Unexpected ring contraction in a dinuclear mercury(II) complex of a pendant-arm macrocyclic complex

Chantrapromma, S.; Fun, H.-K.; Usman, A.; Karalai, C.; Wongratchasee, W.; Ponglimanont, C.; Gou, S.

doi:10.1107/S1600536802006232

Unexpected ring contraction in a dinuclear mercury(II) complex of a pendant-arm macrocyclic complex

S. Chantrapromma, H.-K. Fun, A. Usman, C. Karalai, W. Wongratchasee, C. Ponglimanont and S. Gou

The [2+2] cyclocondensation reaction between sodium 2,6-diformyl-4-chlorophenolate and benzyldiethylenetriamine using the sodium template method, followed by transmetallation with Hg(CH₃COO)₂·2H₂O, gave an unexpected 18-membered macrocyclic product in which ring contractions have occurred to produce two imidazolidine rings. In the dinuclear macrocyclic complex, bis[μ-3,17-dibenzyl-3,6,9,17,20,23-hexaazatetracyclo[23.3.1.1^11,15.0^2,6.0^16,20]tricosa-1(29),9,11,13,15(30),23,25,27-octaene-29,30diolato]bis[diacetatomercury(II)] tetrahydrate diethanol solvate, [Hg₂(C₃₈H₃₈Cl₂N₆O₂)(CH₃COO)₄]·4H₂O·2CH₃CH₂OH, each Hg^II ion is coordinated by the imine N atom and O atom of the macrocyclic ligand and four O atoms from the acetate ligands, to form a centrosymmetric structure. The Hg coordination is irregular and it may be described as a distorted square pyramid.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802006232/ci6106sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536802006232/ci6106Isup2.hkl Contains datablock I

CCDC reference: 185749

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.022 Å
H-atom completeness 89%
R factor = 0.099
wR factor = 0.238
Data-to-parameter ratio = 14.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



RINTA_01  Alert C The value of Rint is greater than 0.10
          Rint given   0.110

PLAT_202  Alert C Isotropic non-H Atoms in Anion/Solvent       =          3

General Notes



FORMU_01  There is a discrepancy between the atom counts in the
          _chemical_formula_sum and the formula from the _atom_site* data.
          Atom count from _chemical_formula_sum:C50 H70 Cl2 Hg2 N6 O16
          Atom count from the _atom_site data:  C50 H62 Cl2 Hg2 N6 O16

CELLZ_01
         From the CIF: _cell_formula_units_Z    1
         From the CIF: _chemical_formula_sum  C50 H70 Cl2 Hg2 N6 O16
         TEST: Compare cell contents of formula and atom_site data

         atom    Z*formula  cif sites diff
         C         50.00     50.00    0.00
         H         70.00     62.00    8.00
         Cl         2.00      2.00    0.00
         Hg         2.00      2.00    0.00
         N          6.00      6.00    0.00
         O         16.00     16.00    0.00
          Difference between formula and atom_site contents detected.
          WARNING: H atoms missing from atom site list. Is this intentional?


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 2 Alert Level C = Please check

Comment top

Much effort has now been focused on pendant-arm macrocyclic complexes due to the fact that the pendant-arm attached to the macrocyclic skeleton can effect the coordination sphere of the metal in the macrocycle (Gou & Fenton, 1994; Zhou et al., 1995; Qian et al., 2000), as well as the potential application of macrocyclic complexes in the extraction or recovery of metals and for modelling of metallo-biosites (Fenton, 1989). A number of pendant-arm macrocyclic complexes have been designed and synthesized by sodium template method (Gou & Fenton, 1994; Zhou et al., 1995; Qian et al., 2000). Recently, we have applied sodium 2,6-diformyl-4-chlorophenolate as a precursor to carry out cyclocondensation reactions with ethylenetriamine derivative by this method and then transmetallation by zinc acetate to obtain a dinuclear Zn^II complex of a Robson macrocycle (Wongratchasee et al., 2002). Herein, we report the structure of a dinuclear mercury complex with the Schiff base macrocyclic ligand in which ring contraction has occurred. The reaction between sodium 2,6-diformyl-4-chlorophenolate and benzyldiethylenetriamine and transmetallation with Hg(CH₃COO)₂·2H₂O has been investigated with the aim of producing the corresponding 24-membered Schiff base macrocycle complex. The macrocyclic complex product resulting from an unexpected ring-contraction reaction gave instead a 18-membered macrocycle, [Hg₂(C₃₈H₃₈Cl₂N₆O₂)(CH₃COO)₄]·4H₂O·2CH₃CH₂OH, (I). The formation of the 18-membered ring was a result of further reaction of the initial 24-membered ring by the nucleophilic additions of the two tertiary amine groups across the C10—N2 bond to form an imidazolidine ring concomitant with the benzyl migration from N2 to N1. Ring contractions have been reported to occur for Schiff base macrocycles as a consequence of nucleophilic addition of secondary amines across an adjacent imine bond (Drew et al., 1981; Adam et al., 1987; Menif et al., 1990).

A displacement ellipsoid plot of (I) with the atomic numbering scheme is shown in Fig. 1. The asymmetric unit consists of one-half of the dinuclear [Hg₂(C₃₈H₃₈Cl₂N₆O₂)(CH₃COO)₄] unit (the other half being generated by a centre of symmetry), two water molecules and one ethanol molecule. The Hg^II is coordinated by an imine N atom and an O atom from the macrocycle ligand and four O atoms from the two acetate ligands. The Hg^II coordination is irregular; if the longest bond, Hg1—O3 [2.594 (16) Å] is not taken into consideration, the coordination around the Hg atom may be described as a distorted square pyramid with the O2 atom as its apex. It is observed that each Hg^II ion has coordinated with ligating atoms outside the cavity of the macrocycle ligand which is a rare example. This may be due to the realtionship between the sizes of the Hg ion and the macrocycle cavity and also due to steric hindrance.

The conformation of the macrocycle is `crown-like' with its skeleton bent back so as to present the imine N atom and O atom to the Hg^II ions. Hence the ring framework here is much more twisted than that of the related zinc complex (Wongratchasee et al., 2002). The effect of the pendant arm and steric requirement of the macrocycle could have forced the two benzene planes of the macrocycle to be mutually anti-parallel. The imidazolidine rings are twisted on C8—C9 with puckering parameters Q = 0.14 (2) Å and ϕ = 238 (6)° (Cremer & Pople, 1975). The phenyl rings C1–C6 and C11–C16 form dihedral angles of 80.1 (8) and 73.2 (7)°, respectively, with the imidazolidine ring. The packing of (I) viewed down the a axis is shown in Fig. 2. In the crystal, the molecules are linked by intermolecular O—H···O and C—H···O hydrogen bonds (Table 2) to form sheet like structures parallel to the bc plane.

Experimental top

The binuclear Hg^II complex of a Robson macrocycle was derived from the [2 + 2] cyclocondensation between sodium 2,6-diformyl-4-chlorophenolate (0.8065 g, 1 mmol) and benzyldiethylenetriamine (0.3385 g, 1 mmol) in ethanol (30 ml) via the sodium template method (Gou & Fenton, 1994) and transmetallation with Hg(CH₃COO)₂·2H₂O (0.3186 g, 1 mmol) in ethanol (25 ml). The solution was refluxed for 1 h under inert nitrogen. After the reaction was completed, the resulting hot clear solution was filtered and left to cool. After one week, yellow single crystals of (I) were deposited; melting and decomposition point 473–479 K. These single crystals were not stable and deteriorated quite rapidly upon exposure to air. We have put much effort to get a good quality single-crystal of (I) but the attempts were not sucessful. Before data collection, the crystal was coated with superglue to delay its deterioration.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 1990).

Figures top

	Fig. 1. The structure of (I) showing 30% probability displacement ellipsoids and the atom-numbering scheme. H atoms and the solvent molecules have been omitted for clarify.
	Fig. 2. Packing of (I) viewed down the a axis.

(I) top

Crystal data top

[Hg₂(C₃₈H₃₈Cl₂N₆O₂)(C₂H₃O₂)₄]·4H₂O·2C₂H₆O	Z = 1
M_r = 1483.20	F(000) = 734
Triclinic, P1	D_x = 1.758 Mg m⁻³
a = 10.1376 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.0131 (2) Å	Cell parameters from 4581 reflections
c = 13.4833 (2) Å	θ = 2.7–25.0°
α = 87.599 (1)°	µ = 5.64 mm⁻¹
β = 71.388 (1)°	T = 293 K
γ = 79.135 (1)°	Plate, yellow
V = 1400.79 (4) Å³	0.12 × 0.10 × 0.08 mm

Data collection top

Siemens SMART CCD area-detector diffractometer	4735 independent reflections
Radiation source: fine-focus sealed tube	2923 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.110
Detector resolution: 8.33 pixels mm^-1	θ_max = 25.0°, θ_min = 2.6°
ω scans	h = −11→12
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −13→12
T_min = 0.551, T_max = 0.661	l = −16→13
6734 measured reflections

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)] = 0.099	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.238	H-atom parameters constrained
S = 0.96	w = 1/[σ²(F_o²) + (0.0692P)²] where P = (F_o² + 2F_c²)/3
4735 reflections	(Δ/σ)_max = 0.001
330 parameters	Δρ_max = 2.46 e Å⁻³
17 restraints	Δρ_min = −3.70 e Å⁻³

Crystal data top

[Hg₂(C₃₈H₃₈Cl₂N₆O₂)(C₂H₃O₂)₄]·4H₂O·2C₂H₆O	γ = 79.135 (1)°
M_r = 1483.20	V = 1400.79 (4) Å³
Triclinic, P1	Z = 1
a = 10.1376 (1) Å	Mo Kα radiation
b = 11.0131 (2) Å	µ = 5.64 mm⁻¹
c = 13.4833 (2) Å	T = 293 K
α = 87.599 (1)°	0.12 × 0.10 × 0.08 mm
β = 71.388 (1)°

Data collection top

Siemens SMART CCD area-detector diffractometer	4735 independent reflections
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	2923 reflections with I > 2σ(I)
T_min = 0.551, T_max = 0.661	R_int = 0.110
6734 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.099	17 restraints
wR(F²) = 0.238	H-atom parameters constrained
S = 0.96	Δρ_max = 2.46 e Å⁻³
4735 reflections	Δρ_min = −3.70 e Å⁻³
330 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	1.21153 (6)	0.25568 (5)	−0.08568 (6)	0.0611 (3)
Cl1	1.1445 (4)	0.2450 (4)	0.3441 (3)	0.0579 (10)
O1	0.8282 (9)	0.5332 (8)	0.0964 (8)	0.043 (2)
H1	0.7648	0.4971	0.0955	0.065*
O2	1.4300 (13)	0.2234 (14)	−0.2160 (11)	0.083 (4)
O3	1.3060 (17)	0.0977 (16)	−0.2410 (13)	0.106 (5)
O4	1.3317 (13)	0.2087 (13)	0.0402 (11)	0.077 (4)
O5	1.2152 (14)	0.0782 (13)	0.0226 (13)	0.092 (5)
N1	0.6177 (10)	0.3686 (10)	0.2240 (9)	0.041 (3)
N2	0.7588 (10)	0.2349 (9)	0.1085 (9)	0.036 (3)
N3	0.9899 (10)	0.2818 (10)	−0.0920 (9)	0.035 (2)
C1	0.4379 (13)	0.4568 (12)	0.3853 (11)	0.051 (4)
C2	0.4373 (16)	0.3586 (16)	0.4503 (12)	0.067 (5)
H2	0.5198	0.2999	0.4396	0.081*
C3	0.3195 (15)	0.344 (2)	0.5306 (13)	0.097 (7)
H3	0.3213	0.2760	0.5743	0.116*
C4	0.1992 (18)	0.4301 (18)	0.5453 (14)	0.091 (8)
H4	0.1167	0.4204	0.5980	0.110*
C5	0.1994 (16)	0.5307 (18)	0.4828 (14)	0.081 (6)
H5	0.1181	0.5912	0.4955	0.097*
C6	0.3174 (12)	0.5436 (17)	0.4020 (13)	0.078 (6)
H6	0.3158	0.6113	0.3585	0.093*
C7	0.5694 (15)	0.4737 (14)	0.2980 (13)	0.057 (4)
H7A	0.5495	0.5492	0.2615	0.069*
H7B	0.6437	0.4812	0.3270	0.069*
C8	0.5172 (14)	0.3197 (14)	0.1846 (11)	0.047 (4)
H8A	0.4753	0.3801	0.1436	0.056*
H8B	0.4427	0.2922	0.2411	0.056*
C9	0.6196 (15)	0.2091 (13)	0.1154 (13)	0.051 (4)
H9A	0.6052	0.1307	0.1486	0.062*
H9B	0.6078	0.2084	0.0469	0.062*
C10	0.7474 (13)	0.3204 (11)	0.1758 (10)	0.033 (3)
C11	0.8693 (11)	0.3610 (10)	0.1926 (10)	0.030 (3)
C12	0.9439 (13)	0.2896 (12)	0.2503 (10)	0.037 (3)
H12	0.9195	0.2151	0.2778	0.044*
C13	1.0536 (13)	0.3306 (12)	0.2658 (11)	0.038 (3)
C14	1.0918 (14)	0.4380 (13)	0.2258 (11)	0.042 (3)
H14	1.1681	0.4630	0.2379	0.050*
C15	1.0187 (13)	0.5120 (11)	0.1666 (10)	0.036 (3)
C16	0.9015 (14)	0.4712 (11)	0.1500 (11)	0.037 (3)
C17	1.0662 (14)	0.6257 (12)	0.1323 (11)	0.042 (3)
H17	1.1519	0.6323	0.1412	0.051*
C18	0.8855 (13)	0.1503 (12)	0.0495 (10)	0.039 (3)
H18A	0.8694	0.0660	0.0607	0.047*
H18B	0.9632	0.1582	0.0746	0.047*
C19	0.9253 (15)	0.1764 (12)	−0.0659 (11)	0.041 (3)
H19A	0.9900	0.1051	−0.1045	0.049*
H19B	0.8409	0.1890	−0.0870	0.049*
C20	1.420 (2)	0.1347 (18)	−0.2645 (14)	0.070 (5)
C21	1.540 (3)	0.082 (3)	−0.3572 (16)	0.155 (15)
H21A	1.5140	0.0167	−0.3882	0.232*
H21B	1.6213	0.0485	−0.3359	0.232*
H21C	1.5626	0.1450	−0.4074	0.232*
C22	1.2933 (13)	0.1128 (14)	0.0607 (11)	0.045 (4)
C23	1.3489 (19)	0.0300 (15)	0.1336 (13)	0.063 (5)
H23A	1.2776	−0.0149	0.1736	0.095*
H23B	1.3738	0.0785	0.1801	0.095*
H23C	1.4313	−0.0271	0.0944	0.095*
C24	1.152 (3)	0.007 (3)	−0.414 (3)	0.182 (15)*
H24A	1.1290	−0.0512	−0.4548	0.218*
H24B	1.2250	0.0478	−0.4595	0.218*
C25	1.021 (3)	0.101 (3)	−0.356 (3)	0.153 (12)*
H25A	0.9809	0.1448	−0.4052	0.230*
H25B	1.0470	0.1578	−0.3166	0.230*
H25C	0.9524	0.0581	−0.3084	0.230*
O6	1.196 (3)	−0.052 (2)	−0.335 (2)	0.191 (10)*
H6A	1.2322	−0.0060	−0.3097	0.286*
O1W	0.3685 (18)	0.4656 (15)	−0.0010 (13)	0.104 (5)
O2W	0.3744 (15)	0.6804 (14)	0.1414 (14)	0.101 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Hg1	0.0413 (4)	0.0444 (4)	0.1008 (6)	0.0017 (3)	−0.0328 (3)	0.0049 (3)
Cl1	0.054 (2)	0.057 (2)	0.072 (3)	−0.0016 (18)	−0.039 (2)	0.0069 (19)
O1	0.035 (5)	0.040 (5)	0.067 (6)	−0.014 (4)	−0.032 (5)	0.009 (5)
O2	0.047 (7)	0.097 (10)	0.099 (10)	−0.011 (7)	−0.017 (6)	−0.004 (9)
O3	0.085 (11)	0.117 (13)	0.119 (13)	−0.034 (10)	−0.025 (9)	−0.015 (10)
O4	0.069 (8)	0.076 (9)	0.092 (9)	−0.004 (7)	−0.040 (7)	−0.003 (8)
O5	0.068 (8)	0.094 (10)	0.136 (13)	0.008 (7)	−0.071 (9)	−0.029 (9)
N1	0.018 (5)	0.042 (6)	0.061 (7)	0.001 (5)	−0.008 (5)	−0.025 (6)
N2	0.023 (5)	0.028 (6)	0.055 (7)	0.002 (4)	−0.011 (5)	−0.019 (5)
N3	0.016 (5)	0.041 (6)	0.049 (7)	−0.003 (4)	−0.011 (4)	−0.006 (5)
C1	0.037 (8)	0.061 (10)	0.057 (10)	0.009 (7)	−0.025 (7)	−0.026 (8)
C2	0.056 (10)	0.083 (13)	0.069 (12)	−0.013 (9)	−0.028 (9)	0.004 (10)
C3	0.094 (17)	0.14 (2)	0.051 (12)	−0.016 (16)	−0.019 (11)	−0.006 (13)
C4	0.051 (11)	0.16 (2)	0.054 (12)	−0.025 (14)	−0.001 (9)	−0.035 (14)
C5	0.041 (10)	0.094 (16)	0.085 (15)	0.012 (10)	0.003 (9)	−0.030 (12)
C6	0.040 (9)	0.098 (14)	0.093 (14)	0.011 (9)	−0.023 (9)	−0.044 (12)
C7	0.040 (8)	0.043 (8)	0.088 (12)	0.010 (7)	−0.026 (8)	−0.022 (8)
C8	0.033 (7)	0.056 (9)	0.051 (9)	0.002 (6)	−0.015 (6)	−0.019 (7)
C9	0.043 (8)	0.037 (8)	0.080 (11)	0.000 (6)	−0.031 (8)	−0.018 (8)
C10	0.030 (7)	0.033 (7)	0.041 (7)	−0.013 (5)	−0.011 (5)	−0.005 (6)
C11	0.017 (6)	0.022 (6)	0.051 (8)	0.001 (5)	−0.013 (5)	−0.003 (6)
C12	0.037 (7)	0.030 (7)	0.044 (8)	−0.004 (6)	−0.014 (6)	−0.007 (6)
C13	0.028 (7)	0.038 (8)	0.049 (8)	0.011 (6)	−0.022 (6)	−0.013 (6)
C14	0.031 (7)	0.042 (8)	0.055 (9)	0.007 (6)	−0.022 (6)	−0.021 (7)
C15	0.030 (7)	0.026 (6)	0.046 (8)	0.002 (5)	−0.007 (6)	−0.016 (6)
C16	0.047 (8)	0.026 (7)	0.044 (8)	0.003 (6)	−0.028 (6)	−0.010 (6)
C17	0.030 (7)	0.045 (8)	0.058 (9)	0.008 (6)	−0.029 (6)	−0.015 (7)
C18	0.034 (7)	0.034 (7)	0.049 (8)	0.008 (6)	−0.019 (6)	−0.007 (6)
C19	0.038 (7)	0.026 (7)	0.057 (9)	−0.006 (6)	−0.011 (6)	−0.010 (6)
C20	0.076 (13)	0.055 (11)	0.078 (13)	−0.004 (10)	−0.029 (10)	0.007 (10)
C21	0.12 (2)	0.24 (4)	0.068 (15)	0.08 (2)	−0.027 (14)	−0.042 (19)
C22	0.022 (7)	0.051 (9)	0.053 (9)	−0.004 (6)	0.001 (6)	−0.022 (8)
C23	0.080 (12)	0.062 (11)	0.059 (10)	−0.007 (9)	−0.041 (9)	0.012 (8)
O1W	0.132 (13)	0.096 (11)	0.105 (12)	−0.024 (10)	−0.066 (10)	0.006 (9)
O2W	0.080 (9)	0.098 (11)	0.141 (13)	0.006 (8)	−0.066 (9)	−0.022 (10)

Geometric parameters (Å, º) top

Hg1—N3	2.239 (9)	C8—H8A	0.97
Hg1—O1ⁱ	2.290 (9)	C8—H8B	0.97
Hg1—O2	2.322 (12)	C9—H9A	0.97
Hg1—O4	2.375 (12)	C9—H9B	0.97
Hg1—O5	2.392 (16)	C10—C11	1.475 (16)
Hg1—O3	2.594 (16)	C11—C16	1.372 (18)
Hg1—C22	2.712 (15)	C11—C12	1.376 (18)
Cl1—C13	1.751 (13)	C12—C13	1.352 (17)
O1—C16	1.285 (16)	C12—H12	0.93
O1—Hg1ⁱ	2.290 (9)	C13—C14	1.35 (2)
O1—H1	0.82	C14—C15	1.395 (19)
O2—C20	1.23 (2)	C14—H14	0.93
O3—C20	1.24 (2)	C15—C16	1.428 (18)
O4—C22	1.186 (18)	C15—C17	1.432 (19)
O5—C22	1.195 (17)	C17—N3ⁱ	1.261 (17)
N1—C10	1.286 (15)	C17—H17	0.93
N1—C7	1.464 (17)	C18—C19	1.51 (2)
N1—C8	1.480 (16)	C18—H18A	0.97
N2—C10	1.299 (15)	C18—H18B	0.97
N2—C18	1.452 (14)	C19—H19A	0.97
N2—C9	1.464 (17)	C19—H19B	0.97
N3—C17ⁱ	1.261 (17)	C20—C21	1.485 (18)
N3—C19	1.415 (16)	C21—H21A	0.96
C1—C2	1.36 (2)	C21—H21B	0.96
C1—C6	1.36 (2)	C21—H21C	0.96
C1—C7	1.51 (2)	C22—C23	1.483 (18)
C2—C3	1.36 (2)	C23—H23A	0.96
C2—H2	0.93	C23—H23B	0.96
C3—C4	1.36 (3)	C23—H23C	0.96
C3—H3	0.93	C24—O6	1.37 (4)
C4—C5	1.36 (3)	C24—C25	1.52 (5)
C4—H4	0.93	C24—H24A	0.97
C5—C6	1.36 (2)	C24—H24B	0.97
C5—H5	0.93	C25—H25A	0.96
C6—H6	0.93	C25—H25B	0.96
C7—H7A	0.97	C25—H25C	0.96
C7—H7B	0.97	O6—H6A	0.82
C8—C9	1.559 (18)

N3—Hg1—O1ⁱ	82.3 (3)	H9A—C9—H9B	109.2
N3—Hg1—O2	132.0 (5)	N1—C10—N2	112.5 (10)
O1ⁱ—Hg1—O2	95.5 (4)	N1—C10—C11	123.5 (10)
N3—Hg1—O4	138.3 (5)	N2—C10—C11	123.9 (11)
O1ⁱ—Hg1—O4	105.7 (4)	C16—C11—C12	123.0 (11)
O2—Hg1—O4	88.6 (5)	C16—C11—C10	117.2 (11)
N3—Hg1—O5	100.3 (4)	C12—C11—C10	119.8 (11)
O1ⁱ—Hg1—O5	147.9 (4)	C13—C12—C11	118.3 (13)
O2—Hg1—O5	105.4 (5)	C13—C12—H12	120.8
O4—Hg1—O5	52.0 (5)	C11—C12—H12	120.8
N3—Hg1—O3	92.2 (5)	C14—C13—C12	121.9 (12)
O1ⁱ—Hg1—O3	126.6 (5)	C14—C13—Cl1	119.0 (10)
O2—Hg1—O3	51.2 (5)	C12—C13—Cl1	119.1 (11)
O4—Hg1—O3	112.5 (5)	C13—C14—C15	121.0 (12)
O5—Hg1—O3	85.4 (5)	C13—C14—H14	119.5
N3—Hg1—C22	121.6 (4)	C15—C14—H14	119.5
O1ⁱ—Hg1—C22	128.7 (4)	C14—C15—C16	118.0 (12)
O2—Hg1—C22	97.0 (4)	C14—C15—C17	115.5 (12)
O4—Hg1—C22	25.9 (4)	C16—C15—C17	126.5 (12)
O5—Hg1—C22	26.1 (4)	O1—C16—C11	120.0 (12)
O3—Hg1—C22	99.1 (5)	O1—C16—C15	122.3 (12)
C16—O1—Hg1ⁱ	124.5 (8)	C11—C16—C15	117.7 (11)
C16—O1—H1	109.5	N3ⁱ—C17—C15	130.1 (12)
Hg1ⁱ—O1—H1	118.0	N3ⁱ—C17—H17	115.0
C20—O2—Hg1	101.1 (11)	C15—C17—H17	115.0
C20—O3—Hg1	87.7 (12)	N2—C18—C19	111.4 (11)
C22—O4—Hg1	93.1 (10)	N2—C18—H18A	109.3
C22—O5—Hg1	92.1 (12)	C19—C18—H18A	109.3
C10—N1—C7	126.0 (11)	N2—C18—H18B	109.3
C10—N1—C8	112.4 (9)	C19—C18—H18B	109.3
C7—N1—C8	121.0 (10)	H18A—C18—H18B	108.0
C10—N2—C18	128.1 (11)	N3—C19—C18	112.6 (11)
C10—N2—C9	111.0 (10)	N3—C19—H19A	109.1
C18—N2—C9	119.3 (10)	C18—C19—H19A	109.1
C17ⁱ—N3—C19	120.7 (11)	N3—C19—H19B	109.1
C17ⁱ—N3—Hg1	123.3 (9)	C18—C19—H19B	109.1
C19—N3—Hg1	115.0 (8)	H19A—C19—H19B	107.8
C2—C1—C6	118.9 (14)	O2—C20—O3	119.6 (17)
C2—C1—C7	121.7 (11)	O2—C20—C21	120 (2)
C6—C1—C7	119.4 (13)	O3—C20—C21	120 (2)
C1—C2—C3	122.1 (16)	C20—C21—H21A	109.5
C1—C2—H2	118.9	C20—C21—H21B	109.5
C3—C2—H2	118.9	H21A—C21—H21B	109.5
C4—C3—C2	118.3 (17)	C20—C21—H21C	109.5
C4—C3—H3	120.9	H21A—C21—H21C	109.5
C2—C3—H3	120.9	H21B—C21—H21C	109.5
C5—C4—C3	120.3 (17)	O4—C22—O5	122.8 (16)
C5—C4—H4	119.9	O4—C22—C23	118.7 (15)
C3—C4—H4	119.9	O5—C22—C23	118.5 (16)
C4—C5—C6	120.8 (16)	O4—C22—Hg1	61.0 (9)
C4—C5—H5	119.6	O5—C22—Hg1	61.8 (10)
C6—C5—H5	119.6	C23—C22—Hg1	175.2 (10)
C5—C6—C1	119.6 (15)	C22—C23—H23A	109.5
C5—C6—H6	120.2	C22—C23—H23B	109.5
C1—C6—H6	120.2	H23A—C23—H23B	109.5
N1—C7—C1	110.7 (12)	C22—C23—H23C	109.5
N1—C7—H7A	109.5	H23A—C23—H23C	109.5
C1—C7—H7A	109.5	H23B—C23—H23C	109.5
N1—C7—H7B	109.5	O6—C24—C25	104 (3)
C1—C7—H7B	109.5	O6—C24—H24A	111.0
H7A—C7—H7B	108.1	C25—C24—H24A	111.0
N1—C8—C9	99.9 (10)	O6—C24—H24B	111.0
N1—C8—H8A	111.8	C25—C24—H24B	111.0
C9—C8—H8A	111.8	H24A—C24—H24B	109.0
N1—C8—H8B	111.8	C24—C25—H25A	109.5
C9—C8—H8B	111.8	C24—C25—H25B	109.5
H8A—C8—H8B	109.5	H25A—C25—H25B	109.5
N2—C9—C8	102.2 (10)	C24—C25—H25C	109.5
N2—C9—H9A	111.3	H25A—C25—H25C	109.5
C8—C9—H9A	111.3	H25B—C25—H25C	109.5
N2—C9—H9B	111.3	C24—O6—H6A	109.5
C8—C9—H9B	111.3

N3—Hg1—O2—C20	−52.5 (15)	C7—N1—C10—C11	3 (2)
O1ⁱ—Hg1—O2—C20	−137.1 (12)	C8—N1—C10—C11	174.1 (12)
O4—Hg1—O2—C20	117.3 (13)	C18—N2—C10—N1	−171.7 (13)
O5—Hg1—O2—C20	67.5 (13)	C9—N2—C10—N1	−6.1 (17)
O3—Hg1—O2—C20	−3.4 (12)	C18—N2—C10—C11	10 (2)
C22—Hg1—O2—C20	92.7 (13)	C9—N2—C10—C11	175.9 (13)
N3—Hg1—O3—C20	149.1 (13)	N1—C10—C11—C16	−74.5 (18)
O1ⁱ—Hg1—O3—C20	67.0 (14)	N2—C10—C11—C16	103.2 (15)
O2—Hg1—O3—C20	3.3 (12)	N1—C10—C11—C12	104.6 (16)
O4—Hg1—O3—C20	−65.3 (14)	N2—C10—C11—C12	−77.6 (18)
O5—Hg1—O3—C20	−110.7 (13)	C16—C11—C12—C13	0 (2)
C22—Hg1—O3—C20	−88.4 (13)	C10—C11—C12—C13	−178.8 (11)
N3—Hg1—O4—C22	59.3 (11)	C11—C12—C13—C14	−0.6 (19)
O1ⁱ—Hg1—O4—C22	155.4 (9)	C11—C12—C13—Cl1	177.0 (10)
O2—Hg1—O4—C22	−109.2 (10)	C12—C13—C14—C15	0 (2)
O5—Hg1—O4—C22	1.6 (8)	Cl1—C13—C14—C15	−177.3 (10)
O3—Hg1—O4—C22	−62.7 (10)	C13—C14—C15—C16	0.4 (19)
N3—Hg1—O5—C22	−146.8 (9)	C13—C14—C15—C17	177.6 (12)
O1ⁱ—Hg1—O5—C22	−54.7 (12)	Hg1ⁱ—O1—C16—C11	149.5 (9)
O2—Hg1—O5—C22	74.1 (10)	Hg1ⁱ—O1—C16—C15	−31.3 (18)
O4—Hg1—O5—C22	−1.6 (8)	C12—C11—C16—O1	179.6 (12)
O3—Hg1—O5—C22	121.8 (10)	C10—C11—C16—O1	−1.3 (18)
O1ⁱ—Hg1—N3—C17ⁱ	24.6 (11)	C12—C11—C16—C15	0.4 (19)
O2—Hg1—N3—C17ⁱ	−66.0 (13)	C10—C11—C16—C15	179.5 (10)
O4—Hg1—N3—C17ⁱ	129.6 (11)	C14—C15—C16—O1	−179.9 (12)
O5—Hg1—N3—C17ⁱ	172.2 (11)	C17—C15—C16—O1	3 (2)
O3—Hg1—N3—C17ⁱ	−102.1 (11)	C14—C15—C16—C11	−0.7 (17)
C22—Hg1—N3—C17ⁱ	155.7 (10)	C17—C15—C16—C11	−177.5 (12)
O1ⁱ—Hg1—N3—C19	−167.1 (9)	C14—C15—C17—N3ⁱ	−168.4 (14)
O2—Hg1—N3—C19	102.3 (10)	C16—C15—C17—N3ⁱ	9 (2)
O4—Hg1—N3—C19	−62.1 (11)	C10—N2—C18—C19	−112.9 (16)
O5—Hg1—N3—C19	−19.5 (10)	C9—N2—C18—C19	82.6 (16)
O3—Hg1—N3—C19	66.2 (9)	C17ⁱ—N3—C19—C18	−118.6 (14)
C22—Hg1—N3—C19	−35.9 (10)	Hg1—N3—C19—C18	72.7 (12)
C6—C1—C2—C3	1 (3)	N2—C18—C19—N3	76.4 (14)
C7—C1—C2—C3	178.9 (17)	Hg1—O2—C20—O3	6 (2)
C1—C2—C3—C4	0 (3)	Hg1—O2—C20—C21	−179.9 (17)
C2—C3—C4—C5	−2 (3)	Hg1—O3—C20—O2	−6 (2)
C3—C4—C5—C6	3 (3)	Hg1—O3—C20—C21	−179.3 (19)
C4—C5—C6—C1	−2 (3)	Hg1—O4—C22—O5	−3.0 (15)
C2—C1—C6—C5	0 (2)	Hg1—O4—C22—C23	174.5 (12)
C7—C1—C6—C5	−178.0 (16)	Hg1—O5—C22—O4	3.0 (15)
C10—N1—C7—C1	−143.6 (14)	Hg1—O5—C22—C23	−174.5 (12)
C8—N1—C7—C1	46.5 (18)	N3—Hg1—C22—O4	−137.9 (9)
C2—C1—C7—N1	60.3 (19)	O1ⁱ—Hg1—C22—O4	−30.9 (11)
C6—C1—C7—N1	−121.7 (15)	O2—Hg1—C22—O4	72.0 (10)
C10—N1—C8—C9	11.2 (16)	O5—Hg1—C22—O4	−177.1 (14)
C7—N1—C8—C9	−177.6 (14)	O3—Hg1—C22—O4	123.8 (10)
C10—N2—C9—C8	12.6 (16)	N3—Hg1—C22—O5	39.2 (10)
C18—N2—C9—C8	179.6 (12)	O1ⁱ—Hg1—C22—O5	146.2 (9)
N1—C8—C9—N2	−13.2 (15)	O2—Hg1—C22—O5	−110.9 (10)
C7—N1—C10—N2	−174.6 (14)	O4—Hg1—C22—O5	177.1 (14)
C8—N1—C10—N2	−3.9 (17)	O3—Hg1—C22—O5	−59.1 (10)

Symmetry code: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1Wⁱⁱ	0.82	2.11	2.69 (2)	128
O6—H6A···O3	0.82	1.89	2.71 (3)	176
C12—H12···O6ⁱⁱⁱ	0.93	2.30	3.21 (3)	164
C17—H17···O2W^iv	0.93	2.41	3.33 (2)	169
C18—H18A···O5ⁱⁱⁱ	0.97	2.41	3.18 (2)	137
C18—H18B···O5	0.97	2.42	3.19 (2)	136

Symmetry codes: (ii) −x+1, −y+1, −z; (iii) −x+2, −y, −z; (iv) x+1, y, z.

Experimental details

Crystal data
Chemical formula	[Hg₂(C₃₈H₃₈Cl₂N₆O₂)(C₂H₃O₂)₄]·4H₂O·2C₂H₆O
M_r	1483.20
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	10.1376 (1), 11.0131 (2), 13.4833 (2)
α, β, γ (°)	87.599 (1), 71.388 (1), 79.135 (1)
V (Å³)	1400.79 (4)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	5.64
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Siemens SMART CCD area-detector diffractometer
Absorption correction	Empirical (using intensity measurements) (SADABS; Sheldrick, 1996)
T_min, T_max	0.551, 0.661
No. of measured, independent and observed [I > 2σ(I)] reflections	6734, 4735, 2923
R_int	0.110
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.099, 0.238, 0.96
No. of reflections	4735
No. of parameters	330
No. of restraints	17
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.46, −3.70

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL and PLATON (Spek, 1990).

Selected geometric parameters (Å, º) top

Hg1—N3	2.239 (9)	Hg1—O5	2.392 (16)
Hg1—O1ⁱ	2.290 (9)	Hg1—O3	2.594 (16)
Hg1—O2	2.322 (12)	O1—Hg1ⁱ	2.290 (9)
Hg1—O4	2.375 (12)

N3—Hg1—O1ⁱ	82.3 (3)	O2—Hg1—O5	105.4 (5)
N3—Hg1—O2	132.0 (5)	O4—Hg1—O5	52.0 (5)
O1ⁱ—Hg1—O2	95.5 (4)	N3—Hg1—O3	92.2 (5)
N3—Hg1—O4	138.3 (5)	O1ⁱ—Hg1—O3	126.6 (5)
O1ⁱ—Hg1—O4	105.7 (4)	O2—Hg1—O3	51.2 (5)
O2—Hg1—O4	88.6 (5)	O4—Hg1—O3	112.5 (5)
N3—Hg1—O5	100.3 (4)	O5—Hg1—O3	85.4 (5)
O1ⁱ—Hg1—O5	147.9 (4)

Symmetry code: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1Wⁱⁱ	0.82	2.11	2.69 (2)	127.7
O6—H6A···O3	0.82	1.89	2.71 (3)	175.5
C12—H12···O6ⁱⁱⁱ	0.93	2.30	3.21 (3)	164.4
C17—H17···O2W^iv	0.93	2.41	3.33 (2)	169.3
C18—H18A···O5ⁱⁱⁱ	0.97	2.41	3.18 (2)	136.5
C18—H18B···O5	0.97	2.42	3.19 (2)	136.2

Symmetry codes: (ii) −x+1, −y+1, −z; (iii) −x+2, −y, −z; (iv) x+1, y, z.

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