catena-Poly[[hexakis­(1H-benzimidazole)bis­(μ²-5-sulfonatosalicylato)tricopper(II)] octa­hydrate]

The crystal structure of the title compound, {[Cu₃(C₇H₃O₆S)₂(C₇H₆N₂)₆]·8H₂O}_n, is built of trinuclear complexes [Cu₃(bz)₆(ssal)₂] (bz = benzimidazole and ssal = 5-sulfonatosalicylate trianion) and uncoordinated water mol­ecules. The mol­ecule of the complex occupies a special position on a crystallographic inversion centre. The Cu atom located on the inversion centre has a square planar coordination made up of the two N atoms of monodentate benzimidazole ligands and the O atoms of two bridging salicylates. The other crystallographically independent Cu atom has a square pyramidal environment formed by the N atoms of two more monodentate benzimidazole ligands, two chelate O atoms of the bridging salicylate and the sulfonate O atom of the sulfonatosalicylate ligand belonging to the neighbouring trimetallic complex. The latter coordination links the mol­ecules of the complex into infinite chains running along the a axis. These chains are further connected by O—H...O and N—H...O hydrogen bonding into a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.010 Å
• H-atom completeness 97%
• Disorder in solvent or counterion
• R factor = 0.070
• wR factor = 0.161
• Data-to-parameter ratio = 11.8

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT220_ALERT_2_B Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.83 Ratio

Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.50 Ratio
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      17.00 Perc.
PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) .....      <O5W'
PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) .....       <O5W
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...         10
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          1

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C56 H58 Cu3 N12 O20 S2
            Atom count from the _atom_site data:  C56 H56 Cu3 N12 O20 S2
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
           From the CIF: _cell_formula_units_Z    1
           From the CIF: _chemical_formula_sum  C56 H58 Cu3 N12 O20 S2
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C         56.00     56.00    0.00
           H         58.00     56.00    2.00
           Cu         3.00      3.00    0.00
           N         12.00     12.00    0.00
           O         20.00     20.00    0.00
           S          2.00      2.00    0.00

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion

---

S1. Comment

5-Sulfosalicylate complexes have lately been receiving considerable attention, and numerous complexes of this kind have been synthesized (Gao et al., 2005; Smith et al., 2005). Among these, two copper complexes with trinuclear units, [Cu₃(2,2'-bipy)₂(ssal)₂(H₂O)₄]·4H₂O, (II) (Wang et al., 2004), and [Cu₃(dpa)₃(ssal)₂]·3H₂O, (III) (Fan & Zhu, 2005) (2,2'-bipy = 2,2'-bipyridine; dpa = 2,2'-dipyridylamine), were reported. We present here a third 5-sulfonatosalicylate copper complex with the trinuclear Cu₃ motif, (I).

The crystal structure of the title compound is built of centrosymmetric trinuclear complexes, [Cu₃(bz)₆(ssal)₂] (bz = benzimidazole and ssal = 5-sulfonatosalicylate trianion), and uncoordinated water molecules; a fragment of the structure of (I) with the trinuclear complex and hydrate water molecules is shown in Fig. 1.

There are two crystallographically independent Cu atoms in each complex. One of them, Cu2, occupies a special position on the crystallographic inversion centre and has a square planar coordination, formed by the N atoms of two monodentate benzimidazole ligands [Cu2—N5 = 2.000 (5) Å] and the O atoms of two bridging sulfonatosalicylates [Cu2—O2 = 1.965 (3) Å]. The other crystallographically independent metal atom, Cu1, has a square pyramidal geometry formed by the N atoms of two more benzimidazole ligands [Cu1—N1 = 1.990 (4) Å and Cu1—N3 = 2.004 (4) Å], two O atoms of the chelate salicylate fragment [Cu1—O1 = 1.935 (4) Å and Cu1—O3 = 1.920 (3) Å] and the O atom of the sulfonate group of the neighbouring trinuclear complex in the apical position of the pyramid [Cu1—O4ⁱⁱ = 2.330 (4) Å; symmetry code (ii): −x, 1 − y, 2 − z]. The latter contact gives rise to infinite chains running along the a axis of the crystal. The structure is further consolidated into a three-dimensional framework by extensive N—H···O and O—H···O hydrogen bonding (Table 2).

Comparison of the two previously reported copper complexes with trinuclear units with (I) shows that the ssal ligands in these three complexes have different coordination modes. In (III), ssal is a µ₅ ligand, while in (I) and (II), the ssal anions are µ₃ ligands; therefore, the structures of (I) and (II) feature one-dimensional chains, whereas the structure of (III) is built of two-dimensional layers. In the trinuclear units the Cu atoms in special positions have four-, six- and four-coordinated environments with square planar, octahedral and distorted tetrahedral geometries for (I), (II) and (III), respectively. The Cu atoms in general positions have either square pyramidal environments, as in (I) and (II), or octahedron geometry, as in (III). The comparison of bond lengths in these three complexes is given in Table 3.

S2. Experimental

A mixture of CuCl₂·2H₂O (0.170 g,1 mmol), 5-sulfosalicylic acid dihydrate (0.126 g, 0.5 mmol), Na₂CO₃ (0.106 g,1 mmol) and benzimidazole (0.236 g, 2 mmol) in water/methanol (v/v 2:1) solution (30 ml) was refluxed for 2 h and filtered. After the mixture had been left to stand for 1 d, green block-shaped crystals of (I) precipitated; these were used for the X-ray diffraction experiment.

S3. Refinement

All aromatic H atoms were placed in calculated positions, with C—H = 0.93 Å and N—H = 0.86 Å, and refined as riding atoms, with U_iso(H) values of 1.2U_eq(C,N). The occupancies of water molecules O4w and O5w were initially refined to 0.60 (3) and 0.54 (2), respectively; they were then fixed at 0.5. A t this stage, the O5w molecule was disordered over two sites with the ratio of 0.341 (17):0.159 (17) for O5w and O5w', respectively. The H atoms of these water molecules could not be located. H atoms of other water molecules were located in difference Fourier maps and were refined with distance restraint of O—H = 0.85 (1) Å and fixed isotropic displacement parameter of U_iso(H) = 0.08 Ų.

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. ORTEP-3 (Farrugia, 1997) view of the stucture of (I). Displacement ellipsoids are drawn at the 30% probability level. The minor component of the disordered water molecule has been omitted for clarity. [Symmetry codes (i): 1 − x, 1 − y, 2 − z; (ii): − x, 1 − y, 2 − z; (iii): 1 + x, y, z.]
	Fig. 2. A view of the one-dimensional network in (I). H atoms and uncoordinated water molecules have been omitted for clarity.

(I)

Crystal data

[Cu3(C7H6N2)6(C7H3SO6)2]·8H2O	Z = 1
Mr = 1473.88	F(000) = 755
Triclinic, P1	Dx = 1.558 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.1489 (6) Å	Cell parameters from 5186 reflections
b = 11.9699 (6) Å	θ = 2.2–27.7°
c = 12.5693 (6) Å	µ = 1.16 mm^−1
α = 99.302 (1)°	T = 295 K
β = 93.690 (1)°	Block, green
γ = 107.155 (1)°	0.33 × 0.21 × 0.10 mm
V = 1570.48 (14) Å^3

Data collection

Bruker APEX area-detector diffractometer	5475 independent reflections
Radiation source: fine-focus sealed tube	5149 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
ϕ and ω scan	θmax = 25.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −13→13
Tmin = 0.701, Tmax = 0.893	k = −14→14
11391 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)] = 0.070	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.161	H-atom parameters constrained
S = 1.22	w = 1/[σ^2(Fo^2) + (0.0484P)^2 + 6.6709P] where P = (Fo^2 + 2Fc^2)/3
5475 reflections	(Δ/σ)max < 0.001
464 parameters	Δρmax = 0.69 e Å^−3
24 restraints	Δρmin = −0.66 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	0.18297 (6)	0.36682 (6)	1.21624 (5)	0.02564 (19)
Cu2	0.5000	0.5000	1.0000	0.0282 (2)
S1	−0.08891 (12)	0.38480 (12)	0.67725 (10)	0.0262 (3)
N1	0.0885 (4)	0.2634 (4)	1.3118 (3)	0.0285 (10)
N2	−0.0283 (5)	0.1999 (4)	1.4381 (4)	0.0344 (11)
H2	−0.0675	0.2022	1.4947	0.041*
N3	0.3475 (4)	0.3837 (4)	1.3016 (4)	0.0315 (10)
N4	0.4885 (5)	0.3356 (5)	1.4015 (4)	0.0491 (14)
H4	0.5202	0.2945	1.4385	0.059*
N5	0.5021 (4)	0.6571 (4)	0.9636 (4)	0.0333 (11)
N6	0.4524 (6)	0.7702 (6)	0.8570 (5)	0.0578 (16)
H6	0.4125	0.7902	0.8061	0.069*
O1	0.2765 (3)	0.4331 (4)	1.1046 (3)	0.0314 (9)
O2	0.3212 (3)	0.4406 (4)	0.9388 (3)	0.0324 (9)
O3	0.0252 (3)	0.3294 (3)	1.1263 (3)	0.0301 (8)
O4	−0.1757 (4)	0.4552 (4)	0.6815 (3)	0.0361 (9)
O5	0.0276 (4)	0.4398 (4)	0.6355 (3)	0.0398 (10)
O6	−0.1529 (4)	0.2634 (3)	0.6171 (3)	0.0359 (9)
O1W	0.1746 (4)	0.6734 (5)	0.7493 (4)	0.0532 (12)
O2W	0.5983 (7)	0.2051 (7)	1.5237 (8)	0.112 (3)
O3W	0.3372 (10)	0.8597 (10)	0.6903 (8)	0.141 (3)
O4W	0.300 (2)	0.015 (2)	1.399 (3)	0.183 (11)	0.50
O5W'	0.575 (6)	0.963 (5)	1.395 (5)	0.14 (2)	0.159 (17)
O5W	0.501 (3)	0.906 (2)	1.287 (2)	0.133 (11)	0.341 (17)
C1	0.0522 (5)	0.1398 (5)	1.2926 (4)	0.0295 (12)
C2	0.0822 (6)	0.0598 (6)	1.2137 (5)	0.0451 (15)
H2C	0.1318	0.0858	1.1603	0.054*
C3	0.0352 (8)	−0.0601 (6)	1.2178 (7)	0.060 (2)
H3	0.0548	−0.1156	1.1669	0.072*
C4	−0.0404 (7)	−0.0991 (6)	1.2960 (6)	0.0575 (19)
H4C	−0.0707	−0.1803	1.2959	0.069*
C5	−0.0719 (6)	−0.0212 (6)	1.3739 (5)	0.0470 (16)
H5	−0.1239	−0.0479	1.4255	0.056*
C6	−0.0224 (5)	0.0993 (5)	1.3719 (4)	0.0314 (12)
C7	0.0381 (5)	0.2941 (5)	1.3987 (4)	0.0310 (12)
H7	0.0473	0.3726	1.4296	0.037*
C8	0.4599 (5)	0.4778 (6)	1.3205 (4)	0.0358 (13)
C9	0.4917 (6)	0.5878 (6)	1.2901 (5)	0.0460 (16)
H9	0.4336	0.6107	1.2494	0.055*
C10	0.6126 (7)	0.6616 (7)	1.3226 (6)	0.061 (2)
H10	0.6366	0.7361	1.3033	0.074*
C11	0.7014 (6)	0.6285 (8)	1.3841 (6)	0.062 (2)
H11	0.7828	0.6813	1.4038	0.074*
C12	0.6717 (6)	0.5226 (7)	1.4151 (6)	0.0534 (18)
H12	0.7304	0.5008	1.4562	0.064*
C13	0.5499 (6)	0.4475 (6)	1.3831 (5)	0.0404 (15)
C14	0.3711 (6)	0.3028 (6)	1.3513 (5)	0.0417 (15)
H14	0.3117	0.2296	1.3515	0.050*
C15	0.5868 (5)	0.7720 (5)	0.9938 (5)	0.0384 (14)
C16	0.6869 (7)	0.8229 (6)	1.0766 (6)	0.0550 (18)
H16	0.7096	0.7774	1.1229	0.066*
C17	0.7509 (8)	0.9415 (7)	1.0877 (8)	0.074 (2)
H17	0.8176	0.9770	1.1428	0.089*
C18	0.7184 (9)	1.0092 (7)	1.0190 (9)	0.082 (3)
H18	0.7646	1.0895	1.0287	0.098*
C19	0.6211 (10)	0.9629 (7)	0.9371 (8)	0.075 (3)
H19	0.6000	1.0094	0.8909	0.090*
C20	0.5560 (7)	0.8442 (6)	0.9265 (6)	0.0493 (17)
C21	0.4249 (6)	0.6621 (6)	0.8824 (5)	0.0427 (15)
H21	0.3582	0.5972	0.8463	0.051*
C22	0.2406 (5)	0.4197 (4)	1.0050 (4)	0.0245 (11)
C23	0.1051 (5)	0.3828 (4)	0.9614 (4)	0.0225 (10)
C24	0.0071 (5)	0.3452 (4)	1.0261 (4)	0.0220 (10)
C25	−0.1185 (5)	0.3222 (5)	0.9793 (4)	0.0263 (11)
H25	−0.1842	0.2978	1.0208	0.032*
C26	−0.1467 (5)	0.3346 (5)	0.8754 (4)	0.0276 (11)
H26	−0.2303	0.3193	0.8472	0.033*
C27	−0.0496 (5)	0.3703 (4)	0.8115 (4)	0.0215 (10)
C28	0.0741 (5)	0.3941 (4)	0.8544 (4)	0.0230 (11)
H28	0.1385	0.4182	0.8117	0.028*
H1B	0.121 (5)	0.678 (6)	0.794 (5)	0.080*
H1A	0.147 (6)	0.607 (4)	0.705 (5)	0.080*
H2A	0.557 (6)	0.146 (6)	1.551 (6)	0.080*
H2B	0.674 (3)	0.231 (6)	1.555 (6)	0.080*
H3A	0.379 (8)	0.933 (2)	0.693 (6)	0.080*
H3B	0.320 (9)	0.825 (6)	0.623 (2)	0.080*
H4A	0.330 (15)	0.033 (17)	1.465 (3)	0.080*	0.50
H4B	0.345 (16)	−0.019 (19)	1.362 (10)	0.080*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0226 (3)	0.0338 (4)	0.0210 (3)	0.0094 (3)	0.0008 (2)	0.0063 (3)
Cu2	0.0166 (4)	0.0405 (6)	0.0258 (5)	0.0042 (4)	0.0020 (3)	0.0104 (4)
S1	0.0270 (7)	0.0324 (7)	0.0194 (6)	0.0114 (6)	−0.0002 (5)	0.0021 (5)
N1	0.028 (2)	0.035 (3)	0.023 (2)	0.011 (2)	0.0018 (18)	0.0057 (19)
N2	0.040 (3)	0.038 (3)	0.025 (2)	0.011 (2)	0.008 (2)	0.005 (2)
N3	0.023 (2)	0.045 (3)	0.028 (2)	0.011 (2)	0.0006 (18)	0.009 (2)
N4	0.039 (3)	0.068 (4)	0.047 (3)	0.027 (3)	−0.008 (2)	0.015 (3)
N5	0.027 (2)	0.038 (3)	0.037 (3)	0.011 (2)	0.003 (2)	0.011 (2)
N6	0.073 (4)	0.065 (4)	0.049 (4)	0.040 (3)	−0.006 (3)	0.019 (3)
O1	0.0195 (18)	0.052 (2)	0.0191 (19)	0.0058 (17)	0.0010 (14)	0.0057 (16)
O2	0.0168 (17)	0.050 (2)	0.027 (2)	0.0023 (17)	0.0011 (15)	0.0148 (17)
O3	0.0215 (18)	0.045 (2)	0.0234 (19)	0.0059 (16)	0.0029 (14)	0.0120 (17)
O4	0.039 (2)	0.044 (2)	0.028 (2)	0.0200 (19)	−0.0031 (17)	0.0042 (17)
O5	0.036 (2)	0.054 (3)	0.028 (2)	0.011 (2)	0.0047 (17)	0.0108 (19)
O6	0.042 (2)	0.035 (2)	0.026 (2)	0.0103 (18)	−0.0023 (17)	−0.0050 (16)
O1W	0.033 (2)	0.078 (4)	0.047 (3)	0.015 (2)	0.004 (2)	0.014 (2)
O2W	0.071 (4)	0.102 (6)	0.154 (7)	0.021 (4)	−0.040 (5)	0.036 (5)
O3W	0.118 (8)	0.161 (9)	0.145 (8)	0.028 (7)	−0.007 (7)	0.074 (7)
O4W	0.124 (17)	0.124 (18)	0.29 (3)	0.002 (12)	−0.067 (18)	0.12 (2)
O5W'	0.14 (2)	0.14 (2)	0.14 (2)	0.042 (7)	0.016 (3)	0.026 (4)
O5W	0.134 (11)	0.133 (11)	0.133 (11)	0.041 (4)	0.0156 (17)	0.026 (2)
C1	0.029 (3)	0.031 (3)	0.029 (3)	0.013 (2)	0.001 (2)	0.004 (2)
C2	0.049 (4)	0.048 (4)	0.036 (3)	0.016 (3)	0.012 (3)	−0.001 (3)
C3	0.072 (5)	0.039 (4)	0.069 (5)	0.024 (4)	0.014 (4)	−0.003 (4)
C4	0.071 (5)	0.034 (4)	0.068 (5)	0.017 (3)	0.009 (4)	0.009 (3)
C5	0.054 (4)	0.040 (4)	0.045 (4)	0.009 (3)	0.002 (3)	0.015 (3)
C6	0.033 (3)	0.036 (3)	0.028 (3)	0.015 (2)	0.001 (2)	0.007 (2)
C7	0.038 (3)	0.030 (3)	0.026 (3)	0.014 (2)	−0.002 (2)	0.004 (2)
C8	0.027 (3)	0.057 (4)	0.023 (3)	0.014 (3)	0.002 (2)	0.005 (3)
C9	0.037 (3)	0.060 (4)	0.034 (3)	0.007 (3)	−0.002 (3)	0.009 (3)
C10	0.054 (5)	0.069 (5)	0.052 (4)	0.001 (4)	0.007 (4)	0.019 (4)
C11	0.028 (3)	0.090 (6)	0.051 (4)	−0.001 (4)	−0.001 (3)	0.003 (4)
C12	0.030 (3)	0.083 (6)	0.044 (4)	0.015 (4)	0.001 (3)	0.009 (4)
C13	0.032 (3)	0.063 (4)	0.026 (3)	0.017 (3)	0.005 (2)	0.004 (3)
C14	0.036 (3)	0.049 (4)	0.042 (4)	0.016 (3)	−0.003 (3)	0.011 (3)
C15	0.032 (3)	0.039 (3)	0.046 (4)	0.013 (3)	0.008 (3)	0.011 (3)
C16	0.049 (4)	0.047 (4)	0.063 (5)	0.009 (3)	−0.004 (3)	0.010 (3)
C17	0.064 (5)	0.046 (5)	0.098 (7)	0.006 (4)	−0.010 (5)	0.005 (4)
C18	0.086 (7)	0.038 (4)	0.115 (8)	0.009 (4)	0.011 (6)	0.014 (5)
C19	0.105 (7)	0.050 (5)	0.085 (6)	0.035 (5)	0.017 (6)	0.029 (5)
C20	0.057 (4)	0.049 (4)	0.051 (4)	0.026 (3)	0.011 (3)	0.014 (3)
C21	0.036 (3)	0.050 (4)	0.044 (4)	0.019 (3)	0.002 (3)	0.007 (3)
C22	0.021 (2)	0.024 (3)	0.028 (3)	0.005 (2)	0.004 (2)	0.006 (2)
C23	0.022 (3)	0.018 (2)	0.025 (3)	0.006 (2)	−0.001 (2)	0.000 (2)
C24	0.026 (3)	0.018 (2)	0.023 (3)	0.008 (2)	0.002 (2)	0.005 (2)
C25	0.024 (3)	0.030 (3)	0.024 (3)	0.007 (2)	0.005 (2)	0.003 (2)
C26	0.022 (3)	0.029 (3)	0.031 (3)	0.009 (2)	−0.003 (2)	0.003 (2)
C27	0.026 (3)	0.020 (2)	0.018 (2)	0.009 (2)	−0.001 (2)	0.0009 (19)
C28	0.022 (2)	0.025 (3)	0.020 (2)	0.004 (2)	0.004 (2)	0.003 (2)

Geometric parameters (Å, º)

Cu1—O1	1.935 (4)	C2—C3	1.386 (10)
Cu1—O3	1.920 (3)	C2—H2C	0.9300
Cu1—O4^i	2.330 (4)	C3—C4	1.384 (10)
Cu1—N1	1.990 (4)	C3—H3	0.9300
Cu1—N3	2.004 (4)	C4—C5	1.377 (10)
Cu2—O2	1.965 (3)	C4—H4C	0.9300
Cu2—O2^ii	1.965 (3)	C5—C6	1.388 (8)
Cu2—N5	2.000 (5)	C5—H5	0.9300
Cu2—N5^ii	2.000 (5)	C7—H7	0.9300
S1—O5	1.446 (4)	C8—C9	1.383 (9)
S1—O4	1.457 (4)	C8—C13	1.400 (8)
S1—O6	1.469 (4)	C9—C10	1.368 (10)
S1—C27	1.765 (5)	C9—H9	0.9300
N1—C7	1.309 (7)	C10—C11	1.402 (11)
N1—C1	1.390 (7)	C10—H10	0.9300
N2—C7	1.342 (7)	C11—C12	1.341 (11)
N2—C6	1.370 (7)	C11—H11	0.9300
N2—H2	0.8600	C12—C13	1.382 (9)
N3—C14	1.313 (8)	C12—H12	0.9300
N3—C8	1.392 (7)	C14—H14	0.9300
N4—C14	1.332 (8)	C15—C16	1.395 (9)
N4—C13	1.377 (9)	C15—C20	1.397 (9)
N4—H4	0.8600	C16—C17	1.366 (10)
N5—C21	1.312 (8)	C16—H16	0.9300
N5—C15	1.396 (8)	C17—C18	1.376 (12)
N6—C21	1.336 (9)	C17—H17	0.9300
N6—C20	1.377 (9)	C18—C19	1.365 (13)
N6—H6	0.8600	C18—H18	0.9300
O1—C22	1.260 (6)	C19—C20	1.372 (11)
O2—C22	1.262 (6)	C19—H19	0.9300
O3—C24	1.316 (6)	C21—H21	0.9300
O4—Cu1^i	2.330 (4)	C22—C23	1.483 (7)
O1W—H1B	0.85 (6)	C23—C28	1.405 (7)
O1W—H1A	0.85 (5)	C23—C24	1.413 (7)
O2W—H2A	0.86 (7)	C24—C25	1.414 (7)
O2W—H2B	0.85 (5)	C25—C26	1.366 (7)
O3W—H3A	0.86 (4)	C25—H25	0.9300
O3W—H3B	0.86 (3)	C26—C27	1.395 (7)
O4W—H4A	0.850 (11)	C26—H26	0.9300
O4W—H4B	0.853 (10)	C27—C28	1.377 (7)
C1—C2	1.392 (8)	C28—H28	0.9300
C1—C6	1.394 (8)
O3—Cu1—O1	91.45 (15)	N1—C7—N2	112.6 (5)
O3—Cu1—N1	87.16 (16)	N1—C7—H7	123.7
O1—Cu1—N1	166.81 (18)	N2—C7—H7	123.7
O3—Cu1—N3	172.30 (18)	C9—C8—N3	131.6 (5)
O1—Cu1—N3	88.85 (17)	C9—C8—C13	119.6 (6)
N1—Cu1—N3	90.79 (18)	N3—C8—C13	108.8 (6)
O3—Cu1—O4^i	97.02 (15)	C10—C9—C8	117.0 (6)
O1—Cu1—O4^i	97.76 (16)	C10—C9—H9	121.5
N1—Cu1—O4^i	95.42 (16)	C8—C9—H9	121.5
N3—Cu1—O4^i	90.56 (17)	C9—C10—C11	122.2 (7)
O2—Cu2—O2^ii	180.000 (1)	C9—C10—H10	118.9
O2—Cu2—N5	87.02 (17)	C11—C10—H10	118.9
O2^ii—Cu2—N5	92.98 (17)	C12—C11—C10	121.5 (7)
O2—Cu2—N5^ii	92.98 (17)	C12—C11—H11	119.3
O2^ii—Cu2—N5^ii	87.02 (17)	C10—C11—H11	119.3
N5—Cu2—N5^ii	180.000 (1)	C11—C12—C13	116.8 (7)
O5—S1—O4	113.4 (3)	C11—C12—H12	121.6
O5—S1—O6	112.0 (2)	C13—C12—H12	121.6
O4—S1—O6	110.3 (2)	N4—C13—C12	131.9 (6)
O5—S1—C27	107.6 (2)	N4—C13—C8	105.3 (5)
O4—S1—C27	107.3 (2)	C12—C13—C8	122.8 (7)
O6—S1—C27	105.9 (2)	N3—C14—N4	113.5 (6)
C7—N1—C1	105.5 (5)	N3—C14—H14	123.2
C7—N1—Cu1	128.5 (4)	N4—C14—H14	123.2
C1—N1—Cu1	125.7 (3)	C16—C15—N5	132.1 (6)
C7—N2—C6	107.7 (5)	C16—C15—C20	118.8 (6)
C7—N2—H2	126.1	N5—C15—C20	109.1 (6)
C6—N2—H2	126.1	C17—C16—C15	118.2 (7)
C14—N3—C8	105.0 (5)	C17—C16—H16	120.9
C14—N3—Cu1	125.4 (4)	C15—C16—H16	120.9
C8—N3—Cu1	129.7 (4)	C16—C17—C18	121.2 (8)
C14—N4—C13	107.4 (5)	C16—C17—H17	119.4
C14—N4—H4	126.3	C18—C17—H17	119.4
C13—N4—H4	126.3	C19—C18—C17	122.4 (8)
C21—N5—C15	105.1 (5)	C19—C18—H18	118.8
C21—N5—Cu2	120.4 (4)	C17—C18—H18	118.8
C15—N5—Cu2	133.3 (4)	C18—C19—C20	116.4 (8)
C21—N6—C20	108.0 (5)	C18—C19—H19	121.8
C21—N6—H6	126.0	C20—C19—H19	121.8
C20—N6—H6	126.0	C19—C20—N6	132.2 (7)
C22—O1—Cu1	128.8 (3)	C19—C20—C15	123.0 (7)
C22—O2—Cu2	116.9 (3)	N6—C20—C15	104.9 (6)
C24—O3—Cu1	127.9 (3)	N5—C21—N6	112.9 (6)
S1—O4—Cu1^i	136.4 (2)	N5—C21—H21	123.6
H1B—O1W—H1A	109 (6)	N6—C21—H21	123.6
H2A—O2W—H2B	109 (7)	O1—C22—O2	120.0 (5)
H3A—O3W—H3B	108 (7)	O1—C22—C23	122.2 (4)
H4A—O4W—H4B	109.4 (19)	O2—C22—C23	117.7 (4)
N1—C1—C2	130.5 (5)	C28—C23—C24	119.3 (4)
N1—C1—C6	108.8 (5)	C28—C23—C22	118.3 (4)
C2—C1—C6	120.6 (5)	C24—C23—C22	122.3 (4)
C3—C2—C1	117.2 (6)	O3—C24—C23	124.4 (4)
C3—C2—H2C	121.4	O3—C24—C25	118.0 (4)
C1—C2—H2C	121.4	C23—C24—C25	117.6 (4)
C4—C3—C2	121.5 (6)	C26—C25—C24	122.2 (5)
C4—C3—H3	119.3	C26—C25—H25	118.9
C2—C3—H3	119.3	C24—C25—H25	118.9
C5—C4—C3	121.9 (7)	C25—C26—C27	119.9 (5)
C5—C4—H4C	119.0	C25—C26—H26	120.1
C3—C4—H4C	119.0	C27—C26—H26	120.1
C4—C5—C6	116.8 (6)	C28—C27—C26	119.6 (4)
C4—C5—H5	121.6	C28—C27—S1	121.5 (4)
C6—C5—H5	121.6	C26—C27—S1	118.9 (4)
N2—C6—C5	132.8 (6)	C27—C28—C23	121.4 (5)
N2—C6—C1	105.3 (5)	C27—C28—H28	119.3
C5—C6—C1	121.9 (5)	C23—C28—H28	119.3
O3—Cu1—N1—C7	−94.1 (5)	C14—N4—C13—C8	0.8 (7)
O1—Cu1—N1—C7	−178.4 (6)	C11—C12—C13—N4	−179.1 (7)
N3—Cu1—N1—C7	93.3 (5)	C11—C12—C13—C8	0.5 (10)
O4^i—Cu1—N1—C7	2.7 (5)	C9—C8—C13—N4	178.5 (5)
O3—Cu1—N1—C1	79.2 (4)	N3—C8—C13—N4	−0.6 (6)
O1—Cu1—N1—C1	−5.0 (10)	C9—C8—C13—C12	−1.2 (9)
N3—Cu1—N1—C1	−93.3 (4)	N3—C8—C13—C12	179.7 (6)
O4^i—Cu1—N1—C1	176.0 (4)	C8—N3—C14—N4	0.3 (7)
O1—Cu1—N3—C14	−135.7 (5)	Cu1—N3—C14—N4	179.4 (4)
N1—Cu1—N3—C14	31.1 (5)	C13—N4—C14—N3	−0.7 (7)
O4^i—Cu1—N3—C14	126.6 (5)	C21—N5—C15—C16	177.5 (7)
O1—Cu1—N3—C8	43.1 (5)	Cu2—N5—C15—C16	−15.1 (10)
N1—Cu1—N3—C8	−150.1 (5)	C21—N5—C15—C20	−0.2 (7)
O4^i—Cu1—N3—C8	−54.7 (5)	Cu2—N5—C15—C20	167.2 (4)
O2—Cu2—N5—C21	−28.0 (4)	N5—C15—C16—C17	−177.8 (7)
O2^ii—Cu2—N5—C21	152.0 (4)	C20—C15—C16—C17	−0.3 (11)
O2—Cu2—N5—C15	166.1 (5)	C15—C16—C17—C18	−0.4 (13)
O2^ii—Cu2—N5—C15	−13.9 (5)	C16—C17—C18—C19	0.5 (16)
O3—Cu1—O1—C22	−17.0 (5)	C17—C18—C19—C20	0.2 (15)
N1—Cu1—O1—C22	66.8 (9)	C18—C19—C20—N6	177.7 (8)
N3—Cu1—O1—C22	155.3 (5)	C18—C19—C20—C15	−0.9 (13)
O4^i—Cu1—O1—C22	−114.3 (5)	C21—N6—C20—C19	−178.8 (8)
N5—Cu2—O2—C22	−109.0 (4)	C21—N6—C20—C15	0.0 (7)
N5^ii—Cu2—O2—C22	71.0 (4)	C16—C15—C20—C19	1.0 (11)
O1—Cu1—O3—C24	2.4 (4)	N5—C15—C20—C19	179.0 (7)
N1—Cu1—O3—C24	−164.4 (4)	C16—C15—C20—N6	−177.9 (6)
O4^i—Cu1—O3—C24	100.4 (4)	N5—C15—C20—N6	0.1 (7)
O5—S1—O4—Cu1^i	−70.1 (4)	C15—N5—C21—N6	0.2 (7)
O6—S1—O4—Cu1^i	163.4 (3)	Cu2—N5—C21—N6	−169.2 (4)
C27—S1—O4—Cu1^i	48.5 (4)	C20—N6—C21—N5	−0.1 (8)
C7—N1—C1—C2	−177.4 (6)	Cu1—O1—C22—O2	−160.2 (4)
Cu1—N1—C1—C2	8.0 (8)	Cu1—O1—C22—C23	21.5 (7)
C7—N1—C1—C6	0.3 (6)	Cu2—O2—C22—O1	−2.5 (7)
Cu1—N1—C1—C6	−174.3 (4)	Cu2—O2—C22—C23	175.9 (3)
N1—C1—C2—C3	177.4 (6)	O1—C22—C23—C28	166.8 (5)
C6—C1—C2—C3	−0.1 (9)	O2—C22—C23—C28	−11.5 (7)
C1—C2—C3—C4	1.1 (11)	O1—C22—C23—C24	−8.5 (8)
C2—C3—C4—C5	−0.4 (12)	O2—C22—C23—C24	173.2 (5)
C3—C4—C5—C6	−1.2 (11)	Cu1—O3—C24—C23	6.8 (7)
C7—N2—C6—C5	179.5 (6)	Cu1—O3—C24—C25	−173.6 (3)
C7—N2—C6—C1	0.7 (6)	C28—C23—C24—O3	178.7 (5)
C4—C5—C6—N2	−176.4 (6)	C22—C23—C24—O3	−6.1 (8)
C4—C5—C6—C1	2.2 (9)	C28—C23—C24—C25	−0.9 (7)
N1—C1—C6—N2	−0.6 (6)	C22—C23—C24—C25	174.4 (5)
C2—C1—C6—N2	177.3 (5)	O3—C24—C25—C26	−179.2 (5)
N1—C1—C6—C5	−179.6 (5)	C23—C24—C25—C26	0.4 (7)
C2—C1—C6—C5	−1.6 (9)	C24—C25—C26—C27	0.4 (8)
C1—N1—C7—N2	0.2 (6)	C25—C26—C27—C28	−0.8 (7)
Cu1—N1—C7—N2	174.6 (4)	C25—C26—C27—S1	179.7 (4)
C6—N2—C7—N1	−0.6 (6)	O5—S1—C27—C28	−8.2 (5)
C14—N3—C8—C9	−178.8 (6)	O4—S1—C27—C28	−130.6 (4)
Cu1—N3—C8—C9	2.2 (9)	O6—S1—C27—C28	111.7 (4)
C14—N3—C8—C13	0.2 (6)	O5—S1—C27—C26	171.3 (4)
Cu1—N3—C8—C13	−178.8 (4)	O4—S1—C27—C26	48.9 (5)
N3—C8—C9—C10	179.8 (6)	O6—S1—C27—C26	−68.8 (4)
C13—C8—C9—C10	0.9 (9)	C26—C27—C28—C23	0.3 (7)
C8—C9—C10—C11	0.0 (11)	S1—C27—C28—C23	179.8 (4)
C9—C10—C11—C12	−0.6 (12)	C24—C23—C28—C27	0.5 (7)
C10—C11—C12—C13	0.4 (11)	C22—C23—C28—C27	−174.9 (4)
C14—N4—C13—C12	−179.5 (7)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O6^iii	0.86	2.01	2.836 (6)	161
N4—H4···O2W	0.86	1.96	2.822 (8)	178
N6—H6···O3W	0.86	2.04	2.894 (10)	172
N6—H6···O1W	0.86	2.60	3.099 (8)	118
O1W—H1B···O3^i	0.85 (6)	1.96 (6)	2.798 (6)	170 (7)
O2W—H2A···O5W′^iv	0.86 (7)	1.90 (7)	2.73 (6)	162 (8)
O2W—H2A···O5W^iv	0.86 (7)	2.31 (6)	3.03 (3)	142 (8)
O2W—H2B···O6^v	0.85 (5)	1.94 (5)	2.781 (8)	170 (8)
O3W—H3A···O5W′^vi	0.86 (4)	1.78 (7)	2.50 (6)	140 (7)
O3W—H3A···O5W^vi	0.86 (4)	1.96 (4)	2.81 (3)	169 (9)
O3W—H3B···O2W^ii	0.86 (3)	2.14 (6)	2.874 (16)	144 (8)
O4W—H4A···O5W′^iv	0.85 (1)	1.98 (9)	2.80 (7)	163 (16)
O4W—H4B···O5W^vii	0.85 (1)	2.36 (6)	3.20 (4)	169 (16)

Symmetry codes: (i) −x, −y+1, −z+2; (ii) −x+1, −y+1, −z+2; (iii) x, y, z+1; (iv) −x+1, −y+1, −z+3; (v) x+1, y, z+1; (vi) −x+1, −y+2, −z+2; (vii) x, y−1, z.