research papers
The experimental charge-density distribution in [Gd(H2O)9](CF3SO3)3 has been analysed and compared with the theoretical density functional theory calculations. Although the Gd—OH2 bonds are mainly ionic, a covalent contribution is detectable when inspecting both the topological parameters of these bonds and the natural bond orbital results. This contribution originates from small electron transfer from the lone pairs of oxygen atoms to empty 5d and 6s spin orbitals of Gd3+.
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520620006903/px5020sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2052520620006903/px5020Isup2.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S2052520620006903/px5020sup3.pdf |
CCDC reference: 2005173
Computing details top
Data collection: CrysAlis PRO 1.171.38.46 (Rigaku OD, 2015); cell refinement: CrysAlis PRO 1.171.38.46 (Rigaku OD, 2015); data reduction: CrysAlis PRO 1.171.38.46 (Rigaku OD, 2015); program(s) used to refine structure: Volkov et al., (2006); molecular graphics: Volkov et al., (2006); software used to prepare material for publication: Volkov et al., (2006).
(I) top
Crystal data top
C3H18F9GdO18S3 | Mo Kα radiation, λ = 0.71073 Å |
Mr = 766.60 | Cell parameters from 61419 reflections |
Hexagonal, P63/m | θ = 2.8–69.8° |
a = 13.7828 (9) Å | µ = 3.14 mm−1 |
c = 7.3148 (5) Å | T = 80 K |
V = 1203.39 (14) Å3 | Irregular, colourless |
Z = 2 | 0.42 × 0.36 × 0.29 mm |
F(000) = 746 |
Data collection top
Xcalibur, Ruby diffractometer | 86103 measured reflections |
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source | 8039 independent reflections |
Graphite monochromator | Rint = 0.021 |
Detector resolution: 10.3456 pixels mm-1 | θmax = 69.8°, θmin = 1.7° |
ω scans | h = −35→29 |
Absorption correction: analytical CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. | k = −36→36 |
Tmin = 0.401, Tmax = 0.542 | l = −14→19 |
Refinement top
Refinement on F2 | 1 restraint |
Least-squares matrix: full | w2 = q/[s2(Fo2) + (0.00 P)2 + 0.20 P + 0.00 + 0.00 sin(th)]
where P = (0.3333 Fo2 + 0.6667 Fc2) q = 1.0 |
R[F2 > 2σ(F2)] = 0.009 | (Δ/σ)max = 0.0004 |
wR(F2) = 0.023 | Δρmax = 0.68 e Å−3 |
S = 1.84 | Δρmin = −0.73 e Å−3 |
5325 reflections | Extinction correction: Becker-Coppens type 1 Lorentzian isotropic, Becker, P.J. & Coppens, P. (1974) Acta Cryst., A30, 129-153. |
203 parameters | Extinction coefficient: 0.441 (4) |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
x | y | z | Uiso*/Ueq | ||
Gd | 0.333333 | 0.666667 | 0.25 | 0.006 | |
S | 0.320081 (3) | 0.379073 (3) | 0.75 | 0.009 | |
F(1) | 0.15829 (3) | 0.19800 (3) | 0.60177 (7) | 0.029 | |
F(2) | 0.28008 (4) | 0.17355 (3) | 0.75 | 0.023 | |
O(W1) | 0.209383 (7) | 0.546060 (8) | 0.485602 (12) | 0.012 | |
O(W2) | 0.143743 (11) | 0.652439 (13) | 0.25 | 0.013 | |
O(3) | 0.383736 (9) | 0.398876 (10) | 0.917112 (13) | 0.014 | |
O(4) | 0.247480 (12) | 0.427253 (12) | 0.75 | 0.013 | |
C | 0.222479 (15) | 0.227605 (14) | 0.75 | 0.016 | |
H(11) | 0.128583 | 0.498817 | 0.457902 | 0.0360 (19)* | |
H(12) | 0.232552 | 0.509706 | 0.579031 | 0.0184 (13)* | |
H(21) | 0.095802 | 0.648151 | 0.354029 | 0.0302 (14)* |
Atomic displacement parameters (Å2) top
U11 | U22 | U33 | U12 | U13 | U23 | |
Gd | 0.006605 (5) | 0.006605 (5) | 0.005956 (6) | 0.003308 (3) | 0 | 0 |
S | 0.011386 (11) | 0.011301 (11) | 0.007684 (10) | 0.007767 (9) | 0 | 0 |
F(1) | 0.02660 (10) | 0.02233 (9) | 0.03731 (13) | 0.01106 (8) | −0.01592 (10) | −0.01108 (9) |
F(2) | 0.02681 (12) | 0.01614 (9) | 0.03071 (13) | 0.01482 (9) | 0 | 0 |
O(W1) | 0.00974 (2) | 0.01254 (2) | 0.01141 (2) | 0.004927 (19) | 0.000690 (18) | 0.003402 (19) |
O(W2) | 0.01188 (3) | 0.01802 (4) | 0.01023 (3) | 0.00941 (3) | 0 | 0 |
O(3) | 0.01731 (3) | 0.02011 (3) | 0.01077 (2) | 0.01298 (3) | −0.00410 (2) | −0.00320 (2) |
O(4) | 0.01688 (4) | 0.01728 (4) | 0.01149 (3) | 0.01342 (4) | 0 | 0 |
C | 0.01587 (5) | 0.01293 (4) | 0.02025 (6) | 0.00762 (4) | 0 | 0 |
Geometric parameters (Å, º) top
GD—O(W1) | 2.4108 (3) | F(1)—F(1)i | 2.9103 (14) |
GD—O(W2) | 2.5208 (4) | F(1)—F(2)i | 3.0359 (16) |
S—O(3) | 1.4488 (3) | F(1)—C | 1.3281 (11) |
S—O(4) | 1.4515 (4) | F(2)—C | 1.3331 (12) |
S—C | 1.8329 (6) | ||
O(W1)—GD—O(W1)ii | 74.542 (11) | O(3)—S—C | 104.183 (19) |
O(W1)—GD—O(W1)iii | 91.263 (15) | O(4)—S—C | 103.88 (3) |
O(W1)—GD—O(W1)iv | 139.070 (6) | S—C—F(1) | 110.29 (7) |
O(W1)—GD—O(W2) | 66.217 (10) | S—C—F(2) | 109.49 (7) |
O(W1)—GD—O(W2)ii | 72.957 (11) | H(11)—O(W1)—H(12) | 110.48 (3) |
O(W1)—GD—O(W2)v | 134.137 (8) | H(21)—O(W2)—H(21)iii | 100.46 (4) |
O(W2)—GD—O(W2)ii | 120.0 | F(1)—C—F(1)vi | 109.45 (17) |
O(3)—S—O(3)vi | 115.07 (3) | F(1)—C—F(2) | 108.64 (7) |
O(3)—S—O(4) | 113.883 (16) |
Symmetry codes: (i) x−y, x, −z+1; (ii) −y+1, x−y+1, z; (iii) x, y, −z+1/2; (iv) −y+1, x−y+1, −z+1/2; (v) −x+y, −x+1, z; (vi) x, y, −z+3/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O(W1)—H(11)···O(3)vii | 0.99 | 1.84 | 2.8123 (4) | 166 |
O(W1)—H(12)···O(4) | 0.99 | 1.77 | 2.7491 (4) | 170 |
O(W2)—H(21)···O(3)viii | 0.99 | 1.93 | 2.9045 (4) | 166 |
Symmetry codes: (vii) x−y, x, z−1/2; (viii) −x+y, −x+1, −z+3/2. |