Tetra-aqua(2,2'-bipyridine-κN,N')magnesium(II) bis-(4-bromo-benzoate).

In the complex cation of the title compound, [Mg(C(10)H(8)N(2))(H(2)O)(4)](C(7)H(4)BrO(2))(2), the Mg(II) atom is coordinated by two N atoms from a 2,2'-bipyridine ligand and four water O atoms in a distorted MgN(2)O(4) octa-hedral geometry. The cation is located on a special position on a twofold rotation axis which passes through the Mg(II) atom and the centroid of the 2,2'-bipyridine ligand. The 2,2'-bipyridine ligands exhibit nearly perfect coplanarity (r.m.s. deviation = 0.0035 Å) . In the crystal, O-H⋯O and C-H⋯O, C-H⋯Br hydrogen bonds and π-π stacking inter-actions [mean inter-planar distance of 3.475 (6) Å between adjacent 2,2'-bipyridine ligands] link the cations and anions into a three-dimensional supra-molecular network. One Br atom is disordered over two sites with occupancy factors of 0.55 and 0.45.

Related literature

For related magnesium(II) complexes with n class="Chemical">1.10-phenanthroline and pyridine ligands, see: Halut-Desportes (1981 ▶); Hao et al. (2008 ▶); Zhang (2004 ▶).

Experimental

Crystal data

[Mg(C10H8N2)(n class="Chemical">H2O)4](C7H4BrO2)2

M = 652.56

Monoclinic,

a = 30.275 (6) Å

b = 12.308 (3) Å

c = 7.5785 (15) Å

β = 103.90 (3)°

V = 2741.2 (11) Å3

Z = 4

Mo Kα radiation

μ = 3.03 mm−1

T = 290 K

0.31 × 0.27 × 0.19 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.406, T max = 0.562

10517 measured reflections

2412 independent reflections

1505 reflections with I > 2σ(I)

R int = 0.063

Refinement

R[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.174

S = 1.08

2412 reflections

171 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.88 e Å−3

Δρmin = −0.49 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536810041474/rk2240sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810041474/rk2240Isup2.hkl

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

[Mg(C10H8N2)(H2O)4](C7H4BrO2)2	F(000) = 1312
Mr = 652.56	Dx = 1.581 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6277 reflections
a = 30.275 (6) Å	θ = 3.2–25.0°
b = 12.308 (3) Å	µ = 3.03 mm−1
c = 7.5785 (15) Å	T = 290 K
β = 103.90 (3)°	Block, colourless
V = 2741.2 (11) Å3	0.31 × 0.27 × 0.19 mm
Z = 4

Rigaku R-AXIS RAPID diffractometer	2412 independent reflections
Radiation source: fine-focus sealed tube	1505 reflections with I > 2σ(I)
graphite	Rint = 0.063
ω–scans	θmax = 25.0°, θmin = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −35→35
Tmin = 0.406, Tmax = 0.562	k = −14→14
10517 measured reflections	l = −9→7

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.174	H-atom parameters constrained
S = 1.08	w = 1/[σ2(Fo2) + (0.0695P)2 + 6.5977P] where P = (Fo2 + 2Fc2)/3
2412 reflections	(Δ/σ)max < 0.001
171 parameters	Δρmax = 0.88 e Å−3
1 restraint	Δρmin = −0.49 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	Occ. (<1)
Mg1	0.0000	0.29391 (14)	0.2500	0.0366 (5)
Br1	0.2137 (3)	0.9201 (5)	0.0828 (12)	0.1255 (19)	0.55
Br1'	0.2127 (4)	0.8733 (7)	0.0939 (16)	0.1255 (19)	0.45
N1	0.04459 (13)	0.1518 (3)	0.2599 (5)	0.0410 (9)
O1	0.05190 (12)	0.4001 (2)	0.2564 (4)	0.0521 (9)
H1A	0.0561	0.4561	0.3166	0.078*
H1B	0.0512	0.4061	0.1480	0.078*
O2	−0.01205 (11)	0.2973 (2)	−0.0269 (4)	0.0494 (8)
H2A	−0.0376	0.3009	−0.0944	0.074*
H2B	0.0036	0.3273	−0.0868	0.074*
O3	0.43473 (11)	0.9050 (2)	0.5752 (4)	0.0480 (8)
O4	0.40497 (12)	0.7957 (3)	0.7472 (5)	0.0646 (10)
C1	0.08821 (17)	0.1562 (4)	0.2545 (6)	0.0514 (12)
H1	0.1024	0.2237	0.2649	0.062*
C2	0.11341 (18)	0.0657 (4)	0.2343 (7)	0.0543 (12)
H2	0.1438	0.0717	0.2302	0.065*
C3	0.09216 (19)	−0.0333 (4)	0.2203 (7)	0.0591 (13)
H3	0.1081	−0.0959	0.2060	0.071*
C4	0.04759 (18)	−0.0403 (4)	0.2274 (6)	0.0510 (12)
H4	0.0332	−0.1074	0.2198	0.061*
C5	0.02400 (15)	0.0542 (3)	0.2461 (5)	0.0393 (10)
C6	0.35589 (17)	0.8637 (4)	0.4824 (6)	0.0466 (11)
C7	0.32382 (19)	0.7824 (4)	0.4683 (7)	0.0623 (14)
H7	0.3305	0.7209	0.5411	0.075*
C8	0.2819 (2)	0.7917 (6)	0.3469 (9)	0.0837 (19)
H8	0.2609	0.7353	0.3331	0.100*
C9	0.2716 (2)	0.8849 (7)	0.2471 (8)	0.089 (2)
C10	0.3022 (2)	0.9671 (7)	0.2613 (8)	0.089 (2)
H10	0.2946	1.0301	0.1932	0.106*
C11	0.34477 (19)	0.9563 (5)	0.3780 (7)	0.0640 (14)
H11	0.3661	1.0117	0.3863	0.077*
C12	0.40163 (16)	0.8535 (3)	0.6125 (6)	0.0423 (10)

	U11	U22	U33	U12	U13	U23
Mg1	0.0387 (12)	0.0345 (10)	0.0359 (10)	0.000	0.0074 (9)	0.000
Br1	0.0583 (7)	0.219 (6)	0.0842 (12)	0.038 (3)	−0.0128 (6)	0.011 (3)
Br1'	0.0583 (7)	0.219 (6)	0.0842 (12)	0.038 (3)	−0.0128 (6)	0.011 (3)
N1	0.043 (2)	0.0397 (19)	0.0380 (19)	0.0001 (17)	0.0041 (16)	0.0003 (15)
O1	0.064 (2)	0.0470 (17)	0.0468 (18)	−0.0141 (15)	0.0161 (17)	−0.0094 (14)
O2	0.047 (2)	0.0625 (19)	0.0367 (16)	−0.0069 (16)	0.0061 (14)	0.0051 (14)
O3	0.045 (2)	0.0515 (17)	0.0492 (18)	−0.0063 (15)	0.0136 (15)	−0.0062 (14)
O4	0.052 (2)	0.078 (2)	0.056 (2)	−0.0141 (19)	−0.0018 (17)	0.0225 (18)
C1	0.042 (3)	0.054 (3)	0.057 (3)	−0.004 (2)	0.008 (2)	0.000 (2)
C2	0.040 (3)	0.062 (3)	0.060 (3)	0.015 (2)	0.012 (2)	0.003 (2)
C3	0.060 (4)	0.054 (3)	0.059 (3)	0.016 (3)	0.007 (3)	−0.002 (2)
C4	0.053 (3)	0.042 (2)	0.055 (3)	0.004 (2)	0.008 (2)	−0.001 (2)
C5	0.042 (3)	0.041 (2)	0.033 (2)	0.0058 (19)	0.0037 (19)	0.0007 (18)
C6	0.041 (3)	0.059 (3)	0.040 (2)	0.006 (2)	0.011 (2)	0.002 (2)
C7	0.049 (3)	0.073 (3)	0.063 (3)	−0.010 (3)	0.011 (3)	−0.002 (3)
C8	0.050 (4)	0.122 (5)	0.076 (4)	−0.020 (4)	0.008 (3)	−0.023 (4)
C9	0.046 (4)	0.164 (7)	0.054 (3)	0.023 (4)	0.009 (3)	0.008 (4)
C10	0.063 (4)	0.140 (6)	0.067 (4)	0.035 (4)	0.023 (3)	0.039 (4)
C11	0.052 (3)	0.081 (4)	0.062 (3)	0.009 (3)	0.019 (3)	0.022 (3)
C12	0.040 (3)	0.042 (2)	0.046 (3)	−0.004 (2)	0.013 (2)	−0.009 (2)

Mg1—O1	2.035 (3)	C2—C3	1.371 (7)
Mg1—O1i	2.035 (3)	C2—H2	0.9300
Mg1—O2	2.042 (3)	C3—C4	1.366 (7)
Mg1—O2i	2.042 (3)	C3—H3	0.9300
Mg1—N1i	2.199 (4)	C4—C5	1.390 (6)
Mg1—N1	2.199 (4)	C4—H4	0.9300
Mg1—H1B	2.3424	C5—C5i	1.468 (9)
Br1—C9	1.939 (10)	C6—C7	1.380 (7)
Br1'—C9	1.885 (11)	C6—C11	1.382 (7)
N1—C1	1.332 (6)	C6—C12	1.500 (7)
N1—C5	1.346 (5)	C7—C8	1.382 (8)
O1—H1A	0.8200	C7—H7	0.9300
O1—H1B	0.8200	C8—C9	1.367 (9)
O2—H2A	0.8199	C8—H8	0.9300
O2—H2B	0.8201	C9—C10	1.358 (10)
O3—C12	1.274 (5)	C10—C11	1.384 (8)
O4—C12	1.228 (5)	C10—H10	0.9300
C1—C2	1.379 (7)	C11—H11	0.9300
C1—H1	0.9300
O1—Mg1—O1i	100.12 (19)	C1—C2—H2	121.1
O1—Mg1—O2	87.58 (13)	C4—C3—C2	120.2 (5)
O1i—Mg1—O2	90.94 (13)	C4—C3—H3	119.9
O1—Mg1—O2i	90.94 (13)	C2—C3—H3	119.9
O1i—Mg1—O2i	87.58 (13)	C3—C4—C5	119.2 (4)
O2—Mg1—O2i	177.69 (19)	C3—C4—H4	120.4
O1—Mg1—N1i	167.24 (14)	C5—C4—H4	120.4
O1i—Mg1—N1i	92.61 (13)	N1—C5—C4	121.0 (4)
O2—Mg1—N1i	91.39 (13)	N1—C5—C5i	116.2 (2)
O2i—Mg1—N1i	90.45 (13)	C4—C5—C5i	122.8 (3)
O1—Mg1—N1	92.61 (13)	C7—C6—C11	118.9 (5)
O1i—Mg1—N1	167.24 (14)	C7—C6—C12	120.8 (4)
O2—Mg1—N1	90.45 (13)	C11—C6—C12	120.3 (4)
O2i—Mg1—N1	91.39 (13)	C6—C7—C8	120.5 (5)
N1i—Mg1—N1	74.7 (2)	C6—C7—H7	119.7
O1—Mg1—H1B	20.1	C8—C7—H7	119.7
O1i—Mg1—H1B	100.5	C9—C8—C7	119.3 (6)
O2—Mg1—H1B	67.5	C9—C8—H8	120.4
O2i—Mg1—H1B	111.0	C7—C8—H8	120.4
N1i—Mg1—H1B	155.1	C10—C9—C8	121.4 (6)
N1—Mg1—H1B	91.7	C10—C9—Br1'	129.1 (6)
C1—N1—C5	118.5 (4)	C8—C9—Br1'	109.5 (6)
C1—N1—Mg1	124.9 (3)	C10—C9—Br1	112.2 (6)
C5—N1—Mg1	116.0 (3)	C8—C9—Br1	126.4 (7)
Mg1—O1—H1A	124.7	Br1'—C9—Br1	17.5 (4)
Mg1—O1—H1B	101.6	C9—C10—C11	119.4 (6)
H1A—O1—H1B	116.4	C9—C10—H10	120.3
Mg1—O2—H2A	123.4	C11—C10—H10	120.3
Mg1—O2—H2B	126.4	C6—C11—C10	120.4 (6)
H2A—O2—H2B	102.4	C6—C11—H11	119.8
N1—C1—C2	123.4 (5)	C10—C11—H11	119.8
N1—C1—H1	118.3	O4—C12—O3	124.1 (4)
C2—C1—H1	118.3	O4—C12—C6	118.3 (4)
C3—C2—C1	117.7 (5)	O3—C12—C6	117.6 (4)
C3—C2—H2	121.1

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O3ii	0.82	1.89	2.702 (4)	172
O1—H1B···O3iii	0.82	1.84	2.640 (4)	165
O2—H2A···O4iv	0.82	1.86	2.679 (7)	175
O2—H2B···O3iii	0.82	2.08	2.790 (5)	145
C2—H2···Br1v	0.93	3.00	3.525 (7)	117
C2—H2···Br1'v	0.93	3.11	3.612 (7)	116
C3—H3···O4vi	0.93	2.53	3.239 (6)	133

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O3i	0.82	1.89	2.702 (4)	172
O1—H1B⋯O3ii	0.82	1.84	2.640 (4)	165
O2—H2A⋯O4iii	0.82	1.86	2.679 (7)	175
O2—H2B⋯O3ii	0.82	2.08	2.790 (5)	145
C2—H2⋯Br1iv	0.93	3.00	3.525 (7)	117
C2—H2⋯Br1′iv	0.93	3.11	3.612 (7)	116
C3—H3⋯O4v	0.93	2.53	3.239 (6)	133

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .