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

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.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.008 Å
• Disorder in main residue
• R factor = 0.060
• wR factor = 0.191
• Data-to-parameter ratio = 13.2

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Mn     -   Cl1     ..      51.65 su

Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         Mn
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C30
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C36
PLAT301_ALERT_3_C Main Residue  Disorder .........................      13.00 Perc.
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          8
PLAT415_ALERT_2_C Short Inter D-H..H-X       H1B    ..  H3      ..       2.11 Ang.
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          4
              H2 O

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
  10 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

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

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

S2. Experimental

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.

S3. Refinement

The dihydroxybenzoic acid is close to an inversion center and was refined with half site occupancy; the benzene ring was refined as a rigid group with the same displacement parameter for C atoms of the benzene ring. H atoms bonded to O atoms were located in a difference Fourier map and refined as riding in as-found relative positions with U_iso(H) = 1.5U_eq(O). Aromatic H atoms were placed in calculated positions with C—H = 0.93 Å, and refined in riding mode with U_iso(H) = 1.2U_eq(C).

Computing details

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

	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)

Crystal data

[MnCl2(C12H8N2)2]·0.5C7H6O4·2H2O	Z = 2
Mr = 599.34	F(000) = 614
Triclinic, P1	Dx = 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) Å^3

Data collection

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

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.191	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.115P)^2 + 0.6925P] where P = (Fo^2 + 2Fc^2)/3
4680 reflections	(Δ/σ)max = 0.001
355 parameters	Δρmax = 0.55 e Å^−3
0 restraints	Δρmin = −1.16 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

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···O2W^i	0.80	2.22	2.752 (6)	124
O2W—H2A···Cl1^ii	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···O1W^iii	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.