Di-μ-chloro-bis({2-[N,N-bis(2-aminoethyl)amino-κ³N]ethylaminium}copper(II)) bis(naphthalene-1,5-disulfonate) pentahydrate

The title compound, [Cu₂(C₆H₁₉N₄)₂Cl₂](C₁₀H₆O₆S₂)₂·5H₂O, is comprised of discrete [Cu₂(tren)₂Cl₂]²⁺ dimers {tren is 2-[N,N-bis(2-amino­ethyl)­amino]­ethyl­aminium} and naphthalene-1,5-di­sulfonate anions. Two Cl⁻ anions bridge two Cu^II ions, each of which is also coordinated by two of the primary and the tertiary amino N atoms of the tren ligand, giving each metal atom a distorted square-pyramidal coordination geometry. The cation lies about an inversion centre and the asymmetric unit also has two independent anions lying about inversion centres.

S1. Comment

Copper(II) complexes with the formula [Cu₂(tren)₂X₂](BPh₄)₂, where X is CN^-, NCO^-, NCS^- or Cl^-, have been studied from both structural and magnetic points of view (Duggan & Hendrickson, 1974a,b; Duggan et al., 1974; Laskowski et al., 1975). Each Cu^II ion in these compounds is five-coordinate in a trigonal-bipyramidal geometry, with tren as a tetradentate ligand and the X^- anion in the axial position. These [Cu₂(tren)₂X₂]²⁺ ions dimerize via a hydrogen bond between the X group and a primary amine of tren coordinated to the second Cu^II ion. Herein, we report a novel dimeric Cu^II cation with the same basic formula as the above but with a different structure, [Cu₂(tren)₂Cl₂](1,5-nds)₂·5H₂O, (I) (1,5-nds is naphthalene-1,5-disulfonate). \sch

Crystals of (I) are comprised of discrete [Cu₂(tren)₂Cl₂]²⁺ cations, 1,5-nds anions and water molecules, as shown in Fig. 1. Two Cl^- anions bridge two Cu^II ions, each of which is also coordinated by two of the primary and the tertiary amino N atoms of the tren ligands, leaving two free ethylamine arms. A search of the Cambridge Structural Database (Release?; Allen & Kennard, 1993) indicates no previous observation of this kind of coordination mode of tren with Cu^II.

The coordination geometry of Cu^II can be described as a distorted square pyramid, as ascertained by Reedijk's τ factor (Addison et al., 1984) of 0.313 for Cu1 and 0.331 for Cu1A (τ = 0 for a square pyramid and 1 for a trigonal bipyramid). Atoms N1, N2 and N3 of the tren ligand and atom Cl1 are nearly coplanar, constituting the base of one pyramid, while Cl1A occupies the apical position. As a result, the geometry of the complex consists of two square pyramids sharing one common base-to-apex edge, with the two bases nearly parallel to each other (dihedral angle of 1.6°).

The reported geometry of Cu^II dimers with the general formula [N₃Cu(µ-Cl)₂CuN₃] has been classified into three types (Rodríguez & Llobet, 1999). The arrangement in (I) belongs to type II. The Cu—N distances are 1.975 (3), 1.983 (2) and 2.081 (2) Å. Obviously, the Cu—N bonds in which N is cis to the basal Cl are slightly shorter than that in which N is trans to the basal Cl. This phenomenon is different from that in [Cu₂(dien)₂Cl₂](ClO₄)₂ (dien is diethylenetriamine?; Hoffmann et al., 1984), with the same geometry and N₃Cl₂ coordination environment, but similar to that in [Cu₂(dpt)₂Cl₂]Cl₂ (dpt is ?; Rodríguez & Llobet, 1999).

With regard to the [Cu(µ-Cl)₂Cu] core, the dimeric unit has unsymmetrical Cu—Cl bridging distances of 2.2819 (7) and 2.6320 (7) Å. The bridging Cu—Cl—Cu angle is 91.46 (3)° and Cl—Cu—Cl is 88.54 (3)°. All of the bond distances and angles are close to those found in [Cu₂(dien)₂Cl₂](ClO₄)₂ (Hoffmann et al., 1984). The Cu···Cu separation is 3.5269 (8) Å, which is slightly shorter than the values reported in analogous compounds (Hoffmann et al., 1984; Rodrí guez & Llobet, 1999).

The coordination mode of tren, the mode of dimerization and the coordination geometry in (I) are quite different from those in [Cu₂(tren)₂Cl₂](BPh₄)₂, (II) (Laskowski et al., 1975), although the two compounds have the same cation formula, [Cu₂(tren)₂Cl₂]²⁺. In (II), each Cu^II centre is coordinated by a Cl^- ligand and all four amino N atoms of tren, and the Cu^II centres are dimerized by two complementary hydrogen bonds between Cl^- and a primary amine of tren. Moreover, the local copper environment in (II) is a distorted trigonal bipyramid (N₄Cl), while in (I) it is a distorted square pyramid (N₃Cl₂).

S2. Experimental

Disodium naphthalene-1,5-disulfonate (0.17 g, 0.5 mmol) was added to an aqueous solution of cupric chloride (0.09 g, 0.5 mmol). The solution was then treated with tris(2-aminoethyl)amine (0.076 g, 0.5 mmol). The resulting solution was allowed to stand at room temperature. After 10 d, blue block crystals of (I) were collected in 10% yield.

S3. Refinement

All H atoms of the tren ligands and on the 1,5-nds anions were placed in idealized positions (N—H = 0.90 and 0.89 Å for NH₂ and NH₃, respectively, and C—H = 0.97 and 0.93 Å for CH₂ and CH, respectively) and refined as riding atoms. The H atoms of water molecules O1W and O2W were located from the difference Fourier map and not refined and those of the O3W water molecule were not located.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. The molecular structure of (I) with 30% probability displacement ellipsoids. H atoms are shown as small spheres of arbitrary radii and only the unique portions are labelled. Only three of the five water molecules are shown.

Di-µ-chloro-bis({2-[N,N-bis(2-aminoethyl)amino-κ³N]ethylaminium}copper(II)) bis(naphthalene-1,5-disulfonate) pentahydrate

Crystal data

[Cu2(C6H19N4)2Cl2]·2C10H6O6S2·5H2O	Z = 1
Mr = 1155.10	F(000) = 600
Triclinic, P1	Dx = 1.616 Mg m^−3
a = 9.9348 (15) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.5498 (17) Å	Cell parameters from 843 reflections
c = 11.9637 (17) Å	θ = 2.3–26.4°
α = 71.806 (3)°	µ = 1.26 mm^−1
β = 75.622 (3)°	T = 293 K
γ = 66.844 (2)°	Block, blue
V = 1186.6 (3) Å^3	0.25 × 0.25 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer	4786 independent reflections
Radiation source: fine-focus sealed tube	4259 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
ϕ and ω scans	θmax = 26.4°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Blessing, 1995)	h = −12→12
Tmin = 0.743, Tmax = 0.884	k = −14→13
7629 measured reflections	l = −14→14

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0786P)^2 + 0.7132P] where P = (Fo^2 + 2Fc^2)/3
4786 reflections	(Δ/σ)max = 0.001
301 parameters	Δρmax = 1.08 e Å^−3
0 restraints	Δρmin = −0.52 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	Occ. (<1)
Cu1	−0.99644 (3)	−0.03706 (3)	0.15407 (2)	0.03066 (12)
S1	−0.33042 (8)	−0.29981 (7)	0.01995 (7)	0.04172 (18)
S2	−0.30605 (8)	−0.22336 (7)	0.49481 (6)	0.04280 (18)
Cl1	−1.18179 (7)	0.01126 (8)	0.04844 (6)	0.04496 (19)
O1	−0.4340 (3)	−0.1793 (2)	−0.0328 (3)	0.0655 (7)
O2	−0.1974 (2)	−0.3501 (2)	−0.0575 (2)	0.0567 (6)
O3	−0.2965 (3)	−0.2938 (3)	0.1295 (2)	0.0621 (6)
O4	−0.2518 (2)	−0.1551 (2)	0.37776 (19)	0.0515 (5)
O5	−0.4109 (2)	−0.2776 (2)	0.4876 (2)	0.0558 (6)
O6	−0.3611 (3)	−0.1457 (3)	0.5810 (2)	0.0719 (8)
O1W	0.0678 (3)	−0.3620 (2)	0.0099 (3)	0.0605 (6)
H1WA	0.1142	−0.4446	0.0218	0.050*
H1WB	−0.0155	−0.3591	0.0039	0.050*
O2W	−0.2953 (3)	0.1065 (3)	0.4091 (3)	0.0697 (7)
H2WA	−0.3048	0.0129	0.4178	0.050*
H2WB	−0.3844	0.1579	0.4084	0.050*
N1	−1.0797 (3)	0.1350 (3)	0.1925 (2)	0.0441 (5)
H1A	−1.0810	0.1976	0.1249	0.053*
H1B	−1.1735	0.1483	0.2291	0.053*
N2	−0.9530 (3)	−0.2261 (2)	0.1912 (2)	0.0473 (6)
H2A	−1.0292	−0.2464	0.2408	0.057*
H2B	−0.9407	−0.2508	0.1240	0.057*
N3	−0.8449 (2)	−0.0830 (3)	0.26754 (19)	0.0380 (5)
N4	−0.4608 (2)	−0.0608 (2)	0.2062 (2)	0.0371 (5)
H4B	−0.4017	−0.0627	0.2523	0.071 (12)*
H4C	−0.4830	0.0152	0.1530	0.062 (11)*
H4D	−0.4149	−0.1246	0.1688	0.057 (10)*
C1	−0.4691 (3)	−0.4500 (3)	−0.0183 (2)	0.0374 (6)
C2	−0.4168 (3)	−0.4199 (3)	0.0643 (3)	0.0402 (6)
C3	−0.4241 (4)	−0.4872 (3)	0.1803 (3)	0.0488 (7)
H3A	−0.3897	−0.4665	0.2345	0.059*
C4	−0.4831 (4)	−0.5872 (3)	0.2186 (3)	0.0542 (8)
H4A	−0.4864	−0.6329	0.2979	0.065*
C5	−0.5354 (4)	−0.6184 (3)	0.1423 (3)	0.0489 (7)
H5A	−0.5748	−0.6849	0.1698	0.059*
C6	−0.0199 (3)	−0.5411 (3)	0.3105 (2)	0.0417 (6)
H6A	−0.0464	−0.5380	0.2401	0.050*
C7	−0.1050 (3)	−0.4509 (3)	0.3727 (2)	0.0372 (6)
H7A	−0.1911	−0.3881	0.3457	0.045*
C8	−0.0649 (3)	−0.4506 (2)	0.4787 (2)	0.0309 (5)
C9	−0.1483 (3)	−0.3554 (3)	0.5453 (2)	0.0342 (5)
C10	−0.1082 (3)	−0.3606 (3)	0.6485 (2)	0.0397 (6)
H10A	−0.1658	−0.2989	0.6918	0.048*
C11	−0.9260 (3)	0.0087 (4)	0.3453 (3)	0.0585 (10)
H11A	−0.8589	0.0092	0.3916	0.070*
H11B	−1.0041	−0.0187	0.3998	0.070*
C12	−0.9914 (4)	0.1425 (4)	0.2700 (3)	0.0584 (9)
H12A	−1.0533	0.2013	0.3201	0.070*
H12B	−0.9132	0.1748	0.2224	0.070*
C13	−0.8221 (4)	−0.2211 (4)	0.3319 (3)	0.0640 (10)
H13A	−0.9020	−0.2258	0.3970	0.077*
H13B	−0.7298	−0.2591	0.3646	0.077*
C14	−0.8181 (4)	−0.2943 (3)	0.2470 (4)	0.0651 (10)
H14A	−0.7316	−0.2984	0.1869	0.078*
H14B	−0.8134	−0.3822	0.2891	0.078*
C15	−0.7044 (3)	−0.0642 (3)	0.2012 (2)	0.0350 (6)
H15A	−0.7275	0.0214	0.1476	0.042*
H15B	−0.6557	−0.1273	0.1532	0.042*
C16	−0.5978 (3)	−0.0776 (4)	0.2800 (2)	0.0463 (7)
H16A	−0.6435	−0.0126	0.3262	0.056*
H16B	−0.5745	−0.1625	0.3347	0.056*
O3W	−0.5574 (19)	−0.4587 (12)	0.4874 (16)	0.200 (7)	0.52

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.02304 (17)	0.0402 (2)	0.02803 (17)	−0.01173 (13)	−0.00347 (12)	−0.00629 (13)
S1	0.0317 (3)	0.0366 (4)	0.0538 (4)	−0.0120 (3)	−0.0006 (3)	−0.0108 (3)
S2	0.0335 (3)	0.0433 (4)	0.0390 (4)	−0.0037 (3)	−0.0083 (3)	−0.0029 (3)
Cl1	0.0272 (3)	0.0796 (5)	0.0297 (3)	−0.0265 (3)	−0.0029 (2)	−0.0056 (3)
O1	0.0579 (14)	0.0404 (12)	0.0882 (19)	−0.0139 (11)	−0.0202 (13)	0.0014 (12)
O2	0.0373 (11)	0.0627 (14)	0.0719 (15)	−0.0221 (10)	0.0135 (10)	−0.0290 (12)
O3	0.0771 (17)	0.0619 (15)	0.0581 (14)	−0.0325 (13)	−0.0105 (12)	−0.0171 (12)
O4	0.0450 (12)	0.0469 (12)	0.0478 (12)	−0.0119 (10)	−0.0121 (9)	0.0078 (9)
O5	0.0321 (10)	0.0681 (15)	0.0554 (13)	−0.0151 (10)	−0.0119 (9)	0.0026 (11)
O6	0.0679 (16)	0.0636 (15)	0.0633 (16)	0.0141 (13)	−0.0183 (13)	−0.0280 (13)
O1W	0.0417 (12)	0.0442 (12)	0.0936 (19)	−0.0108 (10)	−0.0156 (12)	−0.0147 (12)
O2W	0.0385 (12)	0.0605 (15)	0.0806 (18)	−0.0089 (11)	0.0113 (12)	−0.0033 (13)
N1	0.0370 (12)	0.0486 (14)	0.0466 (13)	−0.0146 (11)	0.0009 (10)	−0.0167 (11)
N2	0.0433 (14)	0.0448 (14)	0.0494 (14)	−0.0183 (11)	−0.0032 (11)	−0.0042 (11)
N3	0.0255 (10)	0.0610 (15)	0.0252 (10)	−0.0184 (10)	−0.0019 (8)	−0.0040 (10)
N4	0.0243 (10)	0.0492 (14)	0.0372 (12)	−0.0131 (10)	−0.0050 (9)	−0.0088 (10)
C1	0.0286 (12)	0.0348 (13)	0.0413 (14)	−0.0097 (11)	0.0006 (10)	−0.0050 (11)
C2	0.0338 (13)	0.0378 (14)	0.0417 (14)	−0.0113 (11)	0.0000 (11)	−0.0051 (11)
C3	0.0477 (17)	0.0509 (17)	0.0424 (16)	−0.0184 (14)	−0.0071 (13)	−0.0017 (13)
C4	0.063 (2)	0.062 (2)	0.0333 (14)	−0.0306 (17)	−0.0081 (14)	0.0076 (14)
C5	0.0485 (17)	0.0520 (17)	0.0423 (16)	−0.0241 (14)	−0.0017 (13)	−0.0008 (13)
C6	0.0470 (16)	0.0483 (16)	0.0335 (13)	−0.0170 (13)	−0.0157 (12)	−0.0062 (12)
C7	0.0352 (13)	0.0429 (14)	0.0322 (13)	−0.0131 (11)	−0.0138 (10)	−0.0008 (11)
C8	0.0301 (12)	0.0344 (12)	0.0279 (11)	−0.0145 (10)	−0.0075 (9)	−0.0001 (9)
C9	0.0296 (12)	0.0360 (13)	0.0320 (12)	−0.0102 (10)	−0.0064 (10)	−0.0014 (10)
C10	0.0420 (15)	0.0422 (15)	0.0352 (13)	−0.0138 (12)	−0.0076 (11)	−0.0090 (11)
C11	0.0306 (14)	0.120 (3)	0.0361 (15)	−0.0290 (17)	0.0063 (12)	−0.0378 (18)
C12	0.0424 (17)	0.083 (3)	0.069 (2)	−0.0303 (17)	0.0125 (15)	−0.049 (2)
C13	0.0454 (18)	0.085 (3)	0.0509 (19)	−0.0340 (18)	−0.0211 (15)	0.0248 (18)
C14	0.0391 (17)	0.0441 (17)	0.088 (3)	−0.0122 (14)	−0.0102 (17)	0.0139 (17)
C15	0.0230 (11)	0.0565 (16)	0.0254 (11)	−0.0159 (11)	−0.0027 (9)	−0.0076 (11)
C16	0.0254 (12)	0.083 (2)	0.0310 (13)	−0.0200 (14)	−0.0034 (10)	−0.0125 (14)
O3W	0.245 (19)	0.131 (11)	0.253 (15)	−0.061 (11)	−0.146 (15)	−0.005 (11)

Geometric parameters (Å, º)

Cu1—N2	1.975 (3)	C1—C5^ii	1.445 (4)
Cu1—N1	1.983 (2)	C2—C3	1.362 (4)
Cu1—N3	2.081 (2)	C3—C4	1.399 (5)
Cu1—Cl1	2.2818 (7)	C3—H3A	0.9300
Cu1—Cl1^i	2.6320 (7)	C4—C5	1.351 (5)
Cu1—Cu1^i	3.5269 (8)	C4—H4A	0.9300
S1—O1	1.429 (3)	C5—C1^ii	1.445 (4)
S1—O2	1.438 (2)	C5—H5A	0.9300
S1—O3	1.459 (3)	C6—C7	1.355 (4)
S1—C2	1.787 (3)	C6—C10^iii	1.405 (4)
S2—O6	1.442 (3)	C6—H6A	0.9300
S2—O5	1.442 (2)	C7—C8	1.421 (3)
S2—O4	1.464 (2)	C7—H7A	0.9300
S2—C9	1.778 (3)	C8—C8^iii	1.425 (5)
Cl1—Cu1^i	2.6320 (7)	C8—C9	1.426 (4)
O1W—H1WA	0.8623	C9—C10	1.366 (4)
O1W—H1WB	0.8346	C10—C6^iii	1.405 (4)
O2W—H2WA	1.0922	C10—H10A	0.9300
O2W—H2WB	0.8502	C11—C12	1.501 (6)
N1—C12	1.467 (4)	C11—H11A	0.9700
N1—H1A	0.9000	C11—H11B	0.9700
N1—H1B	0.9000	C12—H12A	0.9700
N2—C14	1.465 (4)	C12—H12B	0.9700
N2—H2A	0.9000	C13—C14	1.496 (6)
N2—H2B	0.9000	C13—H13A	0.9700
N3—C15	1.485 (3)	C13—H13B	0.9700
N3—C11	1.486 (4)	C14—H14A	0.9700
N3—C13	1.491 (4)	C14—H14B	0.9700
N4—C16	1.474 (3)	C15—C16	1.520 (3)
N4—H4B	0.8900	C15—H15A	0.9700
N4—H4C	0.8900	C15—H15B	0.9700
N4—H4D	0.8900	C16—H16A	0.9700
C1—C2	1.407 (4)	C16—H16B	0.9700
C1—C1^ii	1.419 (5)	O3W—O3W^iv	1.20 (3)
N2—Cu1—N1	154.12 (11)	C2—C3—C4	120.5 (3)
N2—Cu1—N3	85.23 (11)	C2—C3—H3A	119.8
N1—Cu1—N3	85.38 (10)	C4—C3—H3A	119.8
N2—Cu1—Cl1	93.80 (8)	C5—C4—C3	121.0 (3)
N1—Cu1—Cl1	92.84 (8)	C5—C4—H4A	119.5
N3—Cu1—Cl1	173.53 (6)	C3—C4—H4A	119.5
N2—Cu1—Cl1^i	98.89 (8)	C4—C5—C1^ii	120.9 (3)
N1—Cu1—Cl1^i	106.26 (8)	C4—C5—H5A	119.6
N3—Cu1—Cl1^i	97.93 (6)	C1^ii—C5—H5A	119.6
Cl1—Cu1—Cl1^i	88.54 (3)	C7—C6—C10^iii	120.6 (2)
N2—Cu1—Cu1^i	99.11 (8)	C7—C6—H6A	119.7
N1—Cu1—Cu1^i	103.94 (8)	C10^iii—C6—H6A	119.7
N3—Cu1—Cu1^i	138.22 (6)	C6—C7—C8	121.1 (2)
Cl1—Cu1—Cu1^i	48.246 (18)	C6—C7—H7A	119.5
Cl1^i—Cu1—Cu1^i	40.297 (16)	C8—C7—H7A	119.5
O1—S1—O2	115.50 (17)	C7—C8—C8^iii	119.1 (3)
O1—S1—O3	111.16 (16)	C7—C8—C9	123.2 (2)
O2—S1—O3	111.10 (16)	C8^iii—C8—C9	117.7 (3)
O1—S1—C2	107.97 (15)	C10—C9—C8	121.3 (2)
O2—S1—C2	105.09 (13)	C10—C9—S2	117.6 (2)
O3—S1—C2	105.28 (15)	C8—C9—S2	120.99 (19)
O6—S2—O5	112.52 (17)	C9—C10—C6^iii	120.2 (3)
O6—S2—O4	112.88 (17)	C9—C10—H10A	119.9
O5—S2—O4	111.88 (14)	C6^iii—C10—H10A	119.9
O6—S2—C9	106.41 (14)	N3—C11—C12	109.5 (2)
O5—S2—C9	107.18 (13)	N3—C11—H11A	109.8
O4—S2—C9	105.38 (12)	C12—C11—H11A	109.8
Cu1—Cl1—Cu1^i	91.46 (3)	N3—C11—H11B	109.8
H1WA—O1W—H1WB	99.8	C12—C11—H11B	109.8
H2WA—O2W—H2WB	102.9	H11A—C11—H11B	108.2
C12—N1—Cu1	110.7 (2)	N1—C12—C11	108.0 (3)
C12—N1—H1A	109.5	N1—C12—H12A	110.1
Cu1—N1—H1A	109.5	C11—C12—H12A	110.1
C12—N1—H1B	109.5	N1—C12—H12B	110.1
Cu1—N1—H1B	109.5	C11—C12—H12B	110.1
H1A—N1—H1B	108.1	H12A—C12—H12B	108.4
C14—N2—Cu1	109.5 (2)	N3—C13—C14	109.0 (3)
C14—N2—H2A	109.8	N3—C13—H13A	109.9
Cu1—N2—H2A	109.8	C14—C13—H13A	109.9
C14—N2—H2B	109.8	N3—C13—H13B	109.9
Cu1—N2—H2B	109.8	C14—C13—H13B	109.9
H2A—N2—H2B	108.2	H13A—C13—H13B	108.3
C15—N3—C11	112.3 (2)	N2—C14—C13	107.9 (3)
C15—N3—C13	112.0 (2)	N2—C14—H14A	110.1
C11—N3—C13	113.0 (3)	C13—C14—H14A	110.1
C15—N3—Cu1	111.72 (15)	N2—C14—H14B	110.1
C11—N3—Cu1	102.17 (17)	C13—C14—H14B	110.1
C13—N3—Cu1	104.97 (18)	H14A—C14—H14B	108.4
C16—N4—H4B	109.5	N3—C15—C16	114.1 (2)
C16—N4—H4C	109.5	N3—C15—H15A	108.7
H4B—N4—H4C	109.5	C16—C15—H15A	108.7
C16—N4—H4D	109.5	N3—C15—H15B	108.7
H4B—N4—H4D	109.5	C16—C15—H15B	108.7
H4C—N4—H4D	109.5	H15A—C15—H15B	107.6
C2—C1—C1^ii	120.4 (3)	N4—C16—C15	110.0 (2)
C2—C1—C5^ii	122.7 (3)	N4—C16—H16A	109.7
C1^ii—C1—C5^ii	116.9 (3)	C15—C16—H16A	109.7
C3—C2—C1	120.3 (3)	N4—C16—H16B	109.7
C3—C2—S1	118.0 (2)	C15—C16—H16B	109.7
C1—C2—S1	121.6 (2)	H16A—C16—H16B	108.2
N2—Cu1—Cl1—Cu1^i	−98.82 (8)	C1—C2—C3—C4	0.2 (5)
N1—Cu1—Cl1—Cu1^i	106.21 (8)	S1—C2—C3—C4	−176.4 (3)
N2—Cu1—N1—C12	72.3 (3)	C2—C3—C4—C5	−0.7 (5)
N3—Cu1—N1—C12	3.3 (2)	C3—C4—C5—C1^ii	0.5 (5)
Cl1—Cu1—N1—C12	177.1 (2)	C10^iii—C6—C7—C8	2.0 (4)
Cl1^i—Cu1—N1—C12	−93.6 (2)	C6—C7—C8—C8^iii	−1.7 (4)
Cu1^i—Cu1—N1—C12	−135.4 (2)	C6—C7—C8—C9	178.0 (3)
N1—Cu1—N2—C14	−83.9 (3)	C7—C8—C9—C10	178.2 (3)
N3—Cu1—N2—C14	−14.9 (2)	C8^iii—C8—C9—C10	−2.1 (4)
Cl1—Cu1—N2—C14	171.5 (2)	C7—C8—C9—S2	−3.3 (4)
Cl1^i—Cu1—N2—C14	82.4 (2)	C8^iii—C8—C9—S2	176.4 (2)
Cu1^i—Cu1—N2—C14	123.3 (2)	O6—S2—C9—C10	−0.3 (3)
N2—Cu1—N3—C15	107.9 (2)	O5—S2—C9—C10	−120.9 (2)
N1—Cu1—N3—C15	−96.2 (2)	O4—S2—C9—C10	119.8 (2)
Cl1^i—Cu1—N3—C15	9.60 (19)	O6—S2—C9—C8	−178.9 (2)
Cu1^i—Cu1—N3—C15	9.6 (3)	O5—S2—C9—C8	60.5 (2)
N2—Cu1—N3—C11	−131.8 (2)	O4—S2—C9—C8	−58.8 (2)
N1—Cu1—N3—C11	24.1 (2)	C8—C9—C10—C6^iii	1.9 (4)
Cl1^i—Cu1—N3—C11	129.89 (19)	S2—C9—C10—C6^iii	−176.7 (2)
Cu1^i—Cu1—N3—C11	129.90 (17)	C15—N3—C11—C12	72.3 (3)
N2—Cu1—N3—C13	−13.6 (2)	C13—N3—C11—C12	−159.8 (2)
N1—Cu1—N3—C13	142.2 (2)	Cu1—N3—C11—C12	−47.6 (3)
Cl1^i—Cu1—N3—C13	−111.96 (19)	Cu1—N1—C12—C11	−30.4 (3)
Cu1^i—Cu1—N3—C13	−111.95 (19)	N3—C11—C12—N1	53.7 (3)
C1^ii—C1—C2—C3	0.5 (5)	C15—N3—C13—C14	−82.1 (3)
C5^ii—C1—C2—C3	179.8 (3)	C11—N3—C13—C14	149.9 (3)
C1^ii—C1—C2—S1	177.0 (3)	Cu1—N3—C13—C14	39.3 (3)
C5^ii—C1—C2—S1	−3.7 (4)	Cu1—N2—C14—C13	40.7 (3)
O1—S1—C2—C3	−124.0 (3)	N3—C13—C14—N2	−54.0 (3)
O2—S1—C2—C3	112.3 (3)	C11—N3—C15—C16	57.6 (3)
O3—S1—C2—C3	−5.1 (3)	C13—N3—C15—C16	−70.9 (3)
O1—S1—C2—C1	59.4 (3)	Cu1—N3—C15—C16	171.7 (2)
O2—S1—C2—C1	−64.3 (3)	N3—C15—C16—N4	178.5 (3)
O3—S1—C2—C1	178.3 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O2^v	0.86	2.12	2.975 (3)	172
O1W—H1WB···O2	0.83	2.07	2.883 (3)	165
O2W—H2WA···O4	1.09	1.98	3.009 (4)	156
O2W—H2WB···O5^vi	0.85	2.28	3.025 (3)	146
O2W—H2WB···O6^vi	0.85	2.56	3.238 (4)	138
N1—H1A···O1W^vii	0.90	2.10	2.982 (4)	167
N1—H1B···O2W^viii	0.90	2.20	2.945 (4)	140
N2—H2A···O4^viii	0.90	2.48	3.226 (4)	141
N2—H2B···O1W^viii	0.90	2.11	2.977 (4)	160
N4—H4B···O4	0.89	2.11	2.941 (3)	154
N4—H4C···O1^vii	0.89	2.00	2.879 (3)	170
N4—H4D···O3	0.89	1.98	2.845 (4)	164

Symmetry codes: (v) −x, −y−1, −z; (vi) −x−1, −y, −z+1; (vii) −x−1, −y, −z; (viii) x−1, y, z.