A double stranded metal–organic assembly accommodating a pair of water trimers in the host cavity and catalysing Glaser coupling

A supramolecular compound, catena-poly{[Cu₂(1,3-μ₂-(1a))₂(μ₂-ter)₂(H₂O)₂]_n·(6H₂O)_n} (1) has been synthesized using (1a) [(1a = N¹,N³,N⁵-trimethyl-N¹,N³,N⁵-tris((pyridin-4-yl)methyl)-1,3,5-benzene tricarboxamide] and terephthalate (ter) as the pillaring unit by self-assembly. The terephthalate units are connected by copper(II) ions forming a single strand, while a pair of such strands are then linked by (1a) via two pyridyl terminal arms bound to copper(II) nodes on either side forming a one-dimensional double stranded assembly propagating along the c axis. The compound crystallizes in the Fdd2 space group. The cavity created in the interior of this double strand assembly trap six water molecules and are stabilized by hydrogen bonding with the host. The arrangement of the pair of acyclic water trimers in isolated cavities of (1) is such that it resembles a closed-bracket-like formation. The Hirshfeld surface analysis of (1) reveals the presence of strong intermolecular hydrogen-bonding interactions between one-dimensional ladder-like units and with the water trimer in the host cavity. The copper(II)-containing coordination polymer also acts as an efficient catalyst for the Glaser–Hay homo-coupling reaction.

Computing details

Data collection: PAL ADSC Quantum-210 ADX Program (Arvai & Nielsen, 1983); cell refinement: HKL3000sm(Otwinowski & Minor, 1997); data reduction: HKL3000sm(Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXT-2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL-2014/7 (Sheldrick, 2015b); molecular graphics: DIAMOND 3 (Putz, Brandenburg, 2007); software used to prepare material for publication: IUCr Word templates.

Figures

(I)

Crystal data

C38H36CuN6O8·3(H2O)	Dx = 1.323 Mg m^−3
Mr = 822.31	Synchrotron radiation, λ = 0.62996 Å
Orthorhombic, Fdd2	Cell parameters from 132372 reflections
a = 27.000 (5) Å	θ = 0.4–33.6°
b = 56.855 (11) Å	µ = 0.43 mm^−1
c = 10.756 (2) Å	T = 100 K
V = 16512 (6) Å^3	Block, blue
Z = 16	0.15 × 0.04 × 0.04 mm
F(000) = 6864

Data collection

ADSC Q210 CCD area detector diffractometer	10839 reflections with I > 2σ(I)
Radiation source: PLSII 2D bending magnet	Rint = 0.022
ω scan	θmax = 26.0°, θmin = 2.0°
Absorption correction: empirical (using intensity measurements) HKL3000sm SCALEPACK(Otwinowski & Minor, 1997)	h = −37→37
Tmin = 0.938, Tmax = 0.983	k = −78→78
42082 measured reflections	l = −13→13
10942 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.034	w = 1/[σ^2(Fo^2) + (0.0597P)^2 + 37.0991P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.095	(Δ/σ)max = 0.009
S = 1.06	Δρmax = 1.43 e Å^−3
10942 reflections	Δρmin = −0.80 e Å^−3
526 parameters	Absolute structure: Refined as a perfect inversion twin.
10 restraints	Absolute structure parameter: 0.5

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. Refined as a 2-component perfect inversion twin.

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

	x	y	z	Uiso*/Ueq
Cu1	0.36791 (2)	0.19590 (2)	−0.07832 (3)	0.00916 (7)
O1	0.37261 (7)	0.19809 (4)	0.7412 (2)	0.0153 (4)
O2	0.30846 (9)	0.22259 (4)	0.7501 (2)	0.0270 (5)
O3	0.36300 (8)	0.19313 (4)	0.1019 (2)	0.0170 (4)
O4	0.30998 (10)	0.22318 (5)	0.0948 (2)	0.0320 (5)
O5	0.43396 (6)	0.17007 (3)	−0.0796 (2)	0.0180 (3)
H1O5	0.4355 (13)	0.1573 (4)	−0.117 (3)	0.022*
H2O5	0.4624 (7)	0.1736 (6)	−0.056 (4)	0.022*
C1	0.33612 (10)	0.20868 (5)	0.1532 (3)	0.0188 (5)
C2	0.33657 (10)	0.20894 (5)	0.2924 (3)	0.0175 (5)
C3	0.36394 (9)	0.19231 (5)	0.3583 (3)	0.0142 (5)
H3	0.3825	0.1808	0.3147	0.017*
C4	0.36417 (9)	0.19256 (5)	0.4877 (3)	0.0137 (5)
H4	0.3829	0.1812	0.5322	0.016*
C5	0.30947 (14)	0.22589 (6)	0.3574 (3)	0.0317 (7)
H5	0.2908	0.2373	0.3131	0.038*
C6	0.33850 (9)	0.21030 (5)	0.6912 (2)	0.0166 (5)
C7	0.33702 (10)	0.20940 (5)	0.5518 (3)	0.0170 (5)
C8	0.30972 (14)	0.22609 (6)	0.4854 (3)	0.0316 (7)
H8	0.2912	0.2377	0.5289	0.038*
O1L	0.50157 (10)	0.31556 (4)	−0.1230 (2)	0.0284 (5)
O2L	0.33608 (8)	0.37009 (5)	0.2000 (2)	0.0298 (5)
O3L	0.55878 (7)	0.37535 (3)	0.3370 (2)	0.0205 (4)
N1L	0.51032 (8)	0.29601 (4)	0.0594 (2)	0.0156 (4)
N2L	0.41584 (7)	0.22296 (3)	−0.05215 (19)	0.0118 (4)
N3L	0.34167 (7)	0.37725 (4)	−0.0071 (2)	0.0152 (4)
N4L	0.18657 (7)	0.32829 (4)	−0.0929 (2)	0.0136 (4)
N5L	0.53332 (7)	0.40872 (4)	0.2435 (2)	0.0167 (4)
N6L	0.71891 (8)	0.42544 (4)	0.2568 (2)	0.0189 (4)
C1L	0.41421 (9)	0.24320 (4)	−0.1146 (3)	0.0181 (5)
H1L	0.3875	0.2458	−0.1705	0.022*
C2L	0.44985 (10)	0.26067 (4)	−0.1016 (3)	0.0202 (5)
H2L	0.4471	0.2750	−0.1466	0.024*
C3L	0.48967 (9)	0.25690 (4)	−0.0218 (3)	0.0170 (5)
C4L	0.49068 (10)	0.23612 (5)	0.0443 (3)	0.0238 (6)
H4L	0.5170	0.2330	0.1006	0.029*
C5L	0.45306 (10)	0.21969 (4)	0.0282 (3)	0.0197 (5)
H5L	0.4538	0.2056	0.0759	0.024*
C6L	0.52969 (9)	0.27525 (4)	−0.0047 (3)	0.0209 (5)
H6L1	0.5573	0.2685	0.0442	0.025*
H6L2	0.5429	0.2799	−0.0870	0.025*
C7L	0.49809 (9)	0.31503 (4)	−0.0086 (3)	0.0150 (4)
C8L	0.50281 (13)	0.29393 (5)	0.1925 (3)	0.0263 (6)
H8L1	0.5346	0.2958	0.2354	0.039*
H8L2	0.4889	0.2784	0.2116	0.039*
H8L3	0.4799	0.3062	0.2205	0.039*
C9L	0.48018 (8)	0.33638 (4)	0.0600 (2)	0.0122 (4)
C10L	0.43072 (8)	0.34312 (4)	0.0488 (2)	0.0138 (4)
H10L	0.4083	0.3338	0.0022	0.017*
C11L	0.17680 (9)	0.35058 (4)	−0.1239 (3)	0.0175 (5)
H11L	0.1458	0.3541	−0.1614	0.021*
C12L	0.20994 (9)	0.36876 (4)	−0.1036 (3)	0.0186 (5)
H12L	0.2015	0.3844	−0.1269	0.022*
C13L	0.25551 (8)	0.36410 (4)	−0.0492 (2)	0.0140 (4)
C14L	0.26688 (9)	0.34069 (5)	−0.0264 (3)	0.0245 (6)
H14L	0.2987	0.3365	0.0041	0.029*
C15L	0.23169 (10)	0.32346 (5)	−0.0483 (3)	0.0249 (6)
H15L	0.2399	0.3075	−0.0310	0.030*
C16L	0.28961 (9)	0.38405 (4)	−0.0143 (3)	0.0191 (5)
H16A	0.2861	0.3968	−0.0765	0.023*
H16B	0.2792	0.3904	0.0673	0.023*
C17L	0.36060 (9)	0.37070 (5)	0.1038 (3)	0.0163 (5)
C18L	0.36987 (10)	0.37957 (6)	−0.1218 (3)	0.0231 (5)
H18A	0.4042	0.3747	−0.1072	0.035*
H18B	0.3692	0.3960	−0.1494	0.035*
H18C	0.3552	0.3695	−0.1861	0.035*
C19L	0.41446 (8)	0.36363 (4)	0.1064 (2)	0.0128 (4)
C20L	0.44744 (8)	0.37771 (4)	0.1725 (3)	0.0138 (4)
H20L	0.4362	0.3917	0.2114	0.017*
C21L	0.68728 (9)	0.41612 (5)	0.1745 (3)	0.0197 (5)
H21L	0.7003	0.4105	0.0980	0.024*
C22L	0.63665 (9)	0.41420 (5)	0.1941 (3)	0.0175 (5)
H22L	0.6159	0.4072	0.1333	0.021*
C23L	0.61703 (8)	0.42272 (4)	0.3044 (3)	0.0152 (4)
C24L	0.64958 (9)	0.43212 (5)	0.3920 (3)	0.0177 (5)
H24L	0.6376	0.4377	0.4696	0.021*
C25L	0.69983 (9)	0.43316 (5)	0.3643 (3)	0.0182 (5)
H25L	0.7217	0.4396	0.4245	0.022*
C26L	0.56222 (9)	0.42227 (4)	0.3330 (3)	0.0190 (5)
H26A	0.5573	0.4155	0.4168	0.023*
H26B	0.5496	0.4386	0.3346	0.023*
C27L	0.53261 (8)	0.38518 (4)	0.2581 (3)	0.0141 (4)
C28L	0.51506 (10)	0.42110 (5)	0.1339 (3)	0.0252 (6)
H28A	0.5095	0.4098	0.0665	0.038*
H28B	0.5395	0.4328	0.1076	0.038*
H28C	0.4838	0.4290	0.1541	0.038*
C29L	0.49724 (8)	0.37113 (4)	0.1813 (3)	0.0125 (4)
C30L	0.51340 (8)	0.35023 (4)	0.1271 (2)	0.0128 (4)
H30L	0.5469	0.3454	0.1358	0.015*
O1W	0.29831 (13)	0.27307 (7)	0.1233 (4)	0.0557 (9)
H1O1	0.2667	0.2751	0.1342	0.067*
H2O1	0.2975	0.2599	0.0823	0.067*
O2W	0.20414 (11)	0.22621 (5)	0.7370 (3)	0.0429 (7)
H1O2	0.2339 (9)	0.2222 (8)	0.752 (6)	0.051*
H2O2	0.2026 (17)	0.2407 (4)	0.757 (5)	0.051*
O3W	0.14946 (10)	0.20195 (5)	0.9284 (4)	0.0406 (6)
H1O3	0.1684 (16)	0.2079 (8)	0.873 (3)	0.049*
H2O3	0.1585 (18)	0.2107 (8)	0.991 (3)	0.049*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.00831 (11)	0.01367 (12)	0.00551 (13)	−0.00198 (9)	0.00044 (9)	0.00018 (9)
O1	0.0149 (8)	0.0244 (9)	0.0065 (10)	−0.0009 (6)	−0.0003 (6)	0.0016 (6)
O2	0.0296 (11)	0.0420 (12)	0.0095 (11)	0.0152 (9)	0.0001 (8)	−0.0031 (8)
O3	0.0210 (9)	0.0225 (9)	0.0075 (10)	−0.0025 (7)	0.0022 (6)	0.0012 (7)
O4	0.0468 (14)	0.0392 (12)	0.0100 (12)	0.0187 (11)	−0.0018 (9)	0.0015 (8)
O5	0.0099 (7)	0.0178 (7)	0.0262 (10)	0.0008 (6)	−0.0028 (7)	−0.0026 (8)
C1	0.0229 (11)	0.0251 (11)	0.0085 (14)	0.0018 (9)	0.0009 (8)	0.0007 (9)
C2	0.0208 (11)	0.0244 (12)	0.0072 (12)	0.0022 (9)	0.0012 (8)	0.0005 (9)
C3	0.0124 (10)	0.0220 (11)	0.0083 (13)	−0.0003 (8)	0.0008 (8)	−0.0007 (9)
C4	0.0113 (10)	0.0215 (11)	0.0083 (14)	0.0001 (8)	−0.0006 (8)	0.0013 (9)
C5	0.0447 (18)	0.0391 (17)	0.0112 (16)	0.0229 (15)	−0.0006 (12)	0.0022 (11)
C6	0.0171 (10)	0.0240 (11)	0.0088 (13)	0.0004 (9)	−0.0001 (8)	0.0010 (8)
C7	0.0164 (10)	0.0263 (12)	0.0082 (12)	0.0037 (9)	−0.0003 (8)	0.0001 (9)
C8	0.0440 (18)	0.0409 (17)	0.0100 (16)	0.0256 (15)	0.0012 (11)	−0.0009 (11)
O1L	0.0457 (13)	0.0231 (10)	0.0165 (11)	0.0016 (9)	0.0023 (9)	−0.0018 (8)
O2L	0.0146 (9)	0.0542 (14)	0.0206 (13)	0.0075 (9)	0.0020 (7)	0.0031 (9)
O3L	0.0174 (8)	0.0201 (8)	0.0240 (11)	−0.0006 (7)	−0.0120 (7)	−0.0002 (7)
N1L	0.0151 (9)	0.0126 (8)	0.0191 (12)	−0.0007 (7)	−0.0056 (7)	−0.0028 (7)
N2L	0.0115 (8)	0.0132 (8)	0.0107 (11)	−0.0016 (6)	−0.0007 (6)	−0.0016 (6)
N3L	0.0074 (8)	0.0178 (9)	0.0203 (12)	−0.0006 (7)	−0.0052 (7)	0.0028 (8)
N4L	0.0077 (8)	0.0179 (9)	0.0152 (11)	−0.0026 (6)	−0.0005 (7)	0.0008 (7)
N5L	0.0093 (8)	0.0153 (9)	0.0255 (12)	−0.0006 (7)	−0.0050 (8)	−0.0028 (8)
N6L	0.0119 (9)	0.0229 (10)	0.0219 (12)	−0.0026 (7)	0.0010 (8)	0.0003 (8)
C1L	0.0150 (10)	0.0179 (10)	0.0213 (14)	−0.0024 (8)	−0.0065 (8)	0.0049 (9)
C2L	0.0184 (11)	0.0153 (10)	0.0269 (16)	−0.0035 (8)	−0.0042 (9)	0.0040 (9)
C3L	0.0117 (10)	0.0131 (9)	0.0260 (14)	−0.0002 (8)	−0.0010 (9)	−0.0055 (9)
C4L	0.0199 (12)	0.0165 (11)	0.0348 (17)	−0.0036 (9)	−0.0152 (11)	0.0005 (10)
C5L	0.0214 (12)	0.0138 (10)	0.0240 (15)	−0.0036 (9)	−0.0106 (10)	0.0012 (9)
C6L	0.0119 (10)	0.0142 (10)	0.0367 (17)	−0.0009 (8)	−0.0015 (10)	−0.0067 (10)
C7L	0.0155 (10)	0.0158 (10)	0.0136 (12)	−0.0023 (8)	−0.0016 (8)	−0.0018 (8)
C8L	0.0382 (15)	0.0179 (11)	0.0229 (17)	−0.0014 (10)	−0.0103 (11)	0.0034 (10)
C9L	0.0112 (9)	0.0130 (9)	0.0124 (12)	−0.0007 (7)	−0.0036 (8)	0.0002 (7)
C10L	0.0095 (9)	0.0179 (10)	0.0142 (12)	−0.0026 (8)	−0.0036 (8)	0.0002 (8)
C11L	0.0092 (9)	0.0213 (11)	0.0220 (13)	−0.0041 (8)	−0.0073 (8)	0.0079 (9)
C12L	0.0108 (10)	0.0179 (10)	0.0272 (16)	−0.0026 (8)	−0.0079 (9)	0.0081 (9)
C13L	0.0067 (8)	0.0153 (9)	0.0199 (13)	0.0002 (7)	−0.0037 (7)	0.0014 (8)
C14L	0.0111 (10)	0.0162 (11)	0.0460 (18)	0.0009 (8)	−0.0121 (11)	0.0030 (11)
C15L	0.0120 (10)	0.0165 (10)	0.046 (2)	−0.0010 (8)	−0.0104 (10)	0.0022 (10)
C16L	0.0084 (9)	0.0167 (10)	0.0320 (16)	0.0006 (8)	−0.0091 (9)	−0.0012 (9)
C17L	0.0077 (9)	0.0206 (11)	0.0206 (14)	0.0000 (8)	−0.0041 (8)	0.0007 (9)
C18L	0.0207 (12)	0.0305 (14)	0.0180 (14)	0.0027 (10)	−0.0041 (9)	0.0061 (10)
C19L	0.0066 (8)	0.0189 (10)	0.0130 (12)	−0.0007 (7)	−0.0040 (7)	0.0018 (8)
C20L	0.0086 (9)	0.0166 (9)	0.0162 (11)	0.0006 (7)	−0.0029 (9)	−0.0004 (9)
C21L	0.0148 (10)	0.0260 (11)	0.0182 (13)	0.0000 (8)	0.0034 (10)	−0.0018 (10)
C22L	0.0131 (10)	0.0225 (11)	0.0168 (14)	−0.0009 (8)	−0.0017 (8)	−0.0044 (9)
C23L	0.0105 (9)	0.0169 (10)	0.0182 (13)	−0.0005 (7)	−0.0002 (8)	−0.0037 (8)
C24L	0.0135 (10)	0.0221 (11)	0.0175 (14)	−0.0036 (8)	0.0007 (8)	−0.0057 (8)
C25L	0.0122 (10)	0.0226 (11)	0.0196 (13)	−0.0039 (8)	−0.0023 (8)	−0.0007 (9)
C26L	0.0103 (9)	0.0186 (11)	0.0281 (15)	−0.0019 (8)	0.0009 (9)	−0.0109 (10)
C27L	0.0077 (9)	0.0162 (10)	0.0185 (12)	−0.0001 (7)	−0.0031 (8)	−0.0028 (8)
C28L	0.0147 (11)	0.0225 (12)	0.0382 (18)	−0.0009 (9)	−0.0083 (10)	0.0092 (11)
C29L	0.0083 (8)	0.0155 (9)	0.0138 (11)	−0.0010 (7)	−0.0033 (8)	−0.0010 (8)
C30L	0.0086 (9)	0.0146 (9)	0.0152 (11)	0.0001 (7)	−0.0027 (7)	−0.0005 (8)
O1W	0.0518 (18)	0.0547 (19)	0.061 (2)	0.0050 (15)	0.0125 (16)	0.0071 (16)
O2W	0.0308 (13)	0.0393 (14)	0.059 (2)	0.0002 (11)	−0.0050 (12)	−0.0004 (13)
O3W	0.0322 (12)	0.0349 (12)	0.0546 (18)	−0.0004 (9)	−0.0063 (13)	−0.0012 (13)

Geometric parameters (Å, º)

Cu1—O1^i	1.949 (2)	C6L—H6L1	0.9900
Cu1—O3	1.949 (2)	C6L—H6L2	0.9900
Cu1—N4L^ii	2.0198 (19)	C7L—C9L	1.500 (3)
Cu1—N2L	2.030 (2)	C8L—H8L1	0.9800
Cu1—O5	2.3104 (17)	C8L—H8L2	0.9800
O1—C6	1.272 (3)	C8L—H8L3	0.9800
O1—Cu1^iii	1.949 (2)	C9L—C10L	1.395 (3)
O2—C6	1.245 (3)	C9L—C30L	1.395 (3)
O3—C1	1.270 (3)	C10L—C19L	1.391 (3)
O4—C1	1.254 (4)	C10L—H10L	0.9500
O5—H1O5	0.832 (13)	C11L—C12L	1.384 (3)
O5—H2O5	0.833 (13)	C11L—H11L	0.9500
C1—C2	1.497 (4)	C12L—C13L	1.388 (3)
C2—C3	1.394 (4)	C12L—H12L	0.9500
C2—C5	1.397 (4)	C13L—C14L	1.388 (3)
C3—C4	1.392 (3)	C13L—C16L	1.508 (3)
C3—H3	0.9500	C14L—C15L	1.385 (3)
C4—C7	1.389 (4)	C14L—H14L	0.9500
C4—H4	0.9500	C15L—H15L	0.9500
C5—C8	1.377 (4)	C16L—H16A	0.9900
C5—H5	0.9500	C16L—H16B	0.9900
C6—C7	1.501 (4)	C17L—C19L	1.509 (3)
C7—C8	1.398 (4)	C18L—H18A	0.9800
C8—H8	0.9500	C18L—H18B	0.9800
O1L—C7L	1.234 (4)	C18L—H18C	0.9800
O2L—C17L	1.229 (3)	C19L—C20L	1.393 (3)
O3L—C27L	1.238 (3)	C20L—C29L	1.399 (3)
N1L—C7L	1.346 (3)	C20L—H20L	0.9500
N1L—C8L	1.452 (4)	C21L—C22L	1.388 (3)
N1L—C6L	1.463 (3)	C21L—H21L	0.9500
N2L—C1L	1.333 (3)	C22L—C23L	1.387 (4)
N2L—C5L	1.338 (3)	C22L—H22L	0.9500
N3L—C17L	1.350 (3)	C23L—C24L	1.395 (3)
N3L—C18L	1.456 (4)	C23L—C26L	1.512 (3)
N3L—C16L	1.460 (3)	C24L—C25L	1.390 (3)
N4L—C11L	1.337 (3)	C24L—H24L	0.9500
N4L—C15L	1.338 (3)	C25L—H25L	0.9500
N4L—Cu1^ii	2.0196 (19)	C26L—H26A	0.9900
N5L—C27L	1.347 (3)	C26L—H26B	0.9900
N5L—C28L	1.459 (4)	C27L—C29L	1.494 (3)
N5L—C26L	1.459 (3)	C28L—H28A	0.9800
N6L—C25L	1.340 (4)	C28L—H28B	0.9800
N6L—C21L	1.340 (4)	C28L—H28C	0.9800
C1L—C2L	1.390 (3)	C29L—C30L	1.394 (3)
C1L—H1L	0.9500	C30L—H30L	0.9500
C2L—C3L	1.393 (4)	O1W—H1O1	0.868 (4)
C2L—H2L	0.9500	O1W—H2O1	0.869 (4)
C3L—C4L	1.379 (4)	O2W—H1O2	0.848 (14)
C3L—C6L	1.513 (3)	O2W—H2O2	0.850 (14)
C4L—C5L	1.391 (3)	O3W—H1O3	0.858 (14)
C4L—H4L	0.9500	O3W—H2O3	0.868 (14)
C5L—H5L	0.9500
O1^i—Cu1—O3	179.02 (10)	H8L1—C8L—H8L3	109.5
O1^i—Cu1—N4L^ii	90.78 (9)	H8L2—C8L—H8L3	109.5
O3—Cu1—N4L^ii	88.43 (9)	C10L—C9L—C30L	120.3 (2)
O1^i—Cu1—N2L	92.76 (8)	C10L—C9L—C7L	119.3 (2)
O3—Cu1—N2L	88.09 (9)	C30L—C9L—C7L	120.3 (2)
N4L^ii—Cu1—N2L	172.33 (8)	C19L—C10L—C9L	119.6 (2)
O1^i—Cu1—O5	89.10 (8)	C19L—C10L—H10L	120.2
O3—Cu1—O5	90.41 (8)	C9L—C10L—H10L	120.2
N4L^ii—Cu1—O5	97.40 (7)	N4L—C11L—C12L	122.8 (2)
N2L—Cu1—O5	89.45 (7)	N4L—C11L—H11L	118.6
C6—O1—Cu1^iii	114.14 (18)	C12L—C11L—H11L	118.6
C1—O3—Cu1	114.50 (19)	C11L—C12L—C13L	119.8 (2)
Cu1—O5—H1O5	127 (2)	C11L—C12L—H12L	120.1
Cu1—O5—H2O5	124 (2)	C13L—C12L—H12L	120.1
H1O5—O5—H2O5	108 (3)	C14L—C13L—C12L	117.0 (2)
O4—C1—O3	124.2 (3)	C14L—C13L—C16L	122.8 (2)
O4—C1—C2	119.9 (3)	C12L—C13L—C16L	120.2 (2)
O3—C1—C2	115.9 (2)	C15L—C14L—C13L	119.8 (2)
C3—C2—C5	119.4 (3)	C15L—C14L—H14L	120.1
C3—C2—C1	120.4 (2)	C13L—C14L—H14L	120.1
C5—C2—C1	120.2 (3)	N4L—C15L—C14L	122.7 (2)
C4—C3—C2	120.3 (3)	N4L—C15L—H15L	118.6
C4—C3—H3	119.9	C14L—C15L—H15L	118.6
C2—C3—H3	119.9	N3L—C16L—C13L	113.7 (2)
C7—C4—C3	120.1 (3)	N3L—C16L—H16A	108.8
C7—C4—H4	120.0	C13L—C16L—H16A	108.8
C3—C4—H4	120.0	N3L—C16L—H16B	108.8
C8—C5—C2	120.2 (3)	C13L—C16L—H16B	108.8
C8—C5—H5	119.9	H16A—C16L—H16B	107.7
C2—C5—H5	119.9	O2L—C17L—N3L	123.2 (2)
O2—C6—O1	124.2 (3)	O2L—C17L—C19L	119.7 (2)
O2—C6—C7	120.7 (2)	N3L—C17L—C19L	117.1 (2)
O1—C6—C7	115.1 (2)	N3L—C18L—H18A	109.5
C4—C7—C8	119.5 (3)	N3L—C18L—H18B	109.5
C4—C7—C6	120.4 (2)	H18A—C18L—H18B	109.5
C8—C7—C6	120.1 (3)	N3L—C18L—H18C	109.5
C5—C8—C7	120.5 (3)	H18A—C18L—H18C	109.5
C5—C8—H8	119.7	H18B—C18L—H18C	109.5
C7—C8—H8	119.7	C10L—C19L—C20L	120.5 (2)
C7L—N1L—C8L	124.6 (2)	C10L—C19L—C17L	121.3 (2)
C7L—N1L—C6L	118.7 (2)	C20L—C19L—C17L	118.2 (2)
C8L—N1L—C6L	116.7 (2)	C19L—C20L—C29L	119.7 (2)
C1L—N2L—C5L	118.0 (2)	C19L—C20L—H20L	120.1
C1L—N2L—Cu1	124.26 (17)	C29L—C20L—H20L	120.1
C5L—N2L—Cu1	117.58 (17)	N6L—C21L—C22L	123.9 (3)
C17L—N3L—C18L	125.1 (2)	N6L—C21L—H21L	118.0
C17L—N3L—C16L	119.0 (2)	C22L—C21L—H21L	118.0
C18L—N3L—C16L	115.8 (2)	C23L—C22L—C21L	118.6 (2)
C11L—N4L—C15L	117.6 (2)	C23L—C22L—H22L	120.7
C11L—N4L—Cu1^ii	121.42 (16)	C21L—C22L—H22L	120.7
C15L—N4L—Cu1^ii	119.71 (18)	C22L—C23L—C24L	118.1 (2)
C27L—N5L—C28L	124.7 (2)	C22L—C23L—C26L	122.8 (2)
C27L—N5L—C26L	117.1 (2)	C24L—C23L—C26L	119.1 (2)
C28L—N5L—C26L	117.3 (2)	C25L—C24L—C23L	119.1 (2)
C25L—N6L—C21L	117.1 (2)	C25L—C24L—H24L	120.4
N2L—C1L—C2L	122.9 (2)	C23L—C24L—H24L	120.4
N2L—C1L—H1L	118.6	N6L—C25L—C24L	123.1 (2)
C2L—C1L—H1L	118.6	N6L—C25L—H25L	118.5
C1L—C2L—C3L	119.1 (2)	C24L—C25L—H25L	118.5
C1L—C2L—H2L	120.4	N5L—C26L—C23L	113.5 (2)
C3L—C2L—H2L	120.4	N5L—C26L—H26A	108.9
C4L—C3L—C2L	117.7 (2)	C23L—C26L—H26A	108.9
C4L—C3L—C6L	120.9 (2)	N5L—C26L—H26B	108.9
C2L—C3L—C6L	121.3 (2)	C23L—C26L—H26B	108.9
C3L—C4L—C5L	119.8 (2)	H26A—C26L—H26B	107.7
C3L—C4L—H4L	120.1	O3L—C27L—N5L	121.3 (2)
C5L—C4L—H4L	120.1	O3L—C27L—C29L	120.2 (2)
N2L—C5L—C4L	122.4 (2)	N5L—C27L—C29L	118.4 (2)
N2L—C5L—H5L	118.8	N5L—C28L—H28A	109.5
C4L—C5L—H5L	118.8	N5L—C28L—H28B	109.5
N1L—C6L—C3L	111.0 (2)	H28A—C28L—H28B	109.5
N1L—C6L—H6L1	109.4	N5L—C28L—H28C	109.5
C3L—C6L—H6L1	109.4	H28A—C28L—H28C	109.5
N1L—C6L—H6L2	109.4	H28B—C28L—H28C	109.5
C3L—C6L—H6L2	109.4	C30L—C29L—C20L	120.0 (2)
H6L1—C6L—H6L2	108.0	C30L—C29L—C27L	119.1 (2)
O1L—C7L—N1L	122.8 (3)	C20L—C29L—C27L	120.6 (2)
O1L—C7L—C9L	119.7 (2)	C29L—C30L—C9L	119.8 (2)
N1L—C7L—C9L	117.5 (2)	C29L—C30L—H30L	120.1
N1L—C8L—H8L1	109.5	C9L—C30L—H30L	120.1
N1L—C8L—H8L2	109.5	H1O1—O1W—H2O1	99.2 (4)
H8L1—C8L—H8L2	109.5	H1O2—O2W—H2O2	105 (3)
N1L—C8L—H8L3	109.5	H1O3—O3W—H2O3	98 (3)
Cu1—O3—C1—O4	7.8 (4)	C11L—C12L—C13L—C14L	4.8 (4)
Cu1—O3—C1—C2	−172.66 (18)	C11L—C12L—C13L—C16L	−173.5 (3)
O4—C1—C2—C3	177.4 (3)	C12L—C13L—C14L—C15L	−5.3 (5)
O3—C1—C2—C3	−2.1 (4)	C16L—C13L—C14L—C15L	173.0 (3)
O4—C1—C2—C5	−2.6 (5)	C11L—N4L—C15L—C14L	4.1 (5)
O3—C1—C2—C5	177.9 (3)	Cu1^ii—N4L—C15L—C14L	−163.4 (3)
C5—C2—C3—C4	0.2 (5)	C13L—C14L—C15L—N4L	0.9 (5)
C1—C2—C3—C4	−179.8 (3)	C17L—N3L—C16L—C13L	−93.5 (3)
C2—C3—C4—C7	0.1 (5)	C18L—N3L—C16L—C13L	90.1 (3)
C3—C2—C5—C8	−0.2 (6)	C14L—C13L—C16L—N3L	25.5 (4)
C1—C2—C5—C8	179.8 (4)	C12L—C13L—C16L—N3L	−156.2 (3)
Cu1^iii—O1—C6—O2	9.6 (4)	C18L—N3L—C17L—O2L	176.2 (3)
Cu1^iii—O1—C6—C7	−171.58 (18)	C16L—N3L—C17L—O2L	0.2 (4)
C3—C4—C7—C8	−0.3 (5)	C18L—N3L—C17L—C19L	−4.5 (4)
C3—C4—C7—C6	−177.9 (3)	C16L—N3L—C17L—C19L	179.5 (2)
O2—C6—C7—C4	−168.1 (3)	C9L—C10L—C19L—C20L	1.5 (4)
O1—C6—C7—C4	13.0 (4)	C9L—C10L—C19L—C17L	−175.9 (2)
O2—C6—C7—C8	14.3 (4)	O2L—C17L—C19L—C10L	110.8 (3)
O1—C6—C7—C8	−164.6 (3)	N3L—C17L—C19L—C10L	−68.5 (3)
C2—C5—C8—C7	0.0 (7)	O2L—C17L—C19L—C20L	−66.6 (3)
C4—C7—C8—C5	0.2 (6)	N3L—C17L—C19L—C20L	114.0 (3)
C6—C7—C8—C5	177.8 (4)	C10L—C19L—C20L—C29L	−0.2 (4)
C5L—N2L—C1L—C2L	1.3 (4)	C17L—C19L—C20L—C29L	177.3 (2)
Cu1—N2L—C1L—C2L	−174.8 (2)	C25L—N6L—C21L—C22L	0.4 (4)
N2L—C1L—C2L—C3L	1.2 (4)	N6L—C21L—C22L—C23L	1.1 (4)
C1L—C2L—C3L—C4L	−2.3 (4)	C21L—C22L—C23L—C24L	−2.1 (4)
C1L—C2L—C3L—C6L	179.6 (3)	C21L—C22L—C23L—C26L	177.8 (3)
C2L—C3L—C4L—C5L	1.0 (4)	C22L—C23L—C24L—C25L	1.7 (4)
C6L—C3L—C4L—C5L	179.0 (3)	C26L—C23L—C24L—C25L	−178.2 (2)
C1L—N2L—C5L—C4L	−2.7 (4)	C21L—N6L—C25L—C24L	−0.8 (4)
Cu1—N2L—C5L—C4L	173.6 (2)	C23L—C24L—C25L—N6L	−0.2 (4)
C3L—C4L—C5L—N2L	1.6 (5)	C27L—N5L—C26L—C23L	81.1 (3)
C7L—N1L—C6L—C3L	−99.9 (3)	C28L—N5L—C26L—C23L	−88.3 (3)
C8L—N1L—C6L—C3L	76.4 (3)	C22L—C23L—C26L—N5L	9.4 (4)
C4L—C3L—C6L—N1L	−109.8 (3)	C24L—C23L—C26L—N5L	−170.8 (2)
C2L—C3L—C6L—N1L	68.2 (4)	C28L—N5L—C27L—O3L	162.3 (3)
C8L—N1L—C7L—O1L	−174.4 (3)	C26L—N5L—C27L—O3L	−6.2 (4)
C6L—N1L—C7L—O1L	1.5 (4)	C28L—N5L—C27L—C29L	−21.1 (4)
C8L—N1L—C7L—C9L	6.4 (4)	C26L—N5L—C27L—C29L	170.4 (2)
C6L—N1L—C7L—C9L	−177.7 (2)	C19L—C20L—C29L—C30L	−1.8 (4)
O1L—C7L—C9L—C10L	69.8 (3)	C19L—C20L—C29L—C27L	−176.3 (2)
N1L—C7L—C9L—C10L	−110.9 (3)	O3L—C27L—C29L—C30L	−46.3 (4)
O1L—C7L—C9L—C30L	−105.8 (3)	N5L—C27L—C29L—C30L	137.0 (3)
N1L—C7L—C9L—C30L	73.5 (3)	O3L—C27L—C29L—C20L	128.2 (3)
C30L—C9L—C10L—C19L	−0.8 (4)	N5L—C27L—C29L—C20L	−48.5 (4)
C7L—C9L—C10L—C19L	−176.4 (2)	C20L—C29L—C30L—C9L	2.5 (4)
C15L—N4L—C11L—C12L	−4.6 (4)	C27L—C29L—C30L—C9L	177.0 (2)
Cu1^ii—N4L—C11L—C12L	162.6 (2)	C10L—C9L—C30L—C29L	−1.2 (4)
N4L—C11L—C12L—C13L	0.1 (5)	C7L—C9L—C30L—C29L	174.4 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H2O1···O4	0.869 (4)	2.120 (3)	2.871 (5)	144.3 (3)
O2W—H1O2···O2	0.85 (1)	2.01 (2)	2.828 (4)	160 (5)
O3W—H1O3···O2W	0.86 (1)	2.04 (2)	2.885 (5)	170 (5)
O5—H1O5···O3L^iv	0.83 (1)	1.93 (2)	2.741 (3)	166 (4)
O5—H2O5···N6L^v	0.83 (1)	1.98 (2)	2.799 (3)	169 (4)
O1W—H1O1···O4^ii	0.868 (4)	2.117 (3)	2.948 (5)	160.1 (3)
O2W—H2O2···O2^ii	0.85 (1)	2.11 (2)	2.934 (4)	163 (5)
O3W—H2O3···O1W^vi	0.87 (1)	2.06 (2)	2.898 (5)	161 (5)

Symmetry codes: (ii) −x+1/2, −y+1/2, z; (iv) −x+1, −y+1/2, z−1/2; (v) −x+5/4, y−1/4, z−1/4; (vi) −x+1/2, −y+1/2, z+1.