Mutual prodrug of cephazolin and benzydamin: 3-[(1-benzyl-1H-indazol-3-yl)­oxy]-N,N-dimethyl­propan-1-aminium 3-{[(5-methyl-1,3,4-thia­diazol-2-yl)sulfan­yl]meth­yl}-8-oxo-7-[(1H-tetra­zol-1-yl)acetamido]-5-thia-1-aza­bicyclo­[4.2.0]octane-2-carboxyl­ate (benzydaminium cephazolinate)

Asghar, A.; Iqbal, M.S.; Tahir, M.N.

doi:10.1107/S1600536809047941

Mutual prodrug of cephazolin and benzydamin: 3-[(1-benzyl-1H-indazol-3-yl)oxy]-N,N-dimethylpropan-1-aminium 3-{[(5-methyl-1,3,4-thiadiazol-2-yl)sulfanyl]methyl}-8-oxo-7-[(1H-tetrazol-1-yl)acetamido]-5-thia-1-azabicyclo[4.2.0]octane-2-carboxylate (benzydaminium cephazolinate)

A. Asghar, M. S. Iqbal and M. N. Tahir

In the crystal of the title molecular salt, C₁₉H₂₄N₃O⁺·C₁₄H₁₃N₈O₄S₃⁻, the cations and anions are linked by N—H

O hydrogen bonds. Short intramolecular C—H

O contacts occur within the anion and intermolecular C—H

O and C—H

π bonds help to establish the packing.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536809047941/hb5219sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536809047941/hb5219Isup2.hkl Contains datablock I

CCDC reference: 758330

checkCIF report

Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.005 Å
R factor = 0.050
wR factor = 0.095
Data-to-parameter ratio = 14.2

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for         N3

Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O2     --  C23     ..       5.53 su
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds (x 1000) Ang ..          6
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          6
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          2
PLAT717_ALERT_1_C D...A   Unknown or Inconsistent Label ..........        CGA
PLAT717_ALERT_1_C D...A   Unknown or Inconsistent Label ..........        CGD
PLAT717_ALERT_1_C D...A   Unknown or Inconsistent Label ..........        CGA

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           26.00
           From the CIF: _reflns_number_total               6750
           Count of symmetry unique reflns         3832
           Completeness (_total/calc)            176.15%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      2918
           Fraction of Friedel pairs measured     0.761
           Are heavy atom types Z>Si present        yes
PLAT791_ALERT_4_G The Model has Chirality at C28     (Verify) ....          R
PLAT791_ALERT_4_G The Model has Chirality at C29     (Verify) ....          R

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

   3 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
   3 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Cephazolin, is a first generation cefalosporin antibiotic and benzydamin hydrochloride is a locally acting nonsteroidal anti-inflammatory drug with local anaesthetic and analgesic properties providing both rapid and extended pain relief as well as a significant anti-inflammatory treatment for the painful inflammatory conditions of mouth and throat (Turnbull, 1995). The title compound (I, Fig. 1) was prepared as a mutual prodrug for the treatment of infections and inflamatory conditions.

No crystal structure has been found related to cation. In the cation the indazol moiety A (C1–C6/N2/N1/C14) and the benzene ring B (C8–C13) are planar with r.m.s. deviations of 0.0258 and 0.0031 Å respectively, from the respective mean square planes. The dihedral angle between A/B is 71.06 (12)°. In this cation, there exist an intramolecular H-bonding of C—H···O type (Table 1, Fig. 1) forming S(5) ring motif (Bernstein et al., 1995) in the envelop form.

In the anion, two five membered heterocyclic rings C (C25/S3/C26/N5/N4) and D (N8—N9/C33) are planar with r. m. s. deviations of 0.0025 and 0.0014 Å respectively, from the respective mean square planes and the dihedral angle between C/D is 38.58 (14)°. The heterocyclic six membered E (C20/C21/C22/N6/C28/S1) is in the twisted form, with the maximum puckering amplitude Q_T = 0.623 (4) Å (Cremer & Pople, 1975) and the four membered ring F (N6/C28–C30) is not planar also. In anion, there exist two S(5) and a S(6) ring motifs (Table 1, Fig. 1). The molecules are stabilized in the form of polymeric chains forming R₂¹(6), R₄²(8), R₂²(10) and other ring motifs (Fig. 2 & Fig. 3).

Related literature top

For medicinal background to cephazolin, see: Turnbull (1995). For ring-puckering analysis, see: Cremer & Pople (1975). For graph-set theory, see: Bernstein et al. (1995).CgA and CgD are the centroids of the C1–C6 and N8–N11/C33 rings, respectively.

Experimental top

Cefazolin sodium (0.238 g; 0.1 mol) and benzydamine hydrochloride (0.173 g; 0.01 mol) were dissolved separately in distilled water (50 ml). Ten milliliter of each solution were mixed and left for two days. The colourless needles of (I) thus obtained were filtered out by suction, washed with distilled water and dried under vacuum.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of (I) with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. The partial packing of (I), which shows that molecules form polymeric chains and ring motifs.
	Fig. 3. The partial packing of (I), which shows that molecules form polymeric networks with various ring motifs.

3-[(1-Benzyl-1H-indazol-3-yl)oxy]-N,N-dimethylpropan-1-aminium 3-{[(5-methyl-1,3,4-thiadiazol-2-yl)sulfanyl]methyl}-8-oxo-7-[(1H-tetrazol-1-yl)acetamido]-5-thia-1-azabicyclo[4.2.0]octane-2-carboxylate top

Crystal data top

C₁₉H₂₄N₃O⁺·C₁₄H₁₃N₈O₄S₃⁻	F(000) = 1600
M_r = 763.92	D_x = 1.413 Mg m⁻³
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 3824 reflections
a = 44.409 (3) Å	θ = 2.6–26.0°
b = 7.1777 (5) Å	µ = 0.27 mm⁻¹
c = 11.2683 (8) Å	T = 296 K
β = 90.587 (8)°	Cut needle, colourless
V = 3591.6 (4) Å³	0.24 × 0.14 × 0.12 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	6750 independent reflections
Radiation source: fine-focus sealed tube	4092 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.088
Detector resolution: 7.60 pixels mm^-1	θ_max = 26.0°, θ_min = 2.6°
ω scans	h = −54→54
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −8→8
T_min = 0.957, T_max = 0.968	l = −13→13
34321 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.095	w = 1/[σ²(F_o²) + (0.0342P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
6750 reflections	Δρ_max = 0.36 e Å⁻³
475 parameters	Δρ_min = −0.23 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 2918 Friedal Pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.07 (7)

Crystal data top

C₁₉H₂₄N₃O⁺·C₁₄H₁₃N₈O₄S₃⁻	V = 3591.6 (4) Å³
M_r = 763.92	Z = 4
Monoclinic, C2	Mo Kα radiation
a = 44.409 (3) Å	µ = 0.27 mm⁻¹
b = 7.1777 (5) Å	T = 296 K
c = 11.2683 (8) Å	0.24 × 0.14 × 0.12 mm
β = 90.587 (8)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	6750 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	4092 reflections with I > 2σ(I)
T_min = 0.957, T_max = 0.968	R_int = 0.088
34321 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.095	Δρ_max = 0.36 e Å⁻³
S = 1.00	Δρ_min = −0.23 e Å⁻³
6750 reflections	Absolute structure: Flack (1983), 2918 Friedal Pairs
475 parameters	Absolute structure parameter: −0.07 (7)
1 restraint

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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 (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.14103 (6)	0.2863 (4)	0.9240 (3)	0.0552 (11)
N1	0.18241 (7)	0.2542 (4)	0.7971 (3)	0.0420 (12)
N2	0.19416 (7)	0.3698 (5)	0.7111 (3)	0.0433 (12)
N3	0.06627 (7)	0.0749 (5)	1.1012 (3)	0.0372 (11)
C1	0.15436 (8)	0.5181 (5)	0.7788 (3)	0.0340 (12)
C2	0.13236 (9)	0.6570 (6)	0.7813 (4)	0.0510 (17)
C3	0.13442 (11)	0.8000 (7)	0.7038 (4)	0.0640 (17)
C4	0.15844 (11)	0.8115 (6)	0.6251 (4)	0.0610 (19)
C5	0.18016 (10)	0.6769 (6)	0.6189 (3)	0.0490 (17)
C6	0.17762 (8)	0.5263 (5)	0.6969 (3)	0.0370 (12)
C7	0.21920 (9)	0.3080 (6)	0.6398 (3)	0.0463 (17)
C8	0.24923 (8)	0.3866 (5)	0.6760 (3)	0.0353 (12)
C9	0.25878 (9)	0.3855 (6)	0.7933 (4)	0.0466 (17)
C10	0.28704 (10)	0.4478 (6)	0.8244 (4)	0.0520 (17)
C11	0.30587 (9)	0.5147 (6)	0.7391 (4)	0.0484 (17)
C12	0.29672 (9)	0.5182 (6)	0.6231 (4)	0.0492 (17)
C13	0.26851 (9)	0.4546 (6)	0.5911 (3)	0.0450 (17)
C14	0.15916 (9)	0.3469 (5)	0.8366 (3)	0.0393 (16)
C15	0.14483 (9)	0.1004 (6)	0.9660 (4)	0.0546 (17)
C16	0.12086 (10)	0.0662 (8)	1.0548 (4)	0.0699 (19)
C17	0.09024 (9)	0.0869 (7)	1.0079 (4)	0.0636 (19)
C18	0.06411 (12)	0.2420 (7)	1.1765 (4)	0.089 (3)
C19	0.03700 (9)	0.0436 (8)	1.0420 (4)	0.0718 (19)
S1	0.10575 (2)	0.19304 (14)	0.49823 (9)	0.0428 (3)
S2	0.14745 (2)	0.56694 (16)	0.18123 (9)	0.0463 (4)
S3	0.20738 (2)	0.44836 (15)	0.08659 (9)	0.0456 (4)
O2	0.05024 (6)	0.8249 (3)	0.3777 (2)	0.0384 (9)
O3	0.08047 (6)	0.7715 (4)	0.2253 (2)	0.0547 (11)
O4	0.02066 (6)	0.4136 (4)	0.3861 (2)	0.0405 (9)
O5	0.02552 (7)	0.0728 (4)	0.7592 (2)	0.0587 (13)
N4	0.19862 (7)	0.4956 (4)	0.3076 (3)	0.0406 (12)
N5	0.22865 (7)	0.4435 (4)	0.2966 (3)	0.0427 (12)
N6	0.06812 (6)	0.4815 (4)	0.4717 (2)	0.0279 (10)
N7	0.03965 (6)	0.0819 (4)	0.5676 (2)	0.0315 (10)
N8	0.02949 (7)	−0.3125 (4)	0.7545 (3)	0.0325 (11)
N9	0.05801 (8)	−0.3400 (5)	0.7855 (3)	0.0603 (16)
N10	0.05818 (10)	−0.4303 (7)	0.8833 (4)	0.0751 (17)
N11	0.02978 (11)	−0.4641 (5)	0.9184 (3)	0.0663 (16)
C20	0.13044 (8)	0.3791 (5)	0.4529 (3)	0.0440 (14)
C21	0.11584 (8)	0.5428 (5)	0.3900 (3)	0.0317 (12)
C22	0.08645 (8)	0.5831 (5)	0.3948 (3)	0.0293 (12)
C23	0.07099 (9)	0.7410 (5)	0.3273 (3)	0.0330 (12)
C24	0.13782 (8)	0.6622 (5)	0.3251 (3)	0.0396 (14)
C25	0.18490 (8)	0.5045 (5)	0.2061 (3)	0.0376 (12)
C26	0.23635 (9)	0.4134 (5)	0.1884 (3)	0.0407 (14)
C27	0.26722 (9)	0.3571 (6)	0.1520 (4)	0.0570 (17)
C28	0.07883 (8)	0.3496 (5)	0.5621 (3)	0.0347 (12)
C29	0.04609 (8)	0.2771 (5)	0.5704 (3)	0.0323 (12)
C30	0.04024 (8)	0.3968 (5)	0.4591 (3)	0.0289 (12)
C31	0.02943 (8)	−0.0044 (5)	0.6644 (3)	0.0340 (12)
C32	0.02179 (8)	−0.2078 (5)	0.6480 (3)	0.0337 (12)
C33	0.01254 (10)	−0.3891 (5)	0.8368 (4)	0.0479 (17)
H2	0.11664	0.65124	0.83513	0.0612*
H3	0.11965	0.89190	0.70279	0.0762*
H3N	0.0701 (8)	−0.035 (5)	1.148 (3)	0.0446*
H4	0.15971	0.91434	0.57520	0.0732*
H5	0.19589	0.68514	0.56533	0.0588*
H7A	0.21521	0.34164	0.55778	0.0555*
H7B	0.22030	0.17314	0.64381	0.0555*
H9	0.24592	0.34200	0.85174	0.0560*
H10	0.29334	0.44458	0.90336	0.0622*
H11	0.32494	0.55774	0.76019	0.0578*
H12	0.30960	0.56374	0.56540	0.0593*
H13	0.26244	0.45759	0.51190	0.0541*
H15A	0.16458	0.08557	1.00236	0.0653*
H15B	0.14299	0.01281	0.90075	0.0653*
H16A	0.12321	−0.05902	1.08589	0.0837*
H16B	0.12364	0.15230	1.12035	0.0837*
H17A	0.08661	−0.00932	0.94905	0.0766*
H17B	0.08860	0.20648	0.96821	0.0766*
H18A	0.05950	0.34834	1.12796	0.1331*
H18B	0.08295	0.26181	1.21710	0.1331*
H18C	0.04846	0.22478	1.23366	0.1331*
H19A	0.03248	0.14682	0.99069	0.1076*
H19B	0.02159	0.03237	1.10070	0.1076*
H19C	0.03785	−0.06890	0.99605	0.1076*
H7N	0.04237	0.01975	0.50338	0.0378*
H20A	0.14087	0.42565	0.52288	0.0529*
H20B	0.14552	0.32694	0.40083	0.0529*
H24A	0.15602	0.67492	0.37270	0.0474*
H24B	0.12927	0.78543	0.31426	0.0474*
H27A	0.27708	0.29376	0.21663	0.0852*
H27B	0.27858	0.46598	0.13134	0.0852*
H27C	0.26590	0.27544	0.08474	0.0852*
H28	0.08607	0.41003	0.63503	0.0418*
H29	0.03622	0.33403	0.63884	0.0385*
H32A	0.00044	−0.22075	0.63099	0.0402*
H32B	0.03281	−0.25736	0.58121	0.0402*
H33	−0.00840	−0.38952	0.83662	0.0575*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.058 (2)	0.0430 (17)	0.065 (2)	0.0076 (15)	0.0274 (16)	0.0174 (15)
N1	0.036 (2)	0.044 (2)	0.046 (2)	0.0012 (17)	0.0080 (18)	0.0076 (17)
N2	0.031 (2)	0.052 (2)	0.047 (2)	0.0036 (18)	0.0123 (17)	0.0080 (18)
N3	0.039 (2)	0.043 (2)	0.0295 (19)	0.0030 (18)	0.0015 (16)	0.0090 (17)
C1	0.030 (2)	0.037 (2)	0.035 (2)	−0.0035 (19)	−0.0037 (19)	0.0030 (19)
C2	0.049 (3)	0.050 (3)	0.054 (3)	0.008 (2)	0.007 (2)	0.009 (2)
C3	0.070 (3)	0.064 (3)	0.058 (3)	0.021 (3)	0.005 (3)	0.014 (3)
C4	0.082 (4)	0.048 (3)	0.053 (3)	0.003 (3)	0.002 (3)	0.013 (2)
C5	0.054 (3)	0.054 (3)	0.039 (3)	−0.015 (3)	0.001 (2)	0.010 (2)
C6	0.034 (2)	0.040 (2)	0.037 (2)	−0.006 (2)	−0.004 (2)	0.002 (2)
C7	0.042 (3)	0.051 (3)	0.046 (3)	−0.002 (2)	0.006 (2)	−0.003 (2)
C8	0.034 (2)	0.036 (2)	0.036 (2)	0.0023 (19)	0.005 (2)	0.003 (2)
C9	0.049 (3)	0.049 (3)	0.042 (3)	−0.007 (2)	0.008 (2)	0.001 (2)
C10	0.059 (3)	0.056 (3)	0.041 (3)	−0.008 (3)	−0.005 (2)	−0.002 (2)
C11	0.040 (3)	0.042 (3)	0.063 (3)	0.007 (2)	−0.003 (2)	0.000 (2)
C12	0.041 (3)	0.052 (3)	0.055 (3)	0.004 (2)	0.014 (2)	0.009 (2)
C13	0.042 (3)	0.051 (3)	0.042 (3)	0.004 (2)	0.006 (2)	0.004 (2)
C14	0.031 (2)	0.047 (3)	0.040 (3)	−0.006 (2)	0.006 (2)	0.009 (2)
C15	0.042 (3)	0.054 (3)	0.068 (3)	0.005 (2)	0.010 (2)	0.015 (3)
C16	0.054 (3)	0.071 (3)	0.085 (4)	0.004 (3)	0.023 (3)	0.042 (3)
C17	0.051 (3)	0.082 (4)	0.058 (3)	−0.010 (3)	0.006 (3)	0.024 (3)
C18	0.128 (5)	0.061 (4)	0.077 (4)	0.019 (3)	−0.010 (4)	−0.030 (3)
C19	0.052 (3)	0.101 (4)	0.062 (3)	−0.009 (3)	−0.015 (2)	0.006 (3)
S1	0.0374 (6)	0.0314 (5)	0.0596 (7)	0.0060 (5)	0.0004 (5)	0.0109 (5)
S2	0.0375 (6)	0.0565 (7)	0.0448 (7)	−0.0009 (6)	0.0007 (5)	0.0019 (6)
S3	0.0463 (7)	0.0527 (7)	0.0380 (6)	0.0001 (6)	0.0054 (5)	−0.0031 (5)
O2	0.0384 (16)	0.0316 (15)	0.0452 (17)	0.0089 (13)	0.0084 (14)	0.0012 (13)
O3	0.067 (2)	0.0582 (19)	0.0393 (17)	0.0184 (16)	0.0200 (16)	0.0246 (15)
O4	0.0324 (15)	0.0485 (17)	0.0406 (16)	−0.0028 (13)	−0.0041 (14)	0.0086 (14)
O5	0.106 (3)	0.0393 (17)	0.0313 (16)	−0.0094 (17)	0.0191 (16)	−0.0010 (15)
N4	0.037 (2)	0.046 (2)	0.039 (2)	0.0003 (16)	0.0038 (16)	0.0039 (16)
N5	0.038 (2)	0.047 (2)	0.043 (2)	0.0016 (18)	0.0012 (17)	0.0032 (18)
N6	0.0282 (18)	0.0253 (17)	0.0302 (17)	−0.0001 (14)	0.0004 (14)	0.0099 (14)
N7	0.0414 (19)	0.0239 (17)	0.0293 (18)	−0.0033 (15)	0.0101 (15)	0.0011 (15)
N8	0.038 (2)	0.0287 (16)	0.0308 (19)	−0.0024 (16)	0.0055 (16)	0.0022 (16)
N9	0.044 (2)	0.080 (3)	0.057 (3)	0.010 (2)	0.000 (2)	0.016 (2)
N10	0.074 (3)	0.090 (3)	0.061 (3)	0.028 (3)	−0.009 (2)	0.022 (3)
N11	0.096 (3)	0.059 (3)	0.044 (2)	0.001 (3)	0.003 (2)	0.020 (2)
C20	0.036 (2)	0.043 (2)	0.053 (3)	−0.003 (2)	0.000 (2)	0.011 (2)
C21	0.031 (2)	0.027 (2)	0.037 (2)	−0.0021 (18)	0.0007 (18)	0.0008 (18)
C22	0.030 (2)	0.028 (2)	0.030 (2)	−0.0067 (18)	0.0040 (17)	0.0024 (18)
C23	0.036 (2)	0.028 (2)	0.035 (2)	−0.0032 (18)	−0.005 (2)	0.0028 (19)
C24	0.035 (2)	0.034 (2)	0.050 (3)	−0.0034 (19)	0.0070 (19)	0.004 (2)
C25	0.040 (2)	0.035 (2)	0.038 (2)	−0.0023 (19)	0.007 (2)	0.0035 (19)
C26	0.037 (2)	0.041 (2)	0.044 (3)	−0.001 (2)	0.003 (2)	−0.003 (2)
C27	0.044 (3)	0.062 (3)	0.065 (3)	0.006 (2)	0.008 (2)	0.001 (2)
C28	0.039 (2)	0.035 (2)	0.030 (2)	0.0001 (19)	0.0014 (19)	0.0055 (18)
C29	0.039 (2)	0.029 (2)	0.029 (2)	0.0000 (19)	0.0081 (18)	0.0008 (18)
C30	0.029 (2)	0.029 (2)	0.029 (2)	0.0037 (19)	0.0095 (19)	−0.0001 (18)
C31	0.036 (2)	0.036 (2)	0.030 (2)	−0.0018 (19)	0.0035 (19)	0.0063 (19)
C32	0.036 (2)	0.033 (2)	0.032 (2)	−0.0091 (18)	0.0000 (18)	0.0061 (18)
C33	0.055 (3)	0.048 (3)	0.041 (3)	−0.007 (2)	0.009 (2)	0.008 (2)

Geometric parameters (Å, º) top

S1—C20	1.805 (4)	C11—C12	1.365 (6)
S1—C28	1.797 (4)	C12—C13	1.378 (6)
S2—C24	1.815 (4)	C15—C16	1.489 (6)
S2—C25	1.742 (4)	C16—C17	1.461 (6)
S3—C26	1.733 (4)	C2—H2	0.9300
S3—C25	1.732 (4)	C3—H3	0.9300
O1—C15	1.425 (5)	C4—H4	0.9300
O1—C14	1.350 (5)	C5—H5	0.9300
O2—C23	1.243 (5)	C7—H7B	0.9700
O3—C23	1.247 (4)	C7—H7A	0.9700
O4—C30	1.197 (4)	C9—H9	0.9300
O5—C31	1.217 (4)	C10—H10	0.9300
N1—N2	1.382 (5)	C11—H11	0.9300
N1—C14	1.310 (5)	C12—H12	0.9300
N2—C7	1.448 (5)	C13—H13	0.9300
N2—C6	1.351 (5)	C15—H15B	0.9700
N3—C17	1.506 (5)	C15—H15A	0.9700
N3—C18	1.473 (6)	C16—H16A	0.9700
N3—C19	1.472 (5)	C16—H16B	0.9700
N3—H3N	0.96 (4)	C17—H17A	0.9700
N4—N5	1.392 (4)	C17—H17B	0.9700
N4—C25	1.292 (5)	C18—H18B	0.9600
N5—C26	1.288 (5)	C18—H18A	0.9600
N6—C28	1.466 (4)	C18—H18C	0.9600
N6—C30	1.385 (4)	C19—H19C	0.9600
N6—C22	1.400 (4)	C19—H19B	0.9600
N7—C31	1.338 (4)	C19—H19A	0.9600
N7—C29	1.430 (5)	C20—C21	1.515 (5)
N8—N9	1.325 (5)	C21—C24	1.496 (5)
N8—C33	1.320 (5)	C21—C22	1.339 (5)
N8—C32	1.454 (5)	C22—C23	1.524 (5)
N9—N10	1.279 (6)	C26—C27	1.491 (6)
N10—N11	1.348 (7)	C28—C29	1.548 (5)
N11—C33	1.307 (6)	C29—C30	1.540 (5)
N7—H7N	0.8600	C31—C32	1.510 (5)
C1—C14	1.406 (5)	C20—H20A	0.9700
C1—C2	1.396 (5)	C20—H20B	0.9700
C1—C6	1.393 (5)	C24—H24A	0.9700
C2—C3	1.351 (7)	C24—H24B	0.9700
C3—C4	1.397 (7)	C27—H27A	0.9600
C4—C5	1.368 (6)	C27—H27B	0.9600
C5—C6	1.399 (5)	C27—H27C	0.9600
C7—C8	1.501 (5)	C28—H28	0.9800
C8—C9	1.384 (6)	C29—H29	0.9800
C8—C13	1.380 (5)	C32—H32A	0.9700
C9—C10	1.374 (6)	C32—H32B	0.9700
C10—C11	1.368 (6)	C33—H33	0.9300

C20—S1—C28	93.40 (17)	C15—C16—H16B	109.00
C24—S2—C25	100.75 (17)	C17—C16—H16B	109.00
C25—S3—C26	87.07 (17)	H16A—C16—H16B	108.00
C14—O1—C15	118.3 (3)	C17—C16—H16A	109.00
N2—N1—C14	103.8 (3)	C16—C17—H17A	109.00
C6—N2—C7	127.5 (3)	C16—C17—H17B	109.00
N1—N2—C6	111.9 (3)	H17A—C17—H17B	108.00
N1—N2—C7	120.2 (3)	N3—C17—H17B	109.00
C17—N3—C18	114.0 (4)	N3—C17—H17A	109.00
C17—N3—C19	108.6 (3)	N3—C18—H18B	109.00
C18—N3—C19	108.8 (4)	N3—C18—H18A	110.00
C17—N3—H3N	108 (2)	H18A—C18—H18C	109.00
C18—N3—H3N	111 (2)	N3—C18—H18C	109.00
C19—N3—H3N	106 (2)	H18A—C18—H18B	109.00
N5—N4—C25	112.2 (3)	H18B—C18—H18C	109.00
N4—N5—C26	113.2 (3)	N3—C19—H19B	109.00
C22—N6—C30	133.6 (3)	N3—C19—H19C	109.00
C22—N6—C28	125.4 (3)	H19A—C19—H19C	109.00
C28—N6—C30	94.1 (3)	H19B—C19—H19C	109.00
C29—N7—C31	120.3 (3)	H19A—C19—H19B	109.00
N9—N8—C32	120.7 (3)	N3—C19—H19A	109.00
C32—N8—C33	131.6 (3)	S1—C20—C21	116.6 (3)
N9—N8—C33	107.6 (3)	C22—C21—C24	122.5 (3)
N8—N9—N10	107.5 (3)	C20—C21—C22	124.2 (3)
N9—N10—N11	110.3 (4)	C20—C21—C24	113.3 (3)
N10—N11—C33	105.2 (4)	N6—C22—C23	115.8 (3)
C29—N7—H7N	120.00	N6—C22—C21	119.1 (3)
C31—N7—H7N	120.00	C21—C22—C23	125.1 (3)
C6—C1—C14	103.5 (3)	O2—C23—C22	117.7 (3)
C2—C1—C6	120.5 (3)	O2—C23—O3	126.5 (3)
C2—C1—C14	135.8 (4)	O3—C23—C22	115.8 (3)
C1—C2—C3	118.5 (4)	S2—C24—C21	112.5 (2)
C2—C3—C4	120.8 (4)	S2—C25—N4	126.6 (3)
C3—C4—C5	122.3 (4)	S2—C25—S3	119.5 (2)
C4—C5—C6	116.9 (4)	S3—C25—N4	114.0 (3)
N2—C6—C1	107.0 (3)	S3—C26—C27	122.4 (3)
C1—C6—C5	120.9 (3)	S3—C26—N5	113.6 (3)
N2—C6—C5	132.1 (3)	N5—C26—C27	124.0 (4)
N2—C7—C8	114.8 (3)	N6—C28—C29	87.8 (2)
C7—C8—C9	121.4 (3)	S1—C28—C29	116.3 (2)
C7—C8—C13	120.0 (3)	S1—C28—N6	109.8 (2)
C9—C8—C13	118.6 (3)	N7—C29—C28	121.0 (3)
C8—C9—C10	120.8 (4)	N7—C29—C30	119.8 (3)
C9—C10—C11	119.9 (4)	C28—C29—C30	85.1 (3)
C10—C11—C12	120.1 (4)	O4—C30—N6	132.0 (3)
C11—C12—C13	120.4 (4)	N6—C30—C29	91.0 (3)
C8—C13—C12	120.3 (3)	O4—C30—C29	137.0 (3)
N1—C14—C1	113.8 (3)	O5—C31—C32	120.9 (3)
O1—C14—N1	124.2 (3)	O5—C31—N7	123.9 (3)
O1—C14—C1	122.1 (3)	N7—C31—C32	115.2 (3)
O1—C15—C16	107.1 (4)	N8—C32—C31	110.4 (3)
C15—C16—C17	114.2 (4)	N8—C33—N11	109.4 (4)
N3—C17—C16	113.8 (4)	S1—C20—H20A	108.00
C1—C2—H2	121.00	S1—C20—H20B	108.00
C3—C2—H2	121.00	C21—C20—H20A	108.00
C4—C3—H3	120.00	C21—C20—H20B	108.00
C2—C3—H3	120.00	H20A—C20—H20B	107.00
C3—C4—H4	119.00	S2—C24—H24A	109.00
C5—C4—H4	119.00	S2—C24—H24B	109.00
C6—C5—H5	122.00	C21—C24—H24A	109.00
C4—C5—H5	122.00	C21—C24—H24B	109.00
N2—C7—H7A	109.00	H24A—C24—H24B	108.00
C8—C7—H7B	109.00	C26—C27—H27A	109.00
N2—C7—H7B	109.00	C26—C27—H27B	109.00
C8—C7—H7A	109.00	C26—C27—H27C	110.00
H7A—C7—H7B	108.00	H27A—C27—H27B	109.00
C10—C9—H9	120.00	H27A—C27—H27C	109.00
C8—C9—H9	120.00	H27B—C27—H27C	109.00
C9—C10—H10	120.00	S1—C28—H28	113.00
C11—C10—H10	120.00	N6—C28—H28	113.00
C12—C11—H11	120.00	C29—C28—H28	113.00
C10—C11—H11	120.00	N7—C29—H29	110.00
C13—C12—H12	120.00	C28—C29—H29	110.00
C11—C12—H12	120.00	C30—C29—H29	110.00
C8—C13—H13	120.00	N8—C32—H32A	110.00
C12—C13—H13	120.00	N8—C32—H32B	110.00
O1—C15—H15B	110.00	C31—C32—H32A	110.00
C16—C15—H15A	110.00	C31—C32—H32B	110.00
O1—C15—H15A	110.00	H32A—C32—H32B	108.00
H15A—C15—H15B	109.00	N8—C33—H33	125.00
C16—C15—H15B	110.00	N11—C33—H33	125.00
C15—C16—H16A	109.00

C20—S1—C28—C29	155.3 (3)	N8—N9—N10—N11	0.1 (5)
C20—S1—C28—N6	57.8 (3)	N9—N10—N11—C33	−0.1 (5)
C28—S1—C20—C21	−47.1 (3)	N10—N11—C33—N8	0.2 (5)
C24—S2—C25—N4	12.6 (4)	C2—C1—C6—N2	−176.6 (3)
C24—S2—C25—S3	−167.0 (2)	C2—C1—C6—C5	2.6 (6)
C25—S2—C24—C21	−111.3 (3)	C14—C1—C2—C3	−175.0 (4)
C25—S3—C26—C27	−179.3 (3)	C14—C1—C6—C5	178.4 (3)
C26—S3—C25—N4	−0.1 (3)	C2—C1—C14—O1	−5.2 (7)
C25—S3—C26—N5	−0.4 (3)	C14—C1—C6—N2	−0.8 (4)
C26—S3—C25—S2	179.6 (2)	C6—C1—C2—C3	−0.9 (6)
C14—O1—C15—C16	−176.1 (3)	C6—C1—C14—N1	−0.5 (4)
C15—O1—C14—C1	171.1 (3)	C2—C1—C14—N1	174.4 (4)
C15—O1—C14—N1	−8.4 (5)	C6—C1—C14—O1	179.9 (3)
N2—N1—C14—C1	1.4 (4)	C1—C2—C3—C4	−1.7 (7)
C14—N1—N2—C7	−175.3 (3)	C2—C3—C4—C5	2.7 (7)
N2—N1—C14—O1	−179.0 (3)	C3—C4—C5—C6	−1.0 (6)
C14—N1—N2—C6	−1.9 (4)	C4—C5—C6—C1	−1.6 (6)
N1—N2—C6—C5	−177.3 (4)	C4—C5—C6—N2	177.3 (4)
C7—N2—C6—C5	−4.6 (7)	N2—C7—C8—C9	48.2 (5)
N1—N2—C7—C8	−102.2 (4)	N2—C7—C8—C13	−134.6 (4)
C6—N2—C7—C8	85.6 (5)	C7—C8—C13—C12	−176.7 (4)
C7—N2—C6—C1	174.5 (3)	C9—C8—C13—C12	0.6 (6)
N1—N2—C6—C1	1.7 (4)	C13—C8—C9—C10	−1.1 (6)
C19—N3—C17—C16	−164.0 (4)	C7—C8—C9—C10	176.1 (4)
C18—N3—C17—C16	74.5 (5)	C8—C9—C10—C11	1.1 (6)
C25—N4—N5—C26	−0.7 (4)	C9—C10—C11—C12	−0.5 (7)
N5—N4—C25—S3	0.4 (4)	C10—C11—C12—C13	0.0 (7)
N5—N4—C25—S2	−179.2 (3)	C11—C12—C13—C8	0.0 (6)
N4—N5—C26—S3	0.6 (4)	O1—C15—C16—C17	59.5 (5)
N4—N5—C26—C27	179.6 (3)	C15—C16—C17—N3	−173.0 (4)
C30—N6—C22—C21	−133.6 (4)	S1—C20—C21—C22	19.2 (5)
C30—N6—C22—C23	49.7 (5)	S1—C20—C21—C24	−163.3 (2)
C28—N6—C22—C23	−167.3 (3)	C20—C21—C22—N6	6.9 (5)
C30—N6—C28—C29	−11.3 (3)	C20—C21—C22—C23	−176.7 (3)
C22—N6—C28—S1	−48.2 (4)	C20—C21—C24—S2	81.3 (3)
C22—N6—C28—C29	−165.4 (3)	C22—C21—C24—S2	−101.2 (4)
C22—N6—C30—O4	−16.5 (7)	C24—C21—C22—N6	−170.3 (3)
C28—N6—C22—C21	9.4 (5)	C24—C21—C22—C23	6.0 (6)
C30—N6—C28—S1	106.0 (2)	N6—C22—C23—O2	32.8 (5)
C22—N6—C30—C29	161.9 (4)	C21—C22—C23—O3	37.0 (5)
C28—N6—C30—O4	−167.1 (4)	N6—C22—C23—O3	−146.5 (3)
C28—N6—C30—C29	11.3 (3)	C21—C22—C23—O2	−143.7 (4)
C29—N7—C31—O5	−1.4 (5)	S1—C28—C29—N7	21.1 (4)
C31—N7—C29—C30	−145.3 (3)	S1—C28—C29—C30	−100.9 (3)
C29—N7—C31—C32	176.6 (3)	N6—C28—C29—N7	132.1 (3)
C31—N7—C29—C28	111.5 (4)	N6—C28—C29—C30	10.1 (2)
N9—N8—C32—C31	−69.8 (4)	N7—C29—C30—O4	44.4 (6)
N9—N8—C33—N11	−0.1 (4)	N7—C29—C30—N6	−133.9 (3)
C32—N8—C33—N11	−177.9 (3)	C28—C29—C30—O4	167.5 (5)
C33—N8—N9—N10	0.0 (4)	C28—C29—C30—N6	−10.7 (3)
C32—N8—N9—N10	178.1 (4)	O5—C31—C32—N8	−38.1 (5)
C33—N8—C32—C31	107.8 (4)	N7—C31—C32—N8	143.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···O3ⁱ	0.96 (4)	1.70 (4)	2.660 (4)	174 (3)
N7—H7N···O2ⁱⁱ	0.8600	2.0200	2.868 (3)	167.00
C18—H18C···O4ⁱⁱⁱ	0.9600	2.5200	3.303 (5)	139.00
C24—H24A···N4	0.9700	2.4100	2.961 (5)	116.00
C24—H24B···O3	0.9700	2.3800	2.882 (4)	112.00
C32—H32A···O2^iv	0.9700	2.2800	3.218 (4)	164.00
C32—H32B···O2ⁱⁱ	0.9700	2.5000	3.318 (4)	142.00
C19—H19B···CgA	0.96	2.91	3.869 (6)	174
C20—H20B···CgD	0.97	2.72	3.642 (4)	158
C29—H29···CgAⁱⁱ	0.98	2.99	3.861 (4)	149

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

Experimental details

Crystal data
Chemical formula	C₁₉H₂₄N₃O⁺·C₁₄H₁₃N₈O₄S₃⁻
M_r	763.92
Crystal system, space group	Monoclinic, C2
Temperature (K)	296
a, b, c (Å)	44.409 (3), 7.1777 (5), 11.2683 (8)
β (°)	90.587 (8)
V (Å³)	3591.6 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
Crystal size (mm)	0.24 × 0.14 × 0.12

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.957, 0.968
No. of measured, independent and observed [I > 2σ(I)] reflections	34321, 6750, 4092
R_int	0.088
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.095, 1.00
No. of reflections	6750
No. of parameters	475
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.23
Absolute structure	Flack (1983), 2918 Friedal Pairs
Absolute structure parameter	−0.07 (7)

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).