Diaqua­bis(4-chloro­benzoato-κO)bis­(N,N-diethyl­nicotinamide-κN1)manganese(II)

Hökelek, T.; Çaylak, N.; Necefoğlu, H.

doi:10.1107/S1600536808005540

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 3| March 2008| Pages m505-m506

doi:10.1107/S1600536808005540

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Diaquabis(4-chlorobenzoato-κO)bis(N,N-diethylnicotinamide-κN¹)manganese(II)

Tuncer Hökelek,^a ^* Nagihan Çaylak ^b and Hacali Necefoğlu ^c

^aDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey, ^bDepartment of Physics, Faculty of Arts and Sciences, Sakarya University, 54187 Esentepe, Adapazarı, Turkey, and ^cDepartment of Chemistry, Kafkas University, 63100 Kars, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

(Received 19 February 2008; accepted 27 February 2008; online 29 February 2008)

The title compound, [Mn(C₇H₄ClO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂], is a monomeric complex with the Mn^II atom lying on an inversion center. It contains two 4-chlorobenzoate and two diethylnicotinamide ligands and two water molecules, all of which are monodentate. The four O atoms in the equatorial plane around the Mn atom form a slightly distorted square-planar arrangement, while the distorted octahedral geometry is completed by two N atoms in the axial positions. In the crystal structure, O—H⋯O hydrogen bonds link the molecules into an infinite chain.

Related literature

For general background, see: Adiwidjaja et al. (1978 ); Amiraslanov et al. (1979 ); Antolini et al. (1982 ); Antsyshkina et al. (1980 ); Nadzhafov et al. (1981 ); Shnulin et al. (1981 ). For related structures, see: Hökelek et al. (1995 , 1997 ); Hökelek et al. (2007 ); Hökelek & Necefoğlu (1996 , 1997 , 2007 ).

Experimental

Crystal data

[Mn(C₇H₄ClO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂]
M_r = 758.54
Triclinic, $[P \overline 1]$
a = 7.3552 (1) Å
b = 8.6465 (2) Å
c = 15.9847 (3) Å
α = 84.500 (16)°
β = 78.616 (17)°
γ = 68.154 (17)°
V = 924.73 (12) Å³
Z = 1
Mo Kα radiation
μ = 0.56 mm⁻¹
T = 294 (2) K
0.30 × 0.15 × 0.10 mm

Data collection

Enraf–Nonius TurboCAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.902, T_max = 0.950
4010 measured reflections
3752 independent reflections
2604 reflections with I > 2σ(I)
R_int = 0.062
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.080
wR(F²) = 0.254
S = 1.04
3752 reflections
225 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.26 e Å⁻³
Δρ_min = −1.31 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Mn—O1	2.141 (3)
Mn—O4	2.205 (4)
Mn—N1	2.281 (4)

O1ⁱ—Mn—O4	90.38 (14)
O1—Mn—O4	89.62 (14)
O1—Mn—N1ⁱ	92.23 (14)
O4—Mn—N1ⁱ	92.72 (14)
O1—Mn—N1	87.77 (14)
O4—Mn—N1	87.28 (14)
Symmetry code: (i) -x, -y+2, -z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H41⋯O2ⁱ	0.99 (4)	1.71 (5)	2.670 (6)	162 (7)
O4—H42⋯O3ⁱⁱ	0.93 (5)	1.85 (5)	2.766 (6)	168 (7)
Symmetry codes: (i) -x, -y+2, -z; (ii) -x-1, -y+2, -z.

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808005540/hy2120sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808005540/hy2120Isup2.hkl

checkCIF report

Comment top

Transition metal complexes with biochemical molecules show interesting physical and/or chemical properties, through which they may find applications in biological systems (Antolini et al., 1982). The structural functions and coordination relationships of the arylcarboxylate ions in manganese(II) complexes of benzoic acid derivatives may be changed, depending on the nature and position of the substituted groups on the benzene ring, the nature of the additional ligand molecule or solvent, and the medium of the synthesis (Adiwidjaja et al., 1978; Amiraslanov et al., 1979; Antsyshkina et al., 1980; Nadzhafov et al., 1981; Shnulin et al., 1981).

N,N-Diethylnicotinamide (DENA) is an important respiratory stimulant. The structures of several complexes obtained by reacting divalent transition metal ions with DENA have been determined in our laboratory, including those of Cu₂(DENA)₂(C₆H₅COO)₄, (II), (Hökelek et al., 1995), [Zn₂(DENA)₂(C₇H₅O₃)₄].2H₂O, (III), (Hökelek & Necefoğlu, 1996), [Co(DENA)₂(C₇H₅O₃)₂(H₂O)₂], (IV), (Hökelek & Necefoğlu, 1997), [Cu(DENA)₂(C₇H₄NO₄)₂(H₂O)₂], (V), (Hökelek et al., 1997) and [Zn(DENA)₂(C₇H₄FO₂)₂(H₂O)₂], (VI), (Hökelek et al., 2007). The structure determination of the title compound, (I), a manganese(II) complex with two chlorobenzoate (CB), two DENA ligands and two water molecules, was undertaken in order to determine the properties of the CB and DENA ligands and also to compare the results obtained with those reported previously.

Compound (I) is a monomeric complex, with the Mn atom lying on a center of symmetry. It contains two CB, two DENA ligands and two water molecules (Fig. 1). All ligands are monodentate. The four O atoms (O1, O4, and their symmetry-related atoms) in the equatorial plane around the Mn atom form a slightly distorted square-planar arrangement, while the slightly distorted octahedral coordination geometry is completed by the two N atoms of the DENA ligands in the axial positions (Table 1 and Fig. 1).

The near equality of the C1—O1 [1.256 (6) Å] and C1—O2 [1.245 (6) Å] bonds in the carboxylate group indicates a delocalized bonding arrangement, rather than localized single and double bonds, and may be compared with the corresponding distances: 1.259 (9) and 1.273 (9) Å in (II), 1.279 (4) and 1.246 (4) Å in (III), 1.251 (6) and 1.254 (7) Å in (IV), 1.278 (3) and 1.246 (3) Å in (V) and 1.265 (6) and 1.275 (6) Å in [Mn(C₉H₁₀NO₂)₂(H₂O)₄].2H₂O, (VII), (Hökelek & Necefoğlu, 2007). This may be due to the intramolecular O—H···O hydrogen bond involving the carboxylate O atom (Table 2). In (I), the average Mn—O bond length is 2.173 (3) Å. The Mn atom is displaced out of the least-squares plane of the carboxylate group (O1/C1/O2) by 0.890 (1) Å; this is reported as 2.185 (4) and 1.365 (3) Å, respectively, in (VII). The dihedral angle between the planar carboxylate group and the benzene ring A (C2 to C7) is 3.0 (4)°, while that between rings A and B (N1/C8 to C12) is 81.0 (4)°.

As can be seen from the packing diagram (Fig. 2), the Mn atoms are located at the corners of the unit cell and the molecules of (I) are linked into infinite chains along the a-axis by intermolecular O—H···O hydrogen bonds (Table 2).

Related literature top

For general background, see: Adiwidjaja et al. (1978); Amiraslanov et al. (1979); Antolini et al. (1982); Antsyshkina et al. (1980); Nadzhafov et al. (1981); Shnulin et al. (1981). For related structures, see: Hökelek et al. (1995, 1997); Hökelek et al. (2007); Hökelek & Necefoğlu (1996, 1997, 2007).

Experimental top

The title compound was prepared by the reaction of Mn(NO₃)₂ (1.79 g, 10 mmol) in H₂O (25 ml) and DENA (3.56 g, 20 mmol) in H₂O (25 ml) with sodium p-chlorobenzoate (3.57 g, 20 mmol) in H₂O (100 ml). The mixture was filtered and set aside to crystallize at ambient temperature for several days, giving colorless single crystals.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 20% probability level. Hydrogen bonds are shown as dashed lines. [Symmetry code: (i) -x, 2 - y, -z.]
	Fig. 2. A packing diagram of the title compound, viewed down the a-axis, showing hydrogen bonds (dashed lines) linking the molecules into chains. H atoms not involved in hydrogen bonds have been omitted for clarity.

Diaquabis(4-chlorobenzoato-κO)bis(N,N-diethylnicotinamide-κN¹)manganese(II) top

Crystal data top

[Mn(C₇H₄ClO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂]	Z = 1
M_r = 758.54	F(000) = 395
Triclinic, P1	D_x = 1.362 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3552 (1) Å	Cell parameters from 25 reflections
b = 8.6465 (2) Å	θ = 5.2–11.6°
c = 15.9847 (3) Å	µ = 0.56 mm⁻¹
α = 84.500 (16)°	T = 294 K
β = 78.616 (17)°	Block, colorless
γ = 68.154 (17)°	0.30 × 0.15 × 0.10 mm
V = 924.73 (12) Å³

Data collection top

Enraf–Nonius TurboCAD-4 diffractometer	2604 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.062
Graphite monochromator	θ_max = 26.3°, θ_min = 3.0°
ω scans	h = −8→9
Absorption correction: ψ scan (North et al., 1968)	k = 0→10
T_min = 0.902, T_max = 0.950	l = −19→19
4010 measured reflections	3 standard reflections every 120 min
3752 independent reflections	intensity decay: 1%

Refinement top

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)] = 0.080	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.254	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.1471P)² + 1.5562P] where P = (F_o² + 2F_c²)/3
3752 reflections	(Δ/σ)_max < 0.001
225 parameters	Δρ_max = 1.26 e Å⁻³
5 restraints	Δρ_min = −1.31 e Å⁻³

Crystal data top

[Mn(C₇H₄ClO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂]	γ = 68.154 (17)°
M_r = 758.54	V = 924.73 (12) Å³
Triclinic, P1	Z = 1
a = 7.3552 (1) Å	Mo Kα radiation
b = 8.6465 (2) Å	µ = 0.56 mm⁻¹
c = 15.9847 (3) Å	T = 294 K
α = 84.500 (16)°	0.30 × 0.15 × 0.10 mm
β = 78.616 (17)°

Data collection top

Enraf–Nonius TurboCAD-4 diffractometer	2604 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.062
T_min = 0.902, T_max = 0.950	3 standard reflections every 120 min
4010 measured reflections	intensity decay: 1%
3752 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.080	5 restraints
wR(F²) = 0.254	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 1.26 e Å⁻³
3752 reflections	Δρ_min = −1.31 e Å⁻³
225 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Mn	0.0000	1.0000	0.0000	0.0323 (3)
Cl	−0.7397 (3)	0.8445 (3)	0.46709 (13)	0.0925 (7)
O1	−0.1119 (5)	0.8758 (4)	0.1086 (2)	0.0408 (8)
O2	0.0744 (5)	0.8690 (5)	0.2036 (3)	0.0508 (10)
O3	−0.8388 (6)	1.3270 (5)	0.1267 (3)	0.0576 (11)
O4	−0.2247 (6)	0.9829 (5)	−0.0681 (2)	0.0463 (9)
H41	−0.195 (10)	1.042 (7)	−0.122 (2)	0.07 (2)*
H42	−0.221 (12)	0.880 (5)	−0.083 (4)	0.08 (2)*
N1	−0.2326 (6)	1.2447 (5)	0.0532 (3)	0.0360 (9)
N2	−0.8349 (8)	1.4183 (8)	0.2506 (4)	0.0649 (15)
C1	−0.0808 (7)	0.8688 (6)	0.1836 (3)	0.0366 (11)
C2	−0.2462 (7)	0.8636 (5)	0.2547 (3)	0.0350 (10)
C3	−0.4206 (7)	0.8580 (6)	0.2372 (3)	0.0381 (11)
H3	−0.4358	0.8589	0.1807	0.046*
C4	−0.5733 (8)	0.8509 (7)	0.3024 (4)	0.0487 (13)
H4	−0.6898	0.8463	0.2904	0.058*
C5	−0.5477 (9)	0.8509 (8)	0.3850 (4)	0.0525 (14)
C6	−0.3789 (9)	0.8586 (8)	0.4047 (4)	0.0533 (14)
H6	−0.3655	0.8585	0.4613	0.064*
C7	−0.2282 (8)	0.8665 (7)	0.3392 (3)	0.0434 (12)
H7	−0.1138	0.8739	0.3520	0.052*
C8	−0.2050 (7)	1.3893 (6)	0.0424 (3)	0.0390 (11)
H8	−0.0855	1.3917	0.0107	0.047*
C9	−0.3452 (8)	1.5356 (6)	0.0760 (4)	0.0461 (13)
H9	−0.3203	1.6343	0.0676	0.055*
C10	−0.5227 (8)	1.5332 (6)	0.1223 (4)	0.0442 (13)
H10	−0.6197	1.6304	0.1458	0.053*
C11	−0.5554 (7)	1.3848 (6)	0.1334 (3)	0.0359 (11)
C12	−0.4080 (7)	1.2446 (6)	0.0965 (3)	0.0380 (11)
H12	−0.4315	1.1453	0.1020	0.046*
C13	−0.7519 (7)	1.3715 (6)	0.1710 (3)	0.0413 (12)
C14	−0.7427 (13)	1.4762 (10)	0.3087 (5)	0.080 (2)
H14A	−0.6247	1.4935	0.2770	0.096*
H14B	−0.8350	1.5823	0.3318	0.096*
C15	−0.6883 (17)	1.3572 (14)	0.3785 (7)	0.132
H15A	−0.6290	1.3989	0.4151	0.132*
H15B	−0.5949	1.2527	0.3558	0.132*
H15C	−0.8052	1.3412	0.4106	0.132*
C16	−1.0402 (11)	1.4197 (10)	0.2815 (6)	0.080 (2)
H16A	−1.1031	1.4942	0.3291	0.096*
H16B	−1.1177	1.4616	0.2362	0.096*
C17	−1.0391 (16)	1.2541 (11)	0.3085 (7)	0.107 (3)
H17A	−1.1734	1.2589	0.3272	0.160*
H17B	−0.9659	1.2137	0.3546	0.160*
H17C	−0.9773	1.1802	0.2614	0.160*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn	0.0261 (5)	0.0275 (5)	0.0373 (6)	−0.0030 (4)	−0.0004 (4)	−0.0107 (4)
Cl	0.0696 (12)	0.144 (2)	0.0638 (12)	−0.0517 (13)	0.0190 (9)	−0.0096 (12)
O1	0.043 (2)	0.0384 (19)	0.0390 (19)	−0.0133 (16)	−0.0033 (15)	−0.0072 (14)
O2	0.034 (2)	0.061 (3)	0.057 (2)	−0.0162 (18)	−0.0097 (17)	−0.0010 (19)
O3	0.043 (2)	0.066 (3)	0.070 (3)	−0.022 (2)	−0.0078 (19)	−0.022 (2)
O4	0.043 (2)	0.046 (2)	0.054 (2)	−0.0195 (17)	−0.0090 (17)	−0.0081 (18)
N1	0.030 (2)	0.026 (2)	0.046 (2)	−0.0054 (16)	−0.0002 (17)	−0.0086 (16)
N2	0.052 (3)	0.079 (4)	0.061 (3)	−0.026 (3)	0.011 (2)	−0.024 (3)
C1	0.031 (2)	0.022 (2)	0.049 (3)	−0.0010 (18)	−0.007 (2)	−0.0055 (19)
C2	0.034 (2)	0.022 (2)	0.044 (3)	−0.0032 (18)	−0.006 (2)	−0.0050 (18)
C3	0.037 (3)	0.033 (3)	0.043 (3)	−0.012 (2)	−0.007 (2)	−0.005 (2)
C4	0.036 (3)	0.058 (3)	0.055 (3)	−0.021 (3)	−0.005 (2)	−0.005 (3)
C5	0.044 (3)	0.055 (3)	0.051 (3)	−0.015 (3)	0.005 (3)	−0.005 (3)
C6	0.055 (3)	0.064 (4)	0.038 (3)	−0.018 (3)	−0.006 (2)	−0.001 (3)
C7	0.036 (3)	0.045 (3)	0.047 (3)	−0.010 (2)	−0.008 (2)	−0.008 (2)
C8	0.032 (2)	0.032 (2)	0.051 (3)	−0.009 (2)	−0.005 (2)	−0.009 (2)
C9	0.042 (3)	0.030 (3)	0.066 (4)	−0.012 (2)	−0.007 (3)	−0.009 (2)
C10	0.040 (3)	0.027 (2)	0.059 (3)	−0.003 (2)	−0.005 (2)	−0.018 (2)
C11	0.031 (2)	0.032 (2)	0.040 (3)	−0.0040 (19)	−0.0066 (19)	−0.0103 (19)
C12	0.030 (2)	0.028 (2)	0.050 (3)	−0.0054 (19)	0.000 (2)	−0.010 (2)
C13	0.031 (2)	0.038 (3)	0.051 (3)	−0.007 (2)	−0.003 (2)	−0.013 (2)
C14	0.085 (5)	0.078 (5)	0.072 (5)	−0.029 (4)	−0.002 (4)	−0.009 (4)
C15	0.180	0.156	0.138	−0.130	−0.127	0.126
C16	0.060 (4)	0.067 (5)	0.098 (6)	−0.015 (4)	0.018 (4)	−0.026 (4)
C17	0.116 (8)	0.071 (6)	0.112 (7)	−0.031 (5)	0.030 (6)	−0.014 (5)

Geometric parameters (Å, º) top

Mn—O1ⁱ	2.141 (3)	C7—C6	1.383 (8)
Mn—O1	2.141 (3)	C7—H7	0.9300
Mn—O4	2.205 (4)	C8—H8	0.9300
Mn—O4ⁱ	2.205 (4)	C9—C8	1.376 (7)
Mn—N1ⁱ	2.281 (4)	C9—H9	0.9300
Mn—N1	2.281 (4)	C10—C9	1.373 (8)
Cl—C5	1.741 (6)	C10—H10	0.9300
O1—C1	1.256 (6)	C11—C12	1.378 (6)
O2—C1	1.245 (6)	C11—C10	1.380 (7)
O3—C13	1.214 (6)	C12—H12	0.9300
O4—H41	0.99 (4)	C13—N2	1.328 (7)
O4—H42	0.93 (5)	C13—C11	1.494 (7)
N1—C8	1.330 (6)	C14—C15	1.453 (9)
N1—C12	1.339 (6)	C14—H14A	0.9700
N2—C14	1.471 (10)	C14—H14B	0.9700
N2—C16	1.489 (9)	C15—H15A	0.9600
C2—C3	1.384 (7)	C15—H15B	0.9600
C2—C7	1.387 (7)	C15—H15C	0.9600
C2—C1	1.502 (7)	C16—C17	1.453 (11)
C3—H3	0.9300	C16—H16A	0.9700
C4—C5	1.369 (8)	C16—H16B	0.9700
C4—C3	1.388 (7)	C17—H17A	0.9600
C4—H4	0.9300	C17—H17B	0.9600
C5—C6	1.366 (9)	C17—H17C	0.9600
C6—H6	0.9300

O1ⁱ—Mn—O1	180.000 (1)	C6—C7—H7	119.7
O1ⁱ—Mn—O4	90.38 (14)	C2—C7—H7	119.7
O1—Mn—O4	89.62 (14)	N1—C8—C9	122.9 (5)
O1ⁱ—Mn—O4ⁱ	89.62 (14)	N1—C8—H8	118.5
O1—Mn—O4ⁱ	90.38 (14)	C9—C8—H8	118.5
O4—Mn—O4ⁱ	180.00 (16)	C10—C9—C8	118.8 (5)
O1ⁱ—Mn—N1ⁱ	87.77 (14)	C10—C9—H9	120.6
O1—Mn—N1ⁱ	92.23 (14)	C8—C9—H9	120.6
O4—Mn—N1ⁱ	92.72 (14)	C9—C10—C11	119.2 (4)
O4ⁱ—Mn—N1ⁱ	87.28 (14)	C9—C10—H10	120.4
O1ⁱ—Mn—N1	92.23 (14)	C11—C10—H10	120.4
O1—Mn—N1	87.77 (14)	C12—C11—C10	118.2 (5)
O4—Mn—N1	87.28 (14)	C12—C11—C13	117.2 (4)
O4ⁱ—Mn—N1	92.72 (14)	C10—C11—C13	123.8 (4)
N1ⁱ—Mn—N1	180.0	N1—C12—C11	123.0 (5)
C1—O1—Mn	127.5 (3)	N1—C12—H12	118.5
Mn—O4—H41	100 (4)	C11—C12—H12	118.5
Mn—O4—H42	121 (5)	O3—C13—N2	120.8 (5)
H41—O4—H42	107 (4)	O3—C13—C11	119.4 (5)
C8—N1—C12	117.7 (4)	N2—C13—C11	119.7 (5)
C8—N1—Mn	123.5 (3)	C15—C14—N2	111.7 (7)
C12—N1—Mn	118.8 (3)	C15—C14—H14A	109.3
C13—N2—C14	124.8 (6)	N2—C14—H14A	109.3
C13—N2—C16	117.3 (6)	C15—C14—H14B	109.3
C14—N2—C16	117.8 (6)	N2—C14—H14B	109.3
O2—C1—O1	125.2 (5)	H14A—C14—H14B	107.9
O2—C1—C2	117.6 (5)	C14—C15—H15A	109.5
O1—C1—C2	117.1 (4)	C14—C15—H15B	109.5
C3—C2—C7	118.6 (5)	H15A—C15—H15B	109.5
C3—C2—C1	120.8 (5)	C14—C15—H15C	109.5
C7—C2—C1	120.6 (5)	H15A—C15—H15C	109.5
C2—C3—C4	121.2 (5)	H15B—C15—H15C	109.5
C2—C3—H3	119.4	C17—C16—N2	111.5 (7)
C4—C3—H3	119.4	C17—C16—H16A	109.3
C5—C4—C3	118.2 (5)	N2—C16—H16A	109.3
C5—C4—H4	120.9	C17—C16—H16B	109.3
C3—C4—H4	120.9	N2—C16—H16B	109.3
C6—C5—C4	122.2 (5)	H16A—C16—H16B	108.0
C6—C5—Cl	119.3 (5)	C16—C17—H17A	109.5
C4—C5—Cl	118.5 (5)	C16—C17—H17B	109.5
C5—C6—C7	119.1 (5)	H17A—C17—H17B	109.5
C5—C6—H6	120.5	C16—C17—H17C	109.5
C7—C6—H6	120.5	H17A—C17—H17C	109.5
C6—C7—C2	120.6 (5)	H17B—C17—H17C	109.5

O4—Mn—O1—C1	−164.0 (4)	C7—C2—C1—O2	2.8 (7)
O4ⁱ—Mn—O1—C1	16.0 (4)	C3—C2—C1—O1	3.3 (6)
N1ⁱ—Mn—O1—C1	103.3 (4)	C7—C2—C1—O1	−175.9 (4)
N1—Mn—O1—C1	−76.7 (4)	C7—C2—C3—C4	−1.7 (7)
O1ⁱ—Mn—N1—C8	−32.0 (4)	C1—C2—C3—C4	179.1 (5)
O1—Mn—N1—C8	148.0 (4)	C5—C4—C3—C2	0.5 (8)
O4—Mn—N1—C8	−122.3 (4)	C3—C4—C5—C6	0.4 (9)
O4ⁱ—Mn—N1—C8	57.7 (4)	C3—C4—C5—Cl	179.2 (4)
O1ⁱ—Mn—N1—C12	146.8 (4)	C4—C5—C6—C7	−0.1 (10)
O1—Mn—N1—C12	−33.2 (4)	Cl—C5—C6—C7	−178.9 (5)
O4—Mn—N1—C12	56.6 (4)	C2—C7—C6—C5	−1.2 (9)
O4ⁱ—Mn—N1—C12	−123.4 (4)	C10—C9—C8—N1	−0.6 (9)
Mn—O1—C1—O2	−31.6 (7)	C11—C10—C9—C8	−0.2 (8)
Mn—O1—C1—C2	146.9 (3)	C12—C11—C10—C9	−0.7 (8)
Mn—N1—C8—C9	−178.9 (4)	C13—C11—C10—C9	−170.7 (5)
C12—N1—C8—C9	2.2 (8)	C10—C11—C12—N1	2.4 (8)
C8—N1—C12—C11	−3.2 (8)	C13—C11—C12—N1	173.1 (5)
Mn—N1—C12—C11	177.9 (4)	O3—C13—N2—C14	−179.1 (6)
C13—N2—C14—C15	−111.0 (9)	C11—C13—N2—C14	−3.4 (10)
C16—N2—C14—C15	72.0 (10)	O3—C13—N2—C16	−2.2 (9)
C13—N2—C16—C17	81.2 (9)	C11—C13—N2—C16	173.5 (5)
C14—N2—C16—C17	−101.6 (9)	O3—C13—C11—C10	114.1 (6)
C3—C2—C7—C6	2.0 (8)	N2—C13—C11—C10	−61.6 (8)
C1—C2—C7—C6	−178.8 (5)	O3—C13—C11—C12	−55.9 (7)
C3—C2—C1—O2	−178.0 (4)	N2—C13—C11—C12	128.3 (6)

Symmetry code: (i) −x, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H41···O2ⁱ	0.99 (4)	1.71 (5)	2.670 (6)	162 (7)
O4—H42···O3ⁱⁱ	0.93 (5)	1.85 (5)	2.766 (6)	168 (7)

Symmetry codes: (i) −x, −y+2, −z; (ii) −x−1, −y+2, −z.

Experimental details

Crystal data
Chemical formula	[Mn(C₇H₄ClO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂]
M_r	758.54
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	7.3552 (1), 8.6465 (2), 15.9847 (3)
α, β, γ (°)	84.500 (16), 78.616 (17), 68.154 (17)
V (Å³)	924.73 (12)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.56
Crystal size (mm)	0.30 × 0.15 × 0.10

Data collection
Diffractometer	Enraf–Nonius TurboCAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.902, 0.950
No. of measured, independent and observed [I > 2σ(I)] reflections	4010, 3752, 2604
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.623

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.080, 0.254, 1.04
No. of reflections	3752
No. of parameters	225
No. of restraints	5
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.26, −1.31

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top

Mn—O1	2.141 (3)	Mn—N1	2.281 (4)
Mn—O4	2.205 (4)

O1ⁱ—Mn—O4	90.38 (14)	O4—Mn—N1ⁱ	92.72 (14)
O1—Mn—O4	89.62 (14)	O1—Mn—N1	87.77 (14)
O1—Mn—N1ⁱ	92.23 (14)	O4—Mn—N1	87.28 (14)

Symmetry code: (i) −x, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H41···O2ⁱ	0.99 (4)	1.71 (5)	2.670 (6)	162 (7)
O4—H42···O3ⁱⁱ	0.93 (5)	1.85 (5)	2.766 (6)	168 (7)

Symmetry codes: (i) −x, −y+2, −z; (ii) −x−1, −y+2, −z.

Acknowledgements

The authors acknowledge the purchase of a CAD-4 diffractometer under grant DPT/TBAG1 of the Scientific and Technical Research Council of Turkey.

References

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