cis-Dichloridobis(1,10-phenanthroline-κ2N,N′)manganese(II)–2,6-dihydroxy­benzoic acid–water (2/1/4)

Yang, Q.; Nie, J.-J.; Xu, D.-J.

doi:10.1107/S1600536808012427

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page m757

doi:10.1107/S1600536808012427

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cis-Dichloridobis(1,10-phenanthroline-κ²N,N′)manganese(II)–2,6-dihydroxybenzoic acid–water (2/1/4)

Qian Yang,^a Jing-Jing Nie ^a and Duan-Jun Xu ^a ^*

^aDepartment of Chemistry, Zhejiang University, People's Republic of China
^*Correspondence e-mail: xudj@mail.hz.zj.cn

(Received 27 April 2008; accepted 28 April 2008; online 3 May 2008)

In the crystal structure of the title compound, [MnCl₂(C₁₂H₈N₂)₂]·0.5C₇H₆O₄·2H₂O, the Mn^II complex assumes a distorted octahedral geometry formed by two chloride anions and two phenanthroline (phen) ligands. The 2,6-dihydroxybenzoic acid molecule is disordered about an inversion center. The face-to-face separations of 3.540 (11) and 3.429 (8) Å between parallel phen ligands indicate the existence of π–π stacking between adjacent Mn^II complexes. Uncoordinated water molecules are linked with complex and dihydroxybenzoic acid molecules via O—H⋯Cl and O—H⋯O hydrogen bonds.

Related literature

For general background, see: Su & Xu (2004 ). For related structures, see: McCann et al. (1998 ); Pan & Xu (2005 ).

Experimental

Crystal data

[MnCl₂(C₁₂H₈N₂)₂]·0.5C₇H₆O₄·2H₂O
M_r = 599.34
Triclinic, $[P \overline 1]$
a = 9.757 (2) Å
b = 11.985 (3) Å
c = 13.261 (3) Å
α = 63.465 (17)°
β = 83.931 (18)°
γ = 76.819 (18)°
V = 1350.8 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.73 mm⁻¹
T = 295 (2) K
0.42 × 0.36 × 0.20 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.735, T_max = 0.860
14401 measured reflections
4680 independent reflections
3662 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.191
S = 1.08
4680 reflections
355 parameters
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −1.16 e Å⁻³

Table 1
Selected bond lengths (Å)

Mn—N1	2.260 (3)
Mn—N2	2.328 (3)
Mn—N3	2.308 (3)
Mn—N4	2.275 (3)
Mn—Cl1	2.440 (2)
Mn—Cl2	2.4387 (13)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1A⋯O3	0.84	2.06	2.834 (13)	152
O1W—H1B⋯O2Wⁱ	0.80	2.22	2.752 (6)	124
O2W—H2A⋯Cl1ⁱⁱ	0.85	2.09	2.904 (6)	162
O2W—H2B⋯Cl1	0.82	2.14	2.946 (4)	164
O1—H1C⋯O3	0.91	1.73	2.476 (18)	137
O2—H2C⋯O4	0.90	1.69	2.444 (19)	139
O4—H4A⋯O1Wⁱⁱⁱ	0.88	2.28	2.886 (13)	125
Symmetry codes: (i) x-1, y, z+1; (ii) -x+2, -y, -z; (iii) -x, -y+1, -z+1.

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); 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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808012427/ng2452sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808012427/ng2452Isup2.hkl

checkCIF report

Comment top

As part of our ongoing investigation on the nature of π-π stacking (Su & Xu, 2004), the title compound incorporating 1,10-phenanthroline (phen) ligand has recently prepared and its crystal structure is reported here.

The crystal consists of Mn^II complex, uncoordinated dihydroxybenzoic acid and lattice water molecules (Fig. 1). The Mn^II complex assumes a distorted octahedral geometry formed by two Cl^- anions and two phen ligands (Table 1), similar to those found in crystal structure of cis-dichloro-bis(1,10-phenanthroline-κ²N,N')manganese(II) (Pan & Xu, 2005; McCann et al., 1998). The two phen ligands of the complex are nearly perpendicular to each other with a dihedral angle of 83.50 (6)°. π-π stacking is observed in the crystal structure (Fig. 2). The face-to-face separation between parallel N2-containing phen and N2ⁱ-containing phen ligands is 3.540 (11) Å, while the face-to-face separation between parallel N3-phen and N3ⁱⁱ-phen ligands is 3.429 (8) Å [symmetry codes: (i) 1 - x,1 - y,-z; (ii) 1 - x,-y,1 - z].

The C30—O4 bond distance is significantly longer than C30—O3 bond distance (Table 1), which suggests that dihydroxybenzoic acid is a neutral molecule in the crystal. The uncoordinated dihydroxybenzoic acid molecule is located in a cavity formed by Mn^II complexes, and is close to an inversion center (Fig. 3). Therefore dihydroxybenzoic acid is disordered in the crystal with different spatial orientations. Lattice water molecules are linked with Mn^II complex and uncoordinated dihydroxybenzoic acid via O—H···Cl and O—H···O hydrogen bonding, respectively (Table 2 and Fig. 1).

Related literature top

For general background, see: Su & Xu (2004). For related structures, see: McCann et al. (1998); Pan & Xu (2005).

Experimental top

Each reagent was commercially available and of analytical grade. MnCl₂^.4H₂O (0.20 g, 1 mmol), 2,6-dihydroxybenzoic acid (0.15 g 1 mmol), 1,10-phenanthroline (0.39 g, 2 mmol) and Na₂CO₃ (0.053 g, 0.5 mmol) were dissolved in water-ethanol solution (15 ml, 10:5). The solution was refluxed for 4 h, and filtered after cooling to room temperature. Yellow single crystals were obtained from the filtrate after 2 d.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); 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).

Figures top

	Fig. 1. The molecular structure of the title compound with 30% probability displacement (arbitrary spheres for H atoms). Dashed lines indicate hydrogen bonding.
	Fig. 2. A diagram showing π-π stacking between phen ligands [symmetry codes: (i) 1 - x,1 - y,-z; (ii) 1 - x,-y,1 - z].
	Fig. 3. A packing diagram of the unit cell, H atoms and one of disordered components of dihydroxybenzoic acid have been omitted for clarity.

cis-Dichloridobis(1,10-phenanthroline- κ²N,N')manganese(II)–2,6-dihydroxybenzoic acid–water (2/1/4) top

Crystal data top

[MnCl₂(C₁₂H₈N₂)₂]·0.5C₇H₆O₄·2H₂O	Z = 2
M_r = 599.34	F(000) = 614
Triclinic, P1	D_x = 1.474 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.757 (2) Å	Cell parameters from 6825 reflections
b = 11.985 (3) Å	θ = 1.8–25.0°
c = 13.261 (3) Å	µ = 0.73 mm⁻¹
α = 63.465 (17)°	T = 295 K
β = 83.931 (18)°	Prism, yellow
γ = 76.819 (18)°	0.42 × 0.36 × 0.20 mm
V = 1350.8 (6) Å³

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	4680 independent reflections
Radiation source: fine-focus sealed tube	3662 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
Detector resolution: 10.00 pixels mm^-1	θ_max = 25.0°, θ_min = 1.7°
ω scans	h = −10→11
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −12→13
T_min = 0.735, T_max = 0.860	l = −15→15
14401 measured reflections

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.191	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.115P)² + 0.6925P] where P = (F_o² + 2F_c²)/3
4680 reflections	(Δ/σ)_max = 0.001
355 parameters	Δρ_max = 0.55 e Å⁻³
0 restraints	Δρ_min = −1.16 e Å⁻³

Crystal data top

[MnCl₂(C₁₂H₈N₂)₂]·0.5C₇H₆O₄·2H₂O	γ = 76.819 (18)°
M_r = 599.34	V = 1350.8 (6) Å³
Triclinic, P1	Z = 2
a = 9.757 (2) Å	Mo Kα radiation
b = 11.985 (3) Å	µ = 0.73 mm⁻¹
c = 13.261 (3) Å	T = 295 K
α = 63.465 (17)°	0.42 × 0.36 × 0.20 mm
β = 83.931 (18)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	4680 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	3662 reflections with I > 2σ(I)
T_min = 0.735, T_max = 0.860	R_int = 0.029
14401 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.191	H-atom parameters constrained
S = 1.09	Δρ_max = 0.55 e Å⁻³
4680 reflections	Δρ_min = −1.16 e Å⁻³
355 parameters

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	Occ. (<1)
Mn	0.81692 (6)	0.12805 (5)	0.21903 (4)	0.0452 (2)
Cl1	0.9994 (2)	0.09801 (17)	0.08753 (14)	0.1086 (6)
Cl2	0.93733 (10)	−0.05166 (9)	0.38297 (8)	0.0543 (3)
N1	0.8875 (3)	0.2844 (3)	0.2384 (3)	0.0512 (8)
N2	0.7264 (4)	0.3198 (3)	0.0676 (3)	0.0558 (8)
N3	0.6117 (3)	0.1579 (3)	0.3159 (2)	0.0467 (7)
N4	0.6685 (3)	0.0238 (3)	0.1901 (3)	0.0531 (8)
O1	0.4543 (14)	0.3988 (12)	0.7173 (9)	0.132 (4)	0.50
H1C	0.3709	0.3781	0.7149	0.197*	0.50
O2	0.4410 (16)	0.5884 (14)	0.3174 (9)	0.146 (4)	0.50
H2C	0.3551	0.5690	0.3274	0.220*	0.50
O3	0.2390 (11)	0.4282 (12)	0.6173 (11)	0.135 (4)	0.50
O4	0.2332 (11)	0.5254 (11)	0.4305 (10)	0.127 (3)	0.50
H4A	0.1410	0.5328	0.4354	0.191*	0.50
O1W	0.0193 (5)	0.2911 (4)	0.6726 (4)	0.1147 (15)
H1A	0.0606	0.3531	0.6449	0.172*
H1B	−0.0422	0.3081	0.7116	0.172*
O2W	0.8797 (5)	0.1644 (5)	−0.1317 (3)	0.1292 (19)
H2A	0.9009	0.0907	−0.1291	0.194*
H2B	0.9163	0.1605	−0.0767	0.194*
C1	0.9627 (5)	0.2673 (5)	0.3244 (4)	0.0654 (12)
H1	0.9819	0.1864	0.3842	0.078*
C2	1.0141 (6)	0.3642 (6)	0.3295 (6)	0.0855 (16)
H2	1.0653	0.3483	0.3915	0.103*
C3	0.9875 (6)	0.4838 (6)	0.2409 (6)	0.0879 (17)
H3	1.0224	0.5495	0.2416	0.105*
C4	0.9086 (5)	0.5059 (4)	0.1508 (5)	0.0719 (13)
C5	0.8757 (7)	0.6265 (5)	0.0563 (6)	0.099 (2)
H5	0.9101	0.6943	0.0530	0.119*
C6	0.7955 (8)	0.6450 (5)	−0.0291 (6)	0.101 (2)
H6	0.7754	0.7256	−0.0891	0.121*
C7	0.7401 (5)	0.5436 (5)	−0.0299 (4)	0.0750 (15)
C8	0.6572 (7)	0.5591 (6)	−0.1146 (4)	0.096 (2)
H8	0.6344	0.6384	−0.1758	0.115*
C9	0.6079 (6)	0.4583 (7)	−0.1093 (4)	0.095 (2)
H9	0.5503	0.4694	−0.1661	0.115*
C10	0.6453 (5)	0.3365 (5)	−0.0163 (4)	0.0746 (14)
H10	0.6135	0.2676	−0.0135	0.089*
C11	0.7730 (4)	0.4222 (4)	0.0615 (3)	0.0560 (10)
C12	0.8574 (4)	0.4022 (4)	0.1523 (3)	0.0529 (9)
C13	0.5854 (4)	0.2205 (4)	0.3785 (3)	0.0559 (10)
H13	0.6523	0.2638	0.3805	0.067*
C14	0.4616 (5)	0.2253 (4)	0.4424 (4)	0.0623 (11)
H14	0.4472	0.2706	0.4855	0.075*
C15	0.3644 (5)	0.1629 (4)	0.4398 (3)	0.0615 (11)
H15	0.2821	0.1644	0.4820	0.074*
C16	0.3863 (4)	0.0947 (4)	0.3733 (3)	0.0530 (10)
C17	0.2874 (4)	0.0270 (4)	0.3665 (4)	0.0643 (12)
H17	0.2036	0.0266	0.4071	0.077*
C18	0.3139 (5)	−0.0362 (5)	0.3023 (4)	0.0709 (13)
H18	0.2469	−0.0780	0.2980	0.085*
C19	0.4431 (4)	−0.0408 (4)	0.2403 (4)	0.0608 (11)
C20	0.4783 (5)	−0.1079 (5)	0.1742 (4)	0.0751 (13)
H20	0.4143	−0.1507	0.1669	0.090*
C21	0.6039 (6)	−0.1109 (6)	0.1212 (5)	0.0800 (15)
H21	0.6277	−0.1575	0.0794	0.096*
C22	0.6973 (5)	−0.0441 (5)	0.1296 (4)	0.0664 (12)
H22	0.7833	−0.0462	0.0921	0.080*
C23	0.5434 (4)	0.0246 (4)	0.2452 (3)	0.0491 (9)
C24	0.5137 (4)	0.0953 (3)	0.3123 (3)	0.0453 (8)
C30	0.2957 (16)	0.4791 (16)	0.5273 (14)	0.098 (4)	0.50
C31	0.4417 (8)	0.4897 (11)	0.5167 (7)	0.0936 (16)	0.50
C32	0.5181 (10)	0.4401 (9)	0.6154 (6)	0.0936 (16)	0.50
C33	0.6607 (9)	0.4420 (9)	0.6100 (7)	0.0936 (16)	0.50
H33	0.7119	0.4088	0.6761	0.112*	0.50
C34	0.7267 (8)	0.4935 (10)	0.5060 (9)	0.0936 (16)	0.50
H34	0.8221	0.4948	0.5024	0.112*	0.50
C35	0.6503 (10)	0.5431 (9)	0.4073 (7)	0.0936 (16)	0.50
H35	0.6945	0.5775	0.3377	0.112*	0.50
C36	0.5077 (10)	0.5412 (9)	0.4127 (6)	0.0936 (16)	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn	0.0442 (4)	0.0484 (4)	0.0457 (3)	−0.0130 (3)	0.0024 (2)	−0.0218 (3)
Cl1	0.1378 (15)	0.1000 (12)	0.0928 (10)	−0.0370 (10)	0.0080 (9)	−0.0421 (9)
Cl2	0.0508 (6)	0.0569 (6)	0.0510 (5)	−0.0092 (4)	−0.0020 (4)	−0.0203 (4)
N1	0.0456 (18)	0.0515 (19)	0.0585 (19)	−0.0100 (14)	0.0004 (14)	−0.0260 (16)
N2	0.0507 (19)	0.061 (2)	0.0484 (17)	−0.0017 (16)	−0.0026 (14)	−0.0216 (16)
N3	0.0403 (17)	0.0464 (17)	0.0496 (16)	−0.0062 (13)	0.0019 (13)	−0.0194 (14)
N4	0.0447 (18)	0.065 (2)	0.0572 (18)	−0.0139 (15)	0.0030 (14)	−0.0323 (17)
O1	0.140 (10)	0.152 (9)	0.093 (7)	−0.070 (8)	0.013 (6)	−0.030 (6)
O2	0.171 (12)	0.210 (13)	0.086 (7)	−0.077 (10)	0.002 (7)	−0.071 (8)
O3	0.103 (7)	0.172 (10)	0.165 (10)	−0.063 (7)	0.031 (7)	−0.095 (9)
O4	0.095 (7)	0.158 (9)	0.146 (9)	−0.001 (6)	−0.006 (7)	−0.091 (8)
O1W	0.141 (4)	0.098 (3)	0.126 (4)	−0.037 (3)	0.024 (3)	−0.068 (3)
O2W	0.099 (3)	0.146 (4)	0.077 (2)	0.022 (3)	0.002 (2)	−0.014 (3)
C1	0.062 (3)	0.068 (3)	0.078 (3)	−0.010 (2)	−0.013 (2)	−0.041 (2)
C2	0.070 (3)	0.097 (4)	0.122 (5)	−0.007 (3)	−0.015 (3)	−0.078 (4)
C3	0.067 (3)	0.089 (4)	0.144 (5)	−0.026 (3)	0.008 (3)	−0.079 (4)
C4	0.064 (3)	0.049 (3)	0.105 (4)	−0.015 (2)	0.026 (3)	−0.040 (3)
C5	0.099 (5)	0.055 (3)	0.127 (5)	−0.027 (3)	0.038 (4)	−0.028 (3)
C6	0.112 (5)	0.047 (3)	0.101 (4)	−0.009 (3)	0.040 (4)	−0.008 (3)
C7	0.070 (3)	0.059 (3)	0.061 (3)	0.005 (2)	0.018 (2)	−0.007 (2)
C8	0.098 (4)	0.085 (4)	0.057 (3)	0.019 (3)	0.004 (3)	−0.009 (3)
C9	0.083 (4)	0.128 (5)	0.050 (3)	0.025 (4)	−0.018 (2)	−0.035 (3)
C10	0.071 (3)	0.093 (4)	0.052 (2)	0.005 (3)	−0.011 (2)	−0.032 (2)
C11	0.053 (2)	0.049 (2)	0.052 (2)	−0.0009 (18)	0.0151 (18)	−0.0174 (18)
C12	0.045 (2)	0.047 (2)	0.064 (2)	−0.0090 (17)	0.0112 (18)	−0.0249 (19)
C13	0.055 (2)	0.056 (2)	0.058 (2)	−0.0078 (19)	0.0042 (18)	−0.028 (2)
C14	0.066 (3)	0.059 (3)	0.058 (2)	−0.001 (2)	0.007 (2)	−0.028 (2)
C15	0.049 (2)	0.060 (3)	0.056 (2)	0.003 (2)	0.0095 (18)	−0.017 (2)
C16	0.039 (2)	0.056 (2)	0.047 (2)	−0.0011 (17)	−0.0008 (16)	−0.0113 (18)
C17	0.042 (2)	0.073 (3)	0.067 (3)	−0.013 (2)	0.0020 (19)	−0.021 (2)
C18	0.047 (2)	0.089 (3)	0.074 (3)	−0.025 (2)	−0.005 (2)	−0.027 (3)
C19	0.051 (2)	0.070 (3)	0.063 (2)	−0.019 (2)	−0.0091 (19)	−0.026 (2)
C20	0.066 (3)	0.093 (4)	0.088 (3)	−0.033 (3)	−0.004 (2)	−0.050 (3)
C21	0.079 (3)	0.103 (4)	0.091 (3)	−0.030 (3)	0.003 (3)	−0.066 (3)
C22	0.065 (3)	0.086 (3)	0.071 (3)	−0.025 (2)	0.009 (2)	−0.052 (3)
C23	0.043 (2)	0.055 (2)	0.0457 (19)	−0.0085 (16)	−0.0057 (15)	−0.0180 (17)
C24	0.0361 (19)	0.049 (2)	0.0396 (17)	−0.0025 (15)	−0.0032 (14)	−0.0116 (16)
C30	0.076 (8)	0.114 (11)	0.116 (12)	−0.018 (8)	0.007 (8)	−0.062 (10)
C31	0.097 (4)	0.090 (3)	0.101 (4)	−0.021 (3)	0.013 (3)	−0.050 (4)
C32	0.097 (4)	0.090 (3)	0.101 (4)	−0.021 (3)	0.013 (3)	−0.050 (4)
C33	0.097 (4)	0.090 (3)	0.101 (4)	−0.021 (3)	0.013 (3)	−0.050 (4)
C34	0.097 (4)	0.090 (3)	0.101 (4)	−0.021 (3)	0.013 (3)	−0.050 (4)
C35	0.097 (4)	0.090 (3)	0.101 (4)	−0.021 (3)	0.013 (3)	−0.050 (4)
C36	0.097 (4)	0.090 (3)	0.101 (4)	−0.021 (3)	0.013 (3)	−0.050 (4)

Geometric parameters (Å, º) top

Mn—N1	2.260 (3)	C7—C11	1.408 (6)
Mn—N2	2.328 (3)	C8—C9	1.370 (9)
Mn—N3	2.308 (3)	C8—H8	0.9300
Mn—N4	2.275 (3)	C9—C10	1.425 (8)
Mn—Cl1	2.440 (2)	C9—H9	0.9300
Mn—Cl2	2.4387 (13)	C10—H10	0.9300
N1—C1	1.334 (5)	C11—C12	1.430 (6)
N1—C12	1.351 (5)	C13—C14	1.405 (6)
N2—C10	1.350 (6)	C13—H13	0.9300
N2—C11	1.370 (6)	C14—C15	1.348 (7)
N3—C13	1.319 (5)	C14—H14	0.9300
N3—C24	1.360 (5)	C15—C16	1.419 (6)
N4—C22	1.347 (5)	C15—H15	0.9300
N4—C23	1.355 (5)	C16—C24	1.410 (5)
O1—C32	1.351 (12)	C16—C17	1.428 (6)
O1—H1C	0.9109	C17—C18	1.344 (7)
O2—C36	1.307 (13)	C17—H17	0.9300
O2—H2C	0.9016	C18—C19	1.434 (7)
O3—C30	1.211 (17)	C18—H18	0.9300
O4—C30	1.305 (17)	C19—C20	1.405 (7)
O4—H4A	0.8817	C19—C23	1.409 (6)
O1W—H1A	0.8434	C20—C21	1.348 (7)
O1W—H1B	0.8012	C20—H20	0.9300
O2W—H2A	0.8461	C21—C22	1.385 (7)
O2W—H2B	0.8246	C21—H21	0.9300
C1—C2	1.396 (7)	C22—H22	0.9300
C1—H1	0.9300	C23—C24	1.449 (5)
C2—C3	1.376 (8)	C30—C31	1.445 (15)
C2—H2	0.9300	C31—C32	1.3900
C3—C4	1.381 (8)	C31—C36	1.3900
C3—H3	0.9300	C32—C33	1.3900
C4—C5	1.421 (8)	C33—C34	1.3900
C4—C12	1.432 (6)	C33—H33	0.9300
C5—C6	1.351 (10)	C34—C35	1.3900
C5—H5	0.9300	C34—H34	0.9300
C6—C7	1.443 (9)	C35—C36	1.3900
C6—H6	0.9300	C35—H35	0.9300
C7—C8	1.373 (8)

N1—Mn—N4	158.51 (12)	N2—C11—C12	117.6 (3)
N1—Mn—N3	90.22 (12)	C7—C11—C12	120.3 (5)
N4—Mn—N3	73.23 (12)	N1—C12—C11	118.7 (4)
N1—Mn—N2	72.54 (12)	N1—C12—C4	121.2 (4)
N4—Mn—N2	92.82 (13)	C11—C12—C4	120.1 (4)
N3—Mn—N2	87.93 (11)	N3—C13—C14	123.4 (4)
N1—Mn—Cl2	97.72 (9)	N3—C13—H13	118.3
N4—Mn—Cl2	97.17 (9)	C14—C13—H13	118.3
N3—Mn—Cl2	94.48 (8)	C15—C14—C13	118.5 (4)
N2—Mn—Cl2	170.00 (10)	C15—C14—H14	120.7
N1—Mn—Cl1	98.05 (9)	C13—C14—H14	120.7
N4—Mn—Cl1	96.38 (9)	C14—C15—C16	120.6 (4)
N3—Mn—Cl1	167.55 (9)	C14—C15—H15	119.7
N2—Mn—Cl1	85.73 (9)	C16—C15—H15	119.7
Cl2—Mn—Cl1	93.61 (6)	C24—C16—C15	116.8 (4)
C1—N1—C12	118.4 (4)	C24—C16—C17	119.8 (4)
C1—N1—Mn	125.0 (3)	C15—C16—C17	123.4 (4)
C12—N1—Mn	116.5 (3)	C18—C17—C16	120.9 (4)
C10—N2—C11	118.8 (4)	C18—C17—H17	119.6
C10—N2—Mn	126.9 (3)	C16—C17—H17	119.6
C11—N2—Mn	114.0 (3)	C17—C18—C19	121.6 (4)
C13—N3—C24	118.4 (3)	C17—C18—H18	119.2
C13—N3—Mn	127.1 (3)	C19—C18—H18	119.2
C24—N3—Mn	114.3 (2)	C20—C19—C23	116.7 (4)
C22—N4—C23	117.9 (4)	C20—C19—C18	124.2 (4)
C22—N4—Mn	126.1 (3)	C23—C19—C18	119.1 (4)
C23—N4—Mn	115.9 (3)	C21—C20—C19	120.6 (4)
C32—O1—H1C	111.8	C21—C20—H20	119.7
C36—O2—H2C	111.9	C19—C20—H20	119.7
C30—O4—H4A	114.1	C20—C21—C22	119.5 (5)
H1A—O1W—H1B	105.4	C20—C21—H21	120.2
H2A—O2W—H2B	107.1	C22—C21—H21	120.2
N1—C1—C2	123.5 (5)	N4—C22—C21	122.5 (4)
N1—C1—H1	118.2	N4—C22—H22	118.7
C2—C1—H1	118.2	C21—C22—H22	118.7
C3—C2—C1	118.6 (5)	N4—C23—C19	122.7 (4)
C3—C2—H2	120.7	N4—C23—C24	117.9 (3)
C1—C2—H2	120.7	C19—C23—C24	119.4 (4)
C2—C3—C4	119.7 (5)	N3—C24—C16	122.3 (4)
C2—C3—H3	120.2	N3—C24—C23	118.6 (3)
C4—C3—H3	120.2	C16—C24—C23	119.2 (4)
C3—C4—C5	123.3 (5)	O3—C30—O4	123.6 (16)
C3—C4—C12	118.6 (5)	O3—C30—C31	123.0 (14)
C5—C4—C12	118.1 (6)	O4—C30—C31	113.3 (14)
C6—C5—C4	121.5 (6)	C32—C31—C36	120.0
C6—C5—H5	119.3	C32—C31—C30	117.6 (8)
C4—C5—H5	119.3	C36—C31—C30	122.4 (8)
C5—C6—C7	122.1 (5)	O1—C32—C31	121.1 (8)
C5—C6—H6	119.0	O1—C32—C33	118.7 (8)
C7—C6—H6	119.0	C31—C32—C33	120.0
C8—C7—C11	118.4 (6)	C32—C33—C34	120.0
C8—C7—C6	123.7 (5)	C32—C33—H33	120.0
C11—C7—C6	117.9 (5)	C34—C33—H33	120.0
C9—C8—C7	120.4 (5)	C35—C34—C33	120.0
C9—C8—H8	119.8	C35—C34—H34	120.0
C7—C8—H8	119.8	C33—C34—H34	120.0
C8—C9—C10	119.5 (5)	C36—C35—C34	120.0
C8—C9—H9	120.2	C36—C35—H35	120.0
C10—C9—H9	120.2	C34—C35—H35	120.0
N2—C10—C9	120.8 (6)	O2—C36—C35	117.5 (9)
N2—C10—H10	119.6	O2—C36—C31	122.5 (9)
C9—C10—H10	119.6	C35—C36—C31	120.0
N2—C11—C7	122.1 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O3	0.84	2.06	2.834 (13)	152
O1W—H1B···O2Wⁱ	0.80	2.22	2.752 (6)	124
O2W—H2A···Cl1ⁱⁱ	0.85	2.09	2.904 (6)	162
O2W—H2B···Cl1	0.82	2.14	2.946 (4)	164
O1—H1C···O3	0.91	1.73	2.476 (18)	137
O2—H2C···O4	0.90	1.69	2.444 (19)	139
O4—H4A···O1Wⁱⁱⁱ	0.88	2.28	2.886 (13)	125
C3—H3···O1W^iv	0.93	2.57	3.356 (9)	143
C5—H5···Cl1^v	0.93	2.64	3.427 (7)	143
C9—H9···O1^vi	0.93	2.41	3.275 (15)	154
C9—H9···O2^vii	0.93	2.39	3.152 (15)	140
C15—H15···Cl2^viii	0.93	2.82	3.674 (5)	153

Symmetry codes: (i) x−1, y, z+1; (ii) −x+2, −y, −z; (iii) −x, −y+1, −z+1; (iv) −x+1, −y+1, −z+1; (v) −x+2, −y+1, −z; (vi) x, y, z−1; (vii) −x+1, −y+1, −z; (viii) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	[MnCl₂(C₁₂H₈N₂)₂]·0.5C₇H₆O₄·2H₂O
M_r	599.34
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	9.757 (2), 11.985 (3), 13.261 (3)
α, β, γ (°)	63.465 (17), 83.931 (18), 76.819 (18)
V (Å³)	1350.8 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.73
Crystal size (mm)	0.42 × 0.36 × 0.20

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.735, 0.860
No. of measured, independent and observed [I > 2σ(I)] reflections	14401, 4680, 3662
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.191, 1.09
No. of reflections	4680
No. of parameters	355
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.55, −1.16

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

Mn—N1	2.260 (3)	Mn—Cl1	2.440 (2)
Mn—N2	2.328 (3)	Mn—Cl2	2.4387 (13)
Mn—N3	2.308 (3)	O3—C30	1.211 (17)
Mn—N4	2.275 (3)	O4—C30	1.305 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O3	0.84	2.06	2.834 (13)	152
O1W—H1B···O2Wⁱ	0.80	2.22	2.752 (6)	124
O2W—H2A···Cl1ⁱⁱ	0.85	2.09	2.904 (6)	162
O2W—H2B···Cl1	0.82	2.14	2.946 (4)	164
O1—H1C···O3	0.91	1.73	2.476 (18)	137
O2—H2C···O4	0.90	1.69	2.444 (19)	139
O4—H4A···O1Wⁱⁱⁱ	0.88	2.28	2.886 (13)	125

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

Acknowledgements

The work was supported by the ZIJIN project of Zhejiang University, China.

References

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