Polymeric di­aqua­tetra-μ-thio­cyanato-manganese(II)­mercury(II) bis(N,N-di­methyl­acet­amide) solvate

In the title complex, {[MnHg(SCN)₄(H₂O)₂]·2C₄H₉NO}_n, each Mn atom is octahedrally coordinated to four equatorial thio­cyanate N atoms and two axial water O atoms. The Mn atom and two O atoms lie on a twofold axis. Two kinds of crystallographically independent Hg atoms (denoted Hg1 and Hg2) are tetrahedrally coordinated with four thiocyanate S atoms and each Hg atom lies on a axis. N,N-Di­methyl­acet­amide mol­ecules are connected to coordinated water mol­ecules through hydrogen bonds. Each pair of Mn and Hg atoms is bridged via one thiocyanate ion. An Mn₂Hg1Hg2(SCN)₄ 16-membered ring is formed as a unit and the four metal atoms are in a chair-form tetrahedral arrangement. The units are linked with one another and form infinite two-dimensional networks.

Computing details

Data collection: XSCANS (Bruker, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL.

(MMTWD)

Crystal data

[MnHg(SCN)4(H2O)2].2C4H9NO	Dx = 1.916 Mg m^−3
Mr = 698.17	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4	Cell parameters from 35 reflections
Hall symbol: P -4	θ = 5.1–14.4°
a = 12.2436 (6) Å	µ = 7.23 mm^−1
c = 8.0708 (6) Å	T = 293 K
V = 1209.86 (12) Å^3	Tetragonal, colourless
Z = 2	0.35 × 0.30 × 0.25 mm
F(000) = 674

Data collection

Bruker P4 diffractometer	1859 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.027
Graphite monochromator	θmax = 30.0°, θmin = 2.4°
θ/2θ scans	h = −1→17
Absorption correction: ψ scans XSCANS (Bruker, 1996)	k = −1→17
Tmin = 0.094, Tmax = 0.164	l = −1→11
2684 measured reflections	3 standard reflections every 97 reflections
2484 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.033	w = 1/[σ^2(Fo^2) + (0.0296P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.076	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.78 e Å^−3
2484 reflections	Δρmin = −0.71 e Å^−3
137 parameters	Extinction correction: SHELXTL (Bruker, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
2 restraints	Extinction coefficient: 0.0093 (4)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.04 (2)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Hg1	0.0000	0.0000	0.0000	0.03518 (19)
Hg2	0.5000	0.5000	0.0000	0.0375 (2)
Mn1	0.5000	0.0000	0.04203 (13)	0.0287 (2)
S1	0.12116 (19)	0.13464 (18)	0.1524 (4)	0.0577 (8)
S2	0.6154 (2)	0.37695 (18)	0.1799 (5)	0.0723 (10)
O1	0.5000	0.0000	−0.2246 (7)	0.0494 (16)
O2	0.5000	0.0000	0.3157 (7)	0.0472 (15)
O3	0.1159 (5)	0.3758 (5)	0.4606 (6)	0.0597 (16)
N1	0.3270 (5)	0.0583 (5)	0.0518 (12)	0.044 (2)
N2	0.5548 (6)	0.1713 (6)	0.0658 (12)	0.051 (3)
N3	0.2233 (6)	0.2374 (5)	0.5356 (8)	0.0486 (19)
C1	0.2421 (6)	0.0872 (6)	0.0891 (15)	0.038 (2)
C2	0.5777 (7)	0.2562 (7)	0.1121 (15)	0.044 (2)
C3	0.2028 (8)	0.3236 (6)	0.4457 (14)	0.051 (2)
C4	0.2933 (7)	0.3632 (8)	0.3312 (12)	0.079 (3)
H4A	0.3164	0.3043	0.2610	0.119*
H4B	0.3541	0.3882	0.3962	0.119*
H4C	0.2665	0.4222	0.2642	0.119*
C5	0.1348 (7)	0.1968 (7)	0.6383 (11)	0.068 (3)
H5A	0.1588	0.1331	0.6973	0.102*
H5B	0.0736	0.1782	0.5694	0.102*
H5C	0.1135	0.2522	0.7159	0.102*
C6	0.3236 (8)	0.1749 (7)	0.5178 (17)	0.077 (4)
H6A	0.3228	0.1146	0.5939	0.116*
H6B	0.3851	0.2210	0.5412	0.116*
H6C	0.3291	0.1477	0.4065	0.116*
H2	0.453 (6)	−0.042 (7)	0.362 (8)	0.08 (3)*
H1	0.454 (8)	−0.027 (11)	−0.293 (8)	0.11 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Hg1	0.0292 (2)	0.0292 (2)	0.0471 (5)	0.000	0.000	0.000
Hg2	0.0318 (2)	0.0318 (2)	0.0488 (5)	0.000	0.000	0.000
Mn1	0.0301 (10)	0.0227 (9)	0.0333 (6)	−0.0010 (10)	0.000	0.000
S1	0.0351 (11)	0.0581 (12)	0.080 (2)	0.0096 (10)	−0.0144 (13)	−0.0378 (14)
S2	0.1042 (19)	0.0260 (10)	0.087 (2)	−0.0077 (12)	−0.0596 (19)	0.0043 (13)
O1	0.051 (6)	0.066 (7)	0.030 (3)	−0.028 (7)	0.000	0.000
O2	0.039 (6)	0.067 (7)	0.035 (3)	−0.016 (7)	0.000	0.000
O3	0.066 (3)	0.068 (4)	0.045 (3)	0.033 (3)	0.005 (3)	0.006 (3)
N1	0.030 (3)	0.045 (4)	0.059 (7)	−0.006 (3)	−0.004 (4)	−0.007 (5)
N2	0.054 (4)	0.032 (4)	0.065 (8)	−0.016 (4)	−0.008 (5)	0.009 (4)
N3	0.052 (4)	0.049 (4)	0.045 (5)	0.017 (3)	−0.002 (3)	−0.006 (3)
C1	0.027 (4)	0.036 (4)	0.050 (6)	−0.007 (3)	−0.012 (4)	0.004 (4)
C2	0.044 (5)	0.043 (5)	0.044 (5)	−0.009 (4)	−0.016 (4)	0.017 (4)
C3	0.069 (5)	0.035 (4)	0.048 (5)	0.007 (4)	−0.011 (5)	−0.011 (4)
C4	0.079 (6)	0.084 (7)	0.075 (7)	−0.021 (6)	0.023 (6)	0.014 (6)
C5	0.075 (6)	0.067 (5)	0.062 (6)	−0.006 (5)	0.006 (5)	0.022 (5)
C6	0.076 (6)	0.066 (6)	0.090 (9)	0.047 (5)	−0.035 (7)	−0.040 (6)

Geometric parameters (Å, º)

Hg1—S1	2.536 (2)	Mn1—N1^vii	2.236 (6)
Hg1—S1^i	2.536 (2)	Mn1—N1	2.236 (6)
Hg1—S1^ii	2.536 (2)	S1—C1	1.671 (8)
Hg1—S1^iii	2.536 (2)	S2—C2	1.643 (9)
Hg2—S2^iv	2.525 (3)	O3—C3	1.247 (10)
Hg2—S2	2.525 (3)	N1—C1	1.139 (8)
Hg2—S2^v	2.525 (3)	N2—C2	1.139 (9)
Hg2—S2^vi	2.525 (3)	N3—C3	1.304 (10)
Mn1—O1	2.152 (6)	N3—C5	1.452 (9)
Mn1—O2	2.209 (6)	N3—C6	1.455 (9)
Mn1—N2	2.211 (7)	C3—C4	1.523 (13)
Mn1—N2^vii	2.211 (7)
S1—Hg1—S1^i	103.61 (7)	N2—Mn1—N1^vii	90.7 (3)
S1—Hg1—S1^ii	103.61 (7)	N2^vii—Mn1—N1^vii	88.9 (3)
S1^i—Hg1—S1^ii	121.96 (16)	O1—Mn1—N1	92.0 (3)
S1—Hg1—S1^iii	121.96 (16)	O2—Mn1—N1	88.0 (3)
S1^i—Hg1—S1^iii	103.61 (7)	N2—Mn1—N1	88.9 (3)
S1^ii—Hg1—S1^iii	103.61 (7)	N2^vii—Mn1—N1	90.7 (3)
S2^iv—Hg2—S2	109.32 (8)	N1^vii—Mn1—N1	175.9 (5)
S2^iv—Hg2—S2^v	109.78 (17)	C1—S1—Hg1	98.3 (3)
S2—Hg2—S2^v	109.32 (8)	C2—S2—Hg2	100.8 (4)
S2^iv—Hg2—S2^vi	109.32 (8)	C1—N1—Mn1	166.7 (9)
S2—Hg2—S2^vi	109.78 (17)	C2—N2—Mn1	165.6 (10)
S2^v—Hg2—S2^vi	109.32 (8)	C3—N3—C5	116.8 (7)
O1—Mn1—O2	180.0	C3—N3—C6	122.2 (9)
O1—Mn1—N2	95.0 (3)	C5—N3—C6	120.4 (7)
O2—Mn1—N2	85.0 (3)	N1—C1—S1	176.4 (9)
O1—Mn1—N2^vii	95.0 (3)	N2—C2—S2	177.9 (9)
O2—Mn1—N2^vii	85.0 (3)	O3—C3—N3	121.7 (9)
N2—Mn1—N2^vii	170.0 (5)	O3—C3—C4	121.0 (8)
O1—Mn1—N1^vii	92.0 (3)	N3—C3—C4	117.1 (8)
O2—Mn1—N1^vii	88.0 (3)

Symmetry codes: (i) y, −x, −z; (ii) −y, x, −z; (iii) −x, −y, z; (iv) y, −x+1, −z; (v) −y+1, x, −z; (vi) −x+1, −y+1, z; (vii) −x+1, −y, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3^i	0.86 (9)	1.98 (10)	2.820 (7)	166 (11)
O2—H2···O3^viii	0.86 (8)	1.94 (7)	2.754 (7)	158 (7)

Symmetry codes: (i) y, −x, −z; (viii) y, −x, −z+1.