Aqua­{2-[(3,5-dichloro-2-oxidobenzyl­idene)amino]-3-(4-hydroxy­phen­yl)propionato-κ³O¹,N,O²}copper(II) sesquihydrate

In the title compound, [Cu(C₁₆H₁₁Cl₂NO₄)(H₂O)]·1.5H₂O, the Cu^II atom is coordinated by two O atoms and one N atom from the 2-[(3,5-dichloro-2-oxidobenzyl­idene)amino]-3-(4-hydroxy­phen­yl)propionate ligand, and by the O atom from a water mol­ecule in a square-planar coordination. There are two formula units in the asymmetric unit. Molecules are further assembled into a three-dimensional network through C—H...Cl contacts, a Cu...Cl weak inter­action [3.161 (2) Å], O—H...O and C—H...O hydrogen bonds. The three water mol­ecules of the asymmetric unit are distributed over five positions with one full and two approximately half occupancies, while a tyrosine side chain in one of the complex mol­ecules is disordered over two positions [occupancies 0.507 (5) and 0.493 (5)].

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.008 Å
Some non-H atoms missing
• Disorder in main residue
• R factor = 0.048
• wR factor = 0.143
• Data-to-parameter ratio = 10.8

checkCIF/PLATON results

No syntax errors found



Alert level A
CHEMS01_ALERT_1_A  The sum formula contains more than one moiety.

Alert level B
CHEMS01_ALERT_1_B  The sum formula contains an invalid character.
            WARNING - The character , is not allowed in the _chemical_formula_su
CHEMS01_ALERT_1_B  The sum formula contains an invalid character.
            WARNING - The character ( is not allowed in the _chemical_formula_su
CHEMS01_ALERT_1_B  The sum formula contains an invalid character.
            WARNING - The character ) is not allowed in the _chemical_formula_su
PLAT420_ALERT_2_B D-H Without Acceptor      >O13    -  >H41    ...          ?

Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)        200 Ang.
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        Cl4
PLAT301_ALERT_3_C Main Residue  Disorder .........................      15.00 Perc.
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      40.00 Perc.
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          8
PLAT417_ALERT_2_C Short Inter D-H..H-D       H36    ..  H37     ..       2.13 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact  C19    ..  C21     ..       3.12 Ang.

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C16 H16 Cl2 Cu1 N1 O6.5
            Atom count from _chemical_formula_moiety:C32 H32 Cl4 Cu2 N2 O13
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G ALERT: Large difference may be due to a
            symmetry error - see SYMMG tests
           From the CIF: _cell_formula_units_Z    4
           From the CIF: _chemical_formula_sum  C16 H13 Cl2 Cu1 N1 O5, 1.5(H2 O1
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C         64.00     64.00    0.00
           H         52.00     64.00  -12.00
           Cl         8.00      8.00    0.00
           Cu         4.00      4.00    0.00
           N          4.00      4.00    0.00
           O         20.00     26.00   -6.00
           ,          6.00      0.00    6.00
           (H         4.00      0.00    4.00
           )          4.00      0.00    4.00
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT793_ALERT_2_G Check the Absolute Configuration of C2     .....          S
PLAT793_ALERT_2_G Check the Absolute Configuration of C18    .....          S
PLAT793_ALERT_2_G Check the Absolute Configuration of C18'   .....          S

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

  13 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   7 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
   0 ALERT type 5 Informative message, check

---

S1. Comment

Schiff base complexes containing amino acids have been studied for many years(Casella & Gullotti, 1986; Wang et al., 1994; Zhang et al., 2003). Schiff bases have played an important role in the development of coordination chemistry as they form stable complexes with most of the transition metals.

In the asymmetric unit there are two Cu^II ions, two L ligand anions, two ligating water molecules and three water hydrate molecules (Fig. 1). The Cu^II cations are coordinated by two O atoms and one N atom from ligand L, then the O atom from an H₂O coordinate to Cu^II. These four atoms form a square-planar coordination centered at the cuprate(II) ions (Fig. 1). The coordination in these two complexes in the asymmetric unit does not seem to be alike. There is a Cu···Cl distance of 3.161 (2) Å indicating a possible weak interaction between the two complexes in the asymmetric unit. Fig. 2 shows that the tyrosine in one of the complexes has two different orientations in this crystal giving a disordered structure. Weak contacts of C–H···Cl and Cu···Cl types and O–H···O hydrogen bonds construct a 3-D network running along the a axis (Fig.3).

Related literature

For related literature, see: Casella & Gullotti (1986); Guthrie et al. (1980); Wang et al. (1994); Zhang et al. (2003).

S2. Experimental

An ethanol solution (5 ml) containing 3,5-dichloro-2-hydroxy-benzaldehyde (0.096 g, 0.5 mmol) was added to an aqueous solution containing 2-amino-3-(4-hydroxy-phenyl)-propionic acid (0.222 g, 2 mmol) and sodium hydroxide (0.091 g, 0.5 mmol). After stirring for 1 h, an aqueous solution of copper chloride (0.1 g, 0.5 mmol) was added to the resulting solution and stirred for 2 h. The green solution was filtered. After 10 days, green block crystals were obtained by slow evaporation of the filtrate (yield: 45.2%, based on Cu).

S3. Refinement

Water H atoms were located in a difference Fourier map and were allowed to ride on the O atom, with U_iso(H) = 1.5U_eq(O). All other H atoms were positioned geometrically and refined as riding, with C–H = 0.93 Å and with U_iso(H) = 1.2 U_eq(C).

Computing details

Data collection: SMART (Bruker, 2004); cell refinement: SMART (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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. A view of the title complex showing 30% probability displacement ellipsoids. H atoms, except for the water molecules, are not shown.
	Fig. 2. The disordered tyrosine view in one of the complexes.
	Fig. 3. The three-dimensional network of Cu···Cl weak interactions and hydrogen bonds shown in dotted lines.

Aqua{2-[(3,5-dichloro-2-oxidobenzylidene)amino]-3-(4-hydroxyphenyl)propionato- κ³O¹,N,O²}copper(II) sesquihydrate

Crystal data

[Cu(C16H11Cl2NO4)(H2O)]·1.5H2O	Z = 4
Mr = 460.74	F(000) = 936
Triclinic, P1	Dx = 1.678 Mg m^−3
a = 10.006 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.899 (2) Å	Cell parameters from 2332 reflections
c = 14.565 (2) Å	θ = 2.3–25.2°
α = 70.469 (2)°	µ = 1.53 mm^−1
β = 87.427 (3)°	T = 293 K
γ = 73.121 (3)°	Plate, green
V = 1823.8 (5) Å^3	0.40 × 0.18 × 0.09 mm

Data collection

Bruker SMART 1000 diffractometer	6315 independent reflections
Radiation source: fine-focus sealed tube	3605 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
ϕ and ω scans	θmax = 25.0°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.580, Tmax = 0.875	k = −12→16
9183 measured reflections	l = −16→17

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.143	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0669P)^2] where P = (Fo^2 + 2Fc^2)/3
6315 reflections	(Δ/σ)max = 0.001
583 parameters	Δρmax = 0.58 e Å^−3
0 restraints	Δρmin = −0.36 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.46267 (7)	0.15476 (5)	0.36588 (4)	0.0406 (2)
Cu2	−0.01499 (6)	0.64742 (5)	−0.11028 (4)	0.0407 (2)
Cl1	0.87069 (17)	−0.11542 (12)	0.34408 (11)	0.0668 (5)
Cl2	1.07017 (15)	−0.16022 (11)	0.69630 (11)	0.0578 (4)
Cl3	0.39713 (16)	0.37698 (11)	−0.12877 (10)	0.0580 (4)
Cl4	0.58637 (15)	0.33274 (11)	0.22575 (11)	0.0597 (4)
N1	0.5002 (4)	0.1767 (3)	0.4841 (3)	0.0349 (10)
N2	0.0214 (5)	0.6696 (4)	0.0075 (3)	0.0556 (13)
O1	0.2819 (4)	0.2595 (3)	0.3616 (2)	0.0447 (9)
O2	0.1508 (4)	0.3508 (3)	0.4497 (3)	0.0621 (12)
O3	0.8857 (4)	0.3483 (4)	0.7126 (3)	0.0699 (12)
H3	0.9506	0.3622	0.6795	0.105*
O4	0.6311 (4)	0.0441 (3)	0.3785 (2)	0.0454 (9)
O5	0.4122 (4)	0.1358 (3)	0.2489 (2)	0.0552 (10)
H33	0.3333	0.1676	0.2174	0.083*
H34	0.4672	0.1072	0.2129	0.083*
O6	−0.1909 (4)	0.7570 (3)	−0.1170 (3)	0.0508 (10)
O7	−0.3148 (4)	0.8569 (3)	−0.0328 (4)	0.0801 (15)
O8	0.4986 (7)	0.8913 (6)	0.0835 (5)	0.051 (2)	0.507 (5)
H8	0.5564	0.8836	0.0429	0.077*	0.507 (5)
O8'	0.4246 (7)	0.9296 (6)	−0.1086 (6)	0.049 (2)	0.493 (5)
H8'	0.4912	0.9095	−0.0691	0.074*	0.493 (5)
O9	0.1554 (3)	0.5378 (3)	−0.0977 (2)	0.0459 (9)
O10	−0.0682 (4)	0.6254 (3)	−0.2247 (2)	0.0547 (10)
H35	−0.1283	0.6714	−0.2690	0.082*
H36	−0.0357	0.5731	−0.2452	0.082*
O11	0.8440 (5)	0.4610 (4)	0.3037 (3)	0.1056 (18)
H37	0.8272	0.5183	0.2548	0.158*
H38	0.8233	0.4217	0.2763	0.158*
O12	0.8592 (8)	0.6491 (7)	0.3412 (6)	0.066 (3)	0.522 (10)
H39	0.8529	0.6666	0.3922	0.098*	0.522 (10)
H40	0.8643	0.5832	0.3637	0.098*	0.522 (10)
O13	0.4751 (9)	0.0597 (6)	0.7508 (5)	0.077 (3)	0.523 (6)
H41	0.4422	0.0976	0.7865	0.116*	0.523 (6)
H42	0.4076	0.0581	0.7184	0.116*	0.523 (6)
O12'	0.9281 (9)	0.5554 (7)	0.4185 (7)	0.066 (4)	0.478 (10)
H39'	0.8473	0.5526	0.4064	0.098*	0.478 (10)
H40'	0.9155	0.5923	0.4561	0.098*	0.478 (10)
O13'	0.3267 (10)	0.1743 (7)	0.8023 (6)	0.077 (3)	0.477 (6)
H41'	0.3386	0.1669	0.8620	0.116*	0.477 (6)
H42'	0.2932	0.1248	0.8019	0.116*	0.477 (6)
C1	0.2626 (6)	0.2932 (4)	0.4349 (4)	0.0468 (14)
C2	0.3934 (5)	0.2649 (4)	0.5020 (4)	0.0404 (13)
H2	0.3698	0.2435	0.5705	0.048*
C3	0.4401 (5)	0.3661 (4)	0.4761 (4)	0.0456 (14)
H3A	0.4656	0.3846	0.4087	0.055*
H3B	0.3613	0.4241	0.4809	0.055*
C4	0.5605 (5)	0.3567 (4)	0.5389 (4)	0.0380 (13)
C5	0.5444 (6)	0.3550 (4)	0.6350 (4)	0.0486 (15)
H5A	0.4579	0.3564	0.6614	0.058*
C6	0.6528 (6)	0.3515 (4)	0.6913 (4)	0.0474 (14)
H6	0.6388	0.3506	0.7551	0.057*
C7	0.7826 (6)	0.3492 (4)	0.6543 (4)	0.0446 (14)
C8	0.8034 (6)	0.3492 (4)	0.5601 (4)	0.0450 (14)
H8A	0.8907	0.3471	0.5344	0.054*
C9	0.6932 (6)	0.3523 (4)	0.5041 (4)	0.0429 (14)
H9	0.7083	0.3513	0.4409	0.051*
C10	0.6014 (5)	0.1182 (4)	0.5469 (4)	0.0380 (13)
H10A	0.6016	0.1323	0.6050	0.046*
C11	0.7153 (5)	0.0322 (4)	0.5356 (4)	0.0383 (12)
C12	0.7253 (5)	0.0025 (4)	0.4506 (4)	0.0395 (13)
C13	0.8490 (6)	−0.0788 (4)	0.4477 (4)	0.0452 (14)
C14	0.9516 (5)	−0.1270 (4)	0.5211 (4)	0.0433 (14)
H14	1.0306	−0.1798	0.5158	0.052*
C15	0.9376 (5)	−0.0971 (4)	0.6025 (4)	0.0438 (14)
C16	0.8219 (5)	−0.0183 (4)	0.6104 (4)	0.0411 (13)
H16	0.8141	0.0017	0.6658	0.049*
C17	−0.2082 (5)	0.7943 (4)	−0.0462 (4)	0.0420 (13)
C18	−0.073 (2)	0.7774 (14)	0.0135 (14)	0.038 (4)	0.507 (5)
H18	−0.0932	0.7705	0.0814	0.045*	0.507 (5)
C19	−0.0263 (11)	0.8773 (8)	−0.0352 (8)	0.045 (3)	0.507 (5)
H19A	−0.0256	0.8894	−0.1047	0.053*	0.507 (5)
H19B	−0.0973	0.9373	−0.0259	0.053*	0.507 (5)
C20	0.1122 (19)	0.8796 (15)	−0.0029 (15)	0.042 (4)	0.507 (5)
C21	0.140 (2)	0.8750 (15)	0.0908 (16)	0.044 (4)	0.507 (5)
H21	0.0745	0.8647	0.1374	0.053*	0.507 (5)
C22	0.2662 (11)	0.8858 (8)	0.1162 (8)	0.046 (3)	0.507 (5)
H22	0.2784	0.8920	0.1767	0.055*	0.507 (5)
C23	0.3739 (14)	0.8875 (10)	0.0528 (10)	0.042 (3)	0.507 (5)
C24	0.347 (6)	0.887 (5)	−0.039 (5)	0.044 (9)	0.507 (5)
H24	0.4177	0.8887	−0.0834	0.053*	0.507 (5)
C25	0.218 (2)	0.8852 (13)	−0.0675 (12)	0.044 (4)	0.507 (5)
H25	0.2023	0.8875	−0.1307	0.053*	0.507 (5)
C18'	−0.101 (2)	0.7389 (15)	0.0366 (14)	0.036 (4)	0.493 (5)
H18'	−0.1411	0.6948	0.0915	0.043*	0.493 (5)
C19'	−0.0505 (10)	0.8163 (8)	0.0707 (8)	0.038 (3)	0.493 (5)
H19C	−0.1274	0.8811	0.0598	0.046*	0.493 (5)
H19D	−0.0285	0.7845	0.1405	0.046*	0.493 (5)
C20'	0.0742 (19)	0.8468 (15)	0.0232 (13)	0.032 (4)	0.493 (5)
C21'	0.0869 (12)	0.8771 (8)	−0.0768 (9)	0.040 (3)	0.493 (5)
H21'	0.0139	0.8811	−0.1167	0.048*	0.493 (5)
C22'	0.2054 (19)	0.9017 (13)	−0.1196 (11)	0.042 (4)	0.493 (5)
H22'	0.2126	0.9191	−0.1867	0.050*	0.493 (5)
C23'	0.313 (5)	0.900 (5)	−0.062 (5)	0.040 (8)	0.493 (5)
C24'	0.3069 (15)	0.8696 (10)	0.0395 (12)	0.042 (3)	0.493 (5)
H24'	0.3785	0.8676	0.0792	0.051*	0.493 (5)
C25'	0.188 (2)	0.8424 (17)	0.0773 (17)	0.046 (5)	0.493 (5)
H25'	0.1842	0.8192	0.1448	0.055*	0.493 (5)
C26	0.1228 (6)	0.6130 (5)	0.0709 (4)	0.0566 (16)
H26	0.1228	0.6290	0.1280	0.068*
C27	0.2371 (5)	0.5265 (4)	0.0609 (4)	0.0420 (13)
C28	0.2481 (5)	0.4970 (4)	−0.0244 (4)	0.0371 (12)
C29	0.3733 (5)	0.4155 (4)	−0.0259 (4)	0.0386 (13)
C30	0.4740 (5)	0.3672 (4)	0.0480 (4)	0.0422 (13)
H30	0.5542	0.3153	0.0431	0.051*
C31	0.4552 (6)	0.3966 (4)	0.1310 (4)	0.0452 (14)
C32	0.3407 (5)	0.4747 (4)	0.1372 (4)	0.0456 (14)
H32	0.3307	0.4943	0.1928	0.055*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0356 (4)	0.0389 (4)	0.0449 (4)	−0.0035 (3)	−0.0044 (3)	−0.0167 (3)
Cu2	0.0304 (4)	0.0523 (4)	0.0438 (4)	−0.0084 (3)	0.0012 (3)	−0.0247 (3)
Cl1	0.0668 (11)	0.0601 (10)	0.0635 (10)	0.0104 (8)	−0.0035 (8)	−0.0319 (8)
Cl2	0.0417 (9)	0.0507 (9)	0.0644 (10)	−0.0008 (7)	−0.0143 (7)	−0.0070 (7)
Cl3	0.0579 (10)	0.0565 (9)	0.0624 (9)	−0.0029 (8)	0.0133 (8)	−0.0366 (8)
Cl4	0.0463 (9)	0.0514 (9)	0.0650 (10)	−0.0010 (7)	−0.0144 (7)	−0.0080 (7)
N1	0.032 (2)	0.029 (2)	0.042 (2)	−0.003 (2)	0.000 (2)	−0.014 (2)
N2	0.034 (3)	0.070 (3)	0.063 (3)	0.014 (2)	−0.008 (2)	−0.045 (3)
O1	0.034 (2)	0.049 (2)	0.051 (2)	−0.0024 (17)	−0.0083 (17)	−0.0244 (19)
O2	0.031 (2)	0.069 (3)	0.090 (3)	0.005 (2)	−0.010 (2)	−0.046 (2)
O3	0.053 (3)	0.105 (4)	0.062 (3)	−0.022 (3)	−0.009 (2)	−0.039 (3)
O4	0.044 (2)	0.041 (2)	0.049 (2)	0.0006 (17)	−0.0049 (19)	−0.0213 (18)
O5	0.045 (2)	0.066 (3)	0.053 (2)	0.002 (2)	−0.0085 (18)	−0.031 (2)
O6	0.043 (2)	0.052 (2)	0.060 (2)	−0.0029 (19)	−0.0139 (19)	−0.030 (2)
O7	0.033 (2)	0.079 (3)	0.144 (4)	0.008 (2)	−0.013 (3)	−0.075 (3)
O8	0.032 (4)	0.060 (5)	0.066 (5)	−0.006 (4)	−0.005 (4)	−0.033 (4)
O8'	0.026 (4)	0.054 (5)	0.067 (6)	−0.013 (4)	0.007 (4)	−0.021 (4)
O9	0.030 (2)	0.062 (2)	0.054 (2)	−0.0033 (18)	−0.0003 (18)	−0.039 (2)
O10	0.054 (3)	0.062 (3)	0.053 (2)	−0.007 (2)	−0.0147 (19)	−0.032 (2)
O11	0.103 (4)	0.138 (5)	0.078 (3)	−0.016 (4)	0.013 (3)	−0.057 (3)
O12	0.060 (6)	0.073 (7)	0.078 (7)	−0.020 (5)	0.012 (5)	−0.042 (6)
O13	0.090 (7)	0.076 (6)	0.069 (6)	−0.022 (5)	−0.004 (5)	−0.030 (5)
O12'	0.060 (6)	0.073 (8)	0.078 (7)	−0.020 (5)	0.012 (5)	−0.042 (6)
O13'	0.090 (8)	0.076 (7)	0.069 (6)	−0.022 (6)	−0.004 (5)	−0.030 (5)
C1	0.041 (4)	0.040 (3)	0.060 (4)	−0.009 (3)	−0.005 (3)	−0.020 (3)
C2	0.030 (3)	0.043 (3)	0.045 (3)	−0.002 (3)	−0.007 (2)	−0.017 (3)
C3	0.043 (3)	0.037 (3)	0.052 (3)	−0.001 (3)	−0.008 (3)	−0.017 (3)
C4	0.038 (3)	0.030 (3)	0.043 (3)	−0.002 (2)	−0.005 (3)	−0.016 (2)
C5	0.037 (3)	0.061 (4)	0.052 (3)	−0.014 (3)	0.010 (3)	−0.024 (3)
C6	0.047 (4)	0.064 (4)	0.034 (3)	−0.014 (3)	0.001 (3)	−0.021 (3)
C7	0.040 (3)	0.047 (3)	0.047 (3)	−0.005 (3)	−0.008 (3)	−0.020 (3)
C8	0.032 (3)	0.050 (3)	0.057 (4)	−0.006 (3)	0.004 (3)	−0.027 (3)
C9	0.048 (4)	0.044 (3)	0.040 (3)	−0.009 (3)	0.006 (3)	−0.023 (3)
C10	0.045 (3)	0.032 (3)	0.036 (3)	−0.008 (3)	−0.003 (3)	−0.012 (2)
C11	0.035 (3)	0.032 (3)	0.044 (3)	−0.006 (2)	−0.002 (2)	−0.011 (2)
C12	0.040 (3)	0.030 (3)	0.045 (3)	−0.008 (3)	0.000 (3)	−0.009 (2)
C13	0.049 (4)	0.035 (3)	0.050 (3)	−0.005 (3)	0.006 (3)	−0.017 (3)
C14	0.036 (3)	0.028 (3)	0.054 (3)	0.001 (2)	−0.002 (3)	−0.007 (3)
C15	0.028 (3)	0.036 (3)	0.055 (3)	−0.004 (3)	−0.006 (3)	−0.002 (3)
C16	0.042 (3)	0.036 (3)	0.046 (3)	−0.012 (3)	0.001 (3)	−0.013 (3)
C17	0.027 (3)	0.035 (3)	0.061 (4)	−0.007 (3)	0.000 (3)	−0.014 (3)
C18	0.027 (9)	0.041 (12)	0.047 (10)	−0.005 (7)	−0.002 (7)	−0.020 (8)
C19	0.032 (7)	0.043 (7)	0.061 (7)	−0.008 (5)	−0.008 (6)	−0.021 (6)
C20	0.031 (12)	0.039 (11)	0.054 (12)	−0.002 (7)	−0.002 (9)	−0.018 (8)
C21	0.032 (11)	0.048 (12)	0.053 (9)	−0.013 (9)	0.005 (7)	−0.017 (8)
C22	0.041 (7)	0.046 (7)	0.053 (7)	−0.011 (5)	0.003 (6)	−0.023 (6)
C23	0.034 (8)	0.040 (7)	0.054 (8)	−0.006 (6)	−0.002 (7)	−0.021 (6)
C24	0.04 (3)	0.040 (16)	0.06 (2)	−0.007 (17)	0.006 (15)	−0.022 (15)
C25	0.036 (9)	0.045 (9)	0.052 (10)	−0.004 (7)	−0.009 (11)	−0.023 (9)
C18'	0.024 (9)	0.038 (12)	0.047 (10)	−0.003 (7)	0.012 (6)	−0.022 (8)
C19'	0.032 (6)	0.040 (7)	0.045 (6)	−0.009 (5)	0.000 (5)	−0.019 (5)
C20'	0.024 (9)	0.036 (11)	0.042 (10)	−0.007 (6)	0.004 (7)	−0.021 (8)
C21'	0.030 (7)	0.042 (7)	0.048 (7)	−0.008 (5)	−0.003 (6)	−0.016 (6)
C22'	0.034 (8)	0.046 (9)	0.049 (9)	−0.009 (6)	−0.004 (9)	−0.021 (9)
C23'	0.03 (2)	0.039 (14)	0.05 (2)	−0.004 (15)	0.003 (14)	−0.022 (15)
C24'	0.034 (9)	0.042 (8)	0.049 (9)	−0.002 (7)	−0.004 (8)	−0.021 (6)
C25'	0.038 (13)	0.049 (12)	0.049 (9)	−0.005 (9)	0.000 (9)	−0.022 (8)
C26	0.040 (4)	0.076 (4)	0.060 (4)	0.005 (3)	−0.003 (3)	−0.048 (3)
C27	0.036 (3)	0.043 (3)	0.047 (3)	−0.001 (3)	0.006 (3)	−0.024 (3)
C28	0.028 (3)	0.043 (3)	0.046 (3)	−0.012 (3)	0.006 (3)	−0.022 (3)
C29	0.036 (3)	0.033 (3)	0.054 (3)	−0.011 (3)	0.015 (3)	−0.025 (3)
C30	0.036 (3)	0.026 (3)	0.060 (4)	−0.003 (2)	0.006 (3)	−0.014 (3)
C31	0.039 (3)	0.039 (3)	0.050 (3)	−0.008 (3)	−0.009 (3)	−0.008 (3)
C32	0.045 (4)	0.045 (3)	0.044 (3)	−0.003 (3)	−0.001 (3)	−0.020 (3)

Geometric parameters (Å, º)

Cu1—O4	1.890 (3)	C8—C9	1.383 (7)
Cu1—N1	1.917 (4)	C8—H8A	0.9300
Cu1—O5	1.919 (3)	C9—H9	0.9300
Cu1—O1	1.953 (3)	C10—C11	1.441 (7)
Cu2—O9	1.896 (3)	C10—H10A	0.9300
Cu2—N2	1.909 (4)	C11—C16	1.406 (7)
Cu2—O10	1.915 (3)	C11—C12	1.422 (7)
Cu2—O6	1.946 (4)	C12—C13	1.423 (7)
Cl1—C13	1.733 (5)	C13—C14	1.366 (7)
Cl2—C15	1.756 (5)	C14—C15	1.371 (7)
Cl3—C29	1.738 (5)	C14—H14	0.9300
Cl4—C31	1.755 (5)	C15—C16	1.374 (7)
N1—C10	1.278 (6)	C16—H16	0.9300
N1—C2	1.463 (6)	C17—C18'	1.49 (2)
N2—C26	1.279 (6)	C17—C18	1.56 (2)
N2—C18'	1.47 (2)	C18—C19	1.527 (17)
N2—C18	1.55 (2)	C18—H18	0.9800
O1—C1	1.290 (6)	C19—C20	1.50 (2)
O2—C1	1.229 (6)	C19—H19A	0.9700
O3—C7	1.361 (6)	C19—H19B	0.9700
O3—H3	0.8200	C20—C21	1.38 (3)
O4—C12	1.301 (6)	C20—C25	1.39 (3)
O5—H33	0.8499	C21—C22	1.39 (3)
O5—H34	0.8498	C21—H21	0.9300
O6—C17	1.285 (6)	C22—C23	1.388 (18)
O7—C17	1.220 (6)	C22—H22	0.9300
O8—C23	1.366 (14)	C23—C24	1.38 (6)
O8—H8	0.8200	C24—C25	1.39 (5)
O8'—C23'	1.38 (7)	C24—H24	0.9300
O8'—H8'	0.8200	C25—H25	0.9300
O9—C28	1.303 (6)	C18'—C19'	1.54 (2)
O10—H35	0.8500	C18'—H18'	0.9800
O10—H36	0.8500	C19'—C20'	1.499 (18)
O11—H37	0.8504	C19'—H19C	0.9700
O11—H38	0.8502	C19'—H19D	0.9700
O12—H39	0.8501	C20'—C21'	1.39 (2)
O12—H40	0.8501	C20'—C25'	1.39 (3)
O13—H41	0.8500	C21'—C22'	1.39 (2)
O13—H42	0.8500	C21'—H21'	0.9300
O12'—H39'	0.8500	C22'—C23'	1.39 (4)
O12'—H40'	0.8500	C22'—H22'	0.9300
O13'—H41'	0.8500	C23'—C24'	1.39 (7)
O13'—H42'	0.8500	C24'—C25'	1.39 (3)
C1—C2	1.543 (7)	C24'—H24'	0.9300
C2—C3	1.532 (7)	C25'—H25'	0.9300
C2—H2	0.9800	C26—C27	1.442 (7)
C3—C4	1.494 (7)	C26—H26	0.9300
C3—H3A	0.9700	C27—C32	1.401 (7)
C3—H3B	0.9700	C27—C28	1.423 (7)
C4—C9	1.392 (7)	C28—C29	1.429 (7)
C4—C5	1.395 (7)	C29—C30	1.358 (7)
C5—C6	1.368 (7)	C30—C31	1.389 (7)
C5—H5A	0.9300	C30—H30	0.9300
C6—C7	1.379 (7)	C31—C32	1.354 (7)
C6—H6	0.9300	C32—H32	0.9300
C7—C8	1.379 (7)
O4—Cu1—N1	94.31 (16)	C15—C16—H16	119.7
O4—Cu1—O5	88.98 (15)	C11—C16—H16	119.7
N1—Cu1—O5	176.21 (16)	O7—C17—O6	125.8 (5)
O4—Cu1—O1	174.80 (15)	O7—C17—C18'	116.7 (9)
N1—Cu1—O1	84.68 (15)	O6—C17—C18'	116.2 (9)
O5—Cu1—O1	91.87 (15)	O7—C17—C18	116.8 (9)
O9—Cu2—N2	94.16 (16)	O6—C17—C18	116.0 (9)
O9—Cu2—O10	89.46 (15)	C19—C18—N2	118.3 (12)
N2—Cu2—O10	174.82 (18)	C19—C18—C17	105.5 (12)
O9—Cu2—O6	177.43 (15)	N2—C18—C17	102.0 (11)
N2—Cu2—O6	83.96 (16)	C19—C18—H18	110.2
O10—Cu2—O6	92.31 (15)	N2—C18—H18	110.2
C10—N1—C2	120.7 (4)	C17—C18—H18	110.2
C10—N1—Cu1	125.7 (3)	C20—C19—C18	118.6 (13)
C2—N1—Cu1	113.5 (3)	C20—C19—H19A	107.7
C26—N2—C18'	118.4 (9)	C18—C19—H19A	107.7
C26—N2—C18	120.1 (8)	C20—C19—H19B	107.7
C26—N2—Cu2	126.6 (4)	C18—C19—H19B	107.7
C18'—N2—Cu2	112.6 (8)	H19A—C19—H19B	107.1
C18—N2—Cu2	112.7 (8)	C21—C20—C25	117.7 (17)
C1—O1—Cu1	114.9 (3)	C21—C20—C19	122.2 (17)
C7—O3—H3	109.5	C25—C20—C19	120.0 (17)
C12—O4—Cu1	127.0 (3)	C20—C21—C22	120.7 (17)
Cu1—O5—H33	124.3	C20—C21—H21	119.6
Cu1—O5—H34	126.9	C22—C21—H21	119.6
H33—O5—H34	107.4	C23—C22—C21	121.1 (14)
C17—O6—Cu2	115.6 (3)	C23—C22—H22	119.5
C23'—O8'—H8'	109.5	C21—C22—H22	119.5
C28—O9—Cu2	126.2 (3)	O8—C23—C24	123 (3)
Cu2—O10—H35	124.6	O8—C23—C22	118.9 (12)
Cu2—O10—H36	130.1	C24—C23—C22	118 (3)
H35—O10—H36	105.1	C23—C24—C25	121 (6)
H39—O12—H40	103.0	C23—C24—H24	119.4
H41—O13—H42	108.7	C25—C24—H24	119.4
H39'—O12'—H40'	105.2	C24—C25—C20	121 (4)
H41'—O13'—H42'	106.2	C24—C25—H25	119.4
O2—C1—O1	124.1 (5)	C20—C25—H25	119.4
O2—C1—C2	119.7 (5)	N2—C18'—C17	109.7 (13)
O1—C1—C2	116.0 (5)	N2—C18'—C19'	107.5 (12)
N1—C2—C3	112.2 (4)	C17—C18'—C19'	113.0 (13)
N1—C2—C1	108.1 (4)	N2—C18'—H18'	108.8
C3—C2—C1	106.6 (4)	C17—C18'—H18'	108.8
N1—C2—H2	109.9	C19'—C18'—H18'	108.8
C3—C2—H2	109.9	C20'—C19'—C18'	116.6 (12)
C1—C2—H2	109.9	C20'—C19'—H19C	108.1
C4—C3—C2	114.6 (4)	C18'—C19'—H19C	108.1
C4—C3—H3A	108.6	C20'—C19'—H19D	108.1
C2—C3—H3A	108.6	C18'—C19'—H19D	108.1
C4—C3—H3B	108.6	H19C—C19'—H19D	107.3
C2—C3—H3B	108.6	C21'—C20'—C25'	115.3 (15)
H3A—C3—H3B	107.6	C21'—C20'—C19'	122.7 (14)
C9—C4—C5	116.4 (5)	C25'—C20'—C19'	122.0 (16)
C9—C4—C3	122.0 (5)	C20'—C21'—C22'	122.1 (14)
C5—C4—C3	121.5 (5)	C20'—C21'—H21'	119.0
C6—C5—C4	121.7 (5)	C22'—C21'—H21'	119.0
C6—C5—H5A	119.2	C23'—C22'—C21'	120 (3)
C4—C5—H5A	119.2	C23'—C22'—H22'	120.2
C5—C6—C7	120.6 (5)	C21'—C22'—H22'	120.2
C5—C6—H6	119.7	O8'—C23'—C22'	117 (5)
C7—C6—H6	119.7	O8'—C23'—C24'	122 (3)
O3—C7—C8	122.3 (5)	C22'—C23'—C24'	121 (5)
O3—C7—C6	118.2 (5)	C25'—C24'—C23'	116 (3)
C8—C7—C6	119.6 (5)	C25'—C24'—H24'	122.0
C7—C8—C9	119.2 (5)	C23'—C24'—H24'	122.0
C7—C8—H8A	120.4	C24'—C25'—C20'	125.8 (19)
C9—C8—H8A	120.4	C24'—C25'—H25'	117.1
C8—C9—C4	122.4 (5)	C20'—C25'—H25'	117.1
C8—C9—H9	118.8	N2—C26—C27	125.2 (5)
C4—C9—H9	118.8	N2—C26—H26	117.4
N1—C10—C11	125.7 (5)	C27—C26—H26	117.4
N1—C10—H10A	117.2	C32—C27—C28	120.9 (5)
C11—C10—H10A	117.2	C32—C27—C26	117.3 (5)
C16—C11—C12	120.5 (5)	C28—C27—C26	121.7 (5)
C16—C11—C10	117.2 (5)	O9—C28—C27	125.5 (5)
C12—C11—C10	122.3 (5)	O9—C28—C29	119.9 (4)
O4—C12—C11	124.6 (5)	C27—C28—C29	114.5 (5)
O4—C12—C13	120.0 (5)	C30—C29—C28	123.9 (5)
C11—C12—C13	115.4 (5)	C30—C29—Cl3	118.6 (4)
C14—C13—C12	123.4 (5)	C28—C29—Cl3	117.6 (4)
C14—C13—Cl1	119.0 (4)	C29—C30—C31	119.0 (5)
C12—C13—Cl1	117.7 (4)	C29—C30—H30	120.5
C13—C14—C15	119.7 (5)	C31—C30—H30	120.5
C13—C14—H14	120.2	C32—C31—C30	120.7 (5)
C15—C14—H14	120.2	C32—C31—Cl4	121.0 (4)
C14—C15—C16	120.6 (5)	C30—C31—Cl4	118.2 (4)
C14—C15—Cl2	119.1 (4)	C31—C32—C27	120.9 (5)
C16—C15—Cl2	120.3 (4)	C31—C32—H32	119.6
C15—C16—C11	120.5 (5)	C27—C32—H32	119.6

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O12^i	0.82	1.88	2.643 (10)	154
O8—H8···O7^ii	0.82	1.70	2.515 (9)	175
O5—H33···O6^iii	0.85	1.89	2.714 (6)	164
O13—H42···Cl1^iv	0.85	2.77	3.555 (9)	154
C26—H26···O3^v	0.93	2.44	3.365 (7)	173

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