Bis[1-hydroxy-4,4,5,5-tetra­methyl-2-(1,3-thia­zol-2-yl-κN)-2,3-dihydro-1H-imidazole-κN3]­dinitratomercury(II)

Chang, J.-L.; Wang, L.-Y.; Jiang, K.

doi:10.1107/S1600536805030060

Bis[1-hydroxy-4,4,5,5-tetramethyl-2-(1,3-thiazol-2-yl-κN)-2,3-dihydro-1H-imidazole-κN³]dinitratomercury(II)

In the title complex, [Hg(NO₃)₂(C₁₀H₁₅N₃OS)₂], the Hg^II ion (site symmetry $\overline{1}$ ) adopts a grossly distorted octahedral geometry by chelation of two neutral Him-thz ligands [Him-thz is 2-(2′-thiazole)-4,4,5,5-tetramethyldihydro-1H-imidazolyl-1-hydroxy] through their thiazole N atoms [Hg—N = 2.846 (2) Å] and reduced imino nitroxide N atoms [Hg—N = 2.055 (2) Å], leading to a five-membered ring, together with two O atoms from two nitrate anions [Hg—O = 2.859 (3) Å]. The molecules form one-dimensional chains by way of intermolecular O—H

O hydrogen bonds.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805030060/hb6265sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536805030060/hb6265Isup2.hkl Contains datablock I

CCDC reference: 287567

checkCIF report

Key indicators

Single-crystal X-ray study
T = 295 K
Mean (C-C) = 0.005 Å
R factor = 0.020
wR factor = 0.056
Data-to-parameter ratio = 17.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.41
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C5
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         N4
PLAT322_ALERT_2_C Check Hybridisation of  S1     in Main Residue .          ?
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.19 Ratio

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 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
   2 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

The engineering of molecular magnets constitutes a major contemporary research aim and has spawned interest in organic radicals as building blocks for the construction of such materials (Yamamoto et al., 2001; Aoki et al., 2003; Iino et al., 2003; Pillet et al., 2001). In the past two decades, there have been a large number of investigations on magneto/structural chemistry of transition metal complexes containing nitronyl and imino nitroxide radicals (Taylor et al., 2003; Zhou et al., 2004; Wang et al., 2003; Ruiz et al., 2000). However, nitroxide radicals can undergo redox reactions with transition metal ions and the mechanistic details of the reduction of the imino radicals are not completely clear. It is likely that the imino radicals are reduced by acidic impurities or other experimental conditions during the reaction process (Jiang et al., 1998; Li et al., 2001). In this paper, we report the synthesis and crystal structure of the title compound, (I) (Fig. 1), Hg(Him-thz)₂(NO₃)₂, where Him-thz = 2-(2'-thiazole)-4,4,5,5-tetramethyldihydro-1H-imidazolyl-1-hydroxy), i.e. the reduced IM-thz radical.

The mercury(II) ion (site symmetry 1) in (I) is six-coordinated in a grossly distorted octahedral HgN₄O₂ environment. Two Him-thz molecules acting as bidentate chelating ligands, coordinate the mercury(II) ion through a very long (Table 1) Hg—N bond to the N atom of the thiazole ring and a short Hg—N bond to the N atom of the imidazole ring leading to a five-membered chelate rings. The mercury coordination is completed by long Hg—O bonds to nearby monodentate nitrate anions. Similar Hg—N and Hg—O bond lengths have been seen in other complexes (Lee et al., 1998; Kim et al., 1998).

Molecules of (I) are linked into chains by way of an O—H···O hydrogen bond (Fig. 2 and Table 2) involving a reduced N—OH group as donor and a nitrate O atom as acceptor.

Experimental top

IM-thz was synthesized using a method in the literature (Ullman et al., 1972 or ??1970). Diethyl ether vapor was diffused into acetonitrile solution (6 ml) containing Hg(NO₃)₂ (0.25 mmol) and IM-thz (0.5 mmol) in a closed vessel in the dark for two weeks, affording red blocks of (I) suitable for X-ray analysis. Analysis calculated for C₂₀H₃₀HgS₂N₈O₈: C 30.98, H 3.90, N 14.46%; found: C 31.03, H 3.81, N 14.37%.

Computing details top

Data collection: APEX II (Bruker, 2004); cell refinement: APEX II; data reduction: SAINT (Bruker 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker 2004); software used to prepare material for publication: SHELXTL.

Figures top

	Fig. 1. View of (I), showing 30% probability displacment ellipsoids (arbitrary spheres for the H atoms). [Symmetry code: (i) 1/2 − x, 1/2 − y, 1 − z.]
	Fig. 2. Detail of (I), showing the intermolecular O—H···O hydrogen bonds as dashed lines.

(I) top

Crystal data top

[Hg(C₁₀H₁₅N₃OS)₂(NO₃)₂]	F(000) = 1528
M_r = 775.22	D_x = 1.839 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6354 reflections
a = 19.758 (4) Å	θ = 2.3–28.7°
b = 13.580 (3) Å	µ = 5.70 mm⁻¹
c = 11.587 (3) Å	T = 295 K
β = 115.739 (3)°	Block, red
V = 2800.3 (11) Å³	0.36 × 0.24 × 0.15 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	3212 independent reflections
Radiation source: fine-focus sealed tube	2498 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −25→25
T_min = 0.202, T_max = 0.425	k = −17→17
11946 measured reflections	l = −15→14

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)] = 0.020	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.056	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0288P)² + 3.1412P] where P = (F_o² + 2F_c²)/3
3212 reflections	(Δ/σ)_max < 0.001
183 parameters	Δρ_max = 0.96 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

[Hg(C₁₀H₁₅N₃OS)₂(NO₃)₂]	V = 2800.3 (11) Å³
M_r = 775.22	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 19.758 (4) Å	µ = 5.70 mm⁻¹
b = 13.580 (3) Å	T = 295 K
c = 11.587 (3) Å	0.36 × 0.24 × 0.15 mm
β = 115.739 (3)°

Data collection top

Bruker SMART APEX CCD diffractometer	3212 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2498 reflections with I > 2σ(I)
T_min = 0.202, T_max = 0.425	R_int = 0.016
11946 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.020	0 restraints
wR(F²) = 0.056	H-atom parameters constrained
S = 1.03	Δρ_max = 0.96 e Å⁻³
3212 reflections	Δρ_min = −0.40 e Å⁻³
183 parameters

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	U_iso*/U_eq
Hg1	0.2500	0.2500	0.5000	0.04859 (6)
S1	0.43205 (5)	0.48240 (6)	0.82883 (8)	0.0656 (2)
O1	0.45347 (14)	0.31673 (16)	0.9825 (2)	0.0702 (6)
H1	0.4980	0.3012	1.0159	0.105*
O2	0.4047 (2)	0.2581 (2)	0.4725 (4)	0.1045 (12)
O3	0.4007 (2)	0.2036 (3)	0.2983 (3)	0.1112 (10)
O4	0.32587 (17)	0.1501 (2)	0.3728 (4)	0.1127 (11)
N1	0.33715 (14)	0.42170 (17)	0.6085 (2)	0.0523 (6)
N2	0.32075 (15)	0.22847 (17)	0.6903 (2)	0.0473 (5)
N3	0.41408 (16)	0.25380 (14)	0.8804 (3)	0.0523 (6)
N4	0.37707 (17)	0.2034 (2)	0.3807 (3)	0.0674 (7)
C1	0.40165 (18)	0.5627 (2)	0.7046 (3)	0.0643 (8)
H1A	0.4167	0.6281	0.7102	0.077*
C2	0.35261 (18)	0.5186 (2)	0.5967 (3)	0.0572 (7)
H2	0.3306	0.5517	0.5188	0.069*
C3	0.37655 (16)	0.3925 (2)	0.7267 (3)	0.0461 (6)
C4	0.37006 (15)	0.2924 (2)	0.7654 (3)	0.0426 (5)
C5	0.33397 (17)	0.1318 (2)	0.7599 (3)	0.0510 (6)
C6	0.37633 (16)	0.1656 (2)	0.9020 (3)	0.0506 (6)
C7	0.3818 (3)	0.0700 (3)	0.7140 (4)	0.0885 (13)
H7A	0.3559	0.0619	0.6228	0.133*
H7B	0.3908	0.0067	0.7547	0.133*
H7C	0.4289	0.1027	0.7356	0.133*
C8	0.2598 (2)	0.0810 (3)	0.7286 (3)	0.0826 (12)
H8A	0.2275	0.1245	0.7472	0.124*
H8B	0.2685	0.0224	0.7794	0.124*
H8C	0.2363	0.0639	0.6394	0.124*
C9	0.4339 (2)	0.0927 (3)	0.9906 (3)	0.0790 (11)
H9A	0.4724	0.0826	0.9622	0.119*
H9B	0.4096	0.0312	0.9892	0.119*
H9C	0.4560	0.1183	1.0763	0.119*
C10	0.3241 (2)	0.1990 (3)	0.9601 (3)	0.0788 (10)
H10A	0.3530	0.2306	1.0409	0.118*
H10B	0.2986	0.1429	0.9728	0.118*
H10C	0.2879	0.2446	0.9030	0.118*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Hg1	0.05756 (10)	0.04837 (9)	0.03641 (8)	−0.00462 (7)	0.01720 (7)	−0.00048 (6)
S1	0.0729 (5)	0.0483 (4)	0.0584 (4)	−0.0122 (4)	0.0124 (4)	−0.0021 (3)
O1	0.0802 (16)	0.0499 (12)	0.0503 (12)	0.0002 (11)	0.0000 (11)	−0.0045 (10)
O2	0.093 (2)	0.118 (3)	0.102 (3)	−0.0023 (16)	0.043 (2)	−0.0382 (18)
O3	0.137 (3)	0.129 (3)	0.091 (2)	0.023 (2)	0.072 (2)	0.017 (2)
O4	0.087 (2)	0.099 (2)	0.161 (3)	−0.0109 (18)	0.062 (2)	−0.017 (2)
N1	0.0614 (14)	0.0444 (12)	0.0481 (13)	0.0018 (11)	0.0209 (11)	0.0033 (10)
N2	0.0561 (14)	0.0448 (12)	0.0390 (12)	−0.0033 (10)	0.0186 (11)	0.0017 (9)
N3	0.0574 (14)	0.0415 (12)	0.0448 (13)	−0.0010 (10)	0.0099 (11)	−0.0008 (9)
N4	0.0658 (18)	0.0631 (18)	0.076 (2)	0.0176 (15)	0.0333 (16)	0.0088 (16)
C1	0.073 (2)	0.0433 (16)	0.073 (2)	−0.0063 (14)	0.0286 (17)	0.0038 (14)
C2	0.0701 (19)	0.0437 (14)	0.0585 (17)	0.0042 (13)	0.0285 (15)	0.0100 (13)
C3	0.0490 (15)	0.0413 (14)	0.0482 (15)	0.0000 (11)	0.0214 (12)	−0.0024 (11)
C4	0.0463 (14)	0.0383 (13)	0.0423 (14)	0.0055 (11)	0.0184 (12)	−0.0001 (11)
C5	0.0664 (18)	0.0409 (14)	0.0477 (15)	−0.0040 (13)	0.0265 (14)	0.0031 (11)
C6	0.0560 (16)	0.0449 (15)	0.0443 (14)	0.0006 (12)	0.0158 (13)	0.0041 (11)
C7	0.147 (4)	0.051 (2)	0.090 (3)	0.020 (2)	0.072 (3)	0.0025 (19)
C8	0.091 (3)	0.081 (2)	0.058 (2)	−0.034 (2)	0.0160 (19)	0.0144 (18)
C9	0.081 (2)	0.0545 (19)	0.074 (2)	0.0032 (17)	0.0088 (19)	0.0239 (17)
C10	0.102 (3)	0.087 (3)	0.060 (2)	0.001 (2)	0.047 (2)	−0.0018 (19)

Geometric parameters (Å, º) top

Hg1—N2	2.055 (2)	C1—H1A	0.9300
Hg1—N1	2.846 (2)	C2—H2	0.9300
Hg1—O4	2.859 (3)	C3—C4	1.455 (4)
Hg1—N2ⁱ	2.055 (2)	C5—C8	1.515 (4)
Hg1—N1ⁱ	2.846 (2)	C5—C7	1.522 (4)
Hg1—O4ⁱ	2.859 (3)	C5—C6	1.558 (4)
S1—C1	1.695 (3)	C6—C9	1.521 (4)
S1—C3	1.722 (3)	C6—C10	1.524 (4)
N3—O1	1.391 (3)	C7—H7A	0.9600
O1—H1	0.8200	C7—H7B	0.9600
O2—N4	1.214 (5)	C7—H7C	0.9600
O3—N4	1.231 (4)	C8—H8A	0.9600
O4—N4	1.215 (4)	C8—H8B	0.9600
N1—C3	1.309 (4)	C8—H8C	0.9600
N1—C2	1.371 (4)	C9—H9A	0.9600
C4—N2	1.313 (4)	C9—H9B	0.9600
N2—C5	1.503 (3)	C9—H9C	0.9600
C4—N3	1.342 (4)	C10—H10A	0.9600
N3—C6	1.488 (4)	C10—H10B	0.9600
C1—C2	1.345 (4)	C10—H10C	0.9600

N2ⁱ—Hg1—N1	110.89 (8)	N2—C4—C3	123.6 (3)
N2—Hg1—N1	69.11 (8)	N3—C4—C3	124.4 (3)
N2ⁱ—Hg1—O4	77.24 (10)	N2—C5—C8	110.2 (3)
N2—Hg1—O4	102.76 (10)	N2—C5—C7	106.4 (2)
N1—Hg1—O4	105.32 (8)	C8—C5—C7	110.4 (3)
N1ⁱ—Hg1—O4	74.68 (10)	N2—C5—C6	101.4 (2)
N2—Hg1—N1ⁱ	110.89 (8)	C8—C5—C6	114.0 (3)
N2ⁱ—Hg1—N1ⁱ	69.11 (8)	C7—C5—C6	113.7 (3)
N2—Hg1—O4ⁱ	77.24 (10)	N3—C6—C9	110.8 (3)
N2ⁱ—Hg1—O4ⁱ	102.76 (10)	N3—C6—C10	108.6 (3)
N1ⁱ—Hg1—O4ⁱ	105.32 (8)	C9—C6—C10	110.3 (3)
N1—Hg1—O4ⁱ	74.68 (10)	N3—C6—C5	97.9 (2)
N2ⁱ—Hg1—N2	180.0	C9—C6—C5	115.0 (3)
O4—Hg1—O4ⁱ	180.0	C10—C6—C5	113.5 (3)
N1—Hg1—N1ⁱ	180.0	C5—C7—H7A	109.5
N4—O4—Hg1	106.5 (2)	C5—C7—H7B	109.5
C1—S1—C3	89.29 (15)	H7A—C7—H7B	109.5
N3—O1—H1	109.5	C5—C7—H7C	109.5
C3—N1—C2	109.8 (2)	H7A—C7—H7C	109.5
C4—N2—C5	108.4 (2)	H7B—C7—H7C	109.5
C4—N2—Hg1	125.50 (19)	C5—C8—H8A	109.5
C5—N2—Hg1	125.36 (18)	C5—C8—H8B	109.5
C4—N3—O1	119.1 (2)	H8A—C8—H8B	109.5
C4—N3—C6	109.0 (2)	C5—C8—H8C	109.5
O1—N3—C6	119.2 (3)	H8A—C8—H8C	109.5
O2—N4—O4	118.2 (4)	H8B—C8—H8C	109.5
O2—N4—O3	120.0 (4)	C6—C9—H9A	109.5
O4—N4—O3	121.7 (4)	C6—C9—H9B	109.5
C2—C1—S1	110.4 (2)	H9A—C9—H9B	109.5
C2—C1—H1A	124.8	C6—C9—H9C	109.5
S1—C1—H1A	124.8	H9A—C9—H9C	109.5
C1—C2—N1	115.9 (3)	H9B—C9—H9C	109.5
C1—C2—H2	122.1	C6—C10—H10A	109.5
N1—C2—H2	122.1	C6—C10—H10B	109.5
N1—C3—C4	120.9 (2)	H10A—C10—H10B	109.5
N1—C3—S1	114.6 (2)	C6—C10—H10C	109.5
C4—C3—S1	124.5 (2)	H10A—C10—H10C	109.5
N2—C4—N3	112.0 (2)	H10B—C10—H10C	109.5

C3—S1—C1—C2	0.3 (3)	Hg1—N2—C5—C8	−46.4 (3)
S1—C1—C2—N1	0.5 (4)	C4—N2—C5—C7	−97.1 (3)
C3—N1—C2—C1	−1.4 (4)	Hg1—N2—C5—C7	73.4 (3)
C2—N1—C3—C4	179.4 (3)	C4—N2—C5—C6	22.1 (3)
C2—N1—C3—S1	1.6 (3)	Hg1—N2—C5—C6	−167.48 (19)
C1—S1—C3—N1	−1.1 (2)	C4—N3—C6—C9	152.1 (3)
C1—S1—C3—C4	−178.9 (3)	O1—N3—C6—C9	−66.6 (3)
C5—N2—C4—N3	−2.4 (3)	C4—N3—C6—C10	−86.6 (3)
Hg1—N2—C4—N3	−172.9 (2)	O1—N3—C6—C10	54.8 (3)
C5—N2—C4—C3	176.6 (2)	C4—N3—C6—C5	31.5 (3)
Hg1—N2—C4—C3	6.1 (4)	O1—N3—C6—C5	172.9 (2)
O1—N3—C4—N2	−161.4 (3)	N2—C5—C6—N3	−30.4 (3)
C6—N3—C4—N2	−20.0 (3)	C8—C5—C6—N3	−148.8 (3)
O1—N3—C4—C3	19.6 (4)	C7—C5—C6—N3	83.4 (3)
C6—N3—C4—C3	161.0 (3)	N2—C5—C6—C9	−147.8 (3)
N1—C3—C4—N2	−6.4 (4)	C8—C5—C6—C9	93.8 (3)
S1—C3—C4—N2	171.3 (2)	C7—C5—C6—C9	−34.0 (4)
N1—C3—C4—N3	172.5 (3)	N2—C5—C6—C10	83.9 (3)
S1—C3—C4—N3	−9.8 (4)	C8—C5—C6—C10	−34.5 (4)
C4—N2—C5—C8	143.2 (3)	C7—C5—C6—C10	−162.2 (3)

Symmetry code: (i) −x+1/2, −y+1/2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱⁱ	0.82	1.96	2.737 (5)	158

Symmetry code: (ii) −x+1, y, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Hg(C₁₀H₁₅N₃OS)₂(NO₃)₂]
M_r	775.22
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	295
a, b, c (Å)	19.758 (4), 13.580 (3), 11.587 (3)
β (°)	115.739 (3)
V (Å³)	2800.3 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.70
Crystal size (mm)	0.36 × 0.24 × 0.15

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.202, 0.425
No. of measured, independent and observed [I > 2σ(I)] reflections	11946, 3212, 2498
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.020, 0.056, 1.03
No. of reflections	3212
No. of parameters	183
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.96, −0.40

Computer programs: APEX II (Bruker, 2004), APEX II, SAINT (Bruker 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker 2004), SHELXTL.

Selected bond lengths (Å) top

Hg1—N2	2.055 (2)	N3—O1	1.391 (3)
Hg1—N1	2.846 (2)	C4—N2	1.313 (4)
Hg1—O4	2.859 (3)	C4—N3	1.342 (4)