Di-μ-bromo-bis­{bromo­[N-(8-quinol­yl)-o-phenyl­enediamine-κ³N,N′,N′′]manganese(II)}

The title compound, [Mn₂Br₄(C₁₅H₁₃N₃)₂], is the first crystallographically characterized metal complex of the N-(8-quinol­yl)-o-phenyl­ene­diamine ligand. The centre of the mol­ecule lies on a crystallographic inversion centre, so the Mn₂(μ-Br)₂ four-membered ring is planar with Mn—Br bond lengths of 2.6210 (5) and 2.7147 (6) Å.

Key indicators

• Single-crystal X-ray study
• T = 120 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.033
• wR factor = 0.071
• Data-to-parameter ratio = 20.2

checkCIF/PLATON results

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Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.96
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N3     -   H3B    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N3     -   H3C    ...          ?

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
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   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
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S1. Comment

Although the tridentate ligand N-(8-quinolyl)-o-phenylendiamine (8-Q-phen) has been known for a long time (Jensen & Nielsen, 1964), no crystallographic data of any metal complex of this ligand have been published; the title compound, (I) (Fig. 1), represents the first example of this type. The centre of the molecule lies on a crystallographic inversion centre, so that the Mn₂Br₂ ring is planar. The Mn atom has a slightly distorted octahedral coordination involving the two bromide bridges, a terminal bromide and the three N-atom donors from an 8-Q-phen ligand with each N atom trans to a Br⁻ anion. Similar XM(µ₂-X)₂MX core geometries are known, for example, Cambridge Structural Database (CSD; Allen, 2002) refcodes AZULOW (Wu et al., 2004), QAMBEM (Davies et al., 2004) and QEMREF (Romero et al., 2001).

As in the crystal structure of the free ligand (Seshadri et al., 2004), (II), the mean planes of the quinolyl system (atoms N1/C1–C9) and the benzene ring (atoms C10–C15) are almost perpendicular, with a dihedral angle of 71.57 (8)° between the planes. In the Mn₂Br₂ four-membered ring, the alternating Mn—Br distances are 2.6210 (5) and 2.7147 (6) Å (Table 1). For the terminal Br atom (Br2), the Mn1—Br2 bond length is, as expected, shorter [2.6096 (6) Å]. In other complexes exhibiting Mn–µ-Br units, the corresponding distances range from 2.581 Å (fourfold Mn coordination in GAYWIM; Pohl et al., 1988) to 2.753 Å (sixfold coordination in XEJFIB; Gillon et al., 2000); the terminal Mn—Br bonds in these compounds are 2.456 and 2.645 Å, respectively. In (I), the Mn—N(amine) bond length [2.340 (2) Å] is considerably longer than the Mn—N(quinolyl) bond [2.245 (2) Å], which is trans to the long Mn—µ-Br bond.

In the ligand, the C—N bond lengths in (I) (Table 1) and (II) are slightly different for atoms N2 [1.448 (4)/1.460 (4) Å in (I) versus 1.384/1.425 Å in (II)] and N3 [1.439 (4) Å in (I) versus 1.381 (3) Å in (II)]. The C—N distances for quinolyl atom N1 are, however, essentially the same in (I) and (II). The crystal packing (Fig. 2) displays an intermolecular N2—H2···Br2ⁱⁱ hydrogen bond [symmetry code: (ii) −x + 1, −y + 1, −z + 2], with H···Br = 2.68 Å and N—H···Br = 152° (values corrected for N—H = 1.03 Å), running along the [010] direction.

S2. Experimental

The title compound was obtained by the reaction of equimolar amounts of MnBr₂ (0.5 mmol) and 8-Q-phen in acetonitrile (15 ml). This solution was stirred for 30 min, refluxed for a further 30 min and then filtered; the Mn complex was crystallized using the vapor pressure equalization method in the presence of diethyl ether. IR (KBr, cm⁻¹): ν strong 1498, 1380, 953, 831, 800, 777, 757; medium 3321, 3257, 3186, 1563, 1458, 1311, 1245, 1198, 1085, 1066, 902, 867, 744, 705, 511, 490.

S3. Refinement

The H atoms were positioned geometrically and allowed to ride on their parent atoms, with N—H = 0.92–0.93 Å, C—H = 0.95 Å and U_iso = 1.2U_eq(parent atom).

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SMART; data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXTL (Bruker, 2002); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. View of (I), showing the atom labeling scheme and displacement ellipsoids at the 50% probability level. Unlabelled atoms (and atoms marked by letter A) are related to the labelled atoms by the symmetry operator (1 − x, −y, 2 − z).
	Fig. 2. The crystal packing viewed approximately along the c axis. The intermolecular hydrogen bonds are shown as dashed lines. H atoms not involved in bridging have been omitted.

Di-µ-bromo-bis{bromo[N-(8-quinolyl)-o-phenylenediamine- κ³N,N',N'']manganese(II)}

Crystal data

[Mn2Br4(C15H13N3)2]	Z = 1
Mr = 900.09	F(000) = 438
Triclinic, P1	Dx = 1.932 Mg m^−3
a = 8.8833 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.8725 (8) Å	Cell parameters from 2034 reflections
c = 9.9162 (8) Å	θ = 2.5–24.9°
α = 103.055 (2)°	µ = 6.01 mm^−1
β = 110.397 (2)°	T = 120 K
γ = 97.351 (2)°	Prism, colourless
V = 773.45 (11) Å^3	0.20 × 0.10 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3837 independent reflections
Radiation source: sealed tube	3167 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
ϕ and ω scans	θmax = 28.3°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −11→11
Tmin = 0.379, Tmax = 0.645	k = −13→13
10807 measured reflections	l = −13→13

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)] = 0.033	Hydrogen site location: difference Fourier map
wR(F^2) = 0.071	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0281P)^2] where P = (Fo^2 + 2Fc^2)/3
3837 reflections	(Δ/σ)max = 0.002
190 parameters	Δρmax = 0.59 e Å^−3
0 restraints	Δρmin = −0.47 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.28160 (3)	0.01963 (3)	0.90887 (3)	0.01656 (8)
Br2	0.59253 (4)	0.36823 (3)	1.17982 (3)	0.02113 (9)
Mn1	0.58697 (5)	0.16284 (5)	0.95876 (5)	0.01370 (11)
N1	0.8275 (3)	0.2578 (3)	0.9531 (3)	0.0144 (5)
N2	0.5193 (3)	0.2896 (3)	0.7812 (3)	0.0151 (5)
H2	0.4825	0.3682	0.8183	0.018*
N3	0.5192 (3)	0.0058 (3)	0.7201 (3)	0.0171 (5)
H3B	0.6089	0.0116	0.6938	0.020*
H3C	0.4854	−0.0867	0.7189	0.020*
C1	0.9749 (4)	0.2481 (3)	1.0410 (4)	0.0199 (7)
H1A	0.9813	0.2026	1.1170	0.024*
C2	1.1225 (4)	0.3014 (3)	1.0284 (4)	0.0203 (7)
H2A	1.2253	0.2935	1.0955	0.024*
C3	1.1154 (4)	0.3640 (3)	0.9190 (4)	0.0214 (7)
H3A	1.2138	0.4001	0.9084	0.026*
C4	0.9613 (4)	0.3757 (3)	0.8202 (3)	0.0171 (6)
C5	0.9439 (4)	0.4379 (3)	0.7020 (4)	0.0229 (7)
H5A	1.0385	0.4731	0.6853	0.027*
C6	0.7920 (4)	0.4478 (3)	0.6117 (4)	0.0242 (7)
H6A	0.7813	0.4882	0.5314	0.029*
C7	0.6505 (4)	0.3985 (3)	0.6368 (3)	0.0206 (7)
H7A	0.5456	0.4069	0.5739	0.025*
C8	0.6631 (4)	0.3386 (3)	0.7508 (3)	0.0162 (6)
C9	0.8193 (4)	0.3236 (3)	0.8437 (3)	0.0146 (6)
C10	0.3854 (4)	0.1929 (3)	0.6496 (3)	0.0158 (6)
C11	0.2542 (4)	0.2383 (3)	0.5623 (3)	0.0197 (7)
H11A	0.2521	0.3366	0.5861	0.024*
C12	0.1252 (4)	0.1406 (4)	0.4398 (4)	0.0241 (7)
H12A	0.0356	0.1721	0.3795	0.029*
C13	0.1283 (4)	−0.0022 (4)	0.4063 (3)	0.0232 (7)
H13A	0.0412	−0.0691	0.3220	0.028*
C14	0.2580 (4)	−0.0485 (3)	0.4954 (3)	0.0205 (7)
H14A	0.2583	−0.1472	0.4727	0.025*
C15	0.3876 (4)	0.0486 (3)	0.6176 (3)	0.0153 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.01334 (15)	0.01613 (16)	0.02014 (16)	0.00310 (11)	0.00482 (12)	0.00804 (12)
Br2	0.01964 (17)	0.01877 (17)	0.02031 (17)	0.00142 (13)	0.00809 (13)	−0.00191 (13)
Mn1	0.0134 (2)	0.0136 (2)	0.0130 (2)	0.00179 (18)	0.00430 (18)	0.00386 (18)
N1	0.0147 (12)	0.0114 (12)	0.0153 (13)	0.0005 (10)	0.0051 (10)	0.0030 (10)
N2	0.0152 (12)	0.0124 (12)	0.0148 (13)	0.0018 (10)	0.0048 (10)	0.0012 (10)
N3	0.0160 (13)	0.0174 (13)	0.0189 (13)	0.0048 (10)	0.0074 (11)	0.0060 (11)
C1	0.0184 (16)	0.0185 (16)	0.0204 (16)	0.0032 (13)	0.0056 (13)	0.0051 (13)
C2	0.0124 (15)	0.0180 (16)	0.0231 (17)	0.0019 (12)	0.0036 (13)	−0.0015 (13)
C3	0.0199 (16)	0.0163 (16)	0.0287 (18)	0.0015 (13)	0.0154 (14)	−0.0003 (14)
C4	0.0186 (16)	0.0126 (15)	0.0195 (16)	0.0023 (12)	0.0095 (13)	0.0013 (12)
C5	0.0301 (19)	0.0159 (16)	0.0273 (18)	0.0017 (14)	0.0192 (15)	0.0044 (14)
C6	0.0338 (19)	0.0190 (17)	0.0231 (18)	0.0032 (15)	0.0142 (15)	0.0092 (14)
C7	0.0215 (16)	0.0200 (16)	0.0190 (16)	0.0049 (13)	0.0048 (13)	0.0081 (13)
C8	0.0183 (15)	0.0119 (14)	0.0148 (15)	−0.0014 (12)	0.0059 (12)	0.0006 (12)
C9	0.0178 (15)	0.0099 (14)	0.0146 (15)	0.0016 (12)	0.0068 (12)	0.0010 (12)
C10	0.0170 (15)	0.0162 (15)	0.0153 (15)	0.0024 (12)	0.0074 (12)	0.0060 (12)
C11	0.0231 (17)	0.0169 (16)	0.0200 (16)	0.0046 (13)	0.0068 (14)	0.0092 (13)
C12	0.0186 (16)	0.0304 (19)	0.0203 (17)	0.0044 (14)	0.0030 (14)	0.0100 (15)
C13	0.0184 (16)	0.0297 (19)	0.0136 (16)	−0.0012 (14)	0.0028 (13)	0.0004 (14)
C14	0.0233 (17)	0.0200 (16)	0.0150 (16)	0.0010 (13)	0.0089 (13)	−0.0007 (13)
C15	0.0171 (15)	0.0184 (15)	0.0117 (14)	0.0041 (12)	0.0069 (12)	0.0045 (12)

Geometric parameters (Å, º)

Br1—Mn1^i	2.6210 (5)	C3—H3A	0.9500
Br1—Mn1	2.7147 (6)	C4—C5	1.414 (4)
Br2—Mn1	2.6096 (6)	C4—C9	1.414 (4)
Mn1—N1	2.245 (2)	C5—C6	1.365 (5)
Mn1—N2	2.340 (2)	C5—H5A	0.9500
Mn1—N3	2.340 (2)	C6—C7	1.413 (4)
Mn1—Br1^i	2.6211 (5)	C6—H6A	0.9500
N1—C1	1.326 (4)	C7—C8	1.368 (4)
N1—C9	1.372 (4)	C7—H7A	0.9500
N2—C10	1.448 (4)	C8—C9	1.421 (4)
N2—C8	1.460 (4)	C10—C11	1.383 (4)
N2—H2	0.9300	C10—C15	1.392 (4)
N3—C15	1.439 (4)	C11—C12	1.391 (4)
N3—H3B	0.9200	C11—H11A	0.9500
N3—H3C	0.9200	C12—C13	1.379 (5)
C1—C2	1.407 (4)	C12—H12A	0.9500
C1—H1A	0.9500	C13—C14	1.387 (4)
C2—C3	1.352 (5)	C13—H13A	0.9500
C2—H2A	0.9500	C14—C15	1.390 (4)
C3—C4	1.416 (4)	C14—H14A	0.9500
Mn1^i—Br1—Mn1	89.813 (17)	C2—C3—H3A	120.0
N1—Mn1—N2	74.48 (9)	C4—C3—H3A	120.0
N1—Mn1—N3	88.69 (9)	C5—C4—C9	119.2 (3)
N2—Mn1—N3	71.32 (9)	C5—C4—C3	123.2 (3)
N1—Mn1—Br2	97.31 (6)	C9—C4—C3	117.6 (3)
N2—Mn1—Br2	94.96 (6)	C6—C5—C4	120.4 (3)
N3—Mn1—Br2	163.06 (6)	C6—C5—H5A	119.8
N1—Mn1—Br1^i	91.66 (6)	C4—C5—H5A	119.8
N2—Mn1—Br1^i	158.02 (6)	C5—C6—C7	120.5 (3)
N3—Mn1—Br1^i	91.77 (6)	C5—C6—H6A	119.8
Br2—Mn1—Br1^i	103.815 (19)	C7—C6—H6A	119.8
N1—Mn1—Br1	168.82 (6)	C8—C7—C6	120.6 (3)
N2—Mn1—Br1	100.28 (6)	C8—C7—H7A	119.7
N3—Mn1—Br1	80.22 (6)	C6—C7—H7A	119.7
Br2—Mn1—Br1	92.953 (17)	C7—C8—C9	119.9 (3)
Br1^i—Mn1—Br1	90.187 (17)	C7—C8—N2	121.7 (3)
C1—N1—C9	117.7 (3)	C9—C8—N2	118.4 (3)
C1—N1—Mn1	125.3 (2)	N1—C9—C4	122.0 (3)
C9—N1—Mn1	116.86 (19)	N1—C9—C8	118.7 (3)
C10—N2—C8	113.0 (2)	C4—C9—C8	119.4 (3)
C10—N2—Mn1	105.78 (17)	C11—C10—C15	120.2 (3)
C8—N2—Mn1	110.55 (18)	C11—C10—N2	122.3 (3)
C10—N2—H2	109.1	C15—C10—N2	117.3 (3)
C8—N2—H2	109.1	C10—C11—C12	120.3 (3)
Mn1—N2—H2	109.1	C10—C11—H11A	119.8
C15—N3—Mn1	106.36 (17)	C12—C11—H11A	119.8
C15—N3—H3B	110.5	C13—C12—C11	119.6 (3)
Mn1—N3—H3B	110.5	C13—C12—H12A	120.2
C15—N3—H3C	110.5	C11—C12—H12A	120.2
Mn1—N3—H3C	110.5	C12—C13—C14	120.3 (3)
H3B—N3—H3C	108.6	C12—C13—H13A	119.9
N1—C1—C2	123.8 (3)	C14—C13—H13A	119.9
N1—C1—H1A	118.1	C13—C14—C15	120.4 (3)
C2—C1—H1A	118.1	C13—C14—H14A	119.8
C3—C2—C1	118.9 (3)	C15—C14—H14A	119.8
C3—C2—H2A	120.6	C14—C15—C10	119.1 (3)
C1—C2—H2A	120.6	C14—C15—N3	122.9 (3)
C2—C3—C4	119.9 (3)	C10—C15—N3	117.8 (3)
Mn1^i—Br1—Mn1—N1	99.6 (3)	C4—C5—C6—C7	1.2 (5)
Mn1^i—Br1—Mn1—N2	160.57 (6)	C5—C6—C7—C8	−0.7 (5)
Mn1^i—Br1—Mn1—N3	91.76 (6)	C6—C7—C8—C9	−1.0 (5)
Mn1^i—Br1—Mn1—Br2	−103.843 (19)	C6—C7—C8—N2	178.7 (3)
Mn1^i—Br1—Mn1—Br1^i	0.0	C10—N2—C8—C7	52.8 (4)
N2—Mn1—N1—C1	176.4 (3)	Mn1—N2—C8—C7	171.1 (2)
N3—Mn1—N1—C1	−112.6 (2)	C10—N2—C8—C9	−127.5 (3)
Br2—Mn1—N1—C1	83.3 (2)	Mn1—N2—C8—C9	−9.2 (3)
Br1^i—Mn1—N1—C1	−20.9 (2)	C1—N1—C9—C4	2.1 (4)
Br1—Mn1—N1—C1	−120.3 (3)	Mn1—N1—C9—C4	−174.1 (2)
N2—Mn1—N1—C9	−7.71 (19)	C1—N1—C9—C8	−178.3 (3)
N3—Mn1—N1—C9	63.3 (2)	Mn1—N1—C9—C8	5.5 (3)
Br2—Mn1—N1—C9	−100.9 (2)	C5—C4—C9—N1	177.8 (3)
Br1^i—Mn1—N1—C9	154.99 (19)	C3—C4—C9—N1	−3.0 (4)
Br1—Mn1—N1—C9	55.6 (5)	C5—C4—C9—C8	−1.8 (4)
N1—Mn1—N2—C10	131.21 (19)	C3—C4—C9—C8	177.5 (3)
N3—Mn1—N2—C10	37.26 (17)	C7—C8—C9—N1	−177.3 (3)
Br2—Mn1—N2—C10	−132.57 (17)	N2—C8—C9—N1	3.0 (4)
Br1^i—Mn1—N2—C10	78.6 (2)	C7—C8—C9—C4	2.3 (4)
Br1—Mn1—N2—C10	−38.65 (18)	N2—C8—C9—C4	−177.4 (2)
N1—Mn1—N2—C8	8.54 (18)	C8—N2—C10—C11	−97.4 (3)
N3—Mn1—N2—C8	−85.41 (19)	Mn1—N2—C10—C11	141.5 (3)
Br2—Mn1—N2—C8	104.77 (17)	C8—N2—C10—C15	86.2 (3)
Br1^i—Mn1—N2—C8	−44.1 (3)	Mn1—N2—C10—C15	−34.8 (3)
Br1—Mn1—N2—C8	−161.32 (17)	C15—C10—C11—C12	−1.5 (5)
N1—Mn1—N3—C15	−110.51 (19)	N2—C10—C11—C12	−177.7 (3)
N2—Mn1—N3—C15	−36.46 (17)	C10—C11—C12—C13	0.5 (5)
Br2—Mn1—N3—C15	0.7 (4)	C11—C12—C13—C14	0.8 (5)
Br1^i—Mn1—N3—C15	157.87 (17)	C12—C13—C14—C15	−1.1 (5)
Br1—Mn1—N3—C15	67.98 (17)	C13—C14—C15—C10	0.1 (4)
C9—N1—C1—C2	0.1 (5)	C13—C14—C15—N3	175.4 (3)
Mn1—N1—C1—C2	175.9 (2)	C11—C10—C15—C14	1.2 (4)
N1—C1—C2—C3	−1.3 (5)	N2—C10—C15—C14	177.6 (3)
C1—C2—C3—C4	0.3 (5)	C11—C10—C15—N3	−174.3 (3)
C2—C3—C4—C5	−179.1 (3)	N2—C10—C15—N3	2.1 (4)
C2—C3—C4—C9	1.7 (4)	Mn1—N3—C15—C14	−143.5 (2)
C9—C4—C5—C6	0.1 (5)	Mn1—N3—C15—C10	31.9 (3)
C3—C4—C5—C6	−179.1 (3)

Symmetry code: (i) −x+1, −y, −z+2.