[1-(2-Oxidobenzyl-idene)-4-phenyl-thio-semicarbazidato-κO,N,S](pyridine-κN)copper(II).

In the structure of the title compound, [Cu(C(14)H(11)N(3)OS)(C(5)H(5)N)], the Cu(II) atom exhibits a slightly distorted square-planar CuN(2)OS coordination polyhedron consisting of a phenyl O, an azomethine N and a thio-amide S atom from the tridentate thio-semicarbazonate dianion, and the N atom of a pyridine mol-ecule. The thio-semicarbazonate ligand exists in the thiol tautomeric form as an E isomer. Rotational disorder of the pyridine and phenyl rings in a 1:1 ratio of the respective components is observed. An extensive network of weak N-H⋯S, C-H⋯O, C-H⋯N and C-H⋯S hydrogen-bonding inter-actions consolidates the structure.

Related literature

For general background to thio­semicarbazonates, see: Garoufilis et al. (2009 ▶); Stanojkovic et al. (2010 ▶); Kaur et al. (2007 ▶). For related structures, see: John et al. (2002 ▶); Naik et al. (2003 ▶); Cao et al. (2007 ▶); Seena & Kurup (2008 ▶).

Experimental

Crystal data

[Cu(C14H11N3OS)(C5H5N)]

M = 411.96

Monoclinic,

a = 18.2958 (17) Å

b = 4.5610 (5) Å

c = 20.473 (2) Å

β = 93.602 (7)°

V = 1705.1 (3) Å3

Z = 4

Mo Kα radiation

μ = 1.42 mm−1

T = 173 K

0.50 × 0.06 × 0.05 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.540, T max = 0.938

19901 measured reflections

3493 independent reflections

2522 reflections with I > 2σ(I)

R int = 0.078

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.080

S = 1.02

3493 reflections

311 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.33 e Å−3

Δρmin = −0.45 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810017381/wm2343sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810017381/wm2343Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu(C14H11N3OS)(C5H5N)]	F(000) = 844
Mr = 411.96	Dx = 1.605 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2588 reflections
a = 18.2958 (17) Å	θ = 2.2–23.9°
b = 4.5610 (5) Å	µ = 1.42 mm−1
c = 20.473 (2) Å	T = 173 K
β = 93.602 (7)°	Needle, brown
V = 1705.1 (3) Å3	0.50 × 0.06 × 0.05 mm
Z = 4

Bruker APEXII CCD diffractometer	3493 independent reflections
Radiation source: fine-focus sealed tube	2522 reflections with I > 2σ(I)
graphite	Rint = 0.078
Detector resolution: 8.33 pixels mm-1	θmax = 26.4°, θmin = 1.5°
φ and ω scans	h = −22→22
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −5→5
Tmin = 0.540, Tmax = 0.938	l = −25→25
19901 measured reflections

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0237P)2 + 1.1058P] where P = (Fo2 + 2Fc2)/3
3493 reflections	(Δ/σ)max = 0.001
311 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.45 e Å−3

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.

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.428933 (18)	0.04089 (8)	0.687460 (17)	0.02260 (12)
S1	0.34247 (4)	0.37030 (18)	0.71230 (4)	0.0274 (2)
N1	0.46424 (12)	0.0759 (5)	0.77777 (11)	0.0194 (5)
N2	0.43213 (12)	0.2699 (5)	0.82056 (11)	0.0207 (6)
N3	0.33957 (14)	0.6080 (6)	0.82989 (13)	0.0224 (6)
H3N	0.3077 (15)	0.674 (6)	0.8115 (14)	0.017 (9)*
N4	0.39751 (13)	0.0530 (5)	0.59166 (11)	0.0223 (6)
O1	0.50312 (10)	−0.2308 (4)	0.66541 (9)	0.0253 (5)
C1	0.55353 (15)	−0.3487 (6)	0.70570 (15)	0.0217 (7)
C2	0.56305 (14)	−0.2790 (6)	0.77319 (14)	0.0200 (7)
C3	0.61943 (15)	−0.4170 (6)	0.81158 (15)	0.0251 (7)
H3A	0.6257	−0.3696	0.8568	0.030*
C4	0.66565 (16)	−0.6175 (7)	0.78620 (16)	0.0288 (8)
H4A	0.7035	−0.7072	0.8131	0.035*
C5	0.65588 (16)	−0.6865 (7)	0.72001 (16)	0.0306 (8)
H5A	0.6874	−0.8251	0.7016	0.037*
C6	0.60151 (16)	−0.5578 (7)	0.68106 (15)	0.0270 (7)
H6A	0.5959	−0.6106	0.6361	0.032*
C7	0.51859 (15)	−0.0705 (6)	0.80498 (14)	0.0214 (7)
H7A	0.5301	−0.0368	0.8503	0.026*
C8	0.37630 (15)	0.4103 (6)	0.79364 (14)	0.0203 (7)
C9	0.35281 (15)	0.6925 (6)	0.89537 (13)	0.0187 (6)
C12	0.37031 (17)	0.8705 (7)	1.02567 (15)	0.0313 (8)
H12A	0.3713	0.9194	1.0708	0.038*
C17	0.3627 (2)	0.0996 (7)	0.45900 (16)	0.0404 (9)
H17A	0.3515	0.1147	0.4132	0.048*
C10A	0.3965 (3)	0.5278 (16)	0.9414 (3)	0.0229 (15)	0.50
H10A	0.4190	0.3501	0.9292	0.027*	0.50
C11A	0.4055 (4)	0.633 (2)	1.0048 (4)	0.029 (2)	0.50
H11A	0.4380	0.5320	1.0350	0.035*	0.50
C13A	0.3313 (3)	1.0474 (15)	0.9773 (3)	0.0267 (14)	0.50
H13A	0.3120	1.2319	0.9892	0.032*	0.50
C14A	0.3216 (3)	0.9506 (15)	0.9135 (3)	0.0238 (14)	0.50
H14A	0.2933	1.0630	0.8821	0.029*	0.50
C15A	0.4434 (3)	0.1199 (15)	0.5460 (3)	0.0262 (15)	0.50
H15A	0.4932	0.1536	0.5598	0.031*	0.50
C16A	0.4238 (4)	0.1436 (16)	0.4804 (3)	0.0291 (16)	0.50
H16A	0.4599	0.1967	0.4513	0.035*	0.50
C18A	0.3023 (3)	0.0198 (13)	0.5036 (3)	0.0263 (14)	0.50
H18A	0.2530	−0.0121	0.4879	0.032*	0.50
C19A	0.3251 (3)	−0.0019 (13)	0.5681 (3)	0.0226 (14)	0.50
H19A	0.2904	−0.0568	0.5985	0.027*	0.50
C10B	0.4197 (4)	0.6784 (15)	0.9301 (3)	0.0228 (15)	0.50
H10B	0.4615	0.6127	0.9090	0.027*	0.50
C11B	0.4269 (5)	0.7590 (17)	0.9955 (4)	0.0270 (19)	0.50
H11B	0.4727	0.7347	1.0194	0.032*	0.50
C13B	0.2999 (3)	0.8776 (14)	0.9931 (3)	0.0250 (14)	0.50
H13B	0.2583	0.9315	1.0160	0.030*	0.50
C14B	0.2924 (3)	0.8055 (14)	0.9280 (3)	0.0226 (14)	0.50
H14B	0.2464	0.8313	0.9045	0.027*	0.50
C15B	0.4194 (3)	0.2973 (15)	0.5609 (3)	0.0230 (14)	0.50
H15B	0.4436	0.4488	0.5857	0.028*	0.50
C16B	0.4073 (3)	0.3304 (16)	0.4944 (3)	0.0259 (15)	0.50
H16B	0.4265	0.4928	0.4720	0.031*	0.50
C18B	0.3501 (3)	−0.1385 (13)	0.4924 (3)	0.0241 (14)	0.50
H18B	0.3295	−0.3044	0.4701	0.029*	0.50
C19B	0.3662 (3)	−0.1547 (14)	0.5595 (3)	0.0258 (15)	0.50
H19B	0.3533	−0.3272	0.5821	0.031*	0.50

	U11	U22	U33	U12	U13	U23
Cu1	0.02066 (19)	0.0297 (2)	0.0176 (2)	0.00297 (17)	0.00239 (14)	−0.00190 (17)
S1	0.0248 (4)	0.0390 (5)	0.0181 (4)	0.0082 (4)	−0.0003 (3)	−0.0037 (4)
N1	0.0165 (12)	0.0212 (13)	0.0207 (14)	0.0006 (11)	0.0025 (10)	−0.0039 (11)
N2	0.0205 (13)	0.0245 (14)	0.0173 (14)	0.0026 (11)	0.0024 (11)	−0.0042 (11)
N3	0.0187 (14)	0.0313 (16)	0.0166 (14)	0.0067 (12)	−0.0022 (12)	−0.0006 (12)
N4	0.0238 (13)	0.0227 (14)	0.0208 (14)	0.0049 (12)	0.0055 (11)	−0.0011 (12)
O1	0.0236 (11)	0.0313 (12)	0.0208 (11)	0.0048 (10)	−0.0005 (9)	−0.0031 (10)
C1	0.0172 (15)	0.0207 (16)	0.0276 (18)	−0.0021 (13)	0.0043 (13)	0.0027 (14)
C2	0.0184 (15)	0.0165 (15)	0.0252 (17)	−0.0038 (12)	0.0017 (13)	0.0027 (13)
C3	0.0254 (16)	0.0245 (17)	0.0251 (17)	0.0002 (14)	−0.0015 (13)	−0.0031 (14)
C4	0.0231 (16)	0.0250 (18)	0.038 (2)	0.0038 (14)	−0.0031 (15)	0.0021 (15)
C5	0.0280 (17)	0.0256 (18)	0.039 (2)	0.0064 (15)	0.0084 (16)	−0.0021 (16)
C6	0.0297 (17)	0.0267 (17)	0.0255 (17)	0.0006 (14)	0.0081 (14)	−0.0019 (14)
C7	0.0213 (15)	0.0228 (16)	0.0198 (16)	−0.0038 (13)	−0.0010 (13)	−0.0040 (13)
C8	0.0177 (15)	0.0228 (17)	0.0208 (16)	−0.0019 (13)	0.0049 (12)	−0.0010 (13)
C9	0.0204 (15)	0.0203 (16)	0.0154 (16)	−0.0019 (13)	0.0017 (12)	−0.0016 (13)
C12	0.0372 (19)	0.036 (2)	0.0198 (17)	0.0057 (16)	−0.0021 (15)	−0.0090 (15)
C17	0.078 (3)	0.028 (2)	0.0147 (18)	0.014 (2)	0.0007 (19)	−0.0043 (15)
C10A	0.026 (4)	0.025 (4)	0.017 (4)	0.007 (3)	−0.001 (3)	−0.001 (3)
C11A	0.020 (4)	0.047 (6)	0.019 (4)	0.005 (4)	−0.003 (3)	0.000 (4)
C13A	0.028 (3)	0.021 (3)	0.032 (4)	0.000 (3)	0.007 (3)	−0.008 (3)
C14A	0.025 (3)	0.025 (4)	0.022 (4)	−0.001 (3)	0.002 (3)	0.003 (3)
C15A	0.020 (3)	0.036 (4)	0.023 (4)	0.007 (3)	0.006 (3)	−0.006 (3)
C16A	0.036 (4)	0.028 (4)	0.024 (4)	0.007 (3)	0.007 (3)	0.006 (3)
C18A	0.025 (3)	0.023 (4)	0.029 (4)	0.004 (3)	−0.009 (3)	−0.006 (3)
C19A	0.019 (3)	0.021 (4)	0.028 (4)	0.000 (3)	0.007 (3)	−0.001 (3)
C10B	0.023 (4)	0.022 (4)	0.025 (4)	0.004 (3)	0.009 (3)	0.002 (3)
C11B	0.024 (5)	0.029 (5)	0.028 (5)	0.002 (3)	−0.009 (4)	0.000 (4)
C13B	0.024 (3)	0.025 (4)	0.026 (4)	0.002 (3)	0.006 (3)	−0.002 (3)
C14B	0.020 (3)	0.026 (4)	0.022 (4)	0.006 (3)	0.002 (3)	0.002 (3)
C15B	0.020 (3)	0.026 (4)	0.023 (4)	0.002 (3)	−0.001 (3)	−0.007 (3)
C16B	0.026 (4)	0.024 (4)	0.028 (4)	0.002 (3)	0.002 (3)	0.006 (3)
C18B	0.027 (3)	0.020 (3)	0.025 (4)	−0.003 (3)	0.002 (3)	−0.009 (3)
C19B	0.030 (4)	0.024 (4)	0.024 (4)	−0.004 (3)	0.011 (3)	−0.002 (3)

Cu1—O1	1.9126 (19)	C12—C11A	1.344 (10)
Cu1—N1	1.926 (2)	C12—C13B	1.414 (7)
Cu1—N4	2.010 (2)	C12—C13A	1.433 (7)
Cu1—S1	2.2626 (8)	C12—H12A	0.9500
S1—C8	1.749 (3)	C17—C16A	1.191 (7)
N1—C7	1.294 (3)	C17—C18B	1.311 (7)
N1—N2	1.400 (3)	C17—C16B	1.491 (8)
N2—C8	1.299 (3)	C17—C18A	1.522 (7)
N3—C8	1.370 (4)	C17—H17A	0.9500
N3—C9	1.401 (4)	C10A—C11A	1.383 (10)
N3—H3N	0.74 (3)	C10A—H10A	0.9500
N4—C19B	1.270 (6)	C11A—H11A	0.9500
N4—C15A	1.330 (6)	C13A—C14A	1.380 (8)
N4—C15B	1.353 (7)	C13A—H13A	0.9500
N4—C19A	1.403 (6)	C14A—H14A	0.9500
O1—C1	1.313 (3)	C15A—C16A	1.373 (9)
C1—C6	1.411 (4)	C15A—H15A	0.9500
C1—C2	1.418 (4)	C16A—H16A	0.9500
C2—C3	1.406 (4)	C18A—C19A	1.363 (8)
C2—C7	1.434 (4)	C18A—H18A	0.9500
C3—C4	1.370 (4)	C19A—H19A	0.9500
C3—H3A	0.9500	C10B—C11B	1.387 (11)
C4—C5	1.392 (4)	C10B—H10B	0.9500
C4—H4A	0.9500	C11B—H11B	0.9500
C5—C6	1.368 (4)	C13B—C14B	1.371 (8)
C5—H5A	0.9500	C13B—H13B	0.9500
C6—H6A	0.9500	C14B—H14B	0.9500
C7—H7A	0.9500	C15B—C16B	1.374 (8)
C9—C14A	1.369 (7)	C15B—H15B	0.9500
C9—C10B	1.379 (7)	C16B—H16B	0.9500
C9—C10A	1.413 (7)	C18B—C19B	1.388 (8)
C9—C14B	1.424 (6)	C18B—H18B	0.9500
C12—C11B	1.338 (9)	C19B—H19B	0.9500
O1—Cu1—N1	94.59 (9)	C18B—C17—C16B	116.1 (4)
O1—Cu1—N4	87.20 (9)	C16A—C17—C18A	121.2 (5)
N1—Cu1—N4	172.99 (10)	C16A—C17—H17A	119.4
O1—Cu1—S1	178.70 (7)	C18B—C17—H17A	122.7
N1—Cu1—S1	85.77 (7)	C16B—C17—H17A	120.4
N4—Cu1—S1	92.29 (7)	C18A—C17—H17A	119.4
C8—S1—Cu1	94.17 (10)	C11A—C10A—C9	118.1 (6)
C7—N1—N2	113.4 (2)	C11A—C10A—H10A	121.0
C7—N1—Cu1	124.9 (2)	C9—C10A—H10A	121.0
N2—N1—Cu1	121.63 (17)	C12—C11A—C10A	123.1 (7)
C8—N2—N1	113.3 (2)	C12—C11A—H11A	118.4
C8—N3—C9	129.6 (3)	C10A—C11A—H11A	118.4
C8—N3—H3N	113 (2)	C14A—C13A—C12	120.2 (5)
C9—N3—H3N	117 (2)	C14A—C13A—H13A	119.9
C19B—N4—C15B	120.6 (4)	C12—C13A—H13A	119.9
C15A—N4—C19A	115.0 (4)	C9—C14A—C13A	120.1 (6)
C19B—N4—Cu1	125.3 (3)	C9—C14A—H14A	120.0
C15A—N4—Cu1	122.5 (3)	C13A—C14A—H14A	120.0
C15B—N4—Cu1	113.7 (3)	N4—C15A—C16A	124.6 (6)
C19A—N4—Cu1	122.4 (3)	N4—C15A—H15A	117.7
C1—O1—Cu1	126.73 (18)	C16A—C15A—H15A	117.7
O1—C1—C6	118.7 (3)	C17—C16A—C15A	121.9 (6)
O1—C1—C2	124.0 (3)	C17—C16A—H16A	119.1
C6—C1—C2	117.3 (3)	C15A—C16A—H16A	119.1
C3—C2—C1	119.0 (3)	C19A—C18A—C17	114.2 (5)
C3—C2—C7	117.4 (3)	C19A—C18A—H18A	122.9
C1—C2—C7	123.5 (3)	C17—C18A—H18A	122.9
C4—C3—C2	122.4 (3)	C18A—C19A—N4	123.0 (5)
C4—C3—H3A	118.8	C18A—C19A—H19A	118.5
C2—C3—H3A	118.8	N4—C19A—H19A	118.5
C3—C4—C5	118.4 (3)	C9—C10B—C11B	120.8 (6)
C3—C4—H4A	120.8	C9—C10B—H10B	119.6
C5—C4—H4A	120.8	C11B—C10B—H10B	119.6
C6—C5—C4	121.0 (3)	C12—C11B—C10B	121.2 (7)
C6—C5—H5A	119.5	C12—C11B—H11B	119.4
C4—C5—H5A	119.5	C10B—C11B—H11B	119.4
C5—C6—C1	121.9 (3)	C14B—C13B—C12	119.0 (5)
C5—C6—H6A	119.1	C14B—C13B—H13B	120.5
C1—C6—H6A	119.1	C12—C13B—H13B	120.5
N1—C7—C2	126.1 (3)	C13B—C14B—C9	120.7 (5)
N1—C7—H7A	117.0	C13B—C14B—H14B	119.7
C2—C7—H7A	117.0	C9—C14B—H14B	119.7
N2—C8—N3	119.6 (3)	N4—C15B—C16B	121.2 (6)
N2—C8—S1	125.1 (2)	N4—C15B—H15B	119.4
N3—C8—S1	115.3 (2)	C16B—C15B—H15B	119.4
C14A—C9—N3	116.5 (4)	C15B—C16B—C17	116.9 (5)
C10B—C9—N3	125.1 (4)	C15B—C16B—H16B	121.5
C14A—C9—C10A	120.2 (4)	C17—C16B—H16B	121.5
N3—C9—C10A	123.3 (4)	C17—C18B—C19B	121.8 (5)
C10B—C9—C14B	117.7 (4)	C17—C18B—H18B	119.1
N3—C9—C14B	117.1 (3)	C19B—C18B—H18B	119.1
C11B—C12—C13B	120.0 (5)	N4—C19B—C18B	122.3 (6)
C11A—C12—C13A	117.5 (5)	N4—C19B—H19B	118.8
C11A—C12—H12A	121.2	C18B—C19B—H19B	118.8
C13A—C12—H12A	121.2
N1—Cu1—S1—C8	1.70 (11)	C13B—C12—C13A—C14A	−77.5 (7)
N4—Cu1—S1—C8	−171.55 (12)	C10B—C9—C14A—C13A	−36.8 (7)
O1—Cu1—N1—C7	−3.4 (2)	N3—C9—C14A—C13A	179.2 (5)
S1—Cu1—N1—C7	177.9 (2)	C10A—C9—C14A—C13A	−1.6 (8)
O1—Cu1—N1—N2	176.30 (19)	C14B—C9—C14A—C13A	78.3 (8)
S1—Cu1—N1—N2	−2.45 (18)	C12—C13A—C14A—C9	−3.7 (9)
C7—N1—N2—C8	−178.1 (2)	C19B—N4—C15A—C16A	44.8 (8)
Cu1—N1—N2—C8	2.2 (3)	C15B—N4—C15A—C16A	−86.2 (8)
O1—Cu1—N4—C19B	70.3 (4)	C19A—N4—C15A—C16A	1.6 (9)
S1—Cu1—N4—C19B	−110.8 (4)	Cu1—N4—C15A—C16A	−177.0 (5)
O1—Cu1—N4—C15A	−55.3 (4)	C18B—C17—C16A—C15A	−44.0 (8)
S1—Cu1—N4—C15A	123.5 (4)	C16B—C17—C16A—C15A	77.8 (8)
O1—Cu1—N4—C15B	−103.2 (3)	C18A—C17—C16A—C15A	1.2 (10)
S1—Cu1—N4—C15B	75.7 (3)	N4—C15A—C16A—C17	−1.4 (12)
O1—Cu1—N4—C19A	126.2 (3)	C16A—C17—C18A—C19A	−1.4 (8)
S1—Cu1—N4—C19A	−55.0 (3)	C18B—C17—C18A—C19A	69.4 (6)
N1—Cu1—O1—C1	4.4 (2)	C16B—C17—C18A—C19A	−41.7 (6)
N4—Cu1—O1—C1	177.6 (2)	C17—C18A—C19A—N4	1.8 (8)
Cu1—O1—C1—C6	176.65 (19)	C19B—N4—C19A—C18A	−73.6 (7)
Cu1—O1—C1—C2	−3.4 (4)	C15A—N4—C19A—C18A	−2.0 (8)
O1—C1—C2—C3	−179.4 (3)	C15B—N4—C19A—C18A	43.1 (7)
C6—C1—C2—C3	0.6 (4)	Cu1—N4—C19A—C18A	176.6 (4)
O1—C1—C2—C7	−0.2 (4)	C14A—C9—C10B—C11B	42.1 (8)
C6—C1—C2—C7	179.8 (3)	N3—C9—C10B—C11B	−178.0 (5)
C1—C2—C3—C4	−0.1 (4)	C10A—C9—C10B—C11B	−78.4 (9)
C7—C2—C3—C4	−179.3 (3)	C14B—C9—C10B—C11B	2.9 (9)
C2—C3—C4—C5	−0.3 (4)	C11A—C12—C11B—C10B	82.0 (13)
C3—C4—C5—C6	0.0 (5)	C13B—C12—C11B—C10B	7.1 (10)
C4—C5—C6—C1	0.6 (5)	C13A—C12—C11B—C10B	−36.3 (8)
O1—C1—C6—C5	179.1 (3)	C9—C10B—C11B—C12	−4.4 (11)
C2—C1—C6—C5	−0.9 (4)	C11B—C12—C13B—C14B	−8.5 (9)
N2—N1—C7—C2	−178.4 (2)	C11A—C12—C13B—C14B	−40.6 (8)
Cu1—N1—C7—C2	1.3 (4)	C13A—C12—C13B—C14B	70.9 (7)
C3—C2—C7—N1	−179.6 (3)	C12—C13B—C14B—C9	7.3 (9)
C1—C2—C7—N1	1.2 (4)	C14A—C9—C14B—C13B	−84.6 (8)
N1—N2—C8—N3	−179.9 (2)	C10B—C9—C14B—C13B	−4.6 (8)
N1—N2—C8—S1	−0.2 (3)	N3—C9—C14B—C13B	176.3 (5)
C9—N3—C8—N2	0.5 (5)	C10A—C9—C14B—C13B	32.3 (8)
C9—N3—C8—S1	−179.3 (2)	C19B—N4—C15B—C16B	1.2 (8)
Cu1—S1—C8—N2	−1.4 (3)	C15A—N4—C15B—C16B	62.1 (7)
Cu1—S1—C8—N3	178.4 (2)	C19A—N4—C15B—C16B	−46.9 (7)
C8—N3—C9—C14A	161.8 (4)	Cu1—N4—C15B—C16B	175.0 (5)
C8—N3—C9—C10B	25.5 (6)	N4—C15B—C16B—C17	5.9 (9)
C8—N3—C9—C10A	−17.5 (6)	C16A—C17—C16B—C15B	−81.2 (8)
C8—N3—C9—C14B	−155.4 (4)	C18B—C17—C16B—C15B	−11.6 (8)
C14A—C9—C10A—C11A	1.0 (9)	C18A—C17—C16B—C15B	38.9 (7)
C10B—C9—C10A—C11A	74.9 (9)	C16A—C17—C18B—C19B	48.0 (7)
N3—C9—C10A—C11A	−179.8 (5)	C16B—C17—C18B—C19B	10.8 (8)
C14B—C9—C10A—C11A	−38.5 (8)	C18A—C17—C18B—C19B	−77.4 (6)
C11B—C12—C11A—C10A	−83.6 (13)	C15A—N4—C19B—C18B	−39.3 (7)
C13B—C12—C11A—C10A	34.8 (9)	C15B—N4—C19B—C18B	−2.7 (8)
C13A—C12—C11A—C10A	−10.2 (10)	C19A—N4—C19B—C18B	81.0 (7)
C9—C10A—C11A—C12	5.2 (11)	Cu1—N4—C19B—C18B	−175.8 (4)
C11B—C12—C13A—C14A	40.7 (8)	C17—C18B—C19B—N4	−3.9 (9)
C11A—C12—C13A—C14A	9.4 (8)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···S1i	0.74 (3)	2.90 (3)	3.593 (3)	157 (3)
C10A—H10A···N2	0.95	2.28	2.852 (7)	118
C10B—H10B···N2	0.95	2.43	2.936 (7)	113
C14B—H14B···S1i	0.95	2.81	3.679 (6)	152
C15B—H15B···O1ii	0.95	2.40	3.339 (7)	169
C16A—H16A···O1iii	0.95	2.53	3.371 (7)	148

Table 1

Selected bond lengths (Å)

Cu1—O1	1.9126 (19)
Cu1—N1	1.926 (2)
Cu1—N4	2.010 (2)
Cu1—S1	2.2626 (8)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯S1i	0.74 (3)	2.90 (3)	3.593 (3)	157 (3)
C10A—H10A⋯N2	0.95	2.28	2.852 (7)	118
C10B—H10B⋯N2	0.95	2.43	2.936 (7)	113
C14B—H14B⋯S1i	0.95	2.81	3.679 (6)	152
C15B—H15B⋯O1ii	0.95	2.40	3.339 (7)	169
C16A—H16A⋯O1iii	0.95	2.53	3.371 (7)	148

Symmetry codes: (i) ; (ii) ; (iii) .