[2,5-Bis(2,2′-bipyridyl-6-yl)-3,4-di­aza­hexa-2,4-diene]di­chlorido­mangan­ese(II): from a mononuclear compound to a three-dimensional supra­molecular framework through C—H...Cl hydrogen bonds and π–π stacking inter­actions

The title compound, [MnCl₂(C₂₄H₂₀N₆)], has been synthesized and characterized based on the multifunctional ligand 2,5-bis­(2,2′-bipyridyl-6-yl)-3,4-di­aza­hexa-2,4-diene (L). The Mn^II centre is five-coordinate with an approximately square-pyramidal geometry. The L ligand acts as a tridendate chelating ligand. The mononuclear mol­ecules are bridged into a one-dimensional chain by two C—H...Cl hydrogen bonds. These chains are assembled into a two-dimensional layer through π–π stacking inter­actions between adjacent uncoordinated bipyridyl groups. Furthermore, a three-dimensional supra­molecular framework is attained through π–π stacking inter­actions between adjacent coordinated bipyridyl groups.

Computing details

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2005) and SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

[2,5-Bis(2,2'-bipyridyl-6-yl)-3,4-diazahexa-2,4-diene]dichloridomanganese(II)

Crystal data

[MnCl2(C24H20N6)]	Z = 2
Mr = 518.30	F(000) = 530
Triclinic, P1	Dx = 1.504 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.5761 (5) Å	Cell parameters from 3657 reflections
b = 8.9118 (6) Å	θ = 1.8–28.1°
c = 16.4088 (9) Å	µ = 0.84 mm^−1
α = 96.192 (5)°	T = 293 K
β = 91.571 (5)°	Block, yellow
γ = 112.971 (6)°	0.43 × 0.32 × 0.21 mm
V = 1144.60 (12) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	4988 independent reflections
Radiation source: fine-focus sealed tube	3957 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
phi and ω scans	θmax = 27.1°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.715, Tmax = 0.844	k = −11→11
12249 measured reflections	l = −21→20

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.094	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0398P)^2 + 0.269P] where P = (Fo^2 + 2Fc^2)/3
4988 reflections	(Δ/σ)max = 0.001
300 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.32 e Å^−3

Special details

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 > 2sigma(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 (Ų)

	x	y	z	Uiso*/Ueq
Mn1	0.78759 (4)	0.86477 (4)	0.15374 (2)	0.03328 (11)
Cl1	0.83218 (8)	0.72832 (8)	0.03265 (4)	0.05034 (17)
Cl2	1.03731 (7)	1.05279 (8)	0.22726 (4)	0.05485 (18)
N1	0.6869 (2)	1.0471 (2)	0.11529 (11)	0.0386 (4)
N2	0.5119 (2)	0.7663 (2)	0.16748 (10)	0.0325 (4)
N3	1.5187 (2)	0.7658 (3)	0.53975 (13)	0.0472 (5)
N4	1.1238 (2)	0.7012 (2)	0.43725 (11)	0.0349 (4)
N5	0.7113 (2)	0.6522 (2)	0.23554 (10)	0.0346 (4)
N6	0.8238 (2)	0.5949 (2)	0.27018 (11)	0.0362 (4)
C1	0.5176 (3)	1.0052 (3)	0.11365 (13)	0.0371 (5)
C2	0.4443 (3)	1.1083 (3)	0.08980 (14)	0.0490 (6)
H2A	0.3273	1.0772	0.0887	0.059*
C3	0.5471 (4)	1.2576 (3)	0.06773 (16)	0.0557 (7)
H3A	0.5001	1.3289	0.0517	0.067*
C4	0.7193 (4)	1.3013 (3)	0.06939 (16)	0.0547 (7)
H4A	0.7907	1.4021	0.0547	0.066*
C5	0.7840 (3)	1.1924 (3)	0.09338 (15)	0.0488 (6)
H5A	0.9008	1.2216	0.0943	0.059*
C6	0.4194 (3)	0.8425 (3)	0.13885 (12)	0.0362 (5)
C7	0.2418 (3)	0.7690 (3)	0.13465 (15)	0.0479 (6)
H7A	0.1771	0.8230	0.1159	0.058*
C8	0.1654 (3)	0.6166 (4)	0.15854 (16)	0.0556 (7)
H8A	0.0476	0.5650	0.1548	0.067*
C9	0.2615 (3)	0.5386 (3)	0.18805 (15)	0.0488 (6)
H9A	0.2100	0.4345	0.2041	0.059*
C10	0.4365 (3)	0.6189 (3)	0.19322 (13)	0.0354 (5)
C11	0.5536 (3)	0.5565 (3)	0.23152 (13)	0.0350 (5)
C12	0.4890 (3)	0.3989 (3)	0.26731 (16)	0.0509 (6)
H12A	0.5679	0.3472	0.2603	0.076*
H12B	0.3809	0.3276	0.2399	0.076*
H12C	0.4764	0.4203	0.3248	0.076*
C13	1.3679 (3)	0.7755 (3)	0.53166 (13)	0.0364 (5)
C14	1.3289 (3)	0.8909 (3)	0.57955 (15)	0.0506 (6)
H14A	1.2232	0.8958	0.5719	0.061*
C15	1.4475 (4)	0.9985 (3)	0.63863 (17)	0.0603 (7)
H15A	1.4222	1.0751	0.6726	0.072*
C16	1.6039 (3)	0.9915 (3)	0.64691 (16)	0.0540 (7)
H16A	1.6875	1.0638	0.6859	0.065*
C17	1.6328 (3)	0.8755 (3)	0.59629 (17)	0.0524 (7)
H17A	1.7397	0.8723	0.6014	0.063*
C18	1.2423 (3)	0.6553 (3)	0.46790 (13)	0.0354 (5)
C19	1.2477 (3)	0.5049 (3)	0.44196 (14)	0.0439 (6)
H19A	1.3313	0.4759	0.4641	0.053*
C20	1.1268 (3)	0.3989 (3)	0.38278 (15)	0.0486 (6)
H20A	1.1258	0.2954	0.3659	0.058*
C21	1.0079 (3)	0.4461 (3)	0.34875 (14)	0.0418 (5)
H21A	0.9273	0.3773	0.3076	0.050*
C22	1.0118 (3)	0.5996 (3)	0.37778 (12)	0.0338 (5)
C23	0.8898 (3)	0.6617 (3)	0.34265 (13)	0.0351 (5)
C24	0.8527 (3)	0.7912 (3)	0.39300 (14)	0.0500 (6)
H24A	0.8653	0.8791	0.3612	0.075*
H24B	0.9305	0.8329	0.4411	0.075*
H24C	0.7385	0.7453	0.4091	0.075*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.02291 (17)	0.03437 (19)	0.0404 (2)	0.00969 (13)	−0.00259 (13)	0.00334 (14)
Cl1	0.0534 (4)	0.0571 (4)	0.0457 (3)	0.0289 (3)	0.0036 (3)	0.0012 (3)
Cl2	0.0396 (3)	0.0465 (4)	0.0632 (4)	0.0046 (3)	−0.0173 (3)	−0.0027 (3)
N1	0.0334 (10)	0.0389 (11)	0.0434 (11)	0.0148 (8)	−0.0029 (8)	0.0048 (8)
N2	0.0252 (9)	0.0402 (10)	0.0313 (9)	0.0129 (8)	−0.0009 (7)	0.0017 (8)
N3	0.0411 (11)	0.0517 (12)	0.0546 (13)	0.0241 (10)	−0.0043 (9)	0.0102 (10)
N4	0.0348 (10)	0.0377 (10)	0.0363 (10)	0.0187 (8)	0.0012 (8)	0.0058 (8)
N5	0.0307 (9)	0.0370 (10)	0.0349 (10)	0.0120 (8)	−0.0029 (7)	0.0059 (8)
N6	0.0322 (9)	0.0376 (10)	0.0393 (10)	0.0143 (8)	−0.0012 (8)	0.0064 (8)
C1	0.0373 (12)	0.0455 (13)	0.0313 (11)	0.0219 (10)	−0.0055 (9)	−0.0035 (10)
C2	0.0512 (15)	0.0592 (17)	0.0452 (14)	0.0344 (13)	−0.0094 (11)	−0.0028 (12)
C3	0.0754 (19)	0.0559 (17)	0.0487 (15)	0.0430 (15)	−0.0153 (13)	−0.0016 (13)
C4	0.0729 (19)	0.0394 (14)	0.0490 (15)	0.0201 (13)	−0.0097 (13)	0.0055 (12)
C5	0.0449 (14)	0.0429 (14)	0.0551 (15)	0.0138 (11)	−0.0061 (11)	0.0081 (12)
C6	0.0299 (11)	0.0504 (14)	0.0304 (11)	0.0201 (10)	−0.0020 (9)	−0.0010 (10)
C7	0.0307 (12)	0.0710 (18)	0.0451 (14)	0.0256 (12)	−0.0052 (10)	0.0008 (12)
C8	0.0236 (12)	0.078 (2)	0.0557 (16)	0.0100 (12)	0.0008 (11)	0.0091 (14)
C9	0.0293 (12)	0.0608 (16)	0.0455 (14)	0.0053 (11)	0.0030 (10)	0.0101 (12)
C10	0.0272 (11)	0.0433 (13)	0.0300 (11)	0.0085 (9)	0.0014 (8)	0.0022 (9)
C11	0.0319 (11)	0.0370 (12)	0.0320 (11)	0.0091 (9)	0.0022 (9)	0.0042 (9)
C12	0.0430 (14)	0.0439 (14)	0.0607 (16)	0.0089 (11)	0.0071 (12)	0.0170 (12)
C13	0.0383 (12)	0.0402 (13)	0.0344 (12)	0.0189 (10)	−0.0018 (9)	0.0081 (10)
C14	0.0455 (14)	0.0562 (16)	0.0542 (15)	0.0287 (12)	−0.0094 (12)	−0.0063 (12)
C15	0.0660 (18)	0.0606 (18)	0.0563 (17)	0.0334 (15)	−0.0131 (14)	−0.0116 (14)
C16	0.0543 (16)	0.0477 (15)	0.0510 (15)	0.0116 (12)	−0.0158 (12)	0.0075 (12)
C17	0.0391 (13)	0.0543 (16)	0.0648 (17)	0.0185 (12)	−0.0106 (12)	0.0157 (14)
C18	0.0367 (12)	0.0428 (13)	0.0326 (11)	0.0214 (10)	0.0038 (9)	0.0076 (10)
C19	0.0491 (14)	0.0480 (14)	0.0450 (13)	0.0306 (12)	−0.0006 (11)	0.0062 (11)
C20	0.0632 (16)	0.0437 (14)	0.0493 (15)	0.0336 (13)	0.0001 (12)	0.0017 (12)
C21	0.0455 (13)	0.0428 (13)	0.0395 (13)	0.0211 (11)	−0.0026 (10)	0.0018 (10)
C22	0.0339 (11)	0.0379 (12)	0.0325 (11)	0.0167 (9)	0.0046 (9)	0.0067 (9)
C23	0.0311 (11)	0.0375 (12)	0.0384 (12)	0.0147 (9)	0.0033 (9)	0.0071 (10)
C24	0.0574 (16)	0.0623 (17)	0.0419 (14)	0.0394 (14)	−0.0056 (12)	−0.0035 (12)

Geometric parameters (Å, º)

Mn1—N1	2.2519 (17)	C8—H8A	0.9300
Mn1—N2	2.2058 (16)	C9—C10	1.383 (3)
Mn1—N5	2.3338 (17)	C9—H9A	0.9300
Mn1—Cl1	2.3358 (7)	C10—C11	1.480 (3)
Mn1—Cl2	2.3391 (7)	C11—C12	1.487 (3)
N1—C5	1.332 (3)	C12—H12A	0.9600
N1—C1	1.350 (3)	C12—H12B	0.9600
N2—C6	1.334 (3)	C12—H12C	0.9600
N2—C10	1.339 (3)	C13—C14	1.377 (3)
N3—C13	1.333 (3)	C13—C18	1.483 (3)
N3—C17	1.335 (3)	C14—C15	1.370 (4)
N4—C22	1.332 (3)	C14—H14A	0.9300
N4—C18	1.339 (2)	C15—C16	1.371 (4)
N5—C11	1.283 (3)	C15—H15A	0.9300
N5—N6	1.390 (2)	C16—C17	1.359 (4)
N6—C23	1.279 (3)	C16—H16A	0.9300
C1—C2	1.381 (3)	C17—H17A	0.9300
C1—C6	1.476 (3)	C18—C19	1.381 (3)
C2—C3	1.373 (4)	C19—C20	1.376 (3)
C2—H2A	0.9300	C19—H19A	0.9300
C3—C4	1.371 (4)	C20—C21	1.372 (3)
C3—H3A	0.9300	C20—H20A	0.9300
C4—C5	1.377 (3)	C21—C22	1.387 (3)
C4—H4A	0.9300	C21—H21A	0.9300
C5—H5A	0.9300	C22—C23	1.491 (3)
C6—C7	1.399 (3)	C23—C24	1.487 (3)
C7—C8	1.365 (4)	C24—H24A	0.9600
C7—H7A	0.9300	C24—H24B	0.9600
C8—C9	1.376 (4)	C24—H24C	0.9600
N1—Mn1—N2	71.90 (7)	N2—C10—C11	114.95 (17)
N1—Mn1—N5	138.36 (7)	C9—C10—C11	123.7 (2)
N2—Mn1—N5	69.49 (6)	N5—C11—C10	115.11 (19)
N1—Mn1—Cl1	106.34 (5)	N5—C11—C12	123.34 (19)
N2—Mn1—Cl1	107.70 (5)	C10—C11—C12	121.43 (19)
N5—Mn1—Cl1	99.73 (5)	C11—C12—H12A	109.5
N1—Mn1—Cl2	97.77 (5)	C11—C12—H12B	109.5
N2—Mn1—Cl2	138.17 (5)	H12A—C12—H12B	109.5
N5—Mn1—Cl2	100.53 (5)	C11—C12—H12C	109.5
Cl1—Mn1—Cl2	114.07 (3)	H12A—C12—H12C	109.5
C5—N1—C1	118.32 (19)	H12B—C12—H12C	109.5
C5—N1—Mn1	123.99 (15)	N3—C13—C14	122.3 (2)
C1—N1—Mn1	117.70 (15)	N3—C13—C18	116.75 (19)
C6—N2—C10	120.60 (18)	C14—C13—C18	120.92 (19)
C6—N2—Mn1	119.37 (15)	C15—C14—C13	119.3 (2)
C10—N2—Mn1	119.29 (13)	C15—C14—H14A	120.4
C13—N3—C17	116.8 (2)	C13—C14—H14A	120.4
C22—N4—C18	118.27 (18)	C14—C15—C16	119.1 (2)
C11—N5—N6	116.08 (17)	C14—C15—H15A	120.5
C11—N5—Mn1	116.89 (13)	C16—C15—H15A	120.5
N6—N5—Mn1	124.71 (12)	C17—C16—C15	117.9 (2)
C23—N6—N5	116.58 (17)	C17—C16—H16A	121.1
N1—C1—C2	121.7 (2)	C15—C16—H16A	121.1
N1—C1—C6	114.86 (18)	N3—C17—C16	124.6 (2)
C2—C1—C6	123.4 (2)	N3—C17—H17A	117.7
C3—C2—C1	118.9 (2)	C16—C17—H17A	117.7
C3—C2—H2A	120.6	N4—C18—C19	122.2 (2)
C1—C2—H2A	120.6	N4—C18—C13	116.17 (18)
C4—C3—C2	119.8 (2)	C19—C18—C13	121.65 (18)
C4—C3—H3A	120.1	C20—C19—C18	118.7 (2)
C2—C3—H3A	120.1	C20—C19—H19A	120.6
C3—C4—C5	118.4 (2)	C18—C19—H19A	120.6
C3—C4—H4A	120.8	C21—C20—C19	119.8 (2)
C5—C4—H4A	120.8	C21—C20—H20A	120.1
N1—C5—C4	122.9 (2)	C19—C20—H20A	120.1
N1—C5—H5A	118.5	C20—C21—C22	117.9 (2)
C4—C5—H5A	118.5	C20—C21—H21A	121.1
N2—C6—C7	120.5 (2)	C22—C21—H21A	121.1
N2—C6—C1	115.30 (18)	N4—C22—C21	123.04 (19)
C7—C6—C1	124.2 (2)	N4—C22—C23	115.78 (18)
C8—C7—C6	118.7 (2)	C21—C22—C23	121.2 (2)
C8—C7—H7A	120.6	N6—C23—C24	125.52 (19)
C6—C7—H7A	120.6	N6—C23—C22	115.43 (18)
C7—C8—C9	120.5 (2)	C24—C23—C22	119.05 (19)
C7—C8—H8A	119.7	C23—C24—H24A	109.5
C9—C8—H8A	119.7	C23—C24—H24B	109.5
C8—C9—C10	118.4 (2)	H24A—C24—H24B	109.5
C8—C9—H9A	120.8	C23—C24—H24C	109.5
C10—C9—H9A	120.8	H24A—C24—H24C	109.5
N2—C10—C9	121.2 (2)	H24B—C24—H24C	109.5
N2—Mn1—N1—C5	176.3 (2)	C1—C6—C7—C8	178.9 (2)
N5—Mn1—N1—C5	153.50 (17)	C6—C7—C8—C9	1.6 (4)
Cl1—Mn1—N1—C5	−80.01 (19)	C7—C8—C9—C10	0.3 (4)
Cl2—Mn1—N1—C5	37.96 (19)	C6—N2—C10—C9	2.5 (3)
N2—Mn1—N1—C1	−4.48 (15)	Mn1—N2—C10—C9	−167.65 (17)
N5—Mn1—N1—C1	−27.2 (2)	C6—N2—C10—C11	−173.82 (18)
Cl1—Mn1—N1—C1	99.26 (15)	Mn1—N2—C10—C11	16.1 (2)
Cl2—Mn1—N1—C1	−142.77 (15)	C8—C9—C10—N2	−2.4 (4)
N1—Mn1—N2—C6	8.31 (15)	C8—C9—C10—C11	173.6 (2)
N5—Mn1—N2—C6	172.38 (17)	N6—N5—C11—C10	−179.06 (17)
Cl1—Mn1—N2—C6	−93.61 (15)	Mn1—N5—C11—C10	−15.5 (2)
Cl2—Mn1—N2—C6	89.58 (16)	N6—N5—C11—C12	4.9 (3)
N1—Mn1—N2—C10	178.55 (17)	Mn1—N5—C11—C12	168.42 (17)
N5—Mn1—N2—C10	−17.38 (15)	N2—C10—C11—N5	0.5 (3)
Cl1—Mn1—N2—C10	76.64 (15)	C9—C10—C11—N5	−175.7 (2)
Cl2—Mn1—N2—C10	−100.18 (16)	N2—C10—C11—C12	176.6 (2)
N2—Mn1—N5—C11	17.58 (15)	C9—C10—C11—C12	0.4 (3)
N1—Mn1—N5—C11	40.7 (2)	C17—N3—C13—C14	−0.8 (3)
Cl1—Mn1—N5—C11	−87.80 (16)	C17—N3—C13—C18	179.0 (2)
Cl2—Mn1—N5—C11	155.28 (15)	N3—C13—C14—C15	−1.1 (4)
N2—Mn1—N5—N6	179.53 (17)	C18—C13—C14—C15	179.1 (2)
N1—Mn1—N5—N6	−157.36 (14)	C13—C14—C15—C16	1.9 (4)
Cl1—Mn1—N5—N6	74.14 (15)	C14—C15—C16—C17	−0.9 (4)
Cl2—Mn1—N5—N6	−42.77 (16)	C13—N3—C17—C16	1.9 (4)
C11—N5—N6—C23	−106.2 (2)	C15—C16—C17—N3	−1.1 (4)
Mn1—N5—N6—C23	91.7 (2)	C22—N4—C18—C19	−2.4 (3)
C5—N1—C1—C2	0.2 (3)	C22—N4—C18—C13	177.71 (18)
Mn1—N1—C1—C2	−179.11 (16)	N3—C13—C18—N4	−154.5 (2)
C5—N1—C1—C6	−180.0 (2)	C14—C13—C18—N4	25.4 (3)
Mn1—N1—C1—C6	0.7 (2)	N3—C13—C18—C19	25.6 (3)
N1—C1—C2—C3	−0.4 (3)	C14—C13—C18—C19	−154.6 (2)
C6—C1—C2—C3	179.8 (2)	N4—C18—C19—C20	−0.1 (3)
C1—C2—C3—C4	0.2 (4)	C13—C18—C19—C20	179.8 (2)
C2—C3—C4—C5	0.1 (4)	C18—C19—C20—C21	2.3 (4)
C1—N1—C5—C4	0.1 (4)	C19—C20—C21—C22	−1.9 (4)
Mn1—N1—C5—C4	179.41 (18)	C18—N4—C22—C21	2.8 (3)
C3—C4—C5—N1	−0.3 (4)	C18—N4—C22—C23	−176.42 (18)
C10—N2—C6—C7	−0.5 (3)	C20—C21—C22—N4	−0.7 (3)
Mn1—N2—C6—C7	169.65 (16)	C20—C21—C22—C23	178.5 (2)
C10—N2—C6—C1	179.11 (18)	N5—N6—C23—C24	1.6 (3)
Mn1—N2—C6—C1	−10.8 (2)	N5—N6—C23—C22	−179.15 (17)
N1—C1—C6—N2	6.4 (3)	N4—C22—C23—N6	157.11 (19)
C2—C1—C6—N2	−173.8 (2)	C21—C22—C23—N6	−22.2 (3)
N1—C1—C6—C7	−174.1 (2)	N4—C22—C23—C24	−23.6 (3)
C2—C1—C6—C7	5.8 (3)	C21—C22—C23—C24	157.1 (2)
N2—C6—C7—C8	−1.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···Cl1^i	0.93	2.85	3.665 (3)	147
C20—H20A···Cl2^ii	0.93	2.83	3.600 (3)	141

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