Bis[μ-2-(2-pyridylmethyl­amino­meth­yl)phenolato]-κ⁴N,N′,O:O;κ⁴O:N,N′,O-bis­­[(thio­cyanato-κN)copper(II)]

The centrosymmetric binuclear complex, [Cu₂(C₁₃H₁₃N₂O)₂(NCS)₂], formed via phenolate oxygen bridges, involves the Cu^II atoms in a distorted square-pyramidal coordination [τ = 0.197 (1)]. A Cu⋯Cu separation of 3.2281 (3) Å is observed. The in-plane Cu—O_phenolate distance [1.9342 (8) Å] is shorter than the axial distance [2.252 (8) Å]. The Cu—N_amine and Cu—N_py distances are similar [2.0095 (10) and 2.0192 (10) Å, respectively]. The Cu—N_{thio­cyanate} distance [1.9678 (11) Å] is in the range found for Cu—N distances in previously determined structures containing coordinated thio­cyanate anions. There is an inter­molecular hydrogen bond between the amine H atom and the S atom of a coordinated thio­cyanate anion.

Related literature

For the chemical properties, ligand binding properties and the synthesis of related copper complexes: Kuzmic et al. (1992); Lim et al. (2006); Rogers & Wolf (2002); Sharma et al. (2008); Yisgedu (2001). For related structures, see: Assey et al. (2009); Biswas et al. (2005); Sarkar et al. (2006); Shakya et al. (2006); Wang & Li (2005); You & Zhu (2004, 2005); You (2005). For the τ parameter, see: Addison et al. (1984).

Experimental

Crystal data

• [Cu₂(C₁₃H₁₃N₂O)₂(NCS)₂]

• M_r = 669.75

• Monoclinic, P 2₁ /c

• a = 7.4747 (1) Å

• b = 16.9237 (3) Å

• c = 11.0714 (2) Å

• β = 91.1317 (18)°

• V = 1400.25 (4) ų

• Z = 2

• Mo Kα radiation

• μ = 1.71 mm⁻¹

• T = 200 K

• 0.44 × 0.37 × 0.28 mm

Data collection

• Oxford Diffraction Gemini R diffractometer

• Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008) T_min = 0.944, T_max = 1.000 (expected range = 0.586–0.620)

• 18586 measured reflections

• 7024 independent reflections

• 4611 reflections with I > 2σ(I)

• R_int = 0.026

Refinement

• R[F² > 2σ(F²)] = 0.029

• wR(F²) = 0.071

• S = 0.89

• 7024 reflections

• 181 parameters

• H-atom parameters constrained

• Δρ_max = 0.44 e Å⁻³

• Δρ_min = −0.49 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cu—O	1.9342 (8)
Cu—N	1.9678 (11)
Cu—N1	2.0095 (10)
Cu—N2	2.0192 (10)
Cu—O^i	2.2526 (8)

O—Cu—N	95.37 (4)
O—Cu—N1	92.66 (3)
N—Cu—N1	153.23 (5)
O—Cu—N2	165.03 (4)
N—Cu—N2	97.14 (4)
N1—Cu—N2	79.76 (4)
O—Cu—O^i	79.39 (3)
N—Cu—O^i	102.22 (4)
N1—Cu—O^i	104.35 (3)
N2—Cu—O^i	89.94 (3)
Symmetry code: (i) -x, -y+1, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯S^ii	0.93	2.48	3.3866 (10)	164
Symmetry code: (ii) -x+1, -y+1, -z+1.

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED; 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: SHELXTL.

Supporting information

S1. Comment

The synthesis and structure determination of copper complexes containing potentially bridging or ambidentate ligands, such as the thiocyanate anion, is of wide interest. The different possible coordination modes of the thiocyanate anion can involve bridging or ambidentate functions. A major obstacle to a more comprehensive study of thiocyanate polynuclear complexes is the lack of rational synthetic procedures. One convenient synthetic strategy is use displacement of weakly coordinated anions such as perchlorate of trifluoromethanesulfonate. In this instance some control over resulting stereochemistry can be achieved.

The present complex was synthesized by displacement of weakly coordinated perchlorate anions from a structurally determined complex (Assey et al., 2009) The crystal structure of the resulting complex, bis{µ-O-[2-((pyridin-2-ylmethylamino)methyl)phenolato]thiocyanatocopper(II)} has been determined. In this instance, two thiocyanate ligands were ligated to the copper(II) complex as a result of displacement of weakly coordinated perchlorate ligands. This method of ligand substitution has been used in the area of chemical sensors such as: competitive assay method involving the displacement of an indicator ligand (Sharma et al., 2008), fluorescence displacement method involving determination of receptor-ligand binding constants (Kuzmic et al., 1992), luminescence molecular sensing based on analyte coordination to the transition metal complexes (Rogers & Wolf, 2002), and the use of ligand substitution for fluorescence sensing in detection of NO in biological aqueous solution (Lim et al., 2006).

The complex contains a reduced Schiff base, 2-{[(pyridine-2-ylmethyl)amino]methyl}phenolato and thiocyanate coordinated to copper. The phenolate O atoms bridge the two copper centres and the two thiocyanate anions are terminally coordinated to each copper through their N donors (Fig. 1 and Table 1). The resulting complex reveals a centre of inversion. The coordination geometry about each Cu^II is distorted square pyramidal (τ = 0.197 (1), Addison et al., 1984) with the bridging O, N_amine, N_pyridine and N_thiocyanate forming the base and a bridging O forming the apex. The Cu—O_base and Cu—O_apex distances are 1.9342 (8) and 2.2526 (8) Å respectively. The Cu—N_thiocyanate distance [1.9678 (11) Å] is in the range observed for other copper(II) complexes containing coordinated thiocyanate (Wang & Li, 2005; You & Zhu, 2004; You, 2005; You & Zhu, 2005). The bond distances to the central copper [Cu—N(1) 2.0095 (10) Å, Cu—N(2) 2.0292 (10) Å, Cu—O 1.9342 (8) Å] are comparable to those observed for related complexes (Shakya et al., 2005) and (Biswas et al., 2005).

Related literature

For the chemical properties and the synthesis of what? the title compound? copper complexes containing the thiocyanate anion?, see: Kuzmic et al. (1992); Lim et al. (2006); Rogers & Wolf (2002); Sharma et al. (2008); Yisgedu (2001). For related structures, see: Assey et al. (2009); Biswas et al. (2005); Sarkar et al. (2006); Shakya et al. (2006); Wang & Li (2005); You & Zhu (2004, 2005); You (2005). For the τ parameter, see: Addison et al. (1984).

S2. Experimental

The complex was synthesized in a three-step process. 1. The ligand (2-pyridylmethyl)(2-hydroxybenzyl)amine (L¹H) was synthesized as described below (Yisgedu, 2001). To 5.4 g (50 mmol) of 2-(2-aminomethyl)pyridine in 10 ml of ethanol was added 6.1 g (50 mmol) of salicylaldehyde in 15 ml of ethanol which resulted in a deep yellow colour. The solution was left to stir for 30 m. A sodium borohydride solution (3 g NaBH₄, 0.4 g NaOH, and 40.0 ml of H₂O) were added dropwise. The solution changed to colourless and was left to stir for 1 h after adding all the NaBH₄ solution. The volume of the solution was reduced to 20 ml after extracting three times with chloroform (3 x 40 ml). The extracts were combined and dried in anhydrous Na₂SO₄ overnight. The Na₂SO₄ was filtered and the filtrate concentrated to give a colourless oil (9.3 g, 87%).

2. Copper(II) perchlorate precursor complex was synthesized as follows (Yisgedu, 2001): 1.64 g (7.7 mmol) of L¹H was mixed with 2.86 g (7.7 mmol) of Cu(ClO₄)₂.6H₂O in 25 ml MeOH and 1.75 ml NaOCH₃. The solution mixture was stirred overnight and a green filtrate of precipitate (2.7 g) was obtained. This was washed with EtOH/MeOH (2:1), then crystallized from CH₃CN/CH₃NO₂.

3. Cu(II) thiocyanate complex was synthesized as follows: 0.1 mmol (0.0835 g) of the dinuclear Cu^II perchlorate complex was dissolved in 15 ml s of EtOH and reacted with 0.25 mmol (0.0203 g) of NaSCN dissolved in 10 ml s EtOH. The mixture was stirred for 18.5 h. A mixture of solids and supernatant were obtained at the end of the reaction. The supernatant was decanted and the solids were re-dissolved in 7.5 ml of DMF, filtered and layered with diethyl ether and left to crystallize. Dark-green crystals suitable for X-ray diffraction were obtained and used for X-ray structure determination.

S3. Refinement

H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H distances of 0.95 and 0.99 Å U_iso(H) = 1.2U_eq(C). The H atom attached to N was idealized with an N–H distance of 0.93 Å.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); 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: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of the dinuclear complex I showing the atom numbering scheme and the 50% probability displacement ellipsoids. The symmetry code for generating the symmetry related dinuclear unit is -x, 1 - y, 1 - z.
	Fig. 2. The molecular packing for I viewed down the a axis.

Bis[µ-2-(2-pyridylmethylaminomethyl)phenolato]- κ⁴N,N',O:O; κ⁴O:N,N',O-bis[(thiocyanato- κN)copper(II)]

Crystal data

[Cu2(C13H13N2O)2(NCS)2]	F(000) = 684
Mr = 669.75	Dx = 1.588 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.4747 (1) Å	Cell parameters from 7409 reflections
b = 16.9237 (3) Å	θ = 4.5–37.4°
c = 11.0714 (2) Å	µ = 1.71 mm^−1
β = 91.1317 (18)°	T = 200 K
V = 1400.25 (4) Å^3	Chunk, dark green
Z = 2	0.44 × 0.37 × 0.28 mm

Data collection

Oxford Diffraction Gemini R diffractometer	7024 independent reflections
Radiation source: fine-focus sealed tube	4611 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
Detector resolution: 10.5081 pixels mm^-1	θmax = 37.5°, θmin = 4.5°
ϕ and ω scans	h = −12→12
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	k = −28→25
Tmin = 0.944, Tmax = 1.000	l = −18→12
18586 measured 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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.071	H-atom parameters constrained
S = 0.89	w = 1/[σ^2(Fo^2) + (0.037P)^2] where P = (Fo^2 + 2Fc^2)/3
7024 reflections	(Δ/σ)max = 0.004
181 parameters	Δρmax = 0.44 e Å^−3
0 restraints	Δρmin = −0.49 e Å^−3

Special details

Experimental. CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.15 (release 10-01-2008 CrysAlis171 .NET) (compiled Jan 10 2008,16:37:18) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
Cu	0.200074 (18)	0.530744 (8)	0.531057 (12)	0.01989 (4)
S	0.40414 (4)	0.472939 (18)	0.13944 (3)	0.02856 (7)
O	0.07568 (10)	0.43052 (4)	0.52958 (7)	0.02117 (15)
N	0.31981 (15)	0.51404 (7)	0.37642 (10)	0.0315 (2)
N1	0.19612 (12)	0.53813 (5)	0.71214 (9)	0.02082 (18)
H1A	0.3146	0.5407	0.7390	0.025*
N2	0.27182 (13)	0.64484 (6)	0.55436 (9)	0.02351 (19)
C	0.35464 (15)	0.49643 (7)	0.27835 (11)	0.0232 (2)
C1	0.13193 (14)	0.37486 (6)	0.60789 (10)	0.0201 (2)
C2	0.15668 (15)	0.29704 (7)	0.56836 (11)	0.0243 (2)
H2A	0.1256	0.2832	0.4875	0.029*
C3	0.22630 (16)	0.23993 (7)	0.64630 (12)	0.0286 (3)
H3A	0.2415	0.1873	0.6185	0.034*
C4	0.27368 (17)	0.25921 (8)	0.76442 (12)	0.0314 (3)
H4A	0.3271	0.2208	0.8163	0.038*
C5	0.24208 (16)	0.33520 (7)	0.80592 (11)	0.0271 (2)
H5A	0.2722	0.3483	0.8873	0.033*
C6	0.16704 (15)	0.39265 (7)	0.73042 (10)	0.0216 (2)
C7	0.11123 (16)	0.47201 (6)	0.77868 (11)	0.0238 (2)
H7A	−0.0205	0.4770	0.7716	0.029*
H7B	0.1453	0.4756	0.8654	0.029*
C8	0.11526 (16)	0.61569 (7)	0.73720 (11)	0.0253 (2)
H8A	0.1373	0.6305	0.8227	0.030*
H8B	−0.0156	0.6136	0.7220	0.030*
C9	0.19939 (15)	0.67555 (6)	0.65499 (11)	0.0232 (2)
C10	0.20102 (17)	0.75594 (7)	0.67794 (12)	0.0293 (3)
H10A	0.1478	0.7766	0.7485	0.035*
C11	0.28194 (18)	0.80584 (7)	0.59583 (14)	0.0351 (3)
H11A	0.2836	0.8613	0.6091	0.042*
C12	0.35985 (17)	0.77426 (7)	0.49476 (13)	0.0330 (3)
H12A	0.4180	0.8075	0.4386	0.040*
C13	0.35215 (17)	0.69330 (7)	0.47618 (12)	0.0287 (2)
H13A	0.4051	0.6715	0.4063	0.034*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.02292 (7)	0.01935 (6)	0.01741 (7)	−0.00059 (5)	0.00062 (5)	−0.00060 (5)
S	0.03068 (15)	0.03244 (15)	0.02262 (15)	0.00118 (12)	0.00194 (11)	−0.00631 (12)
O	0.0239 (4)	0.0196 (3)	0.0198 (4)	0.0005 (3)	−0.0051 (3)	0.0021 (3)
N	0.0326 (6)	0.0367 (6)	0.0256 (5)	−0.0008 (4)	0.0074 (4)	−0.0037 (4)
N1	0.0204 (4)	0.0215 (4)	0.0205 (5)	0.0007 (3)	−0.0009 (3)	−0.0009 (3)
N2	0.0214 (4)	0.0230 (4)	0.0260 (5)	−0.0020 (3)	−0.0025 (4)	0.0003 (4)
C	0.0199 (5)	0.0226 (5)	0.0271 (6)	0.0003 (4)	0.0010 (4)	0.0003 (4)
C1	0.0180 (4)	0.0210 (5)	0.0215 (5)	0.0000 (4)	0.0004 (4)	0.0033 (4)
C2	0.0268 (5)	0.0218 (5)	0.0243 (6)	0.0014 (4)	0.0018 (4)	0.0008 (4)
C3	0.0298 (6)	0.0207 (5)	0.0356 (7)	0.0043 (4)	0.0055 (5)	0.0048 (5)
C4	0.0310 (6)	0.0296 (6)	0.0336 (7)	0.0067 (5)	0.0014 (5)	0.0138 (5)
C5	0.0282 (6)	0.0311 (6)	0.0219 (6)	0.0002 (5)	−0.0026 (4)	0.0068 (5)
C6	0.0216 (5)	0.0229 (5)	0.0204 (5)	−0.0007 (4)	−0.0002 (4)	0.0041 (4)
C7	0.0284 (5)	0.0253 (5)	0.0176 (5)	−0.0001 (4)	0.0024 (4)	0.0015 (4)
C8	0.0280 (6)	0.0230 (5)	0.0249 (6)	0.0006 (4)	0.0024 (4)	−0.0056 (4)
C9	0.0223 (5)	0.0223 (5)	0.0249 (6)	0.0002 (4)	−0.0045 (4)	−0.0026 (4)
C10	0.0313 (6)	0.0236 (5)	0.0329 (7)	0.0002 (5)	−0.0042 (5)	−0.0055 (5)
C11	0.0353 (7)	0.0211 (5)	0.0484 (9)	−0.0039 (5)	−0.0095 (6)	−0.0004 (5)
C12	0.0302 (6)	0.0279 (6)	0.0405 (8)	−0.0065 (5)	−0.0043 (5)	0.0071 (5)
C13	0.0270 (5)	0.0294 (6)	0.0297 (7)	−0.0040 (5)	0.0000 (5)	0.0036 (5)

Geometric parameters (Å, º)

Cu—O	1.9342 (8)	C3—H3A	0.9500
Cu—N	1.9678 (11)	C4—C5	1.3874 (18)
Cu—N1	2.0095 (10)	C4—H4A	0.9500
Cu—N2	2.0192 (10)	C5—C6	1.3929 (16)
Cu—O^i	2.2526 (8)	C5—H5A	0.9500
S—C	1.6378 (12)	C6—C7	1.5073 (16)
O—C1	1.3421 (13)	C7—H7A	0.9900
O—Cu^i	2.2526 (8)	C7—H7B	0.9900
N—C	1.1605 (16)	C8—C9	1.5076 (16)
N1—C8	1.4737 (14)	C8—H8A	0.9900
N1—C7	1.4886 (14)	C8—H8B	0.9900
N1—H1A	0.9300	C9—C10	1.3840 (16)
N2—C13	1.3427 (15)	C10—C11	1.3882 (19)
N2—C9	1.3521 (15)	C10—H10A	0.9500
C1—C2	1.4012 (15)	C11—C12	1.379 (2)
C1—C6	1.4092 (16)	C11—H11A	0.9500
C2—C3	1.3900 (17)	C12—C13	1.3865 (18)
C2—H2A	0.9500	C12—H12A	0.9500
C3—C4	1.387 (2)	C13—H13A	0.9500
O—Cu—N	95.37 (4)	C5—C4—H4A	120.4
O—Cu—N1	92.66 (3)	C4—C5—C6	121.16 (12)
N—Cu—N1	153.23 (5)	C4—C5—H5A	119.4
O—Cu—N2	165.03 (4)	C6—C5—H5A	119.4
N—Cu—N2	97.14 (4)	C5—C6—C1	119.59 (11)
N1—Cu—N2	79.76 (4)	C5—C6—C7	121.35 (11)
O—Cu—O^i	79.39 (3)	C1—C6—C7	118.94 (10)
N—Cu—O^i	102.22 (4)	N1—C7—C6	111.76 (9)
N1—Cu—O^i	104.35 (3)	N1—C7—H7A	109.3
N2—Cu—O^i	89.94 (3)	C6—C7—H7A	109.3
C1—O—Cu	117.75 (7)	N1—C7—H7B	109.3
C1—O—Cu^i	132.06 (7)	C6—C7—H7B	109.3
Cu—O—Cu^i	100.61 (3)	H7A—C7—H7B	107.9
C—N—Cu	164.84 (11)	N1—C8—C9	107.90 (9)
C8—N1—C7	113.33 (9)	N1—C8—H8A	110.1
C8—N1—Cu	104.92 (7)	C9—C8—H8A	110.1
C7—N1—Cu	117.50 (7)	N1—C8—H8B	110.1
C8—N1—H1A	106.8	C9—C8—H8B	110.1
C7—N1—H1A	106.8	H8A—C8—H8B	108.4
Cu—N1—H1A	106.8	N2—C9—C10	121.79 (11)
C13—N2—C9	119.20 (10)	N2—C9—C8	114.69 (9)
C13—N2—Cu	128.51 (9)	C10—C9—C8	123.50 (11)
C9—N2—Cu	111.30 (7)	C9—C10—C11	118.70 (12)
N—C—S	179.16 (12)	C9—C10—H10A	120.7
O—C1—C2	119.97 (10)	C11—C10—H10A	120.7
O—C1—C6	121.46 (10)	C12—C11—C10	119.47 (12)
C2—C1—C6	118.57 (10)	C12—C11—H11A	120.3
C3—C2—C1	120.65 (12)	C10—C11—H11A	120.3
C3—C2—H2A	119.7	C11—C12—C13	119.10 (12)
C1—C2—H2A	119.7	C11—C12—H12A	120.5
C4—C3—C2	120.48 (12)	C13—C12—H12A	120.5
C4—C3—H3A	119.8	N2—C13—C12	121.71 (12)
C2—C3—H3A	119.8	N2—C13—H13A	119.1
C3—C4—C5	119.23 (11)	C12—C13—H13A	119.1
C3—C4—H4A	120.4
N—Cu—O—C1	108.23 (8)	Cu^i—O—C1—C6	−92.44 (11)
N1—Cu—O—C1	−46.20 (8)	O—C1—C2—C3	175.63 (10)
N2—Cu—O—C1	−105.16 (15)	C6—C1—C2—C3	−4.46 (16)
O^i—Cu—O—C1	−150.31 (9)	C1—C2—C3—C4	−0.47 (18)
N—Cu—O—Cu^i	−101.46 (4)	C2—C3—C4—C5	3.37 (18)
N1—Cu—O—Cu^i	104.11 (4)	C3—C4—C5—C6	−1.27 (19)
N2—Cu—O—Cu^i	45.15 (15)	C4—C5—C6—C1	−3.70 (18)
O^i—Cu—O—Cu^i	0.0	C4—C5—C6—C7	172.27 (11)
O—Cu—N—C	37.5 (4)	O—C1—C6—C5	−173.61 (10)
N1—Cu—N—C	144.3 (4)	C2—C1—C6—C5	6.48 (16)
N2—Cu—N—C	−134.3 (4)	O—C1—C6—C7	10.32 (15)
O^i—Cu—N—C	−42.8 (4)	C2—C1—C6—C7	−169.59 (10)
O—Cu—N1—C8	−126.33 (7)	C8—N1—C7—C6	166.99 (10)
N—Cu—N1—C8	126.22 (10)	Cu—N1—C7—C6	44.27 (12)
N2—Cu—N1—C8	40.68 (7)	C5—C6—C7—N1	125.30 (11)
O^i—Cu—N1—C8	−46.61 (7)	C1—C6—C7—N1	−58.71 (14)
O—Cu—N1—C7	0.59 (8)	C7—N1—C8—C9	−174.09 (9)
N—Cu—N1—C7	−106.86 (11)	Cu—N1—C8—C9	−44.65 (10)
N2—Cu—N1—C7	167.59 (8)	C13—N2—C9—C10	1.96 (17)
O^i—Cu—N1—C7	80.31 (8)	Cu—N2—C9—C10	−167.62 (9)
O—Cu—N2—C13	−137.76 (14)	C13—N2—C9—C8	−179.11 (10)
N—Cu—N2—C13	8.72 (11)	Cu—N2—C9—C8	11.31 (12)
N1—Cu—N2—C13	161.81 (11)	N1—C8—C9—N2	22.59 (14)
O^i—Cu—N2—C13	−93.59 (10)	N1—C8—C9—C10	−158.50 (11)
O—Cu—N2—C9	30.60 (19)	N2—C9—C10—C11	−1.00 (19)
N—Cu—N2—C9	177.08 (8)	C8—C9—C10—C11	−179.83 (12)
N1—Cu—N2—C9	−29.83 (8)	C9—C10—C11—C12	−0.7 (2)
O^i—Cu—N2—C9	74.77 (8)	C10—C11—C12—C13	1.4 (2)
Cu—N—C—S	117 (8)	C9—N2—C13—C12	−1.24 (18)
Cu—O—C1—C2	−133.51 (9)	Cu—N2—C13—C12	166.32 (10)
Cu^i—O—C1—C2	87.46 (12)	C11—C12—C13—N2	−0.4 (2)
Cu—O—C1—C6	46.58 (12)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S^ii	0.93	2.48	3.3866 (10)	164

Symmetry code: (ii) −x+1, −y+1, −z+1.