Diaqua-bis-(4-bromo-benzoato-κO)bis-(N,N-diethyl-nicotinamide-κN)manganese(II).

In the crystal structure of 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)], the Mn(II) cation is located on an inversion center and coordinated by two diethyl-nicotinamide (DENA) ligands, two 4-bromo-benzoate (PBB) anions and two water mol-ecules in a distorted octa-hedral geometry. The dihedral angle between the carboxyl-ate group and the adjacent benzene ring is 3.25 (14)°. In the mol-ecule, the pyridine ring and the benzene ring are oriented at a dihedral angle of 77.24 (5)°. In the crystal, inter-molecular C-H⋯O hydrogen bonds link the mol-ecules into a two-dimensional network. Weak inter-molecular C-H⋯O hydrogen bonds and π-π inter-actions between the pyridine rings of neighbouring mol-ecules [centroid-centroid distance = 3.537 (1) Å] further consolidate the crystal packing.

Related literature

For literature on niacin, see: Krishnamachari (1974 ▶). For information on the nicotinic acid derivative N,N-diethyl­nicotinamide, see: Bigoli et al. (1972 ▶). For related structures, see: Hökelek et al. (1996 ▶, 2009a ▶,b ▶); Hökelek & Necefoğlu (1998 ▶, 2007 ▶); Necefoğlu et al. (2011 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

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

M = 847.46

Triclinic,

a = 7.2939 (2) Å

b = 8.5130 (2) Å

c = 16.1252 (4) Å

α = 83.970 (3)°

β = 79.529 (3)°

γ = 68.031 (2)°

V = 912.34 (4) Å3

Z = 1

Mo Kα radiation

μ = 2.61 mm−1

T = 100 K

0.35 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.462, T max = 0.594

16194 measured reflections

4616 independent reflections

4127 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.073

S = 1.09

4616 reflections

233 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.42 e Å−3

Δρmin = −0.39 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 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811031412/xu5285sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811031412/xu5285Isup2.hkl

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

[Mn(C7H4BrO2)2(C10H14N2O)2(H2O)2]	Z = 1
Mr = 847.46	F(000) = 431
Triclinic, P1	Dx = 1.542 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2939 (2) Å	Cell parameters from 9256 reflections
b = 8.5130 (2) Å	θ = 2.6–28.5°
c = 16.1252 (4) Å	µ = 2.61 mm−1
α = 83.970 (3)°	T = 100 K
β = 79.529 (3)°	Block, colorless
γ = 68.031 (2)°	0.35 × 0.25 × 0.20 mm
V = 912.34 (4) Å3

Bruker Kappa APEXII CCD area-detector diffractometer	4616 independent reflections
Radiation source: fine-focus sealed tube	4127 reflections with I > 2σ(I)
graphite	Rint = 0.029
φ and ω scans	θmax = 28.7°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −9→8
Tmin = 0.462, Tmax = 0.594	k = −11→11
16194 measured reflections	l = −21→21

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) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.0308P)2 + 0.6418P] where P = (Fo2 + 2Fc2)/3
4616 reflections	(Δ/σ)max = 0.001
233 parameters	Δρmax = 0.42 e Å−3
2 restraints	Δρmin = −0.39 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 > 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.

	x	y	z	Uiso*/Ueq
Br1	−0.75487 (3)	−0.83337 (3)	0.028844 (11)	0.02549 (7)
Mn1	−1.5000	−1.0000	0.5000	0.01072 (8)
O1	−1.38994 (18)	−0.87032 (15)	0.39214 (7)	0.0149 (2)
O2	−1.58179 (18)	−0.86624 (16)	0.29746 (8)	0.0162 (2)
O3	−2.33701 (19)	−0.67456 (16)	0.62449 (8)	0.0180 (3)
O4	−1.73146 (19)	−1.01296 (16)	0.43251 (8)	0.0164 (2)
H41	−1.695 (5)	−0.972 (4)	0.3842 (14)	0.061 (10)*
H42	−1.724 (4)	−1.107 (2)	0.4215 (17)	0.039 (7)*
N1	−1.7301 (2)	−0.75479 (18)	0.55238 (9)	0.0135 (3)
N2	−2.3337 (2)	−0.57656 (18)	0.74841 (9)	0.0154 (3)
C1	−1.4231 (3)	−0.8666 (2)	0.31747 (10)	0.0132 (3)
C2	−1.2580 (3)	−0.8627 (2)	0.24697 (10)	0.0122 (3)
C3	−1.2803 (3)	−0.8670 (2)	0.16323 (11)	0.0156 (3)
H3	−1.3960	−0.8757	0.1511	0.019*
C4	−1.1308 (3)	−0.8583 (2)	0.09777 (11)	0.0167 (3)
H4	−1.1453	−0.8606	0.0418	0.020*
C5	−0.9600 (3)	−0.8463 (2)	0.11768 (11)	0.0159 (3)
C6	−0.9306 (3)	−0.8470 (2)	0.20023 (11)	0.0158 (3)
H6	−0.8128	−0.8420	0.2121	0.019*
C7	−1.0816 (3)	−0.8554 (2)	0.26481 (10)	0.0145 (3)
H7	−1.0647	−0.8561	0.3207	0.017*
C8	−1.7011 (3)	−0.6072 (2)	0.54066 (10)	0.0142 (3)
H8	−1.5813	−0.6055	0.5095	0.017*
C9	−1.8416 (3)	−0.4569 (2)	0.57292 (11)	0.0158 (3)
H9	−1.8164	−0.3567	0.5635	0.019*
C10	−2.0201 (3)	−0.4589 (2)	0.61946 (11)	0.0148 (3)
H10	−2.1162	−0.3603	0.6426	0.018*
C11	−2.0531 (3)	−0.6112 (2)	0.63100 (10)	0.0131 (3)
C12	−1.9050 (3)	−0.7549 (2)	0.59574 (10)	0.0137 (3)
H12	−1.9281	−0.8561	0.6025	0.016*
C13	−2.2514 (3)	−0.6235 (2)	0.66923 (11)	0.0138 (3)
C14	−2.5372 (3)	−0.5766 (2)	0.77833 (12)	0.0203 (4)
H14A	−2.6183	−0.5272	0.7341	0.024*
H14B	−2.5964	−0.5054	0.8266	0.024*
C15	−2.5430 (3)	−0.7523 (2)	0.80336 (13)	0.0261 (4)
H15A	−2.6787	−0.7433	0.8232	0.039*
H15B	−2.4636	−0.8021	0.8474	0.039*
H15C	−2.4902	−0.8223	0.7553	0.039*
C16	−2.2354 (3)	−0.5264 (2)	0.80695 (11)	0.0192 (4)
H16A	−2.3176	−0.4126	0.8246	0.023*
H16B	−2.1082	−0.5237	0.7775	0.023*
C17	−2.1988 (4)	−0.6441 (3)	0.88473 (14)	0.0370 (5)
H17A	−2.1306	−0.6066	0.9195	0.056*
H17B	−2.1182	−0.7572	0.8678	0.056*
H17C	−2.3246	−0.6427	0.9160	0.056*

	U11	U22	U33	U12	U13	U23
Br1	0.02017 (11)	0.04066 (12)	0.01687 (10)	−0.01507 (9)	0.00437 (7)	−0.00377 (8)
Mn1	0.00970 (17)	0.01062 (15)	0.01099 (16)	−0.00281 (13)	−0.00032 (13)	−0.00241 (12)
O1	0.0165 (6)	0.0158 (6)	0.0132 (5)	−0.0070 (5)	−0.0006 (5)	−0.0021 (4)
O2	0.0120 (6)	0.0194 (6)	0.0172 (6)	−0.0056 (5)	−0.0026 (5)	−0.0003 (5)
O3	0.0163 (6)	0.0198 (6)	0.0203 (6)	−0.0083 (5)	−0.0027 (5)	−0.0043 (5)
O4	0.0175 (6)	0.0174 (6)	0.0167 (6)	−0.0085 (5)	−0.0031 (5)	−0.0022 (5)
N1	0.0128 (7)	0.0138 (6)	0.0136 (6)	−0.0042 (5)	−0.0019 (5)	−0.0025 (5)
N2	0.0155 (7)	0.0146 (6)	0.0152 (7)	−0.0055 (6)	0.0013 (6)	−0.0024 (5)
C1	0.0151 (8)	0.0084 (7)	0.0138 (7)	−0.0024 (6)	0.0003 (6)	−0.0022 (5)
C2	0.0121 (8)	0.0104 (7)	0.0130 (7)	−0.0026 (6)	−0.0011 (6)	−0.0021 (6)
C3	0.0140 (8)	0.0174 (8)	0.0158 (8)	−0.0056 (7)	−0.0024 (6)	−0.0022 (6)
C4	0.0183 (9)	0.0187 (8)	0.0124 (7)	−0.0057 (7)	−0.0014 (7)	−0.0030 (6)
C5	0.0142 (8)	0.0176 (8)	0.0151 (8)	−0.0061 (7)	0.0018 (6)	−0.0023 (6)
C6	0.0126 (8)	0.0178 (8)	0.0181 (8)	−0.0065 (7)	−0.0031 (6)	−0.0009 (6)
C7	0.0179 (9)	0.0138 (7)	0.0125 (7)	−0.0062 (7)	−0.0022 (6)	−0.0019 (6)
C8	0.0126 (8)	0.0157 (7)	0.0150 (7)	−0.0063 (6)	−0.0014 (6)	−0.0011 (6)
C9	0.0188 (9)	0.0133 (7)	0.0172 (8)	−0.0076 (7)	−0.0028 (7)	−0.0017 (6)
C10	0.0158 (8)	0.0112 (7)	0.0155 (7)	−0.0026 (6)	−0.0009 (6)	−0.0040 (6)
C11	0.0129 (8)	0.0154 (7)	0.0114 (7)	−0.0053 (6)	−0.0019 (6)	−0.0020 (6)
C12	0.0141 (8)	0.0120 (7)	0.0150 (7)	−0.0048 (6)	−0.0019 (6)	−0.0014 (6)
C13	0.0132 (8)	0.0095 (7)	0.0165 (8)	−0.0021 (6)	−0.0008 (6)	−0.0016 (6)
C14	0.0173 (9)	0.0177 (8)	0.0233 (9)	−0.0068 (7)	0.0066 (7)	−0.0053 (7)
C15	0.0253 (10)	0.0219 (9)	0.0304 (10)	−0.0119 (8)	0.0064 (8)	−0.0034 (8)
C16	0.0248 (10)	0.0197 (8)	0.0146 (8)	−0.0098 (7)	−0.0015 (7)	−0.0034 (6)
C17	0.0505 (15)	0.0392 (12)	0.0281 (11)	−0.0209 (11)	−0.0191 (11)	0.0106 (9)

Br1—C5	1.9009 (17)	C6—H6	0.9300
Mn1—O1	2.1542 (12)	C7—C2	1.393 (2)
Mn1—O1i	2.1542 (12)	C7—H7	0.9300
Mn1—O4	2.2088 (13)	C8—C9	1.387 (2)
Mn1—O4i	2.2089 (13)	C8—H8	0.9300
Mn1—N1	2.2632 (14)	C9—H9	0.9300
Mn1—N1i	2.2632 (14)	C10—C9	1.385 (2)
O1—C1	1.266 (2)	C10—C11	1.393 (2)
O2—C1	1.256 (2)	C10—H10	0.9300
O3—C13	1.238 (2)	C11—C13	1.503 (2)
O4—H41	0.860 (18)	C12—C11	1.386 (2)
O4—H42	0.823 (17)	C12—H12	0.9300
N1—C8	1.339 (2)	C14—C15	1.521 (2)
N1—C12	1.339 (2)	C14—H14A	0.9700
N2—C13	1.341 (2)	C14—H14B	0.9700
N2—C14	1.475 (2)	C15—H15A	0.9600
N2—C16	1.465 (2)	C15—H15B	0.9600
C1—C2	1.506 (2)	C15—H15C	0.9600
C3—C2	1.395 (2)	C16—C17	1.518 (3)
C3—H3	0.9300	C16—H16A	0.9700
C4—C3	1.391 (2)	C16—H16B	0.9700
C4—C5	1.383 (3)	C17—H17A	0.9600
C4—H4	0.9300	C17—H17B	0.9600
C5—C6	1.385 (2)	C17—H17C	0.9600
C6—C7	1.389 (2)
O1i—Mn1—O1	180.000 (1)	C6—C7—C2	120.84 (15)
O1—Mn1—O4	90.55 (5)	C6—C7—H7	119.6
O1i—Mn1—O4	89.45 (5)	N1—C8—C9	122.95 (16)
O1—Mn1—O4i	89.45 (5)	N1—C8—H8	118.5
O1i—Mn1—O4i	90.55 (5)	C9—C8—H8	118.5
O4—Mn1—O4i	180.00 (5)	C8—C9—H9	120.6
O1—Mn1—N1	92.44 (5)	C10—C9—C8	118.76 (15)
O1i—Mn1—N1	87.56 (5)	C10—C9—H9	120.6
O1—Mn1—N1i	87.56 (5)	C9—C10—C11	118.77 (15)
O1i—Mn1—N1i	92.44 (5)	C9—C10—H10	120.6
O4—Mn1—N1	87.02 (5)	C11—C10—H10	120.6
O4i—Mn1—N1	92.98 (5)	C10—C11—C13	123.27 (15)
O4—Mn1—N1i	92.98 (5)	C12—C11—C10	118.50 (15)
O4i—Mn1—N1i	87.02 (5)	C12—C11—C13	117.68 (14)
N1—Mn1—N1i	180.0	N1—C12—C11	123.06 (15)
C1—O1—Mn1	125.95 (11)	N1—C12—H12	118.5
Mn1—O4—H41	98 (2)	C11—C12—H12	118.5
Mn1—O4—H42	118 (2)	O3—C13—N2	121.63 (16)
H42—O4—H41	103 (3)	O3—C13—C11	117.65 (15)
C8—N1—Mn1	122.84 (11)	N2—C13—C11	120.70 (15)
C12—N1—Mn1	119.21 (11)	N2—C14—C15	113.64 (16)
C12—N1—C8	117.93 (15)	N2—C14—H14A	108.8
C13—N2—C14	117.30 (15)	N2—C14—H14B	108.8
C13—N2—C16	124.64 (15)	C15—C14—H14A	108.8
C16—N2—C14	118.06 (14)	C15—C14—H14B	108.8
O1—C1—C2	117.11 (15)	H14A—C14—H14B	107.7
O2—C1—O1	125.40 (15)	C14—C15—H15A	109.5
O2—C1—C2	117.49 (14)	C14—C15—H15B	109.5
C3—C2—C1	120.22 (15)	C14—C15—H15C	109.5
C7—C2—C1	120.33 (15)	H15A—C15—H15B	109.5
C7—C2—C3	119.45 (15)	H15A—C15—H15C	109.5
C2—C3—H3	119.8	H15B—C15—H15C	109.5
C4—C3—C2	120.44 (16)	N2—C16—C17	113.53 (16)
C4—C3—H3	119.8	N2—C16—H16A	108.9
C3—C4—H4	120.7	N2—C16—H16B	108.9
C5—C4—C3	118.55 (16)	C17—C16—H16A	108.9
C5—C4—H4	120.7	C17—C16—H16B	108.9
C4—C5—Br1	119.00 (13)	H16A—C16—H16B	107.7
C4—C5—C6	122.43 (16)	C16—C17—H17A	109.5
C6—C5—Br1	118.55 (13)	C16—C17—H17B	109.5
C5—C6—C7	118.23 (16)	C16—C17—H17C	109.5
C5—C6—H6	120.9	H17A—C17—H17B	109.5
C7—C6—H6	120.9	H17A—C17—H17C	109.5
C2—C7—H7	119.6	H17B—C17—H17C	109.5
O4—Mn1—O1—C1	−18.28 (14)	C14—N2—C16—C17	63.1 (2)
O4i—Mn1—O1—C1	161.72 (14)	O1—C1—C2—C3	176.80 (15)
N1—Mn1—O1—C1	−105.33 (14)	O1—C1—C2—C7	−3.0 (2)
N1i—Mn1—O1—C1	74.67 (14)	O2—C1—C2—C3	−3.0 (2)
O1—Mn1—N1—C8	−31.20 (13)	O2—C1—C2—C7	177.19 (14)
O1i—Mn1—N1—C8	148.80 (13)	C4—C3—C2—C1	178.07 (15)
O1—Mn1—N1—C12	147.52 (12)	C4—C3—C2—C7	−2.1 (2)
O1i—Mn1—N1—C12	−32.48 (12)	C3—C4—C5—Br1	−179.73 (13)
O4—Mn1—N1—C8	−121.63 (13)	C3—C4—C5—C6	1.7 (3)
O4i—Mn1—N1—C8	58.37 (13)	C5—C4—C3—C2	0.3 (3)
O4—Mn1—N1—C12	57.09 (13)	Br1—C5—C6—C7	179.61 (13)
O4i—Mn1—N1—C12	−122.91 (13)	C4—C5—C6—C7	−1.9 (3)
Mn1—O1—C1—O2	33.9 (2)	C5—C6—C7—C2	−0.1 (2)
Mn1—O1—C1—C2	−145.88 (11)	C6—C7—C2—C1	−178.19 (15)
Mn1—N1—C8—C9	−179.79 (13)	C6—C7—C2—C3	2.0 (2)
C12—N1—C8—C9	1.5 (2)	N1—C8—C9—C10	0.1 (3)
Mn1—N1—C12—C11	179.07 (12)	C11—C10—C9—C8	−1.0 (3)
C8—N1—C12—C11	−2.1 (2)	C9—C10—C11—C12	0.4 (2)
C14—N2—C13—O3	−4.2 (2)	C9—C10—C11—C13	−170.84 (16)
C14—N2—C13—C11	174.13 (15)	C10—C11—C13—O3	117.15 (18)
C16—N2—C13—O3	175.47 (16)	C10—C11—C13—N2	−61.2 (2)
C16—N2—C13—C11	−6.2 (2)	C12—C11—C13—O3	−54.2 (2)
C13—N2—C14—C15	78.2 (2)	C12—C11—C13—N2	127.49 (17)
C16—N2—C14—C15	−101.50 (19)	N1—C12—C11—C10	1.2 (3)
C13—N2—C16—C17	−116.6 (2)	N1—C12—C11—C13	172.96 (15)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H41···O2	0.86 (3)	1.82 (3)	2.6606 (18)	165 (3)
O4—H42···O3ii	0.82 (2)	1.92 (3)	2.742 (2)	166 (3)
C6—H6···O2iii	0.93	2.30	3.168 (3)	155
C10—H10···O2iv	0.93	2.44	3.353 (2)	168

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H41⋯O2	0.86 (3)	1.82 (3)	2.6606 (18)	165 (3)
O4—H42⋯O3	0.82 (2)	1.92 (3)	2.742 (2)	166 (3)
C6—H6⋯O2i	0.93	2.30	3.168 (3)	155
C10—H10⋯O2	0.93	2.44	3.353 (2)	168

Symmetry code: (i) .