μ-(2,6-Bis{[3-(di­methyl­amino)­prop­yl]imino­meth­yl}-4-methyl­phenolato)-μ-hydroxido-bis­[(thio­cyanato-κN)copper(II)]

Meera, M.G.; Selvaraj, P.K.; Viswanathan, B.; Ramkumar, V.

doi:10.1107/S1600536813024768

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 69| Part 10| October 2013| Pages m542-m543

doi:10.1107/S1600536813024768

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μ-(2,6-Bis{[3-(dimethylamino)propyl]iminomethyl}-4-methylphenolato)-μ-hydroxido-bis[(thiocyanato-κN)copper(II)]

M. G. Meera,^a P. Kamatchi Selvaraj,^b ^* B. Viswanathan ^c and V. Ramkumar ^d

^aResearch and Development Centre, Bharathiar University, Tamil Nadu, India, ^bDepartment of Chemistry, Government Arts College, Nandanam, Chennai 600035, Tamil Nadu, India, ^cNational Centre for Catalysis Research, IIT Madras, Chennai 600 036, TamilNadu, India, and ^dDepartment of Chemistry, IIT Madras, Chennai 600 036, TamilNadu, India
^*Correspondence e-mail: porbal96@gmail.com

(Received 31 July 2013; accepted 5 September 2013; online 12 September 2013)

In the title compound, [Cu₂(C₁₉H₃₁N₄O)(OH)(NCS)₂], the molecular structure of the dinuclear complex reveals two pentacoordinated Cu^II ions, which are bridged by the phenolate O atom of the ligand and by an exogenous hydroxide ion. The bridging atoms occupy equatorial positions in the coordination sphere of the metal atoms and complete the equatorial coordination planes with two ligand N atoms, the apical positions being occupied by thiocyanate N atoms. The crystal structure also features π–π stacking interactions involving the benzene rings with a centroid–centroid distance of 3.764 (4)Å. The crystal studied was a non-merohedral twin, with a refined BASF value of 0.203 (2)

Related literature

For related structures, see: Matsufuji et al. (2005 ); Amase et al. (2005 ); Erxleben & Hermann (2000 ); Higuchi et al. (1995 ); Koga et al. (1998 ); Knight et al. (2008 ). For applications and properties of binuclear copper (II) complexes, see: Adams et al. (2000 ); Al-Obaidi (2011 ); Anupama et al. (2012 ); Aytaç (2010 ); Hurley (2002 ); Saha & Koner (2004 ); Sreedaran et al. (2008 ).

Experimental

Crystal data

[Cu₂(C₁₉H₃₁N₄O)(OH)(NCS)₂]
M_r = 591.73
Monoclinic, P 2₁ /n
a = 11.9706 (5) Å
b = 13.7518 (7) Å
c = 16.9887 (8) Å
β = 109.396 (2)°
V = 2637.9 (2) Å³
Z = 4
Mo Kα radiation
μ = 1.80 mm⁻¹
T = 298 K
0.35 × 0.25 × 0.20 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.572, T_max = 0.715
15757 measured reflections
15757 independent reflections
12691 reflections with I > 2σ(I)

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.101
S = 1.01
15757 reflections
303 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.73 e Å⁻³
Δρ_min = −0.53 e Å⁻³

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813024768/bx2448sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813024768/bx2448Isup2.hkl

checkCIF report

Comment top

Binuclear copper (II) complexes are of special interest in their design and synthesis. They have distinct role to play as successful synthetic biomimetic devices capable of representing the active sites of various metalloenzymes (Adams, et al., 2000). They are shown to act as possible catalysts favoring a wide variety of organic transformations in both homogeneous and heterogeneous media (Saha, et al., 2004). They also serve as antifungal and antibacterial agents (Sreedaran, et al., 2008; Al-Obaidi, et al. 2011), as DNA binding and cleaving agents (Hurley, 2002), as molecular magnetic materials and as fluorescent probes (Anupama, et al., 2012). Moreover, the presence of the –C=N– groups, electronegative nitrogen, sulfur and oxygen atoms in the complex, may impart corrosion inhibition properties to the synthesized complex (Aytaç, 2010). In the title compound, C₂₁H₃₂Cu₂N₆O₂S₂, the molecular structure of the dinuclear cation in complex reveals two pentacoordinated cupric ions, which are bridged by the phenolate oxygen O atoms of the ligand and by an exogenous hydroxo ion. Bridging atoms occupy equatorial positions in the coordination sphere of the metals and completes its equatorial coordination plane with two N atoms of the ligand.The apical position is occupied by thiocyanate N atoms. The molecular structure is stabilized by weak O—H···N hydrogen bond interactions. The crystal structure is stablized by π-π stacking interactions involving the benzene rings [Cg1-Cg1ⁱ=3.764 (4)Å] ( symmetry code (i) : -x,-y,-z).The crystal studied was a non-merohedral twin with a refined BASF value of 0.2034 (20)

Related literature top

For related structures, see: Matsufuji et al. (2005); Amase et al. (2005); Erxleben & Hermann (2000); Higuchi et al. (1995); Koga et al. (1998); Knight et al. (2008). For applications and properties of binuclear copper (II) complexes, see: Adams et al. (2000); Al-Obaidi (2011); Anupama et al. (2012); Aytaç (2010); Hurley (2002); Saha & Koner (2004); Sreedaran et al. (2008).

Experimental top

A solution of 2,6-Diformyl-4-methylphenol (0.164 g, 1 mmol) in methanol was slowly added to a solution of 3-(Dimethylamino)propylamine (0.25 ml, 2.0 mmol) in 5 ml of methanol and stirred. The resulting mixture was refluxed for 10 min. To the yellow ligand solution thus obtained was added copper (II) nitrate trihydrate (0.485 g, 2 mmol) and the mixture was refluxed for another 30 min. The addition of sodium thiocyanate (0.162 g, 2 mmol) resulted in the precipitation of light green microcrystals. Single crystals suitable for X-ray diffraction were obtained by recrystallization from acetonitrile.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. ORTEP of the molecule with atoms represented as 30% probability ellipsoids.

µ-(2,6-Bis{[3-(dimethylamino)propyl]iminomethyl}-4-methylphenolato)-µ-hydroxido-bis[(thiocyanato-κN)copper(II)] top

Crystal data top

[Cu₂(C₁₉H₃₁N₄O)(OH)(NCS)₂]	F(000) = 1224
M_r = 591.73	D_x = 1.490 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6965 reflections
a = 11.9706 (5) Å	θ = 2.5–28.5°
b = 13.7518 (7) Å	µ = 1.80 mm⁻¹
c = 16.9887 (8) Å	T = 298 K
β = 109.396 (2)°	Rectangular, green
V = 2637.9 (2) Å³	0.35 × 0.25 × 0.20 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	15757 independent reflections
Radiation source: fine-focus sealed tube	12691 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.000
phi and ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (TWINABS; Bruker, 2004)	h = −14→13
T_min = 0.572, T_max = 0.715	k = −16→16
15757 measured reflections	l = −19→20

Refinement top

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0461P)² + 2.7323P] where P = (F_o² + 2F_c²)/3
15757 reflections	(Δ/σ)_max = 0.001
303 parameters	Δρ_max = 0.73 e Å⁻³
2 restraints	Δρ_min = −0.53 e Å⁻³

Crystal data top

[Cu₂(C₁₉H₃₁N₄O)(OH)(NCS)₂]	V = 2637.9 (2) Å³
M_r = 591.73	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.9706 (5) Å	µ = 1.80 mm⁻¹
b = 13.7518 (7) Å	T = 298 K
c = 16.9887 (8) Å	0.35 × 0.25 × 0.20 mm
β = 109.396 (2)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	15757 independent reflections
Absorption correction: multi-scan (TWINABS; Bruker, 2004)	12691 reflections with I > 2σ(I)
T_min = 0.572, T_max = 0.715	R_int = 0.000
15757 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	2 restraints
wR(F²) = 0.101	H-atom parameters constrained
S = 1.01	Δρ_max = 0.73 e Å⁻³
15757 reflections	Δρ_min = −0.53 e Å⁻³
303 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.14435 (16)	0.08416 (13)	0.14686 (11)	0.0324 (4)
C2	0.02153 (16)	0.09626 (14)	0.13278 (12)	0.0348 (5)
C3	−0.05365 (17)	0.12155 (15)	0.05291 (12)	0.0420 (5)
H3	−0.1340	0.1291	0.0446	0.050*
C4	−0.01470 (18)	0.13587 (14)	−0.01390 (13)	0.0455 (5)
C5	0.10368 (18)	0.12202 (15)	−0.00002 (13)	0.0434 (5)
H5	0.1318	0.1300	−0.0445	0.052*
C6	0.18437 (16)	0.09648 (14)	0.07788 (12)	0.0351 (5)
C7	0.17786 (18)	0.19821 (16)	0.46594 (14)	0.0439 (5)
C8	0.60543 (19)	0.19201 (15)	0.32423 (13)	0.0425 (5)
C9	0.30672 (19)	0.08411 (16)	0.08337 (14)	0.0445 (5)
H9	0.3224	0.0936	0.0338	0.053*
C10	−0.0999 (2)	0.16307 (17)	−0.09907 (13)	0.0642 (7)
H10A	−0.1784	0.1425	−0.1035	0.096*
H10B	−0.0762	0.1317	−0.1415	0.096*
H10C	−0.0990	0.2323	−0.1062	0.096*
C11	−0.03213 (17)	0.08429 (16)	0.19646 (14)	0.0430 (5)
H11	−0.1136	0.0941	0.1793	0.052*
C12	−0.06173 (19)	0.0563 (2)	0.32495 (15)	0.0586 (7)
H12A	−0.1417	0.0738	0.2910	0.070*
H12B	−0.0352	0.1028	0.3703	0.070*
C13	−0.0625 (2)	−0.0435 (2)	0.36024 (16)	0.0645 (7)
H13A	−0.0833	−0.0900	0.3147	0.077*
H13B	−0.1236	−0.0461	0.3860	0.077*
C14	0.0528 (2)	−0.0738 (2)	0.42343 (14)	0.0645 (7)
H14A	0.0759	−0.0250	0.4671	0.077*
H14B	0.0403	−0.1342	0.4488	0.077*
C15	0.1269 (3)	−0.16821 (18)	0.33008 (16)	0.0740 (8)
H15A	0.1060	−0.2252	0.3546	0.111*
H15B	0.1956	−0.1816	0.3146	0.111*
H15C	0.0622	−0.1502	0.2813	0.111*
C16	0.51179 (18)	0.05934 (19)	0.13281 (16)	0.0579 (7)
H16A	0.5629	0.1092	0.1667	0.070*
H16B	0.4998	0.0741	0.0747	0.070*
C17	0.5721 (2)	−0.0382 (2)	0.15419 (18)	0.0704 (8)
H17A	0.5198	−0.0876	0.1207	0.084*
H17B	0.6430	−0.0374	0.1385	0.084*
C18	0.60619 (18)	−0.0670 (2)	0.24424 (17)	0.0659 (8)
H18A	0.6542	−0.1254	0.2525	0.079*
H18B	0.6553	−0.0160	0.2778	0.079*
C19	0.5583 (2)	−0.1110 (2)	0.36522 (16)	0.0779 (8)
H19A	0.6109	−0.1653	0.3714	0.117*
H19B	0.4962	−0.1278	0.3869	0.117*
H19C	0.6016	−0.0563	0.3955	0.117*
C20	0.4338 (2)	−0.16796 (18)	0.23131 (18)	0.0767 (8)
H20A	0.4841	−0.2227	0.2327	0.115*
H20B	0.3930	−0.1498	0.1744	0.115*
H20C	0.3771	−0.1850	0.2578	0.115*
C21	0.2588 (2)	−0.1131 (2)	0.46299 (15)	0.0758 (8)
H21A	0.2788	−0.0594	0.5012	0.114*
H21B	0.3241	−0.1269	0.4438	0.114*
H21C	0.2420	−0.1693	0.4907	0.114*
Cu1	0.393606 (19)	0.039255 (19)	0.259878 (16)	0.03997 (8)
Cu2	0.18605 (2)	0.039242 (19)	0.329566 (15)	0.03923 (8)
N1	0.01670 (14)	0.06201 (12)	0.27351 (11)	0.0400 (4)
N2	0.39640 (14)	0.06200 (12)	0.14674 (11)	0.0410 (4)
N3	0.50620 (14)	−0.08561 (13)	0.27594 (12)	0.0481 (5)
N4	0.15297 (16)	−0.08803 (13)	0.39072 (11)	0.0458 (4)
N5	0.20263 (17)	0.14220 (15)	0.42418 (12)	0.0598 (5)
N6	0.52528 (17)	0.14212 (14)	0.31649 (12)	0.0591 (5)
O1	0.21794 (10)	0.06199 (10)	0.22147 (7)	0.0381 (3)
O11	0.35320 (12)	0.01574 (12)	0.35888 (9)	0.0573 (4)
H11O	0.3851	0.0662	0.3891	0.086*
S3	0.71742 (6)	0.26265 (5)	0.33508 (5)	0.0685 (2)
S4	0.14334 (6)	0.27589 (5)	0.52589 (5)	0.0684 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0350 (10)	0.0254 (10)	0.0345 (11)	−0.0008 (9)	0.0086 (9)	−0.0019 (8)
C2	0.0327 (10)	0.0315 (12)	0.0382 (12)	0.0025 (9)	0.0091 (9)	−0.0039 (9)
C3	0.0379 (11)	0.0365 (13)	0.0444 (13)	0.0055 (9)	0.0038 (10)	−0.0006 (10)
C4	0.0490 (13)	0.0328 (12)	0.0434 (13)	0.0036 (10)	0.0002 (10)	0.0027 (10)
C5	0.0584 (13)	0.0356 (12)	0.0363 (12)	−0.0050 (10)	0.0159 (11)	0.0030 (10)
C6	0.0384 (11)	0.0321 (12)	0.0341 (12)	−0.0051 (9)	0.0111 (9)	−0.0007 (9)
C7	0.0433 (12)	0.0416 (14)	0.0453 (14)	−0.0067 (10)	0.0128 (10)	0.0003 (10)
C8	0.0478 (12)	0.0384 (13)	0.0411 (13)	0.0020 (10)	0.0146 (10)	0.0015 (10)
C9	0.0562 (14)	0.0405 (14)	0.0452 (14)	−0.0060 (11)	0.0280 (12)	0.0002 (11)
C10	0.0714 (16)	0.0580 (15)	0.0468 (15)	0.0076 (13)	−0.0022 (12)	0.0128 (12)
C11	0.0291 (10)	0.0436 (14)	0.0554 (15)	0.0029 (9)	0.0128 (10)	−0.0073 (11)
C12	0.0412 (12)	0.085 (2)	0.0581 (16)	−0.0022 (12)	0.0274 (12)	−0.0124 (14)
C13	0.0553 (14)	0.095 (2)	0.0505 (15)	−0.0254 (14)	0.0273 (13)	−0.0086 (15)
C14	0.0776 (17)	0.0796 (19)	0.0455 (14)	−0.0293 (15)	0.0327 (13)	−0.0004 (13)
C15	0.114 (2)	0.0416 (15)	0.0677 (18)	−0.0107 (15)	0.0310 (16)	−0.0073 (13)
C16	0.0427 (13)	0.0769 (19)	0.0657 (17)	−0.0077 (12)	0.0334 (12)	−0.0049 (14)
C17	0.0498 (14)	0.085 (2)	0.087 (2)	0.0089 (14)	0.0366 (14)	−0.0185 (17)
C18	0.0357 (12)	0.0666 (18)	0.093 (2)	0.0151 (11)	0.0181 (13)	−0.0157 (15)
C19	0.0664 (16)	0.076 (2)	0.075 (2)	0.0375 (15)	0.0012 (14)	0.0123 (15)
C20	0.0779 (18)	0.0373 (15)	0.101 (2)	−0.0023 (13)	0.0113 (16)	−0.0058 (14)
C21	0.0828 (18)	0.083 (2)	0.0554 (17)	−0.0027 (16)	0.0153 (14)	0.0322 (15)
Cu1	0.02982 (13)	0.04586 (17)	0.04599 (17)	0.00438 (11)	0.01494 (12)	0.00773 (12)
Cu2	0.03448 (14)	0.04623 (17)	0.03978 (16)	0.00297 (11)	0.01607 (12)	0.00696 (12)
N1	0.0343 (9)	0.0452 (11)	0.0451 (11)	0.0004 (8)	0.0195 (8)	−0.0037 (9)
N2	0.0367 (9)	0.0420 (11)	0.0504 (11)	−0.0031 (8)	0.0228 (9)	−0.0003 (9)
N3	0.0358 (9)	0.0421 (12)	0.0599 (12)	0.0092 (8)	0.0072 (9)	−0.0043 (9)
N4	0.0599 (11)	0.0428 (11)	0.0362 (10)	−0.0100 (9)	0.0181 (9)	0.0030 (9)
N5	0.0654 (12)	0.0523 (14)	0.0605 (13)	−0.0079 (10)	0.0194 (11)	−0.0186 (11)
N6	0.0564 (12)	0.0493 (13)	0.0695 (14)	−0.0145 (10)	0.0181 (10)	−0.0130 (10)
O1	0.0266 (7)	0.0572 (9)	0.0299 (8)	0.0025 (6)	0.0084 (6)	0.0034 (6)
O11	0.0382 (8)	0.0844 (12)	0.0495 (10)	0.0098 (8)	0.0148 (7)	0.0199 (8)
S3	0.0648 (4)	0.0720 (5)	0.0766 (5)	−0.0241 (3)	0.0340 (4)	0.0000 (4)
S4	0.0654 (4)	0.0669 (5)	0.0845 (5)	−0.0065 (3)	0.0405 (4)	−0.0248 (4)

Geometric parameters (Å, º) top

C1—O1	1.3168 (19)	C15—H15B	0.9600
C1—C6	1.416 (3)	C15—H15C	0.9600
C1—C2	1.419 (2)	C16—N2	1.477 (2)
C2—C3	1.400 (3)	C16—C17	1.510 (3)
C2—C11	1.439 (3)	C16—H16A	0.9700
C3—C4	1.377 (3)	C16—H16B	0.9700
C3—H3	0.9300	C17—C18	1.500 (3)
C4—C5	1.370 (3)	C17—H17A	0.9700
C4—C10	1.514 (2)	C17—H17B	0.9700
C5—C6	1.400 (3)	C18—N3	1.489 (3)
C5—H5	0.9300	C18—H18A	0.9700
C6—C9	1.446 (3)	C18—H18B	0.9700
C7—N5	1.151 (3)	C19—N3	1.477 (3)
C7—S4	1.621 (2)	C19—H19A	0.9600
C8—N6	1.151 (2)	C19—H19B	0.9600
C8—S3	1.616 (2)	C19—H19C	0.9600
C9—N2	1.279 (3)	C20—N3	1.474 (3)
C9—H9	0.9300	C20—H20A	0.9600
C10—H10A	0.9600	C20—H20B	0.9600
C10—H10B	0.9600	C20—H20C	0.9600
C10—H10C	0.9600	C21—N4	1.483 (3)
C11—N1	1.281 (3)	C21—H21A	0.9600
C11—H11	0.9300	C21—H21B	0.9600
C12—N1	1.482 (2)	C21—H21C	0.9600
C12—C13	1.499 (3)	Cu1—O11	1.9255 (15)
C12—H12A	0.9700	Cu1—N2	1.9587 (17)
C12—H12B	0.9700	Cu1—O1	2.0085 (12)
C13—C14	1.499 (3)	Cu1—N6	2.0985 (19)
C13—H13A	0.9700	Cu1—N3	2.1437 (17)
C13—H13B	0.9700	Cu2—O11	1.9219 (14)
C14—N4	1.492 (3)	Cu2—N1	1.9577 (16)
C14—H14A	0.9700	Cu2—O1	2.0203 (12)
C14—H14B	0.9700	Cu2—N5	2.101 (2)
C15—N4	1.470 (3)	Cu2—N4	2.1384 (17)
C15—H15A	0.9600	O11—H11O	0.8715

O1—C1—C6	121.49 (17)	N3—C18—H18A	108.3
O1—C1—C2	120.93 (18)	C17—C18—H18A	108.3
C6—C1—C2	117.58 (16)	N3—C18—H18B	108.3
C3—C2—C1	119.27 (18)	C17—C18—H18B	108.3
C3—C2—C11	116.95 (17)	H18A—C18—H18B	107.4
C1—C2—C11	123.78 (18)	N3—C19—H19A	109.5
C4—C3—C2	123.35 (18)	N3—C19—H19B	109.5
C4—C3—H3	118.3	H19A—C19—H19B	109.5
C2—C3—H3	118.3	N3—C19—H19C	109.5
C5—C4—C3	116.88 (18)	H19A—C19—H19C	109.5
C5—C4—C10	121.9 (2)	H19B—C19—H19C	109.5
C3—C4—C10	121.2 (2)	N3—C20—H20A	109.5
C4—C5—C6	123.2 (2)	N3—C20—H20B	109.5
C4—C5—H5	118.4	H20A—C20—H20B	109.5
C6—C5—H5	118.4	N3—C20—H20C	109.5
C5—C6—C1	119.72 (18)	H20A—C20—H20C	109.5
C5—C6—C9	117.17 (19)	H20B—C20—H20C	109.5
C1—C6—C9	123.11 (18)	N4—C21—H21A	109.5
N5—C7—S4	179.1 (2)	N4—C21—H21B	109.5
N6—C8—S3	179.6 (2)	H21A—C21—H21B	109.5
N2—C9—C6	129.14 (19)	N4—C21—H21C	109.5
N2—C9—H9	115.4	H21A—C21—H21C	109.5
C6—C9—H9	115.4	H21B—C21—H21C	109.5
C4—C10—H10A	109.5	O11—Cu1—N2	167.19 (6)
C4—C10—H10B	109.5	O11—Cu1—O1	76.72 (5)
H10A—C10—H10B	109.5	N2—Cu1—O1	90.78 (6)
C4—C10—H10C	109.5	O11—Cu1—N6	94.66 (7)
H10A—C10—H10C	109.5	N2—Cu1—N6	95.00 (7)
H10B—C10—H10C	109.5	O1—Cu1—N6	126.15 (7)
N1—C11—C2	129.00 (18)	O11—Cu1—N3	94.82 (7)
N1—C11—H11	115.5	N2—Cu1—N3	92.17 (7)
C2—C11—H11	115.5	O1—Cu1—N3	135.42 (6)
N1—C12—C13	111.92 (19)	N6—Cu1—N3	97.86 (7)
N1—C12—H12A	109.2	O11—Cu2—N1	166.83 (7)
C13—C12—H12A	109.2	O11—Cu2—O1	76.52 (5)
N1—C12—H12B	109.2	N1—Cu2—O1	90.62 (6)
C13—C12—H12B	109.2	O11—Cu2—N5	95.13 (7)
H12A—C12—H12B	107.9	N1—Cu2—N5	94.81 (7)
C12—C13—C14	114.5 (2)	O1—Cu2—N5	126.34 (7)
C12—C13—H13A	108.6	O11—Cu2—N4	94.66 (7)
C14—C13—H13A	108.6	N1—Cu2—N4	92.19 (7)
C12—C13—H13B	108.6	O1—Cu2—N4	133.61 (6)
C14—C13—H13B	108.6	N5—Cu2—N4	99.53 (7)
H13A—C13—H13B	107.6	C11—N1—C12	116.86 (17)
N4—C14—C13	115.60 (18)	C11—N1—Cu2	125.65 (14)
N4—C14—H14A	108.4	C12—N1—Cu2	117.46 (14)
C13—C14—H14A	108.4	C9—N2—C16	116.05 (18)
N4—C14—H14B	108.4	C9—N2—Cu1	125.50 (14)
C13—C14—H14B	108.4	C16—N2—Cu1	118.35 (15)
H14A—C14—H14B	107.4	C20—N3—C19	108.8 (2)
N4—C15—H15A	109.5	C20—N3—C18	110.60 (19)
N4—C15—H15B	109.5	C19—N3—C18	107.21 (18)
H15A—C15—H15B	109.5	C20—N3—Cu1	108.21 (13)
N4—C15—H15C	109.5	C19—N3—Cu1	110.66 (14)
H15A—C15—H15C	109.5	C18—N3—Cu1	111.32 (14)
H15B—C15—H15C	109.5	C15—N4—C21	109.2 (2)
N2—C16—C17	112.44 (19)	C15—N4—C14	110.47 (19)
N2—C16—H16A	109.1	C21—N4—C14	107.06 (18)
C17—C16—H16A	109.1	C15—N4—Cu2	107.68 (14)
N2—C16—H16B	109.1	C21—N4—Cu2	110.35 (14)
C17—C16—H16B	109.1	C14—N4—Cu2	112.04 (14)
H16A—C16—H16B	107.8	C7—N5—Cu2	160.80 (18)
C18—C17—C16	115.2 (2)	C8—N6—Cu1	157.66 (19)
C18—C17—H17A	108.5	C1—O1—Cu1	129.96 (12)
C16—C17—H17A	108.5	C1—O1—Cu2	130.01 (12)
C18—C17—H17B	108.5	Cu1—O1—Cu2	100.02 (5)
C16—C17—H17B	108.5	Cu2—O11—Cu1	106.70 (6)
H17A—C17—H17B	107.5	Cu2—O11—H11O	103.5
N3—C18—C17	115.82 (18)	Cu1—O11—H11O	101.1

O1—C1—C2—C3	178.85 (17)	N6—Cu1—N3—C19	67.38 (16)
C6—C1—C2—C3	−1.3 (3)	O11—Cu1—N3—C18	−147.13 (15)
O1—C1—C2—C11	−1.0 (3)	N2—Cu1—N3—C18	43.61 (15)
C6—C1—C2—C11	178.84 (19)	O1—Cu1—N3—C18	136.92 (14)
C1—C2—C3—C4	−0.2 (3)	N6—Cu1—N3—C18	−51.74 (16)
C11—C2—C3—C4	179.66 (19)	C13—C14—N4—C15	−63.7 (3)
C2—C3—C4—C5	1.5 (3)	C13—C14—N4—C21	177.5 (2)
C2—C3—C4—C10	179.94 (19)	C13—C14—N4—Cu2	56.4 (2)
C3—C4—C5—C6	−1.3 (3)	O11—Cu2—N4—C15	−89.45 (16)
C10—C4—C5—C6	−179.73 (19)	N1—Cu2—N4—C15	79.30 (16)
C4—C5—C6—C1	−0.2 (3)	O1—Cu2—N4—C15	−13.65 (19)
C4—C5—C6—C9	179.91 (19)	N5—Cu2—N4—C15	174.54 (16)
O1—C1—C6—C5	−178.67 (17)	O11—Cu2—N4—C21	29.70 (16)
C2—C1—C6—C5	1.5 (3)	N1—Cu2—N4—C21	−161.55 (16)
O1—C1—C6—C9	1.2 (3)	O1—Cu2—N4—C21	105.50 (16)
C2—C1—C6—C9	−178.60 (19)	N5—Cu2—N4—C21	−66.30 (17)
C5—C6—C9—N2	179.3 (2)	O11—Cu2—N4—C14	148.89 (14)
C1—C6—C9—N2	−0.5 (4)	N1—Cu2—N4—C14	−42.37 (15)
C3—C2—C11—N1	−179.7 (2)	O1—Cu2—N4—C14	−135.31 (13)
C1—C2—C11—N1	0.1 (4)	N5—Cu2—N4—C14	52.88 (15)
N1—C12—C13—C14	66.9 (3)	S4—C7—N5—Cu2	103 (13)
C12—C13—C14—N4	−67.0 (3)	O11—Cu2—N5—C7	−179.4 (6)
N2—C16—C17—C18	−63.9 (3)	N1—Cu2—N5—C7	9.3 (6)
C16—C17—C18—N3	66.5 (3)	O1—Cu2—N5—C7	103.6 (6)
C2—C11—N1—C12	179.1 (2)	N4—Cu2—N5—C7	−83.8 (6)
C2—C11—N1—Cu2	1.3 (3)	S3—C8—N6—Cu1	117 (30)
C13—C12—N1—C11	118.7 (2)	O11—Cu1—N6—C8	165.6 (5)
C13—C12—N1—Cu2	−63.2 (2)	N2—Cu1—N6—C8	−22.9 (5)
O11—Cu2—N1—C11	−13.7 (4)	O1—Cu1—N6—C8	−117.5 (5)
O1—Cu2—N1—C11	−1.36 (18)	N3—Cu1—N6—C8	70.0 (5)
N5—Cu2—N1—C11	125.20 (19)	C6—C1—O1—Cu1	−0.5 (2)
N4—Cu2—N1—C11	−135.05 (18)	C2—C1—O1—Cu1	179.35 (13)
O11—Cu2—N1—C12	168.5 (3)	C6—C1—O1—Cu2	−179.45 (13)
O1—Cu2—N1—C12	−179.19 (15)	C2—C1—O1—Cu2	0.4 (2)
N5—Cu2—N1—C12	−52.63 (16)	O11—Cu1—O1—C1	−177.76 (16)
N4—Cu2—N1—C12	47.12 (16)	N2—Cu1—O1—C1	−0.57 (16)
C6—C9—N2—C16	−177.2 (2)	N6—Cu1—O1—C1	96.20 (16)
C6—C9—N2—Cu1	−0.9 (3)	N3—Cu1—O1—C1	−94.45 (17)
C17—C16—N2—C9	−122.6 (2)	O11—Cu1—O1—Cu2	1.45 (6)
C17—C16—N2—Cu1	60.8 (2)	N2—Cu1—O1—Cu2	178.65 (6)
O11—Cu1—N2—C9	13.6 (4)	N6—Cu1—O1—Cu2	−84.59 (9)
O1—Cu1—N2—C9	1.19 (19)	N3—Cu1—O1—Cu2	84.76 (10)
N6—Cu1—N2—C9	−125.21 (18)	O11—Cu2—O1—C1	177.76 (16)
N3—Cu1—N2—C9	136.69 (18)	N1—Cu2—O1—C1	0.62 (16)
O11—Cu1—N2—C16	−170.1 (3)	N5—Cu2—O1—C1	−95.81 (16)
O1—Cu1—N2—C16	177.44 (15)	N4—Cu2—O1—C1	94.24 (16)
N6—Cu1—N2—C16	51.04 (16)	O11—Cu2—O1—Cu1	−1.46 (6)
N3—Cu1—N2—C16	−47.05 (16)	N1—Cu2—O1—Cu1	−178.59 (7)
C17—C18—N3—C20	62.5 (3)	N5—Cu2—O1—Cu1	84.98 (9)
C17—C18—N3—C19	−179.0 (2)	N4—Cu2—O1—Cu1	−84.97 (9)
C17—C18—N3—Cu1	−57.8 (2)	N1—Cu2—O11—Cu1	14.2 (4)
O11—Cu1—N3—C20	91.13 (16)	O1—Cu2—O11—Cu1	1.56 (7)
N2—Cu1—N3—C20	−78.13 (16)	N5—Cu2—O11—Cu1	−124.62 (9)
O1—Cu1—N3—C20	15.2 (2)	N4—Cu2—O11—Cu1	135.36 (8)
N6—Cu1—N3—C20	−173.48 (16)	N2—Cu1—O11—Cu2	−14.3 (4)
O11—Cu1—N3—C19	−28.01 (16)	O1—Cu1—O11—Cu2	−1.57 (7)
N2—Cu1—N3—C19	162.73 (16)	N6—Cu1—O11—Cu2	124.51 (8)
O1—Cu1—N3—C19	−103.96 (16)	N3—Cu1—O11—Cu2	−137.17 (8)

Experimental details

Crystal data
Chemical formula	[Cu₂(C₁₉H₃₁N₄O)(OH)(NCS)₂]
M_r	591.73
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	11.9706 (5), 13.7518 (7), 16.9887 (8)
β (°)	109.396 (2)
V (Å³)	2637.9 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.80
Crystal size (mm)	0.35 × 0.25 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (TWINABS; Bruker, 2004)
T_min, T_max	0.572, 0.715
No. of measured, independent and observed [I > 2σ(I)] reflections	15757, 15757, 12691
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.101, 1.01
No. of reflections	15757
No. of parameters	303
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.73, −0.53

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012).

Acknowledgements

The authors thank the Department of Chemistry, IIT Madras, for the data collection and Dr Babu Varghese, Sophisticated Analytical Instrumentation Facility, Indian Institute of Technology, Chennai 600 036, Tamil Nadu, India, for the help rendered with the single crystal XRD studies. MGM and PKS thank the UGC–MRP, Government of India, for financial support.

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