(NH
4)[Nd(SO
4)
2(H
2O)
3]·H
2O is isotypic with other members of the (NH
4)[
Ln(SO
4)
2(H
2O)
3]·H
2O family (
Ln = lanthanides). It contains NdO
9 polyhedra and SO
4 tetrahedra, which are linked by common edges and vertices, forming a layer-like arrangement parallel to (010). The neodymium cation is nine-coordinated in a distorted monocapped square antiprismatic geometry with two sulfate groups as chelating and two sulfate groups as bridging ligands. O—H
O and N—H
O hydrogen bonds consolidate the structure into a three-dimensional network. The dependence of unit-cell dimensions of the isotypic compounds on the lanthanide atomic number is discussed.
Supporting information
Key indicators
- Single-crystal X-ray study
- T = 291 K
- Mean (S-O) = 0.003 Å
- R factor = 0.024
- wR factor = 0.058
- Data-to-parameter ratio = 22.1
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT220_ALERT_2_C Large Non-Solvent O Ueq(max)/Ueq(min) ... 2.63 Ratio
PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O21
PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O22
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Nd1
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for S2
Alert level G
FORMU01_ALERT_1_G There is a discrepancy between the atom counts in the
_chemical_formula_sum and _chemical_formula_moiety. This is
usually due to the moiety formula being in the wrong format.
Atom count from _chemical_formula_sum: H12 N1 Nd1 O12 S2
Atom count from _chemical_formula_moiety:H16 N2 Nd1 O12 S2
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
6 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
5 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: KM-4 Software (Kuma, 1993); cell refinement: KM-4 Software; data reduction: DATAPROC (Gałdecki et al., 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Sheldrick, 1990), ORTEP-3 (Farrugia, 1997)
and Mercury (Bruno et al., 2002); software used to prepare material for publication: SHELXL97.
Ammonium neodymium(III) bis[sulfate(VI)] tetrahydrate
top
Crystal data top
(NH4)[Nd(SO4)2(H2O)3].H2O | F(000) = 828 |
Mr = 426.47 | Dx = 2.585 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 99 reflections |
a = 6.636 (1) Å | θ = 5–25° |
b = 18.935 (1) Å | µ = 5.18 mm−1 |
c = 8.789 (1) Å | T = 291 K |
β = 97.06 (1)° | Prism, light violet |
V = 1096.0 (2) Å3 | 0.06 × 0.04 × 0.03 mm |
Z = 4 | |
Data collection top
Kuma KM-4 diffractometer | 2939 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.019 |
Graphite monochromator | θmax = 30.1°, θmin = 2.2° |
ω/2θ scans | h = −9→9 |
Absorption correction: numerical (X-RED32; Stoe & Cie, 1999) | k = −1→26 |
Tmin = 0.764, Tmax = 0.869 | l = −1→12 |
3999 measured reflections | 3 standard reflections every 100 reflections |
3224 independent reflections | intensity decay: 72.3% |
Refinement top
Refinement on F2 | Secondary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.025 | H-atom parameters constrained |
wR(F2) = 0.058 | w = 1/[σ2(Fo2) + (0.0232P)2 + 3.8961P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
3224 reflections | Δρmax = 1.58 e Å−3 |
146 parameters | Δρmin = −1.02 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0150 (4) |
Special details top
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 | Uiso*/Ueq | |
Nd1 | 0.14675 (2) | 0.122424 (8) | 0.286321 (17) | 0.01340 (7) | |
S1 | 0.12267 (13) | 0.27684 (4) | 0.41444 (9) | 0.01958 (15) | |
O1 | −0.0465 (4) | 0.22556 (14) | 0.3774 (3) | 0.0271 (5) | |
O2 | 0.3081 (4) | 0.23889 (14) | 0.3843 (3) | 0.0272 (5) | |
O3 | 0.0903 (5) | 0.34036 (14) | 0.3206 (3) | 0.0310 (6) | |
O4 | 0.1364 (6) | 0.29581 (15) | 0.5766 (3) | 0.0380 (7) | |
S2 | −0.31329 (12) | 0.07620 (5) | 0.26382 (12) | 0.02485 (18) | |
O21 | −0.1631 (4) | 0.0782 (2) | 0.4041 (4) | 0.0446 (9) | |
O22 | −0.2053 (4) | 0.11047 (19) | 0.1446 (3) | 0.0364 (7) | |
O23 | −0.3710 (6) | 0.00438 (19) | 0.2278 (7) | 0.0714 (15) | |
O24 | −0.4892 (4) | 0.11915 (15) | 0.2885 (4) | 0.0332 (6) | |
O5 | 0.2464 (5) | 0.10893 (16) | 0.5677 (3) | 0.0354 (7) | |
H5A | 0.2760 | 0.0708 | 0.6001 | 0.053* | |
H5B | 0.1959 | 0.1347 | 0.6201 | 0.053* | |
O6 | 0.1923 (6) | −0.00455 (15) | 0.3348 (4) | 0.0396 (7) | |
H6A | 0.2693 | −0.0229 | 0.2902 | 0.059* | |
H6B | 0.1780 | −0.0252 | 0.4252 | 0.059* | |
O7 | 0.1693 (5) | 0.05489 (15) | 0.0409 (3) | 0.0333 (6) | |
H7A | 0.1227 | 0.0799 | −0.0408 | 0.050* | |
H7B | 0.2792 | 0.0380 | 0.0318 | 0.050* | |
N1 | −0.3460 (6) | 0.2224 (2) | −0.3854 (5) | 0.0449 (10) | |
H1A | −0.4578 | 0.2226 | −0.4626 | 0.067* | |
H1B | −0.3495 | 0.1791 | −0.3198 | 0.067* | |
H1C | −0.3137 | 0.2658 | −0.3492 | 0.067* | |
H1D | −0.2640 | 0.2109 | −0.4701 | 0.067* | |
O8 | −0.3625 (6) | 0.1094 (2) | −0.1641 (4) | 0.0480 (9) | |
H8A | −0.2909 | 0.1178 | −0.0678 | 0.072* | |
H8B | −0.4731 | 0.0867 | −0.1588 | 0.072* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Nd1 | 0.01172 (9) | 0.01511 (9) | 0.01366 (9) | 0.00097 (5) | 0.00271 (5) | 0.00105 (5) |
S1 | 0.0275 (4) | 0.0168 (3) | 0.0144 (3) | 0.0047 (3) | 0.0026 (3) | −0.0021 (3) |
O1 | 0.0222 (12) | 0.0265 (12) | 0.0335 (13) | 0.0034 (10) | 0.0075 (10) | −0.0054 (10) |
O2 | 0.0210 (12) | 0.0253 (12) | 0.0341 (14) | 0.0036 (10) | −0.0015 (10) | −0.0089 (10) |
O3 | 0.0481 (17) | 0.0230 (12) | 0.0225 (12) | 0.0073 (12) | 0.0064 (11) | 0.0052 (10) |
O4 | 0.078 (2) | 0.0222 (12) | 0.0145 (11) | 0.0066 (14) | 0.0064 (13) | −0.0046 (10) |
S2 | 0.0131 (3) | 0.0189 (4) | 0.0441 (5) | −0.0005 (3) | 0.0097 (3) | −0.0029 (3) |
O21 | 0.0226 (13) | 0.063 (2) | 0.0486 (18) | 0.0008 (14) | 0.0060 (12) | 0.0348 (17) |
O22 | 0.0208 (12) | 0.069 (2) | 0.0194 (12) | −0.0113 (13) | 0.0033 (10) | −0.0011 (13) |
O23 | 0.0378 (19) | 0.0303 (17) | 0.150 (5) | −0.0113 (15) | 0.027 (2) | −0.033 (2) |
O24 | 0.0153 (11) | 0.0305 (14) | 0.0546 (18) | 0.0046 (10) | 0.0072 (11) | −0.0069 (13) |
O5 | 0.0485 (18) | 0.0382 (15) | 0.0191 (12) | 0.0166 (13) | 0.0022 (12) | −0.0006 (11) |
O6 | 0.065 (2) | 0.0235 (13) | 0.0345 (15) | 0.0103 (14) | 0.0223 (15) | 0.0074 (11) |
O7 | 0.0471 (17) | 0.0287 (13) | 0.0254 (13) | 0.0095 (12) | 0.0094 (12) | −0.0016 (11) |
N1 | 0.040 (2) | 0.053 (2) | 0.038 (2) | −0.0120 (18) | −0.0095 (16) | 0.0053 (18) |
O8 | 0.0452 (19) | 0.059 (2) | 0.0365 (17) | −0.0136 (16) | −0.0085 (14) | −0.0002 (15) |
Geometric parameters (Å, º) top
Nd1—O4i | 2.402 (3) | S2—O24 | 1.461 (3) |
Nd1—O24ii | 2.414 (3) | S2—O21 | 1.487 (3) |
Nd1—O6 | 2.454 (3) | S2—O22 | 1.489 (3) |
Nd1—O5 | 2.494 (3) | O24—Nd1iv | 2.414 (3) |
Nd1—O22 | 2.519 (3) | O5—H5A | 0.7919 |
Nd1—O1 | 2.520 (3) | O5—H5B | 0.7746 |
Nd1—O7 | 2.527 (3) | O6—H6A | 0.7638 |
Nd1—O21 | 2.554 (3) | O6—H6B | 0.9015 |
Nd1—O2 | 2.554 (3) | O7—H7A | 0.8842 |
Nd1—S1 | 3.1443 (8) | O7—H7B | 0.8092 |
Nd1—S2 | 3.1586 (9) | N1—H1A | 0.9417 |
S1—O3 | 1.459 (3) | N1—H1B | 1.0033 |
S1—O4 | 1.462 (3) | N1—H1C | 0.8992 |
S1—O2 | 1.477 (3) | N1—H1D | 0.9981 |
S1—O1 | 1.490 (3) | O8—H8A | 0.9319 |
O4—Nd1iii | 2.402 (3) | O8—H8B | 0.8568 |
S2—O23 | 1.437 (3) | | |
| | | |
O4i—Nd1—O24ii | 87.53 (12) | O22—Nd1—S2 | 27.58 (7) |
O4i—Nd1—O6 | 139.11 (10) | O1—Nd1—S2 | 73.08 (6) |
O24ii—Nd1—O6 | 82.62 (11) | O7—Nd1—S2 | 87.96 (8) |
O4i—Nd1—O5 | 143.74 (10) | O21—Nd1—S2 | 27.69 (8) |
O24ii—Nd1—O5 | 81.16 (11) | O2—Nd1—S2 | 128.48 (6) |
O6—Nd1—O5 | 73.47 (10) | S1—Nd1—S2 | 100.88 (2) |
O4i—Nd1—O22 | 75.00 (11) | O3—S1—O4 | 109.62 (16) |
O24ii—Nd1—O22 | 150.22 (10) | O3—S1—O2 | 111.58 (17) |
O6—Nd1—O22 | 94.86 (12) | O4—S1—O2 | 109.94 (18) |
O5—Nd1—O22 | 126.73 (10) | O3—S1—O1 | 111.04 (17) |
O4i—Nd1—O1 | 77.10 (10) | O4—S1—O1 | 109.16 (18) |
O24ii—Nd1—O1 | 124.41 (9) | O2—S1—O1 | 105.42 (15) |
O6—Nd1—O1 | 139.53 (9) | O3—S1—Nd1 | 125.05 (11) |
O5—Nd1—O1 | 81.23 (9) | O4—S1—Nd1 | 125.30 (12) |
O22—Nd1—O1 | 75.49 (10) | O2—S1—Nd1 | 53.36 (10) |
O4i—Nd1—O7 | 70.75 (9) | O1—S1—Nd1 | 52.10 (10) |
O24ii—Nd1—O7 | 80.20 (10) | S1—O1—Nd1 | 100.09 (12) |
O6—Nd1—O7 | 68.49 (10) | S1—O2—Nd1 | 99.00 (13) |
O5—Nd1—O7 | 139.31 (9) | S1—O4—Nd1iii | 154.06 (17) |
O22—Nd1—O7 | 71.41 (10) | O23—S2—O24 | 111.31 (19) |
O1—Nd1—O7 | 138.50 (9) | O23—S2—O21 | 109.9 (3) |
O4i—Nd1—O21 | 125.01 (11) | O24—S2—O21 | 109.2 (2) |
O24ii—Nd1—O21 | 147.46 (10) | O23—S2—O22 | 113.3 (3) |
O6—Nd1—O21 | 72.36 (11) | O24—S2—O22 | 108.94 (19) |
O5—Nd1—O21 | 72.13 (11) | O21—S2—O22 | 103.92 (16) |
O22—Nd1—O21 | 55.04 (10) | O23—S2—Nd1 | 120.34 (15) |
O1—Nd1—O21 | 70.04 (11) | O24—S2—Nd1 | 128.34 (12) |
O7—Nd1—O21 | 108.37 (12) | O21—S2—Nd1 | 52.93 (11) |
O4i—Nd1—O2 | 70.94 (9) | O22—S2—Nd1 | 51.54 (11) |
O24ii—Nd1—O2 | 69.01 (9) | S2—O21—Nd1 | 99.39 (15) |
O6—Nd1—O2 | 138.57 (10) | S2—O22—Nd1 | 100.88 (14) |
O5—Nd1—O2 | 72.84 (10) | S2—O24—Nd1iv | 146.13 (17) |
O22—Nd1—O2 | 124.69 (10) | Nd1—O5—H5A | 118.2 |
O1—Nd1—O2 | 55.43 (8) | Nd1—O5—H5B | 116.3 |
O7—Nd1—O2 | 131.16 (10) | H5A—O5—H5B | 117.9 |
O21—Nd1—O2 | 118.11 (11) | Nd1—O6—H6A | 115.6 |
O4i—Nd1—S1 | 71.19 (7) | Nd1—O6—H6B | 123.6 |
O24ii—Nd1—S1 | 96.65 (7) | H6A—O6—H6B | 113.9 |
O6—Nd1—S1 | 149.27 (8) | Nd1—O7—H7A | 111.7 |
O5—Nd1—S1 | 76.05 (7) | Nd1—O7—H7B | 115.6 |
O22—Nd1—S1 | 100.12 (8) | H7A—O7—H7B | 111.1 |
O1—Nd1—S1 | 27.80 (6) | H1A—N1—H1B | 110.3 |
O7—Nd1—S1 | 141.91 (7) | H1A—N1—H1C | 112.5 |
O21—Nd1—S1 | 94.62 (9) | H1B—N1—H1C | 124.4 |
O2—Nd1—S1 | 27.64 (6) | H1A—N1—H1D | 85.3 |
O4i—Nd1—S2 | 101.21 (9) | H1B—N1—H1D | 107.7 |
O24ii—Nd1—S2 | 162.15 (7) | H1C—N1—H1D | 109.5 |
O6—Nd1—S2 | 80.62 (9) | H8A—O8—H8B | 112.4 |
O5—Nd1—S2 | 99.80 (8) | | |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x+1, y, z; (iii) x, −y+1/2, z+1/2; (iv) x−1, y, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5A···O23v | 0.79 | 2.12 | 2.855 (6) | 155 |
O5—H5B···O3iii | 0.77 | 2.03 | 2.739 (4) | 152 |
O6—H6A···O8vi | 0.76 | 2.11 | 2.808 (5) | 151 |
O6—H6A···O23ii | 0.76 | 2.57 | 3.159 (5) | 136 |
O6—H6B···O21v | 0.90 | 1.82 | 2.713 (4) | 172 |
O7—H7A···O3i | 0.88 | 1.93 | 2.777 (4) | 159 |
O7—H7B···O23vi | 0.81 | 2.56 | 3.067 (5) | 122 |
N1—H1A···O2vii | 0.94 | 1.95 | 2.884 (5) | 171 |
N1—H1B···O8 | 1.00 | 1.91 | 2.902 (6) | 169 |
N1—H1C···O22i | 0.90 | 2.45 | 3.302 (6) | 158 |
N1—H1C···O1i | 0.90 | 2.50 | 3.022 (5) | 117 |
N1—H1D···O1viii | 1.00 | 2.11 | 3.053 (5) | 158 |
O8—H8A···O22 | 0.93 | 1.89 | 2.785 (4) | 161 |
O8—H8B···O23ix | 0.86 | 2.06 | 2.800 (5) | 144 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x+1, y, z; (iii) x, −y+1/2, z+1/2; (v) −x, −y, −z+1; (vi) −x, −y, −z; (vii) x−1, y, z−1; (viii) x, y, z−1; (ix) −x−1, −y, −z. |
Crystal data (Å,°,Å3) for the isotypic members of the
(NH4)[Ln(SO4)2(H2O)3](H2O)
family where Ln is a trivalent lanthanide topAtom Name | Atomic Number | a | b | c | β | V | Reference |
Y | 39 | 6.516 (4) | 18.856 (8) | 8.663 (5) | 96.63 (5) | 1057.2 (1) | a# |
La | 57 | 6.720 (1) | 19.0680 (20) | 8.841 (1) | 97.50 (1) | 1123.17 | b |
Nd | 60 | 6.63 | 18.94 | 8.80 | 96.2 | 1099 | d# |
Sm | 62 | 6.582 (2) | 18.886 (7) | 8.736 (4) | 96.88 (4) | 1078.13 | c |
Tb | 65 | 6.522 (4) | 18.8200 (40) | 8.681 (1) | 96.69 (3) | 1058.29 | b |
Dy | 66 | 6.505 (2) | 18.813 (5) | 8.695 (3) | 97.49 (4) | 1055.0 (1) | a# |
Ho | 67 | 6.499 (2) | 18.774 (7) | 8.667 (3) | 97.28 (5) | 1048.9 (1) | a# |
Er | 68 | 6.495 (4) | 18.766 (8) | 8.641 (5) | 97.57 (5) | 1044.0 (1) | a# |
U | 92 | 6.7065 (2) | 19.0328 (6) | 8.8305 (3) | 97.337 (1) | 1117.93 | e |
Pu | 94 | 6.64 (1) | 18.92 (1) | 8.79 (1) | 96.9 (1) | 1094.4 (1) | a# |
Notes: (#) - from powder data;
(a) Iyer & Natarajan (1990);
(b) Kepert et al. (1999);
(c) Eriksson et al. (1974);
(d) Staritzky & Cromer (1956);
(e) Bullock et al. (1980). |