Crystal structure of bis-{μ-4-methyl-N'-[3-(oxido-imino)-butan-2-yl-idene]benzene-sulfono-hydrazidato}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 hy-droxy-imino-tosyl-hydrazone ligand and coordinated by a dimethyl sulfoxide mol-ecule. One O atom from the adjacent hy-droxy-imino-tosyl-hydrazone ligand bridges the Cu(II) cation, forming the centrosymmetric dimeric complex. The cation is in an overall distorted N2O3 square-pyramidal coordination environment. The methyl-benzene ring is twisted with respect to the hydrazine fragment, with a dihedral angle of 89.54 (9)° between the planes. An intra-molecular C-H⋯O hydrogen bond occurs. In the crystal, mol-ecules are linked by weak C-H⋯O and C-H⋯S inter-actions. Weak π-π stacking is also observed between parallel benzene rings of adjacent mol-ecules, the centroid-centroid distance being 3.9592 (17) Å.

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 ▶).

Experimental

Crystal data

[Cu2(C11H13N3O3S)2(C2H6OS)2]

M = 817.95

Triclinic,

a = 7.8097 (3) Å

b = 8.4670 (3) Å

c = 15.1586 (6) Å

α = 74.656 (2)°

β = 75.955 (2)°

γ = 65.042 (2)°

V = 866.47 (6) Å3

Z = 1

Mo Kα radiation

μ = 1.52 mm−1

T = 293 K

0.61 × 0.28 × 0.07 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.457, T max = 0.901

5765 measured reflections

4054 independent reflections

3366 reflections with I > 2σ(I)

R int = 0.015

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.091

S = 1.04

4054 reflections

208 parameters

H-atom parameters constrained

Δρmax = 0.38 e Å−3

Δρmin = −0.42 e Å−3

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

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536814016651/xu5805sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814016651/xu5805Isup2.hkl

Click here for additional data file.

x y z . DOI: 10.1107/S1600536814016651/xu5805fig1.tif

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

Click here for additional data file.

b . DOI: 10.1107/S1600536814016651/xu5805fig2.tif

Mol­ecules of the title compound arranged along b-axis showing the column of the aromatic rings with very weak π–π inter­actions.

CCDC reference: 1014769

Additional supporting information: crystallographic information; 3D view; checkCIF report

[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) Å3

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 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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0467P)2 + 0.3887P] where P = (Fo2 + 2Fc2)/3
4054 reflections	(Δ/σ)max < 0.001
208 parameters	Δρmax = 0.38 e Å−3
0 restraints	Δρmin = −0.42 e Å−3

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.

	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*

	U11	U22	U33	U12	U13	U23
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)

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—O3i	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—Cu1i	1.8798 (16)	C11—H11B	0.9600
N3—C8	1.299 (3)	C11—H11C	0.9600
O3i—Cu1—N2	160.52 (8)	C1—C2—H2	119.3
O3i—Cu1—N3	105.85 (7)	C3—C2—H2	119.3
N2—Cu1—N3	81.34 (8)	C2—C1—C6	119.7 (2)
O3i—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)
O3i—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—Cu1i	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)	O3i—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)
O3i—Cu1—O2—S1	−164.58 (11)	O4—Cu1—N3—C8	−97.30 (15)
N2—Cu1—O2—S1	−1.72 (10)	O3i—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)
O3i—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)
O3i—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)
O3i—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)
Cu1i—O3—N3—C8	−162.43 (15)	C11—C3—C4—C5	−179.6 (3)
Cu1i—O3—N3—Cu1	27.9 (2)	C6—C5—C4—C3	0.1 (5)

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···O1ii	0.93	2.57	3.430 (4)	154
C9—H9A···S2iii	0.96	2.75	3.693 (3)	166
C10—H10C···O1iv	0.96	2.47	3.415 (4)	166

Table 1

Selected bond lengths (Å)

Cu1—N2	1.9580 (19)
Cu1—N3	1.9728 (18)
Cu1—O2	2.0970 (16)
Cu1—O3i	1.8798 (16)
Cu1—O4	2.2517 (17)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

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⋯O1ii	0.93	2.57	3.430 (4)	154
C9—H9A⋯S2iii	0.96	2.75	3.693 (3)	166
C10—H10C⋯O1iv	0.96	2.47	3.415 (4)	166

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