cis-Bis(l-DOPA-κ2N,O)copper(II) monohydrate: synthesis, crystal structure, and approaches to the analysis of pseudosymmetry

O'Brien, P.; Poyner, E.A.; Alraddadi, T.S.; Hursthouse, M.B.; Foxman, B.M.

doi:10.1107/S2053229621006082

cis-Bis(L-DOPA-κ²N,O)copper(II) monohydrate: synthesis, crystal structure, and approaches to the analysis of pseudosymmetry

P. O'Brien, E. A. Poyner, T. S. Alraddadi, M. B. Hursthouse and B. M. Foxman

The crystal structure of the cis isomer of cis-bis(L-DOPA-κ²N,O)copper(II) monohydrate (L-DOPA is 3,4-dihydroxy-L-phenylalanine) (CuLD), [Cu(C₉H₁₀NO₄)₂]·H₂O, is a singular example of a structurally characterized, homoleptic, crystalline metal L-DOPA complex. CuLD crystallizes in the space group P2₁, with Z′ = 2. The two independent molecules are square planar, and are interconnected by a linear hydrogen-bonded chain containing 12 independent hydrogen bonds. The copper ions in both molecules have weak apical intermolecular Cu

O interactions [2.739 (2) and 2.973 (2) Å] with catechol –OH groups. A survey of the Cambridge Structural Database suggested that cis and trans isomers of Cu(NH₂–C–CO₂)₂ amino acid complexes are equally likely to occur. 12 strong O—H

O and N—H

O hydrogen bonds stabilize an unusual linear arrangement of the Cu complexes. The Cu

Cu′ distances along the chain are nearly equal [5.0739 (3) and 5.1107 (3) Å] and the Cu

Cu′

Cu angles are nearly linear [176.75 (1)°]. The MATCH procedure available in the Oxford University Crystals for Windows package was used to carry out a detailed analysis of the relationship between the two independent molecules. MATCH has some particular advantages in studying the details of pseudosymmetry, which include: (i) no atomic-order requirements; (ii) the pseudosymmetry matrix is readily available, which allows quick insight into the symmetry elements involved and their location; and (iii) the differences between molecular centroids, as well as between all atomic positions and torsion angles, are listed. A tutorial presentation is designed to attract new users to the technique. In the present case, a search for a pseudosymmetric relationship between the two independent molecules showed that they are related by a pseudo-4₂ axis along the crystallographic c direction. A detailed analysis shows that the pseudo-4₂ symmetry is disrupted by torsions about the CH₂—C(ipso) bonds, and that there is no supergroup that can be used to describe the crystal structure.

Keywords: Parkinson's disease; homolepic complex; pseudosymmetry; linear packing; crystal structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229621006082/cu3173sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229621006082/cu3173Isup2.hkl Contains datablock I
	Portable Document Format (PDF) file https://doi.org/10.1107/S2053229621006082/cu3173sup3.pdf PDF file of a pseudosymmetry tutorial
	Microsoft Excel (XLSX) file https://doi.org/10.1107/S2053229621006082/cu3173sup4.xlsx Excel file with powder and IR spectra

CCDC reference: 2089247

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: APEX2 (Bruker, 2005); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: PLATON (Spek, 2020), enCIFer (Allen et al., 2004) and publCIF (Westrip, 2010).

cis-Bis(L-3,4-dihydroxyphenylalanine-κ²N,O)copper(II) monohydrate top

Crystal data top

[Cu(C₉H₁₀NO₄)₂]·H₂O	F(000) = 980
M_r = 473.93	D_x = 1.650 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 9886 reflections
a = 9.5938 (3) Å	θ = 2.9–30.1°
b = 20.1903 (6) Å	µ = 1.20 mm⁻¹
c = 10.1806 (3) Å	T = 120 K
β = 104.663 (1)°	Prism fragment, purple
V = 1907.77 (10) Å³	0.42 × 0.12 × 0.10 mm
Z = 4

Data collection top

Bruker–Nonius Kappa APEXII diffractometer	10252 reflections with I > 2.0σ(I)
Graphite monochromator	R_int = 0.043
φ & ω scans	θ_max = 30.1°, θ_min = 2.0°
Absorption correction: numerical Apex2 (Bruker, 2005)	h = −13→13
T_min = 0.87, T_max = 0.89	k = −28→28
42508 measured reflections	l = −14→14
11278 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: difference Fourier map
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.029	Method = Modified Sheldrick w = 1/[σ²(F²) + ( 0.03P)² + 0.42P] , where P = (max(F_o²,0) + 2F_c²)/3
wR(F²) = 0.068	(Δ/σ)_max = 0.007
S = 0.99	Δρ_max = 0.37 e Å⁻³
11278 reflections	Δρ_min = −0.52 e Å⁻³
622 parameters	Absolute structure: (Parsons et al., 2013), 5226 Friedel Pairs
1 restraint	Absolute structure parameter: −0.004 (4)
Primary atom site location: structure-invariant direct methods

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.51301 (2)	0.50311 (3)	0.114284 (19)	0.0142
Cu101	0.49775 (2)	0.50175 (3)	0.608835 (19)	0.0138
O1	0.66157 (14)	0.52981 (8)	0.02848 (13)	0.0188
O2	0.86792 (14)	0.58473 (7)	0.06738 (13)	0.0175
O3	0.83732 (16)	0.54095 (7)	0.80600 (14)	0.0196
O4	0.69969 (15)	0.65695 (8)	0.82795 (14)	0.0177
O5	0.37789 (14)	0.48310 (7)	−0.05574 (13)	0.0160
O6	0.16353 (14)	0.43846 (8)	−0.14624 (13)	0.0183
O7	0.22698 (18)	0.46056 (8)	0.61315 (14)	0.0249
O8	0.10034 (17)	0.33893 (8)	0.62028 (14)	0.0245
O19	0.88092 (17)	0.26056 (9)	0.64716 (17)	0.0225
O20	0.02002 (18)	0.32281 (9)	0.89437 (16)	0.0237
O101	0.55638 (15)	0.43741 (7)	0.49274 (13)	0.0185
O102	0.67228 (15)	0.34191 (7)	0.49476 (14)	0.0195
O103	0.25485 (15)	0.27720 (7)	1.06015 (14)	0.0175
O104	0.46310 (16)	0.31998 (8)	1.26613 (14)	0.0182
O105	0.44158 (14)	0.56480 (7)	0.46285 (12)	0.0145
O106	0.34839 (16)	0.66543 (7)	0.41691 (13)	0.0192
O107	0.41490 (15)	0.63598 (8)	1.17953 (14)	0.0202
O108	0.12458 (16)	0.64519 (8)	1.16640 (14)	0.0193
N1	0.64854 (18)	0.53403 (9)	0.28361 (16)	0.0166
N2	0.36401 (18)	0.47070 (10)	0.19890 (16)	0.0165
N101	0.5965 (2)	0.44406 (9)	0.75873 (17)	0.0181
N102	0.43555 (18)	0.56932 (8)	0.72093 (15)	0.0128
C1	0.76087 (19)	0.56511 (10)	0.10362 (18)	0.0143
C2	0.73929 (19)	0.58521 (10)	0.24212 (18)	0.0137
C3	0.8784 (2)	0.59980 (11)	0.35089 (18)	0.0181
C4	0.84232 (19)	0.61801 (10)	0.48259 (18)	0.0158
C5	0.86094 (19)	0.57200 (10)	0.58780 (19)	0.0165
C6	0.81582 (19)	0.58652 (10)	0.70415 (18)	0.0142
C7	0.74904 (19)	0.64722 (10)	0.71397 (18)	0.0149
C8	0.7333 (2)	0.69388 (10)	0.6109 (2)	0.0186
C9	0.7810 (2)	0.67925 (10)	0.49620 (19)	0.0189
C10	0.2598 (2)	0.45565 (9)	−0.04659 (18)	0.0139
C11	0.24153 (18)	0.44149 (9)	0.09600 (17)	0.0122
C12	0.0957 (2)	0.46224 (10)	0.11855 (18)	0.0165
C13	0.07895 (19)	0.43226 (10)	0.24961 (18)	0.0157
C14	0.1444 (2)	0.46214 (10)	0.37456 (19)	0.0162
C15	0.1511 (2)	0.43058 (10)	0.49633 (19)	0.0168
C16	0.0864 (2)	0.36862 (10)	0.49675 (19)	0.0178
C17	0.0162 (2)	0.33983 (11)	0.3745 (2)	0.0214
C18	0.0143 (2)	0.37065 (11)	0.2517 (2)	0.0205
C101	0.6237 (2)	0.38691 (9)	0.55381 (18)	0.0146
C102	0.6393 (2)	0.38103 (9)	0.70681 (18)	0.0146
C103	0.5424 (2)	0.32370 (10)	0.73150 (19)	0.0181
C104	0.5295 (2)	0.32037 (10)	0.87663 (18)	0.0157
C105	0.3981 (2)	0.30093 (9)	0.90055 (19)	0.0162
C106	0.3807 (2)	0.29868 (9)	1.03136 (19)	0.0148
C107	0.4919 (2)	0.31892 (9)	1.14134 (18)	0.0149
C108	0.6236 (2)	0.33747 (10)	1.11872 (19)	0.0167
C109	0.6426 (2)	0.33724 (10)	0.98777 (19)	0.0169
C110	0.37911 (19)	0.61731 (9)	0.49305 (17)	0.0134
C111	0.33577 (19)	0.61485 (9)	0.62827 (17)	0.0124
C112	0.3276 (2)	0.68284 (9)	0.69264 (18)	0.0138
C113	0.27348 (19)	0.67665 (9)	0.81930 (17)	0.0124
C114	0.36810 (19)	0.66323 (9)	0.94590 (18)	0.0130
C115	0.3175 (2)	0.65288 (9)	1.06027 (17)	0.0133
C116	0.1703 (2)	0.65700 (9)	1.05084 (18)	0.0150
C117	0.0763 (2)	0.67272 (10)	0.9279 (2)	0.0174
C118	0.1273 (2)	0.68117 (10)	0.81228 (18)	0.0158
H11	0.704 (3)	0.5037 (15)	0.323 (2)	0.023 (6)*
H12	0.607 (3)	0.5513 (13)	0.342 (3)	0.026 (7)*
H21	0.396 (3)	0.4438 (15)	0.260 (3)	0.031 (7)*
H22	0.330 (3)	0.5007 (17)	0.233 (3)	0.033 (7)*
H23	0.6818	0.6235	0.2243	0.0148*
H31	0.836 (3)	0.5575 (15)	0.880 (3)	0.036 (8)*
H32	0.9388	0.5606	0.3633	0.0212*
H33	0.9269	0.6358	0.3201	0.0210*
H41	0.713 (3)	0.6919 (16)	0.854 (3)	0.037 (8)*
H51	0.9040	0.5314	0.5808	0.0199*
H71	0.209 (3)	0.4477 (14)	0.676 (3)	0.028 (7)*
H81	0.044 (3)	0.3063 (15)	0.614 (3)	0.032 (7)*
H82	0.6856	0.7330	0.6182	0.0214*
H91	0.7713	0.7109	0.4254	0.0233*
H111	0.2504	0.3937	0.1099	0.0152*
H121	0.0932	0.5107	0.1211	0.0192*
H122	0.0252	0.4472	0.0443	0.0191*
H141	0.1825	0.5045	0.3770	0.0207*
H171	−0.0291	0.2981	0.3751	0.0262*
H181	−0.0335	0.3508	0.1716	0.0247*
H191	0.849 (3)	0.2285 (15)	0.659 (3)	0.024 (7)*
H192	0.819 (4)	0.2775 (16)	0.598 (3)	0.037 (9)*
H201	0.063 (3)	0.3605 (17)	0.873 (3)	0.045 (8)*
H202	−0.022 (4)	0.301 (2)	0.839 (4)	0.057 (11)*
H1011	0.549 (3)	0.4378 (15)	0.819 (3)	0.037 (8)*
H1012	0.661 (3)	0.4643 (14)	0.799 (3)	0.030 (8)*
H1021	0.400 (3)	0.5513 (13)	0.782 (3)	0.023 (6)*
H1022	0.505 (3)	0.5879 (12)	0.765 (3)	0.017 (6)*
H1023	0.7388	0.3716	0.7494	0.0170*
H1031	0.182 (4)	0.2868 (15)	0.998 (3)	0.043 (9)*
H1032	0.5795	0.2817	0.7090	0.0222*
H1033	0.4475	0.3294	0.6722	0.0223*
H1041	0.529 (3)	0.3310 (15)	1.314 (3)	0.033 (8)*
H1051	0.3217	0.2890	0.8278	0.0178*
H1071	0.392 (3)	0.6428 (13)	1.241 (3)	0.023 (7)*
H1081	0.051 (3)	0.6335 (14)	1.145 (3)	0.024 (7)*
H1082	0.6987	0.3516	1.1892	0.0189*
H1091	0.7357	0.3484	0.9729	0.0208*
H1111	0.2417	0.5951	0.6088	0.0143*
H1121	0.2631	0.7108	0.6265	0.0163*
H1122	0.4242	0.6998	0.7147	0.0166*
H1141	0.4650	0.6595	0.9540	0.0165*
H1171	−0.0224	0.6758	0.9212	0.0209*
H1181	0.0648	0.6907	0.7284	0.0192*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01493 (10)	0.02034 (10)	0.00822 (9)	−0.00505 (10)	0.00459 (7)	−0.00047 (10)
Cu101	0.02195 (10)	0.01243 (9)	0.00787 (8)	0.00180 (10)	0.00509 (7)	0.00034 (10)
O1	0.0179 (6)	0.0296 (7)	0.0102 (6)	−0.0077 (6)	0.0059 (5)	−0.0033 (5)
O2	0.0156 (6)	0.0264 (7)	0.0121 (6)	−0.0042 (5)	0.0064 (5)	0.0007 (5)
O3	0.0287 (8)	0.0190 (7)	0.0124 (6)	0.0002 (6)	0.0079 (6)	0.0000 (5)
O4	0.0207 (7)	0.0205 (7)	0.0146 (6)	−0.0013 (5)	0.0095 (5)	−0.0055 (5)
O5	0.0175 (6)	0.0220 (7)	0.0090 (5)	−0.0055 (5)	0.0045 (5)	0.0005 (4)
O6	0.0190 (6)	0.0255 (7)	0.0098 (6)	−0.0052 (5)	0.0030 (5)	−0.0019 (5)
O7	0.0364 (9)	0.0301 (8)	0.0093 (6)	−0.0182 (7)	0.0074 (6)	−0.0039 (6)
O8	0.0326 (8)	0.0262 (8)	0.0143 (6)	−0.0133 (7)	0.0054 (6)	0.0012 (6)
O19	0.0187 (7)	0.0180 (8)	0.0289 (8)	−0.0044 (6)	0.0028 (6)	0.0031 (6)
O20	0.0227 (8)	0.0277 (8)	0.0196 (7)	−0.0065 (7)	0.0031 (6)	0.0017 (6)
O101	0.0300 (8)	0.0154 (6)	0.0108 (6)	0.0045 (6)	0.0067 (5)	0.0011 (5)
O102	0.0232 (7)	0.0221 (7)	0.0138 (6)	0.0052 (5)	0.0061 (5)	−0.0010 (5)
O103	0.0162 (6)	0.0200 (7)	0.0170 (6)	−0.0014 (5)	0.0053 (5)	0.0039 (5)
O104	0.0189 (7)	0.0246 (7)	0.0112 (6)	0.0008 (6)	0.0039 (5)	0.0005 (5)
O105	0.0209 (6)	0.0153 (6)	0.0087 (5)	0.0036 (5)	0.0061 (5)	0.0007 (5)
O106	0.0280 (7)	0.0194 (7)	0.0103 (6)	0.0062 (6)	0.0053 (5)	0.0034 (5)
O107	0.0180 (7)	0.0357 (8)	0.0085 (6)	0.0064 (6)	0.0065 (5)	0.0041 (6)
O108	0.0156 (7)	0.0326 (8)	0.0120 (6)	−0.0080 (6)	0.0075 (5)	−0.0037 (6)
N1	0.0181 (8)	0.0230 (9)	0.0104 (7)	−0.0036 (7)	0.0068 (6)	−0.0010 (6)
N2	0.0171 (8)	0.0246 (9)	0.0086 (7)	−0.0040 (7)	0.0044 (6)	−0.0004 (6)
N101	0.0285 (9)	0.0144 (8)	0.0109 (7)	0.0003 (7)	0.0041 (7)	−0.0009 (6)
N102	0.0153 (7)	0.0143 (7)	0.0095 (6)	−0.0010 (6)	0.0044 (6)	0.0006 (6)
C1	0.0159 (8)	0.0174 (8)	0.0097 (7)	0.0006 (7)	0.0038 (6)	0.0021 (6)
C2	0.0132 (8)	0.0184 (8)	0.0104 (7)	−0.0007 (6)	0.0046 (6)	−0.0005 (6)
C3	0.0140 (8)	0.0293 (10)	0.0118 (8)	−0.0027 (7)	0.0047 (7)	−0.0037 (7)
C4	0.0129 (8)	0.025 (1)	0.0098 (8)	−0.0031 (7)	0.0035 (6)	−0.0043 (7)
C5	0.0140 (8)	0.0209 (9)	0.0143 (8)	−0.0006 (7)	0.0031 (7)	−0.0044 (7)
C6	0.0123 (8)	0.0192 (8)	0.0111 (7)	−0.0042 (7)	0.0027 (6)	−0.0016 (6)
C7	0.0122 (8)	0.0215 (9)	0.0115 (8)	−0.0029 (7)	0.0039 (6)	−0.0043 (7)
C8	0.0184 (9)	0.0190 (9)	0.0182 (9)	0.0002 (7)	0.0044 (7)	−0.0018 (7)
C9	0.0194 (9)	0.0241 (10)	0.0130 (8)	−0.0031 (8)	0.0036 (7)	0.0012 (7)
C10	0.0181 (8)	0.0143 (8)	0.0107 (7)	−0.0009 (7)	0.0063 (6)	−0.0009 (6)
C11	0.0139 (8)	0.0150 (8)	0.0086 (7)	−0.0014 (6)	0.0045 (6)	0.0006 (6)
C12	0.0146 (8)	0.0234 (9)	0.0124 (8)	0.0015 (7)	0.0052 (6)	0.0010 (7)
C13	0.0126 (8)	0.0229 (9)	0.0126 (8)	0.0014 (7)	0.0054 (6)	0.0003 (7)
C14	0.0168 (9)	0.0168 (8)	0.0173 (8)	−0.0019 (7)	0.0084 (7)	−0.0012 (7)
C15	0.0170 (8)	0.0215 (9)	0.0136 (8)	−0.0052 (7)	0.0069 (7)	−0.0040 (7)
C16	0.0182 (9)	0.0230 (10)	0.0131 (8)	−0.0046 (7)	0.0053 (7)	−0.0001 (7)
C17	0.0215 (10)	0.0249 (10)	0.0188 (9)	−0.0093 (8)	0.0071 (8)	−0.0048 (8)
C18	0.0188 (9)	0.0274 (10)	0.0147 (8)	−0.0067 (8)	0.0031 (7)	−0.0062 (7)
C101	0.0159 (8)	0.0163 (8)	0.0111 (7)	−0.0008 (6)	0.0028 (7)	0.0001 (6)
C102	0.0180 (9)	0.0151 (8)	0.0109 (7)	0.0013 (7)	0.0038 (7)	0.0000 (6)
C103	0.0251 (10)	0.0188 (9)	0.0117 (8)	−0.0027 (7)	0.0071 (7)	−0.0003 (7)
C104	0.0215 (9)	0.0146 (8)	0.0120 (8)	0.0012 (7)	0.0062 (7)	0.0003 (6)
C105	0.0198 (9)	0.0134 (8)	0.0146 (8)	0.0002 (7)	0.0029 (7)	0.0007 (6)
C106	0.0171 (8)	0.0121 (8)	0.0159 (8)	0.0011 (7)	0.0056 (7)	0.0028 (6)
C107	0.0181 (9)	0.0134 (8)	0.0133 (8)	0.0034 (7)	0.0045 (7)	0.0024 (6)
C108	0.0180 (9)	0.0190 (9)	0.0129 (8)	0.0013 (7)	0.0036 (7)	0.0015 (7)
C109	0.0179 (9)	0.0176 (9)	0.0160 (8)	0.0004 (7)	0.0058 (7)	0.0028 (7)
C110	0.0151 (8)	0.0163 (8)	0.0086 (7)	−0.0010 (6)	0.0028 (6)	0.0002 (6)
C111	0.0148 (8)	0.0143 (8)	0.0087 (7)	−0.0014 (6)	0.0039 (6)	−0.0011 (6)
C112	0.0179 (8)	0.0144 (8)	0.0100 (7)	0.0014 (7)	0.0053 (6)	−0.0004 (6)
C113	0.0161 (8)	0.0113 (8)	0.0112 (7)	−0.0003 (6)	0.0059 (6)	−0.0007 (6)
C114	0.0127 (8)	0.0152 (8)	0.0119 (8)	0.0000 (6)	0.0047 (6)	0.0001 (6)
C115	0.0171 (8)	0.0139 (8)	0.0091 (7)	0.0008 (6)	0.0037 (6)	0.0002 (6)
C116	0.0185 (9)	0.0163 (9)	0.0126 (8)	−0.0031 (7)	0.0082 (7)	−0.0024 (6)
C117	0.0110 (8)	0.0247 (10)	0.0173 (9)	−0.0009 (7)	0.0052 (7)	−0.0027 (7)
C118	0.0148 (8)	0.0208 (9)	0.0105 (7)	−0.0010 (7)	0.0010 (6)	0.0003 (6)

Geometric parameters (Å, º) top

Cu1—O1	1.9276 (13)	C4—C5	1.395 (3)
Cu1—O5	1.9245 (13)	C4—C9	1.391 (3)
Cu1—N1	1.9792 (16)	C5—C6	1.391 (2)
Cu1—N2	1.9589 (16)	C5—H51	0.929
Cu101—O101	1.9332 (13)	C6—C7	1.398 (3)
Cu101—O105	1.9273 (13)	C7—C8	1.390 (3)
Cu101—N101	1.9623 (17)	C8—C9	1.389 (3)
Cu101—N102	1.9659 (16)	C8—H82	0.925
O1—C1	1.277 (2)	C9—H91	0.950
O2—C1	1.241 (2)	C10—C11	1.533 (2)
O3—C6	1.362 (2)	C11—C12	1.532 (2)
O3—H31	0.83 (3)	C11—H111	0.976
O4—C7	1.374 (2)	C12—C13	1.510 (2)
O4—H41	0.76 (3)	C12—H121	0.979
O5—C10	1.285 (2)	C12—H122	0.929
O6—C10	1.236 (2)	C13—C14	1.404 (3)
O7—C15	1.368 (2)	C13—C18	1.392 (3)
O7—H71	0.75 (3)	C14—C15	1.381 (3)
O8—C16	1.369 (2)	C14—H141	0.927
O8—H81	0.84 (3)	C15—C16	1.397 (3)
O19—H191	0.74 (3)	C16—C17	1.385 (3)
O19—H192	0.76 (3)	C17—C18	1.392 (3)
O20—H201	0.92 (3)	C17—H171	0.949
O20—H202	0.75 (4)	C18—H181	0.920
O101—C101	1.281 (2)	C101—C102	1.531 (2)
O102—C101	1.243 (2)	C102—C103	1.544 (3)
O103—C106	1.382 (2)	C102—H1023	0.962
O103—H1031	0.84 (3)	C103—C104	1.515 (2)
O104—C107	1.367 (2)	C103—H1032	0.969
O104—H1041	0.73 (3)	C103—H1033	0.964
O105—C110	1.293 (2)	C104—C105	1.399 (3)
O106—C110	1.231 (2)	C104—C109	1.397 (3)
O107—C115	1.375 (2)	C105—C106	1.384 (3)
O107—H1071	0.73 (3)	C105—H1051	0.932
O108—C116	1.376 (2)	C106—C107	1.398 (3)
O108—H1081	0.73 (3)	C107—C108	1.392 (3)
N1—C2	1.480 (2)	C108—C109	1.391 (3)
N1—H11	0.84 (3)	C108—H1082	0.924
N1—H12	0.86 (3)	C109—H1091	0.969
N2—C11	1.484 (2)	C110—C111	1.536 (2)
N2—H21	0.82 (3)	C111—C112	1.532 (2)
N2—H22	0.81 (3)	C111—H1111	0.960
N101—C102	1.476 (2)	C112—C113	1.512 (2)
N101—H1011	0.87 (3)	C112—H1121	0.971
N101—H1012	0.77 (3)	C112—H1122	0.960
N102—C111	1.481 (2)	C113—C114	1.402 (2)
N102—H1021	0.86 (3)	C113—C118	1.390 (3)
N102—H1022	0.79 (3)	C114—C115	1.386 (2)
C1—C2	1.531 (2)	C114—H1141	0.916
C2—C3	1.532 (2)	C115—C116	1.394 (3)
C2—H23	0.941	C116—C117	1.382 (3)
C3—C4	1.513 (2)	C117—C118	1.394 (3)
C3—H32	0.971	C117—H1171	0.934
C3—H33	0.958	C118—H1181	0.931

O1—Cu1—O5	93.33 (5)	C12—C11—H111	107.3
O1—Cu1—N1	84.74 (6)	C11—C12—C13	109.18 (15)
O5—Cu1—N1	173.72 (7)	C11—C12—H121	107.9
O1—Cu1—N2	176.72 (8)	C13—C12—H121	111.6
O5—Cu1—N2	85.70 (6)	C11—C12—H122	107.1
N1—Cu1—N2	96.55 (7)	C13—C12—H122	111.6
O101—Cu101—O105	92.31 (5)	H121—C12—H122	109.3
O101—Cu101—N101	85.34 (6)	C12—C13—C14	120.32 (17)
O105—Cu101—N101	167.81 (7)	C12—C13—C18	121.27 (17)
O101—Cu101—N102	177.86 (6)	C14—C13—C18	117.94 (17)
O105—Cu101—N102	85.56 (6)	C13—C14—C15	121.57 (17)
N101—Cu101—N102	96.78 (7)	C13—C14—H141	120.2
Cu1—O1—C1	114.18 (11)	C15—C14—H141	118.2
C6—O3—H31	113 (2)	C14—C15—O7	118.03 (17)
C7—O4—H41	112 (2)	C14—C15—C16	119.75 (17)
Cu1—O5—C10	115.51 (11)	O7—C15—C16	122.17 (17)
C15—O7—H71	114 (2)	C15—C16—O8	117.06 (17)
C16—O8—H81	111.5 (19)	C15—C16—C17	119.25 (18)
H191—O19—H192	103 (3)	O8—C16—C17	123.66 (18)
H201—O20—H202	120 (3)	C16—C17—C18	120.81 (19)
Cu101—O101—C101	115.29 (11)	C16—C17—H171	119.1
C106—O103—H1031	112 (2)	C18—C17—H171	120.1
C107—O104—H1041	106 (2)	C13—C18—C17	120.58 (18)
Cu101—O105—C110	114.48 (11)	C13—C18—H181	120.0
C115—O107—H1071	116 (2)	C17—C18—H181	119.4
C116—O108—H1081	107 (2)	O101—C101—O102	123.49 (17)
Cu1—N1—C2	106.02 (11)	O101—C101—C102	117.58 (16)
Cu1—N1—H11	112.4 (18)	O102—C101—C102	118.89 (16)
C2—N1—H11	107.2 (17)	C101—C102—N101	109.47 (15)
Cu1—N1—H12	114.2 (17)	C101—C102—C103	108.41 (15)
C2—N1—H12	108.6 (18)	N101—C102—C103	110.79 (16)
H11—N1—H12	108 (2)	C101—C102—H1023	107.7
Cu1—N2—C11	110.96 (11)	N101—C102—H1023	110.1
Cu1—N2—H21	112.1 (19)	C103—C102—H1023	110.4
C11—N2—H21	110 (2)	C102—C103—C104	113.15 (15)
Cu1—N2—H22	111 (2)	C102—C103—H1032	110.2
C11—N2—H22	105.8 (19)	C104—C103—H1032	108.5
H21—N2—H22	106 (3)	C102—C103—H1033	108.7
Cu101—N101—C102	110.89 (12)	C104—C103—H1033	108.6
Cu101—N101—H1011	113.6 (19)	H1032—C103—H1033	107.5
C102—N101—H1011	112 (2)	C103—C104—C105	118.81 (17)
Cu101—N101—H1012	105 (2)	C103—C104—C109	122.70 (17)
C102—N101—H1012	113 (2)	C105—C104—C109	118.48 (17)
H1011—N101—H1012	102 (3)	C104—C105—C106	120.68 (17)
Cu101—N102—C111	107.65 (11)	C104—C105—H1051	119.7
Cu101—N102—H1021	111.1 (17)	C106—C105—H1051	119.6
C111—N102—H1021	114.3 (17)	C105—C106—O103	122.62 (17)
Cu101—N102—H1022	108.9 (17)	C105—C106—C107	120.48 (17)
C111—N102—H1022	112.2 (17)	O103—C106—C107	116.89 (16)
H1021—N102—H1022	103 (2)	C106—C107—O104	117.14 (16)
O1—C1—O2	123.22 (16)	C106—C107—C108	119.14 (17)
O1—C1—C2	116.44 (15)	O104—C107—C108	123.72 (17)
O2—C1—C2	120.29 (16)	C107—C108—C109	120.20 (17)
C1—C2—N1	107.71 (15)	C107—C108—H1082	121.1
C1—C2—C3	114.87 (15)	C109—C108—H1082	118.7
N1—C2—C3	113.32 (15)	C104—C109—C108	120.88 (17)
C1—C2—H23	104.5	C104—C109—H1091	119.2
N1—C2—H23	105.7	C108—C109—H1091	119.9
C3—C2—H23	110.1	O105—C110—O106	123.29 (16)
C2—C3—C4	109.53 (15)	O105—C110—C111	115.70 (15)
C2—C3—H32	108.6	O106—C110—C111	120.90 (16)
C4—C3—H32	110.2	C110—C111—N102	108.23 (14)
C2—C3—H33	108.4	C110—C111—C112	114.16 (14)
C4—C3—H33	110.1	N102—C111—C112	112.24 (14)
H32—C3—H33	109.8	C110—C111—H1111	106.4
C3—C4—C5	120.35 (17)	N102—C111—H1111	107.2
C3—C4—C9	120.13 (17)	C112—C111—H1111	108.2
C5—C4—C9	119.38 (17)	C111—C112—C113	110.88 (14)
C4—C5—C6	120.42 (18)	C111—C112—H1121	108.4
C4—C5—H51	120.2	C113—C112—H1121	110.0
C6—C5—H51	119.4	C111—C112—H1122	105.6
C5—C6—O3	119.07 (17)	C113—C112—H1122	110.4
C5—C6—C7	119.51 (17)	H1121—C112—H1122	111.3
O3—C6—C7	121.42 (16)	C112—C113—C114	121.17 (16)
C6—C7—O4	116.62 (16)	C112—C113—C118	120.72 (16)
C6—C7—C8	120.29 (17)	C114—C113—C118	118.05 (16)
O4—C7—C8	123.08 (17)	C113—C114—C115	121.21 (16)
C7—C8—C9	119.64 (18)	C113—C114—H1141	120.3
C7—C8—H82	118.7	C115—C114—H1141	118.4
C9—C8—H82	121.6	C114—C115—O107	118.34 (16)
C4—C9—C8	120.67 (18)	C114—C115—C116	119.85 (16)
C4—C9—H91	119.0	O107—C115—C116	121.75 (16)
C8—C9—H91	120.3	C115—C116—O108	117.86 (16)
O5—C10—O6	123.41 (16)	C115—C116—C117	119.56 (16)
O5—C10—C11	117.61 (15)	O108—C116—C117	122.58 (17)
O6—C10—C11	118.94 (16)	C116—C117—C118	120.35 (17)
C10—C11—N2	109.54 (14)	C116—C117—H1171	119.9
C10—C11—C12	114.76 (15)	C118—C117—H1171	119.7
N2—C11—C12	112.04 (15)	C117—C118—C113	120.90 (17)
C10—C11—H111	107.2	C117—C118—H1181	121.2
N2—C11—H111	105.4	C113—C118—H1181	117.9

O5—Cu1—O1—C1	161.25 (14)	O5—C10—C11—N2	6.5 (2)
N1—Cu1—O1—C1	−12.77 (14)	O5—C10—C11—C12	133.48 (18)
O1—Cu1—O5—C10	173.19 (14)	O6—C10—C11—N2	−175.80 (17)
N2—Cu1—O5—C10	−3.66 (14)	O6—C10—C11—C12	−48.8 (2)
O1—Cu1—N1—C2	26.68 (12)	N2—C11—C12—C13	−66.8 (2)
N2—Cu1—N1—C2	−156.36 (13)	C10—C11—C12—C13	167.48 (15)
O5—Cu1—N2—C11	7.06 (13)	C11—C12—C13—C14	80.9 (2)
N1—Cu1—N2—C11	−178.83 (13)	C11—C12—C13—C18	−91.1 (2)
O101—Cu101—O7—C15	−31.75 (14)	C12—C13—C14—C15	−169.27 (18)
O105—Cu101—O7—C15	62.44 (14)	C18—C13—C14—C15	3.0 (3)
N101—Cu101—O7—C15	−118.04 (14)	C12—C13—C18—C17	171.66 (18)
N102—Cu101—O7—C15	146.05 (14)	C14—C13—C18—C17	−0.5 (3)
O7—Cu101—O101—C101	−91.05 (14)	C13—C14—C15—O7	174.69 (18)
O105—Cu101—O101—C101	170.61 (14)	C13—C14—C15—C16	−2.7 (3)
N101—Cu101—O101—C101	2.60 (14)	O7—C15—C16—O8	0.8 (3)
O7—Cu101—O105—C110	70.03 (13)	O7—C15—C16—C17	−177.36 (19)
O101—Cu101—O105—C110	173.76 (13)	C14—C15—C16—O8	178.10 (18)
N102—Cu101—O105—C110	−6.07 (13)	C14—C15—C16—C17	−0.1 (3)
O7—Cu101—N101—C102	94.08 (13)	O8—C16—C17—C18	−175.54 (19)
O101—Cu101—N101—C102	−8.90 (13)	C15—C16—C17—C18	2.5 (3)
N102—Cu101—N101—C102	171.38 (14)	C16—C17—C18—C13	−2.2 (3)
O7—Cu101—N102—C111	−77.86 (12)	O101—C101—C102—N101	−11.5 (2)
O105—Cu101—N102—C111	20.99 (12)	O101—C101—C102—C103	109.38 (19)
N101—Cu101—N102—C111	−171.04 (12)	O102—C101—C102—N101	170.75 (17)
Cu1—O1—C1—O2	177.24 (15)	O102—C101—C102—C103	−68.3 (2)
Cu1—O1—C1—C2	−5.2 (2)	N101—C102—C103—C104	−50.3 (2)
Cu1—O5—C10—O6	−178.41 (15)	C101—C102—C103—C104	−170.41 (16)
Cu1—O5—C10—C11	−0.8 (2)	C102—C103—C104—C105	144.39 (18)
Cu101—O7—C15—C14	−49.3 (2)	C102—C103—C104—C109	−34.3 (3)
Cu101—O7—C15—C16	127.99 (17)	C103—C104—C105—C106	−178.52 (18)
Cu101—O101—C101—O102	−177.94 (15)	C109—C104—C105—C106	0.2 (3)
Cu101—O101—C101—C102	4.5 (2)	C103—C104—C109—C108	175.96 (19)
Cu101—O105—C110—O106	172.90 (15)	C105—C104—C109—C108	−2.7 (3)
Cu101—O105—C110—C111	−10.8 (2)	C104—C105—C106—O103	−177.28 (17)
Cu1—N1—C2—C1	−34.17 (17)	C104—C105—C106—C107	3.2 (3)
Cu1—N1—C2—C3	−162.38 (13)	O103—C106—C107—O104	−4.3 (3)
Cu1—N2—C11—C10	−8.74 (19)	O103—C106—C107—C108	176.44 (17)
Cu1—N2—C11—C12	−137.27 (13)	C105—C106—C107—O104	175.25 (17)
Cu101—N101—C102—C101	12.65 (19)	C105—C106—C107—C108	−4.0 (3)
Cu101—N101—C102—C103	−106.83 (15)	O104—C107—C108—C109	−177.69 (18)
Cu101—N102—C111—C110	−30.06 (16)	C106—C107—C108—C109	1.5 (3)
Cu101—N102—C111—C112	−156.94 (12)	C107—C108—C109—C104	1.9 (3)
O1—C1—C2—N1	27.4 (2)	O105—C110—C111—N102	27.8 (2)
O1—C1—C2—C3	154.67 (18)	O105—C110—C111—C112	153.59 (16)
O2—C1—C2—N1	−154.97 (18)	O106—C110—C111—N102	−155.76 (17)
O2—C1—C2—C3	−27.7 (3)	O106—C110—C111—C112	−30.0 (2)
N1—C2—C3—C4	−54.8 (2)	N102—C111—C112—C113	−60.7 (2)
C1—C2—C3—C4	−179.20 (17)	C110—C111—C112—C113	175.68 (15)
C2—C3—C4—C5	102.6 (2)	C111—C112—C113—C114	86.0 (2)
C2—C3—C4—C9	−73.0 (2)	C111—C112—C113—C118	−91.1 (2)
C3—C4—C5—C6	−174.21 (18)	C112—C113—C114—C115	−175.36 (17)
C9—C4—C5—C6	1.4 (3)	C118—C113—C114—C115	1.8 (3)
C3—C4—C9—C8	173.12 (18)	C112—C113—C118—C117	177.28 (18)
C5—C4—C9—C8	−2.5 (3)	C114—C113—C118—C117	0.1 (3)
C4—C5—C6—O3	−179.08 (17)	C113—C114—C115—O107	176.11 (17)
C4—C5—C6—C7	1.2 (3)	C113—C114—C115—C116	−1.2 (3)
O3—C6—C7—O4	−3.3 (3)	O107—C115—C116—O108	1.6 (3)
O3—C6—C7—C8	177.55 (18)	O107—C115—C116—C117	−178.54 (18)
C5—C6—C7—O4	176.39 (17)	C114—C115—C116—O108	178.85 (17)
C5—C6—C7—C8	−2.7 (3)	C114—C115—C116—C117	−1.3 (3)
O4—C7—C8—C9	−177.41 (18)	O108—C116—C117—C118	−176.97 (18)
C6—C7—C8—C9	1.6 (3)	C115—C116—C117—C118	3.2 (3)
C7—C8—C9—C4	1.0 (3)	C116—C117—C118—C113	−2.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N101—H1011···O5ⁱ	0.86 (3)	2.49 (3)	3.255 (2)	148 (3)
N101—H1012···O3	0.77 (3)	2.28 (3)	2.972 (2)	150 (3)
N102—H1021···O5ⁱ	0.86 (3)	2.20 (3)	3.024 (2)	159 (3)
N102—H1022···O4	0.80 (3)	2.29 (3)	3.056 (2)	162 (3)
O103—H1031···O20	0.84 (3)	1.80 (4)	2.617 (2)	166 (3)
O104—H1041···O102ⁱ	0.73 (3)	2.01 (3)	2.698 (2)	157 (3)
O107—H1071···O106ⁱ	0.73 (3)	1.99 (3)	2.717 (2)	174 (3)
O107—H1071···O108	0.73 (3)	2.49 (3)	2.761 (2)	105 (3)
N1—H12···O105	0.87 (3)	2.26 (3)	3.081 (2)	158 (3)
O108—H1081···O2ⁱⁱ	0.72 (3)	1.99 (3)	2.704 (2)	167 (3)
N2—H21···O101	0.82 (3)	2.48 (3)	3.164 (2)	141 (3)
N2—H21···O104ⁱⁱⁱ	0.82 (3)	2.58 (3)	3.210 (3)	134 (3)
O3—H31···O1ⁱ	0.83 (3)	2.58 (3)	3.156 (2)	127 (3)
O3—H31···O2ⁱ	0.83 (3)	1.93 (3)	2.7483 (19)	168 (3)
O3—H31···O4	0.83 (3)	2.38 (3)	2.725 (2)	106 (2)
O4—H41···O103^iv	0.75 (3)	1.92 (3)	2.670 (2)	174 (3)
O7—H71···O6ⁱ	0.75 (3)	1.98 (3)	2.706 (2)	165 (3)
O7—H71···O8	0.75 (3)	2.44 (3)	2.749 (2)	107 (2)
O8—H81···O19^v	0.84 (3)	1.92 (3)	2.702 (2)	154 (3)
O19—H191···O106^vi	0.74 (3)	2.25 (3)	2.868 (2)	142 (3)
O19—H191···O108^vii	0.74 (3)	2.41 (3)	3.014 (2)	140 (3)
O19—H192···O102	0.76 (3)	2.01 (3)	2.746 (2)	166 (3)
O20—H201···O6ⁱ	0.92 (3)	1.88 (3)	2.794 (2)	172 (3)
O20—H202···O19^v	0.75 (4)	2.10 (4)	2.827 (2)	163 (4)
C2—H23···O107ⁱⁱⁱ	0.94	2.50	3.184 (2)	130
C11—H111···O103ⁱⁱⁱ	0.98	2.41	3.343 (2)	160
C12—H121···O2^v	0.98	2.57	3.254 (2)	127

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

Selected hydrogen bonds (Å, °) top

D—H···A	D—H	H···A	D···A	D—H···A	Label
N101—H1011···O5ⁱ	0.86 (3)	2.49 (3)	3.255 (2)	148 (3)	a
N101—H1012···O3	0.77 (3)	2.28 (3)	2.972 (2)	150 (3)	b
N102—H1021···O5ⁱ	0.86 (3)	2.20 (3)	3.024 (2)	159 (3)	c
N102—H1022···O4	0.80 (3)	2.29 (3)	3.056 (2)	162 (3)	d
O104—H1041···O102ⁱ	0.73 (3)	2.01 (3)	2.698 (2)	157 (3)	e
O107—H1071···O106ⁱ	0.73 (3)	1.99 (3)	2.717 (2)	174 (3)	f
N1—H12···O105	0.87 (3)	2.26 (3)	3.081 (2)	158 (3)	g
N2—H21···O101	0.82 (3)	2.48 (3)	3.164 (2)	141 (3)	h
N2—H21···O104ⁱⁱ	0.82 (3)	2.58 (3)	3.210 (3)	134 (3)	i
O3—H31···O1ⁱ	0.83 (3)	2.58 (3)	3.156 (2)	127 (3)	j
O3—H31···O2ⁱ	0.83 (3)	1.93 (3)	2.7483 (19)	168 (3)	k
O7—H71···O6ⁱ	0.75 (3)	1.98 (3)	2.706 (2)	165 (3)	l
O19—H191···O106ⁱⁱⁱ	0.74 (3)	2.25 (3)	2.868 (2)	142 (3)
O19—H192···O102	0.76 (3)	2.01 (3)	2.746 (2)	166 (3)

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

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cis-Bis(L-DOPA-κ2N,O)copper(II) monohydrate: synthesis, crystal structure, and approaches to the analysis of pseudosymmetry

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cis-Bis(L-DOPA-κ²N,O)copper(II) monohydrate: synthesis, crystal structure, and approaches to the analysis of pseudosymmetry