2,2′-(Disulfanedi­yl)dibenzoic acid–N,N′-bis­(4-pyridyl­meth­yl)ethane­dithio­amide (1/1)

Arman, H.D.; Miller, T.; Poplaukhin, P.; Tiekink, E.R.T.

doi:10.1107/S1600536810036755

2,2′-(Disulfanediyl)dibenzoic acid–N,N′-bis(4-pyridylmethyl)ethanedithioamide (1/1)

H. D. Arman, T. Miller, P. Poplaukhin and E. R. T. Tiekink

The asymmetric unit of the title co-crystal, C₁₄H₁₄N₄S₂·C₁₄H₁₀O₄S₂, comprises a twisted 2,2′-(disulfanediyl)dibenzoic acid molecule [dihedral angle between the benzene rings = 83.53 (14)°] and a U-shaped molecule of N,N′-bis(4-pyridylmethyl)ethanedithioamide in which intramolecular N—H

S hydrogen bonds are observed. Two molecules of each form a centrosymmetric ring, with an extended chair conformation, mediated by carboxyl–pyridine O—H

N hydrogen bonds between the carboxylic acid groups of two 2,2′-(disulfanediyl)dibenzoic acid molecules and pyridine-N atoms of two N,N'-bis(4-pyridylmethyl)ethanedithioamide molecules. The tetrameric aggregates are linked into a supramolecular chain along the b axis via amide–carbonyl N—H

O hydrogen bonds.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810036755/hg2714sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536810036755/hg2714Isup2.hkl Contains datablock I

CCDC reference: 797789

checkCIF report

Key indicators

Single-crystal X-ray study
T = 98 K
Mean (C-C) = 0.005 Å
R factor = 0.063
wR factor = 0.156
Data-to-parameter ratio = 17.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds (x 1000) Ang ..          5
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C7     -   C8     ...       1.53 Ang.
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          2
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         11
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          1
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600          2

Alert level G
PLAT432_ALERT_2_G Short Inter X...Y Contact  C4     ..  C25     ..       3.20 Ang.
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          4

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Co-crystallization of 2-[(2-carboxyphenyl)disulfanyl]benzoic acid with various pyridine donors has led to the isolation of a variety of supramolecular motifs (Broker & Tiekink, 2007; Broker et al., 2008; Broker & Tiekink, 2010; Arman et al., 2010). Herein, the structure determination of the 1:1 co-crystal obtained from the co-crystallization of 2,2'-(disulfanediyl)dibenzoic acid with N,N'-bis(4-pyridylmethyl)ethanedithioamide is described. The asymmetric unit of the resulting 1:1 co-crystal contains one molecule of 2,2'-(disulfanediyl)dibenzoic acid, Fig. 1, and N,N'-bis(4-pyridylmethyl)ethanedithioamide, Fig. 2.

In the acid, the expected conformation is observed (Broker & Tiekink, 2007), stabilized in part by two close S···O(carbonyl) interactions, i.e. S3···O1 = 2.759 (2) Å and S4···O3 = 2.687 (3) Å; the dihedral angle formed between the benzene rings = 83.53 (14) °. The molecule of N,N'-bis(4-pyridylmethyl)ethanedithioamide adopts a U-shaped conformation as both pyridyl groups lie to the same side of the molecule with the C2—C1—C6—N2 and N3—C9—C10—C11 torsion angles being 40.8 (4) and 146.4 (3) °, respectively. Intramolecular N—H···S hydrogen bonds are noted, Table 1.

The components of the co-crystal are linked into a supramolecular ring whereby each carboxylic acid group of two 2,2'-(disulfanediyl)dibenzoic acid molecules form an O—H···N hydrogen bond with a pyridine-N of two N,N'-bis(4-pyridylmethyl)ethanedithioamide molecules, Fig. 3 and Table 1. The ring has a extended chair conformation as seen from the view in Fig. 4. Chairs stack to form a supramolecular chain with the main connections between the tetrameric aggregates being amide-N3—H···O3-carbonyl hydrogen bonds, Figs 5 & 6 and Table 1.

Related literature top

For related studies on co-crystal formation involving 2-[(2-carboxyphenyl)disulfanyl]benzoic acid, see: Broker & Tiekink (2007, 2010); Broker et al. (2008); Arman et al. (2010).

Experimental top

Equimolar amounts of 2-[(2-carboxyphenyl)disulfanyl]benzoic acid (Fluka) and N,N'-bis(4-pyridylmethyl)ethanedithioamide were dissolved in an 1:1 ethanol/chloroform mixture. Crystals were harvested after a few days of slow evaporation.

Computing details top

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); cell refinement: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); data reduction: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular structure of 2-[(2-carboxyphenyl)disulfanyl]benzoic acid found in the co-crystal of (I) showing atom-labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 2. Molecular structure of N,N'-bis(4-pyridylmethyl)ethanedithioamide found in the co-crystal of (I) showing atom-labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 3. Supramolecular ring in (I). The O—H···N hydrogen bonds are shown as orange dashed lines.
	Fig. 4. Supramolecular ring in (I) viewed side-on to emphasize the chair-like conformation. The O—H···N hydrogen bonds are shown as orange dashed lines.
	Fig. 5. View of the supramolecular chain along the b axis in (I). The O—H···N hydrogen bonds are shown as orange dashed lines. Every second tetrameric aggregate is shown in orange. The N—H···O hydrogen bonds are obscured in this view.
	Fig. 6. Side-on view of the supramolecular chain along the b axis in (I). The O—H···N and N—H···O hydrogen bonds are shown as orange and green dashed lines, respectively. Every second tetrameric aggregate is shown in orange.

2,2'-(Disulfanediyl)dibenzoic acid–N,N'-bis(4-pyridylmethyl)ethanedithioamide (1/1) top

Crystal data top

C₁₄H₁₄N₄S₂·C₁₄H₁₀O₄S₂	F(000) = 1264
M_r = 608.75	D_x = 1.459 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybc	Cell parameters from 11634 reflections
a = 18.502 (5) Å	θ = 2.2–40.8°
b = 10.624 (3) Å	µ = 0.39 mm⁻¹
c = 15.026 (4) Å	T = 98 K
β = 110.235 (5)°	Block, red
V = 2771.3 (13) Å³	0.38 × 0.26 × 0.10 mm
Z = 4

Data collection top

Rigaku AFC12K/SATURN724 diffractometer	5349 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.050
Graphite monochromator	θ_max = 27.5°, θ_min = 2.3°
ω scans	h = −22→24
16758 measured reflections	k = −13→12
6348 independent reflections	l = −19→12

Refinement top

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.156	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ²(F_o²) + (0.0595P)² + 1.5417P] where P = (F_o² + 2F_c²)/3
6348 reflections	(Δ/σ)_max = 0.001
373 parameters	Δρ_max = 0.40 e Å⁻³
4 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₁₄H₁₄N₄S₂·C₁₄H₁₀O₄S₂	V = 2771.3 (13) Å³
M_r = 608.75	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 18.502 (5) Å	µ = 0.39 mm⁻¹
b = 10.624 (3) Å	T = 98 K
c = 15.026 (4) Å	0.38 × 0.26 × 0.10 mm
β = 110.235 (5)°

Data collection top

Rigaku AFC12K/SATURN724 diffractometer	5349 reflections with I > 2σ(I)
16758 measured reflections	R_int = 0.050
6348 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	4 restraints
wR(F²) = 0.156	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	Δρ_max = 0.40 e Å⁻³
6348 reflections	Δρ_min = −0.30 e Å⁻³
373 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.14789 (4)	1.09050 (7)	0.26162 (6)	0.0419 (2)
S2	0.38384 (5)	1.05034 (10)	0.43964 (7)	0.0577 (3)
S3	0.28281 (4)	0.41538 (6)	0.47637 (5)	0.03595 (18)
S4	0.23818 (4)	0.28425 (6)	0.54351 (5)	0.03659 (18)
O1	0.36687 (12)	0.57687 (19)	0.40613 (16)	0.0439 (5)
O2	0.45371 (13)	0.7063 (3)	0.50168 (18)	0.0542 (6)
H1o	0.469 (2)	0.707 (4)	0.455 (2)	0.081*
O3	0.18572 (13)	0.1116 (2)	0.63693 (18)	0.0487 (5)
O4	0.06256 (14)	0.06603 (19)	0.61426 (18)	0.0482 (6)
H2o	0.0915 (19)	0.016 (3)	0.655 (2)	0.072*
N1	0.10469 (15)	0.6043 (2)	0.23918 (19)	0.0389 (6)
N2	0.22644 (15)	0.9846 (3)	0.42551 (19)	0.0445 (6)
H1n	0.2727 (10)	0.978 (3)	0.4689 (19)	0.053*
N3	0.30049 (14)	1.2123 (2)	0.3103 (2)	0.0401 (6)
H2n	0.2547 (10)	1.233 (3)	0.271 (2)	0.048*
N4	0.48896 (14)	1.2348 (3)	0.12994 (19)	0.0439 (6)
C1	0.13990 (17)	0.8058 (3)	0.3642 (2)	0.0363 (6)
C2	0.19777 (17)	0.7309 (3)	0.3524 (2)	0.0389 (6)
H2	0.2504	0.7483	0.3872	0.047*
C3	0.17793 (17)	0.6311 (3)	0.2896 (2)	0.0376 (6)
H3	0.2176	0.5801	0.2820	0.045*
C4	0.04915 (17)	0.6752 (3)	0.2516 (2)	0.0389 (6)
H4	−0.0030	0.6554	0.2163	0.047*
C5	0.06427 (16)	0.7753 (3)	0.3131 (2)	0.0367 (6)
H5	0.0233	0.8230	0.3205	0.044*
C6	0.16015 (19)	0.9164 (3)	0.4317 (2)	0.0465 (7)
H6A	0.1155	0.9740	0.4164	0.056*
H6B	0.1717	0.8858	0.4974	0.056*
C7	0.22516 (16)	1.0588 (3)	0.3541 (2)	0.0365 (6)
C8	0.30383 (17)	1.1141 (3)	0.3643 (2)	0.0395 (7)
C9	0.36528 (19)	1.2963 (3)	0.3191 (3)	0.0514 (9)
H9A	0.4025	1.2903	0.3847	0.062*
H9B	0.3459	1.3839	0.3093	0.062*
C10	0.40742 (17)	1.2706 (3)	0.2513 (2)	0.0414 (7)
C11	0.43798 (18)	1.3709 (3)	0.2185 (3)	0.0476 (7)
H11	0.4306	1.4543	0.2365	0.057*
C12	0.47942 (19)	1.3496 (3)	0.1591 (3)	0.0509 (8)
H12	0.5018	1.4192	0.1385	0.061*
C13	0.45899 (17)	1.1392 (3)	0.1596 (2)	0.0447 (7)
H13	0.4657	1.0572	0.1384	0.054*
C14	0.41768 (18)	1.1519 (3)	0.2208 (3)	0.0470 (7)
H14	0.3969	1.0802	0.2411	0.056*
C15	0.35166 (15)	0.6427 (2)	0.5491 (2)	0.0336 (6)
C16	0.29850 (16)	0.5498 (2)	0.5523 (2)	0.0337 (6)
C17	0.25988 (17)	0.5629 (3)	0.6169 (2)	0.0384 (6)
H17	0.2235	0.5011	0.6193	0.046*
C18	0.27440 (19)	0.6650 (3)	0.6771 (2)	0.0460 (7)
H18	0.2473	0.6728	0.7203	0.055*
C19	0.32744 (19)	0.7565 (3)	0.6763 (3)	0.0482 (8)
H19	0.3373	0.8259	0.7187	0.058*
C20	0.36576 (17)	0.7446 (3)	0.6123 (2)	0.0407 (7)
H20	0.4024	0.8067	0.6112	0.049*
C21	0.39214 (16)	0.6382 (3)	0.4790 (2)	0.0352 (6)
C22	0.13608 (16)	0.3115 (3)	0.4988 (2)	0.0346 (6)
C23	0.08651 (17)	0.2328 (2)	0.5271 (2)	0.0351 (6)
C24	0.00720 (18)	0.2556 (3)	0.4900 (2)	0.0418 (7)
H24	−0.0266	0.2019	0.5078	0.050*
C25	−0.02326 (18)	0.3530 (3)	0.4287 (2)	0.0450 (7)
H25	−0.0773	0.3669	0.4047	0.054*
C26	0.02518 (19)	0.4301 (3)	0.4026 (2)	0.0466 (7)
H26	0.0046	0.4987	0.3610	0.056*
C27	0.10406 (17)	0.4090 (3)	0.4363 (2)	0.0415 (7)
H27	0.1367	0.4622	0.4161	0.050*
C28	0.11699 (17)	0.1310 (3)	0.5979 (2)	0.0369 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0356 (4)	0.0497 (4)	0.0434 (5)	−0.0029 (3)	0.0175 (3)	0.0003 (3)
S2	0.0405 (4)	0.0839 (6)	0.0467 (5)	−0.0025 (4)	0.0127 (4)	−0.0042 (5)
S3	0.0454 (4)	0.0380 (4)	0.0333 (4)	−0.0046 (3)	0.0250 (3)	−0.0045 (3)
S4	0.0435 (4)	0.0368 (3)	0.0357 (4)	−0.0001 (3)	0.0215 (3)	0.0020 (3)
O1	0.0499 (12)	0.0498 (12)	0.0446 (13)	−0.0110 (9)	0.0321 (11)	−0.0096 (10)
O2	0.0440 (12)	0.0843 (16)	0.0417 (14)	−0.0211 (11)	0.0244 (11)	−0.0103 (13)
O3	0.0585 (14)	0.0433 (11)	0.0520 (14)	0.0064 (10)	0.0292 (12)	0.0153 (10)
O4	0.0566 (14)	0.0402 (11)	0.0561 (15)	−0.0004 (10)	0.0300 (12)	0.0117 (10)
N1	0.0505 (14)	0.0356 (12)	0.0407 (14)	−0.0035 (10)	0.0285 (12)	−0.0009 (10)
N2	0.0473 (14)	0.0528 (15)	0.0324 (14)	−0.0135 (12)	0.0125 (12)	−0.0055 (12)
N3	0.0408 (13)	0.0452 (13)	0.0427 (15)	−0.0110 (11)	0.0253 (12)	−0.0135 (11)
N4	0.0355 (12)	0.0631 (16)	0.0361 (15)	0.0073 (11)	0.0160 (11)	0.0018 (12)
C1	0.0486 (16)	0.0363 (13)	0.0296 (15)	−0.0040 (12)	0.0205 (13)	0.0023 (11)
C2	0.0376 (14)	0.0440 (15)	0.0368 (17)	0.0005 (12)	0.0152 (13)	0.0100 (12)
C3	0.0442 (15)	0.0341 (13)	0.0431 (17)	0.0045 (11)	0.0262 (14)	0.0100 (12)
C4	0.0417 (15)	0.0393 (14)	0.0399 (17)	−0.0047 (12)	0.0197 (13)	−0.0018 (12)
C5	0.0422 (15)	0.0372 (13)	0.0379 (16)	−0.0005 (11)	0.0231 (13)	−0.0007 (12)
C6	0.0573 (19)	0.0523 (17)	0.0356 (17)	−0.0154 (15)	0.0231 (15)	−0.0088 (14)
C7	0.0423 (15)	0.0377 (14)	0.0346 (16)	−0.0074 (11)	0.0200 (13)	−0.0092 (12)
C8	0.0415 (15)	0.0451 (15)	0.0371 (16)	−0.0088 (12)	0.0202 (13)	−0.0160 (13)
C9	0.0545 (19)	0.0558 (18)	0.058 (2)	−0.0189 (15)	0.0367 (18)	−0.0220 (16)
C10	0.0378 (15)	0.0480 (16)	0.0438 (18)	−0.0066 (12)	0.0210 (14)	−0.0065 (13)
C11	0.0480 (17)	0.0491 (17)	0.051 (2)	0.0005 (14)	0.0241 (16)	−0.0003 (15)
C12	0.0492 (18)	0.0589 (19)	0.052 (2)	0.0012 (15)	0.0273 (17)	0.0020 (16)
C13	0.0417 (16)	0.0509 (17)	0.0427 (18)	0.0026 (13)	0.0160 (14)	−0.0075 (14)
C14	0.0492 (17)	0.0469 (16)	0.051 (2)	−0.0080 (13)	0.0248 (16)	−0.0093 (14)
C15	0.0333 (13)	0.0394 (14)	0.0313 (15)	−0.0002 (11)	0.0154 (12)	−0.0004 (11)
C16	0.0378 (14)	0.0370 (13)	0.0300 (15)	0.0011 (11)	0.0165 (12)	−0.0008 (11)
C17	0.0444 (15)	0.0408 (14)	0.0382 (17)	−0.0022 (12)	0.0246 (14)	−0.0037 (12)
C18	0.0568 (18)	0.0523 (17)	0.0413 (18)	−0.0017 (14)	0.0326 (16)	−0.0079 (14)
C19	0.0574 (19)	0.0482 (17)	0.0459 (19)	−0.0053 (14)	0.0267 (16)	−0.0164 (14)
C20	0.0425 (15)	0.0432 (15)	0.0402 (17)	−0.0062 (12)	0.0190 (14)	−0.0060 (13)
C21	0.0363 (14)	0.0389 (14)	0.0347 (16)	0.0012 (11)	0.0178 (12)	0.0008 (12)
C22	0.0418 (14)	0.0375 (13)	0.0291 (15)	−0.0049 (11)	0.0182 (12)	−0.0040 (11)
C23	0.0470 (15)	0.0350 (13)	0.0279 (14)	−0.0040 (11)	0.0187 (12)	−0.0023 (11)
C24	0.0481 (16)	0.0431 (15)	0.0391 (17)	−0.0109 (13)	0.0213 (14)	−0.0024 (13)
C25	0.0416 (16)	0.0552 (18)	0.0354 (17)	−0.0042 (13)	0.0099 (14)	0.0021 (14)
C26	0.0497 (17)	0.0499 (17)	0.0370 (18)	−0.0036 (14)	0.0108 (14)	0.0088 (13)
C27	0.0449 (16)	0.0456 (16)	0.0359 (17)	−0.0068 (13)	0.0166 (14)	0.0065 (13)
C28	0.0494 (17)	0.0323 (13)	0.0373 (16)	−0.0010 (12)	0.0255 (14)	−0.0020 (11)

Geometric parameters (Å, º) top

S1—C7	1.648 (3)	C9—C10	1.506 (4)
S2—C8	1.665 (3)	C9—H9A	0.9900
S3—C16	1.788 (3)	C9—H9B	0.9900
S3—S4	2.0535 (10)	C10—C11	1.375 (4)
S4—C22	1.796 (3)	C10—C14	1.378 (4)
O1—C21	1.219 (4)	C11—C12	1.381 (4)
O2—C21	1.292 (3)	C11—H11	0.9500
O2—H1o	0.84 (3)	C12—H12	0.9500
O3—C28	1.220 (4)	C13—C14	1.390 (4)
O4—C28	1.312 (3)	C13—H13	0.9500
O4—H2o	0.85 (3)	C14—H14	0.9500
N1—C3	1.334 (4)	C15—C20	1.404 (4)
N1—C4	1.338 (4)	C15—C16	1.406 (4)
N2—C7	1.325 (4)	C15—C21	1.490 (4)
N2—C6	1.455 (4)	C16—C17	1.397 (4)
N2—H1n	0.88 (3)	C17—C18	1.379 (4)
N3—C8	1.310 (4)	C17—H17	0.9500
N3—C9	1.464 (4)	C18—C19	1.384 (4)
N3—H2n	0.88 (3)	C18—H18	0.9500
N4—C13	1.308 (4)	C19—C20	1.384 (4)
N4—C12	1.329 (4)	C19—H19	0.9500
C1—C5	1.382 (4)	C20—H20	0.9500
C1—C2	1.394 (4)	C22—C27	1.386 (4)
C1—C6	1.512 (4)	C22—C23	1.411 (4)
C2—C3	1.382 (4)	C23—C24	1.399 (4)
C2—H2	0.9500	C23—C28	1.485 (4)
C3—H3	0.9500	C24—C25	1.371 (4)
C4—C5	1.373 (4)	C24—H24	0.9500
C4—H4	0.9500	C25—C26	1.367 (4)
C5—H5	0.9500	C25—H25	0.9500
C6—H6A	0.9900	C26—C27	1.388 (4)
C6—H6B	0.9900	C26—H26	0.9500
C7—C8	1.527 (4)	C27—H27	0.9500

C16—S3—S4	103.44 (10)	N4—C12—C11	122.0 (3)
C22—S4—S3	104.86 (10)	N4—C12—H12	119.0
C21—O2—H1O	108 (3)	C11—C12—H12	119.0
C28—O4—H2O	98 (3)	N4—C13—C14	123.0 (3)
C3—N1—C4	118.6 (3)	N4—C13—H13	118.5
C7—N2—C6	124.7 (3)	C14—C13—H13	118.5
C7—N2—H1N	113 (2)	C10—C14—C13	118.7 (3)
C6—N2—H1N	122 (2)	C10—C14—H14	120.6
C8—N3—C9	124.6 (3)	C13—C14—H14	120.6
C8—N3—H2N	117 (2)	C20—C15—C16	119.1 (3)
C9—N3—H2N	118 (2)	C20—C15—C21	118.8 (2)
C13—N4—C12	118.7 (3)	C16—C15—C21	122.0 (2)
C5—C1—C2	118.1 (3)	C17—C16—C15	119.1 (3)
C5—C1—C6	121.5 (3)	C17—C16—S3	120.9 (2)
C2—C1—C6	120.4 (3)	C15—C16—S3	120.0 (2)
C3—C2—C1	119.4 (3)	C18—C17—C16	120.3 (3)
C3—C2—H2	120.3	C18—C17—H17	119.9
C1—C2—H2	120.3	C16—C17—H17	119.9
N1—C3—C2	121.9 (3)	C17—C18—C19	121.6 (3)
N1—C3—H3	119.0	C17—C18—H18	119.2
C2—C3—H3	119.0	C19—C18—H18	119.2
N1—C4—C5	122.9 (3)	C20—C19—C18	118.5 (3)
N1—C4—H4	118.6	C20—C19—H19	120.7
C5—C4—H4	118.6	C18—C19—H19	120.7
C4—C5—C1	119.1 (3)	C19—C20—C15	121.4 (3)
C4—C5—H5	120.4	C19—C20—H20	119.3
C1—C5—H5	120.4	C15—C20—H20	119.3
N2—C6—C1	111.3 (2)	O1—C21—O2	124.4 (3)
N2—C6—H6A	109.4	O1—C21—C15	121.5 (3)
C1—C6—H6A	109.4	O2—C21—C15	114.1 (3)
N2—C6—H6B	109.4	C27—C22—C23	118.5 (3)
C1—C6—H6B	109.4	C27—C22—S4	121.5 (2)
H6A—C6—H6B	108.0	C23—C22—S4	120.1 (2)
N2—C7—C8	113.5 (3)	C24—C23—C22	118.6 (3)
N2—C7—S1	124.9 (2)	C24—C23—C28	119.9 (2)
C8—C7—S1	121.6 (2)	C22—C23—C28	121.5 (3)
N3—C8—C7	113.9 (3)	C25—C24—C23	122.0 (3)
N3—C8—S2	125.8 (2)	C25—C24—H24	119.0
C7—C8—S2	120.3 (2)	C23—C24—H24	119.0
N3—C9—C10	115.3 (3)	C26—C25—C24	119.1 (3)
N3—C9—H9A	108.4	C26—C25—H25	120.4
C10—C9—H9A	108.4	C24—C25—H25	120.4
N3—C9—H9B	108.4	C25—C26—C27	120.7 (3)
C10—C9—H9B	108.4	C25—C26—H26	119.7
H9A—C9—H9B	107.5	C27—C26—H26	119.7
C11—C10—C14	117.9 (3)	C22—C27—C26	121.1 (3)
C11—C10—C9	118.4 (3)	C22—C27—H27	119.4
C14—C10—C9	123.7 (3)	C26—C27—H27	119.4
C10—C11—C12	119.6 (3)	O3—C28—O4	124.2 (3)
C10—C11—H11	120.2	O3—C28—C23	122.8 (3)
C12—C11—H11	120.2	O4—C28—C23	113.0 (3)

C16—S3—S4—C22	88.06 (13)	C20—C15—C16—S3	−177.1 (2)
C5—C1—C2—C3	1.1 (4)	C21—C15—C16—S3	4.5 (4)
C6—C1—C2—C3	−179.4 (3)	S4—S3—C16—C17	−20.3 (3)
C4—N1—C3—C2	−1.3 (4)	S4—S3—C16—C15	158.2 (2)
C1—C2—C3—N1	0.3 (4)	C15—C16—C17—C18	−0.6 (4)
C3—N1—C4—C5	0.8 (4)	S3—C16—C17—C18	177.9 (2)
N1—C4—C5—C1	0.6 (4)	C16—C17—C18—C19	−0.5 (5)
C2—C1—C5—C4	−1.5 (4)	C17—C18—C19—C20	0.7 (5)
C6—C1—C5—C4	178.9 (3)	C18—C19—C20—C15	0.1 (5)
C7—N2—C6—C1	73.4 (4)	C16—C15—C20—C19	−1.2 (5)
C5—C1—C6—N2	−139.7 (3)	C21—C15—C20—C19	177.3 (3)
C2—C1—C6—N2	40.8 (4)	C20—C15—C21—O1	−157.7 (3)
C6—N2—C7—C8	−177.5 (3)	C16—C15—C21—O1	20.7 (4)
C6—N2—C7—S1	2.1 (4)	C20—C15—C21—O2	20.7 (4)
C9—N3—C8—C7	168.0 (2)	C16—C15—C21—O2	−160.9 (3)
C9—N3—C8—S2	−11.6 (4)	S3—S4—C22—C27	−3.0 (3)
N2—C7—C8—N3	−162.1 (3)	S3—S4—C22—C23	177.0 (2)
S1—C7—C8—N3	18.3 (3)	C27—C22—C23—C24	0.8 (4)
N2—C7—C8—S2	17.4 (3)	S4—C22—C23—C24	−179.2 (2)
S1—C7—C8—S2	−162.20 (17)	C27—C22—C23—C28	−176.5 (3)
C8—N3—C9—C10	98.3 (4)	S4—C22—C23—C28	3.5 (4)
N3—C9—C10—C11	146.4 (3)	C22—C23—C24—C25	−1.2 (4)
N3—C9—C10—C14	−34.1 (5)	C28—C23—C24—C25	176.1 (3)
C14—C10—C11—C12	−2.0 (5)	C23—C24—C25—C26	0.3 (5)
C9—C10—C11—C12	177.6 (3)	C24—C25—C26—C27	1.1 (5)
C13—N4—C12—C11	−1.0 (5)	C23—C22—C27—C26	0.6 (5)
C10—C11—C12—N4	2.1 (5)	S4—C22—C27—C26	−179.5 (3)
C12—N4—C13—C14	−0.2 (5)	C25—C26—C27—C22	−1.5 (5)
C11—C10—C14—C13	0.8 (5)	C24—C23—C28—O3	−175.5 (3)
C9—C10—C14—C13	−178.7 (3)	C22—C23—C28—O3	1.7 (4)
N4—C13—C14—C10	0.3 (5)	C24—C23—C28—O4	3.9 (4)
C20—C15—C16—C17	1.4 (4)	C22—C23—C28—O4	−178.8 (3)
C21—C15—C16—C17	−177.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1o···N4ⁱ	0.84 (3)	1.73 (3)	2.565 (4)	168 (4)
O4—H2o···N1ⁱⁱ	0.85 (3)	1.76 (3)	2.529 (3)	151 (4)
N2—H1n···S2	0.88 (2)	2.37 (2)	2.930 (3)	121 (2)
N3—H2n···O3ⁱⁱⁱ	0.88 (3)	2.58 (3)	3.312 (4)	142 (2)
N3—H2n···S1	0.88 (3)	2.45 (3)	2.959 (3)	117 (2)

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₄N₄S₂·C₁₄H₁₀O₄S₂
M_r	608.75
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	98
a, b, c (Å)	18.502 (5), 10.624 (3), 15.026 (4)
β (°)	110.235 (5)
V (Å³)	2771.3 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.39
Crystal size (mm)	0.38 × 0.26 × 0.10

Data collection
Diffractometer	Rigaku AFC12K/SATURN724 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	16758, 6348, 5349
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.156, 1.13
No. of reflections	6348
No. of parameters	373
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.30

Computer programs: CrystalClear (Molecular Structure Corporation & Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).