Experimental and theoretical structural investigation of an ionic Nd coordination polymer

Research concerning coordination polymers has been intense due to their sig­nificant variability and structural stability. With this in mind, an ionic neo­dym­ium coordination polymer was synthesized, com­posed of an anionic one-di­men­sional polymer inter­connected to a cationic three-dimensional porous <!?tlsb=-0.02pt>poly­mer, poly[dodeca­aqua­bis­(μ-pyridine-4-carbohydrazide-κ²N:O)bis­(μ₂-4-sul­fobenzoato-κ²O:O′)bis­(μ₃-4-sulfobenzoato-κ³O:O′:O′′)trineodymium(III)] catena-poly[aqua­bis­(μ-pyridine-4-carbohydrazide-κ²N:O)bis­(μ₂-4-sulfobenzoato-κ²O:O′)neodymium(III)] 4.33-hydrate, {[Nd₃(C₇H₄O₅S)₄(C₆H₇N₃O)₂(H₂O)₁₂][Nd(C₇H₄O₅S)₂(C₆H₇N₃O)₂(H₂O)]·4.33H₂O}_n. The ligands used were 4-sulfobenzoate (PSB) and pyridine-4-carbohydrazide, popularly known as isoniazid (INH), an anti­biotic drug. The com­pound crystallizes in the monoclinic space group C2/c, with Z = 4. Solid-state calculations suggest that the crystal structure is mainly stabilized by hydrogen bonds, i.e. O—H...O and N—H...O inter­actions among the polymers, and by van der Waals inter­actions involving the organic side chains. This net is tetra­gonal, 2-nodal 3,4-connected, and can be described as the dmd (sqc 528) type.

Computing details

Poly[dodecaaquabis(µ-pyridine-4-carbohydrazide-κ²N:O)bis(µ₂-4-sulfobenzoato-κ²O:O')bis(µ₃-4-sulfobenzoato-κ³O:O':O'')trineodymium(III)] catena-poly[aquabis(µ-pyridine-4-carbohydrazide-κ²N:O)bis(µ₂-4-sulfobenzoato-κ²O:O')neodymium(III)] 4.33-hydrate

Crystal data

[Nd3(C7H4O5S)4(C6H7N3O)2(H2O)12][Nd(C7H4O5S)2(C6H7N3O)2(H2O)]·4.33H2O	F(000) = 5249
Mr = 2638.77	Dx = 1.899 Mg m^−3
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -C 2yc	Cell parameters from 79160 reflections
a = 44.4766 (3) Å	θ = 2.1–79.4°
b = 21.3079 (1) Å	µ = 19.11 mm^−1
c = 10.3339 (1) Å	T = 301 K
β = 109.625 (1)°	Block, colorless
V = 9224.57 (13) Å^3	0.18 × 0.15 × 0.03 mm
Z = 4

Data collection

Rigaku XtaLAB Synergy Dualflex diffractometer with a HyPix detector	9979 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	9556 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.053
Detector resolution: 10 pixels mm^-1	θmax = 79.7°, θmin = 2.1°
ω scans	h = −56→56
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2022)	k = −27→25
Tmin = 0.09, Tmax = 0.727	l = −13→13
135465 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.023	H-atom parameters constrained
wR(F^2) = 0.060	w = 1/[σ^2(Fo^2) + (0.0278P)^2 + 22.8243P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.004
9979 reflections	Δρmax = 0.78 e Å^−3
642 parameters	Δρmin = −0.61 e Å^−3
0 restraints

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

Refinement. A Sinergy diffractometer was used to collect the measures for the crystallographic determination, with copper radiation (λ = 1,54184 Å) at ambient temperature. The data were initially processed using the CrysAlis PRP software (Wang et al., 2016), working in the collection of reflections measured by single-crystal X-ray diffraction, in the determination of the space group, data integration and reduction, as well as potential corrections for absorption and generation of files necessary for structural refinement. OLEX2 (Dolomanov et al., 2009) was employed for structure resolution, in conjunction with the SHELX suite of crystallographic programs (Sheldrick, 2015). The non-hydrogen atoms were refined with anisotropic thermal parameters. The figures were made in Ortep-3 for Windows (Farrugia, 2012), Mercury (Macrae et al., 2020), POV-Ray (POV-Ray, 2004), VMD (Humphrey et al., 1996), Vesta (Momma & Izumi, 2008), MarvinSketch (ChemAxon, 2024) and QtiPlot (Vasilief, 2024).

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Nd1	0.5	0.47761 (2)	0.25	0.02221 (5)
Nd2	0.75844 (2)	0.64031 (2)	0.37579 (2)	0.02047 (4)
Nd3	1	0.51152 (2)	0.25	0.02254 (5)
S1	0.69233 (2)	0.57370 (3)	0.73330 (7)	0.02952 (13)
S2	0.94548 (2)	0.76380 (3)	0.71376 (8)	0.03431 (15)
S3	0.80827 (2)	0.59937 (3)	0.14933 (6)	0.02757 (13)
N1	0.49629 (6)	0.38947 (12)	0.4350 (3)	0.0324 (5)
H1A	0.512203	0.3622	0.448294	0.039*
H1B	0.498746	0.408146	0.514966	0.039*
N2	0.46692 (6)	0.35649 (12)	0.3920 (3)	0.0356 (6)
H2	0.461616	0.332145	0.447081	0.043*
N3	0.35649 (8)	0.27632 (19)	0.1313 (4)	0.0637 (10)
N4	0.76229 (5)	0.65635 (12)	0.6460 (2)	0.0307 (5)
H4A	0.755054	0.694329	0.656132	0.037*
H4B	0.74991	0.628134	0.66699	0.037*
N5	0.79395 (5)	0.64981 (12)	0.7374 (2)	0.0312 (5)
H5	0.798808	0.65806	0.82347	0.037*
N6	0.91449 (6)	0.63679 (13)	0.9347 (3)	0.0389 (6)
O1	0.53584 (5)	0.51368 (10)	0.4590 (2)	0.0331 (4)
O2	0.54310 (5)	0.48225 (11)	0.6712 (2)	0.0356 (5)
O3	0.70740 (5)	0.56490 (13)	0.8798 (2)	0.0481 (6)
O4	0.69401 (6)	0.63679 (12)	0.6870 (3)	0.0574 (7)
O5	0.70459 (6)	0.52986 (13)	0.6554 (3)	0.0543 (6)
O6	0.45498 (5)	0.39941 (11)	0.1816 (2)	0.0400 (5)
O7	0.5	0.59705 (13)	0.25	0.0342 (6)
H7	0.48423	0.622124	0.22486	0.051*	0.5
O8	0.78537 (4)	0.73712 (9)	0.4577 (2)	0.0293 (4)
O9	0.78938 (4)	0.81004 (10)	0.6165 (2)	0.0345 (4)
O10	0.95355 (5)	0.81240 (11)	0.6319 (3)	0.0441 (5)
O11	0.95887 (5)	0.77663 (14)	0.8593 (3)	0.0528 (6)
O12	0.95269 (5)	0.70149 (12)	0.6763 (3)	0.0555 (7)
O13	0.96676 (5)	0.54445 (11)	0.3736 (2)	0.0387 (5)
O14	0.95557 (5)	0.52476 (11)	0.5630 (2)	0.0400 (5)
O15	0.79359 (6)	0.53786 (12)	0.1192 (3)	0.0494 (6)
O16	0.80632 (5)	0.63582 (13)	0.0288 (2)	0.0490 (6)
O17	0.79749 (4)	0.63365 (9)	0.2478 (2)	0.0295 (4)
O18	0.80946 (4)	0.61457 (9)	0.56387 (19)	0.0286 (4)
O19	0.77499 (6)	0.52566 (10)	0.3604 (2)	0.0428 (5)
H19A	0.789425	0.51482	0.435909	0.064*
H19B	0.784305	0.522569	0.300067	0.064*
O20	0.74517 (5)	0.72184 (10)	0.1877 (2)	0.0348 (4)
H20A	0.733305	0.705498	0.112764	0.052*
H20B	0.762072	0.732276	0.171741	0.052*
O21	0.72055 (6)	0.59510 (11)	0.1594 (2)	0.0413 (5)
H21A	0.71672	0.557023	0.173239	0.062*
H21B	0.729573	0.593245	0.098869	0.062*
O22	0.72630 (7)	0.56039 (12)	0.4444 (3)	0.0523 (7)
H22A	0.71367	0.564539	0.489957	0.078*
H22B	0.72512	0.521727	0.422976	0.078*
O23	1.02430 (5)	0.60949 (11)	0.3833 (3)	0.0443 (5)
H23A	1.041839	0.600141	0.44584	0.066*
H23B	1.012387	0.622712	0.427182	0.066*
O24	0.97774 (6)	0.41459 (11)	0.3259 (2)	0.0444 (5)
H24A	0.973633	0.387009	0.262843	0.067*
H24B	0.99214	0.397939	0.393514	0.067*
O25	1.00983 (8)	0.69998 (17)	1.0157 (4)	0.0846 (11)
H25A	0.997051	0.729657	0.97876	0.127*
H25B	1.025141	0.699707	0.983887	0.127*
O26	0.78981 (6)	0.77617 (13)	0.0892 (3)	0.0510 (6)
H26A	0.80802	0.759889	0.101562	0.076*
H26B	0.79344	0.805529	0.147949	0.076*
O27	1	0.7643 (8)	1.25	0.178 (15)	0.3333
H27	0.99045	0.760028	1.164062	0.267*	0.3333
C1	0.58806 (6)	0.51922 (13)	0.6182 (3)	0.0269 (5)
C2	0.61048 (7)	0.49254 (16)	0.7329 (3)	0.0377 (7)
H2A	0.604037	0.463367	0.78521	0.045*
C3	0.64244 (7)	0.50913 (16)	0.7699 (3)	0.0397 (7)
H3	0.657562	0.490646	0.845471	0.048*
C4	0.65145 (6)	0.55374 (13)	0.6922 (3)	0.0278 (5)
C5	0.62920 (7)	0.58184 (15)	0.5804 (3)	0.0346 (6)
H5A	0.635451	0.61274	0.531139	0.041*
C6	0.59750 (7)	0.56370 (15)	0.5420 (3)	0.0341 (6)
H6	0.582531	0.581446	0.464923	0.041*
C7	0.55327 (6)	0.50306 (13)	0.5805 (3)	0.0262 (5)
C8	0.44795 (7)	0.36470 (14)	0.2632 (3)	0.0342 (6)
C9	0.41638 (8)	0.33181 (16)	0.2183 (3)	0.0389 (7)
C10	0.41085 (10)	0.27678 (19)	0.2797 (4)	0.0531 (9)
H10	0.426962	0.257835	0.351075	0.064*
C11	0.38055 (12)	0.2515 (2)	0.2307 (5)	0.0637 (13)
H11	0.376831	0.214394	0.270286	0.076*
C12	0.36237 (9)	0.3289 (2)	0.0747 (5)	0.0607 (11)
H12	0.345641	0.347255	0.005123	0.073*
C13	0.39180 (8)	0.35773 (18)	0.1131 (4)	0.0493 (9)
H13	0.394917	0.393883	0.068842	0.059*
C14	0.83714 (6)	0.77435 (12)	0.5884 (3)	0.0229 (5)
C15	0.85611 (6)	0.81324 (13)	0.6923 (3)	0.0299 (6)
H15	0.846537	0.841371	0.735302	0.036*
C16	0.88912 (7)	0.81035 (14)	0.7322 (3)	0.0336 (6)
H16	0.901706	0.836718	0.800794	0.04*
C17	0.90316 (6)	0.76761 (13)	0.6685 (3)	0.0295 (6)
C18	0.88459 (7)	0.72926 (14)	0.5645 (3)	0.0328 (6)
H18	0.894226	0.700934	0.522156	0.039*
C19	0.85165 (7)	0.73303 (14)	0.5233 (3)	0.0298 (6)
H19	0.839179	0.707868	0.451853	0.036*
C20	0.80135 (6)	0.77421 (12)	0.5511 (3)	0.0233 (5)
C21	0.91364 (6)	0.56023 (12)	0.3687 (3)	0.0242 (5)
C22	0.89305 (7)	0.56673 (15)	0.4439 (3)	0.0323 (6)
H22	0.900837	0.562247	0.538925	0.039*
C23	0.86106 (7)	0.57981 (15)	0.3780 (3)	0.0317 (6)
H23	0.847432	0.584925	0.428493	0.038*
C24	0.84952 (6)	0.58521 (12)	0.2366 (3)	0.0242 (5)
C25	0.86970 (6)	0.57796 (14)	0.1600 (3)	0.0305 (6)
H25	0.861707	0.581037	0.064691	0.037*
C26	0.90177 (6)	0.56615 (14)	0.2268 (3)	0.0302 (6)
H26	0.915472	0.562138	0.176236	0.036*
C27	0.94785 (6)	0.54226 (13)	0.4401 (3)	0.0262 (5)
C28	0.81586 (6)	0.63050 (12)	0.6856 (3)	0.0246 (5)
C29	0.84990 (6)	0.63186 (13)	0.7788 (3)	0.0262 (5)
C30	0.86146 (7)	0.67793 (15)	0.8776 (3)	0.0328 (6)
H30	0.847834	0.707745	0.893592	0.039*
C31	0.89391 (7)	0.67851 (16)	0.9524 (3)	0.0387 (7)
H31	0.901658	0.709653	1.018259	0.046*
C32	0.90305 (7)	0.59361 (15)	0.8379 (4)	0.0400 (7)
H32	0.917259	0.564795	0.823055	0.048*
C33	0.87125 (7)	0.58909 (14)	0.7582 (3)	0.0343 (6)
H33	0.864316	0.557888	0.691875	0.041*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Nd1	0.01703 (9)	0.02842 (10)	0.02173 (9)	0	0.00725 (7)	0
Nd2	0.01642 (6)	0.02576 (7)	0.01968 (7)	0.00133 (5)	0.00666 (5)	−0.00049 (5)
Nd3	0.01473 (8)	0.03235 (10)	0.01963 (9)	0	0.00455 (7)	0
S1	0.0216 (3)	0.0366 (3)	0.0311 (3)	−0.0016 (2)	0.0099 (2)	0.0038 (3)
S2	0.0177 (3)	0.0365 (4)	0.0477 (4)	0.0005 (2)	0.0097 (3)	0.0093 (3)
S3	0.0191 (3)	0.0411 (4)	0.0223 (3)	0.0039 (2)	0.0067 (2)	−0.0033 (2)
N1	0.0281 (11)	0.0330 (12)	0.0367 (13)	−0.0015 (10)	0.0118 (10)	−0.0011 (10)
N2	0.0365 (13)	0.0356 (13)	0.0387 (14)	−0.0113 (10)	0.0179 (11)	−0.0017 (10)
N3	0.0493 (19)	0.083 (3)	0.070 (2)	−0.0340 (18)	0.0344 (18)	−0.035 (2)
N4	0.0193 (10)	0.0422 (13)	0.0295 (12)	0.0028 (9)	0.0066 (9)	−0.0011 (10)
N5	0.0239 (11)	0.0487 (14)	0.0212 (11)	0.0037 (10)	0.0077 (9)	−0.0016 (10)
N6	0.0255 (12)	0.0469 (15)	0.0382 (14)	−0.0005 (10)	0.0025 (10)	0.0085 (11)
O1	0.0251 (9)	0.0436 (12)	0.0273 (10)	−0.0014 (8)	0.0044 (8)	−0.0055 (8)
O2	0.0253 (10)	0.0493 (13)	0.0369 (11)	−0.0005 (8)	0.0166 (9)	0.0034 (9)
O3	0.0357 (12)	0.0693 (16)	0.0343 (12)	−0.0098 (11)	0.0051 (9)	−0.0007 (11)
O4	0.0401 (13)	0.0498 (15)	0.0763 (19)	−0.0119 (11)	0.0116 (13)	0.0231 (13)
O5	0.0467 (14)	0.0661 (17)	0.0595 (16)	0.0094 (12)	0.0303 (13)	−0.0028 (13)
O6	0.0369 (11)	0.0508 (13)	0.0342 (11)	−0.0161 (10)	0.0147 (9)	−0.0014 (10)
O7	0.0253 (13)	0.0313 (14)	0.0438 (16)	0	0.0086 (12)	0
O8	0.0205 (9)	0.0308 (10)	0.0356 (10)	−0.0020 (7)	0.0079 (8)	−0.0022 (8)
O9	0.0207 (9)	0.0486 (12)	0.0344 (10)	0.0049 (8)	0.0094 (8)	−0.0065 (9)
O10	0.0304 (11)	0.0497 (13)	0.0537 (14)	−0.0077 (9)	0.0160 (10)	0.0118 (11)
O11	0.0274 (11)	0.0770 (18)	0.0464 (14)	0.0004 (11)	0.0024 (10)	0.0109 (13)
O12	0.0298 (11)	0.0405 (13)	0.097 (2)	0.0079 (10)	0.0222 (13)	0.0057 (13)
O13	0.0234 (9)	0.0555 (13)	0.0411 (12)	0.0073 (9)	0.0160 (9)	−0.0027 (10)
O14	0.0255 (10)	0.0590 (14)	0.0306 (11)	0.0092 (9)	0.0031 (8)	0.0072 (10)
O15	0.0362 (12)	0.0560 (15)	0.0566 (15)	−0.0112 (11)	0.0164 (11)	−0.0271 (12)
O16	0.0361 (12)	0.0863 (19)	0.0264 (11)	0.0214 (12)	0.0130 (9)	0.0172 (11)
O17	0.0235 (9)	0.0379 (11)	0.0291 (10)	0.0061 (8)	0.0116 (8)	0.0000 (8)
O18	0.0235 (9)	0.0371 (10)	0.0245 (9)	0.0054 (8)	0.0069 (7)	−0.0025 (8)
O19	0.0520 (14)	0.0382 (12)	0.0397 (12)	0.0079 (10)	0.0172 (11)	0.0052 (9)
O20	0.0303 (10)	0.0423 (12)	0.0308 (10)	0.0010 (9)	0.0090 (8)	0.0072 (9)
O21	0.0477 (13)	0.0442 (12)	0.0288 (10)	−0.0075 (10)	0.0086 (9)	−0.0035 (9)
O22	0.0736 (18)	0.0442 (13)	0.0572 (15)	−0.0219 (12)	0.0459 (14)	−0.0130 (11)
O23	0.0273 (10)	0.0464 (13)	0.0511 (13)	−0.0014 (9)	0.0023 (10)	−0.0110 (11)
O24	0.0481 (13)	0.0466 (13)	0.0406 (12)	−0.0093 (10)	0.0176 (10)	0.0031 (10)
O25	0.0615 (19)	0.084 (2)	0.101 (3)	0.0026 (17)	0.0183 (18)	0.045 (2)
O26	0.0400 (13)	0.0584 (15)	0.0509 (14)	−0.0065 (11)	0.0105 (11)	−0.0029 (12)
O27	0.36 (4)	0.049 (9)	0.24 (3)	0	0.25 (3)	0
C1	0.0186 (11)	0.0373 (14)	0.0252 (12)	−0.0006 (10)	0.0078 (10)	−0.0021 (11)
C2	0.0275 (14)	0.0459 (17)	0.0381 (16)	−0.0031 (12)	0.0090 (12)	0.0184 (13)
C3	0.0221 (13)	0.0508 (19)	0.0404 (17)	−0.0012 (12)	0.0027 (12)	0.0191 (14)
C4	0.0217 (12)	0.0320 (14)	0.0308 (13)	0.0005 (10)	0.0104 (10)	0.0028 (11)
C5	0.0280 (14)	0.0434 (17)	0.0333 (15)	−0.0017 (12)	0.0115 (12)	0.0109 (13)
C6	0.0260 (13)	0.0460 (17)	0.0275 (14)	0.0013 (12)	0.0055 (11)	0.0096 (12)
C7	0.0220 (12)	0.0300 (13)	0.0276 (13)	0.0010 (10)	0.0094 (10)	−0.0056 (10)
C8	0.0349 (15)	0.0346 (15)	0.0390 (16)	−0.0097 (12)	0.0204 (13)	−0.0107 (12)
C9	0.0392 (16)	0.0434 (17)	0.0411 (17)	−0.0164 (13)	0.0229 (14)	−0.0150 (14)
C10	0.059 (2)	0.054 (2)	0.050 (2)	−0.0280 (18)	0.0231 (18)	−0.0115 (17)
C11	0.073 (3)	0.068 (3)	0.062 (3)	−0.044 (2)	0.037 (2)	−0.023 (2)
C12	0.0395 (19)	0.075 (3)	0.070 (3)	−0.0122 (19)	0.0215 (19)	−0.024 (2)
C13	0.0392 (18)	0.056 (2)	0.055 (2)	−0.0133 (15)	0.0183 (16)	−0.0129 (17)
C14	0.0187 (11)	0.0250 (12)	0.0258 (12)	0.0002 (9)	0.0085 (9)	0.0034 (10)
C15	0.0264 (13)	0.0301 (14)	0.0338 (14)	0.0020 (10)	0.0109 (11)	−0.0029 (11)
C16	0.0243 (13)	0.0351 (15)	0.0379 (15)	−0.0031 (11)	0.0060 (11)	−0.0041 (12)
C17	0.0196 (12)	0.0308 (14)	0.0384 (15)	−0.0007 (10)	0.0102 (11)	0.0069 (11)
C18	0.0246 (13)	0.0337 (15)	0.0443 (16)	0.0017 (11)	0.0171 (12)	−0.0040 (12)
C19	0.0245 (13)	0.0335 (14)	0.0341 (14)	−0.0034 (11)	0.0133 (11)	−0.0076 (11)
C20	0.0189 (11)	0.0269 (12)	0.0242 (12)	0.0017 (9)	0.0077 (9)	0.0040 (10)
C21	0.0190 (11)	0.0277 (13)	0.0256 (12)	0.0033 (9)	0.0070 (10)	0.0021 (10)
C22	0.0287 (13)	0.0476 (17)	0.0208 (12)	0.0089 (12)	0.0085 (11)	−0.0014 (11)
C23	0.0258 (13)	0.0479 (17)	0.0246 (13)	0.0084 (12)	0.0127 (11)	−0.0007 (12)
C24	0.0201 (11)	0.0280 (13)	0.0252 (12)	0.0036 (9)	0.0082 (10)	0.0012 (10)
C25	0.0263 (13)	0.0442 (16)	0.0221 (12)	0.0065 (11)	0.0096 (10)	0.0055 (11)
C26	0.0234 (12)	0.0443 (16)	0.0270 (13)	0.0065 (11)	0.0137 (11)	0.0061 (12)
C27	0.0198 (12)	0.0278 (13)	0.0295 (13)	0.0034 (10)	0.0061 (10)	−0.0041 (10)
C28	0.0242 (12)	0.0254 (12)	0.0237 (12)	0.0023 (10)	0.0073 (10)	0.0024 (10)
C29	0.0239 (12)	0.0316 (13)	0.0221 (12)	0.0016 (10)	0.0064 (10)	0.0043 (10)
C30	0.0302 (14)	0.0387 (15)	0.0293 (14)	0.0024 (12)	0.0096 (11)	−0.0021 (12)
C31	0.0321 (15)	0.0487 (18)	0.0318 (15)	−0.0061 (13)	0.0062 (12)	−0.0064 (13)
C32	0.0284 (14)	0.0374 (16)	0.0498 (19)	0.0088 (12)	0.0072 (13)	0.0068 (14)
C33	0.0290 (14)	0.0328 (15)	0.0382 (16)	0.0047 (11)	0.0075 (12)	−0.0008 (12)

Geometric parameters (Å, º)

Nd1—O1	2.3417 (19)	O21—H21A	0.8508
Nd1—O1^i	2.3416 (19)	O21—H21B	0.8504
Nd1—O2^ii	2.473 (2)	O22—H22A	0.8501
Nd1—O2^iii	2.473 (2)	O22—H22B	0.8501
Nd1—O6^i	2.517 (2)	O23—H23A	0.8526
Nd1—O6	2.517 (2)	O23—H23B	0.8523
Nd1—O7	2.545 (3)	O24—H24A	0.8505
Nd1—N1	2.724 (2)	O24—H24B	0.8505
Nd1—N1^i	2.724 (2)	O25—H25A	0.8502
Nd2—O8	2.3926 (19)	O25—H25B	0.8497
Nd2—O9^iv	2.4004 (19)	O26—H26A	0.8503
Nd2—O17	2.5160 (18)	O26—H26B	0.8489
Nd2—O18	2.5032 (18)	O27—H27	0.8509
Nd2—O19	2.572 (2)	O27—H27^vii	0.8509
Nd2—O21	2.497 (2)	C1—C6	1.385 (4)
Nd2—O20	2.525 (2)	C1—C2	1.388 (4)
Nd2—O22	2.475 (2)	C1—C7	1.503 (4)
Nd2—N4	2.761 (2)	C2—C3	1.388 (4)
Nd3—O13^v	2.362 (2)	C2—H2A	0.9300
Nd3—O13	2.3621 (19)	C3—C4	1.388 (4)
Nd3—O14^ii	2.381 (2)	C3—H3	0.9300
Nd3—O14^vi	2.381 (2)	C4—C5	1.380 (4)
Nd3—O23	2.535 (2)	C5—C6	1.385 (4)
Nd3—O23^v	2.535 (2)	C5—H5A	0.9300
Nd3—O24^v	2.526 (2)	C6—H6	0.9300
Nd3—O24	2.526 (2)	C8—C9	1.497 (4)
S1—O4	1.437 (2)	C9—C13	1.372 (5)
S1—O3	1.447 (2)	C9—C10	1.394 (5)
S1—O5	1.454 (3)	C10—C11	1.380 (5)
S1—C4	1.774 (3)	C10—H10	0.9300
S2—O11	1.446 (3)	C11—H11	0.9300
S2—O12	1.449 (3)	C12—C13	1.378 (5)
S2—O10	1.456 (2)	C12—H12	0.9300
S2—C17	1.782 (3)	C13—H13	0.9300
S3—O16	1.446 (2)	C14—C19	1.392 (4)
S3—O15	1.451 (3)	C14—C15	1.394 (4)
S3—O17	1.4580 (19)	C14—C20	1.507 (3)
S3—C24	1.777 (3)	C15—C16	1.387 (4)
N1—N2	1.417 (3)	C15—H15	0.9300
N1—H1A	0.8900	C16—C17	1.389 (4)
N1—H1B	0.8900	C16—H16	0.9300
N2—C8	1.326 (4)	C17—C18	1.382 (4)
N2—H2	0.8600	C18—C19	1.384 (4)
N3—C11	1.320 (7)	C18—H18	0.9300
N3—C12	1.329 (6)	C19—H19	0.9300
N4—N5	1.415 (3)	C21—C26	1.387 (4)
N4—H4A	0.8900	C21—C22	1.393 (4)
N4—H4B	0.8900	C21—C27	1.501 (3)
N5—C28	1.325 (3)	C22—C23	1.384 (4)
N5—H5	0.8600	C22—H22	0.9300
N6—C32	1.328 (4)	C23—C24	1.381 (4)
N6—C31	1.332 (4)	C23—H23	0.9300
O1—C7	1.255 (3)	C24—C25	1.391 (4)
O2—C7	1.251 (3)	C25—C26	1.383 (4)
O6—C8	1.238 (4)	C25—H25	0.9300
O7—H7	0.8501	C26—H26	0.9300
O7—H7^i	0.8501	C28—C29	1.497 (4)
O8—C20	1.265 (3)	C29—C33	1.383 (4)
O9—C20	1.251 (3)	C29—C30	1.385 (4)
O13—C27	1.253 (3)	C30—C31	1.390 (4)
O14—C27	1.256 (3)	C30—H30	0.9300
O18—C28	1.240 (3)	C31—H31	0.9300
O19—H19A	0.8593	C32—C33	1.381 (4)
O19—H19B	0.8589	C32—H32	0.9300
O20—H20A	0.8512	C33—H33	0.9300
O20—H20B	0.8511
O1^i—Nd1—O1	141.67 (11)	C28—N5—H5	121.2
O1^i—Nd1—O2^ii	86.90 (7)	N4—N5—H5	121.2
O1—Nd1—O2^ii	80.04 (7)	C32—N6—C31	117.3 (3)
O1^i—Nd1—O2^iii	80.04 (7)	C7—O1—Nd1	149.76 (19)
O1—Nd1—O2^iii	86.90 (7)	C7—O2—Nd1^iii	129.74 (18)
O2^ii—Nd1—O2^iii	139.53 (10)	C8—O6—Nd1	124.26 (19)
O1^i—Nd1—O6^i	135.02 (7)	Nd1—O7—H7	128.9
O1—Nd1—O6^i	74.17 (7)	Nd1—O7—H7^i	128.949 (1)
O2^ii—Nd1—O6^i	71.94 (7)	H7—O7—H7^i	102.1
O2^iii—Nd1—O6^i	140.17 (7)	C20—O8—Nd2	153.45 (18)
O1^i—Nd1—O6	74.17 (7)	C20—O9—Nd2^iv	146.05 (17)
O1—Nd1—O6	135.02 (7)	C27—O13—Nd3	160.6 (2)
O2^ii—Nd1—O6	140.17 (7)	C27—O14—Nd3^vi	141.96 (18)
O2^iii—Nd1—O6	71.94 (7)	S3—O17—Nd2	147.33 (12)
O6^i—Nd1—O6	97.09 (11)	C28—O18—Nd2	124.53 (16)
O1^i—Nd1—O7	70.84 (5)	Nd2—O19—H19A	109.9
O1—Nd1—O7	70.84 (5)	Nd2—O19—H19B	109.6
O2^ii—Nd1—O7	69.76 (5)	H19A—O19—H19B	104.1
O2^iii—Nd1—O7	69.76 (5)	Nd2—O20—H20A	109.4
O6^i—Nd1—O7	131.45 (6)	Nd2—O20—H20B	109.6
O6—Nd1—O7	131.45 (6)	H20A—O20—H20B	104.4
O1^i—Nd1—N1	133.68 (7)	Nd2—O21—H21A	109.3
O1—Nd1—N1	76.23 (7)	Nd2—O21—H21B	109.5
O2^ii—Nd1—N1	134.89 (7)	H21A—O21—H21B	104.5
O2^iii—Nd1—N1	76.77 (7)	Nd2—O22—H22A	129.8
O6^i—Nd1—N1	64.94 (7)	Nd2—O22—H22B	125.7
O6—Nd1—N1	60.72 (7)	H22A—O22—H22B	104.5
O7—Nd1—N1	133.58 (5)	Nd3—O23—H23A	109.5
O1^i—Nd1—N1^i	76.23 (7)	Nd3—O23—H23B	109.5
O1—Nd1—N1^i	133.68 (7)	H23A—O23—H23B	104.4
O2^ii—Nd1—N1^i	76.77 (7)	Nd3—O24—H24A	109.4
O2^iii—Nd1—N1^i	134.89 (7)	Nd3—O24—H24B	109.3
O6^i—Nd1—N1^i	60.72 (7)	H24A—O24—H24B	104.5
O6—Nd1—N1^i	64.94 (7)	H25A—O25—H25B	109.5
O7—Nd1—N1^i	133.58 (5)	H26A—O26—H26B	104.5
N1—Nd1—N1^i	92.84 (11)	H27—O27—H27^vii	167.7
O8—Nd2—O9^iv	87.25 (7)	C6—C1—C2	119.8 (2)
O8—Nd2—O22	139.50 (7)	C6—C1—C7	119.5 (2)
O9^iv—Nd2—O22	71.97 (8)	C2—C1—C7	120.6 (3)
O8—Nd2—O21	139.14 (7)	C1—C2—C3	120.4 (3)
O9^iv—Nd2—O21	81.99 (7)	C1—C2—H2A	119.8
O22—Nd2—O21	73.15 (8)	C3—C2—H2A	119.8
O8—Nd2—O18	72.47 (7)	C4—C3—C2	118.9 (3)
O9^iv—Nd2—O18	130.78 (6)	C4—C3—H3	120.6
O22—Nd2—O18	94.99 (8)	C2—C3—H3	120.6
O21—Nd2—O18	140.71 (7)	C5—C4—C3	121.1 (3)
O8—Nd2—O17	83.25 (7)	C5—C4—S1	119.1 (2)
O9^iv—Nd2—O17	144.88 (7)	C3—C4—S1	119.8 (2)
O22—Nd2—O17	132.76 (7)	C4—C5—C6	119.6 (3)
O21—Nd2—O17	83.40 (7)	C4—C5—H5A	120.2
O18—Nd2—O17	77.87 (6)	C6—C5—H5A	120.2
O8—Nd2—O20	68.83 (7)	C1—C6—C5	120.1 (3)
O9^iv—Nd2—O20	75.03 (7)	C1—C6—H6	119.9
O22—Nd2—O20	133.30 (8)	C5—C6—H6	119.9
O21—Nd2—O20	70.32 (7)	O2—C7—O1	123.8 (2)
O18—Nd2—O20	131.69 (7)	O2—C7—C1	119.1 (2)
O17—Nd2—O20	70.00 (6)	O1—C7—C1	117.0 (2)
O8—Nd2—O19	136.15 (7)	O6—C8—N2	122.8 (3)
O9^iv—Nd2—O19	134.10 (8)	O6—C8—C9	119.6 (3)
O22—Nd2—O19	64.47 (8)	N2—C8—C9	117.6 (3)
O21—Nd2—O19	72.50 (8)	C13—C9—C10	118.9 (3)
O18—Nd2—O19	68.67 (7)	C13—C9—C8	118.2 (3)
O17—Nd2—O19	69.60 (7)	C10—C9—C8	122.9 (3)
O20—Nd2—O19	127.13 (7)	C11—C10—C9	117.4 (4)
O8—Nd2—N4	71.45 (7)	C11—C10—H10	121.3
O9^iv—Nd2—N4	70.53 (7)	C9—C10—H10	121.3
O22—Nd2—N4	68.96 (8)	N3—C11—C10	124.5 (4)
O21—Nd2—N4	138.36 (7)	N3—C11—H11	117.8
O18—Nd2—N4	60.64 (6)	C10—C11—H11	117.8
O17—Nd2—N4	136.01 (6)	N3—C12—C13	123.9 (4)
O20—Nd2—N4	127.78 (7)	N3—C12—H12	118.1
O19—Nd2—N4	104.98 (7)	C13—C12—H12	118.1
O13^v—Nd3—O13	145.44 (12)	C9—C13—C12	118.4 (4)
O13^v—Nd3—O14^ii	99.04 (8)	C9—C13—H13	120.8
O13—Nd3—O14^ii	92.05 (8)	C12—C13—H13	120.8
O13^v—Nd3—O14^vi	92.05 (8)	C19—C14—C15	119.3 (2)
O13—Nd3—O14^vi	99.04 (8)	C19—C14—C20	119.8 (2)
O14^ii—Nd3—O14^vi	142.12 (12)	C15—C14—C20	120.8 (2)
O13^v—Nd3—O24^v	72.14 (8)	C16—C15—C14	120.6 (3)
O13—Nd3—O24^v	142.42 (8)	C16—C15—H15	119.7
O14^ii—Nd3—O24^v	77.73 (8)	C14—C15—H15	119.7
O14^vi—Nd3—O24^v	71.44 (8)	C15—C16—C17	119.2 (3)
O13^v—Nd3—O24	142.42 (8)	C15—C16—H16	120.4
O13—Nd3—O24	72.13 (8)	C17—C16—H16	120.4
O14^ii—Nd3—O24	71.44 (8)	C18—C17—C16	120.7 (2)
O14^vi—Nd3—O24	77.73 (8)	C18—C17—S2	118.7 (2)
O24^v—Nd3—O24	70.32 (11)	C16—C17—S2	120.6 (2)
O13^v—Nd3—O23	79.59 (8)	C17—C18—C19	120.0 (3)
O13—Nd3—O23	72.02 (8)	C17—C18—H18	120.0
O14^ii—Nd3—O23	142.61 (8)	C19—C18—H18	120.0
O14^vi—Nd3—O23	74.94 (8)	C18—C19—C14	120.2 (3)
O24^v—Nd3—O23	134.60 (8)	C18—C19—H19	119.9
O24—Nd3—O23	130.13 (8)	C14—C19—H19	119.9
O13^v—Nd3—O23^v	72.02 (8)	O9—C20—O8	124.1 (2)
O13—Nd3—O23^v	79.59 (8)	O9—C20—C14	117.7 (2)
O14^ii—Nd3—O23^v	74.94 (8)	O8—C20—C14	118.1 (2)
O14^vi—Nd3—O23^v	142.61 (8)	C26—C21—C22	119.5 (2)
O24^v—Nd3—O23^v	130.13 (8)	C26—C21—C27	120.4 (2)
O24—Nd3—O23^v	134.60 (8)	C22—C21—C27	119.9 (2)
O23—Nd3—O23^v	69.10 (11)	C23—C22—C21	120.3 (2)
O4—S1—O3	114.31 (17)	C23—C22—H22	119.8
O4—S1—O5	110.22 (18)	C21—C22—H22	119.8
O3—S1—O5	111.58 (16)	C24—C23—C22	119.6 (2)
O4—S1—C4	107.95 (14)	C24—C23—H23	120.2
O3—S1—C4	107.27 (13)	C22—C23—H23	120.2
O5—S1—C4	104.97 (15)	C23—C24—C25	120.7 (2)
O11—S2—O12	113.62 (17)	C23—C24—S3	120.30 (19)
O11—S2—O10	111.96 (16)	C25—C24—S3	118.9 (2)
O12—S2—O10	112.14 (16)	C26—C25—C24	119.4 (2)
O11—S2—C17	107.09 (14)	C26—C25—H25	120.3
O12—S2—C17	106.30 (14)	C24—C25—H25	120.3
O10—S2—C17	105.05 (13)	C25—C26—C21	120.4 (2)
O16—S3—O15	114.06 (16)	C25—C26—H26	119.8
O16—S3—O17	113.18 (14)	C21—C26—H26	119.8
O15—S3—O17	111.90 (13)	O13—C27—O14	124.0 (2)
O16—S3—C24	106.33 (13)	O13—C27—C21	118.5 (2)
O15—S3—C24	105.61 (14)	O14—C27—C21	117.4 (2)
O17—S3—C24	104.85 (12)	O18—C28—N5	123.1 (2)
N2—N1—Nd1	112.84 (17)	O18—C28—C29	119.7 (2)
N2—N1—H1A	109.0	N5—C28—C29	117.1 (2)
Nd1—N1—H1A	109.0	C33—C29—C30	118.5 (3)
N2—N1—H1B	109.0	C33—C29—C28	119.1 (2)
Nd1—N1—H1B	109.0	C30—C29—C28	122.2 (2)
H1A—N1—H1B	107.8	C29—C30—C31	118.4 (3)
C8—N2—N1	117.3 (2)	C29—C30—H30	120.8
C8—N2—H2	121.4	C31—C30—H30	120.8
N1—N2—H2	121.4	N6—C31—C30	123.5 (3)
C11—N3—C12	116.9 (3)	N6—C31—H31	118.3
N5—N4—Nd2	111.89 (15)	C30—C31—H31	118.3
N5—N4—H4A	109.2	N6—C32—C33	123.7 (3)
Nd2—N4—H4A	109.2	N6—C32—H32	118.2
N5—N4—H4B	109.2	C33—C32—H32	118.2
Nd2—N4—H4B	109.2	C32—C33—C29	118.7 (3)
H4A—N4—H4B	107.9	C32—C33—H33	120.6
C28—N5—N4	117.6 (2)	C29—C33—H33	120.6
Nd1—N1—N2—C8	10.6 (3)	O10—S2—C17—C16	−84.1 (3)
Nd2—N4—N5—C28	−7.5 (3)	C16—C17—C18—C19	−0.3 (5)
O16—S3—O17—Nd2	118.8 (2)	S2—C17—C18—C19	−177.4 (2)
O15—S3—O17—Nd2	−11.7 (3)	C17—C18—C19—C14	−1.4 (5)
C24—S3—O17—Nd2	−125.7 (2)	C15—C14—C19—C18	2.0 (4)
C6—C1—C2—C3	−1.5 (5)	C20—C14—C19—C18	−174.8 (3)
C7—C1—C2—C3	−177.9 (3)	Nd2^iv—O9—C20—O8	−17.0 (5)
C1—C2—C3—C4	1.4 (5)	Nd2^iv—O9—C20—C14	164.4 (2)
C2—C3—C4—C5	0.5 (5)	Nd2—O8—C20—O9	−84.0 (5)
C2—C3—C4—S1	−177.7 (3)	Nd2—O8—C20—C14	94.5 (4)
O4—S1—C4—C5	28.5 (3)	C19—C14—C20—O9	176.7 (3)
O3—S1—C4—C5	152.1 (3)	C15—C14—C20—O9	−0.1 (4)
O5—S1—C4—C5	−89.1 (3)	C19—C14—C20—O8	−1.9 (4)
O4—S1—C4—C3	−153.3 (3)	C15—C14—C20—O8	−178.7 (2)
O3—S1—C4—C3	−29.7 (3)	C26—C21—C22—C23	−0.9 (5)
O5—S1—C4—C3	89.1 (3)	C27—C21—C22—C23	−176.4 (3)
C3—C4—C5—C6	−2.3 (5)	C21—C22—C23—C24	1.2 (5)
S1—C4—C5—C6	175.9 (2)	C22—C23—C24—C25	−0.3 (5)
C2—C1—C6—C5	−0.3 (5)	C22—C23—C24—S3	177.9 (2)
C7—C1—C6—C5	176.1 (3)	O16—S3—C24—C23	148.7 (3)
C4—C5—C6—C1	2.2 (5)	O15—S3—C24—C23	−89.8 (3)
Nd1^iii—O2—C7—O1	−54.0 (4)	O17—S3—C24—C23	28.6 (3)
Nd1^iii—O2—C7—C1	123.3 (2)	O16—S3—C24—C25	−33.1 (3)
Nd1—O1—C7—O2	−59.6 (5)	O15—S3—C24—C25	88.4 (3)
Nd1—O1—C7—C1	123.1 (3)	O17—S3—C24—C25	−153.2 (2)
C6—C1—C7—O2	−154.2 (3)	C23—C24—C25—C26	−1.0 (5)
C2—C1—C7—O2	22.3 (4)	S3—C24—C25—C26	−179.2 (2)
C6—C1—C7—O1	23.3 (4)	C24—C25—C26—C21	1.4 (5)
C2—C1—C7—O1	−160.2 (3)	C22—C21—C26—C25	−0.5 (4)
Nd1—O6—C8—N2	−12.9 (4)	C27—C21—C26—C25	175.0 (3)
Nd1—O6—C8—C9	165.0 (2)	Nd3—O13—C27—O14	73.7 (7)
N1—N2—C8—O6	0.0 (4)	Nd3—O13—C27—C21	−104.9 (6)
N1—N2—C8—C9	−177.9 (3)	Nd3^vi—O14—C27—O13	0.5 (5)
O6—C8—C9—C13	−24.7 (4)	Nd3^vi—O14—C27—C21	179.2 (2)
N2—C8—C9—C13	153.3 (3)	C26—C21—C27—O13	13.4 (4)
O6—C8—C9—C10	156.2 (3)	C22—C21—C27—O13	−171.1 (3)
N2—C8—C9—C10	−25.8 (5)	C26—C21—C27—O14	−165.3 (3)
C13—C9—C10—C11	−0.2 (5)	C22—C21—C27—O14	10.2 (4)
C8—C9—C10—C11	178.9 (3)	Nd2—O18—C28—N5	16.7 (4)
C12—N3—C11—C10	0.9 (6)	Nd2—O18—C28—C29	−159.82 (18)
C9—C10—C11—N3	−1.0 (6)	N4—N5—C28—O18	−4.5 (4)
C11—N3—C12—C13	0.6 (6)	N4—N5—C28—C29	172.1 (2)
C10—C9—C13—C12	1.5 (5)	O18—C28—C29—C33	−32.2 (4)
C8—C9—C13—C12	−177.7 (3)	N5—C28—C29—C33	151.1 (3)
N3—C12—C13—C9	−1.7 (6)	O18—C28—C29—C30	142.1 (3)
C19—C14—C15—C16	−0.9 (4)	N5—C28—C29—C30	−34.6 (4)
C20—C14—C15—C16	175.9 (3)	C33—C29—C30—C31	−0.7 (4)
C14—C15—C16—C17	−0.8 (4)	C28—C29—C30—C31	−175.0 (3)
C15—C16—C17—C18	1.4 (4)	C32—N6—C31—C30	1.5 (5)
C15—C16—C17—S2	178.4 (2)	C29—C30—C31—N6	−0.5 (5)
O11—S2—C17—C18	−147.8 (3)	C31—N6—C32—C33	−1.5 (5)
O12—S2—C17—C18	−26.1 (3)	N6—C32—C33—C29	0.3 (5)
O10—S2—C17—C18	93.0 (3)	C30—C29—C33—C32	0.8 (4)
O11—S2—C17—C16	35.1 (3)	C28—C29—C33—C32	175.2 (3)
O12—S2—C17—C16	156.9 (3)

Symmetry codes: (i) −x+1, y, −z+1/2; (ii) x, −y+1, z−1/2; (iii) −x+1, −y+1, −z+1; (iv) −x+3/2, −y+3/2, −z+1; (v) −x+2, y, −z+1/2; (vi) −x+2, −y+1, −z+1; (vii) −x+2, y, −z+5/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O1^iii	0.89	2.34	2.924 (3)	123
N1—H1A···O11^viii	0.89	2.69	3.381 (4)	136
N2—H2···O10^ix	0.86	2.10	2.894 (4)	153
N4—H4A···O8^iv	0.89	2.31	3.044 (3)	140
N4—H4B···O4	0.89	2.57	3.231 (4)	132
N5—H5···O16^x	0.86	2.09	2.889 (3)	155
O7—H7···O10^xi	0.85	1.96	2.790 (3)	164
O19—H19A···O15^xii	0.86	2.16	2.861 (3)	139
O19—H19B···O15	0.86	2.07	2.890 (4)	159
O20—H20A···O26^xiii	0.85	2.03	2.760 (4)	143
O20—H20B···O26	0.85	1.96	2.771 (4)	159
O21—H21A···O5^ii	0.85	1.92	2.752 (4)	166
O21—H21B···O3^xiv	0.85	2.23	2.823 (3)	127
O22—H22A···O5	0.85	2.02	2.743 (4)	142
O22—H22B···O3^ii	0.85	2.00	2.811 (4)	160
O23—H23A···N6^xv	0.85	2.07	2.801 (4)	143
O23—H23B···O25^xv	0.85	2.10	2.859 (4)	147
O24—H24A···O12^ii	0.85	2.16	2.931 (3)	151
O24—H24B···O25^ii	0.85	2.43	3.156 (4)	144
O25—H25A···O11	0.85	2.00	2.821 (5)	162
O25—H25B···O12^xv	0.85	2.19	2.990 (5)	156
O26—H26A···N3^xvi	0.85	2.10	2.849 (5)	146
O26—H26B···O4^iv	0.85	2.02	2.862 (4)	170
O27—H27···O25	0.85	2.37	2.940 (4)	125

Symmetry codes: (ii) x, −y+1, z−1/2; (iii) −x+1, −y+1, −z+1; (iv) −x+3/2, −y+3/2, −z+1; (viii) −x+3/2, y−1/2, −z+3/2; (ix) x−1/2, y−1/2, z; (x) x, y, z+1; (xi) x−1/2, −y+3/2, z−1/2; (xii) x, −y+1, z+1/2; (xiii) −x+3/2, −y+3/2, −z; (xiv) x, y, z−1; (xv) −x+2, y, −z+3/2; (xvi) x+1/2, y+1/2, z.