catena-Poly[neodymium(III)-bis­[μ-N-(dimorpholinophosphor­yl)benzene­sulfonamidato]-sodium(I)-bis­[μ-N-(dimorpholinophosphor­yl)benzene­sulfonamidato]]

Shatrava, I.O.; Sliva, T.Y.; Ovchynnikov, V.A.; Konovalova, I.S.; Amirkhanov, V.M.

doi:10.1107/S1600536810008214

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Pages m397-m398

doi:10.1107/S1600536810008214

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catena-Poly[neodymium(III)-bis[μ-N-(dimorpholinophosphoryl)benzenesulfonamidato]-sodium(I)-bis[μ-N-(dimorpholinophosphoryl)benzenesulfonamidato]]

Iuliia O. Shatrava,^a ^* Tatyana Yu. Sliva,^a Vladimir A. Ovchynnikov,^a Irina S. Konovalova ^b and Vladimir M. Amirkhanov ^a

^aNational Taras Shevchenko University, Department of Chemistry, Volodymyrska str. 64, 01033 Kyiv, Ukraine, and ^bSTC "Institute for Syngle Crystals", 60 Lenina ave., Khar'kov 61001, Ukraine
^*Correspondence e-mail: shatrava@univ.kiev.ua

(Received 18 February 2010; accepted 3 March 2010; online 13 March 2010)

The cubic crystal structure of the title compound, [NaNd(C₁₄H₂₁N₃O₅PS)₄]_n, is composed of one-dimensional polymeric chains propagating in [100], built up from [Nd(C₁₄H₂₁N₃O₅PS)₄]⁻ anions and sodium cations functioning as linkers. In the complex anion, the Nd³⁺ ion has an eightfold coordination environment formed by the sulfonyl and phosphoryl O atoms of four bidentate chelating N-(dimorpholinophosphoryl)benzenesulfonamidate ligands: the resulting NdO₈ polyhedron can be described as intermediate between dodecahedral and square antiprismatic. The sodium ion adopts an NaO₄ tetrahedral geometry arising from four monodentate benzenesulfonamidate ligands. The resulting crystal structure is unusual because it contains substantial voids (800 Å³ per unit cell), within which there is no evidence of included solvent.

Related literature

For general background to the use of bidentate ligands in ring closure in coordination compounds, see: Casas et al. (1995 ); Amirkhanov et al. (1997 ); Ly & Woollins (1998 ). For applications of the chelates formed, see: Zazybin et al. (2006 ); Karande et al. (2003 ); Morgalyuk et al. (2005 ); Xu & Angell (2000 ). For lanthanide compounds of general formula Na[Ln(L¹)₄]_n where HL¹ is C₆H₅S(O)₂NHPO(OCH₃)₂, see: Moroz et al. (2007 ). For the synthesis of the ligand, see: Kirsanov & Shevchenko (1954 ); Oyamada & Morimura (1960 ). For interpretation of coordination polyhedra, see: Porai-Koshits & Aslanov (1972 ). For bond lengths in similar compounds, see: Sokolov et al. (2007 ); Sokolnicki et al. (1998 ).

Experimental

Crystal data

[NaNd(C₁₄H₂₁N₃O₅PS)₄]
M_r = 1664.72
Cubic, $[P \overline 43n ]$
a = 22.943 (5) Å
V = 12077 (5) Å³
Z = 6
Mo Kα radiation
μ = 0.90 mm⁻¹
T = 293 K
0.60 × 0.40 × 0.30 mm

Data collection

Oxford Diffraction KM-4 Xcalibur diffractometer with a Sapphire3 detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis RED and CrysAlis CCD. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.614, T_max = 0.774
66051 measured reflections
5883 independent reflections
3713 reflections with I > 2σ(I)
R_int = 0.113

Refinement

R[F² > 2σ(F²)] = 0.095
wR(F²) = 0.178
S = 1.42
5883 reflections
174 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 1.17 e Å⁻³
Δρ_min = −0.75 e Å⁻³
Absolute structure: Flack (1983 ), 2727 Friedel pairs
Flack parameter: 0.05 (3)

Table 1
Selected bond lengths (Å)

Nd1—O1	2.376 (4)
Nd1—O2	2.532 (4)
Na1—O3	2.282 (4)

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis RED and CrysAlis CCD. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis RED and CrysAlis CCD. Oxford Diffraction Ltd, Abingdon, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810008214/hb5339sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810008214/hb5339Isup2.hkl

checkCIF report

Comment top

Lots of bidentate ligands under coordination form closure rings through the donor atoms binding to the same metal. The most used ligands are those derived from that containing oxygen, nitrogen, phosphorus and sulphur atoms (Casas et al., 1995; Amirkhanov et al., 1997; Ly et al., 1998). Such chelates may be used in catalysis (Zazybin et al., 2006), metal extraction (Karande et al., 2003; Morgalyuk et al., 2005), bioinorganic chemistry (Xu et al., 2000). Phosphorylated sulphonylamides of a general view RS(O)₂NHP(O)(NR₂)₂ could be applied for obtaining of lanthanide coordination compounds and presence of sulfono-group oxygen atom as addititious coordination centre gives a challenging opportunity to use them as convenient building blocks for syntheses of bi- and poly-nuclear compounds.

The results of lanthanide compounds investigation with one of the phosphorylated sulphonylamides representative – C₆H₅S(O)₂NHPO(OCH₃)₂ (HL¹) of general formula Na[Ln(L¹)₄]_n were already reported (Moroz et al., 2007).

We now report the synthesis and investigation of tetrakis - complex of the composition {Na[Nd(L)₄]}_n, (I) (Fig.1), where L^- is dimorpholinephenylsulphonylamidophosphate (C₆H₅S(O)₂NPO(NC₄H₈O)₂)^-. The synthesis of HL was carried out according to (Oyamada et al., 1960; Kirsanov et al., 1954), using benzenesulfonamide and morpholine.

The molecular structure of title compound contains 1D polymer chain, formed by [Nd(L)₄)]^- anion and sodium cation as a linker. In complex anions the neodymium atoms have 8-fold coordination environment formed by oxygen atoms of SO₂ and PO groups of four bidentate chelate ligands (Fig. 2). According to Porai-Koshits (Porai-Koshits & Aslanov, 1972) the resulting coordination polyhedra can be interpreted as a medium conformation between dodecahedron (δ₁ = δ₂ = δ₃ = δ₄ = 29.5 °) and square antiprism (δ₁ = δ₂ = 0 °; δ₃ = δ₄ = 52.5 °) for Nd atom (interplanar angles in polyhedra for Nd δ₁ = δ₂ = 26.2 °; δ₃ = δ₄ = 51.8 °).

The Nd – O(P) bond lengths (2.376 (4) Å) are shorter than Nd – O(S) (2.532 (4) Å) that can be explained by higher affinity of phosphoryl group to lanthanide ions. The P – O (1.499 (4) Å), N(1) – P (1.613 (6) Å) bond lengths are also comparable with the values observed for similar compounds (Sokolnicki et al., 1998; Sokolov et al., 2007). The average P—N (morpholine substituents) distance (1.628 (7) Å) is larger than P—N(1) bond length in chelate core because of the conjugation in S(O)₂NP(O) fragment. The metallocycles are almost flat with a deviation of the N(1) atom from the mean plane defined by the six atoms NdO(1)P(1) N(1)S(1)O(2) of 0.24496 Å.

The bonding of complex anions in polymer structure is provided by Na ions. The Na polyhedron is a distorted tetrahedron, formed by two SO oxygens from different anions.

The crystal structure is unusual: it contains substantial voids (800 Å³) within which there is no evidence for included solvent (Fig. 3). The crystals remained glass-clear being on air.

Related literature top

For general background to the use of bidentate ligands in ring closure in coordination compounds, see: Casas et al. (1995); Amirkhanov et al. (1997); Ly & Woollins (1998). For applications of the chelates formed, see: Zazybin et al. (2006); Karande et al. (2003); Morgalyuk et al. (2005); Xu & Angell (2000). For lanthanide compounds of general formula Na[Ln(L¹)₄]_n where HL¹ is C₆H₅S(O)₂NHPO(OCH₃)₂, see: Moroz et al. (2007). For the synthesis of the ligand, see: Kirsanov & Shevchenko (1954); Oyamada & Morimura (1960). For interpretation of coordination polyhedra, see: Porai-Koshits & Aslanov (1972). For bond lengths in similar compounds, see: Sokolov et al. (2007); Sokolnicki et al. (1998).

Experimental top

Nd(NO₃)₃7H₂O (0.087 g, 1 mmol) was dissolved in 10 ml of i-PrOH and added to 10 ml of a solution of NaL (0.3 g, 4 mmol) in a mixture of methanol and i-PrOH (1:1). After 30 min the precipitate of NaNO₃ was filtered off. The resulting clear solution was left for crystallization in a vacuum desiccator. The resulting light violet blocks of (I) were separated by filtration after 48 h, washed with cool i-PrOH (5 ml) and finally dried in air. Yield: 85–90%. IR (KBr pellet, cm^-1): 1240, 1030 (s, SO₂) and 1140 (s, PO).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. A view of Na[Nd(L)₄]_n with displacement ellipsoids shown at the 30% probability level. H atoms and morpholine rings have been omitted for clarity.
	Fig. 2. Polyhedror of Nd³⁺ in (I).
	Fig. 3. Motif of packing of (I) viewed along z (all H atoms are omitted for clarity).

catena-Poly[neodymium(III)-bis[µ-N- (dimorpholinophosphoryl)benzenesulfonamidato]-sodium(I)-bis[µ-N- (dimorpholinophosphoryl)benzenesulfonamidato]] top

Crystal data top

[NaNd(C₁₄H₂₁N₃O₅PS)₄]	Mo Kα radiation, λ = 0.71069 Å
M_r = 1664.72	Cell parameters from 68542 reflections
Cubic, P43n	θ = 2.8–32.1°
a = 22.943 (5) Å	µ = 0.90 mm⁻¹
V = 12077 (5) Å³	T = 293 K
Z = 6	Block, light violet
F(000) = 5154	0.60 × 0.40 × 0.30 mm
D_x = 1.373 Mg m⁻³

Data collection top

Oxford Diffraction KM-4 Xcalibur diffractometer with a Sapphire3 detector	5883 independent reflections
Radiation source: fine-focus sealed tube	3713 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.113
Detector resolution: 16.1827 pixels mm^-1	θ_max = 30.0°, θ_min = 2.8°
ω scans	h = −31→32
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	k = −30→32
T_min = 0.614, T_max = 0.774	l = −32→32
66051 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.095	H-atom parameters constrained
wR(F²) = 0.178	w = 1/[σ²(F_o²) + (0.0311P)² + 27.6297P] where P = (F_o² + 2F_c²)/3
S = 1.42	(Δ/σ)_max = 0.053
5883 reflections	Δρ_max = 1.17 e Å⁻³
174 parameters	Δρ_min = −0.75 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 2727 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.05 (3)

Crystal data top

[NaNd(C₁₄H₂₁N₃O₅PS)₄]	Z = 6
M_r = 1664.72	Mo Kα radiation
Cubic, P43n	µ = 0.90 mm⁻¹
a = 22.943 (5) Å	T = 293 K
V = 12077 (5) Å³	0.60 × 0.40 × 0.30 mm

Data collection top

Oxford Diffraction KM-4 Xcalibur diffractometer with a Sapphire3 detector	5883 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	3713 reflections with I > 2σ(I)
T_min = 0.614, T_max = 0.774	R_int = 0.113
66051 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.095	H-atom parameters constrained
wR(F²) = 0.178	w = 1/[σ²(F_o²) + (0.0311P)² + 27.6297P] where P = (F_o² + 2F_c²)/3
S = 1.42	Δρ_max = 1.17 e Å⁻³
5883 reflections	Δρ_min = −0.75 e Å⁻³
174 parameters	Absolute structure: Flack (1983), 2727 Friedel pairs
1 restraint	Absolute structure parameter: 0.05 (3)

Special details top

Experimental. CrysAlis RED, (Oxford Diffraction Ltd., 2007) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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 > σ(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 (Å²) top

	x	y	z	U_iso*/U_eq
Nd1	0.2500	0.0000	0.5000	0.03890 (11)
Na1	0.5000	0.0000	0.5000	0.0591 (11)
P1	0.34264 (7)	−0.11150 (8)	0.56551 (8)	0.0580 (4)
S1	0.38783 (6)	−0.07841 (7)	0.45680 (7)	0.0542 (4)
C1	0.3831 (3)	−0.1414 (3)	0.4113 (3)	0.0561 (17)
N1	0.3939 (2)	−0.1001 (3)	0.5188 (2)	0.0784 (19)
N2	0.3754 (2)	−0.1023 (3)	0.6282 (3)	0.0907 (14)
N3	0.3220 (3)	−0.1790 (3)	0.5648 (4)	0.126 (2)
O2	0.33520 (14)	−0.04482 (17)	0.44606 (16)	0.0497 (10)
O3	0.44068 (16)	−0.0500 (2)	0.4378 (2)	0.0719 (13)
O1	0.28838 (15)	−0.07562 (17)	0.55946 (17)	0.0526 (11)
O4	0.4251 (3)	−0.0792 (4)	0.7367 (2)	0.134 (2)
O5	0.2927 (4)	−0.2972 (3)	0.5510 (4)	0.163 (3)
C2	0.4310 (3)	−0.1778 (3)	0.4091 (3)	0.076 (2)
H2A	0.4651	−0.1699	0.4296	0.092*
C3	0.4246 (4)	−0.2277 (3)	0.3737 (4)	0.108 (3)
H3A	0.4562	−0.2528	0.3701	0.129*
C4	0.3754 (5)	−0.2411 (4)	0.3447 (4)	0.112 (3)
H4A	0.3734	−0.2741	0.3212	0.135*
C5	0.3306 (5)	−0.2067 (4)	0.3505 (4)	0.111 (3)
H5A	0.2960	−0.2167	0.3321	0.133*
C6	0.3325 (4)	−0.1552 (3)	0.3833 (3)	0.079 (2)
H6A	0.3000	−0.1311	0.3859	0.095*
C7	0.4355 (3)	−0.0977 (4)	0.6373 (3)	0.0907 (14)
H7A	0.4509	−0.1370	0.6396	0.109*
H7B	0.4521	−0.0800	0.6026	0.109*
C8	0.4565 (5)	−0.0675 (5)	0.6845 (4)	0.134 (2)
H8A	0.4546	−0.0260	0.6763	0.161*
H8B	0.4972	−0.0776	0.6903	0.161*
C9	0.3442 (3)	−0.1124 (4)	0.6830 (3)	0.0907 (14)
H9A	0.3032	−0.1036	0.6778	0.109*
H9B	0.3477	−0.1531	0.6939	0.109*
C10	0.3674 (4)	−0.0770 (6)	0.7282 (4)	0.134 (2)
H10A	0.3569	−0.0368	0.7201	0.161*
H10B	0.3484	−0.0878	0.7644	0.161*
C12	0.2463 (4)	−0.2556 (2)	0.5500 (5)	0.163 (3)
H12A	0.2280	−0.2535	0.5880	0.196*
H12B	0.2171	−0.2673	0.5218	0.196*
C11	0.2713 (3)	−0.1964 (2)	0.5334 (5)	0.126 (2)
H11A	0.2807	−0.1969	0.4922	0.151*
H11B	0.2414	−0.1671	0.5393	0.151*
C13	0.3666 (4)	−0.2253 (3)	0.5699 (5)	0.126 (2)
H13A	0.3873	−0.2288	0.5332	0.151*
H13B	0.3946	−0.2145	0.5997	0.151*
C14	0.3422 (5)	−0.2777 (4)	0.5838 (6)	0.163 (3)
H14A	0.3308	−0.2761	0.6245	0.196*
H14B	0.3723	−0.3072	0.5805	0.196*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Nd1	0.02596 (19)	0.04536 (15)	0.04536 (15)	0.000	0.000	0.000
Na1	0.0368 (17)	0.078 (3)	0.063 (2)	0.000	0.000	0.000
P1	0.0465 (8)	0.0611 (9)	0.0663 (10)	0.0090 (8)	−0.0157 (8)	−0.0007 (8)
S1	0.0324 (6)	0.0678 (9)	0.0624 (9)	0.0034 (7)	−0.0001 (7)	−0.0180 (8)
C1	0.049 (3)	0.065 (4)	0.055 (3)	0.001 (3)	0.016 (3)	−0.010 (3)
N1	0.054 (3)	0.113 (4)	0.069 (4)	0.041 (3)	−0.004 (3)	−0.008 (3)
N2	0.052 (2)	0.154 (4)	0.066 (2)	−0.005 (3)	−0.0010 (19)	0.018 (3)
N3	0.091 (3)	0.067 (3)	0.219 (6)	0.007 (2)	−0.064 (3)	0.010 (3)
O2	0.0341 (17)	0.059 (2)	0.056 (2)	−0.0013 (18)	0.0033 (18)	−0.009 (2)
O3	0.0338 (19)	0.085 (3)	0.097 (3)	0.001 (2)	0.007 (2)	−0.027 (3)
O1	0.0365 (18)	0.060 (2)	0.061 (2)	0.0045 (18)	0.0008 (18)	0.017 (2)
O4	0.119 (4)	0.212 (5)	0.071 (3)	−0.029 (4)	−0.014 (3)	0.000 (3)
O5	0.194 (6)	0.080 (3)	0.216 (6)	−0.016 (3)	−0.067 (5)	0.034 (4)
C2	0.073 (4)	0.067 (4)	0.090 (5)	0.009 (4)	0.023 (4)	−0.002 (4)
C3	0.143 (7)	0.073 (5)	0.106 (6)	0.021 (5)	0.074 (5)	−0.001 (4)
C4	0.159 (9)	0.077 (5)	0.100 (6)	−0.018 (6)	0.034 (6)	−0.031 (5)
C5	0.137 (8)	0.106 (6)	0.091 (6)	−0.034 (6)	0.003 (6)	−0.041 (5)
C6	0.086 (5)	0.082 (5)	0.070 (4)	−0.009 (4)	−0.007 (4)	−0.009 (4)
C7	0.052 (2)	0.154 (4)	0.066 (2)	−0.005 (3)	−0.0010 (19)	0.018 (3)
C8	0.119 (4)	0.212 (5)	0.071 (3)	−0.029 (4)	−0.014 (3)	0.000 (3)
C9	0.052 (2)	0.154 (4)	0.066 (2)	−0.005 (3)	−0.0010 (19)	0.018 (3)
C10	0.119 (4)	0.212 (5)	0.071 (3)	−0.029 (4)	−0.014 (3)	0.000 (3)
C12	0.194 (6)	0.080 (3)	0.216 (6)	−0.016 (3)	−0.067 (5)	0.034 (4)
C11	0.091 (3)	0.067 (3)	0.219 (6)	0.007 (2)	−0.064 (3)	0.010 (3)
C13	0.091 (3)	0.067 (3)	0.219 (6)	0.007 (2)	−0.064 (3)	0.010 (3)
C14	0.194 (6)	0.080 (3)	0.216 (6)	−0.016 (3)	−0.067 (5)	0.034 (4)

Geometric parameters (Å, º) top

Nd1—O1ⁱ	2.376 (4)	O5—C12	1.429 (10)
Nd1—O1ⁱⁱ	2.376 (4)	O5—C14	1.434 (13)
Nd1—O1	2.376 (4)	C2—C3	1.413 (10)
Nd1—O1ⁱⁱⁱ	2.376 (4)	C2—H2A	0.9300
Nd1—O2ⁱⁱ	2.532 (4)	C3—C4	1.345 (13)
Nd1—O2	2.532 (4)	C3—H3A	0.9300
Nd1—O2ⁱⁱⁱ	2.532 (4)	C4—C5	1.302 (13)
Nd1—O2ⁱ	2.532 (4)	C4—H4A	0.9300
Na1—O3	2.282 (4)	C5—C6	1.400 (11)
Na1—O3^iv	2.282 (4)	C5—H5A	0.9300
Na1—O3^v	2.282 (4)	C6—H6A	0.9300
Na1—O3ⁱⁱ	2.282 (4)	C7—C8	1.374 (12)
Na1—S1	3.2926 (16)	C7—H7A	0.9700
Na1—S1^v	3.2926 (16)	C7—H7B	0.9700
Na1—S1^iv	3.2926 (16)	C8—H8A	0.9700
Na1—S1ⁱⁱ	3.2926 (16)	C8—H8B	0.9700
P1—O1	1.499 (4)	C9—C10	1.421 (13)
P1—N1	1.613 (6)	C9—H9A	0.9700
P1—N3	1.619 (7)	C9—H9B	0.9700
P1—N2	1.637 (7)	C10—H10A	0.9700
S1—O3	1.444 (4)	C10—H10B	0.9700
S1—O2	1.453 (4)	C12—C11	1.524 (5)
S1—N1	1.513 (6)	C12—H12A	0.9700
S1—C1	1.787 (6)	C12—H12B	0.9700
C1—C6	1.365 (10)	C11—H11A	0.9700
C1—C2	1.380 (9)	C11—H11B	0.9700
N2—C7	1.400 (9)	C13—C14	1.364 (12)
N2—C9	1.465 (9)	C13—H13A	0.9700
N3—C11	1.425 (11)	C13—H13B	0.9700
N3—C13	1.478 (10)	C14—H14A	0.9700
O4—C10	1.340 (11)	C14—H14B	0.9700
O4—C8	1.424 (10)

O1ⁱ—Nd1—O1ⁱⁱ	97.89 (6)	S1—N1—P1	127.6 (3)
O1ⁱ—Nd1—O1	97.89 (6)	C7—N2—C9	111.4 (6)
O1ⁱⁱ—Nd1—O1	136.50 (17)	C7—N2—P1	126.4 (5)
O1ⁱ—Nd1—O1ⁱⁱⁱ	136.50 (17)	C9—N2—P1	120.7 (5)
O1ⁱⁱ—Nd1—O1ⁱⁱⁱ	97.89 (6)	C11—N3—C13	113.8 (7)
O1—Nd1—O1ⁱⁱⁱ	97.89 (6)	C11—N3—P1	120.7 (5)
O1ⁱ—Nd1—O2ⁱⁱ	151.18 (12)	C13—N3—P1	119.0 (6)
O1ⁱⁱ—Nd1—O2ⁱⁱ	72.42 (12)	S1—O2—Nd1	140.7 (2)
O1—Nd1—O2ⁱⁱ	74.32 (13)	S1—O3—Na1	122.6 (3)
O1ⁱⁱⁱ—Nd1—O2ⁱⁱ	72.30 (12)	P1—O1—Nd1	139.6 (2)
O1ⁱ—Nd1—O2	72.30 (12)	C10—O4—C8	111.7 (7)
O1ⁱⁱ—Nd1—O2	74.32 (13)	C12—O5—C14	112.9 (8)
O1—Nd1—O2	72.42 (12)	C1—C2—C3	115.3 (7)
O1ⁱⁱⁱ—Nd1—O2	151.18 (12)	C1—C2—H2A	122.4
O2ⁱⁱ—Nd1—O2	78.92 (16)	C3—C2—H2A	122.4
O1ⁱ—Nd1—O2ⁱⁱⁱ	74.32 (13)	C4—C3—C2	123.9 (8)
O1ⁱⁱ—Nd1—O2ⁱⁱⁱ	151.18 (12)	C4—C3—H3A	118.1
O1—Nd1—O2ⁱⁱⁱ	72.30 (12)	C2—C3—H3A	118.1
O1ⁱⁱⁱ—Nd1—O2ⁱⁱⁱ	72.42 (12)	C5—C4—C3	118.2 (9)
O2ⁱⁱ—Nd1—O2ⁱⁱⁱ	126.59 (10)	C5—C4—H4A	120.9
O2—Nd1—O2ⁱⁱⁱ	126.59 (10)	C3—C4—H4A	120.9
O1ⁱ—Nd1—O2ⁱ	72.42 (12)	C4—C5—C6	122.8 (9)
O1ⁱⁱ—Nd1—O2ⁱ	72.30 (12)	C4—C5—H5A	118.6
O1—Nd1—O2ⁱ	151.18 (12)	C6—C5—H5A	118.6
O1ⁱⁱⁱ—Nd1—O2ⁱ	74.32 (13)	C1—C6—C5	118.3 (8)
O2ⁱⁱ—Nd1—O2ⁱ	126.59 (10)	C1—C6—H6A	120.8
O2—Nd1—O2ⁱ	126.59 (10)	C5—C6—H6A	120.8
O2ⁱⁱⁱ—Nd1—O2ⁱ	78.92 (16)	C8—C7—N2	120.1 (8)
O3—Na1—O3^iv	119.6 (2)	C8—C7—H7A	107.3
O3—Na1—O3^v	102.5 (2)	N2—C7—H7A	107.3
O3^iv—Na1—O3^v	106.8 (2)	C8—C7—H7B	107.3
O3—Na1—O3ⁱⁱ	106.8 (2)	N2—C7—H7B	107.3
O3^iv—Na1—O3ⁱⁱ	102.5 (2)	H7A—C7—H7B	106.9
O3^v—Na1—O3ⁱⁱ	119.6 (2)	C7—C8—O4	113.0 (9)
O3—Na1—S1	21.69 (11)	C7—C8—H8A	109.0
O3^iv—Na1—S1	112.32 (11)	O4—C8—H8A	109.0
O3^v—Na1—S1	123.55 (12)	C7—C8—H8B	109.0
O3ⁱⁱ—Na1—S1	89.82 (10)	O4—C8—H8B	109.0
O3—Na1—S1^v	123.55 (12)	H8A—C8—H8B	107.8
O3^iv—Na1—S1^v	89.82 (10)	C10—C9—N2	110.7 (7)
O3^v—Na1—S1^v	21.69 (11)	C10—C9—H9A	109.5
O3ⁱⁱ—Na1—S1^v	112.32 (11)	N2—C9—H9A	109.5
S1—Na1—S1^v	144.97 (6)	C10—C9—H9B	109.5
O3—Na1—S1^iv	112.32 (11)	N2—C9—H9B	109.5
O3^iv—Na1—S1^iv	21.69 (11)	H9A—C9—H9B	108.1
O3^v—Na1—S1^iv	89.82 (10)	O4—C10—C9	117.0 (9)
O3ⁱⁱ—Na1—S1^iv	123.55 (12)	O4—C10—H10A	108.1
S1—Na1—S1^iv	113.77 (6)	C9—C10—H10A	108.1
S1^v—Na1—S1^iv	77.18 (5)	O4—C10—H10B	108.1
O3—Na1—S1ⁱⁱ	89.82 (10)	C9—C10—H10B	108.1
O3^iv—Na1—S1ⁱⁱ	123.55 (12)	H10A—C10—H10B	107.3
O3^v—Na1—S1ⁱⁱ	112.32 (11)	O5—C12—C11	108.6 (7)
O3ⁱⁱ—Na1—S1ⁱⁱ	21.69 (11)	O5—C12—H12A	110.0
S1—Na1—S1ⁱⁱ	77.18 (5)	C11—C12—H12A	110.0
S1^v—Na1—S1ⁱⁱ	113.77 (6)	O5—C12—H12B	110.0
S1^iv—Na1—S1ⁱⁱ	144.97 (6)	C11—C12—H12B	110.0
O1—P1—N1	117.1 (3)	H12A—C12—H12B	108.3
O1—P1—N3	106.4 (3)	N3—C11—C12	115.6 (7)
N1—P1—N3	111.2 (4)	N3—C11—H11A	108.4
O1—P1—N2	113.1 (3)	C12—C11—H11A	108.4
N1—P1—N2	103.2 (3)	N3—C11—H11B	108.4
N3—P1—N2	105.4 (4)	C12—C11—H11B	108.4
O3—S1—O2	114.0 (3)	H11A—C11—H11B	107.5
O3—S1—N1	110.8 (3)	C14—C13—N3	111.6 (8)
O2—S1—N1	114.2 (3)	C14—C13—H13A	109.3
O3—S1—C1	103.8 (3)	N3—C13—H13A	109.3
O2—S1—C1	106.2 (3)	C14—C13—H13B	109.3
N1—S1—C1	106.8 (3)	N3—C13—H13B	109.3
O3—S1—Na1	35.73 (19)	H13A—C13—H13B	108.0
O2—S1—Na1	114.25 (17)	C13—C14—O5	118.5 (10)
N1—S1—Na1	79.9 (2)	C13—C14—H14A	107.7
C1—S1—Na1	131.7 (2)	O5—C14—H14A	107.7
C6—C1—C2	121.4 (6)	C13—C14—H14B	107.7
C6—C1—S1	121.0 (5)	O5—C14—H14B	107.7
C2—C1—S1	117.5 (5)	H14A—C14—H14B	107.1

O3^iv—Na1—S1—O3	−114.4 (4)	O3—S1—O2—Nd1	−121.0 (4)
O3^v—Na1—S1—O3	15.9 (4)	N1—S1—O2—Nd1	7.8 (5)
O3ⁱⁱ—Na1—S1—O3	142.1 (2)	C1—S1—O2—Nd1	125.3 (4)
S1^v—Na1—S1—O3	11.0 (3)	Na1—S1—O2—Nd1	−81.7 (3)
S1^iv—Na1—S1—O3	−90.9 (3)	O1ⁱ—Nd1—O2—S1	−126.9 (4)
S1ⁱⁱ—Na1—S1—O3	124.3 (3)	O1ⁱⁱ—Nd1—O2—S1	129.2 (4)
O3—Na1—S1—O2	−98.0 (4)	O1—Nd1—O2—S1	−22.3 (3)
O3^iv—Na1—S1—O2	147.6 (2)	O1ⁱⁱⁱ—Nd1—O2—S1	51.6 (5)
O3^v—Na1—S1—O2	−82.1 (2)	O2ⁱⁱ—Nd1—O2—S1	54.6 (3)
O3ⁱⁱ—Na1—S1—O2	44.1 (2)	O2ⁱⁱⁱ—Nd1—O2—S1	−73.1 (3)
S1^v—Na1—S1—O2	−86.97 (18)	O2ⁱ—Nd1—O2—S1	−177.7 (3)
S1^iv—Na1—S1—O2	171.15 (19)	O2—S1—O3—Na1	98.6 (3)
S1ⁱⁱ—Na1—S1—O2	26.33 (17)	N1—S1—O3—Na1	−31.9 (4)
O3—Na1—S1—N1	149.9 (4)	C1—S1—O3—Na1	−146.2 (3)
O3^iv—Na1—S1—N1	35.5 (2)	O3^iv—Na1—O3—S1	75.7 (3)
O3^v—Na1—S1—N1	165.7 (2)	O3^v—Na1—O3—S1	−166.5 (4)
O3ⁱⁱ—Na1—S1—N1	−68.0 (2)	O3ⁱⁱ—Na1—O3—S1	−39.9 (2)
S1^v—Na1—S1—N1	160.9 (2)	S1^v—Na1—O3—S1	−172.4 (2)
S1^iv—Na1—S1—N1	59.0 (2)	S1^iv—Na1—O3—S1	98.4 (3)
S1ⁱⁱ—Na1—S1—N1	−85.8 (2)	S1ⁱⁱ—Na1—O3—S1	−53.7 (3)
O3—Na1—S1—C1	46.3 (4)	N1—P1—O1—Nd1	−1.5 (5)
O3^iv—Na1—S1—C1	−68.1 (3)	N3—P1—O1—Nd1	−126.5 (5)
O3^v—Na1—S1—C1	62.2 (3)	N2—P1—O1—Nd1	118.3 (4)
O3ⁱⁱ—Na1—S1—C1	−171.6 (3)	O1ⁱ—Nd1—O1—P1	86.0 (3)
S1^v—Na1—S1—C1	57.3 (3)	O1ⁱⁱ—Nd1—O1—P1	−24.3 (3)
S1^iv—Na1—S1—C1	−44.6 (3)	O1ⁱⁱⁱ—Nd1—O1—P1	−134.7 (4)
S1ⁱⁱ—Na1—S1—C1	170.6 (3)	O2ⁱⁱ—Nd1—O1—P1	−65.6 (4)
O3—S1—C1—C6	−131.8 (6)	O2—Nd1—O1—P1	17.5 (4)
O2—S1—C1—C6	−11.2 (6)	O2ⁱⁱⁱ—Nd1—O1—P1	156.7 (4)
N1—S1—C1—C6	111.1 (6)	O2ⁱ—Nd1—O1—P1	153.6 (3)
Na1—S1—C1—C6	−157.6 (4)	C6—C1—C2—C3	3.4 (10)
O3—S1—C1—C2	53.1 (6)	S1—C1—C2—C3	178.5 (5)
O2—S1—C1—C2	173.7 (5)	C1—C2—C3—C4	−1.8 (12)
N1—S1—C1—C2	−64.0 (6)	C2—C3—C4—C5	−1.3 (14)
Na1—S1—C1—C2	27.4 (7)	C3—C4—C5—C6	2.9 (14)
O3—S1—N1—P1	154.8 (4)	C2—C1—C6—C5	−2.0 (11)
O2—S1—N1—P1	24.4 (6)	S1—C1—C6—C5	−176.9 (6)
C1—S1—N1—P1	−92.7 (5)	C4—C5—C6—C1	−1.4 (13)
Na1—S1—N1—P1	136.6 (5)	C9—N2—C7—C8	−40.8 (12)
O1—P1—N1—S1	−28.1 (6)	P1—N2—C7—C8	153.3 (8)
N3—P1—N1—S1	94.4 (6)	N2—C7—C8—O4	42.8 (13)
N2—P1—N1—S1	−153.0 (5)	C10—O4—C8—C7	−46.7 (13)
O1—P1—N2—C7	−139.0 (7)	C7—N2—C9—C10	41.8 (11)
N1—P1—N2—C7	−11.5 (8)	P1—N2—C9—C10	−151.4 (7)
N3—P1—N2—C7	105.2 (8)	C8—O4—C10—C9	54.2 (13)
O1—P1—N2—C9	56.4 (8)	N2—C9—C10—O4	−52.2 (12)
N1—P1—N2—C9	−176.2 (7)	C14—O5—C12—C11	49.2 (12)
N3—P1—N2—C9	−59.4 (8)	C13—N3—C11—C12	45.9 (12)
O1—P1—N3—C11	29.9 (9)	P1—N3—C11—C12	−162.7 (7)
N1—P1—N3—C11	−98.7 (8)	O5—C12—C11—N3	−48.4 (12)
N2—P1—N3—C11	150.2 (8)	C11—N3—C13—C14	−44.0 (14)
O1—P1—N3—C13	179.8 (8)	P1—N3—C13—C14	164.1 (9)
N1—P1—N3—C13	51.3 (9)	N3—C13—C14—O5	48.7 (16)
N2—P1—N3—C13	−59.9 (9)	C12—O5—C14—C13	−54.3 (15)

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

Experimental details

Crystal data
Chemical formula	[NaNd(C₁₄H₂₁N₃O₅PS)₄]
M_r	1664.72
Crystal system, space group	Cubic, P43n
Temperature (K)	293
a (Å)	22.943 (5)
V (Å³)	12077 (5)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	0.90
Crystal size (mm)	0.60 × 0.40 × 0.30

Data collection
Diffractometer	Oxford Diffraction KM-4 Xcalibur diffractometer with a Sapphire3 detector
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2006)
T_min, T_max	0.614, 0.774
No. of measured, independent and observed [I > 2σ(I)] reflections	66051, 5883, 3713
R_int	0.113
(sin θ/λ)_max (Å⁻¹)	0.704

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.095, 0.178, 1.42
No. of reflections	5883
No. of parameters	174
No. of restraints	1
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0311P)² + 27.6297P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.17, −0.75
Absolute structure	Flack (1983), 2727 Friedel pairs
Absolute structure parameter	0.05 (3)

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

Nd1—O1	2.376 (4)	Na1—O3	2.282 (4)
Nd1—O2	2.532 (4)

References

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