Buy article online - an online subscription or single-article purchase is required to access this article.
The title compound, diammonium tricadmium tetrakis(sulfate) pentahydrate, (NH4)2Cd3(SO4)4·5H2O, was formed during an attempted synthesis of the langbeinite, (NH4)2Cd2(SO4)3. The structure has two layers, one containing Cd octahedra bridged by sulfate groups and the other containing edge-shared Cd octahedra, with NH4 units occupying interstitial positions. The layers are connected by way of Cd-O-S links.
Supporting information
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (S-O) = 0.004 Å
- R factor = 0.038
- wR factor = 0.102
- Data-to-parameter ratio = 13.3
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT417_ALERT_2_B Short Inter D-H..H-D H5 .. H21A .. 2.09 Ang.
PLAT420_ALERT_2_B D-H Without Acceptor O21W - H21A ... ?
Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ?
PLAT220_ALERT_2_C Large Non-Solvent O Ueq(max)/Ueq(min) ... 2.60 Ratio
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for S3
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for S4
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: H18 Cd3 N2 O21 S4
Atom count from _chemical_formula_moiety:H18 Cd3 O21 S4
0 ALERT level A = In general: serious problem
2 ALERT level B = Potentially serious problem
5 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
3 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
0 ALERT type 5 Informative message, check
Data collection: SMART (Bruker, 2004); cell refinement: SMART; data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: PLATON (Spek, 2003).
Crystal data top
(NH4)2Cd3(SO4)4·5H2O | F(000) = 1632 |
Mr = 847.67 | Dx = 2.943 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 856 reflections |
a = 19.678 (9) Å | θ = 0.9–27.9° |
b = 9.872 (5) Å | µ = 3.85 mm−1 |
c = 10.073 (5) Å | T = 294 K |
β = 102.097 (7)° | Block, colorless |
V = 1913.4 (15) Å3 | 0.30 × 0.20 × 0.15 mm |
Z = 4 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 4575 independent reflections |
Radiation source: fine-focus sealed tube | 4148 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.056 |
φ and ω scans | θmax = 28.6°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −25→26 |
Tmin = 0.413, Tmax = 0.562 | k = −13→12 |
20498 measured reflections | l = −13→13 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0542P)2 + 4.2876P] where P = (Fo2 + 2Fc2)/3 |
4575 reflections | (Δ/σ)max = 0.001 |
343 parameters | Δρmax = 1.90 e Å−3 |
0 restraints | Δρmin = −1.57 e Å−3 |
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 | |
Cd1 | 0.343148 (18) | 0.36158 (3) | 0.44652 (3) | 0.01984 (10) | |
Cd2 | 0.324128 (18) | 0.65359 (3) | 0.17267 (3) | 0.01958 (10) | |
Cd3 | 0.059836 (18) | 0.71717 (3) | 0.44325 (3) | 0.02135 (11) | |
S1 | 0.25118 (6) | 0.16060 (10) | 0.61290 (11) | 0.0182 (2) | |
S2 | 0.23205 (6) | 0.64398 (10) | 0.43212 (11) | 0.0147 (2) | |
S3 | 0.43574 (6) | 0.91780 (12) | 0.18731 (11) | 0.0204 (2) | |
S4 | 0.06202 (6) | 0.97405 (11) | 0.21515 (11) | 0.0193 (2) | |
O1 | 0.24434 (18) | 0.0117 (3) | 0.6138 (4) | 0.0274 (8) | |
O2 | 0.3079 (2) | 0.2057 (4) | 0.7243 (4) | 0.0311 (8) | |
O3 | 0.1850 (2) | 0.2220 (4) | 0.6230 (4) | 0.0364 (9) | |
O4 | 0.2693 (2) | 0.2016 (3) | 0.4838 (3) | 0.0280 (8) | |
O5 | 0.25061 (19) | 0.4994 (3) | 0.4482 (4) | 0.0293 (8) | |
O6 | 0.24031 (19) | 0.7071 (4) | 0.5666 (3) | 0.0250 (7) | |
O7 | 0.15821 (18) | 0.6534 (4) | 0.3618 (4) | 0.0264 (8) | |
O8 | 0.27675 (19) | 0.7151 (3) | 0.3548 (4) | 0.0250 (7) | |
O9 | 0.3921 (2) | 0.8329 (4) | 0.2571 (4) | 0.0342 (9) | |
O10 | 0.50218 (19) | 0.9437 (5) | 0.2806 (4) | 0.0385 (10) | |
O11 | 0.4471 (2) | 0.8465 (4) | 0.0644 (4) | 0.0329 (9) | |
O12 | 0.3994 (2) | 1.0471 (4) | 0.1485 (4) | 0.0395 (10) | |
O13 | 0.0358 (2) | 0.8408 (4) | 0.2473 (4) | 0.0325 (9) | |
O14 | 0.0046 (2) | 1.0714 (5) | 0.2073 (4) | 0.0462 (11) | |
O15 | 0.0837 (2) | 0.9635 (4) | 0.0848 (4) | 0.0355 (9) | |
O16 | 0.1200 (2) | 1.0171 (5) | 0.3224 (4) | 0.0403 (10) | |
O17W | 0.4288 (2) | 0.2086 (4) | 0.4279 (6) | 0.0555 (14) | |
O18W | 0.39831 (17) | 0.5272 (3) | 0.3376 (3) | 0.0212 (7) | |
O19W | 0.3813 (2) | 0.5676 (4) | 0.0171 (4) | 0.0335 (9) | |
O20W | 0.11189 (19) | 0.8854 (4) | 0.5834 (4) | 0.0294 (8) | |
O21W | −0.0348 (2) | 0.8281 (5) | 0.5001 (5) | 0.0432 (10) | |
N1 | 0.2530 (3) | 1.0073 (4) | 0.2698 (5) | 0.0305 (9) | |
N2 | 0.1210 (3) | 0.1580 (5) | 0.8520 (6) | 0.0372 (11) | |
H1 | 0.2183 | 1.0123 | 0.3090 | 0.046* | |
H2 | 0.2580 | 1.0787 | 0.2239 | 0.046* | |
H3 | 0.2584 | 0.9242 | 0.2485 | 0.046* | |
H4 | 0.2797 | 1.0216 | 0.3477 | 0.046* | |
H5 | 0.0918 | 0.1369 | 0.7788 | 0.056* | |
H6 | 0.1412 | 0.1935 | 0.7924 | 0.056* | |
H7 | 0.1479 | 0.0889 | 0.8556 | 0.056* | |
H8 | 0.1363 | 0.2059 | 0.9233 | 0.056* | |
H17A | 0.4689 | 0.2323 | 0.4591 | 0.084* | |
H17B | 0.4379 | 0.2188 | 0.5106 | 0.084* | |
H18A | 0.4222 | 0.5779 | 0.3929 | 0.032* | |
H18B | 0.4300 | 0.4983 | 0.3042 | 0.032* | |
H19A | 0.3951 | 0.6171 | −0.0370 | 0.053* | |
H19B | 0.4119 | 0.5124 | 0.0461 | 0.053* | |
H20A | 0.1490 | 0.9025 | 0.5623 | 0.045* | |
H20B | 0.1332 | 0.8553 | 0.6563 | 0.045* | |
H21A | −0.0447 | 0.8687 | 0.4276 | 0.067* | |
H21B | −0.0425 | 0.8495 | 0.5742 | 0.067* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cd1 | 0.02286 (19) | 0.01547 (17) | 0.02107 (19) | −0.00013 (12) | 0.00431 (13) | −0.00026 (11) |
Cd2 | 0.02221 (19) | 0.01520 (17) | 0.02083 (19) | 0.00141 (12) | 0.00335 (13) | −0.00083 (11) |
Cd3 | 0.02472 (19) | 0.01753 (18) | 0.02210 (18) | 0.00201 (12) | 0.00558 (13) | −0.00011 (12) |
S1 | 0.0241 (6) | 0.0131 (5) | 0.0183 (5) | 0.0013 (4) | 0.0063 (4) | 0.0022 (4) |
S2 | 0.0163 (5) | 0.0121 (5) | 0.0158 (5) | 0.0003 (4) | 0.0034 (4) | 0.0001 (4) |
S3 | 0.0185 (5) | 0.0225 (5) | 0.0197 (5) | −0.0023 (4) | 0.0032 (4) | 0.0034 (4) |
S4 | 0.0253 (6) | 0.0136 (5) | 0.0198 (5) | 0.0019 (4) | 0.0064 (4) | 0.0007 (4) |
O1 | 0.0248 (18) | 0.0139 (15) | 0.042 (2) | −0.0021 (13) | 0.0029 (15) | 0.0090 (14) |
O2 | 0.041 (2) | 0.0295 (19) | 0.0196 (17) | −0.0076 (16) | −0.0011 (15) | 0.0011 (14) |
O3 | 0.033 (2) | 0.035 (2) | 0.043 (2) | 0.0115 (17) | 0.0127 (18) | 0.0025 (17) |
O4 | 0.047 (2) | 0.0217 (17) | 0.0177 (16) | −0.0090 (16) | 0.0132 (15) | 0.0002 (13) |
O5 | 0.0310 (19) | 0.0150 (16) | 0.043 (2) | 0.0048 (14) | 0.0111 (16) | 0.0017 (15) |
O6 | 0.0312 (18) | 0.0261 (17) | 0.0185 (16) | −0.0079 (14) | 0.0070 (14) | −0.0037 (13) |
O7 | 0.0204 (17) | 0.035 (2) | 0.0230 (18) | 0.0066 (14) | 0.0023 (14) | −0.0016 (14) |
O8 | 0.0320 (19) | 0.0208 (17) | 0.0259 (17) | −0.0016 (14) | 0.0145 (15) | 0.0012 (13) |
O9 | 0.039 (2) | 0.034 (2) | 0.033 (2) | −0.0187 (17) | 0.0165 (17) | −0.0044 (16) |
O10 | 0.0227 (19) | 0.062 (3) | 0.028 (2) | −0.0122 (18) | −0.0009 (15) | 0.0076 (19) |
O11 | 0.039 (2) | 0.036 (2) | 0.026 (2) | 0.0109 (16) | 0.0095 (16) | 0.0039 (15) |
O12 | 0.061 (3) | 0.028 (2) | 0.0253 (19) | 0.0162 (19) | −0.0003 (18) | 0.0038 (16) |
O13 | 0.043 (2) | 0.0214 (18) | 0.030 (2) | −0.0059 (15) | 0.0004 (17) | 0.0088 (14) |
O14 | 0.059 (3) | 0.042 (2) | 0.039 (2) | 0.034 (2) | 0.012 (2) | 0.0089 (19) |
O15 | 0.050 (2) | 0.031 (2) | 0.033 (2) | −0.0101 (17) | 0.0243 (18) | −0.0102 (16) |
O16 | 0.039 (2) | 0.048 (2) | 0.032 (2) | −0.0153 (19) | 0.0023 (17) | −0.0100 (18) |
O17W | 0.031 (2) | 0.029 (2) | 0.108 (4) | 0.0081 (18) | 0.019 (3) | 0.005 (2) |
O18W | 0.0209 (16) | 0.0197 (16) | 0.0231 (16) | 0.0024 (13) | 0.0044 (13) | 0.0006 (13) |
O19W | 0.048 (2) | 0.0278 (19) | 0.0301 (19) | 0.0090 (17) | 0.0191 (17) | 0.0038 (15) |
O20W | 0.0298 (19) | 0.0319 (19) | 0.0275 (19) | −0.0070 (16) | 0.0080 (15) | −0.0030 (15) |
O21W | 0.036 (2) | 0.048 (3) | 0.050 (3) | 0.0092 (19) | 0.020 (2) | −0.002 (2) |
N1 | 0.039 (3) | 0.022 (2) | 0.030 (2) | 0.0029 (19) | 0.0073 (19) | −0.0032 (17) |
N2 | 0.031 (3) | 0.032 (2) | 0.049 (3) | 0.0028 (19) | 0.009 (2) | 0.002 (2) |
Geometric parameters (Å, º) top
Cd1—O4 | 2.231 (4) | S1—O2 | 1.476 (4) |
Cd1—O5 | 2.276 (4) | S1—O1 | 1.476 (3) |
Cd1—O12i | 2.288 (4) | S2—O6 | 1.469 (3) |
Cd1—O2ii | 2.298 (4) | S2—O8 | 1.470 (3) |
Cd1—O17W | 2.300 (4) | S2—O5 | 1.474 (3) |
Cd1—O18W | 2.357 (3) | S2—O7 | 1.480 (4) |
Cd2—O6iii | 2.240 (3) | S3—O10 | 1.464 (4) |
Cd2—O1ii | 2.256 (3) | S3—O12 | 1.475 (4) |
Cd2—O9 | 2.273 (4) | S3—O9 | 1.480 (4) |
Cd2—O19W | 2.276 (4) | S3—O11 | 1.481 (4) |
Cd2—O8 | 2.307 (3) | S4—O16 | 1.460 (4) |
Cd2—O18W | 2.331 (3) | S4—O15 | 1.467 (4) |
Cd3—O15i | 2.270 (4) | S4—O14 | 1.473 (4) |
Cd3—O14iv | 2.274 (4) | S4—O13 | 1.474 (4) |
Cd3—O20W | 2.279 (4) | O1—Cd2v | 2.256 (3) |
Cd3—O13 | 2.284 (4) | O2—Cd1v | 2.298 (4) |
Cd3—O21W | 2.333 (4) | O6—Cd2i | 2.240 (3) |
Cd3—O7 | 2.342 (4) | O12—Cd1iii | 2.288 (4) |
S1—O3 | 1.460 (4) | O14—Cd3vi | 2.274 (4) |
S1—O4 | 1.476 (3) | O15—Cd3iii | 2.270 (4) |
| | | |
O4—Cd1—O5 | 82.61 (14) | O14iv—Cd3—O7 | 89.01 (16) |
O4—Cd1—O12i | 109.92 (14) | O20W—Cd3—O7 | 96.66 (13) |
O5—Cd1—O12i | 89.82 (16) | O13—Cd3—O7 | 82.96 (14) |
O4—Cd1—O2ii | 83.40 (14) | O21W—Cd3—O7 | 166.74 (15) |
O5—Cd1—O2ii | 95.83 (14) | O3—S1—O4 | 109.3 (2) |
O12i—Cd1—O2ii | 166.15 (15) | O3—S1—O2 | 111.4 (2) |
O4—Cd1—O17W | 93.64 (16) | O4—S1—O2 | 107.7 (2) |
O5—Cd1—O17W | 173.90 (17) | O3—S1—O1 | 109.2 (2) |
O12i—Cd1—O17W | 96.00 (19) | O4—S1—O1 | 108.5 (2) |
O2ii—Cd1—O17W | 78.91 (18) | O2—S1—O1 | 110.5 (2) |
O4—Cd1—O18W | 161.69 (13) | O6—S2—O8 | 108.9 (2) |
O5—Cd1—O18W | 92.06 (12) | O6—S2—O5 | 109.4 (2) |
O12i—Cd1—O18W | 87.48 (13) | O8—S2—O5 | 111.0 (2) |
O2ii—Cd1—O18W | 79.71 (13) | O6—S2—O7 | 108.8 (2) |
O17W—Cd1—O18W | 90.05 (15) | O8—S2—O7 | 110.7 (2) |
O6iii—Cd2—O1ii | 85.21 (14) | O5—S2—O7 | 108.0 (2) |
O6iii—Cd2—O9 | 90.96 (15) | O10—S3—O12 | 109.7 (3) |
O1ii—Cd2—O9 | 169.73 (14) | O10—S3—O9 | 108.9 (2) |
O6iii—Cd2—O19W | 108.76 (13) | O12—S3—O9 | 108.6 (3) |
O1ii—Cd2—O19W | 88.04 (14) | O10—S3—O11 | 110.4 (2) |
O9—Cd2—O19W | 102.22 (15) | O12—S3—O11 | 109.8 (2) |
O6iii—Cd2—O8 | 80.66 (13) | O9—S3—O11 | 109.4 (2) |
O1ii—Cd2—O8 | 91.41 (13) | O16—S4—O15 | 110.8 (3) |
O9—Cd2—O8 | 78.55 (13) | O16—S4—O14 | 108.7 (3) |
O19W—Cd2—O8 | 170.48 (13) | O15—S4—O14 | 111.2 (3) |
O6iii—Cd2—O18W | 163.24 (12) | O16—S4—O13 | 110.6 (2) |
O1ii—Cd2—O18W | 95.60 (13) | O15—S4—O13 | 108.3 (2) |
O9—Cd2—O18W | 85.34 (14) | O14—S4—O13 | 107.2 (3) |
O19W—Cd2—O18W | 88.00 (13) | S1—O1—Cd2v | 131.5 (2) |
O8—Cd2—O18W | 82.59 (13) | S1—O2—Cd1v | 132.8 (2) |
O15i—Cd3—O14iv | 86.25 (17) | S1—O4—Cd1 | 129.0 (2) |
O15i—Cd3—O20W | 100.16 (15) | S2—O5—Cd1 | 139.3 (2) |
O14iv—Cd3—O20W | 171.68 (17) | S2—O6—Cd2i | 128.9 (2) |
O15i—Cd3—O13 | 160.14 (14) | S2—O7—Cd3 | 130.5 (2) |
O14iv—Cd3—O13 | 77.07 (15) | S2—O8—Cd2 | 133.0 (2) |
O20W—Cd3—O13 | 97.52 (14) | S3—O9—Cd2 | 128.2 (2) |
O15i—Cd3—O21W | 106.58 (15) | S3—O12—Cd1iii | 134.0 (2) |
O14iv—Cd3—O21W | 95.64 (18) | S4—O13—Cd3 | 130.4 (2) |
O20W—Cd3—O21W | 77.53 (16) | S4—O14—Cd3vi | 139.8 (3) |
O13—Cd3—O21W | 85.98 (17) | S4—O15—Cd3iii | 123.9 (2) |
O15i—Cd3—O7 | 86.08 (13) | Cd2—O18W—Cd1 | 114.99 (14) |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x, −y+1/2, z−1/2; (iii) x, −y+3/2, z−1/2; (iv) −x, y−1/2, −z+1/2; (v) x, −y+1/2, z+1/2; (vi) −x, y+1/2, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O16 | 0.8600 | 1.9700 | 2.779 (7) | 157.00 |
N1—H2···O2iii | 0.8600 | 2.3400 | 3.100 (6) | 147.00 |
N1—H2···O3iii | 0.8600 | 2.5200 | 3.208 (6) | 138.00 |
N1—H3···O8 | 0.8600 | 2.3200 | 3.017 (5) | 139.00 |
N1—H3···O6iii | 0.8600 | 2.2100 | 2.918 (6) | 139.00 |
N1—H4···O4vii | 0.8600 | 2.2800 | 2.852 (6) | 124.00 |
N1—H4···O19Wi | 0.8600 | 2.5000 | 3.239 (7) | 144.00 |
N2—H5···O13viii | 0.8600 | 2.4800 | 3.038 (7) | 123.00 |
N2—H6···O3 | 0.8600 | 2.0900 | 2.919 (7) | 163.00 |
N2—H7···O5v | 0.8600 | 2.2200 | 2.971 (7) | 146.00 |
N2—H7···O7v | 0.8600 | 2.4000 | 3.157 (7) | 147.00 |
N2—H8···O21Wix | 0.8600 | 2.5900 | 2.997 (7) | 110.00 |
N2—H8···O3v | 0.8600 | 2.1600 | 3.001 (7) | 166.00 |
O17W—H17A···O11x | 0.8200 | 2.0500 | 2.783 (6) | 148.00 |
O18W—H18A···O11i | 0.8200 | 1.8500 | 2.603 (5) | 152.00 |
O18W—H18B···O10x | 0.8200 | 1.8100 | 2.628 (5) | 176.00 |
O19W—H19A···O9iii | 0.8200 | 2.1200 | 2.847 (6) | 148.00 |
O19W—H19B···O10x | 0.8200 | 2.2600 | 2.991 (6) | 148.00 |
O19W—H19B···O17Wii | 0.8200 | 2.5400 | 3.076 (6) | 124.00 |
O20W—H20A···O1vii | 0.8200 | 2.1300 | 2.847 (5) | 146.00 |
O20W—H20B···O7i | 0.8200 | 2.0300 | 2.787 (6) | 154.00 |
O21W—H21B···O16xi | 0.8200 | 2.4100 | 3.098 (6) | 142.00 |
O21W—H21B···O14xi | 0.8200 | 2.3100 | 3.048 (7) | 151.00 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x, −y+1/2, z−1/2; (iii) x, −y+3/2, z−1/2; (v) x, −y+1/2, z+1/2; (vii) x, y+1, z; (viii) −x, −y+1, −z+1; (ix) −x, y−1/2, −z+3/2; (x) −x+1, y−1/2, −z+1/2; (xi) −x, −y+2, −z+1. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.