Bis(2,2'-bipyridine N,N'-dioxide)bis-(tri-cyano-methanido)manganese(II).

In the title complex, [Mn(C(4)N(3))(2)(C(10)H(8)N(2)O(2))(2)], the Mn(II) atom lies on an inversion center and is coordinated by two 2,2'-bipyridine N,N'-dioxide (dpdo) mol-ecules and two tricyano-methanide (tcm) ligands to form a distorted octa-hedral geometry. Weak inter-molecular C-H⋯O or C-H⋯N hydrogen bonds, involving either the O atom of the dpdo mol-ecule and the pyridyl H atom, or the N atom of the tcm anion and the pyridyl H atom, result in the formation of a three-dimensional network structure.

Related literature

For studies of other coordination polymers constructed with tcm, exhibiting a variety of structures, see: Batten & Murray (2003 ▶); Miller & Manson (2001 ▶); Feyerherm et al. (2003 ▶, 2004 ▶); Abrahams et al. (2003 ▶); Manson et al. (1998 ▶, 2000 ▶); Hoshino et al. (1999 ▶); Batten et al. (1998 ▶, 1999 ▶, 2000 ▶); Manson & Schlueter (2004 ▶). For work on manganese–nitroxide complexes, see: Liu et al. (2001 ▶).

Experimental

Crystal data

[Mn(C4N3)2(C10H8N2O2)2]

M = 611.45

Monoclinic,

a = 11.514 (4) Å

b = 16.101 (5) Å

c = 7.143 (2) Å

β = 94.375 (4)°

V = 1320.4 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.56 mm−1

T = 293 K

0.20 × 0.16 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.893, T max = 0.937

6266 measured reflections

2834 independent reflections

1969 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.071

S = 0.90

2834 reflections

196 parameters

H-atom parameters constrained

Δρmax = 0.28 e Å−3

Δρmin = −0.35 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT-Plus (Bruker, 2000 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809013828/dn2445sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809013828/dn2445Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Mn(C4N3)2(C10H8N2O2)2]	F(000) = 622
Mr = 611.45	Dx = 1.538 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 954 reflections
a = 11.514 (4) Å	θ = 3.1–24.8°
b = 16.101 (5) Å	µ = 0.56 mm−1
c = 7.143 (2) Å	T = 293 K
β = 94.375 (4)°	Block, yellow
V = 1320.4 (7) Å3	0.20 × 0.16 × 0.10 mm
Z = 2

Bruker SMART CCD area-detector diffractometer	2834 independent reflections
Radiation source: fine-focus sealed tube	1969 reflections with I > 2σ(I)
graphite	Rint = 0.034
φ and ω scans	θmax = 27.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
Tmin = 0.893, Tmax = 0.937	k = −20→20
6266 measured reflections	l = −5→8

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.071	H-atom parameters constrained
S = 0.90	w = 1/[σ2(Fo2) + (0.0269P)2] where P = (Fo2 + 2Fc2)/3
2834 reflections	(Δ/σ)max < 0.001
196 parameters	Δρmax = 0.28 e Å−3
0 restraints	Δρmin = −0.34 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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.

	x	y	z	Uiso*/Ueq
Mn1	0.5000	0.5000	0.5000	0.02993 (12)
N1	0.64563 (12)	0.36945 (9)	0.7192 (2)	0.0332 (4)
N2	0.41397 (12)	0.43113 (9)	0.8531 (2)	0.0295 (3)
N3	0.67180 (13)	0.55973 (10)	0.5796 (2)	0.0455 (4)
N4	1.03850 (17)	0.50470 (13)	0.7829 (3)	0.0790 (7)
N5	0.96600 (16)	0.72092 (13)	0.4362 (3)	0.0662 (6)
O1	0.57417 (10)	0.37808 (7)	0.56602 (18)	0.0372 (3)
O2	0.46743 (10)	0.49721 (7)	0.78936 (16)	0.0324 (3)
C1	0.76219 (16)	0.36510 (12)	0.7024 (3)	0.0438 (5)
H1	0.7909	0.3727	0.5854	0.053*
C2	0.83767 (17)	0.34971 (12)	0.8549 (4)	0.0508 (6)
H2	0.9172	0.3464	0.8412	0.061*
C3	0.79652 (17)	0.33917 (12)	1.0283 (3)	0.0476 (5)
H3	0.8473	0.3280	1.1327	0.057*
C4	0.67888 (16)	0.34541 (11)	1.0448 (3)	0.0413 (5)
H4	0.6499	0.3388	1.1619	0.050*
C5	0.60310 (15)	0.36128 (10)	0.8902 (3)	0.0326 (4)
C6	0.47602 (15)	0.36233 (11)	0.9049 (3)	0.0306 (4)
C7	0.42058 (17)	0.29644 (12)	0.9818 (3)	0.0407 (5)
H7	0.4629	0.2493	1.0191	0.049*
C8	0.30314 (17)	0.29968 (13)	1.0040 (3)	0.0456 (5)
H8	0.2659	0.2555	1.0580	0.055*
C9	0.24191 (16)	0.36896 (12)	0.9453 (3)	0.0416 (5)
H9	0.1621	0.3716	0.9566	0.050*
C10	0.29796 (15)	0.43425 (12)	0.8701 (3)	0.0356 (5)
H10	0.2560	0.4812	0.8304	0.043*
C11	0.88681 (16)	0.59756 (12)	0.6110 (3)	0.0400 (5)
C12	0.76883 (17)	0.57701 (12)	0.5935 (3)	0.0375 (5)
C13	0.96832 (18)	0.54529 (14)	0.7082 (3)	0.0510 (6)
C14	0.92869 (16)	0.66597 (14)	0.5135 (3)	0.0457 (6)

	U11	U22	U33	U12	U13	U23
Mn1	0.0255 (2)	0.0319 (2)	0.0322 (2)	−0.00346 (17)	0.00101 (17)	0.00237 (19)
N1	0.0290 (8)	0.0270 (8)	0.0434 (10)	0.0017 (7)	0.0015 (8)	−0.0001 (7)
N2	0.0299 (8)	0.0302 (9)	0.0283 (8)	−0.0011 (7)	0.0022 (7)	0.0002 (7)
N3	0.0343 (9)	0.0523 (11)	0.0488 (11)	−0.0114 (8)	−0.0041 (8)	0.0086 (9)
N4	0.0531 (12)	0.0831 (16)	0.0977 (18)	0.0124 (12)	−0.0146 (12)	0.0026 (14)
N5	0.0501 (12)	0.0682 (14)	0.0823 (16)	−0.0136 (10)	0.0188 (11)	0.0018 (12)
O1	0.0382 (7)	0.0355 (7)	0.0373 (8)	0.0019 (6)	−0.0017 (6)	−0.0017 (6)
O2	0.0357 (7)	0.0273 (7)	0.0346 (7)	−0.0034 (6)	0.0051 (6)	0.0036 (6)
C1	0.0307 (11)	0.0434 (12)	0.0586 (14)	0.0050 (9)	0.0128 (11)	0.0003 (11)
C2	0.0276 (10)	0.0438 (13)	0.0807 (18)	0.0037 (9)	0.0020 (12)	0.0016 (12)
C3	0.0373 (12)	0.0405 (12)	0.0627 (15)	0.0046 (9)	−0.0111 (11)	0.0025 (11)
C4	0.0406 (12)	0.0356 (11)	0.0469 (13)	0.0032 (9)	−0.0019 (10)	0.0042 (10)
C5	0.0317 (10)	0.0250 (10)	0.0410 (12)	0.0016 (8)	0.0020 (9)	0.0013 (9)
C6	0.0296 (9)	0.0294 (10)	0.0324 (11)	0.0008 (8)	0.0002 (8)	0.0029 (8)
C7	0.0409 (11)	0.0327 (11)	0.0481 (13)	−0.0008 (9)	0.0019 (10)	0.0098 (10)
C8	0.0415 (12)	0.0456 (13)	0.0502 (13)	−0.0103 (10)	0.0081 (11)	0.0087 (11)
C9	0.0291 (10)	0.0533 (13)	0.0430 (12)	−0.0048 (10)	0.0074 (9)	−0.0001 (11)
C10	0.0288 (10)	0.0435 (12)	0.0346 (11)	0.0061 (9)	0.0018 (9)	−0.0014 (9)
C11	0.0265 (10)	0.0460 (12)	0.0473 (13)	−0.0047 (9)	0.0019 (9)	−0.0035 (10)
C12	0.0376 (11)	0.0382 (12)	0.0360 (12)	−0.0024 (9)	−0.0011 (9)	−0.0021 (9)
C13	0.0349 (12)	0.0564 (14)	0.0612 (16)	−0.0020 (11)	0.0008 (11)	−0.0109 (12)
C14	0.0249 (10)	0.0566 (15)	0.0558 (15)	−0.0023 (10)	0.0056 (10)	−0.0099 (12)

Mn1—O2	2.1291 (13)	C2—H2	0.9300
Mn1—O2i	2.1291 (13)	C3—C4	1.372 (3)
Mn1—O1i	2.1780 (13)	C3—H3	0.9300
Mn1—O1	2.1780 (13)	C4—C5	1.378 (3)
Mn1—N3i	2.2337 (17)	C4—H4	0.9300
Mn1—N3	2.2337 (17)	C5—C6	1.475 (2)
N1—O1	1.3252 (19)	C6—C7	1.374 (2)
N1—C5	1.356 (2)	C7—C8	1.374 (3)
N1—C1	1.358 (2)	C7—H7	0.9300
N2—O2	1.3269 (16)	C8—C9	1.368 (3)
N2—C10	1.351 (2)	C8—H8	0.9300
N2—C6	1.354 (2)	C9—C10	1.365 (2)
N3—C12	1.148 (2)	C9—H9	0.9300
N4—C13	1.140 (3)	C10—H10	0.9300
N5—C14	1.144 (2)	C11—C12	1.394 (2)
C1—C2	1.363 (3)	C11—C13	1.404 (3)
C1—H1	0.9300	C11—C14	1.408 (3)
C2—C3	1.370 (3)
O2—Mn1—O2i	180.0	C2—C3—C4	118.7 (2)
O2—Mn1—O1i	97.70 (4)	C2—C3—H3	120.6
O2i—Mn1—O1i	82.30 (4)	C4—C3—H3	120.6
O2—Mn1—O1	82.30 (4)	C3—C4—C5	120.9 (2)
O2i—Mn1—O1	97.70 (4)	C3—C4—H4	119.6
O1i—Mn1—O1	180.0	C5—C4—H4	119.6
O2—Mn1—N3i	91.14 (5)	N1—C5—C4	119.32 (16)
O2i—Mn1—N3i	88.86 (5)	N1—C5—C6	119.42 (17)
O1i—Mn1—N3i	90.45 (6)	C4—C5—C6	121.05 (18)
O1—Mn1—N3i	89.55 (6)	N2—C6—C7	119.30 (16)
O2—Mn1—N3	88.86 (5)	N2—C6—C5	119.70 (15)
O2i—Mn1—N3	91.14 (5)	C7—C6—C5	120.87 (17)
O1i—Mn1—N3	89.55 (6)	C6—C7—C8	120.52 (18)
O1—Mn1—N3	90.45 (6)	C6—C7—H7	119.7
N3i—Mn1—N3	180.00 (8)	C8—C7—H7	119.7
O1—N1—C5	120.64 (14)	C9—C8—C7	118.95 (18)
O1—N1—C1	119.20 (17)	C9—C8—H8	120.5
C5—N1—C1	120.09 (17)	C7—C8—H8	120.5
O2—N2—C10	119.25 (14)	C10—C9—C8	120.03 (18)
O2—N2—C6	120.05 (14)	C10—C9—H9	120.0
C10—N2—C6	120.68 (15)	C8—C9—H9	120.0
C12—N3—Mn1	164.42 (17)	N2—C10—C9	120.47 (18)
N1—O1—Mn1	118.80 (10)	N2—C10—H10	119.8
N2—O2—Mn1	118.06 (10)	C9—C10—H10	119.8
N1—C1—C2	120.8 (2)	C12—C11—C13	120.78 (19)
N1—C1—H1	119.6	C12—C11—C14	120.63 (18)
C2—C1—H1	119.6	C13—C11—C14	118.19 (17)
C1—C2—C3	120.09 (19)	N3—C12—C11	179.7 (2)
C1—C2—H2	120.0	N4—C13—C11	176.8 (2)
C3—C2—H2	120.0	N5—C14—C11	178.0 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1ii	0.93	2.43	3.350 (2)	171
C10—H10···N4iii	0.93	2.53	3.212 (3)	130

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O1i	0.93	2.43	3.350 (2)	171
C10—H10⋯N4ii	0.93	2.53	3.212 (3)	130

Symmetry codes: (i) ; (ii) .