Cis versus trans arrangement of di­thio­carbazate ligands in bis-chelated Ni and Cu complexes

Two bis-chelated metal complexes of nickel(II) and copper(II) with N,S Schiff bases in a cis configuration are presented and compared with similar species in the CSD having trans-configured ligands.

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.027
• wR factor = 0.081
• Data-to-parameter ratio = 21.1

Structure: II

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.031
• wR factor = 0.074
• Data-to-parameter ratio = 20.4

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level C
PLAT910_ALERT_3_C Missing # of FCF Reflection(s) Below Theta(Min).          6 Note
PLAT918_ALERT_3_C Reflection(s) with I(obs) much Smaller I(calc) .          1 Check
PLAT934_ALERT_3_C Number of (Iobs-Icalc)/Sigma(W) > 10 Outliers ..          1 Check

Alert level G
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Ni1      --S1       .        9.0 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Ni1      --N1       .        5.6 s.u.
PLAT794_ALERT_5_G Tentative Bond Valency for Ni1       (II)      .       2.30 Info
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         10 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   4 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 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
   0 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check




Datablock: II


Alert level C
STRVA01_ALERT_4_C           Flack test results are ambiguous.
           From the CIF: _refine_ls_abs_structure_Flack    0.482
           From the CIF: _refine_ls_abs_structure_Flack_su    0.010
PLAT041_ALERT_1_C Calc. and Reported SumFormula    Strings  Differ     Please Check
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       3.12 Report
PLAT910_ALERT_3_C Missing # of FCF Reflection(s) Below Theta(Min).          6 Note

Alert level G
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          9 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          1 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   4 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   3 ALERT level G = General information/check it is not something unexpected

   2 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
   1 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

Computing details

For both structures, data collection: RAPID-AUTO (Rigaku, 2010); cell refinement: RAPID-AUTO (Rigaku, 2010); data reduction: RAPID-AUTO (Rigaku, 2010); program(s) used to solve structure: SIR92 (Altomare et al., 1994). Program(s) used to refine structure: SHELXL2014/6 (Sheldrick, 2015) for (I); SHELXL2014/7 (Sheldrick, 2015) for (II). For both structures, molecular graphics: CrystalStructure (Rigaku, 2010); software used to prepare material for publication: CrystalStructure (Rigaku, 2010).

Bis[S-n-hexyl 3-(1-phenylethylidene)dithiocarbazato-κ²N³,S]nickel(II) (I)

Crystal data

[Ni(C15H21N2S2)2]	F(000) = 1368
Mr = 645.62	Dx = 1.302 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71075 Å
a = 23.9721 (5) Å	Cell parameters from 4789 reflections
b = 8.3967 (2) Å	θ = 3.3–27.5°
c = 16.6739 (3) Å	µ = 0.87 mm^−1
β = 101.046 (1)°	T = 173 K
V = 3294.05 (12) Å^3	Prism, purple
Z = 4	0.38 × 0.30 × 0.07 mm

Data collection

Rigaku R-AXIS RAPID diffractometer	3589 reflections with I > 2σ(I)
Detector resolution: 10.000 pixels mm^-1	Rint = 0.025
ω scans	θmax = 27.5°, θmin = 3.3°
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995)	h = −30→30
Tmin = 0.684, Tmax = 0.941	k = −10→10
15965 measured reflections	l = −21→21
3768 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.081	H-atom parameters constrained
S = 1.15	w = 1/[σ^2(Fo^2) + (0.0458P)^2 + 1.5849P] where P = (Fo^2 + 2Fc^2)/3
3768 reflections	(Δ/σ)max = 0.002
179 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.33 e Å^−3

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
Ni1	0.5000	1.00787 (2)	0.7500	0.02259 (8)
S1	0.47077 (2)	1.18475 (4)	0.65741 (2)	0.03381 (10)
S2	0.39340 (2)	1.11935 (4)	0.50136 (2)	0.03696 (11)
N1	0.49459 (4)	0.85983 (12)	0.66033 (6)	0.0216 (2)
N2	0.45428 (5)	0.89369 (13)	0.58858 (6)	0.0260 (2)
C1	0.60886 (5)	0.81446 (16)	0.75593 (8)	0.0270 (3)
H1	0.6020	0.9207	0.7371	0.032*
C2	0.65594 (6)	0.78033 (19)	0.81594 (8)	0.0344 (3)
H2	0.6814	0.8631	0.8376	0.041*
C3	0.66588 (6)	0.6262 (2)	0.84440 (9)	0.0379 (3)
H3	0.6981	0.6034	0.8857	0.046*
C4	0.62895 (7)	0.50520 (18)	0.81276 (10)	0.0363 (3)
H4	0.6354	0.3998	0.8331	0.044*
C5	0.58238 (6)	0.53742 (16)	0.75130 (8)	0.0283 (3)
H5	0.5579	0.4534	0.7284	0.034*
C6	0.57150 (5)	0.69294 (15)	0.72306 (7)	0.0230 (2)
C7	0.52256 (5)	0.72868 (14)	0.65686 (7)	0.0220 (2)
C8	0.50807 (6)	0.61449 (16)	0.58659 (8)	0.0304 (3)
H8A	0.4700	0.5709	0.5851	0.046*
H8B	0.5358	0.5275	0.5935	0.046*
H8C	0.5090	0.6706	0.5353	0.046*
C9	0.44213 (6)	1.04365 (16)	0.58425 (8)	0.0269 (3)
C10	0.38023 (7)	0.9506 (2)	0.43216 (8)	0.0369 (3)
H10A	0.3617	0.9900	0.3776	0.044*
H10B	0.4173	0.9042	0.4267	0.044*
C11	0.34357 (6)	0.81914 (19)	0.45734 (8)	0.0347 (3)
H11A	0.3070	0.8649	0.4654	0.042*
H11B	0.3630	0.7733	0.5101	0.042*
C12	0.33199 (7)	0.6872 (2)	0.39342 (9)	0.0406 (3)
H12A	0.3093	0.7315	0.3425	0.049*
H12B	0.3687	0.6502	0.3811	0.049*
C13	0.30051 (6)	0.5448 (2)	0.41990 (9)	0.0359 (3)
H13A	0.3242	0.4961	0.4689	0.043*
H13B	0.2649	0.5824	0.4354	0.043*
C14	0.28614 (7)	0.4183 (2)	0.35383 (10)	0.0437 (4)
H14A	0.3219	0.3761	0.3408	0.052*
H14B	0.2645	0.4686	0.3037	0.052*
C15	0.25158 (8)	0.2802 (2)	0.37790 (12)	0.0532 (4)
H15A	0.2721	0.2320	0.4286	0.080*
H15B	0.2458	0.2002	0.3343	0.080*
H15C	0.2146	0.3195	0.3863	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.02882 (14)	0.01537 (12)	0.02345 (13)	0.000	0.00467 (9)	0.000
S1	0.0469 (2)	0.01795 (16)	0.03453 (18)	0.00174 (13)	0.00255 (15)	0.00438 (12)
S2	0.0389 (2)	0.03350 (19)	0.03533 (19)	0.00545 (14)	−0.00088 (15)	0.01283 (14)
N1	0.0239 (5)	0.0193 (5)	0.0213 (5)	−0.0007 (4)	0.0033 (4)	0.0022 (4)
N2	0.0268 (5)	0.0271 (5)	0.0226 (5)	0.0012 (4)	0.0012 (4)	0.0033 (4)
C1	0.0269 (6)	0.0278 (6)	0.0272 (6)	−0.0019 (5)	0.0077 (5)	−0.0024 (5)
C2	0.0265 (6)	0.0456 (8)	0.0306 (6)	−0.0044 (6)	0.0043 (5)	−0.0074 (6)
C3	0.0269 (7)	0.0561 (9)	0.0294 (6)	0.0087 (6)	0.0021 (5)	0.0032 (6)
C4	0.0313 (7)	0.0396 (8)	0.0386 (8)	0.0105 (5)	0.0078 (6)	0.0116 (6)
C5	0.0268 (6)	0.0244 (6)	0.0344 (7)	0.0033 (5)	0.0077 (5)	0.0024 (5)
C6	0.0222 (6)	0.0250 (6)	0.0231 (5)	0.0017 (4)	0.0071 (4)	−0.0004 (5)
C7	0.0243 (6)	0.0191 (5)	0.0231 (5)	−0.0020 (4)	0.0057 (4)	0.0005 (4)
C8	0.0367 (7)	0.0246 (6)	0.0291 (6)	0.0000 (5)	0.0039 (5)	−0.0056 (5)
C9	0.0282 (6)	0.0249 (6)	0.0274 (6)	0.0010 (5)	0.0052 (5)	0.0061 (5)
C10	0.0378 (8)	0.0472 (8)	0.0250 (6)	0.0008 (7)	0.0040 (5)	0.0060 (6)
C11	0.0303 (7)	0.0472 (8)	0.0263 (6)	−0.0003 (6)	0.0048 (5)	0.0002 (6)
C12	0.0391 (8)	0.0529 (9)	0.0310 (7)	−0.0024 (7)	0.0100 (6)	−0.0052 (7)
C13	0.0292 (7)	0.0482 (8)	0.0296 (7)	0.0020 (6)	0.0039 (5)	−0.0044 (6)
C14	0.0380 (8)	0.0549 (10)	0.0398 (8)	−0.0032 (7)	0.0116 (6)	−0.0123 (7)
C15	0.0461 (10)	0.0583 (11)	0.0551 (10)	−0.0091 (8)	0.0095 (8)	−0.0104 (9)

Geometric parameters (Å, º)

Ni1—N1^i	1.9295 (10)	C7—C8	1.5023 (17)
Ni1—N1	1.9295 (10)	C8—H8A	0.9800
Ni1—S1^i	2.1600 (4)	C8—H8B	0.9800
Ni1—S1	2.1600 (4)	C8—H8C	0.9800
S1—C9	1.7443 (14)	C10—C11	1.519 (2)
S2—C9	1.7493 (13)	C10—H10A	0.9900
S2—C10	1.8163 (17)	C10—H10B	0.9900
N1—C7	1.2963 (16)	C11—C12	1.526 (2)
N1—N2	1.4151 (14)	C11—H11A	0.9900
N2—C9	1.2913 (17)	C11—H11B	0.9900
C1—C2	1.3872 (19)	C12—C13	1.524 (2)
C1—C6	1.3984 (17)	C12—H12A	0.9900
C1—H1	0.9500	C12—H12B	0.9900
C2—C3	1.383 (2)	C13—C14	1.521 (2)
C2—H2	0.9500	C13—H13A	0.9900
C3—C4	1.384 (2)	C13—H13B	0.9900
C3—H3	0.9500	C14—C15	1.523 (3)
C4—C5	1.390 (2)	C14—H14A	0.9900
C4—H4	0.9500	C14—H14B	0.9900
C5—C6	1.3956 (18)	C15—H15A	0.9800
C5—H5	0.9500	C15—H15B	0.9800
C6—C7	1.4794 (17)	C15—H15C	0.9800
S1—Ni1—S1^i	93.12 (2)	N2—C9—S1	124.67 (10)
N1—Ni1—S1	85.68 (3)	N2—C9—S2	120.52 (11)
N1—Ni1—S1^i	163.99 (3)	S1—C9—S2	114.81 (8)
N1—Ni1—N1^i	99.79 (6)	C11—C10—S2	115.51 (10)
N1^i—Ni1—S1^i	85.68 (3)	C11—C10—H10A	108.4
N1^i—Ni1—S1	163.99 (3)	S2—C10—H10A	108.4
C9—S1—Ni1	93.62 (4)	C11—C10—H10B	108.4
C9—S2—C10	103.11 (7)	S2—C10—H10B	108.4
C7—N1—N2	114.09 (10)	H10A—C10—H10B	107.5
C7—N1—Ni1	128.55 (9)	C10—C11—C12	111.85 (12)
N2—N1—Ni1	117.34 (8)	C10—C11—H11A	109.2
C9—N2—N1	110.70 (10)	C12—C11—H11A	109.2
C2—C1—C6	120.22 (13)	C10—C11—H11B	109.2
C2—C1—H1	119.9	C12—C11—H11B	109.2
C6—C1—H1	119.9	H11A—C11—H11B	107.9
C3—C2—C1	120.23 (13)	C13—C12—C11	113.67 (12)
C3—C2—H2	119.9	C13—C12—H12A	108.8
C1—C2—H2	119.9	C11—C12—H12A	108.8
C2—C3—C4	120.03 (13)	C13—C12—H12B	108.8
C2—C3—H3	120.0	C11—C12—H12B	108.8
C4—C3—H3	120.0	H12A—C12—H12B	107.7
C3—C4—C5	120.20 (13)	C14—C13—C12	113.20 (13)
C3—C4—H4	119.9	C14—C13—H13A	108.9
C5—C4—H4	119.9	C12—C13—H13A	108.9
C4—C5—C6	120.18 (13)	C14—C13—H13B	108.9
C4—C5—H5	119.9	C12—C13—H13B	108.9
C6—C5—H5	119.9	H13A—C13—H13B	107.8
C5—C6—C1	119.09 (12)	C13—C14—C15	113.56 (14)
C5—C6—C7	120.78 (11)	C13—C14—H14A	108.9
C1—C6—C7	120.07 (11)	C15—C14—H14A	108.9
N1—C7—C6	118.82 (11)	C13—C14—H14B	108.9
N1—C7—C8	122.19 (11)	C15—C14—H14B	108.9
C6—C7—C8	118.96 (11)	H14A—C14—H14B	107.7
C7—C8—H8A	109.5	C14—C15—H15A	109.5
C7—C8—H8B	109.5	C14—C15—H15B	109.5
H8A—C8—H8B	109.5	H15A—C15—H15B	109.5
C7—C8—H8C	109.5	C14—C15—H15C	109.5
H8A—C8—H8C	109.5	H15A—C15—H15C	109.5
H8B—C8—H8C	109.5	H15B—C15—H15C	109.5

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

Cg is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14A···Cg^ii	0.99	2.75	3.5892 (18)	143

Symmetry code: (ii) −x+1, −y+1, −z+1.

Bis[S-n-hexyl 3-(1-phenylethylidene)dithiocarbazato-κ²N³,S]copper(II) (II)

Crystal data

[Cu(C15H21N2S2)2]	F(000) = 1372
Mr = 650.45	Dx = 1.334 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71075 Å
a = 22.7441 (7) Å	Cell parameters from 4858 reflections
b = 8.8636 (3) Å	θ = 3.3–27.4°
c = 17.0117 (6) Å	µ = 0.96 mm^−1
β = 109.158 (1)°	T = 173 K
V = 3239.53 (19) Å^3	Platelet, brown
Z = 4	0.23 × 0.10 × 0.03 mm

Data collection

Rigaku R-AXIS RAPID diffractometer	6505 reflections with I > 2σ(I)
Detector resolution: 10.000 pixels mm^-1	Rint = 0.025
ω scans	θmax = 27.5°, θmin = 3.3°
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995)	h = −29→29
Tmin = 0.772, Tmax = 0.976	k = −11→11
7274 measured reflections	l = −22→22
7274 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.031	H-atom parameters constrained
wR(F^2) = 0.074	w = 1/[σ^2(Fo^2) + (0.0443P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
7274 reflections	Δρmax = 0.70 e Å^−3
357 parameters	Δρmin = −0.22 e Å^−3
2 restraints	Absolute structure: Refined as an inversion twin
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.482 (10)

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.

Refinement. Refined as a two-component inversion twin

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

	x	y	z	Uiso*/Ueq
Cu1	0.76372 (2)	0.47483 (4)	0.64581 (2)	0.02901 (10)
S1	0.72319 (5)	0.66910 (10)	0.56233 (6)	0.0427 (2)
S2	0.65326 (5)	0.65000 (14)	0.38556 (6)	0.0541 (3)
S3	0.80973 (4)	0.60386 (9)	0.76328 (5)	0.0377 (2)
S4	0.87369 (5)	0.46750 (11)	0.92560 (6)	0.0422 (2)
N1	0.76458 (13)	0.3684 (3)	0.54100 (16)	0.0298 (6)
N2	0.72530 (14)	0.4255 (4)	0.46522 (18)	0.0372 (7)
N3	0.75419 (12)	0.3083 (3)	0.72177 (16)	0.0283 (6)
N4	0.79439 (13)	0.3123 (3)	0.80456 (16)	0.0320 (6)
C1	0.83534 (16)	0.1791 (4)	0.6128 (2)	0.0328 (7)
C2	0.83552 (19)	0.0237 (4)	0.6288 (3)	0.0449 (9)
H2	0.8092	−0.0422	0.5884	0.054*
C3	0.8741 (2)	−0.0326 (5)	0.7033 (3)	0.0593 (13)
H3	0.8732	−0.1374	0.7144	0.071*
C4	0.9139 (2)	0.0595 (6)	0.7618 (3)	0.0577 (12)
H4	0.9401	0.0185	0.8129	0.069*
C5	0.91577 (18)	0.2123 (5)	0.7460 (3)	0.0498 (9)
H5	0.9436	0.2763	0.7860	0.060*
C6	0.87702 (16)	0.2717 (4)	0.6720 (2)	0.0366 (8)
H6	0.8787	0.3764	0.6611	0.044*
C7	0.79159 (15)	0.2419 (4)	0.5351 (2)	0.0339 (7)
C8	0.7800 (2)	0.1604 (5)	0.4547 (2)	0.0489 (10)
H8A	0.7354	0.1395	0.4299	0.073*
H8B	0.8031	0.0651	0.4648	0.073*
H8C	0.7938	0.2230	0.4166	0.073*
C9	0.70540 (17)	0.5602 (5)	0.4723 (2)	0.0389 (8)
C10	0.6477 (2)	0.5274 (5)	0.2988 (3)	0.0504 (10)
H10A	0.6293	0.5855	0.2468	0.061*
H10B	0.6904	0.4983	0.3016	0.061*
C11	0.6101 (2)	0.3855 (6)	0.2931 (3)	0.0636 (13)
H11A	0.5700	0.4110	0.3010	0.076*
H11B	0.6329	0.3158	0.3383	0.076*
C12	0.5971 (2)	0.3049 (5)	0.2076 (3)	0.0570 (11)
H12A	0.6346	0.3124	0.1906	0.068*
H12B	0.5892	0.1965	0.2143	0.068*
C13	0.54203 (19)	0.3702 (5)	0.1394 (2)	0.0470 (9)
H13A	0.5509	0.4772	0.1308	0.056*
H13B	0.5051	0.3677	0.1578	0.056*
C14	0.5267 (2)	0.2878 (5)	0.0568 (3)	0.0598 (11)
H14A	0.5221	0.1788	0.0661	0.072*
H14B	0.5618	0.2997	0.0350	0.072*
C15	0.4673 (2)	0.3451 (5)	−0.0081 (3)	0.0626 (12)
H15A	0.4326	0.3366	0.0137	0.094*
H15B	0.4584	0.2845	−0.0589	0.094*
H15C	0.4728	0.4509	−0.0209	0.094*
C16	0.67196 (15)	0.1824 (4)	0.6188 (2)	0.0299 (7)
C17	0.65939 (18)	0.0441 (4)	0.5760 (2)	0.0390 (8)
H17	0.6801	−0.0451	0.6016	0.047*
C18	0.6168 (2)	0.0384 (4)	0.4966 (3)	0.0469 (10)
H18	0.6090	−0.0543	0.4670	0.056*
C19	0.58533 (18)	0.1674 (5)	0.4601 (2)	0.0453 (9)
H19	0.5562	0.1628	0.4053	0.054*
C20	0.59591 (16)	0.3024 (4)	0.5024 (2)	0.0395 (8)
H20	0.5736	0.3902	0.4773	0.047*
C21	0.63895 (15)	0.3099 (4)	0.5813 (2)	0.0316 (7)
H21	0.6461	0.4033	0.6104	0.038*
C22	0.71886 (15)	0.1898 (4)	0.7031 (2)	0.0299 (7)
C23	0.72371 (19)	0.0637 (4)	0.7638 (2)	0.0434 (9)
H23A	0.7662	0.0234	0.7822	0.065*
H23B	0.6944	−0.0165	0.7368	0.065*
H23C	0.7137	0.1019	0.8120	0.065*
C24	0.82018 (17)	0.4433 (4)	0.8252 (2)	0.0338 (8)
C25	0.87310 (19)	0.2823 (4)	0.9736 (2)	0.0451 (9)
H25A	0.8390	0.2782	0.9978	0.054*
H25B	0.8659	0.2022	0.9309	0.054*
C26	0.93557 (19)	0.2566 (5)	1.0418 (2)	0.0471 (9)
H26A	0.9364	0.1523	1.0630	0.057*
H26B	0.9691	0.2650	1.0167	0.057*
C27	0.94983 (18)	0.3651 (5)	1.1151 (2)	0.0408 (8)
H27A	0.9467	0.4700	1.0941	0.049*
H27B	0.9183	0.3519	1.1432	0.049*
C28	1.01432 (18)	0.3406 (5)	1.1781 (2)	0.0501 (10)
H28A	1.0200	0.2315	1.1909	0.060*
H28B	1.0458	0.3709	1.1524	0.060*
C29	1.02664 (18)	0.4269 (5)	1.2592 (2)	0.0477 (9)
H29A	1.0719	0.4248	1.2901	0.057*
H29B	1.0143	0.5335	1.2462	0.057*
C30	0.99290 (19)	0.3655 (5)	1.3133 (2)	0.0534 (10)
H30A	0.9480	0.3716	1.2842	0.080*
H30B	1.0036	0.4245	1.3648	0.080*
H30C	1.0048	0.2600	1.3266	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.03446 (19)	0.02179 (16)	0.03268 (19)	−0.00067 (18)	0.01359 (15)	−0.00063 (18)
S1	0.0537 (6)	0.0254 (4)	0.0478 (5)	0.0061 (4)	0.0151 (4)	0.0052 (4)
S2	0.0525 (6)	0.0622 (7)	0.0448 (5)	0.0179 (5)	0.0124 (4)	0.0183 (5)
S3	0.0465 (5)	0.0260 (4)	0.0391 (5)	−0.0078 (4)	0.0120 (4)	−0.0041 (3)
S4	0.0466 (5)	0.0408 (5)	0.0335 (5)	−0.0107 (4)	0.0054 (4)	−0.0032 (4)
N1	0.0329 (13)	0.0283 (13)	0.0301 (13)	0.0021 (11)	0.0129 (11)	0.0022 (11)
N2	0.0380 (16)	0.0435 (17)	0.0314 (14)	0.0007 (14)	0.0129 (12)	0.0036 (13)
N3	0.0305 (14)	0.0255 (13)	0.0300 (13)	−0.0037 (11)	0.0115 (11)	−0.0044 (11)
N4	0.0349 (14)	0.0304 (14)	0.0312 (14)	−0.0054 (12)	0.0115 (11)	−0.0032 (11)
C1	0.0354 (18)	0.0269 (16)	0.0435 (19)	0.0024 (14)	0.0227 (15)	0.0011 (15)
C2	0.051 (2)	0.0243 (16)	0.066 (3)	0.0055 (16)	0.027 (2)	0.0049 (18)
C3	0.064 (3)	0.039 (2)	0.085 (3)	0.012 (2)	0.039 (3)	0.020 (2)
C4	0.052 (2)	0.062 (3)	0.062 (3)	0.025 (2)	0.024 (2)	0.025 (2)
C5	0.038 (2)	0.060 (2)	0.051 (2)	0.0027 (19)	0.0147 (17)	0.001 (2)
C6	0.0342 (17)	0.0313 (16)	0.049 (2)	0.0042 (15)	0.0195 (15)	0.0038 (16)
C7	0.0374 (17)	0.0298 (16)	0.0390 (18)	−0.0010 (15)	0.0189 (14)	−0.0029 (14)
C8	0.059 (2)	0.045 (2)	0.044 (2)	0.0051 (19)	0.0178 (19)	−0.0100 (18)
C9	0.0375 (19)	0.0437 (19)	0.0378 (19)	0.0053 (17)	0.0155 (16)	0.0115 (17)
C10	0.041 (2)	0.067 (3)	0.043 (2)	0.0022 (19)	0.0135 (17)	0.0181 (19)
C11	0.053 (2)	0.082 (3)	0.053 (3)	−0.010 (2)	0.014 (2)	0.027 (2)
C12	0.056 (3)	0.049 (2)	0.067 (3)	−0.002 (2)	0.022 (2)	0.013 (2)
C13	0.046 (2)	0.049 (2)	0.053 (2)	−0.0027 (19)	0.0261 (18)	0.0005 (19)
C14	0.069 (3)	0.047 (2)	0.072 (3)	−0.002 (2)	0.034 (2)	−0.008 (2)
C15	0.078 (3)	0.055 (3)	0.055 (3)	−0.009 (2)	0.024 (2)	−0.014 (2)
C16	0.0310 (16)	0.0278 (15)	0.0340 (16)	−0.0067 (13)	0.0149 (13)	−0.0032 (13)
C17	0.045 (2)	0.0290 (18)	0.044 (2)	−0.0014 (16)	0.0158 (16)	−0.0034 (16)
C18	0.052 (2)	0.041 (2)	0.046 (2)	−0.0160 (19)	0.0134 (18)	−0.0131 (18)
C19	0.043 (2)	0.053 (2)	0.0363 (19)	−0.0130 (18)	0.0079 (16)	−0.0038 (17)
C20	0.0335 (17)	0.043 (2)	0.0417 (19)	−0.0036 (16)	0.0125 (15)	0.0017 (17)
C21	0.0328 (16)	0.0302 (16)	0.0348 (17)	−0.0050 (14)	0.0150 (13)	−0.0046 (14)
C22	0.0339 (17)	0.0264 (15)	0.0333 (16)	−0.0009 (13)	0.0163 (13)	−0.0024 (13)
C23	0.051 (2)	0.0363 (18)	0.042 (2)	−0.0107 (18)	0.0138 (17)	0.0035 (17)
C24	0.0337 (18)	0.0371 (19)	0.0301 (17)	−0.0023 (15)	0.0098 (14)	−0.0044 (15)
C25	0.055 (2)	0.0394 (19)	0.0387 (19)	−0.0092 (18)	0.0131 (17)	−0.0028 (16)
C26	0.054 (2)	0.048 (2)	0.0388 (19)	0.0107 (19)	0.0141 (17)	−0.0030 (18)
C27	0.044 (2)	0.041 (2)	0.0378 (18)	0.0061 (17)	0.0138 (16)	−0.0044 (16)
C28	0.042 (2)	0.061 (3)	0.044 (2)	0.0095 (19)	0.0111 (17)	−0.0032 (19)
C29	0.039 (2)	0.050 (2)	0.046 (2)	−0.0037 (18)	0.0040 (16)	−0.0035 (19)
C30	0.047 (2)	0.065 (3)	0.045 (2)	−0.010 (2)	0.0096 (17)	−0.008 (2)

Geometric parameters (Å, º)

Cu1—N1	2.023 (3)	C13—H13A	0.9900
Cu1—N3	2.020 (3)	C13—H13B	0.9900
Cu1—S1	2.2299 (9)	C14—C15	1.524 (7)
Cu1—S3	2.2414 (9)	C14—H14A	0.9900
S1—C9	1.742 (4)	C14—H14B	0.9900
S2—C9	1.752 (4)	C15—H15A	0.9800
S2—C10	1.804 (5)	C15—H15B	0.9800
S3—C24	1.740 (4)	C15—H15C	0.9800
S4—C24	1.755 (4)	C16—C21	1.391 (5)
S4—C25	1.835 (4)	C16—C17	1.406 (5)
N1—C7	1.298 (4)	C16—C22	1.481 (4)
N1—N2	1.400 (4)	C17—C18	1.381 (5)
N2—C9	1.296 (5)	C17—H17	0.9500
N3—C22	1.297 (4)	C18—C19	1.383 (6)
N3—N4	1.406 (4)	C18—H18	0.9500
N4—C24	1.296 (5)	C19—C20	1.376 (5)
C1—C6	1.399 (5)	C19—H19	0.9500
C1—C2	1.404 (5)	C20—C21	1.380 (5)
C1—C7	1.478 (5)	C20—H20	0.9500
C2—C3	1.377 (7)	C21—H21	0.9500
C2—H2	0.9500	C22—C23	1.501 (5)
C3—C4	1.373 (7)	C23—H23A	0.9800
C3—H3	0.9500	C23—H23B	0.9800
C4—C5	1.384 (7)	C23—H23C	0.9800
C4—H4	0.9500	C25—C26	1.528 (5)
C5—C6	1.383 (5)	C25—H25A	0.9900
C5—H5	0.9500	C25—H25B	0.9900
C6—H6	0.9500	C26—C27	1.523 (5)
C7—C8	1.491 (5)	C26—H26A	0.9900
C8—H8A	0.9800	C26—H26B	0.9900
C8—H8B	0.9800	C27—C28	1.522 (5)
C8—H8C	0.9800	C27—H27A	0.9900
C10—C11	1.506 (6)	C27—H27B	0.9900
C10—H10A	0.9900	C28—C29	1.521 (6)
C10—H10B	0.9900	C28—H28A	0.9900
C11—C12	1.559 (7)	C28—H28B	0.9900
C11—H11A	0.9900	C29—C30	1.481 (6)
C11—H11B	0.9900	C29—H29A	0.9900
C12—C13	1.515 (6)	C29—H29B	0.9900
C12—H12A	0.9900	C30—H30A	0.9800
C12—H12B	0.9900	C30—H30B	0.9800
C13—C14	1.519 (6)	C30—H30C	0.9800
S1—Cu1—S3	98.53 (4)	C13—C14—H14B	109.0
N1—Cu1—S1	85.43 (8)	C15—C14—H14B	109.0
N3—Cu1—S1	149.66 (8)	H14A—C14—H14B	107.8
N1—Cu1—S3	152.51 (8)	C14—C15—H15A	109.5
N3—Cu1—S3	85.37 (8)	C14—C15—H15B	109.5
N1—Cu1—N3	104.90 (11)	H15A—C15—H15B	109.5
C9—S1—Cu1	93.45 (13)	C14—C15—H15C	109.5
C9—S2—C10	105.16 (19)	H15A—C15—H15C	109.5
C24—S3—Cu1	93.07 (12)	H15B—C15—H15C	109.5
C24—S4—C25	102.70 (18)	C21—C16—C17	118.9 (3)
C7—N1—N2	114.6 (3)	C21—C16—C22	121.1 (3)
C7—N1—Cu1	127.8 (2)	C17—C16—C22	120.0 (3)
N2—N1—Cu1	117.1 (2)	C18—C17—C16	119.8 (3)
C9—N2—N1	112.6 (3)	C18—C17—H17	120.1
C22—N3—N4	114.4 (3)	C16—C17—H17	120.1
C22—N3—Cu1	128.5 (2)	C17—C18—C19	120.2 (3)
N4—N3—Cu1	116.84 (18)	C17—C18—H18	119.9
C24—N4—N3	112.5 (3)	C19—C18—H18	119.9
C6—C1—C2	118.6 (3)	C20—C19—C18	120.5 (3)
C6—C1—C7	121.4 (3)	C20—C19—H19	119.7
C2—C1—C7	120.0 (3)	C18—C19—H19	119.7
C3—C2—C1	119.6 (4)	C19—C20—C21	119.9 (3)
C3—C2—H2	120.2	C19—C20—H20	120.1
C1—C2—H2	120.2	C21—C20—H20	120.1
C4—C3—C2	121.4 (4)	C20—C21—C16	120.7 (3)
C4—C3—H3	119.3	C20—C21—H21	119.7
C2—C3—H3	119.3	C16—C21—H21	119.7
C3—C4—C5	119.8 (4)	N3—C22—C16	117.7 (3)
C3—C4—H4	120.1	N3—C22—C23	122.3 (3)
C5—C4—H4	120.1	C16—C22—C23	120.0 (3)
C6—C5—C4	119.9 (4)	C22—C23—H23A	109.5
C6—C5—H5	120.1	C22—C23—H23B	109.5
C4—C5—H5	120.1	H23A—C23—H23B	109.5
C5—C6—C1	120.7 (3)	C22—C23—H23C	109.5
C5—C6—H6	119.6	H23A—C23—H23C	109.5
C1—C6—H6	119.6	H23B—C23—H23C	109.5
N1—C7—C1	116.9 (3)	N4—C24—S3	127.5 (3)
N1—C7—C8	122.9 (3)	N4—C24—S4	118.7 (3)
C1—C7—C8	120.2 (3)	S3—C24—S4	113.7 (2)
C7—C8—H8A	109.5	C26—C25—S4	109.3 (3)
C7—C8—H8B	109.5	C26—C25—H25A	109.8
H8A—C8—H8B	109.5	S4—C25—H25A	109.8
C7—C8—H8C	109.5	C26—C25—H25B	109.8
H8A—C8—H8C	109.5	S4—C25—H25B	109.8
H8B—C8—H8C	109.5	H25A—C25—H25B	108.3
N2—C9—S1	127.2 (3)	C27—C26—C25	115.0 (3)
N2—C9—S2	120.1 (3)	C27—C26—H26A	108.5
S1—C9—S2	112.7 (2)	C25—C26—H26A	108.5
C11—C10—S2	116.2 (3)	C27—C26—H26B	108.5
C11—C10—H10A	108.2	C25—C26—H26B	108.5
S2—C10—H10A	108.2	H26A—C26—H26B	107.5
C11—C10—H10B	108.2	C28—C27—C26	112.6 (3)
S2—C10—H10B	108.2	C28—C27—H27A	109.1
H10A—C10—H10B	107.4	C26—C27—H27A	109.1
C10—C11—C12	111.9 (4)	C28—C27—H27B	109.1
C10—C11—H11A	109.2	C26—C27—H27B	109.1
C12—C11—H11A	109.2	H27A—C27—H27B	107.8
C10—C11—H11B	109.2	C29—C28—C27	114.5 (3)
C12—C11—H11B	109.2	C29—C28—H28A	108.6
H11A—C11—H11B	107.9	C27—C28—H28A	108.6
C13—C12—C11	113.3 (4)	C29—C28—H28B	108.6
C13—C12—H12A	108.9	C27—C28—H28B	108.6
C11—C12—H12A	108.9	H28A—C28—H28B	107.6
C13—C12—H12B	108.9	C30—C29—C28	113.6 (4)
C11—C12—H12B	108.9	C30—C29—H29A	108.8
H12A—C12—H12B	107.7	C28—C29—H29A	108.8
C12—C13—C14	113.9 (4)	C30—C29—H29B	108.8
C12—C13—H13A	108.8	C28—C29—H29B	108.8
C14—C13—H13A	108.8	H29A—C29—H29B	107.7
C12—C13—H13B	108.8	C29—C30—H30A	109.5
C14—C13—H13B	108.8	C29—C30—H30B	109.5
H13A—C13—H13B	107.7	H30A—C30—H30B	109.5
C13—C14—C15	112.9 (4)	C29—C30—H30C	109.5
C13—C14—H14A	109.0	H30A—C30—H30C	109.5
C15—C14—H14A	109.0	H30B—C30—H30C	109.5