Synthesis, characterization, and crystal structure of aqua­bis­(4,4′-dimeth­oxy-2,2′-bi­pyridine)[μ-(2R,3R)-tartrato(4−)]dicopper(II) octa­hydrate

The title compound crystallized from the mock-up of a typical electroless copper bath (ECB) as used to deposit copper on printed circuit boards, consisting of a copper(II) salt, soda lye, L-(+)-tartrate as a complexing agent, and 2,2′-bypyridine derivative as a stabilizer. Its layer-like crystal structure is dominated by extensive π stacking and classical hydrogen bonding.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.028
• wR factor = 0.072
• Data-to-parameter ratio = 16.7

checkCIF/PLATON results

No syntax errors found



Alert level C
HYDTR01_ALERT_1_C  The hydrogen treatment should only be one of the following
            keywords
            *  refall
            *  refxyz
            *  refU
            *  noref
            *  undef
            *  constr
            *  none
            *  mixed
            Hydrogen treatment given as heteroxyz
PLAT910_ALERT_3_C Missing # of FCF Reflection(s) Below Theta(Min).         10 Note
PLAT915_ALERT_3_C No Flack x Check Done: Low Friedel Pair Coverage         74 %
PLAT976_ALERT_2_C Check Calcd Resid. Dens.  0.58A   From O68            -0.43 eA-3

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite         24 Note
PLAT063_ALERT_4_G Crystal Size Likely too Large for Beam Size ....       0.83 mm
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          3 Report
PLAT173_ALERT_4_G The CIF-Embedded .res File Contains DANG Records          2 Report
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cu1      --O60      .        9.3 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cu2      --O55      .        8.9 s.u.
PLAT791_ALERT_4_G Model has Chirality at C56         (Chiral SPGR)          S Verify
PLAT794_ALERT_5_G Tentative Bond Valency for Cu1       (II)      .       2.24 Info
PLAT794_ALERT_5_G Tentative Bond Valency for Cu2       (II)      .       2.31 Info
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............         25 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          1 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          5 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   4 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  12 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

---

Computing details

Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

Aqua-1κO-bis(4,4'-dimethoxy-2,2'-bipyridine)-1κ²N,N';2κ²N,N'-[µ-(2R,3R)-2,3-dioxidosuccinato-1κ²O¹,O²:2κ²O³,O⁴]dicopper(II) octahydrate

Crystal data

[Cu2(C12H12N2O2)2(C4H2O6)(H2O)]·8H2O	F(000) = 900
Mr = 867.75	Dx = 1.631 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 8.5134 (4) Å	Cell parameters from 8483 reflections
b = 23.7812 (9) Å	θ = 3.7–32.5°
c = 8.9028 (4) Å	µ = 1.29 mm^−1
β = 101.401 (4)°	T = 150 K
V = 1766.87 (13) Å^3	Plate, dark blue
Z = 2	0.84 × 0.70 × 0.09 mm

Data collection

Agilent Xcalibur diffractometer	8971 independent reflections
Radiation source: fine-focus sealed tube, Agilent Enhance	8476 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
Detector resolution: 16.3031 pixels mm^-1	θmax = 30.0°, θmin = 3.5°
ω scans	h = −11→11
Absorption correction: analytical (CrysAlis PRO; Rigaku OD, 2015)	k = −33→31
Tmin = 0.440, Tmax = 0.886	l = −11→12
19893 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.028	Heteroxyz
wR(F^2) = 0.072	w = 1/[σ^2(Fo^2) + (0.0455P)^2 + 0.0799P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
8971 reflections	Δρmax = 0.49 e Å^−3
536 parameters	Δρmin = −0.50 e Å^−3
25 restraints	Absolute structure: Flack x determined using 2429 quotients [(I^+)-(I^-)]/[(I^+)+(I^-)] (Parsons et al., 2013)
Primary atom site location: dual	Absolute structure parameter: −0.010 (6)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

————————————————————————

l.s. plane 1

————————————————————————

Equation (x, y, z in crystal coordinates):

–6.8237 (16) x + 5.2625 (12) y + 6.259 (2) z = 3.953 (6)

Defining atoms and their deviation from the plane:

N30: –0.014 (2) Å

C31: –0.046 (3) Å

C32: –0.024 (3) Å

C33: 0.024 (3) Å

C34: 0.042 (3) Å

C35: 0.024 (2) Å

O36: 0.055 (2) Å

C37: –0.075 (3) Å

N40: 0.042 (2) Å

C41: 0.018 (3) Å

C42: –0.029 (3) Å

C43: –0.033 (3) Å

C44: –0.014 (3) Å

C45: 0.023 (2) Å

O46: –0.059 (2) Å

C47: 0.065 (3) Å

Rms deviation: 0.041 Å

————————————————————————

l.s. plane 2

————————————————————————

Equation (x, y, z in crystal coordinates):

–6.6296 (17) x + 6.166 (11) y + 6.3561 (18) z = 1.306 (6)

Defining atoms and their deviation from the plane:

N10: –0.025 (2) Å

C11: –0.035 (2) Å

C12: –0.025 (3) Å

C13: –0.001 (3) Å

C14: 0.002 (3) Å

C15: –0.014 (2) Å

O16: 0.013 (2) Å

C17: 0.056 (3) Å

N20: 0.074 (2) Å

C21: 0.043 (2) Å

C22: –0.003 (3) Å

C23: –0.019 (3) Å

C24: –0.046 (2) Å

C25: 0.003 (2) Å

O26: 0.004 (2) Å

C27: –0.026 (3) Å

Rms deviation: 0.032 Å

————————————————————————

Angle between planes 1 and 2: 2.70 (4)°

Refinement. Hydrogen atoms were located on difference Fourier maps for the complex and most water molecules or inferred from neighbouring sites for the water molecule containing O68. Hydrogen positions were refined semi-freely for oxygen-bound atoms with d(O—H) ≈ 0.84 (2) Å, d(H···H) ≈ 1.33 Å, and U_iso(H) = 1.2U_eq(O).

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

	x	y	z	Uiso*/Ueq
C11	1.2715 (3)	0.41601 (12)	1.1226 (3)	0.0182 (5)
H11	1.283890	0.379796	1.168495	0.022*
C12	1.3710 (3)	0.45876 (13)	1.1865 (3)	0.0200 (5)
H12	1.451278	0.452042	1.275142	0.024*
C13	1.3535 (3)	0.51201 (13)	1.1204 (3)	0.0170 (5)
C14	1.2344 (3)	0.52043 (12)	0.9885 (3)	0.0164 (5)
H14	1.219570	0.556191	0.940163	0.020*
C15	1.1396 (3)	0.47504 (12)	0.9311 (3)	0.0145 (5)
C17	1.4390 (4)	0.60720 (13)	1.1263 (4)	0.0245 (6)
H17A	1.456712	0.606259	1.020808	0.037*
H17B	1.518812	0.631776	1.188359	0.037*
H17C	1.331302	0.621650	1.126726	0.037*
C21	0.8061 (3)	0.42851 (13)	0.6374 (3)	0.0193 (5)
H21	0.749051	0.394330	0.612752	0.023*
C22	0.7652 (3)	0.47396 (13)	0.5435 (3)	0.0200 (5)
H22	0.681591	0.471184	0.455702	0.024*
C23	0.8477 (3)	0.52418 (13)	0.5782 (3)	0.0178 (5)
C24	0.9754 (3)	0.52630 (12)	0.7051 (3)	0.0159 (5)
H24	1.037174	0.559525	0.729475	0.019*
C25	1.0079 (3)	0.47817 (11)	0.7933 (3)	0.0145 (5)
C27	0.8802 (4)	0.62092 (14)	0.5171 (4)	0.0300 (7)
H27A	0.865758	0.635393	0.616547	0.045*
H27B	0.836620	0.647981	0.436580	0.045*
H27C	0.994577	0.615298	0.519038	0.045*
C31	0.3834 (3)	0.43168 (13)	0.6794 (3)	0.0205 (5)
H31	0.349432	0.393596	0.668076	0.025*
C32	0.3125 (4)	0.46999 (14)	0.5734 (3)	0.0213 (5)
H32	0.230184	0.458718	0.490547	0.026*
C33	0.3622 (3)	0.52578 (13)	0.5883 (3)	0.0193 (5)
C34	0.4843 (3)	0.54103 (12)	0.7115 (3)	0.0166 (5)
H34	0.521299	0.578745	0.724106	0.020*
C35	0.5496 (3)	0.49946 (12)	0.8148 (3)	0.0154 (5)
C37	0.3456 (4)	0.61790 (14)	0.4770 (4)	0.0290 (7)
H37A	0.338665	0.637059	0.572958	0.043*
H37B	0.280905	0.638229	0.390659	0.043*
H37C	0.457485	0.616927	0.464978	0.043*
C41	0.8415 (3)	0.46603 (13)	1.1602 (3)	0.0192 (5)
H41	0.869537	0.433356	1.220971	0.023*
C42	0.9236 (3)	0.51491 (13)	1.2011 (3)	0.0213 (6)
H42	1.008567	0.515850	1.288088	0.026*
C43	0.8816 (3)	0.56337 (13)	1.1140 (3)	0.0204 (5)
C44	0.7578 (3)	0.56044 (12)	0.9846 (3)	0.0168 (5)
H44	0.727153	0.592557	0.922194	0.020*
C45	0.6817 (3)	0.50923 (12)	0.9505 (3)	0.0160 (5)
C47	0.9181 (4)	0.66188 (15)	1.0865 (5)	0.0335 (7)
H47A	0.933207	0.659815	0.980339	0.050*
H47B	0.983627	0.692454	1.139794	0.050*
H47C	0.804933	0.669051	1.087414	0.050*
C51	0.5003 (3)	0.28733 (12)	0.9647 (3)	0.0164 (5)
C54	0.6577 (3)	0.29477 (12)	1.0809 (3)	0.0152 (5)
H54	0.664279	0.266896	1.165969	0.018*
C56	0.7939 (3)	0.28407 (12)	0.9911 (3)	0.0148 (5)
H56	0.776060	0.246864	0.938153	0.018*
C58	0.9527 (3)	0.28248 (13)	1.1070 (3)	0.0192 (5)
N10	1.1565 (3)	0.42400 (10)	0.9965 (3)	0.0151 (4)
N20	0.9238 (3)	0.43016 (10)	0.7633 (3)	0.0150 (4)
N30	0.4999 (3)	0.44568 (10)	0.7997 (3)	0.0175 (4)
N40	0.7216 (3)	0.46292 (10)	1.0359 (3)	0.0167 (4)
O16	1.4539 (3)	0.55171 (10)	1.1887 (2)	0.0223 (4)
O26	0.7974 (3)	0.56828 (10)	0.4865 (2)	0.0239 (4)
O36	0.2861 (3)	0.56124 (10)	0.4806 (2)	0.0244 (4)
O46	0.9656 (3)	0.60980 (10)	1.1623 (3)	0.0265 (5)
O50	0.4432 (2)	0.33278 (9)	0.8974 (2)	0.0206 (4)
O52	0.4392 (3)	0.24029 (9)	0.9335 (2)	0.0217 (4)
O53	0.6716 (3)	0.34935 (8)	1.1395 (2)	0.0185 (4)
O55	0.7926 (2)	0.32664 (9)	0.8810 (2)	0.0170 (4)
O57	1.0554 (3)	0.31931 (10)	1.0907 (3)	0.0293 (5)
O59	0.9761 (3)	0.24641 (10)	1.2100 (2)	0.0233 (4)
O60	1.1234 (3)	0.32417 (11)	0.7440 (3)	0.0333 (6)
H60A	1.217 (6)	0.321 (2)	0.788 (5)	0.040*
H60B	1.084 (6)	0.300 (2)	0.691 (5)	0.040*
Cu1	0.98891 (3)	0.36813 (2)	0.91447 (4)	0.01545 (7)
Cu2	0.59542 (4)	0.39447 (2)	0.96609 (4)	0.01590 (7)
O61	0.4573 (3)	0.17342 (10)	0.1868 (3)	0.0273 (5)
H61A	0.421 (5)	0.1934 (16)	0.245 (4)	0.033*
H61B	0.450 (5)	0.1945 (16)	0.112 (3)	0.033*
O62	0.6964 (3)	0.27767 (12)	0.6111 (3)	0.0283 (5)
H62A	0.633 (4)	0.2548 (15)	0.623 (5)	0.034*
H62B	0.720 (5)	0.2935 (17)	0.692 (3)	0.034*
O63	0.7991 (3)	0.14628 (10)	0.1929 (3)	0.0292 (5)
H63A	0.852 (4)	0.1759 (14)	0.196 (5)	0.035*
H63B	0.703 (3)	0.1559 (18)	0.192 (5)	0.035*
O64	0.4289 (3)	0.21351 (11)	0.6298 (3)	0.0284 (5)
H64A	0.403 (5)	0.2303 (18)	0.701 (3)	0.034*
H64B	0.364 (4)	0.2296 (18)	0.558 (3)	0.034*
O65	0.3108 (3)	0.25427 (12)	0.3445 (3)	0.0295 (5)
H65A	0.219 (3)	0.2590 (18)	0.297 (4)	0.035*
H65B	0.359 (5)	0.2835 (13)	0.351 (5)	0.035*
O66	0.5228 (3)	0.34554 (12)	0.3780 (3)	0.0312 (5)
H66A	0.562 (5)	0.3509 (19)	0.306 (3)	0.037*
H66B	0.582 (4)	0.330 (2)	0.446 (4)	0.037*
O67	0.9808 (3)	0.24228 (14)	0.5446 (3)	0.0396 (6)
H67A	0.887 (4)	0.251 (2)	0.552 (5)	0.048*
H67B	0.982 (6)	0.243 (2)	0.452 (3)	0.048*
O68	0.0583 (5)	0.37893 (15)	0.4180 (4)	0.0594 (9)
H68A	0.037 (7)	0.3483 (18)	0.359 (5)	0.071*
H68B	0.065 (7)	0.366 (2)	0.515 (3)	0.071*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C11	0.0168 (12)	0.0151 (13)	0.0211 (12)	−0.0010 (10)	0.0000 (9)	0.0043 (10)
C12	0.0184 (12)	0.0220 (14)	0.0180 (12)	−0.0040 (11)	−0.0004 (10)	0.0012 (11)
C13	0.0165 (11)	0.0191 (13)	0.0158 (11)	−0.0048 (10)	0.0038 (9)	−0.0034 (10)
C14	0.0170 (11)	0.0150 (12)	0.0175 (11)	−0.0018 (10)	0.0042 (9)	0.0004 (10)
C15	0.0121 (11)	0.0158 (13)	0.0157 (11)	−0.0003 (9)	0.0033 (9)	−0.0004 (9)
C17	0.0309 (15)	0.0152 (13)	0.0274 (14)	−0.0069 (11)	0.0058 (12)	−0.0028 (11)
C21	0.0177 (12)	0.0203 (14)	0.0196 (12)	−0.0036 (10)	0.0031 (9)	−0.0013 (11)
C22	0.0165 (12)	0.0229 (14)	0.0189 (12)	−0.0005 (10)	−0.0007 (9)	0.0004 (11)
C23	0.0169 (12)	0.0186 (13)	0.0179 (11)	0.0022 (10)	0.0032 (9)	0.0026 (10)
C24	0.0151 (11)	0.0148 (12)	0.0183 (11)	0.0004 (9)	0.0048 (9)	−0.0007 (10)
C25	0.0140 (11)	0.0145 (12)	0.0157 (10)	0.0014 (9)	0.0046 (9)	−0.0005 (9)
C27	0.0337 (16)	0.0181 (15)	0.0348 (16)	0.0021 (12)	−0.0014 (13)	0.0074 (12)
C31	0.0218 (12)	0.0159 (13)	0.0233 (12)	−0.0016 (10)	0.0030 (10)	−0.0001 (11)
C32	0.0222 (12)	0.0211 (14)	0.0193 (12)	−0.0021 (11)	0.0008 (10)	0.0011 (11)
C33	0.0220 (13)	0.0204 (14)	0.0161 (11)	0.0038 (11)	0.0055 (10)	0.0036 (10)
C34	0.0209 (12)	0.0122 (12)	0.0179 (11)	0.0012 (10)	0.0068 (9)	0.0015 (9)
C35	0.0167 (11)	0.0138 (12)	0.0167 (11)	0.0005 (9)	0.0061 (9)	−0.0003 (10)
C37	0.0421 (18)	0.0213 (16)	0.0224 (14)	0.0019 (13)	0.0037 (13)	0.0062 (12)
C41	0.0242 (13)	0.0146 (13)	0.0189 (12)	0.0047 (10)	0.0043 (10)	0.0012 (10)
C42	0.0209 (13)	0.0214 (15)	0.0200 (12)	0.0027 (11)	0.0007 (10)	−0.0017 (11)
C43	0.0208 (13)	0.0176 (13)	0.0239 (12)	−0.0001 (10)	0.0074 (10)	−0.0036 (11)
C44	0.0189 (12)	0.0129 (12)	0.0195 (11)	0.0005 (10)	0.0057 (9)	−0.0012 (10)
C45	0.0179 (11)	0.0147 (13)	0.0174 (11)	0.0021 (9)	0.0079 (9)	0.0004 (10)
C47	0.0354 (17)	0.0169 (15)	0.0461 (19)	−0.0074 (13)	0.0026 (14)	0.0008 (14)
C51	0.0161 (11)	0.0152 (13)	0.0193 (12)	−0.0019 (10)	0.0067 (9)	0.0033 (10)
C54	0.0177 (11)	0.0101 (12)	0.0176 (11)	−0.0009 (9)	0.0028 (9)	0.0014 (9)
C56	0.0144 (11)	0.0133 (12)	0.0155 (10)	−0.0021 (9)	0.0002 (8)	0.0000 (9)
C58	0.0179 (12)	0.0160 (13)	0.0216 (12)	−0.0012 (10)	−0.0012 (9)	0.0015 (10)
N10	0.0141 (9)	0.0144 (11)	0.0161 (9)	−0.0022 (8)	0.0014 (8)	0.0000 (8)
N20	0.0142 (9)	0.0138 (11)	0.0168 (9)	0.0004 (8)	0.0024 (7)	0.0007 (8)
N30	0.0196 (10)	0.0129 (11)	0.0199 (10)	0.0012 (9)	0.0038 (8)	0.0013 (9)
N40	0.0190 (10)	0.0131 (11)	0.0184 (10)	0.0024 (9)	0.0044 (8)	0.0000 (9)
O16	0.0244 (10)	0.0199 (11)	0.0207 (9)	−0.0093 (8)	−0.0003 (8)	−0.0036 (8)
O26	0.0247 (10)	0.0198 (10)	0.0241 (10)	0.0019 (8)	−0.0026 (8)	0.0062 (8)
O36	0.0289 (11)	0.0200 (11)	0.0218 (9)	0.0034 (9)	−0.0011 (8)	0.0063 (8)
O46	0.0256 (10)	0.0192 (11)	0.0326 (11)	−0.0032 (9)	0.0005 (8)	−0.0027 (9)
O50	0.0162 (9)	0.0165 (10)	0.0281 (10)	−0.0012 (8)	0.0017 (8)	0.0054 (8)
O52	0.0233 (10)	0.0175 (10)	0.0240 (9)	−0.0051 (8)	0.0039 (8)	0.0022 (8)
O53	0.0294 (10)	0.0093 (9)	0.0169 (8)	0.0006 (7)	0.0048 (7)	−0.0002 (7)
O55	0.0145 (8)	0.0188 (10)	0.0166 (8)	−0.0041 (7)	0.0007 (6)	0.0039 (7)
O57	0.0209 (10)	0.0231 (12)	0.0374 (12)	−0.0077 (9)	−0.0102 (9)	0.0142 (10)
O59	0.0221 (10)	0.0192 (10)	0.0262 (10)	−0.0021 (8)	−0.0013 (8)	0.0067 (9)
O60	0.0181 (10)	0.0263 (13)	0.0525 (15)	0.0028 (9)	−0.0001 (10)	−0.0113 (11)
Cu1	0.01300 (13)	0.01261 (15)	0.01936 (14)	−0.00242 (12)	−0.00014 (10)	0.00193 (13)
Cu2	0.01896 (15)	0.01035 (14)	0.01850 (14)	0.00071 (13)	0.00396 (10)	0.00248 (12)
O61	0.0383 (13)	0.0166 (11)	0.0283 (11)	0.0021 (9)	0.0101 (10)	0.0035 (9)
O62	0.0311 (12)	0.0342 (14)	0.0183 (10)	−0.0094 (10)	0.0014 (9)	−0.0032 (9)
O63	0.0298 (11)	0.0163 (11)	0.0406 (13)	−0.0026 (9)	0.0051 (10)	0.0010 (10)
O64	0.0360 (13)	0.0240 (12)	0.0227 (10)	−0.0019 (10)	0.0002 (9)	0.0003 (9)
O65	0.0235 (11)	0.0343 (14)	0.0274 (11)	0.0028 (10)	−0.0032 (9)	0.0015 (10)
O66	0.0395 (13)	0.0320 (13)	0.0245 (11)	0.0059 (11)	0.0121 (9)	0.0053 (10)
O67	0.0366 (14)	0.0479 (17)	0.0336 (13)	0.0007 (13)	0.0052 (11)	−0.0124 (12)
O68	0.085 (2)	0.038 (2)	0.0514 (18)	−0.0002 (17)	0.0039 (17)	0.0004 (14)

Geometric parameters (Å, º)

C11—H11	0.9500	C42—C43	1.396 (4)
C11—C12	1.373 (4)	C43—C44	1.401 (4)
C11—N10	1.350 (3)	C43—O46	1.340 (4)
C12—H12	0.9500	C44—H44	0.9500
C12—C13	1.392 (4)	C44—C45	1.385 (4)
C13—C14	1.406 (4)	C45—N40	1.344 (4)
C13—O16	1.336 (3)	C47—H47A	0.9800
C14—H14	0.9500	C47—H47B	0.9800
C14—C15	1.384 (4)	C47—H47C	0.9800
C15—C25	1.491 (4)	C47—O46	1.430 (4)
C15—N10	1.342 (4)	C51—C54	1.532 (4)
C17—H17A	0.9800	C51—O50	1.284 (4)
C17—H17B	0.9800	C51—O52	1.242 (4)
C17—H17C	0.9800	C54—H54	1.0000
C17—O16	1.428 (4)	C54—C56	1.554 (4)
C21—H21	0.9500	C54—O53	1.395 (3)
C21—C22	1.368 (4)	C56—H56	1.0000
C21—N20	1.349 (3)	C56—C58	1.530 (4)
C22—H22	0.9500	C56—O55	1.408 (3)
C22—C23	1.389 (4)	C58—O57	1.266 (4)
C23—C24	1.406 (4)	C58—O59	1.242 (4)
C23—O26	1.346 (3)	N10—Cu1	1.980 (2)
C24—H24	0.9500	N20—Cu1	2.000 (2)
C24—C25	1.385 (4)	N30—Cu2	1.965 (2)
C25—N20	1.346 (4)	N40—Cu2	1.981 (2)
C27—H27A	0.9800	O50—Cu2	1.973 (2)
C27—H27B	0.9800	O53—Cu2	1.887 (2)
C27—H27C	0.9800	O55—Cu1	1.9128 (19)
C27—O26	1.436 (4)	O57—Cu1	1.944 (2)
C31—H31	0.9500	O60—H60A	0.81 (5)
C31—C32	1.364 (4)	O60—H60B	0.77 (5)
C31—N30	1.350 (4)	O60—Cu1	2.322 (3)
C32—H32	0.9500	O61—H61A	0.81 (2)
C32—C33	1.391 (4)	O61—H61B	0.82 (2)
C33—C34	1.402 (4)	O62—H62A	0.79 (2)
C33—O36	1.343 (3)	O62—H62B	0.80 (2)
C34—H34	0.9500	O63—H63A	0.83 (2)
C34—C35	1.389 (4)	O63—H63B	0.85 (2)
C35—C45	1.497 (4)	O64—H64A	0.81 (2)
C35—N30	1.345 (4)	O64—H64B	0.85 (2)
C37—H37A	0.9800	O65—H65A	0.82 (2)
C37—H37B	0.9800	O65—H65B	0.81 (2)
C37—H37C	0.9800	O66—H66A	0.79 (2)
C37—O36	1.442 (4)	O66—H66B	0.80 (2)
C41—H41	0.9500	O67—H67A	0.84 (2)
C41—C42	1.368 (4)	O67—H67B	0.83 (2)
C41—N40	1.351 (4)	O68—H68A	0.90 (3)
C42—H42	0.9500	O68—H68B	0.91 (2)
O55···Cu2	2.549 (2)
C12—C11—H11	119.1	H47A—C47—H47B	109.5
N10—C11—H11	119.1	H47A—C47—H47C	109.5
N10—C11—C12	121.8 (3)	H47B—C47—H47C	109.5
C11—C12—H12	120.2	O46—C47—H47A	109.5
C11—C12—C13	119.6 (2)	O46—C47—H47B	109.5
C13—C12—H12	120.2	O46—C47—H47C	109.5
C12—C13—C14	118.8 (3)	O50—C51—C54	114.7 (2)
O16—C13—C12	116.4 (2)	O52—C51—C54	121.8 (2)
O16—C13—C14	124.7 (3)	O52—C51—O50	123.4 (2)
C13—C14—H14	121.0	C51—C54—H54	110.2
C15—C14—C13	118.0 (3)	C51—C54—C56	106.0 (2)
C15—C14—H14	121.0	C56—C54—H54	110.2
C14—C15—C25	123.6 (3)	O53—C54—C51	111.0 (2)
N10—C15—C14	122.7 (2)	O53—C54—H54	110.2
N10—C15—C25	113.6 (2)	O53—C54—C56	109.1 (2)
H17A—C17—H17B	109.5	C54—C56—H56	109.1
H17A—C17—H17C	109.5	C58—C56—C54	107.9 (2)
H17B—C17—H17C	109.5	C58—C56—H56	109.1
O16—C17—H17A	109.5	O55—C56—C54	109.6 (2)
O16—C17—H17B	109.5	O55—C56—H56	109.1
O16—C17—H17C	109.5	O55—C56—C58	111.8 (2)
C22—C21—H21	118.6	O57—C58—C56	116.4 (2)
N20—C21—H21	118.6	O59—C58—C56	120.4 (2)
N20—C21—C22	122.8 (3)	O59—C58—O57	123.3 (3)
C21—C22—H22	120.4	C11—N10—Cu1	124.3 (2)
C21—C22—C23	119.2 (2)	C15—N10—C11	119.1 (2)
C23—C22—H22	120.4	C15—N10—Cu1	116.08 (17)
C22—C23—C24	119.1 (3)	C21—N20—Cu1	126.8 (2)
O26—C23—C22	116.7 (2)	C25—N20—C21	117.9 (2)
O26—C23—C24	124.2 (3)	C25—N20—Cu1	115.24 (17)
C23—C24—H24	121.2	C31—N30—Cu2	125.1 (2)
C25—C24—C23	117.5 (3)	C35—N30—C31	118.7 (2)
C25—C24—H24	121.2	C35—N30—Cu2	116.03 (19)
C24—C25—C15	122.8 (2)	C41—N40—Cu2	125.2 (2)
N20—C25—C15	113.9 (2)	C45—N40—C41	119.0 (3)
N20—C25—C24	123.4 (2)	C45—N40—Cu2	115.79 (18)
H27A—C27—H27B	109.5	C13—O16—C17	118.4 (2)
H27A—C27—H27C	109.5	C23—O26—C27	118.6 (2)
H27B—C27—H27C	109.5	C33—O36—C37	118.7 (2)
O26—C27—H27A	109.5	C43—O46—C47	118.6 (2)
O26—C27—H27B	109.5	C51—O50—Cu2	108.45 (17)
O26—C27—H27C	109.5	C54—O53—Cu2	103.46 (15)
C32—C31—H31	118.7	C56—O55—Cu1	112.06 (15)
N30—C31—H31	118.7	C56—O55—Cu2	99.39 (15)
N30—C31—C32	122.7 (3)	Cu1—O55—Cu2	103.52 (9)
C31—C32—H32	120.4	C58—O57—Cu1	114.07 (18)
C31—C32—C33	119.1 (3)	H60A—O60—H60B	119 (5)
C33—C32—H32	120.4	Cu1—O60—H60A	107 (3)
C32—C33—C34	119.1 (3)	Cu1—O60—H60B	122 (4)
O36—C33—C32	115.9 (3)	N10—Cu1—N20	80.60 (9)
O36—C33—C34	125.1 (3)	N10—Cu1—O60	97.51 (9)
C33—C34—H34	120.9	N20—Cu1—O60	89.96 (10)
C35—C34—C33	118.2 (3)	O55—Cu1—N10	161.28 (9)
C35—C34—H34	120.9	O55—Cu1—N20	99.09 (9)
C34—C35—C45	124.2 (2)	O55—Cu1—O57	85.65 (8)
N30—C35—C34	122.3 (2)	O55—Cu1—O60	101.20 (9)
N30—C35—C45	113.5 (2)	O57—Cu1—N10	91.69 (9)
H37A—C37—H37B	109.5	O57—Cu1—N20	168.93 (10)
H37A—C37—H37C	109.5	O57—Cu1—O60	98.98 (11)
H37B—C37—H37C	109.5	N30—Cu2—N40	81.11 (10)
O36—C37—H37A	109.5	N30—Cu2—O50	94.51 (10)
O36—C37—H37B	109.5	N30—Cu2—O55	111.51 (8)
O36—C37—H37C	109.5	N40—Cu2—O55	105.38 (8)
C42—C41—H41	119.1	O50—Cu2—N40	172.01 (10)
N40—C41—H41	119.1	O50—Cu2—O55	82.41 (8)
N40—C41—C42	121.9 (3)	O53—Cu2—N30	173.36 (10)
C41—C42—H42	120.2	O53—Cu2—N40	97.64 (9)
C41—C42—C43	119.5 (3)	O53—Cu2—O50	85.94 (9)
C43—C42—H42	120.2	O53—Cu2—O55	75.12 (7)
C42—C43—C44	119.0 (3)	H61A—O61—H61B	100 (4)
O46—C43—C42	116.1 (3)	H62A—O62—H62B	105 (4)
O46—C43—C44	124.9 (3)	H63A—O63—H63B	107 (4)
C43—C44—H44	121.1	H64A—O64—H64B	97 (4)
C45—C44—C43	117.9 (3)	H65A—O65—H65B	110 (4)
C45—C44—H44	121.1	H66A—O66—H66B	113 (4)
C44—C45—C35	123.9 (2)	H67A—O67—H67B	106 (4)
N40—C45—C35	113.3 (2)	H68A—O68—H68B	104 (4)
N40—C45—C44	122.8 (2)
C11—C12—C13—C14	−0.6 (4)	C42—C43—C44—C45	0.7 (4)
C11—C12—C13—O16	179.8 (3)	C42—C43—O46—C47	−174.1 (3)
C12—C11—N10—C15	0.4 (4)	C43—C44—C45—C35	−179.0 (2)
C12—C11—N10—Cu1	−170.9 (2)	C43—C44—C45—N40	0.1 (4)
C12—C13—C14—C15	0.3 (4)	C44—C43—O46—C47	6.1 (4)
C12—C13—O16—C17	−179.2 (3)	C44—C45—N40—C41	−0.3 (4)
C13—C14—C15—C25	179.2 (2)	C44—C45—N40—Cu2	179.6 (2)
C13—C14—C15—N10	0.3 (4)	C45—C35—N30—C31	−178.6 (2)
C14—C13—O16—C17	1.2 (4)	C45—C35—N30—Cu2	5.5 (3)
C14—C15—C25—C24	4.0 (4)	C51—C54—C56—C58	−171.8 (2)
C14—C15—C25—N20	−175.8 (2)	C51—C54—C56—O55	66.2 (3)
C14—C15—N10—C11	−0.7 (4)	C51—C54—O53—Cu2	−41.2 (2)
C14—C15—N10—Cu1	171.4 (2)	C54—C51—O50—Cu2	3.5 (3)
C15—C25—N20—C21	−177.6 (2)	C54—C56—C58—O57	−118.9 (3)
C15—C25—N20—Cu1	2.6 (3)	C54—C56—C58—O59	61.3 (3)
C21—C22—C23—C24	2.7 (4)	C54—C56—O55—Cu1	119.29 (19)
C21—C22—C23—O26	−176.8 (3)	C54—C56—O55—Cu2	10.5 (2)
C22—C21—N20—C25	−2.7 (4)	C54—O53—Cu2—N40	−152.04 (16)
C22—C21—N20—Cu1	177.2 (2)	C54—O53—Cu2—O50	35.14 (17)
C22—C23—C24—C25	−2.7 (4)	C54—O53—Cu2—O55	−48.08 (15)
C22—C23—O26—C27	−179.3 (3)	C56—C54—O53—Cu2	75.3 (2)
C23—C24—C25—C15	−179.8 (2)	C56—C58—O57—Cu1	−2.3 (4)
C23—C24—C25—N20	0.0 (4)	C58—C56—O55—Cu1	−0.3 (3)
C24—C23—O26—C27	1.2 (4)	C58—C56—O55—Cu2	−109.1 (2)
C24—C25—N20—C21	2.6 (4)	N10—C11—C12—C13	0.2 (4)
C24—C25—N20—Cu1	−177.2 (2)	N10—C15—C25—C24	−177.0 (2)
C25—C15—N10—C11	−179.7 (2)	N10—C15—C25—N20	3.3 (3)
C25—C15—N10—Cu1	−7.7 (3)	N20—C21—C22—C23	0.0 (4)
C31—C32—C33—C34	0.2 (4)	N30—C31—C32—C33	0.5 (4)
C31—C32—C33—O36	−179.4 (3)	N30—C35—C45—C44	176.4 (2)
C32—C31—N30—C35	−0.8 (4)	N30—C35—C45—N40	−2.7 (3)
C32—C31—N30—Cu2	174.7 (2)	N40—C41—C42—C43	1.0 (4)
C32—C33—C34—C35	−0.5 (4)	O16—C13—C14—C15	180.0 (3)
C32—C33—O36—C37	−171.8 (3)	O26—C23—C24—C25	176.8 (3)
C33—C34—C35—C45	179.2 (2)	O36—C33—C34—C35	179.1 (3)
C33—C34—C35—N30	0.2 (4)	O46—C43—C44—C45	−179.5 (3)
C34—C33—O36—C37	8.5 (4)	O50—C51—C54—C56	−92.3 (3)
C34—C35—C45—C44	−2.7 (4)	O50—C51—C54—O53	26.1 (3)
C34—C35—C45—N40	178.2 (2)	O52—C51—C54—C56	84.0 (3)
C34—C35—N30—C31	0.5 (4)	O52—C51—C54—O53	−157.6 (3)
C34—C35—N30—Cu2	−175.4 (2)	O52—C51—O50—Cu2	−172.7 (2)
C35—C45—N40—C41	178.8 (2)	O53—C54—C56—C58	68.6 (3)
C35—C45—N40—Cu2	−1.2 (3)	O53—C54—C56—O55	−53.4 (3)
C41—C42—C43—C44	−1.2 (4)	O55—C56—C58—O57	1.8 (4)
C41—C42—C43—O46	179.0 (3)	O55—C56—C58—O59	−178.1 (3)
C42—C41—N40—C45	−0.2 (4)	O59—C58—O57—Cu1	177.5 (2)
C42—C41—N40—Cu2	179.8 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O60—H60A···O50^i	0.81 (5)	2.00 (5)	2.802 (3)	167 (5)
O60—H60B···O67	0.77 (5)	1.98 (5)	2.750 (4)	177 (5)
O61—H61A···O65	0.81 (2)	2.02 (3)	2.813 (4)	166 (4)
O61—H61B···O52^ii	0.82 (2)	1.92 (2)	2.739 (3)	177 (4)
O62—H62A···O64	0.79 (2)	2.01 (3)	2.774 (3)	164 (5)
O62—H62B···O55	0.80 (2)	1.85 (2)	2.650 (3)	174 (5)
O63—H63A···O59^ii	0.83 (2)	1.97 (2)	2.806 (3)	178 (4)
O63—H63B···O61	0.85 (2)	2.13 (2)	2.970 (3)	176 (4)
O64—H64A···O52	0.81 (2)	2.05 (3)	2.762 (3)	146 (4)
O64—H64B···O65	0.85 (2)	1.95 (3)	2.719 (3)	149 (4)
O65—H65A···O59^iii	0.82 (2)	2.08 (3)	2.871 (3)	162 (4)
O65—H65B···O66	0.81 (2)	2.01 (2)	2.801 (4)	167 (4)
O66—H66A···O53^ii	0.79 (2)	1.91 (3)	2.680 (3)	169 (5)
O66—H66B···O62	0.80 (2)	2.02 (3)	2.808 (4)	167 (5)
O67—H67A···O62	0.84 (2)	1.91 (3)	2.737 (4)	168 (5)
O67—H67B···O59^ii	0.83 (2)	2.15 (2)	2.973 (3)	178 (5)
O68—H68A···O57^iii	0.90 (3)	2.52 (4)	3.236 (4)	138 (5)
O68—H68B···O60^iv	0.91 (2)	2.23 (3)	3.129 (5)	169 (5)

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