(Acetato-κO)diaqua­[2-(1H-benzotriazol-1-yl)acetato-κO](1,10-phenanthroline-κ2N,N′)manganese(II) dihydrate

Zeng, L.

doi:10.1107/S1600536812007404

metal-organic compounds

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Volume 68| Part 3| March 2012| Page m329

doi:10.1107/S1600536812007404

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(Acetato-κO)diaqua[2-(1H-benzotriazol-1-yl)acetato-κO](1,10-phenanthroline-κ²N,N′)manganese(II) dihydrate

Ling Zeng ^a ^*

^aCollege of Chemistry and Chemical Engineering of Bohai University, Jinzhou, Liaoning 121000, People's Republic of China
^*Correspondence e-mail: zengling1976@163.com

(Received 18 February 2012; accepted 18 February 2012; online 24 February 2012)

In the hydrated title complex, [Mn(C₈H₆N₃O₂)(CH₃CO₂)(C₁₂H₈N₂)(H₂O)₂]·2H₂O, the Mn^II atom is coordinated by two N atoms from a 1,10-phenanthroline ligand, two water O atoms, a monodentate acetate anion and an O-monodentate 2-(1H-benzotriazol-1-yl)acetate ligand, resulting in a distorted cis-MnN₂O₄ octahedral coordination geometry. The water O atoms are in a trans arrangement and one of them forms an intramolecular O—H⋯O hydrogen bond to the uncoordinated O atom of the acetate ion. In the crystal, the complex molecules and water molecules are connected by O—H⋯O and O—H⋯N hydrogen bonds to generate a three-dimensional network.

Related literature

For related structures, see: Zheng et al. (2010 ); Zeng & Wang (2012 ).

Experimental

Crystal data

[Mn(C₈H₆N₃O₂)(C₂H₃O₂)(C₁₂H₈N₂)(H₂O)₂]·2H₂O
M_r = 542.41
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.877 (1) Å
b = 17.383 (3) Å
c = 20.033 (3) Å
V = 2394.9 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.61 mm⁻¹
T = 296 K
0.22 × 0.18 × 0.16 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.878, T_max = 0.909
16178 measured reflections
4247 independent reflections
3921 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.066
S = 1.00
4247 reflections
325 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.16 e Å⁻³
Absolute structure: Flack (1983 ), 1798 Friedel pairs
Flack parameter: −0.028 (15)

Table 1
Selected geometric parameters (Å, °)

Mn1—O1	2.1009 (14)
Mn1—O3	2.1522 (14)
Mn1—O5	2.2221 (16)
Mn1—O6	2.2807 (16)
Mn1—N4	2.2532 (16)
Mn1—N5	2.2935 (16)

N4—Mn1—N5	73.09 (6)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H23⋯N3ⁱ	0.85	1.99	2.838 (2)	173
O5—H24⋯O6ⁱⁱ	0.85	2.14	2.987 (2)	172
O6—H25⋯O8ⁱⁱⁱ	0.85	1.88	2.732 (2)	175
O6—H26⋯O4	0.85	1.80	2.621 (2)	161
O7—H27⋯O4ⁱⁱ	0.85	1.97	2.807 (3)	166
O7—H28⋯O3	0.85	2.06	2.911 (2)	174
O8—H29⋯O7	0.85	2.04	2.890 (3)	176
O8—H30⋯O2^iv	0.85	1.93	2.773 (2)	171
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+1, z-{\script{1\over 2}}]$ ; (ii) x-1, y, z; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812007404/hb6645sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812007404/hb6645Isup2.hkl

checkCIF report

Comment top

Construction of supramolecular architectures with intersting physical properties has grown rapidly owing to their potential use as new functional materials. Many intriguing supramolecular assemblies have been prepared by metal coordination or hydrogen bonding interactions. As a flexible ligand, 2-(1H-benzo[d][1,2,3]triazol-1-yl)acetic acid contains a carboxylate group and a triazole to construct MOFs (Zheng et al., 2010). We have also been interested in this systems (Zeng et al., 2012). As continuation of previous work, herein we report the synthesis and crystal structure of the title new complex (I).

As shown in Figure 1, The Mn(II) atom is six-coordinated by two N atoms from one 1,10-phenanthroline ligand, two O atoms from water molecules, one O atom from an acetate anion and one O atom from 2-(1H-benzo[d][1,2,3]triazol-1-yl)acetate anion in a distorted octahedral geometry (Table 1). The equatorial plane is defined by N4, N5, O1 and O3 with a mean deviation of 0.2357 (1) Å from the least-squares plane. The axial positions are occupied by O5 and O6 with an O5—Mn1—O6 angle of 179.46 (5) °. The Mn—O and Mn—N bond distance fall in range of 2.1009 (14) to 2.2935 (16) Å. The deprotonated 2-(1H-benzo[d][1,2,3]triazol-1-yl)acetic acid ligand adopt a monodentate coordination mode, which is different another manganese complex of this ligand (Zheng et al., 2010). An extensive three-dimensional hydrogen-bonding network formed by classical O—H···O and O—H···N interactions between the title complex molecules and the uncoodinated water molecules consolidate the crystal packing(Table 2).

Related literature top

For related structures, see: Zheng et al. (2010); Zeng & Wang (2012).

Experimental top

A mixture of Mn(Ac)₂ (0.5 mmol), 2-(1H-benzo[d][1,2,3]triazol-1-yl)acetic acid (0.5 mmol) and 1,10-phenanthroline(0.5 mmol) was dissolved in water (30 ml) and methanol (10 ml). and the pH of the solution was adjusted to 6–7 with 0.2 M aqueous NaOH and the solution was stirred for 3 h at room temperature. The solution was flitered and the flitrate was allowed to stand at room temperature. After slow evaporation over 2 weeks, light yellow blocks were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Molecular structure of the title compound with 40% probability displacement ellopsoids. Hydrogen bonds are shown as dashed lines).

(Acetato-κO)diaqua[2-(1H-benzotriazol-1-yl)acetato- κO](1,10-phenanthroline-κ²N,N') manganese(II) dihydrate top

Crystal data top

[Mn(C₈H₆N₃O₂)(C₂H₃O₂)(C₁₂H₈N₂)(H₂O)₂]·2H₂O	F(000) = 1124
M_r = 542.41	D_x = 1.504 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 6090 reflections
a = 6.877 (1) Å	θ = 2.3–25.1°
b = 17.383 (3) Å	µ = 0.61 mm⁻¹
c = 20.033 (3) Å	T = 296 K
V = 2394.9 (6) Å³	Block, light yellow
Z = 4	0.22 × 0.18 × 0.16 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	4247 independent reflections
Radiation source: fine-focus sealed tube	3921 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −8→8
T_min = 0.878, T_max = 0.909	k = −20→17
16178 measured reflections	l = −23→23

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.066	w = 1/[σ²(F_o²) + (0.0345P)² + 0.244P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
4247 reflections	Δρ_max = 0.20 e Å⁻³
325 parameters	Δρ_min = −0.16 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1798 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.028 (15)

Crystal data top

[Mn(C₈H₆N₃O₂)(C₂H₃O₂)(C₁₂H₈N₂)(H₂O)₂]·2H₂O	V = 2394.9 (6) Å³
M_r = 542.41	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.877 (1) Å	µ = 0.61 mm⁻¹
b = 17.383 (3) Å	T = 296 K
c = 20.033 (3) Å	0.22 × 0.18 × 0.16 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	4247 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	3921 reflections with I > 2σ(I)
T_min = 0.878, T_max = 0.909	R_int = 0.029
16178 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.066	Δρ_max = 0.20 e Å⁻³
S = 1.00	Δρ_min = −0.16 e Å⁻³
4247 reflections	Absolute structure: Flack (1983), 1798 Friedel pairs
325 parameters	Absolute structure parameter: −0.028 (15)
1 restraint

Special details top

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.

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

	x	y	z	U_iso*/U_eq
Mn1	0.48232 (4)	0.569128 (16)	0.144955 (13)	0.03039 (9)
O1	0.3490 (3)	0.62223 (10)	0.22730 (6)	0.0460 (4)
O2	0.2052 (2)	0.64743 (9)	0.32397 (7)	0.0447 (4)
O3	0.5219 (2)	0.45338 (8)	0.18058 (7)	0.0418 (4)
O4	0.8210 (2)	0.45172 (9)	0.22318 (9)	0.0517 (4)
O5	0.1767 (2)	0.54730 (10)	0.11431 (7)	0.0458 (4)
H23	0.1486	0.5276	0.0767	0.069*
H24	0.0736	0.5646	0.1323	0.069*
O6	0.7967 (2)	0.59177 (9)	0.17539 (7)	0.0424 (4)
H25	0.8153	0.6291	0.2021	0.064*
H26	0.8158	0.5514	0.1984	0.064*
O7	0.1737 (3)	0.37049 (11)	0.22114 (9)	0.0654 (5)
H27	0.0775	0.4010	0.2181	0.098*
H28	0.2695	0.3973	0.2078	0.098*
O8	0.1294 (3)	0.20584 (10)	0.23428 (9)	0.0627 (5)
H29	0.1366	0.2544	0.2300	0.094*
H30	0.0210	0.1928	0.2173	0.094*
N1	0.4872 (3)	0.57294 (9)	0.39664 (7)	0.0361 (4)
N2	0.4403 (3)	0.50889 (11)	0.43050 (9)	0.0429 (5)
N3	0.4474 (3)	0.52448 (11)	0.49445 (9)	0.0434 (5)
N4	0.5099 (3)	0.68006 (9)	0.08755 (7)	0.0368 (4)
N5	0.5326 (3)	0.53668 (9)	0.03534 (7)	0.0339 (4)
C1	0.3324 (3)	0.61825 (12)	0.29005 (9)	0.0336 (5)
C2	0.4949 (4)	0.57245 (13)	0.32387 (9)	0.0488 (6)
H2A	0.4886	0.5196	0.3086	0.059*
H2B	0.6192	0.5933	0.3098	0.059*
C3	0.5260 (3)	0.63196 (12)	0.43862 (9)	0.0341 (5)
C4	0.5872 (4)	0.70775 (14)	0.42952 (13)	0.0484 (6)
H4	0.6056	0.7289	0.3874	0.058*
C5	0.6184 (4)	0.74899 (16)	0.48687 (15)	0.0603 (7)
H5A	0.6593	0.7998	0.4833	0.072*
C6	0.5913 (4)	0.71776 (19)	0.55020 (14)	0.0636 (7)
H6A	0.6137	0.7485	0.5874	0.076*
C7	0.5332 (4)	0.64393 (16)	0.55946 (11)	0.0537 (7)
H7	0.5162	0.6234	0.6019	0.064*
C8	0.5003 (4)	0.60032 (12)	0.50197 (9)	0.0373 (5)
C9	0.5099 (4)	0.74978 (12)	0.11341 (12)	0.0505 (6)
H9	0.5076	0.7546	0.1596	0.061*
C10	0.5130 (5)	0.81644 (13)	0.07508 (15)	0.0637 (7)
H10	0.5148	0.8646	0.0953	0.076*
C11	0.5133 (5)	0.80988 (14)	0.00765 (15)	0.0626 (7)
H11	0.5120	0.8539	−0.0188	0.075*
C12	0.5157 (4)	0.73761 (13)	−0.02219 (11)	0.0485 (6)
C13	0.5152 (5)	0.7250 (2)	−0.09288 (13)	0.0670 (8)
H13	0.5122	0.7671	−0.1215	0.080*
C14	0.5191 (5)	0.65418 (19)	−0.11858 (11)	0.0636 (8)
H14	0.5179	0.6482	−0.1647	0.076*
C15	0.5248 (4)	0.58742 (15)	−0.07722 (10)	0.0483 (6)
C16	0.5316 (4)	0.51232 (17)	−0.10186 (11)	0.0578 (7)
H16	0.5319	0.5036	−0.1477	0.069*
C17	0.5376 (4)	0.45219 (16)	−0.05881 (13)	0.0545 (7)
H17	0.5406	0.4020	−0.0747	0.065*
C18	0.5393 (3)	0.46666 (13)	0.00980 (11)	0.0437 (6)
H18	0.5455	0.4250	0.0389	0.052*
C19	0.5254 (3)	0.59700 (12)	−0.00732 (9)	0.0338 (5)
C20	0.5160 (3)	0.67305 (11)	0.01976 (9)	0.0341 (5)
C21	0.6669 (3)	0.41917 (13)	0.20661 (9)	0.0349 (5)
C22	0.6497 (4)	0.33410 (13)	0.21677 (14)	0.0557 (7)
H22A	0.6840	0.3080	0.1762	0.084*
H22B	0.5183	0.3215	0.2287	0.084*
H22C	0.7359	0.3183	0.2519	0.084*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.03638 (17)	0.03095 (16)	0.02383 (13)	0.00024 (15)	0.00013 (13)	0.00160 (11)
O1	0.0583 (11)	0.0556 (10)	0.0240 (7)	0.0128 (9)	0.0010 (7)	−0.0032 (7)
O2	0.0480 (10)	0.0552 (10)	0.0310 (8)	0.0156 (9)	0.0037 (7)	0.0004 (7)
O3	0.0390 (9)	0.0354 (8)	0.0509 (8)	0.0020 (8)	−0.0088 (8)	0.0104 (6)
O4	0.0420 (10)	0.0405 (10)	0.0726 (11)	0.0014 (8)	−0.0154 (9)	0.0022 (8)
O5	0.0341 (9)	0.0671 (11)	0.0362 (8)	−0.0008 (8)	−0.0004 (7)	−0.0153 (7)
O6	0.0447 (9)	0.0406 (9)	0.0419 (8)	−0.0057 (7)	−0.0029 (7)	−0.0001 (7)
O7	0.0470 (11)	0.0570 (11)	0.0921 (14)	0.0034 (10)	0.0073 (10)	0.0243 (11)
O8	0.0586 (12)	0.0496 (11)	0.0799 (12)	−0.0010 (9)	−0.0242 (10)	0.0122 (9)
N1	0.0415 (10)	0.0395 (10)	0.0273 (7)	0.0077 (13)	−0.0013 (8)	0.0017 (7)
N2	0.0453 (12)	0.0393 (11)	0.0441 (10)	0.0049 (9)	−0.0028 (9)	0.0036 (9)
N3	0.0438 (12)	0.0478 (12)	0.0387 (10)	0.0015 (9)	−0.0006 (9)	0.0117 (8)
N4	0.0414 (11)	0.0318 (9)	0.0371 (8)	0.0015 (10)	0.0050 (9)	0.0001 (7)
N5	0.0321 (10)	0.0371 (9)	0.0324 (8)	0.0040 (8)	0.0019 (8)	−0.0032 (7)
C1	0.0427 (13)	0.0319 (11)	0.0261 (10)	0.0007 (10)	0.0013 (9)	−0.0037 (9)
C2	0.0563 (15)	0.0632 (15)	0.0269 (9)	0.0230 (18)	0.0022 (11)	−0.0051 (9)
C3	0.0321 (12)	0.0371 (11)	0.0330 (9)	0.0049 (10)	0.0012 (9)	0.0013 (8)
C4	0.0407 (14)	0.0443 (15)	0.0603 (15)	0.0040 (11)	0.0029 (12)	0.0121 (12)
C5	0.0494 (17)	0.0433 (15)	0.0882 (16)	−0.0034 (13)	−0.0059 (15)	−0.0134 (14)
C6	0.0537 (17)	0.075 (2)	0.0617 (13)	0.0075 (15)	−0.0164 (13)	−0.0298 (13)
C7	0.0493 (16)	0.0760 (18)	0.0358 (11)	0.0113 (15)	−0.0073 (12)	−0.0072 (11)
C8	0.0317 (12)	0.0489 (12)	0.0315 (9)	0.0066 (12)	−0.0012 (10)	0.0035 (9)
C9	0.0559 (16)	0.0359 (13)	0.0599 (13)	−0.0002 (14)	0.0089 (14)	−0.0057 (10)
C10	0.0580 (18)	0.0285 (12)	0.105 (2)	−0.0003 (14)	0.0102 (19)	0.0030 (13)
C11	0.0507 (17)	0.0422 (14)	0.095 (2)	0.0008 (15)	0.0110 (17)	0.0320 (14)
C12	0.0333 (13)	0.0524 (14)	0.0600 (13)	0.0024 (13)	0.0046 (12)	0.0270 (11)
C13	0.0529 (17)	0.095 (2)	0.0532 (14)	−0.0038 (19)	0.0006 (15)	0.0428 (15)
C14	0.0526 (17)	0.108 (2)	0.0303 (10)	−0.007 (2)	0.0014 (12)	0.0226 (13)
C15	0.0337 (12)	0.0810 (18)	0.0302 (10)	−0.0027 (14)	0.0055 (10)	−0.0009 (10)
C16	0.0446 (16)	0.094 (2)	0.0348 (11)	−0.0011 (16)	0.0051 (12)	−0.0204 (13)
C17	0.0375 (13)	0.0660 (16)	0.0600 (14)	0.0016 (13)	0.0025 (12)	−0.0336 (13)
C18	0.0378 (14)	0.0416 (13)	0.0518 (12)	0.0042 (11)	−0.0007 (11)	−0.0119 (10)
C19	0.0247 (11)	0.0483 (12)	0.0283 (9)	−0.0001 (10)	0.0041 (9)	0.0031 (8)
C20	0.0269 (11)	0.0401 (11)	0.0354 (9)	0.0010 (11)	0.0015 (9)	0.0101 (8)
C21	0.0406 (13)	0.0348 (12)	0.0294 (10)	0.0048 (11)	0.0032 (9)	0.0034 (9)
C22	0.0520 (17)	0.0395 (14)	0.0756 (17)	0.0032 (12)	−0.0033 (14)	0.0150 (13)

Geometric parameters (Å, º) top

Mn1—O1	2.1009 (14)	C4—C5	1.371 (4)
Mn1—O3	2.1522 (14)	C4—H4	0.9300
Mn1—O5	2.2221 (16)	C5—C6	1.392 (4)
Mn1—O6	2.2807 (16)	C5—H5A	0.9300
Mn1—N4	2.2532 (16)	C6—C7	1.357 (4)
Mn1—N5	2.2935 (16)	C6—H6A	0.9300
O1—C1	1.264 (2)	C7—C8	1.397 (3)
O2—C1	1.218 (2)	C7—H7	0.9300
O3—C21	1.272 (3)	C9—C10	1.390 (3)
O4—C21	1.247 (3)	C9—H9	0.9300
O5—H23	0.8499	C10—C11	1.356 (4)
O5—H24	0.8499	C10—H10	0.9300
O6—H25	0.8500	C11—C12	1.391 (4)
O6—H26	0.8500	C11—H11	0.9300
O7—H27	0.8500	C12—C20	1.402 (3)
O7—H28	0.8501	C12—C13	1.433 (4)
O8—H29	0.8499	C13—C14	1.334 (4)
O8—H30	0.8500	C13—H13	0.9300
N1—N2	1.343 (2)	C14—C15	1.427 (4)
N1—C3	1.353 (3)	C14—H14	0.9300
N1—C2	1.459 (2)	C15—C16	1.396 (4)
N2—N3	1.310 (3)	C15—C19	1.410 (3)
N3—C8	1.376 (3)	C16—C17	1.356 (4)
N4—C9	1.318 (3)	C16—H16	0.9300
N4—C20	1.364 (2)	C17—C18	1.397 (3)
N5—C18	1.321 (3)	C17—H17	0.9300
N5—C19	1.354 (2)	C18—H18	0.9300
C1—C2	1.530 (3)	C19—C20	1.430 (3)
C2—H2A	0.9700	C21—C22	1.497 (3)
C2—H2B	0.9700	C22—H22A	0.9600
C3—C8	1.394 (3)	C22—H22B	0.9600
C3—C4	1.395 (3)	C22—H22C	0.9600

O1—Mn1—O3	101.87 (6)	C7—C6—C5	122.2 (2)
O1—Mn1—O5	83.06 (6)	C7—C6—H6A	118.9
O3—Mn1—O5	92.96 (6)	C5—C6—H6A	118.9
O1—Mn1—N4	93.52 (6)	C6—C7—C8	116.6 (2)
O3—Mn1—N4	163.47 (6)	C6—C7—H7	121.7
O5—Mn1—N4	94.87 (7)	C8—C7—H7	121.7
O1—Mn1—O6	97.35 (6)	N3—C8—C3	108.16 (17)
O3—Mn1—O6	87.29 (6)	N3—C8—C7	130.8 (2)
O5—Mn1—O6	179.46 (5)	C3—C8—C7	121.0 (2)
N4—Mn1—O6	84.77 (7)	N4—C9—C10	123.3 (2)
O1—Mn1—N5	157.76 (6)	N4—C9—H9	118.3
O3—Mn1—N5	93.93 (6)	C10—C9—H9	118.3
O5—Mn1—N5	80.56 (6)	C11—C10—C9	118.7 (2)
N4—Mn1—N5	73.09 (6)	C11—C10—H10	120.6
O6—Mn1—N5	98.95 (6)	C9—C10—H10	120.6
C1—O1—Mn1	142.76 (15)	C10—C11—C12	120.3 (2)
C21—O3—Mn1	132.21 (14)	C10—C11—H11	119.9
Mn1—O5—H23	121.9	C12—C11—H11	119.9
Mn1—O5—H24	127.7	C11—C12—C20	117.7 (2)
H23—O5—H24	109.1	C11—C12—C13	124.2 (2)
Mn1—O6—H25	116.2	C20—C12—C13	118.0 (2)
Mn1—O6—H26	98.5	C14—C13—C12	121.5 (2)
H25—O6—H26	105.5	C14—C13—H13	119.3
H27—O7—H28	103.8	C12—C13—H13	119.3
H29—O8—H30	106.1	C13—C14—C15	121.8 (2)
N2—N1—C3	111.23 (15)	C13—C14—H14	119.1
N2—N1—C2	120.56 (18)	C15—C14—H14	119.1
C3—N1—C2	128.20 (18)	C16—C15—C19	117.5 (2)
N3—N2—N1	108.26 (17)	C16—C15—C14	123.8 (2)
N2—N3—C8	108.36 (17)	C19—C15—C14	118.7 (2)
C9—N4—C20	118.25 (17)	C17—C16—C15	119.8 (2)
C9—N4—Mn1	125.90 (14)	C17—C16—H16	120.1
C20—N4—Mn1	115.74 (13)	C15—C16—H16	120.1
C18—N5—C19	118.07 (17)	C16—C17—C18	119.2 (2)
C18—N5—Mn1	127.06 (14)	C16—C17—H17	120.4
C19—N5—Mn1	114.11 (12)	C18—C17—H17	120.4
O2—C1—O1	126.6 (2)	N5—C18—C17	123.1 (2)
O2—C1—C2	119.59 (17)	N5—C18—H18	118.4
O1—C1—C2	113.76 (18)	C17—C18—H18	118.4
N1—C2—C1	114.38 (19)	N5—C19—C15	122.4 (2)
N1—C2—H2A	108.7	N5—C19—C20	118.57 (16)
C1—C2—H2A	108.7	C15—C19—C20	119.05 (19)
N1—C2—H2B	108.7	N4—C20—C12	121.69 (19)
C1—C2—H2B	108.7	N4—C20—C19	117.48 (16)
H2A—C2—H2B	107.6	C12—C20—C19	120.83 (18)
N1—C3—C8	103.98 (17)	O4—C21—O3	124.3 (2)
N1—C3—C4	133.98 (19)	O4—C21—C22	118.6 (2)
C8—C3—C4	122.0 (2)	O3—C21—C22	117.1 (2)
C5—C4—C3	115.6 (2)	C21—C22—H22A	109.5
C5—C4—H4	122.2	C21—C22—H22B	109.5
C3—C4—H4	122.2	H22A—C22—H22B	109.5
C4—C5—C6	122.6 (3)	C21—C22—H22C	109.5
C4—C5—H5A	118.7	H22A—C22—H22C	109.5
C6—C5—H5A	118.7	H22B—C22—H22C	109.5

O3—Mn1—O1—C1	25.8 (3)	N2—N3—C8—C3	0.1 (3)
O5—Mn1—O1—C1	117.4 (3)	N2—N3—C8—C7	−177.9 (3)
N4—Mn1—O1—C1	−148.1 (3)	N1—C3—C8—N3	−0.1 (3)
O6—Mn1—O1—C1	−63.0 (3)	C4—C3—C8—N3	−177.6 (2)
N5—Mn1—O1—C1	160.1 (2)	N1—C3—C8—C7	178.2 (2)
O1—Mn1—O3—C21	−96.90 (18)	C4—C3—C8—C7	0.7 (4)
O5—Mn1—O3—C21	179.57 (17)	C6—C7—C8—N3	177.7 (3)
N4—Mn1—O3—C21	61.4 (3)	C6—C7—C8—C3	−0.1 (4)
O6—Mn1—O3—C21	0.04 (17)	C20—N4—C9—C10	0.9 (4)
N5—Mn1—O3—C21	98.84 (18)	Mn1—N4—C9—C10	−175.1 (2)
C3—N1—N2—N3	0.0 (3)	N4—C9—C10—C11	1.0 (5)
C2—N1—N2—N3	178.9 (2)	C9—C10—C11—C12	−1.7 (5)
N1—N2—N3—C8	−0.1 (3)	C10—C11—C12—C20	0.5 (5)
O1—Mn1—N4—C9	22.2 (2)	C10—C11—C12—C13	179.7 (3)
O3—Mn1—N4—C9	−136.5 (2)	C11—C12—C13—C14	179.5 (3)
O5—Mn1—N4—C9	105.5 (2)	C20—C12—C13—C14	−1.3 (5)
O6—Mn1—N4—C9	−74.9 (2)	C12—C13—C14—C15	−0.3 (5)
N5—Mn1—N4—C9	−175.9 (3)	C13—C14—C15—C16	−179.1 (3)
O1—Mn1—N4—C20	−153.93 (19)	C13—C14—C15—C19	0.3 (5)
O3—Mn1—N4—C20	47.4 (3)	C19—C15—C16—C17	0.3 (4)
O5—Mn1—N4—C20	−70.61 (18)	C14—C15—C16—C17	179.7 (3)
O6—Mn1—N4—C20	108.99 (19)	C15—C16—C17—C18	−0.8 (4)
N5—Mn1—N4—C20	7.98 (17)	C19—N5—C18—C17	−0.6 (3)
O1—Mn1—N5—C18	−123.4 (2)	Mn1—N5—C18—C17	168.77 (17)
O3—Mn1—N5—C18	12.03 (19)	C16—C17—C18—N5	1.0 (4)
O5—Mn1—N5—C18	−80.32 (19)	C18—N5—C19—C15	0.1 (3)
N4—Mn1—N5—C18	−178.4 (2)	Mn1—N5—C19—C15	−170.66 (17)
O6—Mn1—N5—C18	99.90 (19)	C18—N5—C19—C20	179.4 (2)
O1—Mn1—N5—C19	46.3 (3)	Mn1—N5—C19—C20	8.6 (3)
O3—Mn1—N5—C19	−178.25 (15)	C16—C15—C19—N5	0.1 (4)
O5—Mn1—N5—C19	89.40 (15)	C14—C15—C19—N5	−179.4 (2)
N4—Mn1—N5—C19	−8.68 (15)	C16—C15—C19—C20	−179.2 (2)
O6—Mn1—N5—C19	−90.38 (15)	C14—C15—C19—C20	1.3 (4)
Mn1—O1—C1—O2	−161.02 (19)	C9—N4—C20—C12	−2.1 (4)
Mn1—O1—C1—C2	20.0 (4)	Mn1—N4—C20—C12	174.27 (19)
N2—N1—C2—C1	110.1 (2)	C9—N4—C20—C19	177.1 (2)
C3—N1—C2—C1	−71.2 (3)	Mn1—N4—C20—C19	−6.5 (3)
O2—C1—C2—N1	−4.1 (3)	C11—C12—C20—N4	1.4 (4)
O1—C1—C2—N1	174.9 (2)	C13—C12—C20—N4	−177.8 (3)
N2—N1—C3—C8	0.1 (3)	C11—C12—C20—C19	−177.7 (2)
C2—N1—C3—C8	−178.7 (2)	C13—C12—C20—C19	3.0 (4)
N2—N1—C3—C4	177.1 (2)	N5—C19—C20—N4	−1.6 (3)
C2—N1—C3—C4	−1.7 (5)	C15—C19—C20—N4	177.7 (2)
N1—C3—C4—C5	−177.2 (3)	N5—C19—C20—C12	177.6 (2)
C8—C3—C4—C5	−0.6 (4)	C15—C19—C20—C12	−3.1 (4)
C3—C4—C5—C6	0.0 (4)	Mn1—O3—C21—O4	7.5 (3)
C4—C5—C6—C7	0.5 (4)	Mn1—O3—C21—C22	−171.64 (16)
C5—C6—C7—C8	−0.4 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H23···N3ⁱ	0.85	1.99	2.838 (2)	173
O5—H24···O6ⁱⁱ	0.85	2.14	2.987 (2)	172
O6—H25···O8ⁱⁱⁱ	0.85	1.88	2.732 (2)	175
O6—H26···O4	0.85	1.80	2.621 (2)	161
O7—H27···O4ⁱⁱ	0.85	1.97	2.807 (3)	166
O7—H28···O3	0.85	2.06	2.911 (2)	174
O8—H29···O7	0.85	2.04	2.890 (3)	176
O8—H30···O2^iv	0.85	1.93	2.773 (2)	171

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

Experimental details

Crystal data
Chemical formula	[Mn(C₈H₆N₃O₂)(C₂H₃O₂)(C₁₂H₈N₂)(H₂O)₂]·2H₂O
M_r	542.41
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	6.877 (1), 17.383 (3), 20.033 (3)
V (Å³)	2394.9 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.61
Crystal size (mm)	0.22 × 0.18 × 0.16

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.878, 0.909
No. of measured, independent and observed [I > 2σ(I)] reflections	16178, 4247, 3921
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.066, 1.00
No. of reflections	4247
No. of parameters	325
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.16
Absolute structure	Flack (1983), 1798 Friedel pairs
Absolute structure parameter	−0.028 (15)

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Mn1—O1	2.1009 (14)	Mn1—O6	2.2807 (16)
Mn1—O3	2.1522 (14)	Mn1—N4	2.2532 (16)
Mn1—O5	2.2221 (16)	Mn1—N5	2.2935 (16)

N4—Mn1—N5	73.09 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H23···N3ⁱ	0.85	1.99	2.838 (2)	173
O5—H24···O6ⁱⁱ	0.85	2.14	2.987 (2)	172
O6—H25···O8ⁱⁱⁱ	0.85	1.88	2.732 (2)	175
O6—H26···O4	0.85	1.80	2.621 (2)	161
O7—H27···O4ⁱⁱ	0.85	1.97	2.807 (3)	166
O7—H28···O3	0.85	2.06	2.911 (2)	174
O8—H29···O7	0.85	2.04	2.890 (3)	176
O8—H30···O2^iv	0.85	1.93	2.773 (2)	171

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

References

Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zeng, L. & Wang, Q. (2012). Acta Cryst. E68, m196. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zheng, Z. B., Wu, R. T., Li, J. K., Han, Y. F. & Lu, J. R. (2010). J. Coord. Chem. 63, 1118–1129. Web of Science CSD CrossRef CAS Google Scholar

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Volume 68| Part 3| March 2012| Page m329

doi:10.1107/S1600536812007404

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