(2,9-Dimethyl-1,10-phenanthroline)(4-hydroxy-pyridine-2,6-dicarboxyl-ato)copper(II) trihydrate.

In the title complex, [Cu(C(7)H(3)NO(5))(C(14)H(12)N(2))]·3H(2)O, there are two independent neutral mol-ecules of the Cu complex along with six mol-ecules of water of hydration in the asymmetric unit. The Cu(II )atoms in each complex adopt a distorted square-pyramidal coordination geometry being penta-coordinated by one N and two O atoms of 4-hydroxy-pyridine-2,6-dicarboxyl-ate anions and two N atoms of 2,9-dimethyl-1,10-phenanthroline (dmp) molecules. In the crystal structure, there are O-H⋯O and C-H⋯O hydrogen bonds and five π-π stacking inter-actions with centroid-centroid distances in the range 3.620 (1)-3.712 (1) Å. In addition, a C-H⋯π inter-action between a heterocyclic ring of dmp is observed to reinforce the crystal cohesion.

Related literature

For related structures, see: Zhou et al. (2003 ▶, 2007 ▶); Ramos Silva et al. (2008 ▶); Aghabozorg, Ilaie et al. (2008 ▶); Aghabozorg, Manteghi & Sheshmani (2008 ▶); Aghabozorg, Motyeian, Attar Ghara­m­aleki et al. (2008 ▶); Aghabozorg, Motyeian, Soleiman­nejad et al. (2008 ▶); King et al. (2005 ▶); Lin et al. (2008 ▶).

Experimental

Crystal data

[Cu(C7H3NO5)(C14H12N2)]·3H2O

M = 506.95

Triclinic,

a = 10.0212 (2) Å

b = 14.8645 (3) Å

c = 15.4418 (3) Å

α = 91.193 (1)°

β = 106.836 (1)°

γ = 109.263 (1)°

V = 2061.05 (7) Å3

Z = 4

Mo Kα radiation

μ = 1.12 mm−1

T = 150 K

0.18 × 0.18 × 0.16 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.824, T max = 0.842

46562 measured reflections

12549 independent reflections

9400 reflections with I > 2σ(I)

R int = 0.043

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.127

S = 1.06

12549 reflections

601 parameters

H-atom parameters constrained

Δρmax = 0.92 e Å−3

Δρmin = −0.88 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; 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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809021588/pv2164sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809021588/pv2164Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu(C7H3NO5)(C14H12N2)]·3H2O	Z = 4
Mr = 506.95	F(000) = 1044
Triclinic, P1	Dx = 1.634 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.0212 (2) Å	Cell parameters from 10056 reflections
b = 14.8645 (3) Å	θ = 2.3–30.3°
c = 15.4418 (3) Å	µ = 1.12 mm−1
α = 91.193 (1)°	T = 150 K
β = 106.836 (1)°	Block, blue
γ = 109.263 (1)°	0.18 × 0.18 × 0.16 mm
V = 2061.05 (7) Å3

Bruker SMART CCD area-detector diffractometer	12549 independent reflections
Radiation source: fine-focus sealed tube	9400 reflections with I > 2σ(I)
graphite	Rint = 0.043
φ and ω scans	θmax = 30.7°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→13
Tmin = 0.824, Tmax = 0.842	k = −21→21
46562 measured reflections	l = −22→22

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0696P)2 + 0.1969P] where P = (Fo2 + 2Fc2)/3
12549 reflections	(Δ/σ)max = 0.002
601 parameters	Δρmax = 0.92 e Å−3
0 restraints	Δρmin = −0.87 e Å−3

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.

	x	y	z	Uiso*/Ueq
Cu1	0.18000 (3)	0.776157 (17)	0.315608 (16)	0.01236 (7)
Cu2	0.89377 (3)	0.750300 (18)	0.759838 (16)	0.01373 (7)
O1	−0.02604 (16)	0.67332 (11)	0.27155 (10)	0.0178 (3)
O2	−0.17402 (17)	0.56098 (11)	0.15312 (10)	0.0217 (3)
O3	0.15699 (18)	0.65953 (12)	−0.06028 (10)	0.0229 (3)
H3C	0.2339	0.6929	−0.0720	0.034*
O4	0.51539 (17)	0.92317 (11)	0.22333 (11)	0.0221 (3)
O5	0.36783 (16)	0.88012 (10)	0.31126 (9)	0.0150 (3)
O6	1.10226 (17)	0.84891 (11)	0.79318 (10)	0.0186 (3)
O7	1.27334 (17)	0.95980 (12)	0.90676 (10)	0.0214 (3)
O8	0.95793 (17)	0.90993 (11)	1.13195 (10)	0.0196 (3)
H8C	0.8778	0.8871	1.1441	0.029*
O9	0.57249 (17)	0.62956 (11)	0.87302 (10)	0.0206 (3)
O10	0.70852 (16)	0.65093 (11)	0.77791 (10)	0.0169 (3)
N1	0.17688 (18)	0.82702 (12)	0.43438 (11)	0.0115 (3)
N2	0.28176 (19)	0.68645 (12)	0.40714 (11)	0.0139 (3)
N3	0.16794 (19)	0.74652 (12)	0.19294 (11)	0.0128 (3)
N4	0.75691 (19)	0.81640 (12)	0.65962 (11)	0.0140 (3)
N5	0.89303 (19)	0.68955 (12)	0.64437 (11)	0.0133 (3)
N6	0.91937 (19)	0.79431 (12)	0.88159 (11)	0.0125 (3)
C1	0.3294 (2)	0.61610 (15)	0.39115 (14)	0.0163 (4)
C2	0.3859 (3)	0.56796 (17)	0.46299 (15)	0.0220 (5)
H2	0.4153	0.5160	0.4500	0.026*
C3	0.3985 (3)	0.59535 (17)	0.55083 (15)	0.0220 (5)
H3	0.4387	0.5637	0.5990	0.026*
C4	0.3513 (2)	0.67093 (15)	0.56916 (14)	0.0158 (4)
C5	0.3611 (2)	0.70513 (16)	0.65927 (14)	0.0191 (4)
H5	0.4016	0.6764	0.7099	0.023*
C6	0.3133 (2)	0.77814 (16)	0.67294 (14)	0.0174 (4)
H6	0.3218	0.8005	0.7331	0.021*
C7	0.2502 (2)	0.82174 (15)	0.59763 (13)	0.0151 (4)
C8	0.1995 (2)	0.89834 (15)	0.60858 (14)	0.0164 (4)
H8	0.2080	0.9241	0.6676	0.020*
C9	0.1379 (2)	0.93450 (15)	0.53255 (14)	0.0164 (4)
H9	0.1034	0.9858	0.5390	0.020*
C10	0.1248 (2)	0.89678 (14)	0.44484 (13)	0.0133 (4)
C11	0.2379 (2)	0.78919 (14)	0.50869 (13)	0.0125 (4)
C12	0.2918 (2)	0.71320 (15)	0.49419 (13)	0.0137 (4)
C13	0.0502 (2)	0.93156 (15)	0.36039 (14)	0.0154 (4)
H13A	0.1012	0.9314	0.3151	0.023*
H13B	0.0545	0.9970	0.3755	0.023*
H13C	−0.0541	0.8890	0.3354	0.023*
C14	0.3228 (3)	0.58905 (17)	0.29559 (15)	0.0211 (5)
H14A	0.2223	0.5775	0.2542	0.032*
H14B	0.3469	0.5306	0.2926	0.032*
H14C	0.3948	0.6414	0.2775	0.032*
C15	−0.0619 (2)	0.63130 (15)	0.19051 (14)	0.0153 (4)
C16	0.0507 (2)	0.67360 (15)	0.14055 (13)	0.0141 (4)
C17	0.0453 (2)	0.64275 (15)	0.05485 (14)	0.0162 (4)
H17	−0.0378	0.5905	0.0178	0.019*
C18	0.1649 (2)	0.68981 (16)	0.02292 (14)	0.0172 (4)
C19	0.2855 (2)	0.76720 (15)	0.07962 (14)	0.0162 (4)
H19	0.3673	0.8008	0.0595	0.019*
C20	0.2825 (2)	0.79327 (14)	0.16487 (13)	0.0130 (4)
C21	0.4010 (2)	0.87260 (15)	0.23753 (14)	0.0151 (4)
C22	0.6861 (2)	0.87632 (14)	0.66901 (14)	0.0137 (4)
C23	0.6090 (2)	0.91006 (15)	0.59242 (14)	0.0162 (4)
H23	0.5584	0.9520	0.6004	0.019*
C24	0.6071 (2)	0.88225 (15)	0.50639 (14)	0.0161 (4)
H24	0.5564	0.9055	0.4549	0.019*
C25	0.6811 (2)	0.81892 (15)	0.49529 (14)	0.0145 (4)
C26	0.6880 (2)	0.78837 (15)	0.40854 (13)	0.0160 (4)
H26	0.6412	0.8111	0.3553	0.019*
C27	0.7608 (2)	0.72721 (15)	0.40165 (13)	0.0160 (4)
H27	0.7655	0.7083	0.3438	0.019*
C28	0.8305 (2)	0.69104 (15)	0.48090 (13)	0.0143 (4)
C29	0.9066 (2)	0.62694 (15)	0.47755 (14)	0.0164 (4)
H29	0.9132	0.6054	0.4211	0.020*
C30	0.9709 (2)	0.59608 (15)	0.55649 (14)	0.0164 (4)
H30	1.0218	0.5527	0.5545	0.020*
C31	0.9624 (2)	0.62803 (14)	0.64040 (14)	0.0147 (4)
C32	0.8278 (2)	0.72104 (14)	0.56680 (13)	0.0125 (4)
C33	0.7531 (2)	0.78780 (14)	0.57459 (13)	0.0127 (4)
C34	1.0325 (3)	0.59555 (16)	0.72729 (14)	0.0188 (4)
H34A	1.1303	0.6440	0.7588	0.028*
H34B	1.0442	0.5344	0.7136	0.028*
H34C	0.9688	0.5869	0.7664	0.028*
C35	0.6941 (3)	0.90849 (16)	0.76295 (14)	0.0191 (4)
H35A	0.6582	0.8522	0.7931	0.029*
H35B	0.6318	0.9480	0.7597	0.029*
H35C	0.7974	0.9464	0.7979	0.029*
C35A	1.1514 (2)	0.89664 (15)	0.87318 (14)	0.0157 (4)
C36	1.0421 (2)	0.86719 (14)	0.92753 (13)	0.0133 (4)
C37	1.0587 (2)	0.90636 (15)	1.01326 (13)	0.0146 (4)
H37	1.1471	0.9575	1.0465	0.018*
C38	0.9421 (2)	0.86912 (15)	1.05067 (13)	0.0147 (4)
C39	0.8153 (2)	0.79024 (15)	1.00122 (14)	0.0145 (4)
H39	0.7363	0.7624	1.0256	0.017*
C40	0.8096 (2)	0.75499 (14)	0.91681 (13)	0.0128 (4)
C41	0.6861 (2)	0.67159 (15)	0.85124 (14)	0.0155 (4)
O1S	−0.36552 (18)	0.52690 (11)	0.25879 (11)	0.0233 (3)
H1B	−0.4325	0.4749	0.2290	0.028*
H1A	−0.2950	0.5259	0.2391	0.028*
O2S	0.72446 (18)	0.85157 (12)	1.18104 (11)	0.0242 (4)
H2A	0.6820	0.8915	1.1861	0.029*
H2B	0.6744	0.7933	1.1823	0.029*
O3S	0.40048 (19)	0.73524 (13)	−0.09847 (11)	0.0281 (4)
H3B	0.4591	0.7047	−0.0971	0.034*
H3A	0.4522	0.7936	−0.0772	0.034*
O4S	0.3462 (3)	0.52186 (14)	0.02695 (14)	0.0551 (7)
H4A	0.3905	0.4814	0.0346	0.066*
H4B	0.2978	0.5028	−0.0292	0.066*
O5S	0.55325 (19)	0.92630 (12)	−0.07300 (11)	0.0282 (4)
H5B	0.6076	0.9614	−0.0227	0.034*
H5A	0.4795	0.9447	−0.0935	0.034*
O6S	0.5503 (2)	0.66922 (13)	0.16038 (13)	0.0351 (4)
H6A	0.4896	0.6346	0.1111	0.042*
H6B	0.5865	0.6312	0.1911	0.042*

	U11	U22	U33	U12	U13	U23
Cu1	0.01313 (13)	0.01541 (13)	0.00901 (11)	0.00463 (10)	0.00468 (9)	0.00021 (9)
Cu2	0.01492 (13)	0.01556 (13)	0.01061 (12)	0.00421 (10)	0.00533 (10)	−0.00019 (9)
O1	0.0158 (7)	0.0226 (8)	0.0127 (7)	0.0029 (6)	0.0059 (6)	−0.0018 (6)
O2	0.0183 (8)	0.0235 (8)	0.0176 (7)	0.0011 (7)	0.0048 (6)	−0.0016 (6)
O3	0.0210 (8)	0.0347 (10)	0.0137 (7)	0.0086 (7)	0.0080 (6)	−0.0042 (6)
O4	0.0183 (8)	0.0214 (8)	0.0247 (8)	0.0000 (6)	0.0123 (7)	−0.0027 (6)
O5	0.0160 (7)	0.0162 (7)	0.0120 (6)	0.0042 (6)	0.0051 (6)	−0.0003 (5)
O6	0.0203 (8)	0.0212 (8)	0.0140 (7)	0.0039 (6)	0.0093 (6)	−0.0007 (6)
O7	0.0144 (7)	0.0267 (9)	0.0194 (7)	0.0004 (7)	0.0081 (6)	−0.0014 (6)
O8	0.0171 (8)	0.0261 (8)	0.0135 (7)	0.0026 (7)	0.0081 (6)	−0.0056 (6)
O9	0.0188 (8)	0.0188 (8)	0.0212 (8)	−0.0010 (6)	0.0109 (7)	−0.0023 (6)
O10	0.0184 (8)	0.0164 (7)	0.0143 (7)	0.0022 (6)	0.0075 (6)	−0.0020 (6)
N1	0.0109 (8)	0.0130 (8)	0.0103 (7)	0.0031 (6)	0.0042 (6)	0.0006 (6)
N2	0.0137 (8)	0.0163 (8)	0.0127 (8)	0.0064 (7)	0.0043 (7)	0.0008 (6)
N3	0.0140 (8)	0.0163 (8)	0.0106 (7)	0.0070 (7)	0.0054 (7)	0.0029 (6)
N4	0.0169 (9)	0.0143 (8)	0.0107 (7)	0.0053 (7)	0.0045 (7)	0.0009 (6)
N5	0.0152 (8)	0.0143 (8)	0.0105 (7)	0.0050 (7)	0.0046 (7)	−0.0008 (6)
N6	0.0135 (8)	0.0137 (8)	0.0105 (7)	0.0051 (7)	0.0037 (7)	0.0011 (6)
C1	0.0146 (10)	0.0162 (10)	0.0172 (9)	0.0052 (8)	0.0042 (8)	0.0001 (8)
C2	0.0249 (12)	0.0241 (12)	0.0224 (11)	0.0168 (10)	0.0058 (9)	0.0033 (9)
C3	0.0238 (11)	0.0256 (12)	0.0205 (10)	0.0140 (10)	0.0062 (9)	0.0072 (9)
C4	0.0130 (10)	0.0190 (10)	0.0161 (9)	0.0066 (8)	0.0042 (8)	0.0031 (8)
C5	0.0174 (10)	0.0261 (12)	0.0144 (9)	0.0081 (9)	0.0049 (8)	0.0069 (8)
C6	0.0159 (10)	0.0233 (11)	0.0120 (9)	0.0060 (9)	0.0040 (8)	0.0022 (8)
C7	0.0139 (9)	0.0195 (10)	0.0114 (9)	0.0046 (8)	0.0050 (8)	0.0012 (7)
C8	0.0172 (10)	0.0187 (10)	0.0136 (9)	0.0048 (8)	0.0074 (8)	−0.0010 (8)
C9	0.0185 (10)	0.0165 (10)	0.0163 (9)	0.0068 (8)	0.0079 (8)	0.0001 (8)
C10	0.0114 (9)	0.0151 (10)	0.0137 (9)	0.0032 (8)	0.0064 (8)	0.0016 (7)
C11	0.0110 (9)	0.0140 (9)	0.0118 (8)	0.0034 (7)	0.0038 (7)	0.0025 (7)
C12	0.0120 (9)	0.0154 (10)	0.0135 (9)	0.0041 (8)	0.0048 (8)	0.0007 (7)
C13	0.0159 (10)	0.0172 (10)	0.0154 (9)	0.0077 (8)	0.0062 (8)	0.0035 (8)
C14	0.0252 (12)	0.0223 (11)	0.0191 (10)	0.0126 (10)	0.0071 (9)	−0.0003 (8)
C15	0.0146 (10)	0.0181 (10)	0.0136 (9)	0.0062 (8)	0.0044 (8)	0.0021 (8)
C16	0.0149 (10)	0.0166 (10)	0.0122 (9)	0.0072 (8)	0.0045 (8)	0.0010 (7)
C17	0.0146 (10)	0.0184 (10)	0.0136 (9)	0.0061 (8)	0.0015 (8)	−0.0015 (8)
C18	0.0188 (10)	0.0261 (11)	0.0104 (9)	0.0125 (9)	0.0048 (8)	0.0007 (8)
C19	0.0161 (10)	0.0219 (11)	0.0143 (9)	0.0093 (9)	0.0070 (8)	0.0035 (8)
C20	0.0140 (9)	0.0143 (9)	0.0119 (9)	0.0071 (8)	0.0035 (8)	0.0022 (7)
C21	0.0168 (10)	0.0156 (10)	0.0153 (9)	0.0078 (8)	0.0065 (8)	0.0014 (7)
C22	0.0129 (9)	0.0126 (9)	0.0154 (9)	0.0037 (8)	0.0051 (8)	0.0006 (7)
C23	0.0138 (10)	0.0148 (10)	0.0202 (10)	0.0050 (8)	0.0058 (8)	0.0009 (8)
C24	0.0134 (10)	0.0155 (10)	0.0171 (9)	0.0043 (8)	0.0023 (8)	0.0027 (8)
C25	0.0137 (9)	0.0145 (9)	0.0132 (9)	0.0027 (8)	0.0038 (8)	0.0016 (7)
C26	0.0159 (10)	0.0187 (10)	0.0109 (9)	0.0037 (8)	0.0034 (8)	0.0028 (7)
C27	0.0158 (10)	0.0175 (10)	0.0106 (9)	0.0014 (8)	0.0033 (8)	−0.0007 (7)
C28	0.0136 (9)	0.0141 (9)	0.0121 (9)	0.0008 (8)	0.0042 (8)	−0.0018 (7)
C29	0.0184 (10)	0.0168 (10)	0.0135 (9)	0.0039 (8)	0.0075 (8)	−0.0021 (7)
C30	0.0189 (10)	0.0165 (10)	0.0148 (9)	0.0082 (8)	0.0047 (8)	−0.0021 (8)
C31	0.0157 (10)	0.0130 (9)	0.0142 (9)	0.0034 (8)	0.0050 (8)	−0.0005 (7)
C32	0.0134 (9)	0.0125 (9)	0.0107 (8)	0.0029 (8)	0.0044 (7)	−0.0007 (7)
C33	0.0122 (9)	0.0125 (9)	0.0121 (8)	0.0024 (7)	0.0041 (7)	−0.0004 (7)
C34	0.0243 (11)	0.0219 (11)	0.0147 (9)	0.0137 (9)	0.0059 (9)	0.0026 (8)
C35	0.0225 (11)	0.0203 (11)	0.0174 (10)	0.0103 (9)	0.0075 (9)	−0.0003 (8)
C35A	0.0168 (10)	0.0193 (10)	0.0133 (9)	0.0075 (8)	0.0067 (8)	0.0013 (8)
C36	0.0141 (9)	0.0149 (9)	0.0125 (9)	0.0067 (8)	0.0049 (8)	0.0018 (7)
C37	0.0130 (9)	0.0157 (10)	0.0131 (9)	0.0040 (8)	0.0026 (8)	−0.0009 (7)
C38	0.0164 (10)	0.0178 (10)	0.0113 (9)	0.0075 (8)	0.0050 (8)	−0.0001 (7)
C39	0.0137 (9)	0.0166 (10)	0.0145 (9)	0.0047 (8)	0.0068 (8)	0.0022 (7)
C40	0.0132 (9)	0.0134 (9)	0.0121 (9)	0.0044 (8)	0.0048 (8)	0.0013 (7)
C41	0.0170 (10)	0.0136 (9)	0.0156 (9)	0.0050 (8)	0.0050 (8)	0.0017 (7)
O1S	0.0214 (8)	0.0210 (8)	0.0231 (8)	0.0006 (7)	0.0087 (7)	−0.0034 (6)
O2S	0.0240 (9)	0.0206 (8)	0.0346 (9)	0.0076 (7)	0.0189 (8)	0.0060 (7)
O3S	0.0223 (9)	0.0335 (10)	0.0307 (9)	0.0096 (8)	0.0120 (7)	−0.0012 (7)
O4S	0.0751 (17)	0.0324 (11)	0.0303 (11)	0.0164 (11)	−0.0206 (11)	−0.0035 (9)
O5S	0.0257 (9)	0.0347 (10)	0.0237 (8)	0.0149 (8)	0.0026 (7)	−0.0078 (7)
O6S	0.0297 (10)	0.0243 (9)	0.0404 (11)	0.0075 (8)	−0.0028 (8)	0.0039 (8)

Cu1—N3	1.8959 (16)	C14—H14A	0.9800
Cu1—N1	1.9818 (16)	C14—H14B	0.9800
Cu1—O5	2.0234 (15)	C14—H14C	0.9800
Cu1—O1	2.0306 (15)	C15—C16	1.523 (3)
Cu1—N2	2.2263 (17)	C16—C17	1.372 (3)
Cu2—N6	1.8940 (16)	C17—C18	1.404 (3)
Cu2—N5	1.9787 (16)	C17—H17	0.9500
Cu2—O6	2.0257 (16)	C18—C19	1.407 (3)
Cu2—O10	2.0528 (15)	C19—C20	1.376 (3)
Cu2—N4	2.2281 (17)	C19—H19	0.9500
O1—C15	1.282 (2)	C20—C21	1.519 (3)
O2—C15	1.230 (3)	C22—C23	1.414 (3)
O3—C18	1.324 (2)	C22—C35	1.489 (3)
O3—H3C	0.8400	C23—C24	1.376 (3)
O4—C21	1.229 (3)	C23—H23	0.9500
O5—C21	1.287 (2)	C24—C25	1.412 (3)
O6—C35A	1.286 (2)	C24—H24	0.9500
O7—C35A	1.224 (3)	C25—C33	1.402 (3)
O8—C38	1.326 (2)	C25—C26	1.433 (3)
O8—H8C	0.8400	C26—C27	1.360 (3)
O9—C41	1.250 (3)	C26—H26	0.9500
O10—C41	1.267 (2)	C27—C28	1.433 (3)
N1—C10	1.331 (3)	C27—H27	0.9500
N1—C11	1.362 (2)	C28—C32	1.401 (3)
N2—C1	1.330 (3)	C28—C29	1.412 (3)
N2—C12	1.360 (3)	C29—C30	1.369 (3)
N3—C20	1.328 (3)	C29—H29	0.9500
N3—C16	1.335 (3)	C30—C31	1.406 (3)
N4—C22	1.338 (3)	C30—H30	0.9500
N4—C33	1.358 (2)	C31—C34	1.494 (3)
N5—C31	1.328 (3)	C32—C33	1.448 (3)
N5—C32	1.361 (2)	C34—H34A	0.9800
N6—C36	1.332 (3)	C34—H34B	0.9800
N6—C40	1.336 (3)	C34—H34C	0.9800
C1—C2	1.414 (3)	C35—H35A	0.9800
C1—C14	1.498 (3)	C35—H35B	0.9800
C2—C3	1.366 (3)	C35—H35C	0.9800
C2—H2	0.9500	C35A—C36	1.525 (3)
C3—C4	1.407 (3)	C36—C37	1.377 (3)
C3—H3	0.9500	C37—C38	1.408 (3)
C4—C12	1.403 (3)	C37—H37	0.9500
C4—C5	1.436 (3)	C38—C39	1.411 (3)
C5—C6	1.358 (3)	C39—C40	1.373 (3)
C5—H5	0.9500	C39—H39	0.9500
C6—C7	1.431 (3)	C40—C41	1.517 (3)
C6—H6	0.9500	O1S—H1B	0.8500
C7—C11	1.404 (3)	O1S—H1A	0.8500
C7—C8	1.417 (3)	O2S—H2A	0.8500
C8—C9	1.369 (3)	O2S—H2B	0.8500
C8—H8	0.9500	O3S—H3B	0.8500
C9—C10	1.408 (3)	O3S—H3A	0.8500
C9—H9	0.9500	O4S—H4A	0.8500
C10—C13	1.499 (3)	O4S—H4B	0.8500
C11—C12	1.442 (3)	O5S—H5B	0.8501
C13—H13A	0.9800	O5S—H5A	0.8501
C13—H13B	0.9800	O6S—H6A	0.8500
C13—H13C	0.9800	O6S—H6B	0.8501
N3—Cu1—N1	168.68 (7)	O1—C15—C16	114.46 (18)
N3—Cu1—O5	80.32 (7)	N3—C16—C17	120.63 (19)
N1—Cu1—O5	97.54 (6)	N3—C16—C15	111.38 (17)
N3—Cu1—O1	80.62 (7)	C17—C16—C15	127.92 (19)
N1—Cu1—O1	99.73 (6)	C16—C17—C18	118.77 (19)
O5—Cu1—O1	159.59 (6)	C16—C17—H17	120.6
N3—Cu1—N2	111.53 (7)	C18—C17—H17	120.6
N1—Cu1—N2	79.77 (6)	O3—C18—C17	117.9 (2)
O5—Cu1—N2	99.28 (6)	O3—C18—C19	123.2 (2)
O1—Cu1—N2	94.45 (6)	C17—C18—C19	118.94 (19)
N6—Cu2—N5	168.36 (7)	C20—C19—C18	118.6 (2)
N6—Cu2—O6	80.28 (7)	C20—C19—H19	120.7
N5—Cu2—O6	96.98 (7)	C18—C19—H19	120.7
N6—Cu2—O10	80.35 (7)	N3—C20—C19	120.70 (19)
N5—Cu2—O10	100.13 (7)	N3—C20—C21	111.76 (17)
O6—Cu2—O10	158.49 (6)	C19—C20—C21	127.53 (19)
N6—Cu2—N4	111.71 (7)	O4—C21—O5	125.7 (2)
N5—Cu2—N4	79.92 (7)	O4—C21—C20	120.64 (18)
O6—Cu2—N4	103.56 (6)	O5—C21—C20	113.69 (18)
O10—Cu2—N4	92.23 (6)	N4—C22—C23	121.14 (18)
C15—O1—Cu1	114.37 (13)	N4—C22—C35	117.98 (18)
C18—O3—H3C	109.5	C23—C22—C35	120.86 (18)
C21—O5—Cu1	114.81 (13)	C24—C23—C22	120.11 (19)
C35A—O6—Cu2	115.27 (13)	C24—C23—H23	119.9
C38—O8—H8C	109.5	C22—C23—H23	119.9
C41—O10—Cu2	113.04 (13)	C23—C24—C25	119.45 (19)
C10—N1—C11	119.81 (17)	C23—C24—H24	120.3
C10—N1—Cu1	123.96 (13)	C25—C24—H24	120.3
C11—N1—Cu1	116.18 (13)	C33—C25—C24	116.83 (18)
C1—N2—C12	118.95 (17)	C33—C25—C26	120.08 (18)
C1—N2—Cu1	132.37 (14)	C24—C25—C26	123.07 (18)
C12—N2—Cu1	108.69 (13)	C27—C26—C25	120.69 (19)
C20—N3—C16	122.35 (18)	C27—C26—H26	119.7
C20—N3—Cu1	118.70 (14)	C25—C26—H26	119.7
C16—N3—Cu1	118.67 (14)	C26—C27—C28	120.59 (19)
C22—N4—C33	118.74 (17)	C26—C27—H27	119.7
C22—N4—Cu2	132.73 (14)	C28—C27—H27	119.7
C33—N4—Cu2	108.52 (13)	C32—C28—C29	117.11 (18)
C31—N5—C32	120.07 (17)	C32—C28—C27	119.93 (18)
C31—N5—Cu2	123.70 (14)	C29—C28—C27	122.94 (18)
C32—N5—Cu2	115.96 (13)	C30—C29—C28	119.35 (19)
C36—N6—C40	121.98 (17)	C30—C29—H29	120.3
C36—N6—Cu2	119.09 (14)	C28—C29—H29	120.3
C40—N6—Cu2	118.81 (14)	C29—C30—C31	120.65 (19)
N2—C1—C2	120.68 (19)	C29—C30—H30	119.7
N2—C1—C14	118.75 (18)	C31—C30—H30	119.7
C2—C1—C14	120.56 (19)	N5—C31—C30	120.39 (18)
C3—C2—C1	120.7 (2)	N5—C31—C34	118.18 (18)
C3—C2—H2	119.6	C30—C31—C34	121.43 (18)
C1—C2—H2	119.6	N5—C32—C28	122.42 (18)
C2—C3—C4	119.2 (2)	N5—C32—C33	118.02 (17)
C2—C3—H3	120.4	C28—C32—C33	119.56 (18)
C4—C3—H3	120.4	N4—C33—C25	123.71 (18)
C12—C4—C3	116.91 (19)	N4—C33—C32	117.22 (17)
C12—C4—C5	119.85 (18)	C25—C33—C32	119.07 (17)
C3—C4—C5	123.25 (19)	C31—C34—H34A	109.5
C6—C5—C4	120.74 (19)	C31—C34—H34B	109.5
C6—C5—H5	119.6	H34A—C34—H34B	109.5
C4—C5—H5	119.6	C31—C34—H34C	109.5
C5—C6—C7	120.63 (19)	H34A—C34—H34C	109.5
C5—C6—H6	119.7	H34B—C34—H34C	109.5
C7—C6—H6	119.7	C22—C35—H35A	109.5
C11—C7—C8	117.47 (18)	C22—C35—H35B	109.5
C11—C7—C6	119.89 (18)	H35A—C35—H35B	109.5
C8—C7—C6	122.64 (18)	C22—C35—H35C	109.5
C9—C8—C7	118.74 (18)	H35A—C35—H35C	109.5
C9—C8—H8	120.6	H35B—C35—H35C	109.5
C7—C8—H8	120.6	O7—C35A—O6	126.1 (2)
C8—C9—C10	121.01 (19)	O7—C35A—C36	120.32 (18)
C8—C9—H9	119.5	O6—C35A—C36	113.61 (18)
C10—C9—H9	119.5	N6—C36—C37	120.64 (19)
N1—C10—C9	120.49 (18)	N6—C36—C35A	111.47 (17)
N1—C10—C13	117.63 (17)	C37—C36—C35A	127.89 (19)
C9—C10—C13	121.87 (18)	C36—C37—C38	118.71 (19)
N1—C11—C7	122.41 (18)	C36—C37—H37	120.6
N1—C11—C12	117.98 (17)	C38—C37—H37	120.6
C7—C11—C12	119.60 (18)	O8—C38—C37	117.86 (19)
N2—C12—C4	123.42 (18)	O8—C38—C39	122.96 (19)
N2—C12—C11	117.32 (17)	C37—C38—C39	119.18 (18)
C4—C12—C11	119.27 (18)	C40—C39—C38	117.95 (19)
C10—C13—H13A	109.5	C40—C39—H39	121.0
C10—C13—H13B	109.5	C38—C39—H39	121.0
H13A—C13—H13B	109.5	N6—C40—C39	121.46 (19)
C10—C13—H13C	109.5	N6—C40—C41	110.82 (17)
H13A—C13—H13C	109.5	C39—C40—C41	127.72 (19)
H13B—C13—H13C	109.5	O9—C41—O10	125.6 (2)
C1—C14—H14A	109.5	O9—C41—C40	118.47 (18)
C1—C14—H14B	109.5	O10—C41—C40	115.93 (18)
H14A—C14—H14B	109.5	H1B—O1S—H1A	99.2
C1—C14—H14C	109.5	H2A—O2S—H2B	115.2
H14A—C14—H14C	109.5	H3B—O3S—H3A	108.5
H14B—C14—H14C	109.5	H4A—O4S—H4B	96.6
O2—C15—O1	125.8 (2)	H5B—O5S—H5A	107.1
O2—C15—C16	119.72 (18)	H6A—O6S—H6B	104.7
N3—Cu1—O1—C15	6.39 (14)	N1—C11—C12—N2	1.9 (3)
N1—Cu1—O1—C15	174.92 (14)	C7—C11—C12—N2	−177.88 (18)
O5—Cu1—O1—C15	27.6 (3)	N1—C11—C12—C4	−178.17 (18)
N2—Cu1—O1—C15	−104.72 (15)	C7—C11—C12—C4	2.0 (3)
N3—Cu1—O5—C21	−7.58 (14)	Cu1—O1—C15—O2	172.45 (17)
N1—Cu1—O5—C21	−176.34 (14)	Cu1—O1—C15—C16	−5.7 (2)
O1—Cu1—O5—C21	−28.8 (3)	C20—N3—C16—C17	1.1 (3)
N2—Cu1—O5—C21	102.87 (14)	Cu1—N3—C16—C17	−172.68 (15)
N6—Cu2—O6—C35A	−3.25 (15)	C20—N3—C16—C15	178.32 (17)
N5—Cu2—O6—C35A	−171.81 (15)	Cu1—N3—C16—C15	4.5 (2)
O10—Cu2—O6—C35A	−29.3 (3)	O2—C15—C16—N3	−177.16 (18)
N4—Cu2—O6—C35A	106.93 (15)	O1—C15—C16—N3	1.1 (3)
N6—Cu2—O10—C41	9.37 (14)	O2—C15—C16—C17	−0.2 (3)
N5—Cu2—O10—C41	177.56 (14)	O1—C15—C16—C17	178.1 (2)
O6—Cu2—O10—C41	35.4 (2)	N3—C16—C17—C18	−0.5 (3)
N4—Cu2—O10—C41	−102.29 (14)	C15—C16—C17—C18	−177.25 (19)
N3—Cu1—N1—C10	3.2 (5)	C16—C17—C18—O3	−179.41 (19)
O5—Cu1—N1—C10	81.50 (16)	C16—C17—C18—C19	−0.3 (3)
O1—Cu1—N1—C10	−87.56 (16)	O3—C18—C19—C20	179.71 (19)
N2—Cu1—N1—C10	179.63 (17)	C17—C18—C19—C20	0.7 (3)
N3—Cu1—N1—C11	−174.1 (3)	C16—N3—C20—C19	−0.7 (3)
O5—Cu1—N1—C11	−95.83 (14)	Cu1—N3—C20—C19	173.04 (15)
O1—Cu1—N1—C11	95.11 (14)	C16—N3—C20—C21	−179.77 (17)
N2—Cu1—N1—C11	2.30 (14)	Cu1—N3—C20—C21	−6.0 (2)
N3—Cu1—N2—C1	−2.5 (2)	C18—C19—C20—N3	−0.2 (3)
N1—Cu1—N2—C1	178.3 (2)	C18—C19—C20—C21	178.70 (19)
O5—Cu1—N2—C1	−85.68 (19)	Cu1—O5—C21—O4	−174.05 (17)
O1—Cu1—N2—C1	79.16 (19)	Cu1—O5—C21—C20	6.4 (2)
N3—Cu1—N2—C12	178.01 (13)	N3—C20—C21—O4	179.77 (18)
N1—Cu1—N2—C12	−1.23 (13)	C19—C20—C21—O4	0.8 (3)
O5—Cu1—N2—C12	94.83 (14)	N3—C20—C21—O5	−0.7 (2)
O1—Cu1—N2—C12	−100.33 (14)	C19—C20—C21—O5	−179.62 (19)
N1—Cu1—N3—C20	87.4 (4)	C33—N4—C22—C23	−0.3 (3)
O5—Cu1—N3—C20	7.40 (14)	Cu2—N4—C22—C23	178.15 (15)
O1—Cu1—N3—C20	−179.94 (16)	C33—N4—C22—C35	−178.77 (18)
N2—Cu1—N3—C20	−88.83 (15)	Cu2—N4—C22—C35	−0.3 (3)
N1—Cu1—N3—C16	−98.6 (4)	N4—C22—C23—C24	−0.7 (3)
O5—Cu1—N3—C16	−178.60 (16)	C35—C22—C23—C24	177.7 (2)
O1—Cu1—N3—C16	−5.94 (15)	C22—C23—C24—C25	0.8 (3)
N2—Cu1—N3—C16	85.17 (16)	C23—C24—C25—C33	0.1 (3)
N6—Cu2—N4—C22	−3.4 (2)	C23—C24—C25—C26	−178.3 (2)
N5—Cu2—N4—C22	177.0 (2)	C33—C25—C26—C27	1.7 (3)
O6—Cu2—N4—C22	−88.16 (19)	C24—C25—C26—C27	180.0 (2)
O10—Cu2—N4—C22	77.12 (19)	C25—C26—C27—C28	0.8 (3)
N6—Cu2—N4—C33	175.18 (13)	C26—C27—C28—C32	−2.0 (3)
N5—Cu2—N4—C33	−4.43 (13)	C26—C27—C28—C29	179.6 (2)
O6—Cu2—N4—C33	90.39 (14)	C32—C28—C29—C30	1.2 (3)
O10—Cu2—N4—C33	−104.33 (13)	C27—C28—C29—C30	179.7 (2)
N6—Cu2—N5—C31	1.4 (5)	C28—C29—C30—C31	−0.4 (3)
O6—Cu2—N5—C31	76.98 (17)	C32—N5—C31—C30	0.9 (3)
O10—Cu2—N5—C31	−89.94 (17)	Cu2—N5—C31—C30	−172.86 (15)
N4—Cu2—N5—C31	179.58 (18)	C32—N5—C31—C34	179.94 (19)
N6—Cu2—N5—C32	−172.7 (3)	Cu2—N5—C31—C34	6.1 (3)
O6—Cu2—N5—C32	−97.06 (15)	C29—C30—C31—N5	−0.7 (3)
O10—Cu2—N5—C32	96.02 (15)	C29—C30—C31—C34	−179.7 (2)
N4—Cu2—N5—C32	5.54 (14)	C31—N5—C32—C28	−0.1 (3)
N5—Cu2—N6—C36	82.3 (4)	Cu2—N5—C32—C28	174.19 (15)
O6—Cu2—N6—C36	5.06 (14)	C31—N5—C32—C33	179.80 (19)
O10—Cu2—N6—C36	175.67 (16)	Cu2—N5—C32—C33	−5.9 (2)
N4—Cu2—N6—C36	−95.77 (15)	C29—C28—C32—N5	−1.0 (3)
N5—Cu2—N6—C40	−101.6 (4)	C27—C28—C32—N5	−179.53 (18)
O6—Cu2—N6—C40	−178.89 (16)	C29—C28—C32—C33	179.15 (19)
O10—Cu2—N6—C40	−8.27 (14)	C27—C28—C32—C33	0.6 (3)
N4—Cu2—N6—C40	80.28 (16)	C22—N4—C33—C25	1.2 (3)
C12—N2—C1—C2	1.7 (3)	Cu2—N4—C33—C25	−177.56 (16)
Cu1—N2—C1—C2	−177.74 (16)	C22—N4—C33—C32	−178.47 (18)
C12—N2—C1—C14	−178.02 (19)	Cu2—N4—C33—C32	2.7 (2)
Cu1—N2—C1—C14	2.5 (3)	C24—C25—C33—N4	−1.1 (3)
N2—C1—C2—C3	−2.8 (3)	C26—C25—C33—N4	177.31 (19)
C14—C1—C2—C3	176.9 (2)	C24—C25—C33—C32	178.58 (19)
C1—C2—C3—C4	1.5 (4)	C26—C25—C33—C32	−3.0 (3)
C2—C3—C4—C12	0.7 (3)	N5—C32—C33—N4	1.7 (3)
C2—C3—C4—C5	−179.6 (2)	C28—C32—C33—N4	−178.42 (18)
C12—C4—C5—C6	0.0 (3)	N5—C32—C33—C25	−178.02 (18)
C3—C4—C5—C6	−179.7 (2)	C28—C32—C33—C25	1.9 (3)
C4—C5—C6—C7	0.8 (3)	Cu2—O6—C35A—O7	−179.46 (18)
C5—C6—C7—C11	−0.2 (3)	Cu2—O6—C35A—C36	1.2 (2)
C5—C6—C7—C8	−179.7 (2)	C40—N6—C36—C37	−1.5 (3)
C11—C7—C8—C9	1.8 (3)	Cu2—N6—C36—C37	174.45 (15)
C6—C7—C8—C9	−178.7 (2)	C40—N6—C36—C35A	178.38 (17)
C7—C8—C9—C10	0.0 (3)	Cu2—N6—C36—C35A	−5.7 (2)
C11—N1—C10—C9	2.6 (3)	O7—C35A—C36—N6	−176.72 (19)
Cu1—N1—C10—C9	−174.66 (15)	O6—C35A—C36—N6	2.7 (2)
C11—N1—C10—C13	−176.24 (18)	O7—C35A—C36—C37	3.1 (3)
Cu1—N1—C10—C13	6.5 (3)	O6—C35A—C36—C37	−177.47 (19)
C8—C9—C10—N1	−2.2 (3)	N6—C36—C37—C38	−1.2 (3)
C8—C9—C10—C13	176.5 (2)	C35A—C36—C37—C38	178.94 (19)
C10—N1—C11—C7	−0.7 (3)	C36—C37—C38—O8	−177.71 (18)
Cu1—N1—C11—C7	176.72 (15)	C36—C37—C38—C39	2.9 (3)
C10—N1—C11—C12	179.48 (18)	O8—C38—C39—C40	178.69 (19)
Cu1—N1—C11—C12	−3.1 (2)	C37—C38—C39—C40	−1.9 (3)
C8—C7—C11—N1	−1.5 (3)	C36—N6—C40—C39	2.5 (3)
C6—C7—C11—N1	178.99 (19)	Cu2—N6—C40—C39	−173.44 (15)
C8—C7—C11—C12	178.31 (19)	C36—N6—C40—C41	−178.16 (17)
C6—C7—C11—C12	−1.2 (3)	Cu2—N6—C40—C41	5.9 (2)
C1—N2—C12—C4	0.6 (3)	C38—C39—C40—N6	−0.7 (3)
Cu1—N2—C12—C4	−179.87 (16)	C38—C39—C40—C41	−179.95 (19)
C1—N2—C12—C11	−179.53 (18)	Cu2—O10—C41—O9	171.00 (17)
Cu1—N2—C12—C11	0.0 (2)	Cu2—O10—C41—C40	−8.8 (2)
C3—C4—C12—N2	−1.8 (3)	N6—C40—C41—O9	−177.29 (18)
C5—C4—C12—N2	178.5 (2)	C39—C40—C41—O9	2.0 (3)
C3—C4—C12—C11	178.3 (2)	N6—C40—C41—O10	2.5 (3)
C5—C4—C12—C11	−1.4 (3)	C39—C40—C41—O10	−178.16 (19)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3C···O3S	0.84	1.75	2.572 (2)	166
O8—H8C···O2S	0.84	1.72	2.553 (2)	173
O1S—H1B···O9i	0.85	2.01	2.833 (2)	163
O1S—H1A···O2	0.85	2.01	2.794 (2)	153
O2S—H2A···O4ii	0.85	2.10	2.861 (2)	149
O2S—H2A···O7iii	0.85	2.64	3.136 (2)	118
O2S—H2B···O6Sii	0.85	1.81	2.649 (2)	168
O3S—H3B···O9iv	0.85	1.97	2.798 (2)	166
O3S—H3A···O5S	0.85	1.89	2.702 (2)	160
O4S—H4A···O9v	0.85	2.26	2.957 (3)	140
O4S—H4B···O2vi	0.85	1.97	2.811 (2)	171
O5S—H5B···O7vii	0.85	1.94	2.787 (2)	178
O5S—H5A···O7viii	0.85	2.15	2.938 (2)	154
O6S—H6A···O4S	0.85	1.95	2.764 (3)	160
O6S—H6B···O1Six	0.85	2.00	2.840 (2)	170
C13—H13B···Cg1x	0.98	2.76	3.372 (2)	121

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3C⋯O3S	0.84	1.75	2.572 (2)	166
O8—H8C⋯O2S	0.84	1.72	2.553 (2)	173
O1S—H1B⋯O9i	0.85	2.01	2.833 (2)	163
O1S—H1A⋯O2	0.85	2.01	2.794 (2)	153
O2S—H2A⋯O4ii	0.85	2.10	2.861 (2)	149
O2S—H2A⋯O7iii	0.85	2.64	3.136 (2)	118
O2S—H2B⋯O6Sii	0.85	1.81	2.649 (2)	168
O3S—H3B⋯O9iv	0.85	1.97	2.798 (2)	166
O3S—H3A⋯O5S	0.85	1.89	2.702 (2)	160
O4S—H4A⋯O9v	0.85	2.26	2.957 (3)	140
O4S—H4B⋯O2vi	0.85	1.97	2.811 (2)	171
O5S—H5B⋯O7vii	0.85	1.94	2.787 (2)	178
O5S—H5A⋯O7viii	0.85	2.15	2.938 (2)	154
O6S—H6A⋯O4S	0.85	1.95	2.764 (3)	160
O6S—H6B⋯O1Six	0.85	2.00	2.840 (2)	170
C13—H13B⋯Cg1x	0.98	2.76	3.372 (2)	121

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) ; (ix) ; (x) . Cg1 is the centroid of the N4/C22–C25,C33 ring.