A new photoluminescent coordination polymer constructed with an N-donor ligand having extended coordination capabilities derived from quinoline and pyridine

Employment of the organic 2-(pyridin-4-yl)quinoline-4-carb­oxy­lic acid ligand with extended coordination capabilities leads to the formation of the one-dimensional copper(II) coordination polymer catena-poly[[di­aqua­copper(II)]-bis­[μ-2-(pyridin-4-yl)quinoline-4-carboxyl­ato]-κ²N²:O;κ²O:N], {[Cu(C₁₅H₉N₂O₂)₂(H₂O)₂]·2H₂O}_n, under hydro­thermal conditions. The ligand, isolated as its hydro­chloride salt, namely, 4-(4-carb­oxy­quinolin-2-yl)pyridinium chloride monohydrate, C₁₅H₁₁N₂O₂⁺·Cl⁻·H₂O, reveals a pseudosymmetry element (translation a/2) in its crystal structure. The additional pyridyl N atom, in com­parison with the previously reported analogues with an arene ring instead of the pyridyl ring in the present ligand mol­ecule, promotes the formation of a one-dimensional coordination polymer, rather than discrete mol­ecules. This polymer shows photoluminescent properties with bathochromic/hypsochromic shifts of the ligand absorption bands, leading to a single band at 479 nm. The Cu^II ions are involved in weak anti­ferromagnetic inter­actions within dimeric units, as evidenced by SQUID magnetometry.

Computing details

For both structures, data collection: CrysAlis PRO (Rigaku OD, 2017); cell refinement: CrysAlis PRO (Rigaku OD, 2017); data reduction: CrysAlis PRO (Rigaku OD, 2017); program(s) used to solve structure: SHELTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

catena-Poly[[diaquacopper(II)]-bis[µ-2-(pyridin-4-yl)quinoline-4-carboxylato]-κ²N²,O;κ²O,N] (blue26ok)

Crystal data

[Cu(C15H9N2O2)2(H2O)2]·2H2O	Z = 1
Mr = 634.09	F(000) = 327
Triclinic, P1	Dx = 1.503 Mg m^−3
a = 8.647 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.819 (3) Å	Cell parameters from 3141 reflections
c = 10.125 (2) Å	θ = 2.2–25.5°
α = 70.58 (2)°	µ = 0.84 mm^−1
β = 79.61 (3)°	T = 100 K
γ = 75.26 (3)°	Block, blue/green
V = 700.3 (4) Å^3	0.20 × 0.18 × 0.15 mm

Data collection

Oxford Diffraction Xcalibur Ruby diffractometer	2397 reflections with I > 2σ(I)
CCD scans	Rint = 0.031
Absorption correction: analytical (CrysAlis PRO; Rigaku OD, 2017)	θmax = 28.8°, θmin = 2.2°
Tmin = 0.867, Tmax = 0.940	h = −10→11
4791 measured reflections	k = −11→10
3141 independent reflections	l = −13→11

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.053	H-atom parameters constrained
wR(F^2) = 0.108	w = 1/[σ^2(Fo^2) + (0.0448P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max < 0.001
3141 reflections	Δρmax = 0.92 e Å^−3
196 parameters	Δρmin = −0.36 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq
Cu1	0.500000	1.000000	0.000000	0.01642 (17)
O1	0.3010 (2)	0.9513 (2)	0.1250 (2)	0.0181 (5)
O2	0.2854 (3)	0.7167 (3)	0.0924 (2)	0.0321 (6)
O1W	0.2261 (3)	0.4049 (2)	0.1788 (2)	0.0315 (6)
H1WA	0.237114	0.501935	0.166367	0.047*
H1WB	0.153431	0.389267	0.247677	0.047*
O2W	0.5056 (2)	0.8188 (2)	−0.1296 (2)	0.0231 (5)
H2WA	0.444246	0.766755	−0.064635	0.035*
H2WB	0.585136	0.749325	−0.152145	0.035*
N1	0.0033 (3)	0.6870 (3)	0.5775 (2)	0.0160 (5)
N2	0.3666 (3)	0.1778 (3)	0.8565 (2)	0.0168 (5)
C1	0.1575 (3)	0.7750 (3)	0.3026 (3)	0.0155 (6)
C2	0.0135 (3)	0.8792 (3)	0.3388 (3)	0.0154 (6)
C3	−0.0599 (3)	1.0275 (3)	0.2441 (3)	0.0193 (7)
H3	−0.012569	1.061998	0.149708	0.023*
C4	−0.1986 (4)	1.1217 (4)	0.2876 (3)	0.0223 (7)
H4	−0.247212	1.221336	0.223372	0.027*
C5	−0.2697 (4)	1.0718 (4)	0.4268 (3)	0.0218 (7)
H5	−0.366016	1.138649	0.455546	0.026*
C6	−0.2034 (3)	0.9299 (3)	0.5214 (3)	0.0185 (6)
H6	−0.253362	0.898440	0.615121	0.022*
C7	−0.0592 (3)	0.8285 (3)	0.4800 (3)	0.0155 (6)
C8	0.1395 (3)	0.5940 (3)	0.5397 (3)	0.0158 (6)
C9	0.2181 (3)	0.6343 (3)	0.4019 (3)	0.0175 (6)
H9	0.313843	0.562980	0.378152	0.021*
C10	0.2543 (3)	0.8177 (4)	0.1587 (3)	0.0183 (7)
C11	0.2129 (3)	0.4456 (3)	0.6501 (3)	0.0164 (6)
C12	0.3270 (3)	0.3172 (3)	0.6151 (3)	0.0181 (6)
H12	0.354292	0.319308	0.519398	0.022*
C13	0.3997 (3)	0.1878 (3)	0.7199 (3)	0.0179 (6)
H13	0.476818	0.101558	0.694121	0.022*
C14	0.2525 (3)	0.2975 (3)	0.8913 (3)	0.0193 (7)
H14	0.224036	0.289304	0.988125	0.023*
C15	0.1750 (3)	0.4312 (3)	0.7933 (3)	0.0188 (6)
H15	0.095966	0.513638	0.822671	0.023*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0165 (3)	0.0143 (3)	0.0107 (3)	−0.0012 (2)	0.0006 (2)	0.0037 (2)
O1	0.0182 (11)	0.0133 (10)	0.0171 (10)	−0.0033 (9)	0.0018 (8)	0.0009 (8)
O2	0.0469 (15)	0.0266 (12)	0.0241 (12)	−0.0176 (11)	0.0144 (11)	−0.0112 (11)
O1W	0.0348 (14)	0.0218 (12)	0.0305 (13)	−0.0074 (10)	0.0149 (11)	−0.0069 (10)
O2W	0.0216 (11)	0.0222 (11)	0.0195 (11)	−0.0042 (9)	0.0032 (9)	−0.0015 (9)
N1	0.0161 (13)	0.0146 (12)	0.0135 (12)	−0.0017 (10)	−0.0018 (10)	−0.0006 (10)
N2	0.0165 (13)	0.0162 (12)	0.0123 (12)	−0.0013 (10)	0.0012 (10)	−0.0005 (10)
C1	0.0174 (15)	0.0165 (15)	0.0116 (14)	−0.0049 (12)	−0.0016 (12)	−0.0020 (12)
C2	0.0155 (15)	0.0146 (14)	0.0145 (14)	−0.0047 (12)	−0.0016 (12)	−0.0011 (12)
C3	0.0210 (16)	0.0187 (15)	0.0146 (14)	−0.0031 (13)	−0.0034 (13)	−0.0004 (12)
C4	0.0230 (17)	0.0168 (15)	0.0242 (16)	−0.0011 (13)	−0.0091 (14)	−0.0012 (13)
C5	0.0172 (16)	0.0198 (16)	0.0267 (17)	0.0006 (13)	−0.0028 (13)	−0.0080 (14)
C6	0.0174 (15)	0.0184 (15)	0.0171 (15)	−0.0030 (12)	0.0010 (12)	−0.0042 (12)
C7	0.0165 (15)	0.0139 (14)	0.0145 (14)	−0.0020 (12)	−0.0014 (12)	−0.0032 (12)
C8	0.0189 (15)	0.0145 (14)	0.0119 (14)	−0.0064 (12)	0.0000 (12)	0.0002 (12)
C9	0.0179 (15)	0.0153 (15)	0.0152 (14)	−0.0001 (12)	−0.0004 (12)	−0.0025 (12)
C10	0.0164 (15)	0.0184 (16)	0.0142 (14)	0.0002 (12)	−0.0025 (12)	0.0003 (12)
C11	0.0181 (15)	0.0163 (15)	0.0130 (14)	−0.0049 (12)	−0.0038 (12)	−0.0001 (12)
C12	0.0213 (16)	0.0185 (15)	0.0107 (14)	−0.0026 (13)	0.0009 (12)	−0.0022 (12)
C13	0.0198 (16)	0.0161 (15)	0.0138 (14)	−0.0012 (12)	0.0006 (12)	−0.0025 (12)
C14	0.0222 (16)	0.0197 (15)	0.0118 (14)	−0.0028 (13)	0.0009 (13)	−0.0020 (12)
C15	0.0195 (16)	0.0176 (15)	0.0145 (14)	0.0004 (12)	0.0005 (12)	−0.0027 (12)

Geometric parameters (Å, º)

Cu1—O1	1.994 (2)	C2—C7	1.426 (4)
Cu1—O1^i	1.994 (2)	C3—C4	1.367 (4)
Cu1—N2^ii	2.017 (2)	C3—H3	0.9500
Cu1—N2^iii	2.017 (2)	C4—C5	1.403 (4)
Cu1—O2W	2.368 (2)	C4—H4	0.9500
Cu1—O2W^i	2.368 (2)	C5—C6	1.359 (4)
O1—C10	1.262 (3)	C5—H5	0.9500
O2—C10	1.235 (3)	C6—C7	1.422 (4)
O1W—H1WA	0.8499	C6—H6	0.9500
O1W—H1WB	0.8500	C8—C9	1.410 (4)
O2W—H2WA	0.8500	C8—C11	1.492 (4)
O2W—H2WB	0.8500	C9—H9	0.9500
N1—C8	1.327 (4)	C11—C15	1.397 (4)
N1—C7	1.362 (3)	C11—C12	1.398 (4)
N2—C13	1.339 (4)	C12—C13	1.376 (4)
N2—C14	1.344 (4)	C12—H12	0.9500
C1—C9	1.362 (4)	C13—H13	0.9500
C1—C2	1.416 (4)	C14—C15	1.372 (4)
C1—C10	1.524 (4)	C14—H14	0.9500
C2—C3	1.413 (4)	C15—H15	0.9500
O1—Cu1—O1^i	180.0	C5—C4—H4	119.8
O1—Cu1—N2^ii	89.53 (9)	C6—C5—C4	121.3 (3)
O1^i—Cu1—N2^ii	90.47 (9)	C6—C5—H5	119.3
O1—Cu1—N2^iii	90.47 (9)	C4—C5—H5	119.3
O1^i—Cu1—N2^iii	89.53 (9)	C5—C6—C7	120.0 (3)
N2^ii—Cu1—N2^iii	180.0	C5—C6—H6	120.0
O1—Cu1—O2W	95.24 (8)	C7—C6—H6	120.0
O1^i—Cu1—O2W	84.76 (8)	N1—C7—C6	118.3 (2)
N2^ii—Cu1—O2W	92.18 (9)	N1—C7—C2	122.9 (3)
N2^iii—Cu1—O2W	87.82 (9)	C6—C7—C2	118.8 (2)
O1—Cu1—O2W^i	84.76 (8)	N1—C8—C9	122.3 (2)
O1^i—Cu1—O2W^i	95.24 (8)	N1—C8—C11	117.8 (2)
N2^ii—Cu1—O2W^i	87.82 (9)	C9—C8—C11	119.8 (3)
N2^iii—Cu1—O2W^i	92.18 (9)	C1—C9—C8	120.3 (3)
O2W—Cu1—O2W^i	180.0	C1—C9—H9	119.8
C10—O1—Cu1	125.15 (19)	C8—C9—H9	119.8
H1WA—O1W—H1WB	104.1	O2—C10—O1	127.6 (3)
Cu1—O2W—H2WA	91.1	O2—C10—C1	117.9 (2)
Cu1—O2W—H2WB	128.4	O1—C10—C1	114.5 (3)
H2WA—O2W—H2WB	108.3	C15—C11—C12	116.9 (3)
C8—N1—C7	118.3 (2)	C15—C11—C8	121.5 (3)
C13—N2—C14	117.5 (2)	C12—C11—C8	121.6 (3)
C13—N2—Cu1^iv	120.14 (19)	C13—C12—C11	119.7 (3)
C14—N2—Cu1^iv	122.07 (19)	C13—C12—H12	120.2
C9—C1—C2	119.3 (3)	C11—C12—H12	120.2
C9—C1—C10	117.8 (3)	N2—C13—C12	123.0 (3)
C2—C1—C10	122.9 (2)	N2—C13—H13	118.5
C3—C2—C1	123.9 (3)	C12—C13—H13	118.5
C3—C2—C7	119.2 (3)	N2—C14—C15	123.0 (3)
C1—C2—C7	116.8 (2)	N2—C14—H14	118.5
C4—C3—C2	120.3 (3)	C15—C14—H14	118.5
C4—C3—H3	119.8	C14—C15—C11	119.8 (3)
C2—C3—H3	119.8	C14—C15—H15	120.1
C3—C4—C5	120.3 (3)	C11—C15—H15	120.1
C3—C4—H4	119.8
C9—C1—C2—C3	−179.9 (3)	C11—C8—C9—C1	−175.9 (2)
C10—C1—C2—C3	3.8 (4)	Cu1—O1—C10—O2	−25.3 (4)
C9—C1—C2—C7	0.2 (4)	Cu1—O1—C10—C1	150.54 (18)
C10—C1—C2—C7	−176.2 (3)	C9—C1—C10—O2	58.0 (4)
C1—C2—C3—C4	−179.7 (3)	C2—C1—C10—O2	−125.6 (3)
C7—C2—C3—C4	0.3 (4)	C9—C1—C10—O1	−118.3 (3)
C2—C3—C4—C5	−0.1 (5)	C2—C1—C10—O1	58.1 (4)
C3—C4—C5—C6	−0.1 (5)	N1—C8—C11—C15	−20.8 (4)
C4—C5—C6—C7	0.0 (4)	C9—C8—C11—C15	156.9 (3)
C8—N1—C7—C6	−178.7 (3)	N1—C8—C11—C12	161.5 (3)
C8—N1—C7—C2	1.3 (4)	C9—C8—C11—C12	−20.7 (4)
C5—C6—C7—N1	−179.8 (3)	C15—C11—C12—C13	−2.1 (4)
C5—C6—C7—C2	0.3 (4)	C8—C11—C12—C13	175.6 (2)
C3—C2—C7—N1	179.6 (3)	C14—N2—C13—C12	2.7 (4)
C1—C2—C7—N1	−0.4 (4)	Cu1^iv—N2—C13—C12	−171.7 (2)
C3—C2—C7—C6	−0.4 (4)	C11—C12—C13—N2	−0.1 (4)
C1—C2—C7—C6	179.6 (3)	C13—N2—C14—C15	−3.0 (4)
C7—N1—C8—C9	−1.9 (4)	Cu1^iv—N2—C14—C15	171.2 (2)
C7—N1—C8—C11	175.7 (2)	N2—C14—C15—C11	0.8 (5)
C2—C1—C9—C8	−0.8 (4)	C12—C11—C15—C14	1.8 (4)
C10—C1—C9—C8	175.7 (3)	C8—C11—C15—C14	−176.0 (3)
N1—C8—C9—C1	1.8 (4)

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

4-(4-Carboxyquinolin-2-yl)pyridinium chloride monohydrate (kk6dc)

Crystal data

C15H11N2O2^+·Cl^−·H2O	F(000) = 1264
Mr = 304.72	Dx = 1.496 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.402 (3) Å	Cell parameters from 5674 reflections
b = 13.243 (3) Å	θ = 2.9–28.8°
c = 24.421 (3) Å	µ = 0.29 mm^−1
β = 95.08 (3)°	T = 100 K
V = 2706.6 (12) Å^3	Block, colorless
Z = 8	0.20 × 0.19 × 0.18 mm

Data collection

Rigaku KM-4-CCD Sapphire diffractometer	3590 reflections with I > 2σ(I)
/w scans	Rint = 0.087
Absorption correction: analytical	θmax = 28.9°, θmin = 2.9°
Tmin = 0.789, Tmax = 0.879	h = −8→11
24472 measured reflections	k = −17→17
6671 independent reflections	l = −32→32

Refinement

Refinement on F^2	4 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.057	H-atom parameters constrained
wR(F^2) = 0.111	w = 1/[σ^2(Fo^2) + (0.0297P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
6671 reflections	Δρmax = 0.46 e Å^−3
379 parameters	Δρmin = −0.48 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq
Cl1	0.91536 (8)	0.24177 (5)	0.71555 (3)	0.02375 (18)
Cl2	0.42052 (8)	1.21720 (5)	0.73040 (3)	0.02464 (18)
O1	0.5546 (3)	0.50085 (14)	0.60208 (8)	0.0307 (5)
H1O	0.567910	0.447139	0.620982	0.046*
O2	0.5066 (2)	0.56028 (14)	0.68382 (8)	0.0292 (5)
C1	0.4911 (3)	0.6744 (2)	0.60864 (11)	0.0170 (6)
C2	0.4145 (3)	0.74426 (19)	0.63890 (11)	0.0153 (6)
H2	0.384562	0.726750	0.674291	0.018*
C3	0.3802 (3)	0.84175 (19)	0.61755 (11)	0.0150 (6)
N1	0.4195 (3)	0.87148 (16)	0.56908 (9)	0.0178 (5)
C4	0.4982 (3)	0.8052 (2)	0.53859 (11)	0.0177 (6)
C5	0.5443 (3)	0.8400 (2)	0.48721 (11)	0.0200 (6)
H5	0.519682	0.907187	0.475751	0.024*
C6	0.6231 (3)	0.7785 (2)	0.45440 (11)	0.0238 (7)
H6	0.653147	0.802619	0.420163	0.029*
C7	0.6600 (3)	0.6794 (2)	0.47097 (12)	0.0239 (7)
H7	0.714885	0.636922	0.447561	0.029*
C8	0.6192 (3)	0.6424 (2)	0.51988 (11)	0.0206 (7)
H8	0.645969	0.574867	0.530008	0.025*
C9	0.5369 (3)	0.7039 (2)	0.55595 (11)	0.0169 (6)
C10	0.5190 (3)	0.5733 (2)	0.63549 (12)	0.0187 (6)
C11	0.2945 (3)	0.91601 (19)	0.64906 (11)	0.0170 (6)
C12	0.2209 (3)	1.00039 (19)	0.62229 (11)	0.0201 (6)
H12	0.228719	1.010592	0.584116	0.024*
C13	0.1381 (3)	1.0676 (2)	0.65159 (12)	0.0211 (7)
H13	0.089191	1.124807	0.633668	0.025*
N2	0.1257 (3)	1.05332 (16)	0.70514 (9)	0.0185 (5)
H2N	0.072084	1.098824	0.720653	0.028*
C14	0.1958 (3)	0.9762 (2)	0.73233 (12)	0.0215 (7)
H14	0.186051	0.968981	0.770593	0.026*
C15	0.2825 (3)	0.9065 (2)	0.70543 (11)	0.0207 (7)
H15	0.334064	0.852184	0.725232	0.025*
C20	0.9949 (3)	0.66492 (19)	0.60295 (11)	0.0164 (6)
C21	0.9134 (3)	0.73338 (19)	0.63219 (11)	0.0169 (6)
H21	0.874836	0.714179	0.666093	0.020*
C22	0.8871 (3)	0.83198 (19)	0.61189 (11)	0.0165 (6)
N21	0.9329 (3)	0.86286 (16)	0.56428 (9)	0.0175 (5)
C23	1.0097 (3)	0.7954 (2)	0.53355 (11)	0.0175 (6)
C24	1.0549 (3)	0.8287 (2)	0.48219 (11)	0.0229 (7)
H24	1.034660	0.896673	0.471214	0.028*
C25	1.1265 (3)	0.7656 (2)	0.44832 (11)	0.0246 (7)
H25	1.154835	0.789000	0.413722	0.030*
C26	1.1589 (3)	0.6651 (2)	0.46451 (12)	0.0243 (7)
H26	1.208320	0.620920	0.440472	0.029*
C27	1.1202 (3)	0.6302 (2)	0.51452 (12)	0.0229 (7)
H27	1.143846	0.562258	0.524798	0.028*
C28	1.0457 (3)	0.69371 (19)	0.55079 (11)	0.0168 (6)
C29	1.0198 (3)	0.5617 (2)	0.62803 (11)	0.0194 (6)
O20	1.1530 (2)	0.51821 (14)	0.61637 (8)	0.0287 (5)
H2O	1.170214	0.461559	0.632158	0.043*
O21	0.9256 (3)	0.52524 (15)	0.65667 (9)	0.0366 (6)
C30	0.8033 (3)	0.90785 (19)	0.64361 (11)	0.0169 (6)
C31	0.7371 (3)	0.9937 (2)	0.61695 (12)	0.0203 (6)
H31	0.746623	1.003744	0.578856	0.024*
C32	0.6582 (3)	1.0634 (2)	0.64650 (12)	0.0220 (7)
H32	0.613109	1.121901	0.628753	0.026*
N22	0.6447 (3)	1.04891 (16)	0.70013 (10)	0.0208 (5)
H22N	0.593229	1.092452	0.717828	0.031*
C33	0.7059 (3)	0.9683 (2)	0.72726 (12)	0.0217 (7)
H33	0.693180	0.960300	0.765280	0.026*
C34	0.7879 (3)	0.8965 (2)	0.69967 (11)	0.0193 (6)
H34	0.833665	0.839658	0.718869	0.023*
O1W	1.1739 (2)	0.33460 (14)	0.65140 (8)	0.0269 (5)
H1W	1.094678	0.316230	0.668337	0.040*
H2W	1.254364	0.305381	0.668007	0.040*
O2W	0.6212 (2)	0.32842 (14)	0.64808 (8)	0.0280 (5)
H3W	0.712373	0.313241	0.663783	0.042*
H4W	0.554554	0.309784	0.670298	0.042*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0252 (4)	0.0192 (4)	0.0268 (4)	0.0030 (3)	0.0015 (3)	−0.0030 (3)
Cl2	0.0241 (4)	0.0191 (4)	0.0302 (4)	0.0020 (3)	−0.0010 (3)	−0.0034 (3)
O1	0.0588 (15)	0.0135 (10)	0.0201 (12)	0.0112 (10)	0.0060 (10)	0.0039 (9)
O2	0.0474 (14)	0.0207 (11)	0.0205 (12)	0.0046 (10)	0.0095 (10)	0.0040 (9)
C1	0.0209 (15)	0.0166 (14)	0.0132 (15)	−0.0020 (12)	−0.0009 (12)	0.0009 (12)
C2	0.0181 (14)	0.0152 (13)	0.0128 (14)	−0.0015 (12)	0.0026 (11)	0.0013 (12)
C3	0.0156 (14)	0.0153 (14)	0.0138 (15)	−0.0024 (11)	−0.0002 (12)	0.0001 (11)
N1	0.0233 (13)	0.0164 (12)	0.0137 (13)	−0.0002 (10)	0.0019 (10)	−0.0001 (10)
C4	0.0196 (15)	0.0184 (15)	0.0145 (15)	−0.0039 (12)	−0.0024 (12)	0.0020 (12)
C5	0.0237 (16)	0.0150 (14)	0.0210 (16)	−0.0006 (12)	−0.0003 (13)	0.0025 (12)
C6	0.0304 (17)	0.0256 (17)	0.0158 (16)	−0.0039 (13)	0.0035 (13)	0.0009 (13)
C7	0.0288 (17)	0.0228 (16)	0.0208 (17)	0.0020 (13)	0.0068 (14)	−0.0022 (13)
C8	0.0259 (17)	0.0149 (14)	0.0213 (17)	0.0020 (12)	0.0026 (13)	−0.0008 (12)
C9	0.0176 (15)	0.0179 (14)	0.0147 (15)	−0.0022 (12)	−0.0006 (12)	−0.0018 (12)
C10	0.0215 (16)	0.0164 (15)	0.0181 (16)	0.0034 (12)	0.0007 (13)	−0.0006 (12)
C11	0.0180 (15)	0.0145 (14)	0.0181 (16)	−0.0030 (11)	0.0007 (12)	−0.0009 (12)
C12	0.0289 (17)	0.0152 (14)	0.0156 (16)	−0.0035 (12)	−0.0010 (13)	0.0002 (12)
C13	0.0278 (17)	0.0130 (14)	0.0221 (17)	0.0025 (12)	0.0001 (13)	0.0004 (12)
N2	0.0216 (13)	0.0136 (12)	0.0204 (14)	0.0007 (10)	0.0033 (11)	−0.0030 (10)
C14	0.0317 (17)	0.0151 (15)	0.0182 (17)	−0.0006 (13)	0.0060 (13)	0.0006 (12)
C15	0.0274 (17)	0.0187 (15)	0.0158 (16)	0.0001 (13)	0.0011 (13)	0.0019 (12)
C20	0.0209 (15)	0.0152 (14)	0.0128 (15)	−0.0033 (12)	−0.0008 (12)	−0.0015 (11)
C21	0.0170 (14)	0.0193 (15)	0.0144 (14)	−0.0013 (12)	0.0011 (11)	0.0040 (12)
C22	0.0189 (15)	0.0154 (14)	0.0149 (15)	−0.0019 (12)	−0.0005 (12)	−0.0011 (12)
N21	0.0226 (13)	0.0175 (12)	0.0123 (13)	−0.0019 (10)	0.0011 (10)	0.0011 (10)
C23	0.0183 (15)	0.0208 (15)	0.0130 (15)	−0.0033 (12)	−0.0021 (12)	−0.0005 (12)
C24	0.0272 (17)	0.0193 (15)	0.0220 (17)	−0.0005 (13)	0.0009 (14)	0.0034 (13)
C25	0.0315 (18)	0.0308 (18)	0.0120 (15)	−0.0003 (14)	0.0043 (13)	0.0013 (13)
C26	0.0292 (17)	0.0231 (16)	0.0215 (17)	0.0074 (14)	0.0074 (13)	−0.0011 (14)
C27	0.0262 (17)	0.0210 (16)	0.0221 (17)	0.0050 (13)	0.0052 (14)	0.0020 (13)
C28	0.0189 (15)	0.0179 (15)	0.0135 (15)	−0.0022 (12)	0.0008 (12)	−0.0018 (11)
C29	0.0212 (16)	0.0189 (15)	0.0181 (16)	0.0012 (12)	0.0016 (13)	0.0005 (12)
O20	0.0341 (12)	0.0215 (11)	0.0312 (13)	0.0100 (10)	0.0074 (10)	0.0105 (9)
O21	0.0449 (14)	0.0259 (12)	0.0427 (15)	0.0095 (11)	0.0248 (12)	0.0130 (10)
C30	0.0190 (15)	0.0132 (14)	0.0182 (16)	−0.0049 (12)	−0.0001 (12)	−0.0007 (12)
C31	0.0256 (16)	0.0186 (15)	0.0161 (16)	−0.0018 (12)	−0.0003 (13)	0.0012 (12)
C32	0.0270 (16)	0.0166 (14)	0.0220 (17)	0.0010 (12)	0.0001 (13)	0.0056 (13)
N22	0.0248 (13)	0.0132 (12)	0.0246 (14)	0.0016 (10)	0.0042 (11)	−0.0047 (10)
C33	0.0274 (17)	0.0221 (16)	0.0157 (16)	−0.0023 (13)	0.0031 (13)	0.0007 (12)
C34	0.0241 (16)	0.0162 (14)	0.0177 (17)	0.0006 (12)	0.0032 (13)	0.0011 (12)
O1W	0.0324 (12)	0.0234 (11)	0.0250 (12)	0.0071 (9)	0.0038 (9)	0.0071 (9)
O2W	0.0333 (12)	0.0223 (11)	0.0285 (12)	0.0087 (9)	0.0027 (10)	0.0064 (9)

Geometric parameters (Å, º)

O1—C10	1.311 (3)	C20—C29	1.505 (4)
O1—H1O	0.8499	C21—C22	1.407 (4)
O2—C10	1.206 (3)	C21—H21	0.9500
C1—C2	1.379 (4)	C22—N21	1.322 (3)
C1—C9	1.430 (4)	C22—C30	1.484 (4)
C1—C10	1.499 (4)	N21—C23	1.365 (3)
C2—C3	1.412 (3)	C23—C24	1.413 (4)
C2—H2	0.9500	C23—C28	1.435 (4)
C3—N1	1.317 (3)	C24—C25	1.354 (4)
C3—C11	1.475 (4)	C24—H24	0.9500
N1—C4	1.360 (3)	C25—C26	1.407 (4)
C4—C5	1.422 (4)	C25—H25	0.9500
C4—C9	1.436 (4)	C26—C27	1.372 (4)
C5—C6	1.355 (4)	C26—H26	0.9500
C5—H5	0.9500	C27—C28	1.408 (4)
C6—C7	1.400 (4)	C27—H27	0.9500
C6—H6	0.9500	C29—O21	1.203 (3)
C7—C8	1.362 (4)	C29—O20	1.312 (3)
C7—H7	0.9500	O20—H2O	0.8500
C8—C9	1.423 (4)	C30—C34	1.394 (4)
C8—H8	0.9500	C30—C31	1.400 (4)
C11—C15	1.395 (4)	C31—C32	1.378 (4)
C11—C12	1.410 (4)	C31—H31	0.9500
C12—C13	1.370 (4)	C32—N22	1.338 (3)
C12—H12	0.9500	C32—H32	0.9500
C13—N2	1.334 (3)	N22—C33	1.335 (3)
C13—H13	0.9500	N22—H22N	0.8601
N2—C14	1.327 (3)	C33—C34	1.384 (4)
N2—H2N	0.8601	C33—H33	0.9500
C14—C15	1.378 (4)	C34—H34	0.9500
C14—H14	0.9500	O1W—H1W	0.8500
C15—H15	0.9500	O1W—H2W	0.8499
C20—C21	1.374 (4)	O2W—H3W	0.8498
C20—C28	1.431 (4)	O2W—H4W	0.8500
C10—O1—H1O	107.5	C21—C20—C29	116.5 (2)
C2—C1—C9	118.3 (2)	C28—C20—C29	124.2 (2)
C2—C1—C10	115.3 (2)	C20—C21—C22	119.9 (2)
C9—C1—C10	126.4 (2)	C20—C21—H21	120.0
C1—C2—C3	120.4 (2)	C22—C21—H21	120.0
C1—C2—H2	119.8	N21—C22—C21	123.2 (2)
C3—C2—H2	119.8	N21—C22—C30	116.0 (2)
N1—C3—C2	123.1 (2)	C21—C22—C30	120.7 (2)
N1—C3—C11	116.3 (2)	C22—N21—C23	118.0 (2)
C2—C3—C11	120.6 (2)	N21—C23—C24	117.4 (3)
C3—N1—C4	118.2 (2)	N21—C23—C28	123.4 (2)
N1—C4—C5	117.3 (2)	C24—C23—C28	119.2 (3)
N1—C4—C9	123.4 (3)	C25—C24—C23	121.2 (3)
C5—C4—C9	119.4 (3)	C25—C24—H24	119.4
C6—C5—C4	120.8 (3)	C23—C24—H24	119.4
C6—C5—H5	119.6	C24—C25—C26	119.8 (3)
C4—C5—H5	119.6	C24—C25—H25	120.1
C5—C6—C7	120.0 (3)	C26—C25—H25	120.1
C5—C6—H6	120.0	C27—C26—C25	120.9 (3)
C7—C6—H6	120.0	C27—C26—H26	119.5
C8—C7—C6	121.6 (3)	C25—C26—H26	119.5
C8—C7—H7	119.2	C26—C27—C28	120.8 (3)
C6—C7—H7	119.2	C26—C27—H27	119.6
C7—C8—C9	120.7 (3)	C28—C27—H27	119.6
C7—C8—H8	119.6	C27—C28—C20	125.8 (2)
C9—C8—H8	119.6	C27—C28—C23	118.0 (3)
C8—C9—C1	125.8 (3)	C20—C28—C23	116.1 (2)
C8—C9—C4	117.5 (3)	O21—C29—O20	124.6 (3)
C1—C9—C4	116.7 (2)	O21—C29—C20	121.7 (3)
O2—C10—O1	123.2 (3)	O20—C29—C20	113.6 (2)
O2—C10—C1	122.1 (3)	C29—O20—H2O	113.8
O1—C10—C1	114.6 (2)	C34—C30—C31	118.5 (3)
C15—C11—C12	117.5 (3)	C34—C30—C22	121.9 (2)
C15—C11—C3	122.4 (2)	C31—C30—C22	119.6 (2)
C12—C11—C3	120.1 (2)	C32—C31—C30	119.3 (3)
C13—C12—C11	119.7 (3)	C32—C31—H31	120.3
C13—C12—H12	120.2	C30—C31—H31	120.3
C11—C12—H12	120.2	N22—C32—C31	120.2 (3)
N2—C13—C12	120.5 (3)	N22—C32—H32	119.9
N2—C13—H13	119.8	C31—C32—H32	119.9
C12—C13—H13	119.8	C33—N22—C32	122.6 (2)
C14—N2—C13	122.0 (2)	C33—N22—H22N	118.4
C14—N2—H2N	123.0	C32—N22—H22N	119.1
C13—N2—H2N	114.9	N22—C33—C34	119.6 (3)
N2—C14—C15	120.4 (3)	N22—C33—H33	120.2
N2—C14—H14	119.8	C34—C33—H33	120.2
C15—C14—H14	119.8	C33—C34—C30	119.8 (3)
C14—C15—C11	119.9 (3)	C33—C34—H34	120.1
C14—C15—H15	120.1	C30—C34—H34	120.1
C11—C15—H15	120.1	H1W—O1W—H2W	105.2
C21—C20—C28	119.3 (2)	H3W—O2W—H4W	105.2
C9—C1—C2—C3	1.1 (4)	C28—C20—C21—C22	−2.8 (4)
C10—C1—C2—C3	−179.3 (2)	C29—C20—C21—C22	179.1 (2)
C1—C2—C3—N1	−0.7 (4)	C20—C21—C22—N21	2.2 (4)
C1—C2—C3—C11	178.4 (2)	C20—C21—C22—C30	−178.3 (2)
C2—C3—N1—C4	−0.7 (4)	C21—C22—N21—C23	−0.1 (4)
C11—C3—N1—C4	−179.8 (2)	C30—C22—N21—C23	−179.6 (2)
C3—N1—C4—C5	−177.9 (2)	C22—N21—C23—C24	178.6 (2)
C3—N1—C4—C9	1.6 (4)	C22—N21—C23—C28	−1.3 (4)
N1—C4—C5—C6	−179.9 (2)	N21—C23—C24—C25	−177.7 (2)
C9—C4—C5—C6	0.5 (4)	C28—C23—C24—C25	2.2 (4)
C4—C5—C6—C7	−0.1 (4)	C23—C24—C25—C26	−0.8 (4)
C5—C6—C7—C8	−0.2 (4)	C24—C25—C26—C27	−0.6 (4)
C6—C7—C8—C9	0.0 (4)	C25—C26—C27—C28	0.5 (4)
C7—C8—C9—C1	−178.5 (3)	C26—C27—C28—C20	177.7 (3)
C7—C8—C9—C4	0.4 (4)	C26—C27—C28—C23	0.9 (4)
C2—C1—C9—C8	178.7 (3)	C21—C20—C28—C27	−175.4 (3)
C10—C1—C9—C8	−0.8 (4)	C29—C20—C28—C27	2.5 (4)
C2—C1—C9—C4	−0.3 (4)	C21—C20—C28—C23	1.5 (4)
C10—C1—C9—C4	−179.8 (2)	C29—C20—C28—C23	179.4 (2)
N1—C4—C9—C8	179.8 (2)	N21—C23—C28—C27	177.7 (2)
C5—C4—C9—C8	−0.7 (4)	C24—C23—C28—C27	−2.2 (4)
N1—C4—C9—C1	−1.1 (4)	N21—C23—C28—C20	0.5 (4)
C5—C4—C9—C1	178.4 (2)	C24—C23—C28—C20	−179.3 (2)
C2—C1—C10—O2	−14.9 (4)	C21—C20—C29—O21	30.5 (4)
C9—C1—C10—O2	164.6 (3)	C28—C20—C29—O21	−147.4 (3)
C2—C1—C10—O1	163.9 (2)	C21—C20—C29—O20	−148.3 (2)
C9—C1—C10—O1	−16.5 (4)	C28—C20—C29—O20	33.8 (4)
N1—C3—C11—C15	−162.7 (3)	N21—C22—C30—C34	−161.8 (3)
C2—C3—C11—C15	18.2 (4)	C21—C22—C30—C34	18.7 (4)
N1—C3—C11—C12	17.3 (4)	N21—C22—C30—C31	18.2 (4)
C2—C3—C11—C12	−161.8 (2)	C21—C22—C30—C31	−161.3 (2)
C15—C11—C12—C13	−1.7 (4)	C34—C30—C31—C32	−0.6 (4)
C3—C11—C12—C13	178.3 (2)	C22—C30—C31—C32	179.4 (2)
C11—C12—C13—N2	−0.5 (4)	C30—C31—C32—N22	−0.1 (4)
C12—C13—N2—C14	2.0 (4)	C31—C32—N22—C33	0.2 (4)
C13—N2—C14—C15	−1.1 (4)	C32—N22—C33—C34	0.5 (4)
N2—C14—C15—C11	−1.1 (4)	N22—C33—C34—C30	−1.3 (4)
C12—C11—C15—C14	2.5 (4)	C31—C30—C34—C33	1.3 (4)
C3—C11—C15—C14	−177.5 (3)	C22—C30—C34—C33	−178.7 (2)