Diaqua-bis(2-bromo-benzoato-κO)bis-(N,N-diethyl-nicotinamide-κN)manganese(II).

The title Mn(II) complex, [Mn(C(7)H(4)BrO(2))(2)(C(10)H(14)N(2)O)(2)(H(2)O)(2)], is centrosymmetric. The mol-ecule contains two 2-bromo-benzoate (BB) and two diethyl-nicotinamide (DENA) ligands and two water mol-ecules, all ligands being monodentate. The four O atoms in the equatorial plane around the Mn atom form a slightly distorted square-planar arrangement, while the distorted octa-hedral coordination is completed by the two N atoms of the DENA ligands in the axial positions. The dihedral angle between the carboxyl group and the adjacent benzene ring is 79.95 (11)°, while the pyridine and benzene rings are oriented at a dihedral angle of 45.66 (6)°. In the crystal structure, inter-molecular O-H⋯O hydrogen bonds link the mol-ecules into infinite chains.

Related literature

For general background, see: Antolini et al. (1982 ▶); Bigoli et al. (1972 ▶); Nadzhafov et al. (1981 ▶); Shnulin et al. (1981 ▶). For related structures, see: Hökelek et al. (1995 ▶, 1997 ▶, 2007 ▶, 2008 ▶); Hökelek & Necefoğlu (1996 ▶, 1997 ▶, 2007 ▶).

Experimental

Crystal data

[Mn(C7H4BrO2)2(C10H14N2O)2(H2O)2]

M = 847.46

Monoclinic,

a = 13.3022 (2) Å

b = 10.2746 (2) Å

c = 15.0010 (3) Å

β = 114.798 (1)°

V = 1861.21 (6) Å3

Z = 2

Mo Kα radiation

μ = 2.56 mm−1

T = 100 K

0.45 × 0.40 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.326, T max = 0.525

17076 measured reflections

4637 independent reflections

3922 reflections with I > 2σ(I)

R int = 0.057

Refinement

R[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.071

S = 1.03

4637 reflections

233 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.59 e Å−3

Δρmin = −0.59 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680901383X/xu2511sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680901383X/xu2511Isup2.hkl

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

[Mn(C7H4BrO2)2(C10H14N2O)2(H2O)2]	F(000) = 862
Mr = 847.46	Dx = 1.512 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9053 reflections
a = 13.3022 (2) Å	θ = 2.5–28.3°
b = 10.2746 (2) Å	µ = 2.56 mm−1
c = 15.0010 (3) Å	T = 100 K
β = 114.798 (1)°	Block, colorless
V = 1861.21 (6) Å3	0.45 × 0.40 × 0.25 mm
Z = 2

Bruker Kappa APEXII CCD area-detector diffractometer	4637 independent reflections
Radiation source: fine-focus sealed tube	3922 reflections with I > 2σ(I)
graphite	Rint = 0.057
φ and ω scans	θmax = 28.3°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −17→15
Tmin = 0.326, Tmax = 0.525	k = −12→13
17076 measured reflections	l = −16→20

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.071	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0399P)2] where P = (Fo2 + 2Fc2)/3
4637 reflections	(Δ/σ)max < 0.001
233 parameters	Δρmax = 0.59 e Å−3
2 restraints	Δρmin = −0.59 e Å−3

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.

	x	y	z	Uiso*/Ueq
Br1	0.176953 (14)	0.137004 (17)	0.070995 (13)	0.02474 (7)
Mn1	0.5000	0.0000	0.0000	0.00895 (8)
O1	0.46956 (9)	0.04297 (11)	0.12498 (8)	0.0153 (2)
O2	0.35938 (11)	−0.11949 (11)	0.12779 (10)	0.0265 (3)
O3	0.06295 (9)	0.11431 (10)	−0.39690 (8)	0.0144 (2)
O4	0.61923 (9)	0.16153 (10)	0.03877 (9)	0.0134 (2)
H41	0.6063 (18)	0.2388 (16)	0.0553 (16)	0.041 (6)*
H42	0.632 (2)	0.172 (2)	−0.0145 (17)	0.052 (7)*
N1	0.35321 (11)	0.13017 (12)	−0.09491 (10)	0.0123 (3)
N2	0.01375 (11)	−0.00098 (12)	−0.29333 (10)	0.0152 (3)
C1	0.40415 (13)	−0.01189 (14)	0.15435 (12)	0.0136 (3)
C2	0.38124 (13)	0.06516 (15)	0.22986 (12)	0.0141 (3)
C3	0.45806 (14)	0.06857 (16)	0.32723 (13)	0.0200 (4)
H3	0.5218	0.0181	0.3470	0.024*
C4	0.44137 (15)	0.14586 (17)	0.39540 (14)	0.0240 (4)
H4	0.4930	0.1461	0.4606	0.029*
C5	0.34710 (15)	0.22313 (17)	0.36604 (14)	0.0242 (4)
H5	0.3369	0.2772	0.4113	0.029*
C6	0.26873 (15)	0.21982 (16)	0.27000 (13)	0.0219 (4)
H6	0.2052	0.2706	0.2504	0.026*
C7	0.28573 (14)	0.14001 (15)	0.20293 (13)	0.0171 (3)
C8	0.35223 (13)	0.25953 (15)	−0.08357 (12)	0.0139 (3)
H8	0.4130	0.2986	−0.0338	0.017*
C9	0.26460 (13)	0.33756 (15)	−0.14278 (12)	0.0149 (3)
H9	0.2667	0.4270	−0.1325	0.018*
C10	0.17407 (13)	0.28093 (15)	−0.21728 (11)	0.0134 (3)
H10	0.1152	0.3315	−0.2591	0.016*
C11	0.17314 (12)	0.14640 (14)	−0.22823 (11)	0.0113 (3)
C12	0.26426 (13)	0.07572 (15)	−0.16601 (11)	0.0128 (3)
H12	0.2636	−0.0141	−0.1740	0.015*
C13	0.07865 (12)	0.08409 (14)	−0.31173 (11)	0.0117 (3)
C14	−0.08298 (13)	−0.05404 (16)	−0.37648 (12)	0.0168 (3)
H14A	−0.0981	−0.1413	−0.3605	0.020*
H14B	−0.0667	−0.0597	−0.4336	0.020*
C15	−0.18463 (14)	0.03062 (18)	−0.40047 (13)	0.0235 (4)
H15A	−0.2464	−0.0065	−0.4547	0.035*
H15B	−0.1704	0.1165	−0.4176	0.035*
H15C	−0.2014	0.0354	−0.3442	0.035*
C16	0.02318 (16)	−0.0346 (2)	−0.19523 (13)	0.0260 (4)
H16A	−0.0491	−0.0271	−0.1944	0.031*
H16B	0.0723	0.0271	−0.1480	0.031*
C17	0.06717 (17)	−0.1714 (2)	−0.16447 (16)	0.0389 (5)
H17A	0.0675	−0.1908	−0.1018	0.058*
H17B	0.1412	−0.1772	−0.1598	0.058*
H17C	0.0206	−0.2325	−0.2124	0.058*

	U11	U22	U33	U12	U13	U23
Br1	0.02537 (11)	0.02991 (12)	0.01674 (11)	0.00564 (7)	0.00666 (8)	0.00140 (7)
Mn1	0.01037 (16)	0.00854 (16)	0.00656 (16)	0.00002 (11)	0.00220 (13)	−0.00012 (12)
O1	0.0178 (6)	0.0177 (6)	0.0119 (6)	−0.0049 (4)	0.0078 (5)	−0.0046 (5)
O2	0.0454 (8)	0.0146 (6)	0.0338 (8)	−0.0101 (5)	0.0306 (7)	−0.0087 (5)
O3	0.0192 (6)	0.0130 (5)	0.0066 (6)	−0.0024 (4)	0.0010 (5)	0.0012 (4)
O4	0.0178 (6)	0.0090 (6)	0.0128 (6)	−0.0001 (4)	0.0057 (5)	−0.0003 (5)
N1	0.0136 (6)	0.0121 (7)	0.0091 (7)	0.0002 (5)	0.0027 (5)	−0.0007 (5)
N2	0.0166 (7)	0.0172 (7)	0.0090 (7)	−0.0036 (5)	0.0025 (6)	0.0004 (5)
C1	0.0171 (8)	0.0119 (8)	0.0119 (8)	0.0026 (6)	0.0062 (6)	0.0009 (6)
C2	0.0206 (8)	0.0114 (8)	0.0144 (8)	−0.0035 (6)	0.0115 (7)	−0.0020 (6)
C3	0.0202 (8)	0.0218 (9)	0.0188 (9)	−0.0021 (7)	0.0091 (7)	−0.0042 (7)
C4	0.0269 (10)	0.0301 (10)	0.0152 (9)	−0.0074 (7)	0.0090 (8)	−0.0064 (7)
C5	0.0345 (10)	0.0221 (9)	0.0237 (10)	−0.0058 (7)	0.0198 (9)	−0.0100 (8)
C6	0.0277 (9)	0.0199 (9)	0.0241 (10)	0.0020 (7)	0.0167 (8)	−0.0021 (7)
C7	0.0220 (8)	0.0163 (8)	0.0156 (9)	−0.0026 (6)	0.0105 (7)	−0.0008 (7)
C8	0.0146 (7)	0.0141 (8)	0.0103 (8)	−0.0026 (6)	0.0026 (6)	−0.0029 (6)
C9	0.0192 (8)	0.0099 (7)	0.0134 (8)	0.0001 (6)	0.0046 (7)	−0.0010 (6)
C10	0.0153 (7)	0.0116 (8)	0.0108 (8)	0.0034 (6)	0.0031 (6)	0.0030 (6)
C11	0.0132 (7)	0.0121 (7)	0.0069 (7)	−0.0014 (5)	0.0026 (6)	−0.0001 (6)
C12	0.0159 (7)	0.0100 (7)	0.0107 (8)	−0.0001 (6)	0.0039 (6)	−0.0005 (6)
C13	0.0126 (7)	0.0072 (7)	0.0113 (8)	0.0023 (5)	0.0009 (6)	−0.0006 (6)
C14	0.0180 (8)	0.0154 (8)	0.0133 (8)	−0.0069 (6)	0.0029 (7)	−0.0026 (7)
C15	0.0183 (9)	0.0289 (10)	0.0187 (9)	−0.0024 (7)	0.0034 (7)	0.0039 (8)
C16	0.0259 (9)	0.0396 (11)	0.0107 (9)	−0.0125 (8)	0.0057 (7)	0.0022 (8)
C17	0.0293 (11)	0.0481 (13)	0.0277 (12)	−0.0096 (9)	0.0005 (9)	0.0242 (10)

Br1—C7	1.8999 (18)	C6—H6	0.9300
Mn1—O1	2.1238 (10)	C7—C2	1.392 (2)
Mn1—O1i	2.1238 (10)	C7—C6	1.388 (2)
Mn1—O4	2.1987 (11)	C8—C9	1.386 (2)
Mn1—O4i	2.1987 (11)	C8—H8	0.9300
Mn1—N1i	2.3014 (13)	C9—H9	0.9300
Mn1—N1	2.3014 (13)	C10—C9	1.382 (2)
O1—C1	1.2611 (17)	C10—C11	1.391 (2)
O2—C1	1.2396 (19)	C10—H10	0.9300
O3—C13	1.2444 (18)	C11—C12	1.385 (2)
O4—H41	0.870 (15)	C12—H12	0.9300
O4—H42	0.89 (2)	C13—C11	1.496 (2)
N1—C8	1.3407 (19)	C14—C15	1.519 (2)
N1—C12	1.339 (2)	C14—H14A	0.9700
N2—C13	1.3362 (19)	C14—H14B	0.9700
N2—C14	1.471 (2)	C15—H15A	0.9600
N2—C16	1.465 (2)	C15—H15B	0.9600
C2—C1	1.514 (2)	C15—H15C	0.9600
C2—C3	1.388 (2)	C16—H16A	0.9700
C3—H3	0.9300	C16—H16B	0.9700
C4—C3	1.384 (2)	C17—C16	1.518 (3)
C4—C5	1.391 (3)	C17—H17A	0.9600
C4—H4	0.9300	C17—H17B	0.9600
C5—H5	0.9300	C17—H17C	0.9600
C6—C5	1.380 (3)
O1—Mn1—O1i	180.00 (5)	C6—C7—Br1	118.70 (13)
O1—Mn1—O4	89.60 (4)	C6—C7—C2	121.48 (17)
O1i—Mn1—O4	90.40 (4)	N1—C8—C9	122.84 (14)
O1—Mn1—O4i	90.40 (4)	N1—C8—H8	118.6
O1i—Mn1—O4i	89.60 (4)	C9—C8—H8	118.6
O1—Mn1—N1i	90.07 (4)	C8—C9—H9	120.4
O1i—Mn1—N1i	89.93 (4)	C10—C9—C8	119.22 (14)
O1—Mn1—N1	89.93 (4)	C10—C9—H9	120.4
O1i—Mn1—N1	90.07 (4)	C9—C10—C11	118.39 (14)
O4—Mn1—O4i	180.00 (6)	C9—C10—H10	120.8
O4—Mn1—N1i	86.81 (4)	C11—C10—H10	120.8
O4i—Mn1—N1i	93.19 (4)	C10—C11—C13	119.12 (13)
O4—Mn1—N1	93.19 (4)	C12—C11—C10	118.64 (14)
O4i—Mn1—N1	86.81 (4)	C12—C11—C13	122.03 (13)
N1i—Mn1—N1	180.00 (7)	N1—C12—C11	123.30 (14)
C1—O1—Mn1	129.08 (10)	N1—C12—H12	118.4
Mn1—O4—H41	123.9 (14)	C11—C12—H12	118.4
Mn1—O4—H42	103.8 (16)	O3—C13—N2	122.04 (14)
H41—O4—H42	106.6 (19)	O3—C13—C11	118.24 (13)
C8—N1—Mn1	123.27 (10)	N2—C13—C11	119.71 (13)
C12—N1—Mn1	119.15 (10)	N2—C14—C15	111.35 (14)
C12—N1—C8	117.58 (13)	N2—C14—H14A	109.4
C13—N2—C14	118.59 (13)	N2—C14—H14B	109.4
C13—N2—C16	124.83 (14)	C15—C14—H14A	109.4
C16—N2—C14	116.15 (13)	C15—C14—H14B	109.4
O1—C1—C2	114.36 (13)	H14A—C14—H14B	108.0
O2—C1—O1	126.53 (14)	C14—C15—H15A	109.5
O2—C1—C2	119.11 (13)	C14—C15—H15B	109.5
C3—C2—C1	120.67 (14)	C14—C15—H15C	109.5
C3—C2—C7	118.09 (14)	H15A—C15—H15B	109.5
C7—C2—C1	121.15 (15)	H15A—C15—H15C	109.5
C2—C3—H3	119.5	H15B—C15—H15C	109.5
C4—C3—C2	121.09 (16)	N2—C16—C17	112.52 (16)
C4—C3—H3	119.5	N2—C16—H16A	109.1
C3—C4—C5	119.76 (17)	N2—C16—H16B	109.1
C3—C4—H4	120.1	C17—C16—H16A	109.1
C5—C4—H4	120.1	C17—C16—H16B	109.1
C6—C5—C4	120.18 (16)	H16A—C16—H16B	107.8
C6—C5—H5	119.9	C16—C17—H17A	109.5
C4—C5—H5	119.9	C16—C17—H17B	109.5
C5—C6—C7	119.34 (16)	C16—C17—H17C	109.5
C5—C6—H6	120.3	H17A—C17—H17B	109.5
C7—C6—H6	120.3	H17A—C17—H17C	109.5
C2—C7—Br1	119.80 (12)	H17B—C17—H17C	109.5
O1—Mn1—N1—C12	−114.25 (11)	C3—C2—C1—O1	−77.81 (19)
O1i—Mn1—N1—C12	65.75 (11)	C3—C2—C1—O2	101.89 (19)
O4—Mn1—N1—C12	156.15 (11)	C7—C2—C1—O1	98.69 (18)
O4i—Mn1—N1—C12	−23.85 (11)	C7—C2—C1—O2	−81.6 (2)
O1—Mn1—N1—C8	66.53 (12)	C1—C2—C3—C4	175.46 (14)
O1i—Mn1—N1—C8	−113.47 (12)	C7—C2—C3—C4	−1.1 (2)
O4—Mn1—N1—C8	−23.07 (12)	C5—C4—C3—C2	−1.0 (2)
O4i—Mn1—N1—C8	156.93 (12)	C3—C4—C5—C6	2.0 (3)
O4—Mn1—O1—C1	179.20 (13)	C7—C6—C5—C4	−0.8 (2)
O4i—Mn1—O1—C1	−0.80 (13)	Br1—C7—C2—C1	4.3 (2)
N1i—Mn1—O1—C1	−94.00 (13)	Br1—C7—C2—C3	−179.13 (11)
N1—Mn1—O1—C1	86.00 (13)	C6—C7—C2—C1	−174.25 (14)
Mn1—O1—C1—O2	15.7 (2)	C6—C7—C2—C3	2.3 (2)
Mn1—O1—C1—C2	−164.62 (10)	Br1—C7—C6—C5	−179.91 (12)
Mn1—N1—C8—C9	178.27 (11)	C2—C7—C6—C5	−1.4 (2)
C12—N1—C8—C9	−1.0 (2)	N1—C8—C9—C10	−0.3 (2)
Mn1—N1—C12—C11	−178.48 (11)	C11—C10—C9—C8	1.8 (2)
C8—N1—C12—C11	0.8 (2)	C10—C11—C12—N1	0.7 (2)
C14—N2—C13—O3	−3.8 (2)	C13—C11—C12—N1	175.36 (13)
C14—N2—C13—C11	175.90 (13)	C9—C10—C11—C12	−1.9 (2)
C16—N2—C13—O3	−175.90 (15)	C9—C10—C11—C13	−176.78 (13)
C16—N2—C13—C11	3.8 (2)	O3—C13—C11—C10	61.46 (19)
C13—N2—C14—C15	−89.33 (17)	O3—C13—C11—C12	−113.21 (16)
C13—N2—C16—C17	−109.22 (18)	N2—C13—C11—C10	−118.22 (16)
C14—N2—C16—C17	78.48 (18)	N2—C13—C11—C12	67.11 (19)
C16—N2—C14—C15	83.48 (18)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H41···O3ii	0.87 (2)	1.86 (2)	2.7207 (16)	168 (2)
O4—H42···O2i	0.89 (2)	1.83 (2)	2.6658 (19)	155 (2)

Table 1

Selected bond lengths (Å)

Mn1—O1	2.1238 (10)
Mn1—O4	2.1987 (11)
Mn1—N1	2.3014 (13)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H41⋯O3i	0.870 (18)	1.86 (2)	2.7207 (16)	168 (2)
O4—H42⋯O2ii	0.89 (2)	1.83 (2)	2.6658 (19)	155.1 (19)

Symmetry codes: (i) ; (ii) .