The title complex, {[CdHg(SCN)4(H2O)]·C4H8O2S}n, comprises slightly distorted CdN4O2 octahedra and HgS4 tetrahedra where the donor atoms are derived from ambidentate thiocyanate ligands and, in the case of cadmium, also from water molecules. Pairs of Cd atoms are bridged by two water molecules, forming a parallelogram, and each water molecule is hydrogen bonded to a sulfolane molecule. Pairs of Cd and Hg atoms are connected by —SCN— bridges, which leads to the formation of a three-dimensional —Cd—NCS—Hg— network.
Supporting information
CCDC reference: 621514
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.017 Å
- R factor = 0.039
- wR factor = 0.080
- Data-to-parameter ratio = 19.1
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for S2
PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for S3
PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for S4
PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for N1
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Hg1
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Cd1
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C1
PLAT243_ALERT_4_C High 'Solvent' Ueq as Compared to Neighbors for C6
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for S5
PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 17
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 4
S1 -C1 -N1 -CD1 13.00 0.00 1.555 1.555 1.555 1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 5
N1 -C1 -S1 -HG1 8.00 0.00 1.555 1.555 1.555 1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 6
N2 -C2 -S2 -HG1 3.00 0.00 1.455 1.555 1.555 1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 7
N3 -C3 -S3 -HG1 -155.00 13.00 4.565 1.555 1.555 1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 8
N4 -C4 -S4 -HG1 16.00 0.00 4.566 1.555 1.555 1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 15
C2 -N2 -CD1 -N1 -113.00 8.00 1.655 1.555 1.555 1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 16
C2 -N2 -CD1 -N4 -19.00 8.00 1.655 1.555 1.555 1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 17
C2 -N2 -CD1 -N3 158.00 8.00 1.655 1.555 1.555 1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 18
C2 -N2 -CD1 -O1 59.00 8.00 1.655 1.555 1.555 1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 19
C2 -N2 -CD1 -O1 80.00 8.00 1.655 1.555 1.555 3.756
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 20
C1 -N1 -CD1 -N2 -83.00 5.00 1.555 1.555 1.555 1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 21
C1 -N1 -CD1 -N4 -177.00 5.00 1.555 1.555 1.555 1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 22
C1 -N1 -CD1 -N3 18.00 5.00 1.555 1.555 1.555 1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 23
C1 -N1 -CD1 -O1 100.00 5.00 1.555 1.555 1.555 1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 24
C1 -N1 -CD1 -O1 26.00 6.00 1.555 1.555 1.555 3.756
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.16 Ratio
Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
26 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
7 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
18 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
Data collection: XSCANS (Bruker, 1996); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: WinGX (Farrugia, 1999).
Poly[[µ-aquatetra-µ-thiocyanato-cadmium(II)mercury(II)] sulfolane solvate]
top
Crystal data top
[CdHg(NCS)4(H2O)]·C4H8O2S | F(000) = 1272 |
Mr = 683.49 | Dx = 2.447 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 36 reflections |
a = 8.7219 (7) Å | θ = 5.8–12.5° |
b = 17.3525 (19) Å | µ = 9.98 mm−1 |
c = 12.2719 (14) Å | T = 293 K |
β = 92.457 (9)° | Block, colourless |
V = 1855.6 (3) Å3 | 0.12 × 0.09 × 0.08 mm |
Z = 4 | |
Data collection top
Bruker P4 diffractometer | 2711 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.026 |
Graphite monochromator | θmax = 26.5°, θmin = 2.0° |
ω scans | h = −1→10 |
Absorption correction: ψ scan (XSCANS; Bruker,1996) | k = −21→1 |
Tmin = 0.296, Tmax = 0.449 | l = −15→15 |
4929 measured reflections | 3 standard reflections every 97 reflections |
3843 independent reflections | intensity decay: none |
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)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.080 | w = 1/[σ2(Fo2) + (0.0311P)2 + 0.2895P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
3843 reflections | Δρmax = 1.46 e Å−3 |
201 parameters | Δρmin = −1.09 e Å−3 |
15 restraints | Extinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00413 (15) |
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 | |
C1 | 0.8246 (10) | 0.2687 (5) | 0.5794 (6) | 0.038 (2) | |
C2 | 0.3488 (10) | 0.1905 (5) | 0.4195 (6) | 0.038 (2) | |
C3 | 0.5277 (10) | 0.4278 (5) | 0.2626 (6) | 0.038 (2) | |
C4 | 0.3626 (9) | 0.3650 (5) | 0.7391 (6) | 0.0334 (19) | |
C5 | 0.5002 (16) | 0.1339 (6) | 0.6885 (8) | 0.087 (4) | |
H5A | 0.5792 | 0.1532 | 0.6424 | 0.104* | |
H5B | 0.4005 | 0.1474 | 0.6558 | 0.104* | |
C6 | 0.520 (2) | 0.1668 (8) | 0.8015 (10) | 0.144 (6) | |
H6A | 0.6222 | 0.1878 | 0.8117 | 0.172* | |
H6B | 0.4471 | 0.2087 | 0.8093 | 0.172* | |
C7 | 0.4950 (17) | 0.1089 (7) | 0.8864 (9) | 0.118 (6) | |
H7A | 0.4006 | 0.1210 | 0.9217 | 0.142* | |
H7B | 0.5783 | 0.1124 | 0.9411 | 0.142* | |
C8 | 0.4859 (15) | 0.0287 (7) | 0.8453 (8) | 0.071 (3) | |
H8A | 0.3859 | 0.0067 | 0.8577 | 0.086* | |
H8B | 0.5638 | −0.0031 | 0.8818 | 0.086* | |
N1 | 0.8819 (10) | 0.2168 (5) | 0.5415 (6) | 0.057 (2) | |
N2 | 1.2398 (9) | 0.1656 (5) | 0.4509 (5) | 0.049 (2) | |
N3 | 1.0571 (10) | 0.0909 (4) | 0.6777 (5) | 0.053 (2) | |
N4 | 0.9207 (8) | 0.1141 (5) | 0.3200 (5) | 0.0461 (19) | |
O1 | 0.8359 (6) | 0.0092 (3) | 0.5101 (4) | 0.0354 (13) | |
H1A | 0.7599 | 0.0110 | 0.4502 | 0.043* | |
H1B | 0.7836 | 0.0132 | 0.5781 | 0.043* | |
O2 | 0.3985 (10) | −0.0045 (5) | 0.6441 (8) | 0.109 (3) | |
O3 | 0.6692 (8) | 0.0090 (5) | 0.6886 (5) | 0.074 (2) | |
S1 | 0.7418 (3) | 0.34510 (15) | 0.63344 (18) | 0.0519 (6) | |
S2 | 0.5085 (3) | 0.22741 (17) | 0.3757 (2) | 0.0646 (8) | |
S3 | 0.4886 (4) | 0.46124 (17) | 0.38470 (19) | 0.0684 (8) | |
S4 | 0.2751 (3) | 0.33371 (17) | 0.62600 (16) | 0.0534 (7) | |
S5 | 0.5164 (3) | 0.03430 (16) | 0.70505 (17) | 0.0459 (6) | |
Cd1 | 1.01620 (7) | 0.11203 (3) | 0.49525 (4) | 0.03190 (16) | |
Hg1 | 0.50522 (4) | 0.34171 (2) | 0.50450 (2) | 0.03929 (13) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.041 (5) | 0.037 (5) | 0.035 (4) | 0.008 (4) | −0.006 (4) | 0.000 (4) |
C2 | 0.044 (5) | 0.036 (5) | 0.035 (4) | −0.007 (4) | −0.001 (4) | −0.006 (4) |
C3 | 0.052 (5) | 0.033 (5) | 0.030 (4) | −0.004 (5) | 0.002 (4) | 0.007 (4) |
C4 | 0.040 (5) | 0.033 (5) | 0.027 (4) | 0.005 (4) | 0.003 (3) | 0.003 (3) |
C5 | 0.130 (12) | 0.052 (8) | 0.076 (8) | −0.002 (8) | −0.018 (8) | 0.028 (6) |
C6 | 0.178 (11) | 0.112 (10) | 0.139 (9) | −0.005 (9) | −0.017 (9) | −0.011 (8) |
C7 | 0.132 (13) | 0.160 (16) | 0.064 (8) | −0.009 (13) | 0.021 (8) | −0.041 (10) |
C8 | 0.087 (9) | 0.081 (9) | 0.049 (6) | 0.015 (7) | 0.034 (6) | 0.014 (6) |
N1 | 0.072 (6) | 0.050 (5) | 0.049 (4) | 0.017 (5) | 0.001 (4) | −0.006 (4) |
N2 | 0.048 (5) | 0.056 (5) | 0.043 (4) | −0.016 (5) | 0.002 (3) | −0.007 (4) |
N3 | 0.083 (6) | 0.045 (5) | 0.030 (4) | 0.011 (5) | 0.006 (4) | 0.002 (3) |
N4 | 0.057 (5) | 0.052 (5) | 0.029 (3) | −0.009 (4) | 0.000 (3) | 0.003 (3) |
O1 | 0.030 (3) | 0.042 (4) | 0.034 (3) | −0.002 (3) | 0.002 (2) | −0.003 (3) |
O2 | 0.075 (6) | 0.120 (8) | 0.127 (8) | −0.005 (6) | −0.043 (5) | −0.044 (6) |
O3 | 0.053 (4) | 0.115 (7) | 0.056 (4) | 0.014 (5) | 0.019 (3) | −0.011 (4) |
S1 | 0.0478 (14) | 0.0545 (16) | 0.0526 (13) | 0.0110 (13) | −0.0089 (11) | −0.0223 (12) |
S2 | 0.0622 (17) | 0.0665 (19) | 0.0676 (15) | −0.0300 (15) | 0.0326 (13) | −0.0354 (14) |
S3 | 0.126 (2) | 0.0458 (14) | 0.0343 (11) | 0.0064 (16) | 0.0121 (13) | 0.0006 (11) |
S4 | 0.0429 (13) | 0.084 (2) | 0.0332 (10) | −0.0130 (14) | 0.0038 (9) | −0.0126 (12) |
S5 | 0.0443 (13) | 0.0559 (15) | 0.0376 (11) | −0.0003 (13) | 0.0023 (10) | −0.0045 (11) |
Cd1 | 0.0392 (3) | 0.0301 (3) | 0.0267 (3) | −0.0017 (3) | 0.0037 (2) | 0.0016 (3) |
Hg1 | 0.0463 (2) | 0.0411 (2) | 0.03063 (17) | −0.0033 (2) | 0.00353 (12) | −0.00160 (17) |
Geometric parameters (Å, º) top
C1—N1 | 1.140 (10) | C8—H8B | 0.9700 |
C1—S1 | 1.660 (9) | Hg1—S1 | 2.547 (2) |
C2—N2i | 1.127 (10) | Hg1—S2 | 2.537 (2) |
C2—S2 | 1.645 (9) | Hg1—S3 | 2.543 (3) |
C3—N3ii | 1.131 (9) | Hg1—S4 | 2.555 (2) |
C3—S3 | 1.655 (8) | Cd1—N1 | 2.248 (8) |
C4—N4iii | 1.153 (9) | N2—C2iv | 1.127 (10) |
C4—S4 | 1.648 (8) | Cd1—O1 | 2.390 (5) |
C5—C6 | 1.502 (9) | Cd1—O1v | 2.470 (5) |
C5—S5 | 1.746 (11) | Cd1—N2 | 2.248 (8) |
C5—H5A | 0.9700 | N3—C3vi | 1.131 (9) |
C5—H5B | 0.9700 | Cd1—N3 | 2.282 (7) |
C6—C7 | 1.469 (9) | N4—C4vii | 1.153 (9) |
C6—H6A | 0.9700 | Cd1—N4 | 2.273 (6) |
C6—H6B | 0.9700 | O1—H1A | 0.9700 |
C7—C8 | 1.481 (9) | O1—H1B | 0.9700 |
C7—H7A | 0.9700 | O2—S5 | 1.416 (8) |
C7—H7B | 0.9700 | O3—S5 | 1.426 (7) |
C8—S5 | 1.755 (9) | O1—Cd1v | 2.470 (5) |
C8—H8A | 0.9700 | | |
| | | |
S1—Hg1—S2 | 112.00 (9) | C6—C5—H5A | 110.7 |
S1—Hg1—S3 | 111.41 (10) | S5—C5—H5A | 110.7 |
S1—Hg1—S4 | 105.94 (8) | C6—C5—H5B | 110.7 |
S2—Hg1—S3 | 106.22 (9) | S5—C5—H5B | 110.7 |
S2—Hg1—S4 | 110.56 (8) | H5A—C5—H5B | 108.8 |
S3—Hg1—S4 | 110.79 (10) | C7—C6—C5 | 112.4 (11) |
O1—Cd1—O1v | 73.28 (19) | C7—C6—H6A | 109.1 |
O1—Cd1—N1 | 103.4 (3) | C5—C6—H6A | 109.1 |
O1—Cd1—N2 | 155.1 (2) | C7—C6—H6B | 109.1 |
O1—Cd1—N3 | 83.1 (2) | C5—C6—H6B | 109.1 |
O1—Cd1—N4 | 82.4 (2) | H6A—C6—H6B | 107.9 |
O1v—Cd1—N1 | 166.8 (2) | C6—C7—C8 | 114.1 (10) |
O1v—Cd1—N2 | 83.5 (2) | C6—C7—H7A | 108.7 |
O1v—Cd1—N3 | 80.2 (2) | C8—C7—H7A | 108.7 |
O1v—Cd1—N4 | 99.1 (2) | C6—C7—H7B | 108.7 |
N1—Cd1—N2 | 101.2 (3) | C8—C7—H7B | 108.7 |
N1—Cd1—N3 | 86.8 (3) | H7A—C7—H7B | 107.6 |
N1—Cd1—N4 | 93.0 (3) | C7—C8—S5 | 105.9 (8) |
N2—Cd1—N3 | 101.7 (3) | C7—C8—H8A | 110.6 |
N2—Cd1—N4 | 92.9 (2) | S5—C8—H8A | 110.6 |
N3—Cd1—N4 | 165.1 (3) | C7—C8—H8B | 110.6 |
Hg1—S1—C1 | 95.1 (3) | S5—C8—H8B | 110.6 |
Hg1—S2—C2 | 93.9 (3) | H8A—C8—H8B | 108.7 |
Hg1—S3—C3 | 103.2 (3) | Cd1—O1—H1A | 110.4 |
Hg1—S4—C4 | 97.3 (3) | Cd1v—O1—H1A | 110.4 |
Cd1—N1—C1 | 170.0 (7) | Cd1—O1—H1B | 110.4 |
Cd1—N2—C2iv | 173.9 (7) | Cd1v—O1—H1B | 110.4 |
Cd1—N3—C3vi | 156.6 (8) | H1A—O1—H1B | 108.6 |
Cd1—N4—C4vii | 161.7 (7) | O2—S5—O3 | 116.2 (5) |
Cd1—O1—Cd1v | 106.72 (19) | O2—S5—C5 | 110.8 (6) |
S1—C1—N1 | 179.3 (9) | O3—S5—C5 | 111.1 (6) |
S2—C2—N2i | 179.0 (8) | O2—S5—C8 | 110.8 (7) |
S3—C3—N3ii | 176.0 (8) | O3—S5—C8 | 107.7 (5) |
S4—C4—N4iii | 178.0 (8) | C5—S5—C8 | 98.8 (5) |
C6—C5—S5 | 105.3 (8) | | |
| | | |
S5—C5—C6—C7 | −18.4 (19) | C4vii—N4—Cd1—N3 | 106 (2) |
C5—C6—C7—C8 | 11 (2) | C4vii—N4—Cd1—O1 | 121 (2) |
C6—C7—C8—S5 | 2.2 (17) | C4vii—N4—Cd1—O1v | −168 (2) |
S1—C1—N1—Cd1 | 127 (79) | C3vi—N3—Cd1—N2 | 177.5 (18) |
N1—C1—S1—Hg1 | 78 (81) | C3vi—N3—Cd1—N1 | 76.7 (18) |
N2i—C2—S2—Hg1 | −29 (59) | C3vi—N3—Cd1—N4 | −13 (3) |
N3ii—C3—S3—Hg1 | −155 (13) | C3vi—N3—Cd1—O1 | −27.2 (18) |
N4iii—C4—S4—Hg1 | −157 (24) | C3vi—N3—Cd1—O1v | −101.4 (18) |
C6—C5—S5—O2 | 133.9 (11) | Cd1v—O1—Cd1—N2 | 21.4 (6) |
C6—C5—S5—O3 | −95.4 (11) | Cd1v—O1—Cd1—N1 | −166.8 (2) |
C6—C5—S5—C8 | 17.6 (12) | Cd1v—O1—Cd1—N4 | 102.0 (3) |
C7—C8—S5—O2 | −128.2 (10) | Cd1v—O1—Cd1—N3 | −81.8 (3) |
C7—C8—S5—O3 | 103.7 (10) | Cd1v—O1—Cd1—O1v | 0.0 |
C7—C8—S5—C5 | −11.9 (11) | C2—S2—Hg1—S3 | −118.7 (3) |
C2iv—N2—Cd1—N1 | −113 (8) | C2—S2—Hg1—S1 | 119.5 (3) |
C2iv—N2—Cd1—N4 | −19 (8) | C2—S2—Hg1—S4 | 1.6 (3) |
C2iv—N2—Cd1—N3 | 158 (8) | C3—S3—Hg1—S2 | −13.3 (4) |
C2iv—N2—Cd1—O1 | 59 (8) | C3—S3—Hg1—S1 | 108.9 (3) |
C2iv—N2—Cd1—O1v | 80 (8) | C3—S3—Hg1—S4 | −133.4 (3) |
C1—N1—Cd1—N2 | −83 (5) | C1—S1—Hg1—S2 | 3.1 (3) |
C1—N1—Cd1—N4 | −177 (5) | C1—S1—Hg1—S3 | −115.7 (3) |
C1—N1—Cd1—N3 | 18 (5) | C1—S1—Hg1—S4 | 123.7 (3) |
C1—N1—Cd1—O1 | 100 (5) | C4—S4—Hg1—S2 | 140.9 (3) |
C1—N1—Cd1—O1v | 26 (6) | C4—S4—Hg1—S3 | −101.6 (3) |
C4vii—N4—Cd1—N2 | −84 (2) | C4—S4—Hg1—S1 | 19.4 (3) |
C4vii—N4—Cd1—N1 | 17 (2) | | |
Symmetry codes: (i) x−1, y, z; (ii) x−1/2, −y+1/2, z−1/2; (iii) x−1/2, −y+1/2, z+1/2; (iv) x+1, y, z; (v) −x+2, −y, −z+1; (vi) x+1/2, −y+1/2, z+1/2; (vii) x+1/2, −y+1/2, z−1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O2viii | 0.97 | 1.77 | 2.727 (9) | 170 |
O1—H1B···O3 | 0.97 | 1.72 | 2.680 (8) | 170 |
Symmetry code: (viii) −x+1, −y, −z+1. |