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Quantum crystallographic refinement of heavy-element-containing compounds is a challenge, because many physical effects have to be accounted for adequately. Here, the impact and magnitude of relativistic effects are compared with those of electron correlation, polarization through the environment, choice of basis set and treatment of thermal motion effects on the structure factors of diphenylmercury(II) [Hg(Ph)2] and dicyanomercury(II) [Hg(CN)2]. Furthermore, the individual atomic contributions to the structure factors are explored in detail (using Mulliken population analysis and the exponential decay of atomic displacement parameters) to compare the contributions of lighter atoms, especially hydrogen atoms, against mercury. Subsequently, relativistic Hirshfeld atom refinement (HAR) is validated against theoretical structure factors of Hg(Ph)2 and Hg(CN)2, starting from perturbed geometries, to test if the relativistic variant of HAR leads to multiple solutions. Generally, relativistic HAR is successful, leading to a perfect match with the reference geometries, but some limitations are pointed out.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053273319008027/ib5077sup1.cif
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053273319008027/ib5077Isup2.hkl
Contains datablock I

CCDC reference: 1920799

Computing details top

(I) top
Crystal data top
C12H10HgV = 479.32 (1) Å3
Mr = 354.80Z = 2.0
Monoclinic, p121/n1Dx = 2.458 Mg m3
Hall symbol: -p 2ynCell parameters from 1098 reflections
a = 5.622200 (1) Åθ = 0.01–1.1°
b = 8.091200 (1) ŵ = 0.0 mm1
c = 10.585200 (1) ÅT = 298 K
β = 95.485000 (1)°This is a theoertical study, not applicable
Data collection top
This is a theoertical study
diffractometer
Rint = 0.1
1098 measured reflectionsh =
1098 independent reflectionsk =
1098 reflections with F > 0 & |F_calc| > 103l =
Refinement top
Least-squares matrix: full3 constraints
R[F2 > 2σ(F2)] = 0.0000Hydrogen site location: HAR
wR(F2) = 0.0000All H-atom parameters refined
S = 0.001Weighting scheme based on measured s.u.'s w = 1/σ(F)
1098 reflections(Δ/σ)max = 0.004
105 parametersΔρmax = 0.001 e Å3
0 restraintsΔρmin = 0.001 e Å3
Special details top

Refinement. . If constraints were applied they are defined by zero eigenvalues of the least-squares hessian, see the value of _refine_ls_SVD_threshold

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Hg0.500000 (1)0.500000 (1)0.500000 (1)0.018600 (1)
C10.771100 (1)0.620800 (1)0.414600 (1)0.019599 (1)
C20.916700 (1)0.739700 (1)0.477900 (1)0.019233 (1)
C31.104700 (1)0.812600 (1)0.423300 (1)0.019133 (1)
C41.153200 (1)0.768400 (1)0.300300 (1)0.018666 (1)
C51.009200 (1)0.651600 (1)0.235500 (1)0.020466 (1)
C60.820600 (1)0.577900 (1)0.291700 (1)0.021200 (1)
H10.885901 (3)0.771901 (2)0.561099 (1)0.022999 (9)
H21.201200 (2)0.892800 (2)0.469300 (1)0.022998 (10)
H31.282297 (2)0.817500 (2)0.262300 (1)0.021997 (10)
H41.038799 (2)0.621101 (2)0.151801 (1)0.023998 (10)
H50.724601 (3)0.497401 (2)0.245700 (2)0.025999 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Hg0.016917 (1)0.017900 (1)0.022300 (1)0.000629 (1)0.008701 (1)0.004500 (1)
C10.016192 (1)0.018599 (1)0.024700 (1)0.004825 (1)0.005547 (1)0.005701 (1)
C20.024037 (1)0.017200 (1)0.017399 (1)0.003053 (1)0.006840 (1)0.000700 (1)
C30.018120 (1)0.017300 (1)0.022500 (1)0.002806 (1)0.004639 (1)0.000200 (1)
C40.017779 (1)0.018899 (1)0.019800 (1)0.001667 (1)0.004282 (1)0.003900 (1)
C50.023844 (1)0.023000 (1)0.015399 (1)0.001594 (1)0.006250 (1)0.002100 (1)
C60.021936 (1)0.019000 (1)0.022999 (1)0.001531 (1)0.003891 (1)0.000400 (1)
H10.022996 (9)0.023000 (11)0.023002 (9)0.000000 (8)0.002199 (7)0.000009 (8)
H20.022996 (10)0.023000 (12)0.022996 (9)0.000003 (8)0.002197 (7)0.000001 (8)
H30.021998 (10)0.021993 (11)0.021999 (9)0.000001 (7)0.002096 (7)0.000005 (7)
H40.023999 (9)0.024002 (11)0.023993 (9)0.000004 (8)0.002291 (7)0.000001 (8)
H50.025999 (11)0.026002 (12)0.025997 (10)0.000009 (7)0.002486 (8)0.000000 (7)
Geometric parameters (Å, º) top
Hg—C12.0878 (1)C5—C61.3980 (1)
C1—C21.3927 (1)C2—H10.9501 (1)
C1—C61.3998 (1)C3—H20.9498 (1)
C2—C31.3842 (1)C4—H30.9499 (1)
C3—C41.4019 (1)C5—H40.9496 (1)
C4—C51.3831 (1)C6—H50.9500 (1)
Hg—C1—C2122.3378 (1)C1—C6—H5119.5175 (10)
Hg—C1—C6120.2986 (1)C2—C3—H2119.9129 (9)
C1—C2—C3122.0489 (1)C3—C2—H1118.9665 (9)
C1—C6—C5121.0603 (2)C3—C4—H3120.7257 (9)
C2—C1—C6117.2881 (1)C4—C3—H2119.8780 (9)
C2—C3—C4120.2091 (2)C4—C5—H4119.5912 (9)
C3—C4—C5118.5752 (1)C5—C4—H3120.6990 (8)
C4—C5—C6120.8144 (1)C5—C6—H5119.4221 (10)
C1—C2—H1118.9845 (9)C6—C5—H4119.5945 (9)
 

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