0D to 3D Pr^III metal–organic networks crystal engineered for optimal iodine adsorption

Four new praseodymium(III) metal–organic compounds varying in dimensionality from 0D to 3D have been designed and synthesized based on N-heterocyclic polycarb­ox­ylic acids, including pyridine-2,6-di­carb­ox­ylic acid (H₂pydc) and pyrazine-2,3-di­carb­ox­ylic acid (H₂pzdc). Altering the concentration of piperazine (pip, ancillary ligand) enables control over the dimensionality of the compound by switching between the 0D [H₂pip][Hpip][Pr(pydc)₃]·4H₂O (I) and the 1D {[Pr(pydc)(Hpydc)(H₂O)₂]·4H₂O}_n (II) coordination polymer (CP). Upon replacing H₂pydc with H₂pzdc, CP II is converted to the 2D CP [Pr(pzdc)(Hpzdc)(H₂O)₃]_n (III) and using the metalloligand [Zn(Hpzdc)₂(H₂O)₂]²⁻, the 3D heterometallic CP {[Pr₂Zn(pzdc)₄(H₂O)₆]·2H₂O}_n (IV) is formed. Com­pound IV shows high stability in the absence of uncoordinated solvent molecules and is stable up to 400°C, even in the presence of humidity. Therefore, IV was utilized for iodine adsorption in the vapour phase and in the presence of humidity. The results confirm the remarkable potential of IV for reversible adsorption of iodine vapour.

Computing details

Data collection: CrysAlis CCD 1.171.38.41 (Rigaku Oxford Diffraction, 2015 for (II); CrysAlis CCD 1.171.38.43 (Rigaku Oxford Diffraction, 2015) for (I), (III), (IV). Cell refinement: CrysAlis RED 1.171.38.41 (Rigaku Oxford Diffraction, 2015) for (II); CrysAlis PRO 1.171.38.43 (Rigaku Oxford Diffraction, 2015) for (I), (III), (IV). Data reduction: CrysAlis RED 1.171.38.41 (Rigaku Oxford Diffraction, 2015) for (II); CrysAlis PRO 1.171.38.43 (Rigaku Oxford Diffraction, 2015) for (I), (III), (IV). Program(s) used to solve structure: SHELXT (Sheldrick, 2014) for (II); SHELXT-2014/7 (Sheldrick, 2014) for (I), (III), (IV). Program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2014) for (II); SHELXL2018/3 (Sheldrick, 2018) for (I), (III), (IV). For all structures, molecular graphics: Brandenburg & Putz (2006). Diamond 3.0. Crystal and Molecular Structure Visualisation, University of Bonn, Germany. Software used to prepare material for publication: SHELXL2014/7 (Sheldrick, 2014) for (II); SHELXL2018/3 (Sheldrick, 2018) for (I), (III), (IV).

(II)

Crystal data

C14H13N2O11Pr·3(H2O)	F(000) = 1152
Mr = 580.22	Dx = 1.952 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.9898 (3) Å	Cell parameters from 19570 reflections
b = 11.2016 (2) Å	θ = 3.0–29.6°
c = 12.9061 (3) Å	µ = 2.55 mm^−1
β = 102.499 (2)°	T = 100 K
V = 1974.56 (7) Å^3	Parallelepiped, light purple
Z = 4	0.25 × 0.23 × 0.12 mm

Data collection

KUMA KM-4 with CCD detector diffractometer	5139 independent reflections
Radiation source: fine-focus sealed X-ray tube	4530 reflections with I > 2σ(I)
Detector resolution: 10.6249 pixels mm^-1	Rint = 0.034
ω–scan	θmax = 29.7°, θmin = 2.4°
Absorption correction: multi-scan CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −18→19
Tmin = 0.797, Tmax = 1.000	k = −15→15
37026 measured reflections	l = −17→17

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.022	Hydrogen site location: mixed
wR(F^2) = 0.054	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0262P)^2 + 2.8293P] where P = (Fo^2 + 2Fc^2)/3
5139 reflections	(Δ/σ)max = 0.003
297 parameters	Δρmax = 0.83 e Å^−3
0 restraints	Δρmin = −0.66 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.

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 > 2sigma(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.

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

	x	y	z	Uiso*/Ueq
Pr	0.73237 (2)	0.70456 (2)	0.84946 (2)	0.00644 (4)
N11	0.54939 (14)	0.70735 (17)	0.86605 (15)	0.0114 (4)
C12	0.50321 (18)	0.8110 (2)	0.8691 (2)	0.0168 (5)
C13	0.4048 (2)	0.8173 (3)	0.8696 (3)	0.0337 (8)
H13	0.373733	0.892255	0.872830	0.040*
C14	0.3523 (2)	0.7117 (3)	0.8655 (4)	0.0484 (11)
H14	0.284135	0.713615	0.863979	0.058*
C15	0.3995 (2)	0.6040 (3)	0.8635 (3)	0.0346 (7)
H15	0.364988	0.530661	0.861311	0.042*
C16	0.49851 (18)	0.6057 (2)	0.8648 (2)	0.0174 (5)
C17	0.56755 (17)	0.9196 (2)	0.87167 (19)	0.0135 (5)
O11	0.65638 (11)	0.90127 (14)	0.86827 (13)	0.0121 (3)
O12	0.52943 (13)	1.01944 (16)	0.87675 (15)	0.0215 (4)
C18	0.56032 (18)	0.4960 (2)	0.86578 (19)	0.0153 (5)
O13	0.64659 (12)	0.50579 (14)	0.86184 (13)	0.0127 (3)
O14	0.51622 (14)	0.39584 (16)	0.87173 (16)	0.0256 (4)
H14A	0.563 (3)	0.319 (3)	0.871 (3)	0.038*
N21	0.83501 (13)	0.94937 (16)	0.48072 (14)	0.0074 (3)
C22	0.82904 (15)	0.95285 (19)	0.58277 (17)	0.0080 (4)
C23	0.86426 (16)	1.0478 (2)	0.64901 (17)	0.0105 (4)
H23	0.861520	1.046713	0.721913	0.013*
C24	0.90350 (17)	1.1440 (2)	0.60561 (18)	0.0118 (4)
H24	0.926146	1.211717	0.648230	0.014*
C25	0.90984 (16)	1.1418 (2)	0.49963 (17)	0.0109 (4)
H25	0.936444	1.207506	0.468787	0.013*
C26	0.87634 (16)	1.04127 (19)	0.44007 (17)	0.0090 (4)
C27	0.77706 (16)	0.84760 (19)	0.61813 (17)	0.0089 (4)
O21	0.78411 (12)	0.83371 (14)	0.71566 (12)	0.0110 (3)
O22	0.72902 (12)	0.78198 (13)	0.54523 (12)	0.0102 (3)
C28	0.88354 (16)	1.0260 (2)	0.32526 (17)	0.0094 (4)
O23	0.84894 (12)	0.92945 (14)	0.28121 (12)	0.0111 (3)
O24	0.92303 (12)	1.10709 (14)	0.28357 (12)	0.0140 (3)
O1	0.87691 (12)	0.81719 (15)	0.93787 (13)	0.0131 (3)
H1A	0.924869	0.800761	0.908968	0.020*
H1B	0.895739	0.792678	1.001990	0.020*
O2	0.63504 (13)	0.65305 (16)	0.67061 (13)	0.0181 (4)
H2A	0.625204	0.577960	0.666213	0.027*
H2B	0.668702	0.667633	0.624315	0.027*
O3	0.95883 (12)	0.81047 (14)	1.14848 (13)	0.0117 (3)
H3A	0.994651	0.751122	1.173431	0.018*
H3B	0.924363	0.831130	1.192400	0.018*
O4	0.96669 (13)	1.05707 (15)	0.09487 (13)	0.0147 (3)
H4A	0.950684	1.073540	0.153290	0.022*
H4B	0.982865	0.983843	0.094650	0.022*
O5	0.80055 (16)	0.09574 (18)	0.91051 (19)	0.0350 (5)
H5A	0.831171	0.091769	0.975331	0.052*
H5B	0.763173	0.035248	0.895378	0.052*
O6	0.62634 (19)	0.22155 (19)	0.8839 (3)	0.0599 (9)
H6A	0.688444	0.217171	0.893522	0.090*
H6B	0.607666	0.149403	0.885745	0.090*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pr	0.00711 (7)	0.00665 (6)	0.00570 (6)	0.00042 (4)	0.00165 (4)	0.00058 (4)
N11	0.0101 (9)	0.0136 (10)	0.0110 (9)	−0.0015 (7)	0.0033 (8)	−0.0008 (7)
C12	0.0125 (12)	0.0152 (12)	0.0230 (13)	−0.0013 (9)	0.0043 (10)	−0.0004 (9)
C13	0.0144 (14)	0.0184 (14)	0.072 (2)	0.0002 (10)	0.0170 (15)	−0.0051 (14)
C14	0.0168 (15)	0.0276 (17)	0.108 (3)	−0.0023 (12)	0.0283 (19)	−0.0064 (18)
C15	0.0163 (14)	0.0231 (15)	0.069 (2)	−0.0067 (11)	0.0182 (14)	−0.0017 (15)
C16	0.0157 (12)	0.0160 (12)	0.0219 (12)	−0.0046 (9)	0.0071 (10)	−0.0002 (10)
C17	0.0128 (11)	0.0121 (11)	0.0156 (11)	0.0006 (9)	0.0031 (9)	−0.0009 (9)
O11	0.0098 (8)	0.0112 (8)	0.0156 (8)	0.0009 (6)	0.0035 (6)	0.0008 (6)
O12	0.0144 (9)	0.0150 (9)	0.0349 (11)	0.0057 (7)	0.0044 (8)	−0.0021 (8)
C18	0.0180 (12)	0.0145 (12)	0.0134 (11)	−0.0034 (9)	0.0030 (9)	0.0012 (9)
O13	0.0126 (8)	0.0101 (8)	0.0152 (8)	−0.0018 (6)	0.0025 (7)	0.0008 (6)
O14	0.0223 (10)	0.0124 (9)	0.0427 (12)	−0.0064 (7)	0.0085 (9)	0.0036 (8)
N21	0.0059 (9)	0.0089 (9)	0.0073 (8)	0.0003 (7)	0.0010 (7)	0.0006 (7)
C22	0.0070 (10)	0.0073 (10)	0.0100 (10)	0.0016 (8)	0.0022 (8)	0.0017 (8)
C23	0.0128 (11)	0.0117 (11)	0.0070 (10)	0.0009 (8)	0.0018 (8)	0.0002 (8)
C24	0.0142 (11)	0.0092 (11)	0.0118 (11)	−0.0017 (8)	0.0024 (9)	−0.0027 (8)
C25	0.0121 (11)	0.0090 (11)	0.0115 (11)	−0.0006 (8)	0.0023 (9)	0.0016 (8)
C26	0.0072 (10)	0.0097 (10)	0.0099 (10)	0.0015 (8)	0.0014 (8)	0.0006 (8)
C27	0.0087 (10)	0.0071 (10)	0.0117 (10)	0.0021 (8)	0.0040 (8)	−0.0002 (8)
O21	0.0151 (8)	0.0119 (8)	0.0058 (7)	−0.0015 (6)	0.0023 (6)	0.0010 (6)
O22	0.0115 (8)	0.0115 (8)	0.0076 (7)	−0.0035 (6)	0.0022 (6)	−0.0016 (6)
C28	0.0088 (10)	0.0096 (10)	0.0097 (10)	0.0005 (8)	0.0019 (8)	0.0007 (8)
O23	0.0154 (8)	0.0101 (7)	0.0085 (7)	−0.0032 (6)	0.0044 (6)	−0.0024 (6)
O24	0.0203 (9)	0.0118 (8)	0.0119 (8)	−0.0047 (7)	0.0081 (7)	0.0010 (6)
O1	0.0115 (8)	0.0188 (9)	0.0088 (8)	−0.0020 (6)	0.0015 (6)	0.0008 (6)
O2	0.0211 (9)	0.0226 (9)	0.0108 (8)	−0.0108 (7)	0.0038 (7)	0.0015 (7)
O3	0.0144 (8)	0.0117 (8)	0.0099 (8)	0.0030 (6)	0.0046 (6)	0.0001 (6)
O4	0.0211 (9)	0.0120 (8)	0.0136 (8)	−0.0030 (7)	0.0095 (7)	−0.0022 (6)
O5	0.0288 (12)	0.0167 (10)	0.0523 (14)	−0.0066 (8)	−0.0071 (10)	0.0030 (9)
O6	0.0290 (13)	0.0141 (11)	0.136 (3)	−0.0004 (9)	0.0169 (16)	0.0014 (14)

Geometric parameters (Å, º)

Pr—O1	2.4462 (16)	C22—C23	1.386 (3)
Pr—O21	2.4779 (15)	C22—C27	1.507 (3)
Pr—O2	2.4808 (16)	C23—C24	1.382 (3)
Pr—O11	2.4811 (16)	C23—H23	0.9500
Pr—O23^i	2.5122 (15)	C24—C25	1.390 (3)
Pr—O22^i	2.5416 (15)	C24—H24	0.9500
Pr—O13	2.5507 (16)	C25—C26	1.387 (3)
Pr—N11	2.615 (2)	C25—H25	0.9500
Pr—N21^i	2.6176 (18)	C26—C28	1.516 (3)
N11—C12	1.334 (3)	C27—O21	1.251 (3)
N11—C16	1.341 (3)	C27—O22	1.266 (3)
C12—C13	1.380 (4)	C28—O24	1.244 (3)
C12—C17	1.509 (3)	C28—O23	1.268 (3)
C13—C14	1.388 (4)	O1—H1A	0.8553
C13—H13	0.9500	O1—H1B	0.8574
C14—C15	1.379 (4)	O2—H2A	0.8522
C14—H14	0.9500	O2—H2B	0.8528
C15—C16	1.382 (4)	O3—H3A	0.8526
C15—H15	0.9500	O3—H3B	0.8518
C16—C18	1.501 (3)	O4—H4A	0.8520
C17—O12	1.247 (3)	O4—H4B	0.8511
C17—O11	1.270 (3)	O5—H5A	0.8546
C18—O13	1.224 (3)	O5—H5B	0.8524
C18—O14	1.291 (3)	O6—H14A	1.40 (4)
O14—H14A	1.08 (4)	O6—H6A	0.8521
N21—C22	1.338 (3)	O6—H6B	0.8512
N21—C26	1.342 (3)
O1—Pr—O21	71.78 (5)	N11—C16—C15	122.7 (2)
O1—Pr—O2	141.79 (5)	N11—C16—C18	113.1 (2)
O21—Pr—O2	70.83 (5)	C15—C16—C18	124.2 (2)
O1—Pr—O11	79.91 (5)	O12—C17—O11	125.4 (2)
O21—Pr—O11	75.27 (5)	O12—C17—C12	117.7 (2)
O2—Pr—O11	97.88 (6)	O11—C17—C12	116.9 (2)
O1—Pr—O23^i	86.44 (5)	C17—O11—Pr	126.18 (14)
O21—Pr—O23^i	78.16 (5)	O13—C18—O14	124.6 (2)
O2—Pr—O23^i	78.58 (6)	O13—C18—C16	119.9 (2)
O11—Pr—O23^i	152.80 (5)	O14—C18—C16	115.5 (2)
O1—Pr—O22^i	72.36 (5)	C18—O13—Pr	124.21 (15)
O21—Pr—O22^i	136.82 (5)	C18—O14—H14A	113.3 (19)
O2—Pr—O22^i	144.51 (5)	C22—N21—C26	119.10 (19)
O11—Pr—O22^i	75.50 (5)	C22—N21—Pr^ii	120.92 (14)
O23^i—Pr—O22^i	122.48 (5)	C26—N21—Pr^ii	118.35 (14)
O1—Pr—O13	140.68 (5)	N21—C22—C23	122.7 (2)
O21—Pr—O13	139.96 (5)	N21—C22—C27	114.34 (18)
O2—Pr—O13	71.60 (5)	C23—C22—C27	122.94 (19)
O11—Pr—O13	123.49 (5)	C24—C23—C22	117.9 (2)
O23^i—Pr—O13	81.39 (5)	C24—C23—H23	121.1
O22^i—Pr—O13	83.07 (5)	C22—C23—H23	121.1
O1—Pr—N11	132.90 (6)	C23—C24—C25	120.0 (2)
O21—Pr—N11	119.27 (6)	C23—C24—H24	120.0
O2—Pr—N11	74.28 (6)	C25—C24—H24	120.0
O11—Pr—N11	62.20 (6)	C26—C25—C24	118.3 (2)
O23^i—Pr—N11	139.22 (6)	C26—C25—H25	120.9
O22^i—Pr—N11	71.87 (6)	C24—C25—H25	120.9
O13—Pr—N11	61.52 (6)	N21—C26—C25	121.9 (2)
O1—Pr—N21^i	75.85 (5)	N21—C26—C28	114.90 (19)
O21—Pr—N21^i	129.31 (5)	C25—C26—C28	123.2 (2)
O2—Pr—N21^i	124.24 (6)	O21—C27—O22	126.1 (2)
O11—Pr—N21^i	135.10 (5)	O21—C27—C22	117.64 (19)
O23^i—Pr—N21^i	61.74 (5)	O22—C27—C22	116.27 (19)
O22^i—Pr—N21^i	61.40 (5)	C27—O21—Pr	143.38 (14)
O13—Pr—N21^i	65.42 (5)	C27—O22—Pr^ii	125.67 (14)
N11—Pr—N21^i	111.38 (6)	O24—C28—O23	126.2 (2)
C12—N11—C16	118.7 (2)	O24—C28—C26	118.03 (19)
C12—N11—Pr	120.12 (15)	O23—C28—C26	115.75 (19)
C16—N11—Pr	121.02 (15)	C28—O23—Pr^ii	124.49 (13)
N11—C12—C13	122.3 (2)	Pr—O1—H1A	109.4
N11—C12—C17	114.3 (2)	Pr—O1—H1B	109.6
C13—C12—C17	123.3 (2)	H1A—O1—H1B	104.2
C12—C13—C14	118.4 (3)	Pr—O2—H2A	109.9
C12—C13—H13	120.8	Pr—O2—H2B	109.4
C14—C13—H13	120.8	H2A—O2—H2B	104.4
C15—C14—C13	119.7 (3)	H3A—O3—H3B	109.4
C15—C14—H14	120.1	H4A—O4—H4B	109.4
C13—C14—H14	120.1	H5A—O5—H5B	109.6
C14—C15—C16	118.1 (3)	H14A—O6—H6A	131.8
C14—C15—H15	121.0	H14A—O6—H6B	123.6
C16—C15—H15	121.0	H6A—O6—H6B	104.5

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x, −y+3/2, z−1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O14—H14A···O6	1.08 (4)	1.40 (4)	2.471 (3)	173 (3)
O6—H14A···O13	1.40 (4)	2.41 (3)	3.215 (3)	112.3 (19)
C25—H25···O3^iii	0.95	2.59	3.481 (3)	156
O1—H1A···O4^iv	0.86	2.21	2.711 (2)	118
O1—H1B···O3	0.86	1.92	2.713 (2)	154
O2—H2A···O12^v	0.85	2.21	2.702 (2)	116
O2—H2B···O22	0.85	1.94	2.712 (2)	150
O3—H3A···O24^vi	0.85	1.99	2.840 (2)	174
O3—H3B···O23^vii	0.85	2.04	2.866 (2)	163
O4—H4A···O24	0.85	1.84	2.695 (2)	177
O4—H4B···O3^viii	0.85	2.11	2.856 (2)	145
O5—H5A···O4^ix	0.85	2.20	2.976 (3)	150
O5—H5B···O11^x	0.85	2.09	2.939 (3)	171
O6—H6A···O5	0.85	2.05	2.772 (3)	142
O6—H6B···O12^x	0.85	1.81	2.630 (3)	161

Symmetry codes: (iii) −x+2, y+1/2, −z+3/2; (iv) −x+2, −y+2, −z+1; (v) −x+1, y−1/2, −z+3/2; (vi) −x+2, y−1/2, −z+3/2; (vii) x, y, z+1; (viii) x, y, z−1; (ix) x, y−1, z+1; (x) x, y−1, z.

(I)

Crystal data

C21H9N3O12Pr·C4H12N2·C4H11N2·4(H2O)[+solvent]	Z = 1
Mr = 1767.18	F(000) = 900
Triclinic, P1	Dx = 1.572 Mg m^−3
a = 10.1302 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.4807 (6) Å	Cell parameters from 5618 reflections
c = 17.8828 (11) Å	θ = 2.8–25.9°
α = 86.979 (4)°	µ = 1.38 mm^−1
β = 80.143 (5)°	T = 100 K
γ = 87.451 (4)°	Parallelepiped, light-yellow
V = 1866.81 (18) Å^3	0.21 × 0.18 × 0.15 mm

Data collection

KUMA KM-4 with CCD detector diffractometer	7325 independent reflections
Radiation source: fine-focus sealed X-ray tube	5816 reflections with I > 2σ(I)
Detector resolution: 10.6249 pixels mm^-1	Rint = 0.081
ω–scan	θmax = 26.0°, θmin = 2.5°
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −12→12
Tmin = 0.887, Tmax = 1.000	k = −12→12
28543 measured reflections	l = −22→22

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.061	Hydrogen site location: mixed
wR(F^2) = 0.164	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.093P)^2 + 1.2435P] where P = (Fo^2 + 2Fc^2)/3
7325 reflections	(Δ/σ)max = 0.001
490 parameters	Δρmax = 4.87 e Å^−3
0 restraints	Δρmin = −1.58 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.

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 > 2sigma(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.

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

	x	y	z	Uiso*/Ueq
Pr	0.50206 (3)	0.48944 (3)	0.24776 (2)	0.01043 (13)
N1	0.4932 (5)	0.7406 (4)	0.2430 (3)	0.0084 (10)
O1	0.6835 (4)	0.6031 (4)	0.1613 (3)	0.0148 (10)
O2	0.3382 (4)	0.3172 (4)	0.2770 (3)	0.0176 (10)
O3	0.6799 (4)	0.3130 (4)	0.2245 (3)	0.0156 (10)
O4	0.3121 (4)	0.6000 (4)	0.3299 (3)	0.0158 (10)
O5	0.6628 (4)	0.5427 (4)	0.3313 (3)	0.0170 (10)
O6	0.3459 (4)	0.5568 (4)	0.1571 (3)	0.0158 (10)
O7	0.1827 (4)	0.7715 (4)	0.3675 (3)	0.0186 (10)
O8	0.8017 (5)	0.7751 (4)	0.1218 (3)	0.0195 (11)
N2	0.5216 (5)	0.3669 (4)	0.1216 (3)	0.0132 (11)
O9	0.2517 (4)	0.5284 (4)	0.0547 (3)	0.0191 (10)
O10	0.2071 (5)	0.1873 (4)	0.3585 (3)	0.0211 (11)
N3	0.4864 (5)	0.3641 (4)	0.3784 (3)	0.0125 (11)
O11	0.8043 (4)	0.1732 (4)	0.1503 (3)	0.0192 (10)
O12	0.7532 (5)	0.5144 (5)	0.4375 (3)	0.0219 (11)
N4	1.0071 (5)	0.5852 (4)	0.4341 (3)	0.0134 (11)
H4A	1.053728	0.640287	0.399403	0.016*
H4B	0.923791	0.579773	0.422126	0.016*
N5	−0.0152 (5)	0.5872 (5)	0.0605 (3)	0.0152 (12)
H5A	0.068641	0.584884	0.072475	0.018*
H5B	−0.067538	0.642204	0.091604	0.018*
C1	0.7022 (6)	0.7227 (6)	0.1575 (4)	0.0110 (13)
C2	0.7091 (6)	0.2519 (5)	0.1640 (4)	0.0116 (13)
C3	0.5895 (6)	0.8044 (5)	0.1995 (4)	0.0114 (13)
C4	0.3870 (6)	0.8027 (5)	0.2831 (4)	0.0120 (13)
C5	0.2841 (6)	0.7194 (5)	0.3307 (4)	0.0109 (13)
C6	0.3348 (6)	0.5010 (6)	0.0968 (3)	0.0106 (12)
C7	0.6172 (6)	0.2735 (5)	0.1057 (4)	0.0137 (13)
C8	0.5704 (6)	0.3917 (6)	0.4263 (4)	0.0159 (14)
C9	0.3030 (6)	0.2567 (5)	0.3405 (4)	0.0150 (14)
O13	0.1033 (5)	0.3443 (5)	0.2139 (3)	0.0268 (12)
H13A	0.081743	0.422405	0.209671	0.040*
H13B	0.171379	0.341402	0.235874	0.040*
C10	0.6694 (6)	0.4916 (6)	0.3972 (4)	0.0142 (13)
C11	0.4376 (6)	0.3931 (6)	0.0739 (3)	0.0140 (13)
C12	0.3948 (6)	0.2753 (5)	0.3991 (4)	0.0149 (14)
O14	−0.0469 (5)	0.5596 (5)	0.2728 (3)	0.0293 (12)
H14A	−0.111394	0.601630	0.296862	0.044*
H14B	−0.027377	0.602717	0.231204	0.044*
N6	−0.0557 (5)	0.1425 (5)	0.2724 (3)	0.0177 (12)
H6A	0.013718	0.196260	0.260866	0.021*
H6B	−0.104045	0.149798	0.233802	0.021*
C13	1.0761 (7)	0.4566 (6)	0.4292 (4)	0.0178 (14)
H131	1.170174	0.463593	0.436591	0.021*
H132	1.077205	0.423971	0.378167	0.021*
C14	0.4734 (7)	1.0045 (6)	0.2329 (4)	0.0223 (16)
H14	0.465912	1.095071	0.227363	0.027*
C15	0.3762 (7)	0.9365 (6)	0.2795 (4)	0.0200 (15)
H15	0.302533	0.979880	0.308976	0.024*
C16	0.9947 (6)	0.6366 (6)	0.5107 (4)	0.0136 (13)
H161	0.943504	0.719346	0.512158	0.016*
H162	1.085069	0.651791	0.521784	0.016*
C17	0.5838 (7)	0.9365 (6)	0.1937 (4)	0.0205 (15)
H17	0.654793	0.981171	0.163192	0.025*
O15	0.1220 (5)	0.7269 (5)	0.1836 (4)	0.0334 (13)
H15A	0.198806	0.690419	0.179684	0.050*
H15B	0.134642	0.797809	0.158426	0.050*
C18	−0.0704 (7)	0.4579 (6)	0.0733 (4)	0.0159 (14)
H181	−0.164937	0.462066	0.065404	0.019*
H182	−0.068698	0.427312	0.126466	0.019*
C19	0.4401 (7)	0.3263 (6)	0.0076 (4)	0.0200 (15)
H19	0.375946	0.345806	−0.024704	0.024*
C20	−0.0091 (6)	0.6349 (5)	−0.0201 (4)	0.0164 (14)
H201	0.033116	0.719013	−0.027574	0.020*
H202	−0.101145	0.646286	−0.031697	0.020*
C21	0.6286 (7)	0.2050 (6)	0.0406 (4)	0.0185 (14)
H21	0.697210	0.140485	0.030006	0.022*
C22	0.3822 (7)	0.2096 (6)	0.4694 (4)	0.0214 (15)
H22	0.316754	0.146608	0.483365	0.026*
C23	0.5374 (8)	0.2322 (6)	−0.0092 (4)	0.0252 (17)
H23	0.542910	0.186117	−0.054089	0.030*
C24	0.5637 (7)	0.3303 (7)	0.4977 (4)	0.0239 (16)
H24	0.622892	0.350819	0.530796	0.029*
C25	0.4685 (7)	0.2385 (7)	0.5192 (4)	0.0256 (17)
H25	0.461645	0.195210	0.567606	0.031*
C26	−0.0018 (7)	0.0075 (6)	0.2795 (4)	0.0238 (16)
H261	0.051337	−0.017219	0.230311	0.029*
H262	0.057949	0.000967	0.318068	0.029*
C27	−0.1424 (8)	0.1802 (7)	0.3441 (4)	0.0287 (18)
H271	−0.180155	0.268035	0.337697	0.034*
H272	−0.088979	0.178531	0.385646	0.034*
N7	−0.2086 (8)	−0.0436 (6)	0.3716 (4)	0.045 (2)
H7A	−0.246074	−0.103997	0.390847	0.054*
C28	−0.1142 (8)	−0.0801 (6)	0.3022 (5)	0.0305 (18)
H281	−0.076834	−0.167359	0.311035	0.037*
H282	−0.164885	−0.082557	0.259652	0.037*
O16	0.1386 (8)	−0.0283 (7)	0.4728 (5)	0.066 (2)
H16A	0.143687	0.050219	0.460743	0.098*
H16B	0.121115	−0.032433	0.521237	0.098*
C29	−0.2564 (8)	0.0854 (7)	0.3639 (5)	0.0341 (19)
H291	−0.313744	0.109048	0.412098	0.041*
H292	−0.312509	0.092420	0.323563	0.041*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pr	0.0088 (2)	0.01219 (19)	0.0107 (2)	−0.00075 (13)	−0.00297 (13)	0.00020 (12)
N1	0.004 (2)	0.014 (2)	0.008 (3)	−0.003 (2)	−0.003 (2)	−0.0008 (19)
O1	0.020 (2)	0.0033 (19)	0.019 (3)	0.0007 (17)	0.0014 (19)	0.0002 (16)
O2	0.020 (3)	0.014 (2)	0.019 (3)	−0.0004 (19)	−0.002 (2)	−0.0034 (18)
O3	0.020 (2)	0.009 (2)	0.019 (3)	0.0048 (18)	−0.006 (2)	−0.0051 (18)
O4	0.021 (3)	0.009 (2)	0.018 (3)	0.0016 (18)	−0.003 (2)	−0.0030 (17)
O5	0.016 (2)	0.015 (2)	0.019 (3)	−0.0026 (18)	−0.001 (2)	−0.0029 (18)
O6	0.017 (2)	0.013 (2)	0.019 (3)	0.0053 (18)	−0.0058 (19)	−0.0034 (18)
O7	0.012 (2)	0.017 (2)	0.023 (3)	0.0021 (18)	0.007 (2)	−0.0035 (19)
O8	0.016 (3)	0.011 (2)	0.027 (3)	−0.0063 (19)	0.008 (2)	−0.0003 (19)
N2	0.013 (3)	0.011 (2)	0.015 (3)	−0.004 (2)	0.001 (2)	0.000 (2)
O9	0.012 (2)	0.029 (3)	0.018 (3)	−0.0008 (19)	−0.005 (2)	−0.005 (2)
O10	0.021 (3)	0.011 (2)	0.029 (3)	−0.0077 (19)	0.004 (2)	−0.0023 (19)
N3	0.015 (3)	0.008 (2)	0.015 (3)	0.004 (2)	−0.002 (2)	−0.002 (2)
O11	0.017 (2)	0.015 (2)	0.026 (3)	0.0075 (19)	−0.001 (2)	−0.0068 (19)
O12	0.014 (2)	0.039 (3)	0.015 (3)	0.001 (2)	−0.008 (2)	−0.005 (2)
N4	0.013 (3)	0.013 (3)	0.014 (3)	−0.002 (2)	−0.002 (2)	0.003 (2)
N5	0.017 (3)	0.012 (2)	0.017 (3)	0.001 (2)	−0.002 (2)	−0.004 (2)
C1	0.008 (3)	0.015 (3)	0.010 (3)	−0.003 (2)	−0.003 (3)	0.000 (2)
C2	0.012 (3)	0.006 (3)	0.015 (4)	−0.001 (2)	−0.002 (3)	0.003 (2)
C3	0.012 (3)	0.010 (3)	0.013 (3)	−0.004 (2)	−0.003 (3)	0.002 (2)
C4	0.007 (3)	0.012 (3)	0.018 (4)	0.001 (2)	−0.004 (3)	−0.002 (2)
C5	0.012 (3)	0.010 (3)	0.012 (3)	−0.001 (2)	−0.002 (3)	−0.001 (2)
C6	0.006 (3)	0.018 (3)	0.009 (3)	−0.006 (2)	−0.002 (2)	0.001 (2)
C7	0.015 (3)	0.008 (3)	0.016 (4)	−0.005 (2)	0.002 (3)	−0.002 (2)
C8	0.011 (3)	0.019 (3)	0.017 (4)	0.004 (3)	0.002 (3)	−0.003 (3)
C9	0.012 (3)	0.006 (3)	0.022 (4)	−0.003 (2)	0.011 (3)	−0.003 (2)
O13	0.024 (3)	0.028 (3)	0.030 (3)	−0.007 (2)	−0.010 (2)	0.002 (2)
C10	0.009 (3)	0.019 (3)	0.014 (4)	0.010 (3)	−0.001 (3)	−0.006 (3)
C11	0.018 (4)	0.018 (3)	0.006 (3)	−0.004 (3)	−0.002 (3)	0.002 (2)
C12	0.016 (3)	0.011 (3)	0.016 (4)	0.006 (3)	0.001 (3)	0.000 (2)
O14	0.022 (3)	0.032 (3)	0.032 (3)	0.001 (2)	0.000 (2)	0.006 (2)
N6	0.016 (3)	0.013 (3)	0.023 (3)	−0.001 (2)	0.002 (2)	−0.004 (2)
C13	0.021 (4)	0.015 (3)	0.015 (4)	0.002 (3)	0.003 (3)	−0.007 (3)
C14	0.020 (4)	0.014 (3)	0.031 (4)	0.004 (3)	−0.001 (3)	−0.003 (3)
C15	0.009 (3)	0.022 (3)	0.029 (4)	0.001 (3)	0.000 (3)	−0.009 (3)
C16	0.013 (3)	0.014 (3)	0.013 (4)	0.002 (2)	0.001 (3)	−0.005 (2)
C17	0.020 (4)	0.016 (3)	0.022 (4)	−0.003 (3)	0.005 (3)	0.000 (3)
O15	0.018 (3)	0.028 (3)	0.053 (4)	0.008 (2)	−0.003 (3)	−0.002 (3)
C18	0.017 (4)	0.017 (3)	0.014 (4)	−0.004 (3)	−0.002 (3)	−0.002 (2)
C19	0.021 (4)	0.024 (3)	0.015 (4)	−0.005 (3)	−0.001 (3)	−0.003 (3)
C20	0.013 (3)	0.009 (3)	0.026 (4)	0.002 (2)	−0.001 (3)	−0.001 (3)
C21	0.015 (3)	0.018 (3)	0.021 (4)	−0.002 (3)	0.002 (3)	−0.005 (3)
C22	0.021 (4)	0.019 (3)	0.018 (4)	0.002 (3)	0.009 (3)	0.008 (3)
C23	0.040 (5)	0.024 (4)	0.014 (4)	−0.001 (3)	−0.007 (3)	−0.012 (3)
C24	0.021 (4)	0.032 (4)	0.019 (4)	0.015 (3)	−0.003 (3)	−0.009 (3)
C25	0.022 (4)	0.034 (4)	0.017 (4)	0.008 (3)	0.003 (3)	0.009 (3)
C26	0.030 (4)	0.023 (4)	0.018 (4)	0.009 (3)	−0.003 (3)	−0.005 (3)
C27	0.034 (5)	0.025 (4)	0.027 (4)	−0.001 (3)	0.000 (3)	−0.015 (3)
N7	0.058 (5)	0.020 (3)	0.047 (5)	−0.009 (3)	0.022 (4)	0.007 (3)
C28	0.031 (4)	0.017 (3)	0.042 (5)	−0.002 (3)	−0.002 (4)	−0.001 (3)
O16	0.059 (5)	0.072 (5)	0.068 (5)	−0.014 (4)	−0.004 (4)	−0.030 (4)
C29	0.034 (5)	0.034 (4)	0.030 (5)	−0.004 (4)	0.007 (4)	−0.003 (3)

Geometric parameters (Å, º)

Pr—O2	2.481 (4)	O14—H14A	0.8396
Pr—O5	2.489 (4)	O14—H14B	0.8472
Pr—O4	2.493 (4)	N6—C27	1.486 (9)
Pr—O1	2.493 (4)	N6—C26	1.501 (8)
Pr—O6	2.508 (4)	N6—H6A	0.9100
Pr—O3	2.523 (4)	N6—H6B	0.9100
Pr—N3	2.602 (5)	C13—C16^i	1.519 (9)
Pr—N1	2.627 (5)	C13—H131	0.9900
Pr—N2	2.629 (5)	C13—H132	0.9900
N1—C3	1.321 (8)	C14—C15	1.375 (9)
N1—C4	1.349 (7)	C14—C17	1.401 (9)
O1—C1	1.273 (7)	C14—H14	0.9500
O2—C9	1.275 (8)	C15—H15	0.9500
O3—C2	1.270 (7)	C16—H161	0.9900
O4—C5	1.272 (7)	C16—H162	0.9900
O5—C10	1.279 (8)	C17—H17	0.9500
O6—C6	1.278 (7)	O15—H15A	0.8449
O7—C5	1.242 (7)	O15—H15B	0.8510
O8—C1	1.232 (7)	C18—C20^ii	1.505 (8)
N2—C11	1.315 (8)	C18—H181	0.9900
N2—C7	1.352 (8)	C18—H182	0.9900
O9—C6	1.237 (7)	C19—C23	1.371 (10)
O10—C9	1.228 (7)	C19—H19	0.9500
N3—C12	1.337 (8)	C20—H201	0.9900
N3—C8	1.356 (8)	C20—H202	0.9900
O11—C2	1.241 (7)	C21—C23	1.401 (10)
O12—C10	1.242 (8)	C21—H21	0.9500
N4—C16	1.483 (8)	C22—C25	1.402 (10)
N4—C13	1.491 (7)	C22—H22	0.9500
N4—H4A	0.9100	C23—H23	0.9500
N4—H4B	0.9100	C24—C25	1.386 (10)
N5—C18	1.481 (7)	C24—H24	0.9500
N5—C20	1.492 (8)	C25—H25	0.9500
N5—H5A	0.9100	C26—C28	1.483 (10)
N5—H5B	0.9100	C26—H261	0.9900
C1—C3	1.512 (8)	C26—H262	0.9900
C2—C7	1.515 (9)	C27—C29	1.540 (10)
C3—C17	1.383 (8)	C27—H271	0.9900
C4—C15	1.400 (8)	C27—H272	0.9900
C4—C5	1.508 (8)	N7—C29	1.423 (9)
C6—C11	1.526 (8)	N7—C28	1.487 (10)
C7—C21	1.385 (9)	N7—H7A	0.7854
C8—C24	1.391 (9)	C28—H281	0.9900
C8—C10	1.493 (9)	C28—H282	0.9900
C9—C12	1.540 (9)	O16—H16A	0.8408
O13—H13A	0.8408	O16—H16B	0.8534
O13—H13B	0.8482	C29—H291	0.9900
C11—C19	1.404 (9)	C29—H292	0.9900
C12—C22	1.390 (9)
O2—Pr—O5	124.60 (15)	N2—C11—C19	123.0 (6)
O2—Pr—O4	78.41 (14)	N2—C11—C6	114.7 (5)
O5—Pr—O4	91.89 (14)	C19—C11—C6	122.2 (6)
O2—Pr—O1	151.99 (15)	N3—C12—C22	121.7 (6)
O5—Pr—O1	75.36 (15)	N3—C12—C9	114.6 (5)
O4—Pr—O1	123.89 (13)	C22—C12—C9	123.7 (6)
O2—Pr—O6	80.08 (14)	H14A—O14—H14B	103.7
O5—Pr—O6	150.65 (14)	C27—N6—C26	111.1 (5)
O4—Pr—O6	76.76 (14)	C27—N6—H6A	109.4
O1—Pr—O6	88.51 (14)	C26—N6—H6A	109.4
O2—Pr—O3	86.43 (14)	C27—N6—H6B	109.4
O5—Pr—O3	77.34 (14)	C26—N6—H6B	109.4
O4—Pr—O3	151.87 (15)	H6A—N6—H6B	108.0
O1—Pr—O3	78.88 (14)	N4—C13—C16^i	110.7 (5)
O6—Pr—O3	124.01 (14)	N4—C13—H131	109.5
O2—Pr—N3	62.05 (15)	C16^i—C13—H131	109.5
O5—Pr—N3	62.66 (15)	N4—C13—H132	109.5
O4—Pr—N3	76.18 (15)	C16^i—C13—H132	109.5
O1—Pr—N3	134.54 (15)	H131—C13—H132	108.1
O6—Pr—N3	136.90 (15)	C15—C14—C17	118.1 (6)
O3—Pr—N3	75.79 (15)	C15—C14—H14	120.9
O2—Pr—N1	136.61 (14)	C17—C14—H14	120.9
O5—Pr—N1	76.36 (14)	C14—C15—C4	119.4 (6)
O4—Pr—N1	62.05 (14)	C14—C15—H15	120.3
O1—Pr—N1	61.84 (14)	C4—C15—H15	120.3
O6—Pr—N1	74.41 (14)	N4—C16—C13^i	110.6 (5)
O3—Pr—N1	136.96 (14)	N4—C16—H161	109.5
N3—Pr—N1	119.42 (15)	C13^i—C16—H161	109.5
O2—Pr—N2	74.64 (15)	N4—C16—H162	109.5
O5—Pr—N2	134.66 (15)	C13^i—C16—H162	109.5
O4—Pr—N2	133.44 (15)	H161—C16—H162	108.1
O1—Pr—N2	77.42 (14)	C3—C17—C14	120.0 (6)
O6—Pr—N2	61.78 (15)	C3—C17—H17	120.0
O3—Pr—N2	62.24 (15)	C14—C17—H17	120.0
N3—Pr—N2	120.57 (15)	H15A—O15—H15B	104.9
N1—Pr—N2	120.00 (15)	N5—C18—C20^ii	111.1 (5)
C3—N1—C4	120.9 (5)	N5—C18—H181	109.4
C3—N1—Pr	120.0 (4)	C20^ii—C18—H181	109.4
C4—N1—Pr	119.1 (4)	N5—C18—H182	109.4
C1—O1—Pr	126.3 (4)	C20^ii—C18—H182	109.4
C9—O2—Pr	127.5 (4)	H181—C18—H182	108.0
C2—O3—Pr	125.4 (4)	C23—C19—C11	118.3 (6)
C5—O4—Pr	127.2 (4)	C23—C19—H19	120.8
C10—O5—Pr	126.0 (4)	C11—C19—H19	120.8
C6—O6—Pr	126.0 (4)	N5—C20—C18^ii	110.6 (5)
C11—N2—C7	119.0 (5)	N5—C20—H201	109.5
C11—N2—Pr	121.0 (4)	C18^ii—C20—H201	109.5
C7—N2—Pr	120.0 (4)	N5—C20—H202	109.5
C12—N3—C8	120.0 (6)	C18^ii—C20—H202	109.5
C12—N3—Pr	120.7 (4)	H201—C20—H202	108.1
C8—N3—Pr	119.3 (4)	C7—C21—C23	119.0 (6)
C16—N4—C13	112.4 (5)	C7—C21—H21	120.5
C16—N4—H4A	109.1	C23—C21—H21	120.5
C13—N4—H4A	109.1	C12—C22—C25	118.4 (6)
C16—N4—H4B	109.1	C12—C22—H22	120.8
C13—N4—H4B	109.1	C25—C22—H22	120.8
H4A—N4—H4B	107.9	C19—C23—C21	119.0 (6)
C18—N5—C20	111.5 (5)	C19—C23—H23	120.5
C18—N5—H5A	109.3	C21—C23—H23	120.5
C20—N5—H5A	109.3	C25—C24—C8	118.2 (7)
C18—N5—H5B	109.3	C25—C24—H24	120.9
C20—N5—H5B	109.3	C8—C24—H24	120.9
H5A—N5—H5B	108.0	C24—C25—C22	120.0 (7)
O8—C1—O1	125.3 (6)	C24—C25—H25	120.0
O8—C1—C3	119.0 (5)	C22—C25—H25	120.0
O1—C1—C3	115.7 (5)	C28—C26—N6	109.8 (6)
O11—C2—O3	125.1 (6)	C28—C26—H261	109.7
O11—C2—C7	117.7 (6)	N6—C26—H261	109.7
O3—C2—C7	117.1 (5)	C28—C26—H262	109.7
N1—C3—C17	120.9 (6)	N6—C26—H262	109.7
N1—C3—C1	115.3 (5)	H261—C26—H262	108.2
C17—C3—C1	123.8 (5)	N6—C27—C29	108.5 (5)
N1—C4—C15	120.7 (6)	N6—C27—H271	110.0
N1—C4—C5	115.9 (5)	C29—C27—H271	110.0
C15—C4—C5	123.5 (5)	N6—C27—H272	110.0
O7—C5—O4	126.0 (6)	C29—C27—H272	110.0
O7—C5—C4	118.6 (5)	H271—C27—H272	108.4
O4—C5—C4	115.3 (5)	C29—N7—C28	110.7 (6)
O9—C6—O6	126.3 (6)	C29—N7—H7A	130.1
O9—C6—C11	117.6 (5)	C28—N7—H7A	109.9
O6—C6—C11	116.1 (5)	C26—C28—N7	114.1 (6)
N2—C7—C21	121.6 (6)	C26—C28—H281	108.7
N2—C7—C2	114.7 (5)	N7—C28—H281	108.7
C21—C7—C2	123.7 (6)	C26—C28—H282	108.7
N3—C8—C24	121.7 (6)	N7—C28—H282	108.7
N3—C8—C10	115.5 (6)	H281—C28—H282	107.6
C24—C8—C10	122.7 (6)	H16A—O16—H16B	105.0
O10—C9—O2	127.4 (7)	N7—C29—C27	112.8 (7)
O10—C9—C12	118.6 (6)	N7—C29—H291	109.0
O2—C9—C12	114.0 (5)	C27—C29—H291	109.0
H13A—O13—H13B	105.2	N7—C29—H292	109.0
O12—C10—O5	125.9 (6)	C27—C29—H292	109.0
O12—C10—C8	117.6 (6)	H291—C29—H292	107.8
O5—C10—C8	116.5 (6)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O7^iii	0.91	1.94	2.781 (7)	154
N4—H4B···O12	0.91	1.86	2.698 (7)	152
N5—H5A···O9	0.91	1.90	2.732 (7)	151
N5—H5B···O1^iv	0.91	2.65	3.270 (7)	126
N5—H5B···O8^iv	0.91	1.91	2.780 (7)	159
N6—H6A···O13	0.91	1.91	2.767 (7)	155
N6—H6B···O11^iv	0.91	1.89	2.798 (8)	176
C13—H131···O4^iii	0.99	2.59	3.117 (8)	113
C13—H131···O12^i	0.99	2.53	3.209 (8)	126
C15—H15···O10^v	0.95	2.48	3.317 (8)	146
C16—H162···O12^i	0.99	2.50	3.190 (8)	126
C17—H17···O11^v	0.95	2.55	3.383 (8)	147
C18—H181···O1^iv	0.99	2.58	3.095 (8)	112
C18—H181···O9^ii	0.99	2.45	3.164 (8)	129
C18—H182···O13	0.99	2.63	3.443 (8)	140
C19—H19···O1^vi	0.95	2.64	3.496 (8)	151
C20—H202···O9^ii	0.99	2.53	3.218 (8)	127

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

(III)

Crystal data

C12H11N4O11Pr	Dx = 2.183 Mg m^−3
Mr = 528.16	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 7873 reflections
a = 7.9007 (4) Å	θ = 2.8–26.2°
b = 14.6884 (5) Å	µ = 3.11 mm^−1
c = 27.6980 (13) Å	T = 100 K
V = 3214.3 (2) Å^3	Parallelepiped, colourless
Z = 8	0.25 × 0.14 × 0.10 mm
F(000) = 2064

Data collection

KUMA KM-4 with CCD detector diffractometer	3801 independent reflections
Radiation source: fine-focus sealed X-ray tube	2752 reflections with I > 2σ(I)
Detector resolution: 10.6249 pixels mm^-1	Rint = 0.076
ω–scan	θmax = 27.8°, θmin = 2.8°
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −10→10
Tmin = 0.763, Tmax = 1.000	k = −19→19
52105 measured reflections	l = −36→36

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.051	Hydrogen site location: mixed
wR(F^2) = 0.111	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.044P)^2 + 7.8115P] where P = (Fo^2 + 2Fc^2)/3
3801 reflections	(Δ/σ)max = 0.002
256 parameters	Δρmax = 2.86 e Å^−3
0 restraints	Δρmin = −1.12 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.

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 > 2sigma(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.

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

	x	y	z	Uiso*/Ueq
Pr	0.48728 (4)	0.61073 (2)	0.62835 (2)	0.00916 (11)
N1	0.3517 (6)	0.6093 (3)	0.53425 (19)	0.0136 (11)
C2	0.3036 (7)	0.5256 (4)	0.5191 (2)	0.0113 (12)
C3	0.2290 (8)	0.5104 (4)	0.4746 (2)	0.0133 (13)
N4	0.2029 (6)	0.5844 (3)	0.44616 (19)	0.0138 (11)
H4N	0.150527	0.577085	0.418383	0.017*
C5	0.2541 (7)	0.6685 (4)	0.4588 (2)	0.0164 (13)
H5	0.239833	0.718670	0.437621	0.020*
C6	0.3280 (7)	0.6795 (4)	0.5036 (2)	0.0122 (12)
H6	0.363536	0.738620	0.513099	0.015*
C7	0.3340 (7)	0.4488 (4)	0.5545 (2)	0.0128 (12)
O1	0.4351 (5)	0.4669 (3)	0.58857 (15)	0.0132 (9)
O2	0.2620 (5)	0.3763 (3)	0.54671 (16)	0.0161 (9)
C8	0.1789 (7)	0.4195 (3)	0.4527 (2)	0.0108 (12)
O3	0.0271 (5)	0.4013 (2)	0.45289 (16)	0.0146 (9)
O4	0.3026 (5)	0.3745 (2)	0.43566 (15)	0.0107 (9)
N11	0.8329 (6)	0.3538 (3)	0.7313 (2)	0.0158 (11)
C12	0.8571 (7)	0.4430 (4)	0.7223 (2)	0.0139 (13)
C13	0.8914 (7)	0.5044 (4)	0.7595 (2)	0.0098 (12)
N14	0.8920 (6)	0.4787 (3)	0.80534 (19)	0.0149 (11)
C15	0.8652 (8)	0.3887 (4)	0.8146 (2)	0.0175 (14)
H14	0.864891	0.367601	0.847006	0.021*
C16	0.8382 (8)	0.3272 (4)	0.7770 (2)	0.0175 (14)
H16	0.823208	0.264591	0.784337	0.021*
C17	0.8373 (7)	0.4689 (4)	0.6701 (2)	0.0124 (12)
O11	0.7227 (5)	0.5241 (3)	0.65889 (16)	0.0174 (10)
O12	0.9294 (6)	0.4264 (3)	0.63951 (16)	0.0160 (10)
C18	0.9353 (7)	0.6044 (4)	0.7516 (2)	0.0109 (12)
O13	0.9766 (5)	0.6280 (2)	0.70995 (15)	0.0132 (9)
O14	0.9285 (5)	0.6540 (3)	0.78803 (15)	0.0137 (9)
O1W	0.1724 (5)	0.6122 (3)	0.62895 (16)	0.0133 (9)
H1A	0.133141	0.658754	0.612291	0.020*
H1B	0.134005	0.622683	0.658266	0.020*
O2W	0.4080 (5)	0.7723 (3)	0.61148 (16)	0.0139 (9)
H2A	0.398033	0.783140	0.579469	0.021*
H2B	0.491767	0.810939	0.620063	0.021*
O3W	0.7172 (5)	0.7219 (3)	0.65719 (15)	0.0152 (9)
H3A	0.808162	0.692248	0.667266	0.023*
H3B	0.684005	0.751496	0.683324	0.023*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pr	0.00849 (17)	0.00732 (17)	0.01167 (19)	0.00026 (13)	0.00022 (12)	−0.00031 (12)
N1	0.010 (3)	0.013 (2)	0.017 (3)	0.0008 (19)	0.001 (2)	0.002 (2)
C2	0.004 (3)	0.012 (3)	0.018 (3)	0.005 (2)	0.001 (2)	0.003 (2)
C3	0.014 (3)	0.011 (3)	0.015 (3)	0.003 (2)	0.003 (2)	−0.003 (2)
N4	0.014 (3)	0.013 (2)	0.015 (3)	0.000 (2)	−0.003 (2)	0.001 (2)
C5	0.013 (3)	0.015 (3)	0.022 (4)	0.001 (2)	0.003 (3)	0.004 (3)
C6	0.012 (3)	0.008 (3)	0.017 (3)	0.002 (2)	0.003 (2)	−0.001 (2)
C7	0.011 (3)	0.014 (3)	0.013 (3)	0.004 (2)	0.003 (2)	0.002 (3)
O1	0.011 (2)	0.0138 (18)	0.015 (2)	−0.0001 (16)	−0.0007 (17)	0.0015 (18)
O2	0.016 (2)	0.015 (2)	0.017 (3)	−0.0047 (17)	−0.0022 (18)	0.0000 (18)
C8	0.009 (3)	0.009 (3)	0.014 (3)	0.000 (2)	0.000 (2)	0.002 (2)
O3	0.008 (2)	0.0144 (17)	0.022 (2)	−0.0034 (16)	0.0001 (17)	−0.0052 (17)
O4	0.008 (2)	0.0078 (16)	0.017 (2)	0.0000 (15)	0.0021 (16)	−0.0016 (17)
N11	0.007 (2)	0.017 (3)	0.023 (3)	0.003 (2)	−0.002 (2)	0.001 (2)
C12	0.010 (3)	0.011 (3)	0.021 (4)	−0.007 (2)	0.000 (2)	−0.003 (3)
C13	0.007 (3)	0.010 (2)	0.012 (3)	0.001 (2)	0.002 (2)	0.000 (2)
N14	0.008 (3)	0.013 (2)	0.024 (3)	0.000 (2)	−0.005 (2)	0.000 (2)
C15	0.022 (3)	0.013 (3)	0.018 (4)	−0.005 (2)	−0.002 (3)	0.002 (3)
C16	0.018 (3)	0.008 (3)	0.026 (4)	−0.005 (2)	0.002 (3)	0.001 (3)
C17	0.008 (3)	0.010 (3)	0.019 (4)	−0.007 (2)	−0.003 (2)	0.000 (2)
O11	0.016 (2)	0.0140 (19)	0.022 (3)	0.0011 (18)	−0.0030 (19)	0.0006 (18)
O12	0.017 (2)	0.012 (2)	0.018 (3)	0.0057 (17)	−0.0028 (18)	−0.0015 (18)
C18	0.007 (3)	0.014 (3)	0.012 (3)	0.003 (2)	−0.006 (2)	−0.001 (3)
O13	0.011 (2)	0.0136 (17)	0.015 (2)	0.0002 (16)	0.0014 (17)	0.0003 (17)
O14	0.014 (2)	0.0132 (18)	0.014 (2)	0.0009 (16)	−0.0049 (18)	−0.0004 (18)
O1W	0.007 (2)	0.018 (2)	0.015 (2)	0.0022 (17)	0.0010 (16)	−0.0018 (19)
O2W	0.011 (2)	0.0119 (19)	0.018 (2)	−0.0017 (16)	−0.0050 (18)	0.0024 (18)
O3W	0.011 (2)	0.0117 (18)	0.023 (3)	−0.0009 (16)	−0.0046 (18)	−0.0036 (18)

Geometric parameters (Å, º)

Pr—O11	2.407 (4)	C8—O3	1.229 (7)
Pr—O1	2.418 (4)	C8—O4	1.270 (7)
Pr—O4^i	2.439 (4)	N11—C16	1.324 (8)
Pr—O14^ii	2.446 (4)	N11—C12	1.348 (7)
Pr—O1W	2.488 (4)	C12—C13	1.398 (8)
Pr—O2W	2.499 (4)	C12—C17	1.502 (9)
Pr—O3W	2.570 (4)	C13—N14	1.323 (8)
Pr—N14^ii	2.775 (5)	C13—C18	1.525 (7)
Pr—N1	2.818 (5)	N14—C15	1.363 (7)
N1—C6	1.350 (7)	C15—C16	1.395 (8)
N1—C2	1.354 (7)	C15—H14	0.9500
C2—C3	1.383 (8)	C16—H16	0.9500
C2—C7	1.514 (8)	C17—O11	1.254 (7)
C3—N4	1.358 (7)	C17—O12	1.279 (7)
C3—C8	1.520 (7)	C18—O14	1.246 (7)
N4—C5	1.346 (7)	C18—O13	1.247 (7)
N4—H4N	0.8800	O1W—H1A	0.8809
C5—C6	1.379 (9)	O1W—H1B	0.8801
C5—H5	0.9500	O2W—H2A	0.9042
C6—H6	0.9500	O2W—H2B	0.9032
C7—O2	1.227 (7)	O3W—H3A	0.8852
C7—O1	1.265 (7)	O3W—H3B	0.8843
O11—Pr—O1	80.21 (14)	N4—C5—C6	118.0 (6)
O11—Pr—O4^i	77.09 (14)	N4—C5—H5	121.0
O1—Pr—O4^i	82.09 (13)	C6—C5—H5	121.0
O11—Pr—O14^ii	87.22 (14)	N1—C6—C5	122.3 (5)
O1—Pr—O14^ii	128.75 (13)	N1—C6—H6	118.9
O4^i—Pr—O14^ii	142.63 (14)	C5—C6—H6	118.9
O11—Pr—O1W	140.80 (14)	O2—C7—O1	127.3 (5)
O1—Pr—O1W	80.81 (13)	O2—C7—C2	117.4 (5)
O4^i—Pr—O1W	133.21 (14)	O1—C7—C2	115.3 (5)
O14^ii—Pr—O1W	78.54 (14)	C7—O1—Pr	129.1 (4)
O11—Pr—O2W	139.60 (14)	O3—C8—O4	129.8 (5)
O1—Pr—O2W	134.58 (14)	O3—C8—C3	116.3 (5)
O4^i—Pr—O2W	87.14 (13)	O4—C8—C3	113.9 (5)
O14^ii—Pr—O2W	83.27 (13)	C8—O4—Pr^i	138.4 (4)
O1W—Pr—O2W	75.07 (13)	C16—N11—C12	117.4 (5)
O11—Pr—O3W	71.36 (13)	N11—C12—C13	121.2 (6)
O1—Pr—O3W	144.81 (14)	N11—C12—C17	114.3 (5)
O4^i—Pr—O3W	71.84 (13)	C13—C12—C17	124.6 (5)
O14^ii—Pr—O3W	71.04 (14)	N14—C13—C12	121.6 (5)
O1W—Pr—O3W	134.36 (13)	N14—C13—C18	114.4 (5)
O2W—Pr—O3W	68.39 (13)	C12—C13—C18	124.0 (5)
O11—Pr—N14^ii	66.90 (14)	C13—N14—C15	117.1 (5)
O1—Pr—N14^ii	69.20 (14)	C13—N14—Pr^iii	115.8 (3)
O4^i—Pr—N14^ii	136.72 (13)	C15—N14—Pr^iii	126.6 (4)
O14^ii—Pr—N14^ii	60.21 (13)	N14—C15—C16	120.7 (6)
O1W—Pr—N14^ii	74.37 (14)	N14—C15—H14	119.6
O2W—Pr—N14^ii	136.02 (14)	C16—C15—H14	119.6
O3W—Pr—N14^ii	115.47 (14)	N11—C16—C15	121.8 (5)
O11—Pr—N1	127.92 (14)	N11—C16—H16	119.1
O1—Pr—N1	60.46 (13)	C15—C16—H16	119.1
O4^i—Pr—N1	65.60 (14)	O11—C17—O12	124.2 (6)
O14^ii—Pr—N1	143.66 (14)	O11—C17—C12	118.5 (6)
O1W—Pr—N1	68.05 (14)	O12—C17—C12	117.0 (5)
O2W—Pr—N1	74.88 (13)	C17—O11—Pr	170.5 (4)
O3W—Pr—N1	124.13 (14)	O14—C18—O13	126.8 (5)
N14^ii—Pr—N1	120.24 (14)	O14—C18—C13	115.8 (5)
C6—N1—C2	117.3 (5)	O13—C18—C13	117.4 (5)
C6—N1—Pr	129.0 (4)	C18—O14—Pr^iii	127.4 (3)
C2—N1—Pr	113.7 (4)	Pr—O1W—H1A	110.8
N1—C2—C3	122.9 (5)	Pr—O1W—H1B	110.6
N1—C2—C7	115.5 (5)	H1A—O1W—H1B	103.1
C3—C2—C7	121.7 (5)	Pr—O2W—H2A	111.8
N4—C3—C2	116.9 (5)	Pr—O2W—H2B	111.3
N4—C3—C8	115.6 (5)	H2A—O2W—H2B	102.2
C2—C3—C8	127.4 (5)	Pr—O3W—H3A	111.1
C5—N4—C3	122.4 (5)	Pr—O3W—H3B	110.9
C5—N4—H4N	118.8	H3A—O3W—H3B	103.0
C3—N4—H4N	118.8

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1/2, y, −z+3/2; (iii) x+1/2, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4N···O12^i	0.88	1.72	2.597 (7)	171
C5—H5···O4^iv	0.95	2.31	3.127 (7)	143
C6—H6···O2^iv	0.95	2.44	3.207 (7)	138
C15—H14···O1^iii	0.95	2.37	2.970 (8)	121
C16—H16···O13^v	0.95	2.56	3.292 (7)	134
C16—H16···O14^vi	0.95	2.57	3.318 (7)	136
O1W—H1B···O13^vii	0.88	1.90	2.735 (6)	158
O2W—H2A···O2^iv	0.90	2.07	2.712 (6)	127
O2W—H2B···O12^viii	0.90	1.89	2.716 (6)	152
O3W—H3A···O13	0.89	2.02	2.870 (6)	162
O3W—H3B···N11^viii	0.88	2.01	2.851 (7)	158

Symmetry codes: (i) −x+1, −y+1, −z+1; (iii) x+1/2, y, −z+3/2; (iv) −x+1/2, y+1/2, z; (v) −x+2, y−1/2, −z+3/2; (vi) −x+3/2, y−1/2, z; (vii) x−1, y, z; (viii) −x+3/2, y+1/2, z.

(IV)

Crystal data

C24H20N8O22Pr2Zn·2(H2O)	F(000) = 1128
Mr = 1155.70	Dx = 2.298 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 6.1336 (2) Å	Cell parameters from 5676 reflections
b = 22.6987 (8) Å	θ = 3.2–31.1°
c = 11.9981 (4) Å	µ = 3.70 mm^−1
β = 91.196 (3)°	T = 100 K
V = 1670.07 (10) Å^3	Parallelepiped, colourless
Z = 2	0.22 × 0.09 × 0.08 mm

Data collection

KUMA KM-4 with CCD detector diffractometer	5542 independent reflections
Radiation source: fine-focus sealed X-ray tube	4195 reflections with I > 2σ(I)
Detector resolution: 10.6249 pixels mm^-1	Rint = 0.060
ω–scan	θmax = 32.6°, θmin = 2.5°
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −9→8
Tmin = 0.918, Tmax = 1.000	k = −33→29
20894 measured reflections	l = −18→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: mixed
wR(F^2) = 0.070	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0198P)^2 + 1.1093P] where P = (Fo^2 + 2Fc^2)/3
5542 reflections	(Δ/σ)max = 0.001
274 parameters	Δρmax = 1.41 e Å^−3
0 restraints	Δρmin = −0.96 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.

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 > 2sigma(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.

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

	x	y	z	Uiso*/Ueq
Pr	0.43969 (3)	0.64572 (2)	0.44235 (2)	0.00534 (5)
Zn	1.000000	0.500000	0.000000	0.00879 (12)
N1	0.6444 (5)	0.70098 (13)	0.2628 (2)	0.0080 (6)
C2	0.5250 (5)	0.74357 (15)	0.2134 (3)	0.0066 (7)
C3	0.5961 (5)	0.77310 (15)	0.1186 (3)	0.0072 (7)
N4	0.8010 (5)	0.76470 (13)	0.0834 (2)	0.0081 (6)
C5	0.9187 (5)	0.72203 (16)	0.1322 (3)	0.0087 (7)
H5	1.061702	0.714321	0.107016	0.010*
C6	0.8372 (5)	0.68870 (16)	0.2189 (3)	0.0088 (7)
H6	0.920236	0.656551	0.247489	0.011*
C7	0.3219 (6)	0.76196 (16)	0.2756 (3)	0.0085 (7)
O1	0.2588 (4)	0.72606 (11)	0.34865 (19)	0.0095 (5)
O2	0.2438 (4)	0.81059 (11)	0.2544 (2)	0.0116 (5)
C8	0.4618 (6)	0.81407 (16)	0.0450 (3)	0.0086 (7)
O3	0.2701 (4)	0.80021 (11)	0.01956 (19)	0.0090 (5)
O4	0.5619 (4)	0.85859 (11)	0.0083 (2)	0.0115 (5)
N11	0.7518 (5)	0.56232 (13)	0.0085 (2)	0.0088 (6)
C12	0.6110 (5)	0.54902 (16)	0.0891 (3)	0.0079 (7)
C13	0.4370 (6)	0.58657 (16)	0.1083 (3)	0.0091 (7)
N14	0.4045 (5)	0.63667 (13)	0.0506 (2)	0.0109 (6)
C15	0.5465 (6)	0.64801 (17)	−0.0288 (3)	0.0106 (7)
H15	0.527989	0.682757	−0.072122	0.013*
C16	0.7201 (6)	0.61117 (16)	−0.0508 (3)	0.0096 (7)
H16	0.817324	0.620845	−0.108672	0.012*
C17	0.6572 (6)	0.49241 (16)	0.1530 (3)	0.0094 (7)
O11	0.7926 (4)	0.45782 (11)	0.1104 (2)	0.0103 (5)
O12	0.5578 (4)	0.48544 (12)	0.2405 (2)	0.0155 (6)
C18	0.2623 (6)	0.57313 (16)	0.1910 (3)	0.0081 (7)
O13	0.2660 (4)	0.60033 (11)	0.2814 (2)	0.0117 (5)
O14	0.1140 (4)	0.53817 (11)	0.1597 (2)	0.0119 (5)
O1W	0.3275 (5)	0.53961 (11)	0.4838 (2)	0.0187 (6)
H1A	0.250425	0.524924	0.427649	0.028*
H1B	0.236228	0.538218	0.539457	0.028*
O2W	0.7460 (4)	0.58334 (11)	0.3848 (2)	0.0147 (6)
H2A	0.716728	0.546273	0.395931	0.022*
H2B	0.859787	0.589662	0.427740	0.022*
O3W	0.5262 (5)	0.61214 (12)	0.6343 (2)	0.0227 (7)
H3A	0.418467	0.591500	0.660252	0.034*
H3B	0.534006	0.642257	0.679336	0.034*
O4W	0.0320 (5)	0.47626 (14)	0.3579 (2)	0.0254 (7)
H4A	0.092099	0.442690	0.365176	0.038*
H4B	0.033772	0.483084	0.288271	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pr	0.00536 (8)	0.00519 (9)	0.00548 (8)	0.00021 (8)	0.00003 (6)	−0.00010 (7)
Zn	0.0073 (3)	0.0097 (3)	0.0094 (3)	0.0006 (2)	0.0020 (2)	−0.0002 (2)
N1	0.0080 (13)	0.0080 (15)	0.0078 (13)	0.0000 (12)	−0.0009 (11)	0.0012 (11)
C2	0.0081 (16)	0.0029 (16)	0.0088 (16)	−0.0020 (13)	−0.0010 (13)	−0.0010 (12)
C3	0.0060 (15)	0.0070 (17)	0.0085 (16)	−0.0015 (13)	−0.0013 (13)	−0.0023 (13)
N4	0.0091 (14)	0.0070 (15)	0.0081 (14)	−0.0007 (12)	−0.0004 (11)	0.0002 (11)
C5	0.0042 (15)	0.0099 (18)	0.0121 (17)	−0.0010 (13)	−0.0005 (13)	0.0007 (13)
C6	0.0064 (15)	0.0069 (17)	0.0130 (17)	0.0003 (14)	−0.0019 (13)	0.0007 (14)
C7	0.0086 (16)	0.0089 (18)	0.0079 (16)	0.0011 (14)	0.0016 (13)	−0.0034 (13)
O1	0.0087 (12)	0.0132 (14)	0.0065 (12)	0.0022 (10)	0.0023 (9)	0.0023 (10)
O2	0.0172 (13)	0.0087 (13)	0.0089 (12)	0.0068 (11)	0.0002 (10)	0.0000 (10)
C8	0.0072 (16)	0.0113 (18)	0.0073 (16)	0.0022 (14)	0.0025 (13)	0.0010 (13)
O3	0.0054 (11)	0.0114 (14)	0.0100 (12)	0.0015 (10)	0.0003 (9)	0.0011 (10)
O4	0.0072 (11)	0.0118 (14)	0.0157 (12)	0.0007 (11)	0.0048 (10)	0.0063 (11)
N11	0.0110 (14)	0.0090 (15)	0.0064 (13)	−0.0016 (12)	0.0002 (11)	−0.0019 (11)
C12	0.0063 (15)	0.0096 (18)	0.0077 (15)	0.0000 (14)	−0.0018 (12)	−0.0037 (13)
C13	0.0124 (17)	0.0078 (18)	0.0070 (15)	−0.0023 (14)	−0.0017 (13)	−0.0025 (13)
N14	0.0118 (15)	0.0097 (17)	0.0110 (14)	−0.0005 (12)	−0.0020 (12)	−0.0025 (12)
C15	0.0133 (17)	0.0085 (18)	0.0100 (16)	−0.0012 (15)	−0.0023 (13)	−0.0003 (14)
C16	0.0092 (16)	0.0083 (18)	0.0115 (17)	−0.0037 (14)	0.0029 (13)	0.0005 (13)
C17	0.0082 (16)	0.0100 (18)	0.0098 (16)	−0.0015 (14)	−0.0019 (13)	−0.0058 (14)
O11	0.0099 (12)	0.0072 (13)	0.0138 (12)	0.0008 (10)	0.0031 (10)	0.0012 (10)
O12	0.0206 (14)	0.0162 (15)	0.0100 (12)	0.0072 (12)	0.0062 (11)	0.0042 (10)
C18	0.0087 (16)	0.0068 (17)	0.0088 (16)	0.0059 (14)	−0.0033 (13)	−0.0003 (13)
O13	0.0106 (12)	0.0128 (14)	0.0115 (12)	0.0015 (11)	−0.0003 (10)	−0.0057 (10)
O14	0.0119 (12)	0.0152 (14)	0.0085 (12)	−0.0015 (11)	−0.0004 (10)	−0.0030 (10)
O1W	0.0286 (16)	0.0096 (14)	0.0175 (14)	−0.0049 (12)	−0.0128 (12)	0.0014 (11)
O2W	0.0100 (13)	0.0073 (13)	0.0269 (15)	0.0012 (11)	0.0034 (11)	−0.0015 (11)
O3W	0.0427 (19)	0.0131 (15)	0.0120 (14)	−0.0147 (14)	−0.0085 (13)	0.0021 (11)
O4W	0.0287 (17)	0.035 (2)	0.0127 (14)	−0.0167 (15)	−0.0026 (13)	0.0014 (13)

Geometric parameters (Å, º)

Pr—O1	2.402 (2)	C7—O1	1.264 (4)
Pr—O13	2.417 (2)	C8—O3	1.249 (4)
Pr—O2W	2.463 (2)	C8—O4	1.267 (4)
Pr—O4^i	2.466 (2)	N11—C16	1.330 (4)
Pr—O3W	2.473 (3)	N11—C12	1.344 (4)
Pr—O3^ii	2.528 (2)	C12—C13	1.389 (5)
Pr—O1W	2.557 (3)	C12—C17	1.520 (5)
Pr—N4^i	2.789 (3)	C13—N14	1.344 (4)
Pr—N1	2.811 (3)	C13—C18	1.506 (5)
Zn—N11	2.082 (3)	N14—C15	1.329 (4)
Zn—N11^iii	2.082 (3)	C15—C16	1.384 (5)
Zn—O11^iii	2.088 (2)	C15—H15	0.9500
Zn—O11	2.088 (2)	C16—H16	0.9500
Zn—O14^iv	2.204 (2)	C17—O12	1.235 (4)
Zn—O14^v	2.204 (2)	C17—O11	1.259 (4)
N1—C6	1.334 (4)	C18—O13	1.248 (4)
N1—C2	1.343 (4)	C18—O14	1.258 (4)
C2—C3	1.399 (5)	O1W—H1A	0.8801
C2—C7	1.523 (5)	O1W—H1B	0.8810
C3—N4	1.348 (4)	O2W—H2A	0.8714
C3—C8	1.514 (5)	O2W—H2B	0.8707
N4—C5	1.336 (4)	O3W—H3A	0.8726
C5—C6	1.387 (5)	O3W—H3B	0.8719
C5—H5	0.9500	O4W—H4A	0.8502
C6—H6	0.9500	O4W—H4B	0.8501
C7—O2	1.228 (4)
O1—Pr—O13	76.00 (8)	N4—C3—C2	119.7 (3)
O1—Pr—O2W	130.75 (8)	N4—C3—C8	113.8 (3)
O13—Pr—O2W	81.78 (8)	C2—C3—C8	126.4 (3)
O1—Pr—O4^i	75.66 (8)	C5—N4—C3	117.6 (3)
O13—Pr—O4^i	80.67 (8)	C5—N4—Pr^vi	128.7 (2)
O2W—Pr—O4^i	142.62 (9)	C3—N4—Pr^vi	112.7 (2)
O1—Pr—O3W	139.28 (9)	N4—C5—C6	121.6 (3)
O13—Pr—O3W	134.05 (9)	N4—C5—H5	119.2
O2W—Pr—O3W	86.22 (9)	C6—C5—H5	119.2
O4^i—Pr—O3W	82.75 (9)	N1—C6—C5	121.2 (3)
O1—Pr—O3^ii	99.31 (8)	N1—C6—H6	119.4
O13—Pr—O3^ii	146.76 (8)	C5—C6—H6	119.4
O2W—Pr—O3^ii	76.80 (8)	O2—C7—O1	126.8 (3)
O4^i—Pr—O3^ii	130.77 (8)	O2—C7—C2	117.7 (3)
O3W—Pr—O3^ii	69.74 (9)	O1—C7—C2	115.4 (3)
O1—Pr—O1W	133.05 (8)	C7—O1—Pr	132.0 (2)
O13—Pr—O1W	68.76 (9)	O3—C8—O4	125.2 (3)
O2W—Pr—O1W	73.92 (9)	O3—C8—C3	119.1 (3)
O4^i—Pr—O1W	69.00 (9)	O4—C8—C3	115.5 (3)
O3W—Pr—O1W	65.29 (9)	C8—O3—Pr^vii	135.3 (2)
O3^ii—Pr—O1W	127.09 (8)	C8—O4—Pr^vi	123.1 (2)
O1—Pr—N4^i	65.59 (8)	C16—N11—C12	118.9 (3)
O13—Pr—N4^i	131.34 (8)	C16—N11—Zn	129.7 (2)
O2W—Pr—N4^i	146.43 (9)	C12—N11—Zn	111.4 (2)
O4^i—Pr—N4^i	62.22 (8)	N11—C12—C13	119.3 (3)
O3W—Pr—N4^i	73.86 (9)	N11—C12—C17	115.9 (3)
O3^ii—Pr—N4^i	71.10 (8)	C13—C12—C17	124.8 (3)
O1W—Pr—N4^i	118.82 (9)	N14—C13—C12	122.6 (3)
O1—Pr—N1	60.78 (8)	N14—C13—C18	114.3 (3)
O13—Pr—N1	76.96 (8)	C12—C13—C18	123.0 (3)
O2W—Pr—N1	71.70 (8)	C15—N14—C13	116.2 (3)
O4^i—Pr—N1	134.52 (8)	N14—C15—C16	122.6 (3)
O3W—Pr—N1	139.52 (9)	N14—C15—H15	118.7
O3^ii—Pr—N1	72.36 (8)	C16—C15—H15	118.7
O1W—Pr—N1	134.08 (9)	N11—C16—C15	120.4 (3)
N4^i—Pr—N1	106.64 (8)	N11—C16—H16	119.8
N11—Zn—N11^iii	180.00 (12)	C15—C16—H16	119.8
N11—Zn—O11^iii	100.09 (10)	O12—C17—O11	127.3 (4)
N11^iii—Zn—O11^iii	79.91 (10)	O12—C17—C12	116.5 (3)
N11—Zn—O11	79.91 (10)	O11—C17—C12	116.1 (3)
N11^iii—Zn—O11	100.09 (10)	C17—O11—Zn	112.8 (2)
O11^iii—Zn—O11	180.00 (10)	O13—C18—O14	124.8 (3)
N11—Zn—O14^iv	95.21 (10)	O13—C18—C13	118.1 (3)
N11^iii—Zn—O14^iv	84.79 (10)	O14—C18—C13	116.8 (3)
O11^iii—Zn—O14^iv	79.34 (9)	C18—O13—Pr	154.9 (2)
O11—Zn—O14^iv	100.66 (9)	C18—O14—Zn^viii	136.1 (2)
N11—Zn—O14^v	84.79 (10)	Pr—O1W—H1A	110.5
N11^iii—Zn—O14^v	95.21 (10)	Pr—O1W—H1B	111.0
O11^iii—Zn—O14^v	100.66 (9)	H1A—O1W—H1B	103.1
O11—Zn—O14^v	79.34 (9)	Pr—O2W—H2A	110.5
O14^iv—Zn—O14^v	180.00 (12)	Pr—O2W—H2B	110.2
C6—N1—C2	117.1 (3)	H2A—O2W—H2B	103.5
C6—N1—Pr	128.5 (2)	Pr—O3W—H3A	110.4
C2—N1—Pr	114.3 (2)	Pr—O3W—H3B	110.1
N1—C2—C3	121.8 (3)	H3A—O3W—H3B	103.4
N1—C2—C7	115.2 (3)	H4A—O4W—H4B	104.5
C3—C2—C7	122.6 (3)

Symmetry codes: (i) x−1/2, −y+3/2, z+1/2; (ii) x+1/2, −y+3/2, z+1/2; (iii) −x+2, −y+1, −z; (iv) −x+1, −y+1, −z; (v) x+1, y, z; (vi) x+1/2, −y+3/2, z−1/2; (vii) x−1/2, −y+3/2, z−1/2; (viii) x−1, y, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O3^v	0.95	2.57	3.121 (4)	118
C6—H6···O13^v	0.95	2.50	3.379 (4)	154
C6—H6···O2W	0.95	2.59	3.169 (4)	120
C15—H15···O2^vi	0.95	2.49	3.040 (4)	117
C16—H16···O2^vi	0.95	2.30	2.941 (4)	124
O1W—H1A···O4W	0.88	1.92	2.742 (4)	156
O1W—H1B···O4W^ix	0.88	2.10	2.962 (4)	165
O2W—H2A···O12	0.87	2.50	3.031 (4)	120
O2W—H2A···O1W^x	0.87	2.44	3.242 (4)	153
O2W—H2A···O4W^v	0.87	2.55	3.019 (4)	115
O2W—H2B···O4^ii	0.87	1.95	2.751 (4)	152
O3W—H3A···O12^x	0.87	2.12	2.731 (4)	127
O3W—H3B···O2^ii	0.87	1.89	2.618 (4)	140

Symmetry codes: (ii) x+1/2, −y+3/2, z+1/2; (v) x+1, y, z; (vi) x+1/2, −y+3/2, z−1/2; (ix) −x, −y+1, −z+1; (x) −x+1, −y+1, −z+1.