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

In the monomeric title complex, [Mn(C(7)H(4)ClO(2))(2)(C(10)H(14)N(2)O)(2)(H(2)O)(2)], the Mn(II) atom is located on a crystallographic centre of inversion. The asymmetric unit contains one 2-chloro-benzoate (CB) ligand, one diethyl-nicotinamide (DENA) ligand and one coordinated water mol-ecule, 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 slightly distorted octa-hedral coordination is completed by the two pyridine N atoms of the DENA ligands in the axial positions. The dihedral angle between the carboxyl group and the adjacent benzene ring is 77.9 (11)°, while the pyridine and benzene rings are oriented at a dihedral angle of 45.94 (5)°. In the crystal structure, inter-molecular O-H⋯O hydrogen bonds link the mol-ecules into infinite chains.

Related literature

For general backgroud to transition metal complexes with biochemically active ligands, 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(C7H4ClO2)2(C10H14N2O)2(n class="Chemical">H2O)2]

M = 758.54

Monoclinic,

a = 13.2840 (2) Å

b = 10.2499 (3) Å

c = 15.0023 (4) Å

β = 114.988 (1)°

V = 1851.50 (8) Å3

Z = 2

Mo Kα radiation

μ = 0.55 mm−1

T = 100 K

0.46 × 0.44 × 0.27 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.778, T max = 0.864

16951 measured reflections

4635 independent reflections

3984 reflections with I > 2σ(I)

R int = 0.048

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.091

S = 1.07

4635 reflections

233 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.17 e Å−3

Δρmin = −0.38 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/S160053680901318X/im2110sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680901318X/im2110Isup2.hkl

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

[Mn(C7H4ClO2)2(C10H14N2O)2(H2O)2]	F(000) = 790
Mr = 758.54	Dx = 1.361 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8796 reflections
a = 13.2840 (2) Å	θ = 2.5–28.4°
b = 10.2499 (3) Å	µ = 0.55 mm−1
c = 15.0023 (4) Å	T = 100 K
β = 114.988 (1)°	Block, colorless
V = 1851.50 (8) Å3	0.46 × 0.44 × 0.27 mm
Z = 2

Bruker Kappa APEXII CCD area-detector diffractometer	4635 independent reflections
Radiation source: fine-focus sealed tube	3984 reflections with I > 2σ(I)
graphite	Rint = 0.048
φ and ω scans	θmax = 28.4°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −17→17
Tmin = 0.778, Tmax = 0.864	k = −13→13
16951 measured reflections	l = −18→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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0439P)2 + 0.6941P] where P = (Fo2 + 2Fc2)/3
4635 reflections	(Δ/σ)max < 0.001
233 parameters	Δρmax = 1.17 e Å−3
3 restraints	Δρmin = −0.38 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
Mn1	0.5000	0.0000	0.0000	0.01025 (9)
Cl1	0.18512 (4)	−0.13983 (4)	0.08159 (3)	0.02988 (11)
O1	0.46966 (9)	−0.04216 (10)	0.12506 (7)	0.0170 (2)
O2	0.35458 (12)	0.11652 (11)	0.12485 (10)	0.0316 (3)
O3	0.93810 (8)	0.11259 (9)	0.39721 (7)	0.0163 (2)
O4	0.61938 (8)	−0.16212 (10)	0.03910 (7)	0.0146 (2)
H41	0.634 (2)	−0.173 (2)	−0.0135 (13)	0.053 (7)*
H42	0.6079 (18)	−0.2422 (16)	0.0558 (15)	0.038 (6)*
N1	0.64747 (10)	0.13022 (11)	0.09437 (8)	0.0142 (2)
N2	0.98935 (11)	0.00083 (12)	0.29330 (9)	0.0175 (3)
C1	0.40228 (12)	0.01065 (14)	0.15298 (10)	0.0158 (3)
C2	0.38071 (12)	−0.06704 (14)	0.22885 (10)	0.0168 (3)
C3	0.45941 (14)	−0.07053 (16)	0.32641 (11)	0.0230 (3)
H3	0.5231	−0.0196	0.3459	0.028*
C4	0.44378 (15)	−0.14936 (17)	0.39502 (12)	0.0274 (4)
H4	0.4965	−0.1505	0.4600	0.033*
C5	0.34943 (15)	−0.22608 (17)	0.36617 (13)	0.0279 (4)
H5	0.3396	−0.2800	0.4117	0.033*
C6	0.26970 (15)	−0.22309 (16)	0.26997 (12)	0.0247 (3)
H6	0.2061	−0.2742	0.2506	0.030*
C7	0.28603 (13)	−0.14272 (15)	0.20293 (11)	0.0198 (3)
C8	0.64781 (12)	0.26020 (14)	0.08373 (10)	0.0161 (3)
H8	0.5867	0.2994	0.0340	0.019*
C9	0.73522 (12)	0.33862 (14)	0.14366 (10)	0.0167 (3)
H9	0.7324	0.4284	0.1340	0.020*
C10	0.82671 (12)	0.28205 (13)	0.21802 (10)	0.0150 (3)
H10	0.8856	0.3329	0.2601	0.018*
C11	0.82833 (11)	0.14699 (13)	0.22827 (10)	0.0136 (3)
C12	0.73728 (12)	0.07548 (14)	0.16547 (10)	0.0146 (3)
H12	0.7385	−0.0147	0.1730	0.017*
C13	0.92349 (11)	0.08431 (13)	0.31200 (10)	0.0134 (3)
C14	0.98096 (15)	−0.03017 (19)	0.19502 (12)	0.0299 (4)
H14A	1.0537	−0.0218	0.1951	0.036*
H14B	0.9320	0.0323	0.1482	0.036*
C15	0.93702 (17)	−0.1674 (2)	0.16204 (15)	0.0459 (6)
H15A	0.9385	−0.1857	0.0998	0.069*
H15B	0.8621	−0.1737	0.1555	0.069*
H15C	0.9828	−0.2294	0.2100	0.069*
C16	1.08576 (12)	−0.05400 (15)	0.37696 (11)	0.0192 (3)
H16A	1.1004	−0.1414	0.3606	0.023*
H16B	1.0688	−0.0601	0.4337	0.023*
C17	1.18844 (14)	0.02997 (17)	0.40244 (12)	0.0259 (4)
H17A	1.2498	−0.0080	0.4570	0.039*
H17B	1.1745	0.1161	0.4198	0.039*
H17C	1.2059	0.0350	0.3466	0.039*

	U11	U22	U33	U12	U13	U23
Mn1	0.01013 (14)	0.01034 (14)	0.00924 (14)	−0.00008 (10)	0.00310 (11)	0.00017 (10)
Cl1	0.0296 (2)	0.0346 (2)	0.0235 (2)	−0.00607 (17)	0.00939 (16)	−0.00069 (15)
O1	0.0177 (5)	0.0201 (5)	0.0156 (5)	0.0057 (4)	0.0093 (4)	0.0049 (4)
O2	0.0518 (8)	0.0195 (6)	0.0413 (7)	0.0159 (5)	0.0369 (7)	0.0131 (5)
O3	0.0187 (5)	0.0141 (5)	0.0116 (5)	0.0021 (4)	0.0019 (4)	−0.0019 (4)
O4	0.0170 (5)	0.0107 (5)	0.0161 (5)	0.0004 (4)	0.0068 (4)	0.0007 (4)
N1	0.0140 (6)	0.0132 (6)	0.0127 (5)	−0.0008 (4)	0.0030 (5)	0.0004 (4)
N2	0.0168 (6)	0.0199 (6)	0.0127 (6)	0.0039 (5)	0.0031 (5)	−0.0002 (4)
C1	0.0193 (7)	0.0144 (7)	0.0163 (7)	−0.0006 (5)	0.0099 (6)	−0.0003 (5)
C2	0.0211 (7)	0.0145 (7)	0.0197 (7)	0.0043 (6)	0.0135 (6)	0.0028 (5)
C3	0.0220 (8)	0.0259 (8)	0.0227 (8)	0.0017 (6)	0.0111 (6)	0.0043 (6)
C4	0.0296 (9)	0.0337 (9)	0.0204 (8)	0.0064 (7)	0.0121 (7)	0.0087 (6)
C5	0.0381 (10)	0.0270 (9)	0.0276 (8)	0.0046 (7)	0.0226 (8)	0.0100 (7)
C6	0.0293 (9)	0.0221 (8)	0.0303 (8)	−0.0027 (7)	0.0198 (7)	0.0022 (6)
C7	0.0242 (8)	0.0198 (7)	0.0191 (7)	0.0017 (6)	0.0125 (6)	0.0006 (5)
C8	0.0147 (6)	0.0157 (7)	0.0142 (6)	0.0016 (5)	0.0025 (5)	0.0023 (5)
C9	0.0196 (7)	0.0111 (6)	0.0166 (7)	−0.0005 (5)	0.0050 (6)	0.0010 (5)
C10	0.0150 (6)	0.0141 (7)	0.0134 (6)	−0.0028 (5)	0.0035 (5)	−0.0020 (5)
C11	0.0136 (6)	0.0147 (6)	0.0102 (6)	0.0008 (5)	0.0029 (5)	0.0001 (5)
C12	0.0155 (6)	0.0120 (6)	0.0132 (6)	−0.0001 (5)	0.0031 (5)	0.0002 (5)
C13	0.0125 (6)	0.0099 (6)	0.0140 (6)	−0.0027 (5)	0.0018 (5)	−0.0001 (5)
C14	0.0262 (9)	0.0466 (11)	0.0154 (7)	0.0147 (8)	0.0072 (6)	−0.0029 (7)
C15	0.0322 (10)	0.0573 (13)	0.0357 (10)	0.0100 (9)	0.0022 (8)	−0.0289 (9)
C16	0.0181 (7)	0.0180 (7)	0.0174 (7)	0.0069 (6)	0.0037 (6)	0.0022 (5)
C17	0.0189 (8)	0.0314 (9)	0.0235 (8)	0.0012 (7)	0.0051 (6)	−0.0036 (6)

Mn1—O1	2.1233 (10)	C6—H6	0.9300
Mn1—O1i	2.1233 (10)	C7—C2	1.386 (2)
Mn1—O4i	2.1987 (10)	C7—C6	1.386 (2)
Mn1—O4	2.1987 (10)	C8—C9	1.3859 (19)
Mn1—N1i	2.2980 (12)	C8—H8	0.9300
Mn1—N1	2.2980 (12)	C9—C10	1.3828 (19)
Cl1—C7	1.7464 (16)	C9—H9	0.9300
O1—C1	1.2595 (18)	C10—H10	0.9300
O2—C1	1.2375 (18)	C11—C10	1.3920 (19)
O3—C13	1.2435 (17)	C11—C12	1.3875 (19)
O4—H41	0.896 (12)	C12—H12	0.9300
O4—H42	0.890 (15)	C13—C11	1.4991 (18)
N1—C8	1.3420 (18)	C14—C15	1.523 (3)
N1—C12	1.3419 (17)	C14—H14A	0.9700
N2—C13	1.3355 (19)	C14—H14B	0.9700
N2—C14	1.466 (2)	C15—H15A	0.9600
N2—C16	1.4742 (18)	C15—H15B	0.9600
C2—C1	1.512 (2)	C15—H15C	0.9600
C2—C3	1.394 (2)	C16—C17	1.519 (2)
C3—C4	1.392 (2)	C16—H16A	0.9700
C3—H3	0.9300	C16—H16B	0.9700
C4—C5	1.385 (3)	C17—H17A	0.9600
C4—H4	0.9300	C17—H17B	0.9600
C5—H5	0.9300	C17—H17C	0.9600
C6—C5	1.384 (2)
O1—Mn1—O1i	180.00 (8)	C6—C7—Cl1	118.68 (13)
O1—Mn1—O4i	90.28 (4)	C6—C7—C2	122.05 (15)
O1i—Mn1—O4i	89.72 (4)	N1—C8—C9	122.86 (13)
O1—Mn1—O4	89.72 (4)	N1—C8—H8	118.6
O1i—Mn1—O4	90.28 (4)	C9—C8—H8	118.6
O1—Mn1—N1i	89.75 (4)	C8—C9—H9	120.3
O1i—Mn1—N1i	90.25 (4)	C10—C9—C8	119.35 (13)
O1—Mn1—N1	90.25 (4)	C10—C9—H9	120.3
O1i—Mn1—N1	89.75 (4)	C9—C10—C11	118.26 (13)
O4i—Mn1—O4	180.00 (6)	C9—C10—H10	120.9
O4i—Mn1—N1i	86.76 (4)	C11—C10—H10	120.9
O4—Mn1—N1i	93.24 (4)	C12—C11—C10	118.82 (13)
O4i—Mn1—N1	93.24 (4)	C12—C11—C13	121.82 (12)
O4—Mn1—N1	86.76 (4)	C10—C11—C13	119.15 (12)
N1i—Mn1—N1	180.00 (10)	N1—C12—C11	123.10 (13)
Mn1—O4—H41	105.2 (15)	N1—C12—H12	118.5
Mn1—O4—H42	125.6 (14)	C11—C12—H12	118.5
H41—O4—H42	105.1 (19)	O3—C13—N2	122.25 (12)
C1—O1—Mn1	129.29 (9)	O3—C13—C11	118.14 (13)
C8—N1—Mn1	123.24 (9)	N2—C13—C11	119.60 (12)
C12—N1—Mn1	119.15 (9)	N2—C14—C15	112.51 (16)
C12—N1—C8	117.59 (12)	N2—C14—H14A	109.1
C13—N2—C14	124.89 (12)	N2—C14—H14B	109.1
C13—N2—C16	118.42 (12)	C15—C14—H14A	109.1
C14—N2—C16	116.32 (13)	C15—C14—H14B	109.1
O1—C1—C2	114.28 (12)	H14A—C14—H14B	107.8
O2—C1—O1	126.65 (14)	C14—C15—H15A	109.5
O2—C1—C2	119.07 (13)	C14—C15—H15B	109.5
C3—C2—C1	120.47 (14)	C14—C15—H15C	109.5
C7—C2—C1	121.43 (13)	H15A—C15—H15B	109.5
C7—C2—C3	117.99 (14)	H15A—C15—H15C	109.5
C2—C3—H3	119.6	H15B—C15—H15C	109.5
C4—C3—C2	120.76 (16)	N2—C16—C17	111.28 (13)
C4—C3—H3	119.6	N2—C16—H16A	109.4
C3—C4—H4	120.1	N2—C16—H16B	109.4
C5—C4—C3	119.78 (15)	C17—C16—H16A	109.4
C5—C4—H4	120.1	C17—C16—H16B	109.4
C4—C5—H5	119.8	H16A—C16—H16B	108.0
C6—C5—C4	120.42 (15)	C16—C17—H17A	109.5
C6—C5—H5	119.8	C16—C17—H17B	109.5
C5—C6—C7	118.98 (16)	C16—C17—H17C	109.5
C5—C6—H6	120.5	H17A—C17—H17B	109.5
C7—C6—H6	120.5	H17A—C17—H17C	109.5
C2—C7—Cl1	119.26 (11)	H17B—C17—H17C	109.5
O1—Mn1—N1—C8	−112.21 (12)	C3—C2—C1—O1	75.74 (18)
O1i—Mn1—N1—C8	67.79 (12)	C3—C2—C1—O2	−104.05 (18)
O1—Mn1—N1—C12	66.18 (11)	C7—C2—C1—O1	−100.36 (17)
O1i—Mn1—N1—C12	−113.82 (11)	C7—C2—C1—O2	79.85 (19)
O4i—Mn1—O1—C1	2.94 (12)	C1—C2—C3—C4	−175.23 (15)
O4—Mn1—O1—C1	−177.06 (12)	C7—C2—C3—C4	1.0 (2)
O4i—Mn1—N1—C8	−21.92 (12)	C2—C3—C4—C5	0.5 (3)
O4—Mn1—N1—C8	158.08 (12)	C3—C4—C5—C6	−1.1 (3)
O4i—Mn1—N1—C12	156.47 (11)	C7—C6—C5—C4	0.3 (3)
O4—Mn1—N1—C12	−23.53 (11)	C6—C7—C2—C1	174.34 (14)
N1i—Mn1—O1—C1	−83.82 (12)	C6—C7—C2—C3	−1.8 (2)
N1—Mn1—O1—C1	96.18 (12)	Cl1—C7—C2—C1	−4.3 (2)
Mn1—O1—C1—O2	−16.0 (2)	Cl1—C7—C2—C3	179.50 (12)
Mn1—O1—C1—C2	164.20 (9)	C2—C7—C6—C5	1.2 (2)
Mn1—N1—C8—C9	177.23 (11)	Cl1—C7—C6—C5	179.86 (13)
C12—N1—C8—C9	−1.2 (2)	N1—C8—C9—C10	0.0 (2)
Mn1—N1—C12—C11	−177.57 (11)	C8—C9—C10—C11	1.5 (2)
C8—N1—C12—C11	0.9 (2)	C12—C11—C10—C9	−1.7 (2)
C14—N2—C13—O3	−175.90 (15)	C13—C11—C10—C9	−176.41 (13)
C16—N2—C13—O3	−3.2 (2)	C10—C11—C12—N1	0.5 (2)
C14—N2—C13—C11	4.1 (2)	C13—C11—C12—N1	175.09 (13)
C16—N2—C13—C11	176.82 (12)	O3—C13—C11—C10	62.17 (19)
C13—N2—C14—C15	−108.92 (18)	O3—C13—C11—C12	−112.38 (16)
C16—N2—C14—C15	78.20 (18)	N2—C13—C11—C10	−117.81 (15)
C13—N2—C16—C17	−90.68 (17)	N2—C13—C11—C12	67.64 (19)
C14—N2—C16—C17	82.69 (17)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H41···O2i	0.90 (2)	1.83 (2)	2.666 (2)	154 (2)
O4—H42···O3ii	0.89 (2)	1.86 (2)	2.729 (1)	166 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H41⋯O2i	0.90 (2)	1.83 (2)	2.666 (2)	154 (2)
O4—H42⋯O3ii	0.89 (2)	1.86 (2)	2.729 (1)	166 (2)

Symmetry codes: (i) ; (ii) .