 (2)	0.0408 (7)
C24	0.9245 (4)	0.8819 (3)	0.2571 (2)	0.0410 (7)
H21	0.8933	0.3540	1.1329	0.080*
H22	0.8257	0.2447	1.0899	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.0782 (3)	0.0516 (3)	0.0424 (2)	0.0280 (2)	0.0261 (2)	0.01513 (18)
Cl	0.1269 (10)	0.0612 (6)	0.0689 (6)	0.0554 (6)	0.0474 (6)	0.0265 (5)
S1	0.0924 (7)	0.0542 (5)	0.0473 (5)	0.0400 (5)	0.0363 (5)	0.0194 (4)
S2	0.1115 (8)	0.0570 (5)	0.0471 (5)	0.0482 (6)	0.0408 (5)	0.0252 (4)
O1	0.114 (2)	0.086 (2)	0.0517 (16)	0.0437 (18)	0.0439 (16)	0.0072 (14)
O2	0.091 (2)	0.0713 (17)	0.0437 (13)	0.0325 (15)	0.0192 (13)	0.0277 (12)
O3	0.106 (3)	0.078 (2)	0.118 (3)	0.033 (2)	−0.009 (2)	0.014 (2)
N1	0.104 (3)	0.0583 (18)	0.0461 (16)	0.0377 (18)	0.0370 (17)	0.0196 (14)
N2	0.086 (2)	0.0499 (16)	0.0397 (15)	0.0324 (16)	0.0295 (14)	0.0106 (12)
N3	0.094 (2)	0.0521 (17)	0.0433 (15)	0.0298 (17)	0.0299 (15)	0.0177 (13)
N4	0.080 (2)	0.0488 (16)	0.0430 (15)	0.0275 (15)	0.0242 (14)	0.0193 (13)
N5	0.072 (2)	0.0485 (16)	0.0445 (16)	0.0235 (15)	0.0192 (14)	0.0077 (13)
N6	0.0641 (19)	0.0489 (16)	0.0375 (14)	0.0147 (14)	0.0146 (13)	0.0086 (12)
N7	0.0649 (19)	0.0439 (15)	0.0449 (15)	0.0192 (14)	0.0199 (13)	0.0106 (12)
N8	0.0664 (19)	0.0458 (15)	0.0351 (14)	0.0190 (14)	0.0181 (13)	0.0107 (12)
C1	0.064 (2)	0.0449 (18)	0.0354 (16)	0.0181 (16)	0.0157 (15)	0.0067 (13)
C2	0.063 (2)	0.0462 (18)	0.0346 (16)	0.0191 (16)	0.0153 (15)	0.0097 (14)
C3	0.088 (3)	0.055 (2)	0.058 (2)	0.033 (2)	0.019 (2)	0.0121 (18)
C4	0.098 (3)	0.061 (2)	0.056 (2)	0.029 (2)	0.015 (2)	0.0237 (19)
C5	0.083 (3)	0.062 (2)	0.0393 (18)	0.016 (2)	0.0186 (18)	0.0152 (16)
C6	0.056 (2)	0.0507 (19)	0.0354 (16)	0.0089 (16)	0.0146 (15)	0.0047 (14)
C7	0.059 (2)	0.053 (2)	0.0427 (18)	0.0131 (17)	0.0186 (16)	0.0041 (15)
C8	0.0477 (19)	0.0480 (18)	0.0380 (16)	0.0097 (15)	0.0124 (14)	−0.0023 (14)
C9	0.059 (2)	0.0462 (19)	0.061 (2)	0.0181 (17)	0.0181 (18)	−0.0004 (17)
C10	0.065 (2)	0.0461 (19)	0.063 (2)	0.0166 (18)	0.0121 (19)	0.0144 (17)
C11	0.069 (2)	0.051 (2)	0.0474 (19)	0.0136 (18)	0.0151 (17)	0.0144 (16)
C12	0.0461 (18)	0.0418 (17)	0.0370 (15)	0.0102 (14)	0.0123 (13)	0.0011 (13)
C13	0.052 (2)	0.0445 (17)	0.0359 (16)	0.0119 (15)	0.0134 (14)	0.0061 (13)
C14	0.071 (2)	0.0466 (19)	0.056 (2)	0.0219 (18)	0.0252 (18)	0.0086 (16)
C15	0.068 (2)	0.057 (2)	0.053 (2)	0.0187 (19)	0.0251 (18)	−0.0025 (17)
C16	0.060 (2)	0.065 (2)	0.0349 (16)	0.0125 (18)	0.0183 (15)	0.0040 (15)
C17	0.0491 (19)	0.0470 (18)	0.0352 (15)	0.0122 (15)	0.0106 (13)	0.0072 (13)
C18	0.057 (2)	0.0517 (19)	0.0383 (17)	0.0130 (16)	0.0137 (15)	0.0121 (15)
C19	0.056 (2)	0.0448 (17)	0.0360 (16)	0.0147 (15)	0.0138 (14)	0.0092 (14)
C20	0.070 (2)	0.050 (2)	0.052 (2)	0.0265 (18)	0.0145 (17)	0.0134 (16)
C21	0.076 (3)	0.054 (2)	0.051 (2)	0.0280 (19)	0.0222 (18)	0.0012 (17)
C22	0.081 (3)	0.055 (2)	0.0406 (18)	0.0209 (19)	0.0262 (18)	0.0080 (16)
C23	0.0504 (19)	0.0401 (16)	0.0350 (15)	0.0109 (14)	0.0121 (14)	0.0083 (13)
C24	0.0478 (19)	0.0429 (17)	0.0343 (15)	0.0091 (15)	0.0120 (14)	0.0058 (13)

Geometric parameters (Å, º)

Cu—S2	2.2084 (10)	C4—H10	0.9300
Cu—S1	2.2158 (10)	C5—C6	1.370 (5)
Cu—Cl	2.2429 (10)	C5—H11	0.9300
S1—C1	1.722 (3)	C6—C13	1.389 (4)
S2—C2	1.715 (3)	C6—C7	1.493 (5)
O1—C7	1.203 (4)	C7—C8	1.491 (5)
O2—C18	1.212 (4)	C8—C9	1.363 (5)
O3—H21	0.864	C8—C12	1.397 (4)
O3—H22	0.865	C9—C10	1.384 (5)
N1—C1	1.316 (4)	C9—H12	0.9300
N1—H1	0.8600	C10—C11	1.379 (5)
N1—H2	0.8600	C10—H13	0.9300
N2—C1	1.306 (4)	C11—H14	0.9300
N2—H3	0.8600	C12—C13	1.488 (4)
N2—H4	0.8600	C14—C15	1.374 (5)
N3—C2	1.315 (4)	C14—H15	0.9300
N3—H5	0.8600	C15—C16	1.383 (5)
N3—H6	0.8600	C15—H16	0.9300
N4—C2	1.315 (4)	C16—C17	1.374 (5)
N4—H7	0.8600	C16—H17	0.9300
N4—H8	0.8600	C17—C24	1.399 (4)
N5—C13	1.327 (4)	C17—C18	1.484 (5)
N5—C3	1.340 (5)	C18—C19	1.494 (4)
N6—C12	1.332 (4)	C19—C20	1.369 (5)
N6—C11	1.347 (5)	C19—C23	1.398 (4)
N7—C24	1.325 (4)	C20—C21	1.391 (5)
N7—C14	1.344 (4)	C20—H18	0.9300
N8—C23	1.326 (4)	C21—C22	1.385 (5)
N8—C22	1.342 (4)	C21—H19	0.9300
C3—C4	1.389 (5)	C22—H20	0.9300
C3—H9	0.9300	C23—C24	1.487 (4)
C4—C5	1.377 (6)
S2—Cu—S1	113.96 (4)	C8—C9—H12	121.5
S2—Cu—Cl	122.77 (4)	C10—C9—H12	121.5
S1—Cu—Cl	123.15 (4)	C11—C10—C9	119.7 (3)
C1—S1—Cu	110.24 (11)	C11—C10—H13	120.2
C2—S2—Cu	110.75 (11)	C9—C10—H13	120.2
H21—O3—H22	105.1	N6—C11—C10	124.8 (3)
C1—N1—H1	120.0	N6—C11—H14	117.6
C1—N1—H2	120.0	C10—C11—H14	117.6
H1—N1—H2	120.0	N6—C12—C8	124.9 (3)
C1—N2—H3	120.0	N6—C12—C13	126.6 (3)
C1—N2—H4	120.0	C8—C12—C13	108.6 (3)
H3—N2—H4	120.0	N5—C13—C6	124.7 (3)
C2—N3—H5	120.0	N5—C13—C12	126.8 (3)
C2—N3—H6	120.0	C6—C13—C12	108.6 (3)
H5—N3—H6	120.0	N7—C14—C15	124.9 (3)
C2—N4—H7	120.0	N7—C14—H15	117.5
C2—N4—H8	120.0	C15—C14—H15	117.5
H7—N4—H8	120.0	C14—C15—C16	119.4 (3)
C13—N5—C3	115.1 (3)	C14—C15—H16	120.3
C12—N6—C11	114.1 (3)	C16—C15—H16	120.3
C24—N7—C14	114.8 (3)	C17—C16—C15	117.0 (3)
C23—N8—C22	114.5 (3)	C17—C16—H17	121.5
N2—C1—N1	119.2 (3)	C15—C16—H17	121.5
N2—C1—S1	122.1 (2)	C16—C17—C24	119.3 (3)
N1—C1—S1	118.8 (3)	C16—C17—C18	132.3 (3)
N4—C2—N3	119.0 (3)	C24—C17—C18	108.3 (3)
N4—C2—S2	122.2 (2)	O2—C18—C17	126.6 (3)
N3—C2—S2	118.8 (3)	O2—C18—C19	127.0 (3)
N5—C3—C4	124.2 (4)	C17—C18—C19	106.3 (3)
N5—C3—H9	117.9	C20—C19—C23	119.5 (3)
C4—C3—H9	117.9	C20—C19—C18	132.2 (3)
C5—C4—C3	119.4 (4)	C23—C19—C18	108.0 (3)
C5—C4—H10	120.3	C19—C20—C21	116.9 (3)
C3—C4—H10	120.3	C19—C20—H18	121.6
C6—C5—C4	117.2 (3)	C21—C20—H18	121.6
C6—C5—H11	121.4	C22—C21—C20	119.2 (3)
C4—C5—H11	121.4	C22—C21—H19	120.4
C5—C6—C13	119.5 (3)	C20—C21—H19	120.4
C5—C6—C7	131.7 (3)	N8—C22—C21	125.0 (3)
C13—C6—C7	108.8 (3)	N8—C22—H20	117.5
O1—C7—C8	126.8 (3)	C21—C22—H20	117.5
O1—C7—C6	127.7 (3)	N8—C23—C19	124.9 (3)
C8—C7—C6	105.5 (3)	N8—C23—C24	126.3 (3)
C9—C8—C12	119.6 (3)	C19—C23—C24	108.7 (3)
C9—C8—C7	131.9 (3)	N7—C24—C17	124.4 (3)
C12—C8—C7	108.5 (3)	N7—C24—C23	126.8 (3)
C8—C9—C10	116.9 (3)	C17—C24—C23	108.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N5	0.86	2.12	2.937 (4)	158
N1—H2···O3	0.86	2.08	2.864 (5)	152
N2—H3···N6	0.86	2.20	3.052 (4)	171
N2—H4···Cl	0.86	2.48	3.337 (3)	172
N3—H5···N7	0.86	2.11	2.930 (4)	160
N3—H6···S2^i	0.86	2.64	3.468 (4)	161
N4—H7···N8	0.86	2.20	3.053 (4)	172
N4—H8···Cl	0.86	2.48	3.331 (3)	169
O3—H21···S1^ii	0.86	2.54	3.247 (4)	140
O3—H22···O2^iii	0.86	1.98	2.848 (4)	176

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