Copper(II)- and gold(III)-mediated cyclization of a thio­urea to a substituted 2-amino­benzo­thia­zole

Benzo­thia­zole derivatives are a class of privileged mol­ecules due to their biological activity and pharmaceutical applications. One route to these mol­ecules is via intra­molecular cyclization of thio­ureas to form substituted 2-amino­benzo­thia­zoles, but this often requires harsh conditions or employs expensive metal catalysts. Herein, the copper(II)- and gold(III)-mediated cyclizations of thio­ureas to substituted 2-amino­benzo­thia­zoles are reported. The single-crystal X-ray structures of the thio­urea N-(3-meth­oxy­phen­yl)-N′-(pyridin-2-yl)thio­urea, C₁₃H₁₃N₃OS, and the inter­mediate metal complexes aqua­bis­[5-meth­oxy-N-(pyridin-2-yl-κN)-1,3-benzo­thia­zol-2-amine-κN³]copper(II)­ dinitrate, [Cu(C₁₃H₁₁N₃OS)₂(H₂O)](NO₃)₂, and bis­{2-[(5-meth­oxy-1,3-benzo­thia­zol-2-yl)amino]­pyridin-1-ium} di­chlorido­gold(I) chloride monohydrate, (C₁₃H₁₂N₃OS)₂[AuCl₂]Cl·H₂O, are reported. The copper complex exhibits a distorted trigonal–bipyramidal geometry, with direct metal-to-benzo­thia­zole-ligand coordination, while the gold complex is a salt containing the protonated uncoordinated benzo­thia­zole, and offers evidence that metal reduction (in this case, Au^III to Au^I) is required for the cyclization to proceed. As such, this study provides further mechanistic insight into the role of the metal cations in these transformations.

Computing details

For all structures, data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

N-(3-Methoxyphenyl)-N'-(pyridin-2-yl)thiourea (n17037)

Crystal data

C13H13N3OS	Z = 2
Mr = 259.32	F(000) = 272
Triclinic, P1	Dx = 1.374 Mg m^−3
a = 8.4341 (2) Å	Cu Kα radiation, λ = 1.54184 Å
b = 8.6991 (2) Å	Cell parameters from 11716 reflections
c = 10.1083 (2) Å	θ = 4.8–65.6°
α = 91.249 (2)°	µ = 2.22 mm^−1
β = 113.506 (2)°	T = 173 K
γ = 110.292 (2)°	Prism, colorless
V = 626.73 (3) Å^3	0.50 × 0.32 × 0.11 mm

Data collection

Bruker APEXII CCD diffractometer	2125 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Cu) X-ray Source	2096 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ω and φ scans	θmax = 65.6°, θmin = 4.9°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	h = −9→9
Tmin = 0.668, Tmax = 1.000	k = −10→9
12480 measured reflections	l = −11→11

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.084	w = 1/[σ^2(Fo^2) + (0.0415P)^2 + 0.2867P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max < 0.001
2125 reflections	Δρmax = 0.25 e Å^−3
172 parameters	Δρmin = −0.26 e Å^−3
1 restraint

Special details

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.

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

	x	y	z	Uiso*/Ueq
S1	0.37970 (5)	0.74874 (4)	0.88794 (4)	0.02876 (15)
O1	0.28022 (18)	0.16770 (13)	0.55060 (13)	0.0385 (3)
N1	0.87028 (18)	1.03625 (15)	0.77940 (14)	0.0266 (3)
N2	0.69580 (18)	0.98474 (15)	0.91734 (14)	0.0236 (3)
H2	0.680 (3)	1.026 (2)	0.9837 (19)	0.031 (5)*
N3	0.55882 (18)	0.76960 (15)	0.71919 (14)	0.0244 (3)
H3	0.648 (3)	0.821 (2)	0.701 (2)	0.040 (5)*
C1	1.0155 (2)	1.1378 (2)	0.75682 (18)	0.0305 (4)
H1	1.032837	1.102259	0.675841	0.037*
C2	1.1401 (2)	1.29027 (19)	0.84484 (18)	0.0303 (4)
H2A	1.240860	1.358462	0.825316	0.036*
C3	1.1143 (2)	1.34169 (19)	0.96316 (18)	0.0297 (4)
H3A	1.197544	1.446526	1.025915	0.036*
C4	0.9675 (2)	1.23997 (19)	0.98894 (17)	0.0268 (3)
H4	0.948182	1.272457	1.069814	0.032*
C5	0.84737 (19)	1.08752 (17)	0.89301 (15)	0.0215 (3)
C6	0.5532 (2)	0.83663 (17)	0.83584 (15)	0.0215 (3)
C7	0.4118 (2)	0.62124 (18)	0.61906 (16)	0.0225 (3)
C8	0.4249 (2)	0.46847 (18)	0.64025 (16)	0.0239 (3)
H8	0.528426	0.461636	0.721088	0.029*
C9	0.2840 (2)	0.32518 (18)	0.54118 (16)	0.0247 (3)
C10	0.1332 (2)	0.33607 (19)	0.42311 (17)	0.0297 (4)
H10	0.036818	0.238022	0.355995	0.036*
C11	0.1238 (2)	0.4893 (2)	0.40360 (18)	0.0349 (4)
H11	0.020819	0.496461	0.322431	0.042*
C12	0.2633 (2)	0.6337 (2)	0.50136 (18)	0.0313 (4)
H12	0.256619	0.739342	0.487419	0.038*
C13	0.4251 (3)	0.1471 (2)	0.6749 (2)	0.0457 (5)
H13A	0.402596	0.028361	0.670313	0.069*
H13B	0.425443	0.190958	0.765138	0.069*
H13C	0.546803	0.207955	0.674384	0.069*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0302 (2)	0.0208 (2)	0.0309 (2)	−0.00158 (16)	0.01936 (18)	−0.00503 (15)
O1	0.0508 (7)	0.0212 (6)	0.0308 (6)	0.0126 (5)	0.0071 (5)	−0.0007 (5)
N1	0.0268 (7)	0.0217 (6)	0.0297 (7)	0.0043 (5)	0.0155 (6)	−0.0001 (5)
N2	0.0258 (6)	0.0191 (6)	0.0226 (6)	0.0028 (5)	0.0126 (5)	−0.0036 (5)
N3	0.0230 (7)	0.0203 (6)	0.0260 (7)	0.0017 (5)	0.0131 (5)	−0.0042 (5)
C1	0.0311 (8)	0.0276 (8)	0.0350 (9)	0.0076 (7)	0.0198 (7)	0.0035 (7)
C2	0.0268 (8)	0.0248 (8)	0.0388 (9)	0.0057 (6)	0.0174 (7)	0.0077 (7)
C3	0.0252 (8)	0.0206 (7)	0.0316 (8)	0.0014 (6)	0.0076 (7)	−0.0001 (6)
C4	0.0270 (8)	0.0235 (8)	0.0246 (8)	0.0053 (6)	0.0100 (6)	−0.0012 (6)
C5	0.0210 (7)	0.0193 (7)	0.0220 (7)	0.0070 (6)	0.0082 (6)	0.0034 (6)
C6	0.0232 (7)	0.0165 (7)	0.0220 (7)	0.0063 (6)	0.0087 (6)	0.0005 (6)
C7	0.0224 (7)	0.0202 (7)	0.0232 (7)	0.0035 (6)	0.0127 (6)	−0.0041 (6)
C8	0.0257 (8)	0.0252 (8)	0.0198 (7)	0.0088 (6)	0.0101 (6)	0.0002 (6)
C9	0.0329 (8)	0.0196 (7)	0.0218 (7)	0.0076 (6)	0.0145 (6)	−0.0006 (6)
C10	0.0281 (8)	0.0245 (8)	0.0253 (8)	0.0037 (6)	0.0072 (6)	−0.0058 (6)
C11	0.0292 (8)	0.0332 (9)	0.0304 (9)	0.0116 (7)	0.0024 (7)	−0.0021 (7)
C12	0.0332 (9)	0.0240 (8)	0.0338 (9)	0.0126 (7)	0.0107 (7)	0.0002 (7)
C13	0.0624 (12)	0.0315 (9)	0.0382 (10)	0.0249 (9)	0.0114 (9)	0.0076 (8)

Geometric parameters (Å, º)

S1—C6	1.6910 (15)	C3—C4	1.375 (2)
O1—C9	1.3655 (19)	C4—H4	0.9500
O1—C13	1.428 (2)	C4—C5	1.398 (2)
N1—C1	1.347 (2)	C7—C8	1.386 (2)
N1—C5	1.3303 (19)	C7—C12	1.381 (2)
N2—H2	0.833 (17)	C8—H8	0.9500
N2—C5	1.4007 (19)	C8—C9	1.392 (2)
N2—C6	1.3689 (19)	C9—C10	1.389 (2)
N3—H3	0.828 (17)	C10—H10	0.9500
N3—C6	1.3290 (19)	C10—C11	1.377 (2)
N3—C7	1.4352 (18)	C11—H11	0.9500
C1—H1	0.9500	C11—C12	1.390 (2)
C1—C2	1.375 (2)	C12—H12	0.9500
C2—H2A	0.9500	C13—H13A	0.9800
C2—C3	1.389 (2)	C13—H13B	0.9800
C3—H3A	0.9500	C13—H13C	0.9800
C9—O1—C13	117.87 (13)	N3—C6—N2	117.86 (13)
C5—N1—C1	117.73 (13)	C8—C7—N3	119.07 (13)
C5—N2—H2	115.5 (13)	C12—C7—N3	119.58 (13)
C6—N2—H2	113.8 (13)	C12—C7—C8	121.32 (14)
C6—N2—C5	129.96 (13)	C7—C8—H8	120.5
C6—N3—H3	117.5 (14)	C7—C8—C9	118.93 (14)
C6—N3—C7	123.30 (13)	C9—C8—H8	120.5
C7—N3—H3	119.1 (14)	O1—C9—C8	124.51 (14)
N1—C1—H1	118.3	O1—C9—C10	115.24 (13)
N1—C1—C2	123.43 (15)	C10—C9—C8	120.24 (14)
C2—C1—H1	118.3	C9—C10—H10	120.1
C1—C2—H2A	121.0	C11—C10—C9	119.82 (14)
C1—C2—C3	118.07 (14)	C11—C10—H10	120.1
C3—C2—H2A	121.0	C10—C11—H11	119.6
C2—C3—H3A	120.2	C10—C11—C12	120.72 (15)
C4—C3—C2	119.63 (14)	C12—C11—H11	119.6
C4—C3—H3A	120.2	C7—C12—C11	118.96 (15)
C3—C4—H4	120.9	C7—C12—H12	120.5
C3—C4—C5	118.25 (14)	C11—C12—H12	120.5
C5—C4—H4	120.9	O1—C13—H13A	109.5
N1—C5—N2	118.64 (13)	O1—C13—H13B	109.5
N1—C5—C4	122.89 (13)	O1—C13—H13C	109.5
C4—C5—N2	118.47 (13)	H13A—C13—H13B	109.5
N2—C6—S1	118.69 (11)	H13A—C13—H13C	109.5
N3—C6—S1	123.46 (11)	H13B—C13—H13C	109.5
O1—C9—C10—C11	−179.94 (15)	C6—N2—C5—C4	175.50 (14)
N1—C1—C2—C3	0.0 (2)	C6—N3—C7—C8	−94.15 (17)
N3—C7—C8—C9	−178.66 (13)	C6—N3—C7—C12	87.82 (19)
N3—C7—C12—C11	178.71 (14)	C7—N3—C6—S1	4.4 (2)
C1—N1—C5—N2	179.20 (13)	C7—N3—C6—N2	−175.49 (13)
C1—N1—C5—C4	−0.5 (2)	C7—C8—C9—O1	−179.53 (14)
C1—C2—C3—C4	0.2 (2)	C7—C8—C9—C10	0.1 (2)
C2—C3—C4—C5	−0.6 (2)	C8—C7—C12—C11	0.7 (2)
C3—C4—C5—N1	0.7 (2)	C8—C9—C10—C11	0.4 (2)
C3—C4—C5—N2	−178.94 (13)	C9—C10—C11—C12	−0.3 (3)
C5—N1—C1—C2	0.1 (2)	C10—C11—C12—C7	−0.2 (3)
C5—N2—C6—S1	−175.35 (12)	C12—C7—C8—C9	−0.7 (2)
C5—N2—C6—N3	4.6 (2)	C13—O1—C9—C8	3.6 (2)
C6—N2—C5—N1	−4.2 (2)	C13—O1—C9—C10	−176.05 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1^i	0.83 (2)	2.62 (2)	3.3882 (13)	154 (2)
N3—H3···N1	0.83 (2)	1.99 (2)	2.6624 (17)	138 (2)

Symmetry code: (i) −x+1, −y+2, −z+2.

Aquabis[5-methoxy-N-(pyridin-2-yl-κN)benzothiazol-2-amine-κN³]copper(II) dinitrate (b17199)

Crystal data

[Cu(C13H11N3OS)2(H2O)](NO3)2	Dx = 1.679 Mg m^−3
Mr = 720.19	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcn	Cell parameters from 62086 reflections
a = 18.1534 (4) Å	θ = 2.2–39.5°
b = 7.1814 (1) Å	µ = 0.98 mm^−1
c = 21.8523 (4) Å	T = 110 K
V = 2848.81 (9) Å^3	Prism, green
Z = 4	0.33 × 0.23 × 0.17 mm
F(000) = 1476

Data collection

Bruker APEXII CCD diffractometer	2703 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	2703 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
ω and φ scans	θmax = 25.7°, θmin = 2.9°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	h = −22→17
Tmin = 0.835, Tmax = 1.000	k = −8→8
72311 measured reflections	l = −26→26

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.105	w = 1/[σ^2(Fo^2) + (0.0189P)^2 + 9.2626P] where P = (Fo^2 + 2Fc^2)/3
S = 1.34	(Δ/σ)max < 0.001
2703 reflections	Δρmax = 0.79 e Å^−3
215 parameters	Δρmin = −0.66 e Å^−3
3 restraints

Special details

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.500000	0.47025 (8)	0.750000	0.01397 (16)
S1	0.35592 (5)	0.40264 (13)	0.58540 (4)	0.0215 (2)
O1	0.66894 (15)	0.2340 (4)	0.56003 (12)	0.0299 (6)
O2	0.500000	0.1889 (5)	0.750000	0.0364 (10)
H2A	0.5393 (11)	0.1272 (12)	0.759 (3)	0.055*	0.5
H2B	0.468 (2)	0.1274 (12)	0.729 (2)	0.055*	0.5
N1	0.41384 (14)	0.6490 (4)	0.77375 (12)	0.0149 (6)
N2	0.33369 (15)	0.5337 (4)	0.69802 (13)	0.0179 (6)
H2	0.2892 (12)	0.525 (6)	0.6845 (16)	0.021*
N3	0.45591 (15)	0.4536 (4)	0.66819 (12)	0.0145 (6)
C1	0.42390 (19)	0.7627 (5)	0.82261 (15)	0.0190 (7)
H1	0.472590	0.782092	0.837217	0.023*
C2	0.3669 (2)	0.8512 (5)	0.85188 (16)	0.0238 (8)
H2C	0.375935	0.931356	0.885621	0.029*
C3	0.2957 (2)	0.8207 (5)	0.83105 (16)	0.0245 (8)
H3	0.255062	0.873649	0.852165	0.029*
C4	0.28424 (18)	0.7144 (5)	0.78011 (16)	0.0204 (7)
H4	0.236004	0.695842	0.764397	0.024*
C5	0.34564 (18)	0.6334 (4)	0.75162 (15)	0.0166 (7)
C6	0.38493 (18)	0.4711 (5)	0.65788 (14)	0.0159 (7)
C7	0.49227 (19)	0.3806 (4)	0.61717 (15)	0.0179 (7)
C8	0.5671 (2)	0.3422 (5)	0.61330 (15)	0.0209 (7)
H8	0.598738	0.364950	0.647094	0.025*
C9	0.5946 (2)	0.2700 (5)	0.55917 (16)	0.0229 (8)
C10	0.5492 (2)	0.2336 (5)	0.50918 (16)	0.0248 (8)
H10	0.569235	0.183235	0.472601	0.030*
C11	0.4744 (2)	0.2715 (5)	0.51330 (16)	0.0246 (8)
H11	0.442796	0.248001	0.479545	0.030*
C12	0.44650 (19)	0.3441 (5)	0.56721 (15)	0.0199 (7)
C13	0.7001 (2)	0.1407 (6)	0.50876 (18)	0.0347 (10)
H13A	0.696266	0.220385	0.472504	0.052*
H13B	0.673452	0.024068	0.501516	0.052*
H13C	0.752063	0.113305	0.516961	0.052*
O3	0.36773 (14)	0.0698 (4)	0.70721 (12)	0.0281 (6)
O4	0.29737 (14)	−0.0570 (4)	0.63928 (12)	0.0302 (6)
O5	0.41492 (14)	−0.0873 (4)	0.63256 (13)	0.0340 (7)
N4	0.36037 (15)	−0.0238 (4)	0.65980 (13)	0.0197 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0135 (3)	0.0163 (3)	0.0122 (3)	0.000	−0.0014 (2)	0.000
S1	0.0219 (4)	0.0260 (5)	0.0168 (4)	−0.0031 (4)	−0.0056 (3)	0.0002 (3)
O1	0.0295 (14)	0.0349 (15)	0.0252 (13)	0.0057 (12)	0.0083 (11)	−0.0043 (12)
O2	0.046 (3)	0.0155 (18)	0.048 (2)	0.000	−0.033 (2)	0.000
N1	0.0120 (13)	0.0151 (13)	0.0177 (13)	0.0017 (11)	0.0007 (10)	0.0004 (11)
N2	0.0121 (13)	0.0196 (15)	0.0218 (14)	−0.0023 (11)	−0.0011 (11)	0.0020 (12)
N3	0.0183 (14)	0.0141 (14)	0.0112 (12)	−0.0012 (11)	0.0000 (10)	0.0014 (11)
C1	0.0197 (17)	0.0173 (16)	0.0200 (16)	0.0001 (13)	−0.0019 (13)	−0.0021 (14)
C2	0.032 (2)	0.0183 (18)	0.0214 (17)	0.0021 (15)	0.0020 (15)	−0.0016 (14)
C3	0.0248 (18)	0.0224 (18)	0.0264 (18)	0.0071 (15)	0.0091 (15)	0.0028 (15)
C4	0.0143 (16)	0.0193 (17)	0.0276 (18)	0.0011 (13)	0.0016 (14)	0.0063 (15)
C5	0.0180 (16)	0.0117 (15)	0.0202 (16)	−0.0021 (12)	0.0008 (13)	0.0037 (13)
C6	0.0215 (16)	0.0136 (16)	0.0127 (15)	−0.0039 (13)	−0.0017 (13)	0.0024 (13)
C7	0.0266 (18)	0.0109 (15)	0.0162 (15)	−0.0008 (14)	0.0011 (13)	0.0016 (12)
C8	0.0248 (18)	0.0191 (17)	0.0189 (16)	−0.0013 (15)	0.0002 (14)	−0.0018 (14)
C9	0.0259 (18)	0.0180 (17)	0.0249 (18)	0.0003 (15)	0.0053 (15)	0.0007 (15)
C10	0.038 (2)	0.0168 (17)	0.0194 (18)	−0.0019 (16)	0.0061 (15)	−0.0022 (14)
C11	0.038 (2)	0.0204 (18)	0.0155 (17)	−0.0066 (16)	−0.0015 (15)	0.0000 (14)
C12	0.0251 (18)	0.0169 (16)	0.0178 (16)	−0.0037 (14)	0.0003 (14)	0.0029 (14)
C13	0.040 (2)	0.036 (2)	0.028 (2)	0.0104 (19)	0.0169 (17)	−0.0028 (18)
O3	0.0310 (14)	0.0261 (14)	0.0272 (13)	−0.0052 (11)	0.0005 (11)	−0.0018 (12)
O4	0.0180 (13)	0.0412 (17)	0.0314 (14)	−0.0043 (12)	−0.0017 (11)	−0.0054 (13)
O5	0.0202 (13)	0.0452 (17)	0.0367 (15)	0.0088 (13)	0.0059 (11)	0.0007 (14)
N4	0.0165 (14)	0.0191 (15)	0.0234 (15)	−0.0001 (12)	0.0011 (12)	0.0047 (12)

Geometric parameters (Å, º)

Cu1—O2	2.020 (4)	C2—H2C	0.9500
Cu1—N1^i	2.089 (3)	C2—C3	1.387 (5)
Cu1—N1	2.089 (3)	C3—H3	0.9500
Cu1—N3^i	1.962 (3)	C3—C4	1.366 (5)
Cu1—N3	1.962 (3)	C4—H4	0.9500
S1—C6	1.740 (3)	C4—C5	1.403 (5)
S1—C12	1.743 (4)	C7—C8	1.388 (5)
O1—C9	1.374 (4)	C7—C12	1.397 (5)
O1—C13	1.423 (4)	C8—H8	0.9500
O2—H2A^i	0.861 (7)	C8—C9	1.385 (5)
O2—H2A	0.861 (14)	C9—C10	1.393 (5)
O2—H2B^i	0.861 (7)	C10—H10	0.9500
O2—H2B	0.861 (14)	C10—C11	1.387 (5)
N1—C1	1.357 (4)	C11—H11	0.9500
N1—C5	1.334 (4)	C11—C12	1.384 (5)
N2—H2	0.861 (18)	C13—H13A	0.9800
N2—C5	1.390 (4)	C13—H13B	0.9800
N2—C6	1.355 (4)	C13—H13C	0.9800
N3—C6	1.314 (4)	O3—N4	1.242 (4)
N3—C7	1.398 (4)	O4—N4	1.251 (4)
C1—H1	0.9500	O5—N4	1.242 (4)
C1—C2	1.372 (5)
O2—Cu1—N1	127.91 (8)	C4—C3—H3	120.1
O2—Cu1—N1^i	127.91 (7)	C3—C4—H4	120.9
N1^i—Cu1—N1	104.18 (15)	C3—C4—C5	118.2 (3)
N3—Cu1—O2	86.51 (8)	C5—C4—H4	120.9
N3^i—Cu1—O2	86.51 (8)	N1—C5—N2	119.6 (3)
N3—Cu1—N1	87.61 (11)	N1—C5—C4	122.8 (3)
N3—Cu1—N1^i	96.69 (11)	N2—C5—C4	117.6 (3)
N3^i—Cu1—N1^i	87.61 (11)	N2—C6—S1	118.4 (2)
N3^i—Cu1—N1	96.69 (11)	N3—C6—S1	115.2 (2)
N3—Cu1—N3^i	173.03 (16)	N3—C6—N2	126.4 (3)
C6—S1—C12	89.44 (16)	C8—C7—N3	125.8 (3)
C9—O1—C13	117.9 (3)	C8—C7—C12	119.8 (3)
Cu1—O2—H2A	121.0	C12—C7—N3	114.4 (3)
Cu1—O2—H2A^i	121.0 (8)	C7—C8—H8	120.7
Cu1—O2—H2B	120.9	C9—C8—C7	118.6 (3)
Cu1—O2—H2B^i	120.9 (8)	C9—C8—H8	120.7
H2A—O2—H2A^i	118.0	O1—C9—C8	114.4 (3)
H2A—O2—H2B	114.6	O1—C9—C10	123.8 (3)
H2A^i—O2—H2B^i	114.6	C8—C9—C10	121.8 (3)
H2B—O2—H2B^i	118.2	C9—C10—H10	120.3
C1—N1—Cu1	117.7 (2)	C11—C10—C9	119.4 (3)
C5—N1—Cu1	123.6 (2)	C11—C10—H10	120.3
C5—N1—C1	117.4 (3)	C10—C11—H11	120.4
C5—N2—H2	118 (3)	C12—C11—C10	119.2 (3)
C6—N2—H2	113 (3)	C12—C11—H11	120.4
C6—N2—C5	127.5 (3)	C7—C12—S1	109.7 (3)
C6—N3—Cu1	123.4 (2)	C11—C12—S1	129.1 (3)
C6—N3—C7	111.2 (3)	C11—C12—C7	121.2 (3)
C7—N3—Cu1	123.8 (2)	O1—C13—H13A	109.5
N1—C1—H1	118.5	O1—C13—H13B	109.5
N1—C1—C2	122.9 (3)	O1—C13—H13C	109.5
C2—C1—H1	118.5	H13A—C13—H13B	109.5
C1—C2—H2C	120.8	H13A—C13—H13C	109.5
C1—C2—C3	118.5 (3)	H13B—C13—H13C	109.5
C3—C2—H2C	120.8	O3—N4—O4	120.0 (3)
C2—C3—H3	120.1	O3—N4—O5	120.8 (3)
C4—C3—C2	119.9 (3)	O5—N4—O4	119.1 (3)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2B···O3	0.86	1.92	2.715 (3)	151 (3)
O2—H2A···O3^i	0.86	1.89	2.715 (3)	160
N2—H2···O4^ii	0.86 (2)	1.95 (2)	2.781 (4)	162 (4)
C1—H1···O5^iii	0.95	2.34	3.268 (4)	165

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

Bis{2-[(5-methoxy-1,3-benzothiazol-2-yl)amino]pyridin-1-ium} dichloridogold(I) chloride monohydrate (b18056)

Crystal data

(C13H12N3OS)2[AuCl2]Cl·H2O	Z = 2
Mr = 837.96	F(000) = 820
Triclinic, P1	Dx = 1.907 Mg m^−3
a = 10.0052 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.5940 (2) Å	Cell parameters from 104589 reflections
c = 12.9412 (1) Å	θ = 2.0–50.4°
α = 111.867 (1)°	µ = 5.50 mm^−1
β = 97.271 (1)°	T = 110 K
γ = 99.755 (1)°	Prism, colorless
V = 1459.03 (3) Å^3	0.31 × 0.11 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer	5973 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	5961 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
ω and φ scans	θmax = 26.4°, θmin = 2.1°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	h = −12→12
Tmin = 0.473, Tmax = 1.000	k = −15→15
85384 measured reflections	l = −16→16

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.018	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.041	w = 1/[σ^2(Fo^2) + (0.0122P)^2 + 2.4258P] where P = (Fo^2 + 2Fc^2)/3
S = 1.21	(Δ/σ)max = 0.004
5973 reflections	Δρmax = 0.76 e Å^−3
396 parameters	Δρmin = −0.85 e Å^−3
5 restraints

Special details

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.

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

	x	y	z	Uiso*/Ueq
S2	0.41939 (6)	0.75769 (5)	0.72552 (5)	0.01731 (12)
O2	0.69431 (19)	0.54362 (16)	0.99756 (15)	0.0200 (4)
N4	0.6790 (2)	0.59876 (18)	0.46614 (18)	0.0151 (4)
H4	0.685 (3)	0.588 (3)	0.524 (2)	0.026 (9)*
N5	0.5244 (2)	0.71619 (19)	0.53596 (18)	0.0166 (4)
H5	0.475 (3)	0.762 (2)	0.527 (3)	0.030 (9)*
N6	0.6055 (2)	0.63748 (18)	0.66463 (17)	0.0162 (4)
C14	0.7519 (3)	0.5493 (2)	0.3865 (2)	0.0188 (5)
H14	0.809858	0.500715	0.398392	0.023*
C15	0.7421 (3)	0.5692 (2)	0.2899 (2)	0.0203 (5)
H15	0.792297	0.534357	0.233677	0.024*
C16	0.6570 (3)	0.6418 (2)	0.2745 (2)	0.0192 (5)
H16	0.650252	0.657322	0.207853	0.023*
C17	0.5831 (3)	0.6909 (2)	0.3550 (2)	0.0176 (5)
H17	0.524868	0.739685	0.344054	0.021*
C18	0.5944 (2)	0.6682 (2)	0.4532 (2)	0.0147 (5)
C19	0.5267 (2)	0.6976 (2)	0.6343 (2)	0.0151 (5)
C20	0.5867 (2)	0.6376 (2)	0.7700 (2)	0.0154 (5)
C21	0.6560 (2)	0.5815 (2)	0.8265 (2)	0.0158 (5)
H21	0.719188	0.537189	0.793601	0.019*
C22	0.6301 (2)	0.5923 (2)	0.9322 (2)	0.0162 (5)
C23	0.5347 (3)	0.6558 (2)	0.9798 (2)	0.0169 (5)
H23	0.518375	0.661493	1.052217	0.020*
C24	0.4644 (3)	0.7100 (2)	0.9233 (2)	0.0180 (5)
H24	0.399545	0.752526	0.955570	0.022*
C25	0.4912 (2)	0.7005 (2)	0.8175 (2)	0.0149 (5)
C26	0.7772 (3)	0.4653 (3)	0.9462 (2)	0.0249 (6)
H26A	0.721112	0.401457	0.875988	0.037*
H26B	0.811827	0.432201	0.998916	0.037*
H26C	0.855757	0.508348	0.928260	0.037*
S1	0.67232 (6)	1.00715 (5)	0.96345 (5)	0.01600 (12)
O1	0.93392 (19)	0.79817 (16)	1.24720 (14)	0.0197 (4)
N1	0.9505 (2)	0.85301 (18)	0.71852 (18)	0.0162 (4)
H1	0.960 (3)	0.849 (3)	0.779 (2)	0.025 (8)*
N2	0.7788 (2)	0.95630 (18)	0.77372 (17)	0.0158 (4)
H2	0.723 (3)	0.993 (3)	0.755 (3)	0.041 (10)*
N3	0.8627 (2)	0.88981 (18)	0.91125 (17)	0.0149 (4)
C1	1.0317 (3)	0.8078 (2)	0.6446 (2)	0.0195 (5)
H1A	1.097152	0.768019	0.663529	0.023*
C2	1.0195 (3)	0.8194 (2)	0.5435 (2)	0.0219 (5)
H2A	1.075907	0.787838	0.491432	0.026*
C3	0.9224 (3)	0.8786 (2)	0.5176 (2)	0.0204 (5)
H3	0.911822	0.886335	0.446918	0.024*
C4	0.8424 (3)	0.9256 (2)	0.5936 (2)	0.0182 (5)
H4A	0.777686	0.966903	0.576547	0.022*
C5	0.8574 (2)	0.9118 (2)	0.6971 (2)	0.0155 (5)
C6	0.7823 (2)	0.9451 (2)	0.8760 (2)	0.0140 (5)
C7	0.8413 (2)	0.8923 (2)	1.0163 (2)	0.0143 (5)
C8	0.9101 (2)	0.8387 (2)	1.0766 (2)	0.0148 (5)
H8	0.978627	0.798434	1.048471	0.018*
C9	0.8748 (3)	0.8464 (2)	1.1788 (2)	0.0161 (5)
C10	0.7728 (3)	0.9049 (2)	1.2202 (2)	0.0177 (5)
H10	0.750185	0.907910	1.290212	0.021*
C11	0.7047 (3)	0.9584 (2)	1.1609 (2)	0.0179 (5)
H11	0.635812	0.998071	1.189050	0.021*
C12	0.7408 (2)	0.9520 (2)	1.0584 (2)	0.0146 (5)
C13	1.0300 (3)	0.7290 (2)	1.2054 (2)	0.0228 (5)
H13A	0.984946	0.664647	1.131747	0.034*
H13B	1.060746	0.696365	1.259637	0.034*
H13C	1.110250	0.778632	1.196026	0.034*
Au1	0.95986 (2)	0.55935 (2)	0.71308 (2)	0.01682 (3)
Cl1	1.11166 (7)	0.70866 (6)	0.86031 (6)	0.02465 (13)
Cl2	0.80710 (7)	0.41058 (6)	0.56663 (6)	0.02767 (14)
O3	0.3768 (2)	0.87843 (19)	0.5227 (2)	0.0272 (4)
H3A	0.425 (4)	0.938 (3)	0.566 (3)	0.037 (11)*
H3B	0.380 (4)	0.885 (4)	0.465 (3)	0.053 (13)*
Cl3	0.58921 (7)	1.10213 (6)	0.71166 (6)	0.02530 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S2	0.0189 (3)	0.0197 (3)	0.0165 (3)	0.0097 (2)	0.0050 (2)	0.0082 (2)
O2	0.0229 (9)	0.0241 (9)	0.0196 (9)	0.0095 (8)	0.0066 (7)	0.0135 (8)
N4	0.0166 (10)	0.0163 (10)	0.0163 (10)	0.0052 (8)	0.0042 (8)	0.0099 (8)
N5	0.0184 (10)	0.0189 (10)	0.0182 (10)	0.0090 (8)	0.0051 (8)	0.0113 (9)
N6	0.0172 (10)	0.0193 (10)	0.0150 (10)	0.0059 (8)	0.0044 (8)	0.0091 (8)
C14	0.0179 (12)	0.0181 (12)	0.0214 (13)	0.0056 (10)	0.0050 (10)	0.0080 (10)
C15	0.0219 (13)	0.0198 (12)	0.0187 (12)	0.0054 (10)	0.0069 (10)	0.0061 (10)
C16	0.0213 (13)	0.0181 (12)	0.0168 (12)	0.0013 (10)	0.0019 (10)	0.0074 (10)
C17	0.0189 (12)	0.0182 (12)	0.0170 (12)	0.0045 (10)	0.0012 (10)	0.0093 (10)
C18	0.0133 (11)	0.0129 (11)	0.0173 (12)	0.0018 (9)	0.0022 (9)	0.0064 (9)
C19	0.0142 (11)	0.0149 (11)	0.0175 (12)	0.0036 (9)	0.0033 (9)	0.0080 (10)
C20	0.0142 (11)	0.0154 (11)	0.0151 (11)	0.0001 (9)	0.0018 (9)	0.0063 (9)
C21	0.0146 (11)	0.0182 (12)	0.0180 (12)	0.0049 (9)	0.0047 (9)	0.0104 (10)
C22	0.0153 (11)	0.0149 (11)	0.0187 (12)	0.0005 (9)	0.0016 (9)	0.0089 (10)
C23	0.0167 (12)	0.0183 (12)	0.0150 (11)	0.0018 (9)	0.0043 (9)	0.0066 (10)
C24	0.0172 (12)	0.0188 (12)	0.0178 (12)	0.0046 (10)	0.0054 (10)	0.0064 (10)
C25	0.0137 (11)	0.0140 (11)	0.0173 (12)	0.0035 (9)	0.0024 (9)	0.0068 (9)
C26	0.0271 (14)	0.0308 (15)	0.0249 (14)	0.0147 (12)	0.0070 (11)	0.0162 (12)
S1	0.0184 (3)	0.0168 (3)	0.0156 (3)	0.0082 (2)	0.0054 (2)	0.0073 (2)
O1	0.0275 (10)	0.0230 (9)	0.0139 (8)	0.0104 (8)	0.0053 (7)	0.0108 (7)
N1	0.0191 (10)	0.0169 (10)	0.0148 (10)	0.0046 (8)	0.0040 (8)	0.0086 (9)
N2	0.0180 (10)	0.0185 (10)	0.0160 (10)	0.0078 (8)	0.0051 (8)	0.0104 (8)
N3	0.0169 (10)	0.0155 (10)	0.0144 (10)	0.0039 (8)	0.0041 (8)	0.0081 (8)
C1	0.0207 (13)	0.0183 (12)	0.0217 (13)	0.0058 (10)	0.0083 (10)	0.0088 (10)
C2	0.0269 (14)	0.0206 (13)	0.0181 (12)	0.0048 (11)	0.0099 (11)	0.0065 (10)
C3	0.0241 (13)	0.0212 (13)	0.0149 (12)	−0.0002 (10)	0.0039 (10)	0.0087 (10)
C4	0.0195 (12)	0.0189 (12)	0.0172 (12)	0.0030 (10)	0.0019 (10)	0.0095 (10)
C5	0.0159 (11)	0.0140 (11)	0.0153 (11)	0.0004 (9)	0.0017 (9)	0.0061 (9)
C6	0.0124 (11)	0.0136 (11)	0.0154 (11)	0.0016 (9)	0.0030 (9)	0.0060 (9)
C7	0.0150 (11)	0.0135 (11)	0.0122 (11)	0.0005 (9)	0.0021 (9)	0.0040 (9)
C8	0.0158 (11)	0.0154 (11)	0.0153 (11)	0.0048 (9)	0.0046 (9)	0.0076 (9)
C9	0.0182 (12)	0.0146 (11)	0.0147 (11)	0.0021 (9)	0.0015 (9)	0.0063 (9)
C10	0.0218 (13)	0.0179 (12)	0.0130 (11)	0.0036 (10)	0.0066 (10)	0.0053 (10)
C11	0.0197 (12)	0.0161 (12)	0.0167 (12)	0.0053 (10)	0.0059 (10)	0.0043 (10)
C12	0.0156 (11)	0.0122 (11)	0.0145 (11)	0.0025 (9)	0.0017 (9)	0.0044 (9)
C13	0.0249 (13)	0.0271 (14)	0.0240 (13)	0.0124 (11)	0.0062 (11)	0.0158 (11)
Au1	0.01572 (5)	0.01910 (5)	0.01926 (5)	0.00721 (4)	0.00532 (4)	0.00985 (4)
Cl1	0.0202 (3)	0.0280 (3)	0.0226 (3)	0.0066 (3)	0.0017 (2)	0.0073 (3)
Cl2	0.0290 (3)	0.0211 (3)	0.0284 (3)	0.0057 (3)	−0.0016 (3)	0.0074 (3)
O3	0.0301 (11)	0.0249 (11)	0.0333 (12)	0.0103 (9)	0.0100 (10)	0.0163 (10)
Cl3	0.0242 (3)	0.0298 (3)	0.0319 (3)	0.0131 (3)	0.0070 (3)	0.0202 (3)

Geometric parameters (Å, º)

S2—C19	1.747 (2)	O1—C9	1.376 (3)
S2—C25	1.746 (2)	O1—C13	1.428 (3)
O2—C22	1.373 (3)	N1—H1	0.80 (3)
O2—C26	1.426 (3)	N1—C1	1.359 (3)
N4—H4	0.81 (3)	N1—C5	1.347 (3)
N4—C14	1.360 (3)	N2—H2	0.852 (15)
N4—C18	1.354 (3)	N2—C5	1.360 (3)
N5—H5	0.851 (15)	N2—C6	1.379 (3)
N5—C18	1.361 (3)	N3—C6	1.294 (3)
N5—C19	1.375 (3)	N3—C7	1.393 (3)
N6—C19	1.301 (3)	C1—H1A	0.9500
N6—C20	1.400 (3)	C1—C2	1.363 (4)
C14—H14	0.9500	C2—H2A	0.9500
C14—C15	1.358 (4)	C2—C3	1.401 (4)
C15—H15	0.9500	C3—H3	0.9500
C15—C16	1.400 (4)	C3—C4	1.373 (4)
C16—H16	0.9500	C4—H4A	0.9500
C16—C17	1.372 (4)	C4—C5	1.406 (3)
C17—H17	0.9500	C7—C8	1.397 (3)
C17—C18	1.398 (3)	C7—C12	1.401 (3)
C20—C21	1.392 (3)	C8—H8	0.9500
C20—C25	1.400 (3)	C8—C9	1.385 (3)
C21—H21	0.9500	C9—C10	1.404 (3)
C21—C22	1.386 (3)	C10—H10	0.9500
C22—C23	1.403 (3)	C10—C11	1.383 (4)
C23—H23	0.9500	C11—H11	0.9500
C23—C24	1.378 (4)	C11—C12	1.396 (3)
C24—H24	0.9500	C13—H13A	0.9800
C24—C25	1.394 (3)	C13—H13B	0.9800
C26—H26A	0.9800	C13—H13C	0.9800
C26—H26B	0.9800	Au1—Cl1	2.2592 (7)
C26—H26C	0.9800	Au1—Cl2	2.2560 (7)
S1—C6	1.747 (2)	O3—H3A	0.78 (3)
S1—C12	1.745 (2)	O3—H3B	0.78 (3)
C25—S2—C19	88.15 (11)	C9—O1—C13	117.33 (19)
C22—O2—C26	117.14 (19)	C1—N1—H1	120 (2)
C14—N4—H4	121 (2)	C5—N1—H1	117 (2)
C18—N4—H4	117 (2)	C5—N1—C1	122.5 (2)
C18—N4—C14	122.3 (2)	C5—N2—H2	115 (2)
C18—N5—H5	118 (2)	C5—N2—C6	125.4 (2)
C18—N5—C19	125.7 (2)	C6—N2—H2	119 (2)
C19—N5—H5	117 (2)	C6—N3—C7	110.1 (2)
C19—N6—C20	109.9 (2)	N1—C1—H1A	119.9
N4—C14—H14	119.9	N1—C1—C2	120.3 (2)
C15—C14—N4	120.2 (2)	C2—C1—H1A	119.9
C15—C14—H14	119.9	C1—C2—H2A	120.6
C14—C15—H15	120.6	C1—C2—C3	118.8 (2)
C14—C15—C16	118.9 (2)	C3—C2—H2A	120.6
C16—C15—H15	120.6	C2—C3—H3	119.8
C15—C16—H16	119.7	C4—C3—C2	120.5 (2)
C17—C16—C15	120.6 (2)	C4—C3—H3	119.8
C17—C16—H16	119.7	C3—C4—H4A	120.4
C16—C17—H17	120.4	C3—C4—C5	119.2 (2)
C16—C17—C18	119.3 (2)	C5—C4—H4A	120.4
C18—C17—H17	120.4	N1—C5—N2	120.6 (2)
N4—C18—N5	119.9 (2)	N1—C5—C4	118.7 (2)
N4—C18—C17	118.7 (2)	N2—C5—C4	120.6 (2)
N5—C18—C17	121.3 (2)	N2—C6—S1	119.11 (18)
N5—C19—S2	119.11 (18)	N3—C6—S1	117.41 (18)
N6—C19—S2	117.11 (18)	N3—C6—N2	123.5 (2)
N6—C19—N5	123.8 (2)	N3—C7—C8	124.4 (2)
N6—C20—C25	114.7 (2)	N3—C7—C12	114.6 (2)
C21—C20—N6	124.3 (2)	C8—C7—C12	121.0 (2)
C21—C20—C25	120.9 (2)	C7—C8—H8	121.2
C20—C21—H21	121.0	C9—C8—C7	117.5 (2)
C22—C21—C20	117.9 (2)	C9—C8—H8	121.2
C22—C21—H21	121.0	O1—C9—C8	124.0 (2)
O2—C22—C21	123.5 (2)	O1—C9—C10	114.6 (2)
O2—C22—C23	115.5 (2)	C8—C9—C10	121.5 (2)
C21—C22—C23	121.0 (2)	C9—C10—H10	119.4
C22—C23—H23	119.4	C11—C10—C9	121.2 (2)
C24—C23—C22	121.2 (2)	C11—C10—H10	119.4
C24—C23—H23	119.4	C10—C11—H11	121.1
C23—C24—H24	121.0	C10—C11—C12	117.7 (2)
C23—C24—C25	118.1 (2)	C12—C11—H11	121.1
C25—C24—H24	121.0	C7—C12—S1	110.12 (17)
C20—C25—S2	110.04 (18)	C11—C12—S1	128.73 (19)
C24—C25—S2	129.11 (19)	C11—C12—C7	121.1 (2)
C24—C25—C20	120.9 (2)	O1—C13—H13A	109.5
O2—C26—H26A	109.5	O1—C13—H13B	109.5
O2—C26—H26B	109.5	O1—C13—H13C	109.5
O2—C26—H26C	109.5	H13A—C13—H13B	109.5
H26A—C26—H26B	109.5	H13A—C13—H13C	109.5
H26A—C26—H26C	109.5	H13B—C13—H13C	109.5
H26B—C26—H26C	109.5	Cl2—Au1—Cl1	179.62 (3)
C12—S1—C6	87.80 (11)	H3A—O3—H3B	102 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···O3	0.85 (2)	1.91 (2)	2.758 (3)	173 (3)
N2—H2···Cl3	0.85 (2)	2.23 (2)	3.084 (2)	176 (4)
C3—H3···O1^i	0.95	2.46	3.284 (3)	145
O3—H3A···Cl3	0.78 (3)	2.39 (3)	3.155 (2)	171 (4)
O3—H3B···Cl3^ii	0.78 (3)	2.41 (3)	3.188 (2)	174 (4)

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