Crystal structure of bis­{μ-4-methyl-N′-[3-(oxido­imino)­butan-2-yl­idene]benzene­sulfono­hydrazidato}bis­[(dimethyl sulfoxide-κO)copper(II)]

In the title compound, [Cu₂(C₁₁H₁₃N₃O₃S)₂(C₂H₆OS)₂], the Cu^II cation is N,N′,O-chelated by a deprotonated hy­droxy­imino-tosyl­hydrazone ligand and coordinated by a dimethyl sulfoxide mol­ecule. One O atom from the adjacent hy­droxy­imino-tosyl­hydrazone ligand bridges the Cu^II cation, forming the centrosymmetric dimeric complex. The cation is in an overall distorted N₂O₃ square-pyramidal coordination environment. The methyl­benzene ring is twisted with respect to the hydrazine fragment, with a dihedral angle of 89.54 (9)° between the planes. An intra­molecular C—H...O hydrogen bond occurs. In the crystal, mol­ecules are linked by weak C—H...O and C—H...S inter­actions. Weak π–π stacking is also observed between parallel benzene rings of adjacent mol­ecules, the centroid–centroid distance being 3.9592 (17) Å.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.032
• wR factor = 0.091
• Data-to-parameter ratio = 19.5

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low .......      0.934 Note

Author Response: The missing of data quality is due to the data collection. We had a problem with the detector of the diffractometer. The value should be around 0.6, this is true, but we think that the actual data do not compromise the structure solution and refinement. As the structure seems to be in order, and there are no possibility to be another molecule than this presented, we decide to submit the article with the present data. The question is important to the crystallography, but of the point of view of the chemistry, the compound was characterised successfully.

Alert level C
PLAT242_ALERT_2_C Low       Ueq as Compared to Neighbors for .....         S2 Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600        139 Report

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT063_ALERT_4_G Crystal Size Likely too Large for Beam Size ....       0.61 mm
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal ..........    0.00200 Degree
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT380_ALERT_4_G Incorrectly? Oriented X(sp2)-Methyl Moiety .....        C11 Check
PLAT380_ALERT_4_G Incorrectly? Oriented X(sp2)-Methyl Moiety .....         C9 Check
PLAT380_ALERT_4_G Incorrectly? Oriented X(sp2)-Methyl Moiety .....        C10 Check
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          8 Note
PLAT793_ALERT_4_G The Model has Chirality at S1      .............          S Verify
PLAT794_ALERT_5_G Tentative Bond Valency for Cu1     (II)    .....       2.24 Note
PLAT910_ALERT_3_G Missing # of FCF Reflections Below Th(Min) .....          1 Report
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        145 Note

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

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

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S1. Structural commentary

Hy­droxy­imino-tosyl­hydrazone derivatives are N,O-donors that show an application as complexing agents (Beger et al., 1991). In the crystal structure of the title compound the Cu^II cations are five-coordinated by one crystallographically independent deprotonated hy­droxy­imino-tosyl­hydrazone derivative, one DMSO molecule and one O-atom from a second, symmetry generated, hy­droxy­imino-tosyl­hydrazone derivative into dimers (Fig. 1). The metal centres are in a slightly distorted pyramidal environment. The aromatic ring and the N1/N2/C7/C8/N3/O3-fragment angle amount to 89,54 (09)°. In this complex molecule significant structural changes of the N–O and N–N bonds. For the uncoordinated ligand the N–O and N–N bonds distances amount to 1.4084 (16) Å and 1.3807 (16) Å. These distances indicate the double bond character for the N–N and the single bond character for the N–O bond (Bulhosa et al., 2012). In contrast, in the title compound, the acidic hydrogen of the hydrazine fragment is removed and the negative charge is delocalized over the N–N–C–C–N–O fragment. Therefore, N–N and N–O distances amount to 1.367 (3) Å and 1.343 (2) Å. Additionally, the complexes are linked by N–O bridges into dimers (Fig. 2). Finally, the dimers are arranged along the b-axis with very weak π–π inter­actions.

S2. Synthesis and crystallization

Starting materials were commercially available and were used without further purification. The ligand synthesis was adapted from a procedure reported previously and its structure is already published (Bulhosa et al., 2012). N'-[3-(Hy­droxy­imino)­butan- 2-yl­idene]-4-methyl­benzene-1-sulfono­hydrazide was dissolved in methanol (2 mmol/40 mL) with stirring maintained for 30 min and deprotonated with sodium, while the solution turns yellow. At the same time, a solution of copper(II) acetate monohydrate (1 mmol/40 mL) in methanol was prepared under continuous stirring. A mixture of both solutions was maintained with stirring at room temperature for 6 h. The methanol was removed by evaporation and crystals suitable for X-ray diffraction were obtained in DMSO by the slow evaporation of the solvent.

S3. Refinement

H atoms attached to C atoms were positioned with idealized geometry and were refined isotropically with U_iso(H) set to 1.2 times U_eq(C) for the aromatic and 1.5 times U_eq(C) for methyl H atoms using a riding model with C—H = 0.93 Å and C—H = 0.96 Å, respectively.

Related literature

For the synthesis and applications of hydroxyimino-tosylhydrazones as complexing agents, see: Beger et al. (1991). For the crystal structure of the 4-methyl-N'-[3-(hydroxyimino)butan-2-ylidene]benzenesulfonohydrazide ligand, see: Bulhosa et al. (2012).

Computing details

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

Figures

	Fig. 1. : The molecular structure of the title compound with labeling and displacement ellipsoids drawn at the 40% probability level showing the dimeric structure. Symmetry code: (i)-x + 1,-y + 1,-z + 1
	Fig. 2. : Molecules of the title compound arranged along b-axis showing the column of the aromatic rings with very weak π–π interactions.

Bis{µ-4-methyl-N'-[3-(oxidoimino)butan-2-ylidene]benzenesulfonohydrazidato}-κ⁴O,N,N':O';κ⁴O':O,N,N'-bis[(dimethyl sulfoxide-κO)copper(II)]

Crystal data

[Cu2(C11H13N3O3S)2(C2H6OS)2]	Z = 1
Mr = 817.95	F(000) = 422
Triclinic, P1	Dx = 1.568 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8097 (3) Å	Cell parameters from 7693 reflections
b = 8.4670 (3) Å	θ = 2.8–28.1°
c = 15.1586 (6) Å	µ = 1.52 mm^−1
α = 74.656 (2)°	T = 293 K
β = 75.955 (2)°	Block, black
γ = 65.042 (2)°	0.61 × 0.28 × 0.07 mm
V = 866.47 (6) Å^3

Data collection

Bruker APEXII CCD diffractometer	4054 independent reflections
Radiation source: fine-focus sealed tube, Bruker Kappa CCD	3366 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.015
ϕ and ω scans	θmax = 28.4°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −10→10
Tmin = 0.457, Tmax = 0.901	k = −11→7
5765 measured reflections	l = −20→18

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.091	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0467P)^2 + 0.3887P] where P = (Fo^2 + 2Fc^2)/3
4054 reflections	(Δ/σ)max < 0.001
208 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.42 e Å^−3

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 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 (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.58200 (4)	0.31552 (3)	0.593265 (18)	0.02826 (9)
S1	0.77302 (8)	0.04077 (8)	0.74973 (4)	0.03261 (14)
S2	0.14080 (8)	0.50296 (8)	0.67789 (4)	0.03775 (15)
O2	0.6646 (2)	0.2330 (2)	0.72499 (11)	0.0355 (4)
N2	0.7236 (3)	0.0618 (2)	0.59334 (13)	0.0287 (4)
C10	0.6295 (4)	0.1222 (3)	0.35609 (16)	0.0370 (5)
H10A	0.5581	0.2316	0.3194	0.056*
H10B	0.5663	0.0413	0.3685	0.056*
H10C	0.7556	0.0715	0.3231	0.056*
C7	0.7440 (3)	0.0142 (3)	0.51572 (15)	0.0293 (4)
O4	0.2837 (2)	0.3281 (2)	0.65248 (12)	0.0386 (4)
O1	0.9442 (3)	−0.0107 (3)	0.78807 (13)	0.0480 (5)
N1	0.8225 (3)	−0.0535 (3)	0.66265 (13)	0.0361 (4)
O3	0.4716 (2)	0.4478 (2)	0.40297 (11)	0.0346 (4)
N3	0.5685 (3)	0.3140 (2)	0.46524 (12)	0.0281 (4)
C8	0.6430 (3)	0.1565 (3)	0.44490 (15)	0.0271 (4)
C2	0.3225 (4)	−0.0775 (4)	0.88982 (19)	0.0486 (7)
H2	0.1983	−0.0485	0.8810	0.058*
C1	0.4370 (4)	−0.0029 (4)	0.82421 (17)	0.0400 (6)
H1	0.3897	0.0761	0.7719	0.048*
C6	0.6226 (3)	−0.0460 (3)	0.83647 (15)	0.0332 (5)
C9	0.8650 (4)	−0.1691 (3)	0.49726 (19)	0.0417 (6)
H9A	0.9189	−0.2428	0.5517	0.062*
H9B	0.9659	−0.1646	0.4470	0.062*
H9C	0.7878	−0.2174	0.4813	0.062*
C3	0.3885 (5)	−0.1948 (4)	0.96864 (19)	0.0526 (7)
C5	0.6905 (4)	−0.1601 (4)	0.91562 (18)	0.0471 (6)
H5	0.8141	−0.1876	0.9251	0.057*
C4	0.5723 (5)	−0.2326 (4)	0.9805 (2)	0.0583 (8)
H4	0.6181	−0.3091	1.0337	0.070*
C021	0.1846 (5)	0.5082 (5)	0.7870 (2)	0.0674 (9)
H02A	0.3027	0.5237	0.7789	0.101*
H02B	0.1927	0.3987	0.8286	0.101*
H02C	0.0821	0.6049	0.8122	0.101*
C022	−0.0802 (4)	0.4738 (5)	0.7154 (3)	0.0650 (9)
H02D	−0.1256	0.4685	0.6633	0.097*
H02E	−0.1723	0.5718	0.7436	0.097*
H02F	−0.0618	0.3656	0.7597	0.097*
C11	0.2614 (6)	−0.2742 (5)	1.0403 (3)	0.0812 (12)
H11A	0.1395	−0.2329	1.0205	0.122*
H11B	0.2444	−0.2393	1.0982	0.122*
H11C	0.3194	−0.4011	1.0480	0.122*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.03260 (15)	0.02483 (15)	0.02657 (15)	−0.00907 (11)	−0.00598 (10)	−0.00532 (10)
S1	0.0312 (3)	0.0331 (3)	0.0312 (3)	−0.0074 (2)	−0.0101 (2)	−0.0054 (2)
S2	0.0296 (3)	0.0328 (3)	0.0422 (3)	−0.0086 (2)	−0.0041 (2)	0.0001 (2)
O2	0.0420 (9)	0.0315 (9)	0.0331 (8)	−0.0111 (7)	−0.0110 (7)	−0.0062 (7)
N2	0.0290 (9)	0.0258 (9)	0.0288 (9)	−0.0084 (7)	−0.0051 (7)	−0.0038 (7)
C10	0.0443 (13)	0.0342 (13)	0.0342 (12)	−0.0130 (10)	−0.0068 (10)	−0.0115 (10)
C7	0.0272 (10)	0.0285 (11)	0.0315 (11)	−0.0107 (9)	−0.0015 (8)	−0.0071 (9)
O4	0.0341 (9)	0.0360 (9)	0.0434 (10)	−0.0108 (7)	−0.0056 (7)	−0.0080 (7)
O1	0.0360 (9)	0.0588 (12)	0.0493 (11)	−0.0131 (9)	−0.0180 (8)	−0.0081 (9)
N1	0.0388 (11)	0.0311 (10)	0.0289 (9)	−0.0027 (8)	−0.0078 (8)	−0.0057 (8)
O3	0.0486 (10)	0.0259 (8)	0.0310 (8)	−0.0119 (7)	−0.0166 (7)	−0.0023 (6)
N3	0.0315 (9)	0.0268 (9)	0.0270 (9)	−0.0129 (7)	−0.0048 (7)	−0.0034 (7)
C8	0.0265 (10)	0.0282 (11)	0.0277 (10)	−0.0122 (8)	−0.0009 (8)	−0.0071 (8)
C2	0.0486 (15)	0.0597 (18)	0.0432 (15)	−0.0256 (14)	−0.0016 (12)	−0.0154 (13)
C1	0.0441 (14)	0.0450 (14)	0.0322 (12)	−0.0163 (11)	−0.0121 (10)	−0.0049 (11)
C6	0.0394 (12)	0.0306 (12)	0.0276 (11)	−0.0080 (9)	−0.0097 (9)	−0.0069 (9)
C9	0.0451 (14)	0.0316 (12)	0.0417 (14)	−0.0051 (10)	−0.0072 (11)	−0.0117 (11)
C3	0.073 (2)	0.0493 (17)	0.0369 (14)	−0.0293 (15)	0.0038 (13)	−0.0115 (12)
C5	0.0512 (16)	0.0452 (15)	0.0355 (13)	−0.0083 (12)	−0.0157 (11)	−0.0011 (11)
C4	0.081 (2)	0.0475 (17)	0.0336 (14)	−0.0170 (16)	−0.0146 (14)	0.0048 (12)
C021	0.071 (2)	0.070 (2)	0.057 (2)	−0.0141 (18)	−0.0073 (16)	−0.0295 (17)
C022	0.0335 (14)	0.060 (2)	0.091 (3)	−0.0199 (14)	0.0026 (15)	−0.0057 (18)
C11	0.111 (3)	0.077 (3)	0.057 (2)	−0.055 (2)	0.020 (2)	−0.0123 (19)

Geometric parameters (Å, º)

Cu1—N2	1.9580 (19)	C2—C1	1.378 (4)
Cu1—N3	1.9728 (18)	C2—C3	1.385 (4)
Cu1—O2	2.0970 (16)	C2—H2	0.9300
Cu1—O3^i	1.8798 (16)	C1—C6	1.385 (3)
Cu1—O4	2.2517 (17)	C1—H1	0.9300
S1—O1	1.4376 (18)	C6—C5	1.385 (3)
S1—O2	1.4745 (17)	C9—H9A	0.9600
S1—N1	1.606 (2)	C9—H9B	0.9600
S1—C6	1.765 (2)	C9—H9C	0.9600
S2—O4	1.5114 (18)	C3—C4	1.379 (5)
S2—C022	1.781 (3)	C3—C11	1.507 (4)
S2—C021	1.783 (3)	C5—C4	1.384 (4)
N2—C7	1.295 (3)	C5—H5	0.9300
N2—N1	1.367 (3)	C4—H4	0.9300
C10—C8	1.486 (3)	C021—H02A	0.9600
C10—H10A	0.9600	C021—H02B	0.9600
C10—H10B	0.9600	C021—H02C	0.9600
C10—H10C	0.9600	C022—H02D	0.9600
C7—C8	1.467 (3)	C022—H02E	0.9600
C7—C9	1.498 (3)	C022—H02F	0.9600
O3—N3	1.343 (2)	C11—H11A	0.9600
O3—Cu1^i	1.8798 (16)	C11—H11B	0.9600
N3—C8	1.299 (3)	C11—H11C	0.9600
O3^i—Cu1—N2	160.52 (8)	C1—C2—H2	119.3
O3^i—Cu1—N3	105.85 (7)	C3—C2—H2	119.3
N2—Cu1—N3	81.34 (8)	C2—C1—C6	119.7 (2)
O3^i—Cu1—O2	90.50 (6)	C2—C1—H1	120.1
N2—Cu1—O2	80.08 (7)	C6—C1—H1	120.1
N3—Cu1—O2	160.90 (7)	C1—C6—C5	119.9 (2)
O3^i—Cu1—O4	95.33 (7)	C1—C6—S1	119.73 (18)
N2—Cu1—O4	101.95 (7)	C5—C6—S1	120.4 (2)
N3—Cu1—O4	96.11 (7)	C7—C9—H9A	109.5
O2—Cu1—O4	92.01 (7)	C7—C9—H9B	109.5
O1—S1—O2	116.12 (11)	H9A—C9—H9B	109.5
O1—S1—N1	109.45 (11)	C7—C9—H9C	109.5
O2—S1—N1	110.60 (10)	H9A—C9—H9C	109.5
O1—S1—C6	105.75 (11)	H9B—C9—H9C	109.5
O2—S1—C6	107.02 (11)	C4—C3—C2	117.8 (3)
N1—S1—C6	107.42 (11)	C4—C3—C11	121.2 (3)
O4—S2—C022	105.09 (14)	C2—C3—C11	121.0 (3)
O4—S2—C021	106.15 (14)	C4—C5—C6	119.1 (3)
C022—S2—C021	98.59 (18)	C4—C5—H5	120.4
S1—O2—Cu1	114.45 (9)	C6—C5—H5	120.4
C7—N2—N1	120.75 (19)	C3—C4—C5	121.9 (3)
C7—N2—Cu1	114.72 (15)	C3—C4—H4	119.0
N1—N2—Cu1	123.60 (15)	C5—C4—H4	119.0
C8—C10—H10A	109.5	S2—C021—H02A	109.5
C8—C10—H10B	109.5	S2—C021—H02B	109.5
H10A—C10—H10B	109.5	H02A—C021—H02B	109.5
C8—C10—H10C	109.5	S2—C021—H02C	109.5
H10A—C10—H10C	109.5	H02A—C021—H02C	109.5
H10B—C10—H10C	109.5	H02B—C021—H02C	109.5
N2—C7—C8	114.58 (19)	S2—C022—H02D	109.5
N2—C7—C9	123.5 (2)	S2—C022—H02E	109.5
C8—C7—C9	121.8 (2)	H02D—C022—H02E	109.5
S2—O4—Cu1	116.15 (10)	S2—C022—H02F	109.5
N2—N1—S1	110.24 (15)	H02D—C022—H02F	109.5
N3—O3—Cu1^i	120.90 (13)	H02E—C022—H02F	109.5
C8—N3—O3	117.04 (18)	C3—C11—H11A	109.5
C8—N3—Cu1	113.71 (15)	C3—C11—H11B	109.5
O3—N3—Cu1	128.55 (14)	H11A—C11—H11B	109.5
N3—C8—C7	115.07 (19)	C3—C11—H11C	109.5
N3—C8—C10	122.8 (2)	H11A—C11—H11C	109.5
C7—C8—C10	122.1 (2)	H11B—C11—H11C	109.5
C1—C2—C3	121.5 (3)
O1—S1—O2—Cu1	132.54 (11)	O3^i—Cu1—N3—C8	165.37 (15)
N1—S1—O2—Cu1	7.05 (14)	N2—Cu1—N3—C8	3.91 (15)
C6—S1—O2—Cu1	−109.67 (11)	O2—Cu1—N3—C8	17.4 (3)
O3^i—Cu1—O2—S1	−164.58 (11)	O4—Cu1—N3—C8	−97.30 (15)
N2—Cu1—O2—S1	−1.72 (10)	O3^i—Cu1—N3—O3	−24.6 (2)
N3—Cu1—O2—S1	−15.2 (3)	N2—Cu1—N3—O3	173.91 (18)
O4—Cu1—O2—S1	100.06 (11)	O2—Cu1—N3—O3	−172.62 (17)
O3^i—Cu1—N2—C7	−112.5 (2)	O4—Cu1—N3—O3	72.70 (17)
N3—Cu1—N2—C7	0.93 (15)	O3—N3—C8—C7	−178.83 (17)
O2—Cu1—N2—C7	−174.63 (16)	Cu1—N3—C8—C7	−7.6 (2)
O4—Cu1—N2—C7	95.40 (16)	O3—N3—C8—C10	1.8 (3)
O3^i—Cu1—N2—N1	56.5 (3)	Cu1—N3—C8—C10	173.05 (16)
N3—Cu1—N2—N1	170.01 (18)	N2—C7—C8—N3	8.5 (3)
O2—Cu1—N2—N1	−5.55 (17)	C9—C7—C8—N3	−169.7 (2)
O4—Cu1—N2—N1	−95.52 (17)	N2—C7—C8—C10	−172.10 (19)
N1—N2—C7—C8	−174.51 (18)	C9—C7—C8—C10	9.6 (3)
Cu1—N2—C7—C8	−5.1 (2)	C3—C2—C1—C6	0.4 (4)
N1—N2—C7—C9	3.7 (3)	C2—C1—C6—C5	−1.7 (4)
Cu1—N2—C7—C9	173.13 (18)	C2—C1—C6—S1	176.8 (2)
C022—S2—O4—Cu1	176.67 (15)	O1—S1—C6—C1	173.2 (2)
C021—S2—O4—Cu1	−79.50 (17)	O2—S1—C6—C1	48.8 (2)
O3^i—Cu1—O4—S2	−1.22 (11)	N1—S1—C6—C1	−70.0 (2)
N2—Cu1—O4—S2	169.76 (11)	O1—S1—C6—C5	−8.3 (2)
N3—Cu1—O4—S2	−107.83 (11)	O2—S1—C6—C5	−132.7 (2)
O2—Cu1—O4—S2	89.47 (11)	N1—S1—C6—C5	108.5 (2)
C7—N2—N1—S1	179.00 (16)	C1—C2—C3—C4	1.1 (4)
Cu1—N2—N1—S1	10.5 (2)	C1—C2—C3—C11	179.4 (3)
O1—S1—N1—N2	−139.82 (16)	C1—C6—C5—C4	1.5 (4)
O2—S1—N1—N2	−10.66 (19)	S1—C6—C5—C4	−177.0 (2)
C6—S1—N1—N2	105.82 (17)	C2—C3—C4—C5	−1.4 (5)
Cu1^i—O3—N3—C8	−162.43 (15)	C11—C3—C4—C5	−179.6 (3)
Cu1^i—O3—N3—Cu1	27.9 (2)	C6—C5—C4—C3	0.1 (5)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O4	0.93	2.39	3.299 (3)	166
C2—H2···O1^ii	0.93	2.57	3.430 (4)	154
C9—H9A···S2^iii	0.96	2.75	3.693 (3)	166
C10—H10C···O1^iv	0.96	2.47	3.415 (4)	166

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