Crystal structure of tris­(ethyl­enedi­ammonium) hexasulfatopraseodymium(III) hexa­hydrate

Held, P.

doi:10.1107/S1600536814020704

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Volume 70| Part 10| October 2014| Pages 235-237

doi:10.1107/S1600536814020704

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Crystal structure of tris(ethylenediammonium) hexasulfatopraseodymium(III) hexahydrate

Peter Held ^a ^*

^aInstitut für Kristallographie, Universität zu Köln, Greinstrasse 6, D-50939 Köln, Germany
^*Correspondence e-mail: peter.held@uni-koeln.de

Edited by M. Weil, Vienna University of Technology, Austria (Received 1 September 2014; accepted 15 September 2014; online 20 September 2014)

In the title salt, (C₂H₁₀N₂)₃[Pr₂(SO₄)₆]·6H₂O, the Pr^III cation is surrounded ninefold by five sulfate groups (two monodentate and three chelating) and by one water molecule [range of Pr—O bond lengths 2.383 (3) to 2.582 (3) Å]. The [Pr(SO₄)₅(H₂O)] groups are arranged in sheets parallel to (010). Two crystal water molecules and two ethylenediammonium cations (one with point group symmetry -1) connect the sheets via O—H⋯O and N—H⋯O hydrogen bonds from weak up to medium strength into a three-dimensional framework structure.

Keywords: crystal structure; praseodymium; ethylenediammonium; hydrogen bonds.

CCDC reference: 1024418

1. Chemical context

In the course of a systematic search for new `double salts' of simple secondary amines and mono- or divalent cations of various inorganic acids, the structures of (C₂H₁₀N₂)[Li₂(SO₄)₂] and (C₂H₈N)[Cu(HSO₄)(SO₄)(H₂O)₄] have been described previously (Held, 2003 , 2014 ). In continuation of these studies, lithium was replaced by trivalent praseodymium, yielding crystals of the title compound with composition (C₂H₁₀N₂)₃[Pr₂(SO₄)₆]·6H₂O.

2. Structural commentary

The asymmetric unit of the title compound contains three (SO₄)²⁻ anions, one and a half [NH₂(CH₃)]²⁺ cations (the other half being generated by inversion symmetry), one Pr³⁺ cation as well as three water molecules (Fig. 1). The Pr³⁺ cation is surrounded by nine O atoms from five sulfate groups, two of which are monodentately bonding and three chelating, and of one water molecule. The averaged Pr—O distance in the resulting distorted monocapped square-antiprism, [Pr(SO₄)₅(H₂O)], is 2.52 (7) Å. Praseodymium reaches an overall bond-valence sum (Brown & Altermatt, 1985 ) of 3.23 valence units. The S—O distances are nearly equal [average distance 1.479 (13) Å], however, the O—S—O angles vary [average bond angle 109.48 (2.05)°] clearly. One sulfate group (S2) interconnects two [PrO₉] polyhedra via two common edges parallel to [001], while another sulfate group (S3) connects via a common edge and a common vertex parallel to [100], leading to the formation of sheets parallel to (010).

Figure 1
The molecular entities in the structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) x, −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ; (ii) x + 1, y, z; (iii) −x, −y, −z + 1].

3. Supramolecular features

Hydrogen bonds of medium strength involving water molecules as donor groups and O atoms of the sulfate anions as acceptor groups interconnect neighbouring [Pr(SO₄)₅(H₂O)] units. Together with relatively weaker N—H⋯O hydrogen bonds of the ammonium groups atoms to sulfate anions, a three-dimensional framework is formed (Table 1, Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H11⋯O32	0.72 (8)	2.53 (8)	2.974 (6)	121 (7)
O1—H12⋯O13	0.78 (6)	1.92 (6)	2.674 (5)	162 (6)
O2—H21⋯O3	1.00 (12)	1.89 (12)	2.858 (7)	163 (9)
O2—H22⋯O21ⁱ	0.77 (8)	2.29 (8)	2.905 (6)	137 (7)
O3—H31⋯O11ⁱⁱ	0.87 (7)	1.95 (8)	2.795 (5)	165 (7)
O3—H32⋯O12ⁱⁱⁱ	0.80 (8)	2.00 (8)	2.766 (5)	162 (8)
N1—H1A⋯O33	0.87 (8)	2.48 (8)	3.291 (5)	155 (6)
N1—H1B⋯O3	0.88 (7)	1.92 (7)	2.758 (6)	158 (6)
N1—H1C⋯O13^iv	0.99 (9)	1.85 (9)	2.841 (6)	176 (7)
N2—H2A⋯O24	0.76 (7)	2.21 (7)	2.976 (5)	177 (7)
N2—H2B⋯O22^v	0.83 (8)	2.17 (8)	2.967 (6)	162 (7)
N2—H2C⋯O34^vi	0.94 (7)	2.20 (6)	3.020 (5)	146 (5)
N3—H3A⋯O2^vii	0.85 (7)	2.12 (7)	2.901 (8)	153 (6)
N3—H3B⋯O11	0.90 (7)	1.95 (8)	2.847 (6)	175 (6)
N3—H3C⋯O33	0.87 (7)	2.20 (7)	3.066 (5)	173 (6)
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) x, y, z+1; (iii) -x+1, -y, -z+1; (iv) -x, -y, -z+1; (v) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vi) x, y, z-1; (vii) x-1, y, z-1.

Figure 2
(100)-projection of the crystal structure of the title compound. Hydrogen bonds are shown as light-grey dashed lines. Colour scheme: (SO₄) tetrahedra (yellow), monocapped antiprism [PrO₉] (red), O (blue), N (green), C (grey), H (white).

4. Synthesis and crystallization

The title compound was obtained by reaction of an aqueous solution of praseodymium(III) sulfate with ethylenediamine and sulfuric acid (18 mol/l) in a stoichiometric ratio 1:1:2. The title compound crystallized by slow evaporation of the solvent at room temperature in form of light-green crystals with dimensions up to 3 mm within a few weeks.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms were clearly discernible from difference Fourier maps. Methylene H atoms were refined with a riding-model constraint, using a C—H distance of 0.97 Å and U_iso(H) = 1.2U_eq(C). Ammonium and water H atoms were refined freely.

Table 2
Experimental details

Crystal data
Chemical formula	(C₂H₁₀N₂)₃[Pr₂(SO₄)₆]·6H₂O
M_r	1152.70
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	6.6174 (8), 26.668 (4), 10.0264 (13)
β (°)	104.446 (15)
V (Å³)	1713.4 (4)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	3.29
Crystal size (mm)	0.22 × 0.21 × 0.20

Data collection
Diffractometer	Stoe IPDS-II
Absorption correction	Multi-scan (X-SHAPE and X-RED32; Stoe & Cie, 2002 )
T_min, T_max	0.491, 0.620
No. of measured, independent and observed [I > 2σ(I)] reflections	14346, 3922, 3091
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.662

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.069, 0.97
No. of reflections	3923
No. of parameters	311
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.72, −1.08
Computer programs: X-AREA (Stoe & Cie, 2002), SIR92 (Altomare et al., 1993 ), SHELXL97 (Sheldrick, 2008 ), ATOMS (Dowty, 2002 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1024418

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536814020704/wm5057sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814020704/wm5057Isup2.hkl

checkCIF report

Chemical context top

In the course of a systematic search for new `double salts' of simple secondary amines and mono- or divalent cations of various inorganic acids, the structures of (C₂N₂H₁₀)[Li₂(SO₄)₂] and (C₂H₈N)[Cu(HSO₄)(SO₄)(H₂O)₄] have been described previously (Held, 2003, 2014). In continuation of these studies, lithium was replaced by trivalent praseodymium, yielding crystals of the title compound with composition (C₂H₁₀N₂)₃[Pr₂(SO₄)₆]·6H₂O.

Structural commentary top

The asymmetric unit of the title compound contains three (SO₄)^2- anions, one and a half [NH₂(CH₃)]²⁺ cations (the other half being generated by inversion symmetry), one Pr³⁺ cation as well as three water molecules (Fig. 1). The Pr³⁺ cation is surrounded by nine O atoms from five sulfate groups, two of which are monodentately bonding and three chelating, and of one water molecule. The averaged Pr—O distance in the resulting distorted monocapped square-antiprism, [Pr(SO₄)₅(H₂O)], is 2.52 (7) Å. Praseodymium reaches an overall bond-valence sum (Brown & Altermatt, 1985) of 3.23 valence units. The S—O distances are nearly equal [average distance 1.479 (13) Å], however, the O—S—O angles vary [average bond angle 109.48 (2.05)°] clearly. One sulfate group (S2) interconnects two [PrO₉] polyhedra via two common edges parallel to [001], while another sulfate group (S3) connects via a common edge and a common vertex parallel to [100], leading to the formation of sheets parallel to (010).

Supramolecular features top

Hydrogen bonds of medium strength involving water molecules as donor groups and O atoms of the sulfate anions as acceptor groups interconnect neighbouring [Pr(SO₄)₅(H₂O)] units. Together with relatively weaker N—H···O hydrogen bonds of the ammonium groups atoms to sulfate anions, a three-dimensional framework is formed (Table 1, Fig. 2).

Synthesis and crystallization top

Refinement top

Related literature top

For related literature, see: Brown & Altermatt (1985); Held (2003, 2014).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-AREA (Stoe & Cie, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ATOMS (Dowty, 2002); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular entities in the structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) x, -y+1/2, z+1/2; (ii) x+1, y, z; (iii) -x, -y, -z+1].
	Fig. 2. (100)-projection of the crystal structure of the title compound. Hydrogen bonds are shown as light-grey dashed lines. Colour scheme: (SO₄) tetrahedra (yellow), monocapped antiprism [PrO₉] (red), O (blue), N (green), C (grey), H (white).

Tris(ethylenediammonium) hexasulfatopraseodymium(III) hexahydrate top

Crystal data top

(C₂H₁₀N₂)₃[Pr₂(SO₄)₆]·6H₂O	F(000) = 1148
M_r = 1152.70	D_x = 2.234 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 6.6174 (8) Å	θ = 20.0–24.3°
b = 26.668 (4) Å	µ = 3.29 mm⁻¹
c = 10.0264 (13) Å	T = 295 K
β = 104.446 (15)°	Parallelepiped, light-green
V = 1713.4 (4) Å³	0.22 × 0.21 × 0.20 mm
Z = 2

Data collection top

Stoe IPDS-II diffractometer	3922 independent reflections
Radiation source: fine-focus sealed tube	3091 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ω and ϕ scans	θ_max = 28.1°, θ_min = 2.6°
Absorption correction: multi-scan (X-SHAPE and X-RED32; Stoe & Cie, 2002)	h = −8→8
T_min = 0.491, T_max = 0.620	k = −34→35
14346 measured reflections	l = −13→13

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)] = 0.028	All H-atom parameters refined
wR(F²) = 0.069	w = 1/[σ²(F_o²) + (0.0454P)²] where P = (F_o² + 2F_c²)/3
S = 0.97	(Δ/σ)_max < 0.001
3923 reflections	Δρ_max = 0.72 e Å⁻³
311 parameters	Δρ_min = −1.08 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0150 (6)

Crystal data top

(C₂H₁₀N₂)₃[Pr₂(SO₄)₆]·6H₂O	V = 1713.4 (4) Å³
M_r = 1152.70	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.6174 (8) Å	µ = 3.29 mm⁻¹
b = 26.668 (4) Å	T = 295 K
c = 10.0264 (13) Å	0.22 × 0.21 × 0.20 mm
β = 104.446 (15)°

Data collection top

Stoe IPDS-II diffractometer	3922 independent reflections
Absorption correction: multi-scan (X-SHAPE and X-RED32; Stoe & Cie, 2002)	3091 reflections with I > 2σ(I)
T_min = 0.491, T_max = 0.620	R_int = 0.044
14346 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.069	All H-atom parameters refined
S = 0.97	Δρ_max = 0.72 e Å⁻³
3923 reflections	Δρ_min = −1.08 e Å⁻³
311 parameters

Special details top

Experimental. A suitable single-crystal was carefully selected under a polarizing microscope and mounted in a glass capillary. The scattering intensities were collected on an imaging plate diffractometer (IPDS II, Stoe & Cie) equipped with a fine focus sealed tube X-ray source (Mo Kα, λ = 0.71073 Å) operating at 50 kV and 30 mA. Intensity data for the title compound were collected at room temperature by ω-scans in 180 frames (0 < ω < 180°; ϕ = 0° and 90°, Δω = 2°, exposure time of 10 min) in the 2Θ range 2.29 to 59.53°. Structure solution and refinement were carried out using the programs SIR97 (Altomare et al., 1999) and SHELXL97 (Sheldrick, 2008). The last cycles of refinement included atomic positions and anisotropic parameters for all atoms. The final difference maps were free of any chemically significant features. The refinement was based on F² for ALL reflections.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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
Pr	0.54622 (3)	0.177147 (7)	0.465046 (19)	0.01075 (8)
S1	0.40656 (17)	0.06427 (3)	0.24648 (10)	0.0167 (2)
S2	0.52984 (15)	0.25100 (3)	0.21431 (9)	0.01307 (18)
S3	0.03251 (16)	0.15704 (4)	0.54283 (9)	0.0158 (2)
O11	0.1979 (5)	0.05421 (12)	0.1565 (3)	0.0283 (7)
O12	0.5682 (6)	0.05230 (12)	0.1764 (3)	0.0294 (7)
O13	0.4331 (5)	0.03414 (11)	0.3740 (3)	0.0269 (7)
O14	0.4203 (5)	0.11866 (10)	0.2836 (3)	0.0259 (7)
O21	0.5603 (5)	0.30594 (11)	0.2203 (3)	0.0205 (6)
O22	0.7151 (5)	0.22494 (11)	0.3007 (3)	0.0205 (6)
O23	0.3524 (5)	0.23557 (10)	0.2694 (3)	0.0183 (6)
O24	0.4972 (5)	0.23684 (10)	0.0667 (3)	0.0177 (6)
O31	0.1767 (5)	0.17700 (11)	0.4653 (3)	0.0222 (6)
O32	0.1426 (6)	0.12685 (14)	0.6597 (4)	0.0382 (9)
O33	−0.1327 (5)	0.12693 (11)	0.4480 (3)	0.0235 (6)
O34	−0.0807 (5)	0.19921 (12)	0.5890 (3)	0.0227 (6)
O1	0.5360 (6)	0.09619 (12)	0.5899 (4)	0.0298 (8)
H11	0.505 (12)	0.097 (3)	0.654 (8)	0.06 (2)*
H12	0.501 (9)	0.074 (2)	0.539 (6)	0.030 (15)*
O2	0.5314 (10)	0.1112 (3)	0.9028 (7)	0.100 (3)
H21	0.438 (17)	0.082 (4)	0.883 (10)	0.12 (4)*
H22	0.495 (12)	0.138 (3)	0.877 (8)	0.06 (2)*
O3	0.2361 (7)	0.03214 (16)	0.8914 (4)	0.0380 (9)
H31	0.220 (11)	0.033 (3)	0.975 (8)	0.056 (19)*
H32	0.310 (13)	0.009 (3)	0.888 (8)	0.07 (3)*
N1	−0.0784 (7)	0.02857 (16)	0.6520 (5)	0.0283 (8)
H1A	−0.090 (11)	0.060 (3)	0.623 (7)	0.06 (2)*
H1B	−0.005 (11)	0.032 (3)	0.738 (7)	0.053 (19)*
H1C	−0.204 (14)	0.008 (3)	0.646 (9)	0.08 (3)*
C1	0.0524 (8)	0.0008 (2)	0.5757 (5)	0.0300 (10)
H1D	0.082 (10)	−0.034 (3)	0.615 (6)	0.048 (17)*
H1E	0.173 (11)	0.014 (2)	0.595 (6)	0.045 (18)*
N2	0.0775 (8)	0.20727 (16)	−0.1020 (4)	0.0257 (8)
H2A	0.183 (11)	0.216 (2)	−0.057 (7)	0.040 (18)*
H2B	−0.011 (12)	0.230 (3)	−0.113 (7)	0.06 (2)*
H2C	0.086 (10)	0.199 (2)	−0.192 (7)	0.042 (16)*
C2	0.0133 (9)	0.16060 (18)	−0.0433 (5)	0.0278 (10)
H2D	0.115 (10)	0.136 (2)	−0.031 (6)	0.044 (17)*
H2E	−0.095 (13)	0.144 (3)	−0.107 (8)	0.08 (3)*
N3	−0.1249 (8)	0.12597 (16)	0.1435 (5)	0.0279 (9)
H3A	−0.245 (11)	0.119 (2)	0.094 (6)	0.039 (17)*
H3B	−0.023 (12)	0.103 (3)	0.153 (7)	0.06 (2)*
H3C	−0.126 (11)	0.129 (3)	0.230 (8)	0.05 (2)*
C3	−0.0508 (8)	0.17187 (17)	0.0867 (5)	0.0257 (9)
H3D	0.054 (10)	0.184 (2)	0.148 (6)	0.031 (15)*
H3E	−0.145 (9)	0.197 (2)	0.085 (6)	0.035 (15)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pr	0.01069 (13)	0.01111 (11)	0.01082 (11)	0.00001 (7)	0.00336 (7)	−0.00053 (8)
S1	0.0203 (6)	0.0136 (4)	0.0153 (4)	−0.0014 (3)	0.0026 (3)	−0.0027 (3)
S2	0.0144 (5)	0.0144 (4)	0.0107 (4)	0.0007 (3)	0.0038 (3)	0.0022 (3)
S3	0.0113 (5)	0.0182 (4)	0.0184 (4)	0.0002 (3)	0.0046 (3)	0.0041 (4)
O11	0.0219 (18)	0.0306 (17)	0.0283 (16)	−0.0023 (13)	−0.0014 (13)	−0.0069 (13)
O12	0.032 (2)	0.0285 (17)	0.0332 (17)	0.0017 (13)	0.0178 (14)	−0.0027 (13)
O13	0.037 (2)	0.0216 (15)	0.0219 (15)	−0.0055 (13)	0.0063 (13)	0.0041 (12)
O14	0.038 (2)	0.0132 (14)	0.0225 (15)	−0.0009 (12)	0.0005 (13)	−0.0048 (11)
O21	0.0296 (18)	0.0156 (13)	0.0170 (13)	−0.0024 (11)	0.0070 (12)	−0.0003 (10)
O22	0.0148 (16)	0.0265 (15)	0.0203 (14)	0.0032 (11)	0.0045 (11)	0.0095 (11)
O23	0.0148 (16)	0.0227 (14)	0.0192 (13)	−0.0006 (11)	0.0075 (11)	0.0064 (11)
O24	0.0223 (16)	0.0190 (14)	0.0128 (13)	0.0025 (11)	0.0064 (11)	0.0012 (10)
O31	0.0144 (16)	0.0258 (15)	0.0290 (15)	−0.0014 (11)	0.0101 (11)	0.0065 (12)
O32	0.0218 (19)	0.049 (2)	0.042 (2)	0.0036 (15)	0.0032 (15)	0.0301 (17)
O33	0.0167 (17)	0.0166 (14)	0.0376 (17)	−0.0033 (11)	0.0076 (12)	−0.0072 (12)
O34	0.0159 (17)	0.0282 (16)	0.0243 (15)	−0.0017 (12)	0.0057 (12)	−0.0115 (12)
O1	0.050 (2)	0.0174 (16)	0.0246 (17)	−0.0035 (14)	0.0150 (16)	−0.0012 (14)
O2	0.067 (4)	0.106 (5)	0.101 (5)	−0.043 (4)	−0.026 (3)	0.074 (4)
O3	0.049 (3)	0.039 (2)	0.0219 (17)	0.0071 (18)	0.0004 (15)	−0.0071 (15)
N1	0.030 (2)	0.023 (2)	0.033 (2)	−0.0027 (16)	0.0083 (17)	−0.0027 (17)
C1	0.023 (3)	0.037 (3)	0.028 (2)	0.001 (2)	0.0030 (19)	−0.004 (2)
N2	0.026 (3)	0.025 (2)	0.026 (2)	−0.0076 (17)	0.0056 (17)	0.0038 (16)
C2	0.036 (3)	0.023 (2)	0.030 (2)	0.0009 (19)	0.020 (2)	0.0038 (18)
N3	0.026 (3)	0.033 (2)	0.028 (2)	−0.0022 (17)	0.0126 (18)	0.0050 (17)
C3	0.028 (3)	0.022 (2)	0.030 (2)	−0.0035 (18)	0.0127 (19)	0.0000 (18)

Geometric parameters (Å, º) top

Pr—O14	2.383 (3)	O34—Pr^iv	2.541 (3)
Pr—O31	2.446 (3)	O1—H11	0.72 (8)
Pr—O1	2.505 (3)	O1—H12	0.78 (6)
Pr—O34ⁱ	2.541 (3)	O2—H21	1.00 (12)
Pr—O22	2.551 (3)	O2—H22	0.77 (8)
Pr—O33ⁱ	2.553 (3)	O3—H31	0.87 (7)
Pr—O24ⁱⁱ	2.564 (3)	O3—H32	0.80 (8)
Pr—O21ⁱⁱ	2.577 (3)	N1—C1	1.487 (6)
Pr—O23	2.582 (3)	N1—H1A	0.87 (8)
Pr—S3ⁱ	3.1621 (11)	N1—H1B	0.88 (7)
Pr—S2ⁱⁱ	3.1725 (9)	N1—H1C	0.99 (9)
Pr—S2	3.1741 (9)	C1—C1^v	1.504 (9)
S1—O12	1.454 (3)	C1—H1D	1.01 (7)
S1—O11	1.473 (3)	C1—H1E	0.84 (7)
S1—O13	1.483 (3)	N2—C2	1.483 (6)
S1—O14	1.495 (3)	N2—H2A	0.76 (7)
S2—O23	1.475 (3)	N2—H2B	0.83 (8)
S2—O21	1.478 (3)	N2—H2C	0.94 (7)
S2—O22	1.485 (3)	C2—C3	1.499 (7)
S2—O24	1.490 (3)	C2—H2D	0.92 (7)
S3—O32	1.458 (3)	C2—H2E	0.94 (8)
S3—O31	1.472 (3)	N3—C3	1.484 (6)
S3—O34	1.488 (3)	N3—H3A	0.85 (7)
S3—O33	1.492 (3)	N3—H3B	0.90 (7)
O21—Prⁱⁱⁱ	2.577 (3)	N3—H3C	0.87 (7)
O24—Prⁱⁱⁱ	2.564 (3)	C3—H3D	0.87 (6)
O33—Pr^iv	2.553 (3)	C3—H3E	0.92 (6)

O14—Pr—O31	80.82 (11)	O31—S3—O33	109.05 (18)
O14—Pr—O1	76.67 (11)	O34—S3—O33	105.04 (17)
O31—Pr—O1	81.17 (12)	S1—O14—Pr	144.42 (18)
O14—Pr—O34ⁱ	129.57 (10)	S2—O21—Prⁱⁱⁱ	99.34 (13)
O31—Pr—O34ⁱ	148.16 (10)	S2—O22—Pr	100.34 (14)
O1—Pr—O34ⁱ	95.70 (12)	S2—O23—Pr	99.30 (14)
O14—Pr—O22	87.71 (10)	S2—O24—Prⁱⁱⁱ	99.60 (14)
O31—Pr—O22	126.92 (9)	S3—O31—Pr	141.33 (18)
O1—Pr—O22	145.50 (11)	S3—O33—Pr^iv	99.49 (14)
O34ⁱ—Pr—O22	70.82 (9)	S3—O34—Pr^iv	100.13 (14)
O14—Pr—O33ⁱ	75.16 (10)	Pr—O1—H11	117 (6)
O31—Pr—O33ⁱ	148.01 (9)	Pr—O1—H12	112 (4)
O1—Pr—O33ⁱ	73.03 (12)	H11—O1—H12	121 (7)
O34ⁱ—Pr—O33ⁱ	55.31 (9)	H21—O2—H22	122 (8)
O22—Pr—O33ⁱ	73.30 (10)	H31—O3—H32	107 (7)
O14—Pr—O24ⁱⁱ	146.56 (10)	C1—N1—H1A	108 (5)
O31—Pr—O24ⁱⁱ	77.02 (10)	C1—N1—H1B	108 (5)
O1—Pr—O24ⁱⁱ	123.41 (11)	H1A—N1—H1B	102 (6)
O34ⁱ—Pr—O24ⁱⁱ	78.58 (9)	C1—N1—H1C	106 (5)
O22—Pr—O24ⁱⁱ	85.94 (9)	H1A—N1—H1C	120 (7)
O33ⁱ—Pr—O24ⁱⁱ	133.31 (9)	H1B—N1—H1C	111 (6)
O14—Pr—O21ⁱⁱ	142.34 (10)	N1—C1—C1^v	110.7 (5)
O31—Pr—O21ⁱⁱ	77.75 (10)	N1—C1—H1D	110 (4)
O1—Pr—O21ⁱⁱ	69.73 (11)	C1^v—C1—H1D	111 (4)
O34ⁱ—Pr—O21ⁱⁱ	71.56 (10)	N1—C1—H1E	109 (4)
O22—Pr—O21ⁱⁱ	129.86 (10)	C1^v—C1—H1E	114 (4)
O33ⁱ—Pr—O21ⁱⁱ	109.50 (10)	H1D—C1—H1E	102 (5)
O24ⁱⁱ—Pr—O21ⁱⁱ	54.92 (8)	C2—N2—H2A	109 (5)
O14—Pr—O23	78.58 (10)	C2—N2—H2B	114 (5)
O31—Pr—O23	72.22 (9)	H2A—N2—H2B	112 (7)
O1—Pr—O23	146.05 (12)	C2—N2—H2C	106 (4)
O34ⁱ—Pr—O23	118.03 (10)	H2A—N2—H2C	112 (6)
O22—Pr—O23	54.71 (9)	H2B—N2—H2C	104 (6)
O33ⁱ—Pr—O23	121.97 (10)	N2—C2—C3	110.4 (4)
O24ⁱⁱ—Pr—O23	70.99 (9)	N2—C2—H2D	112 (4)
O21ⁱⁱ—Pr—O23	122.48 (9)	C3—C2—H2D	112 (4)
O12—S1—O11	110.7 (2)	N2—C2—H2E	112 (5)
O12—S1—O13	110.8 (2)	C3—C2—H2E	110 (5)
O11—S1—O13	108.69 (19)	H2D—C2—H2E	100 (6)
O12—S1—O14	109.09 (19)	C3—N3—H3A	108 (4)
O11—S1—O14	108.60 (19)	C3—N3—H3B	107 (5)
O13—S1—O14	108.92 (17)	H3A—N3—H3B	118 (6)
O23—S2—O21	111.99 (17)	C3—N3—H3C	113 (5)
O23—S2—O22	105.65 (16)	H3A—N3—H3C	111 (6)
O21—S2—O22	110.84 (18)	H3B—N3—H3C	99 (6)
O23—S2—O24	111.67 (17)	N3—C3—C2	111.2 (4)
O21—S2—O24	106.03 (16)	N3—C3—H3D	109 (4)
O22—S2—O24	110.75 (17)	C2—C3—H3D	110 (4)
O32—S3—O31	111.4 (2)	N3—C3—H3E	109 (4)
O32—S3—O34	110.9 (2)	C2—C3—H3E	118 (4)
O31—S3—O34	109.50 (18)	H3D—C3—H3E	99 (5)
O32—S3—O33	110.8 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H11···O32	0.72 (8)	2.53 (8)	2.974 (6)	121 (7)
O1—H12···O13	0.78 (6)	1.92 (6)	2.674 (5)	162 (6)
O2—H21···O3	1.00 (12)	1.89 (12)	2.858 (7)	163 (9)
O2—H22···O21ⁱⁱ	0.77 (8)	2.29 (8)	2.905 (6)	137 (7)
O3—H31···O11^vi	0.87 (7)	1.95 (8)	2.795 (5)	165 (7)
O3—H32···O12^vii	0.80 (8)	2.00 (8)	2.766 (5)	162 (8)
N1—H1A···O33	0.87 (8)	2.48 (8)	3.291 (5)	155 (6)
N1—H1B···O3	0.88 (7)	1.92 (7)	2.758 (6)	158 (6)
N1—H1C···O13^v	0.99 (9)	1.85 (9)	2.841 (6)	176 (7)
N2—H2A···O24	0.76 (7)	2.21 (7)	2.976 (5)	177 (7)
N2—H2B···O22^viii	0.83 (8)	2.17 (8)	2.967 (6)	162 (7)
N2—H2C···O34^ix	0.94 (7)	2.20 (6)	3.020 (5)	146 (5)
N3—H3A···O2^x	0.85 (7)	2.12 (7)	2.901 (8)	153 (6)
N3—H3B···O11	0.90 (7)	1.95 (8)	2.847 (6)	175 (6)
N3—H3C···O33	0.87 (7)	2.20 (7)	3.066 (5)	173 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H11···O32	0.72 (8)	2.53 (8)	2.974 (6)	121 (7)
O1—H12···O13	0.78 (6)	1.92 (6)	2.674 (5)	162 (6)
O2—H21···O3	1.00 (12)	1.89 (12)	2.858 (7)	163 (9)
O2—H22···O21ⁱ	0.77 (8)	2.29 (8)	2.905 (6)	137 (7)
O3—H31···O11ⁱⁱ	0.87 (7)	1.95 (8)	2.795 (5)	165 (7)
O3—H32···O12ⁱⁱⁱ	0.80 (8)	2.00 (8)	2.766 (5)	162 (8)
N1—H1A···O33	0.87 (8)	2.48 (8)	3.291 (5)	155 (6)
N1—H1B···O3	0.88 (7)	1.92 (7)	2.758 (6)	158 (6)
N1—H1C···O13^iv	0.99 (9)	1.85 (9)	2.841 (6)	176 (7)
N2—H2A···O24	0.76 (7)	2.21 (7)	2.976 (5)	177 (7)
N2—H2B···O22^v	0.83 (8)	2.17 (8)	2.967 (6)	162 (7)
N2—H2C···O34^vi	0.94 (7)	2.20 (6)	3.020 (5)	146 (5)
N3—H3A···O2^vii	0.85 (7)	2.12 (7)	2.901 (8)	153 (6)
N3—H3B···O11	0.90 (7)	1.95 (8)	2.847 (6)	175 (6)
N3—H3C···O33	0.87 (7)	2.20 (7)	3.066 (5)	173 (6)

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

Experimental details

Crystal data
Chemical formula	(C₂H₁₀N₂)₃[Pr₂(SO₄)₆]·6H₂O
M_r	1152.70
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	6.6174 (8), 26.668 (4), 10.0264 (13)
β (°)	104.446 (15)
V (Å³)	1713.4 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.29
Crystal size (mm)	0.22 × 0.21 × 0.20

Data collection
Diffractometer	Stoe IPDS-II diffractometer
Absorption correction	Multi-scan (X-SHAPE and X-RED32; Stoe & Cie, 2002)
T_min, T_max	0.491, 0.620
No. of measured, independent and observed [I > 2σ(I)] reflections	14346, 3922, 3091
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.662

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.069, 0.97
No. of reflections	3923
No. of parameters	311
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.72, −1.08

Computer programs: X-AREA (Stoe & Cie, 2002), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ATOMS (Dowty, 2002), publCIF (Westrip, 2010).

Acknowledgements

The author would like to thank Professor G. Meyer and Dr I. Pantenburg from the Institute of Inorganic Chemistry of the University of Cologne for the opportunity to collect data at the single-crystal diffractometer.

References

Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350. CrossRef Web of Science IUCr Journals Google Scholar
Brown, I. D. & Altermatt, D. (1985). Acta Cryst. B41, 244–247. CrossRef CAS Web of Science IUCr Journals Google Scholar
Dowty, E. (2002). ATOMS. Shape Software, Kingsport, Tennessee, USA. Google Scholar
Held, P. (2003). Z. Kristallogr. New Cryst. Struct. 218, 13–14. CAS Google Scholar
Held, P. (2014). Acta Cryst. E70, m119. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2002). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany. Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 70| Part 10| October 2014| Pages 235-237

doi:10.1107/S1600536814020704

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure of tris­­(ethyl­enedi­ammonium) hexa­sulfatopraseodymium(III) hexa­hydrate

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Synthesis and crystallization

5. Refinement

Supporting information

Acknowledgements

References

research communications

Crystal structure of tris(ethylenediammonium) hexasulfatopraseodymium(III) hexahydrate

3. Supramolecular features