Aqua­(3-carboxyl­atophenoxy­acetato-κO)bis­(1,10-phenanthroline-κ²N,N′)manganese(II) tetra­hydrate

The dicarboxyl­ate ligand in the title compound, [Mn(C₉H₆O₅)(C₁₂H₈N₂)₂(H₂O)]·4H₂O, coordinates in a monodentate manner to the Mn^II atom through the carboxylate group on the benzene ring. The two O atoms in the octahedral configuration around the Mn^II atom are cis to each other. Extensive hydrogen bonding leads to a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.007 Å
• Disorder in main residue
• R factor = 0.066
• wR factor = 0.184
• Data-to-parameter ratio = 12.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for        C33
PLAT417_ALERT_2_B Short Inter D-H..H-D       H1W1   ..  H2W1    ..       2.09 Ang.

Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.629     0.911
            Tmin(prime) and Tmax expected:      0.833     0.910
            RR(prime) =      0.754
            Please check that your absorption correction is appropriate.
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.75
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.55 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C32
PLAT301_ALERT_3_C Main Residue  Disorder .........................       8.00 Perc.
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          7
PLAT410_ALERT_2_C Short Intra H...H Contact  H27    ..  H32C    ..       1.94 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........         10
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          3
              H2 O

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

   1 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
   4 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion

---

S1. Comment

The carboxyphenoxyacetate ligand is a multidentate ligand with both rigid and flexible parts. As part of an investigation of carboxyphenoxyacetate complexes, we present here the X-ray structure of the title Mn^II complex, (I).

The molecular structure of (I) is shown in Fig. 1. The bis(phenanthroline)-chelated Mn^II complex of 3-carboxylphenoxyacetate exists as a monoaqua-coordinated tetrahydrate. The octahedral coordination geometry around the Mn^II atom is similar to that in the bis(phenanthroline)-chelated Mn^II complex with 4-carboxyphenoxyacetate (Huo et al., 2005). The 3-carboxylphenoxyacetate dianion coordinates in a monodentate fashion to the Mn^II atom through the carboxyl group on the benzene ring. The carboxyl group of the oxyacetate arm is free from coordination, but it engages in hydrogen-bonding interactions (Table 2). The two coordinated O atoms are cis to each other. The coordinated bond distances and angles are normal compared with those for reported related structures. Extensive hydrogen bonds (Table 2) lead to a three-dimensional network.

S2. Experimental

Manganese dichloride hexahydrate (0.47 g, 2 mmol), 1,10-phenanthroline (0.80 g, 4 mmol) and 3-carboxyphenoxyacetic acid (0.39 g, 2 mmol) were dissolved in a small volume of hot water. The clear solution was set aside for several days to obtain yellow prismatic block-shaped? crystals of (I). Analysis calculated for C₃₃H₃₂MnN₄O₁₀: C 56.64, H 4.61, N 8.01%; found: C 56.67, H 4.59, N 7.99%.

S3. Refinement

The C-bound H atoms were positioned geometrically (C—H = 0.93 or 0.97 Å) and were included in the refinement in the riding-model approximation, with U_iso(H) = 1.2 times U_eq(C). The H atoms of the water molecules were placed at chemically sensible positions on the basis of hydrogen bonds but they were not refined; their displacement parameters were similarly tied. The water molecules were restrained to behave in an approximately isotropic manner. All H···H contacts exceed 2 Å.

The oxyacetate arm of the dianion is disordered over two positions; the occupancies refined to 0.44 (1) and 0.56 (1). A number of restraints were imposed. The O3—C32 and O3–C-32' distances were restrained to be within 0.01 Å of each other, as were the C32—C33 and C32'—C33' pair. The four C—O distances of the —CO₂ portion were also restrained in this manner; owing to this restraint, the electrons in the portion are assumed to be delocalized. The vibrations of the disordered atoms were restrained to behave in a nearly isotropic fashion.

Computing details

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. ORTEPII plot of (I). Displacement ellipsoids are drawn at the 30% probability level, and H atoms are drawn as spheres of arbitrary radii. The minor disordered component has been omitted for clarity.

Aqua(3-carboxylatophenoxyacetato-κO)bis(1,10-phenanthroline- κ²N,N')manganese(II) tetrahydrate

Crystal data

[Mn(C9H6O5)(C12H8N2)2(H2O)]·4H2O	Z = 2
Mr = 699.57	F(000) = 726
Triclinic, P1	Dx = 1.437 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.123 (2) Å	Cell parameters from 14540 reflections
b = 14.134 (3) Å	θ = 3.1–27.5°
c = 15.655 (3) Å	µ = 0.47 mm^−1
α = 110.51 (3)°	T = 295 K
β = 90.95 (3)°	Block, yellow
γ = 104.70 (3)°	0.38 × 0.26 × 0.20 mm
V = 1617.3 (8) Å^3

Data collection

Rigaku R-AXIS RAPID IP diffractometer	5673 independent reflections
Radiation source: fine-focus sealed tube	3748 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
ω scans	θmax = 25.0°, θmin = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −8→9
Tmin = 0.629, Tmax = 0.911	k = −16→16
12644 measured reflections	l = −18→18

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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.184	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.1002P)^2 + 0.5697P] where P = (Fo^2 + 2Fc^2)/3
5673 reflections	(Δ/σ)max = 0.001
470 parameters	Δρmax = 0.58 e Å^−3
80 restraints	Δρmin = −0.37 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mn1	0.21393 (8)	0.26715 (4)	0.25808 (4)	0.0538 (2)
O1	0.4247 (4)	0.3438 (2)	0.2083 (2)	0.064 (1)
O2	0.5954 (4)	0.2380 (2)	0.1689 (3)	0.081 (1)
O3	0.6852 (5)	0.6298 (3)	0.0817 (3)	0.099 (1)
O1w	0.3542 (4)	0.1530 (2)	0.2520 (2)	0.080 (1)
O2w	0.308 (1)	0.0358 (6)	0.3592 (7)	0.234 (4)
O3w	0.205 (2)	−0.1812 (7)	0.2507 (7)	0.320 (6)
O4w	0.475 (2)	0.877 (1)	0.4501 (13)	0.416 (9)
O5w	0.955 (2)	0.8805 (5)	0.4553 (5)	0.277 (5)
N1	0.2696 (4)	0.3477 (2)	0.4129 (2)	0.055 (1)
N2	0.1274 (4)	0.4158 (2)	0.2958 (2)	0.056 (1)
N3	0.0654 (5)	0.1943 (3)	0.1147 (2)	0.058 (1)
N4	−0.0254 (4)	0.1465 (2)	0.2644 (2)	0.057 (1)
C1	0.2428 (5)	0.4446 (3)	0.4472 (3)	0.053 (1)
C2	0.3350 (6)	0.3139 (4)	0.4708 (3)	0.068 (1)
C3	0.3758 (7)	0.3702 (4)	0.5639 (3)	0.076 (1)
C4	0.3512 (6)	0.4674 (4)	0.5990 (3)	0.079 (1)
C5	0.2840 (6)	0.5086 (3)	0.5410 (3)	0.064 (1)
C6	0.2574 (7)	0.6111 (4)	0.5708 (4)	0.084 (2)
C7	0.1912 (7)	0.6463 (4)	0.5130 (4)	0.088 (2)
C8	0.1463 (6)	0.5823 (3)	0.4170 (3)	0.066 (1)
C9	0.0740 (7)	0.6142 (4)	0.3535 (5)	0.088 (2)
C10	0.0310 (7)	0.5484 (4)	0.2643 (4)	0.087 (2)
C11	0.0590 (6)	0.4493 (4)	0.2388 (4)	0.073 (1)
C12	0.1712 (5)	0.4819 (3)	0.3851 (3)	0.054 (1)
C13	−0.0780 (5)	0.1140 (3)	0.1040 (3)	0.055 (1)
C14	0.1087 (6)	0.2173 (4)	0.0425 (3)	0.065 (1)
C15	0.0170 (7)	0.1645 (4)	−0.0452 (3)	0.078 (1)
C16	−0.1242 (7)	0.0822 (4)	−0.0564 (3)	0.077 (2)
C17	−0.1768 (6)	0.0546 (3)	0.0178 (3)	0.066 (1)
C18	−0.3233 (7)	−0.0297 (4)	0.0110 (4)	0.078 (2)
C19	−0.3704 (6)	−0.0509 (3)	0.0859 (4)	0.082 (2)
C20	−0.2751 (6)	0.0072 (3)	0.1735 (4)	0.064 (1)
C21	−0.3172 (7)	−0.0124 (4)	0.2525 (5)	0.085 (2)
C22	−0.2159 (7)	0.0434 (4)	0.3339 (4)	0.085 (2)
C23	−0.0684 (6)	0.1230 (3)	0.3374 (4)	0.070 (1)
C24	−0.1269 (5)	0.0896 (3)	0.1828 (3)	0.055 (1)
C25	0.5460 (5)	0.3131 (3)	0.1665 (3)	0.057 (1)
C26	0.6300 (5)	0.3742 (3)	0.1093 (3)	0.059 (1)
C27	0.6149 (6)	0.4746 (3)	0.1244 (3)	0.062 (1)
C28	0.6913 (6)	0.5293 (4)	0.0725 (4)	0.075 (1)
C29	0.7789 (7)	0.4819 (5)	0.0015 (5)	0.096 (2)
C30	0.7941 (7)	0.3834 (5)	−0.0131 (4)	0.097 (2)
C31	0.7216 (6)	0.3294 (4)	0.0402 (3)	0.071 (1)
O4'	0.927 (1)	0.7319 (7)	0.2157 (8)	0.088 (3)	0.44 (1)
O5'	0.730 (2)	0.7828 (9)	0.3093 (9)	0.101 (5)	0.44 (1)
C32'	0.616 (2)	0.686 (2)	0.157 (1)	0.075 (8)	0.44 (1)
C33'	0.776 (2)	0.738 (1)	0.2316 (9)	0.073 (5)	0.44 (1)
O4	0.523 (2)	0.7644 (7)	0.3035 (7)	0.150 (6)	0.56 (1)
O5	0.794 (3)	0.741 (1)	0.277 (1)	0.144 (8)	0.56 (1)
C32	0.593 (3)	0.682 (2)	0.148 (1)	0.13 (1)	0.56 (1)
C33	0.640 (2)	0.736 (1)	0.254 (1)	0.111 (5)	0.56 (1)
H1w1	0.3510	0.1414	0.3017	0.096*
H1w2	0.4575	0.1769	0.2443	0.096*
H2w1	0.3104	−0.0097	0.3046	0.281*
H2w2	0.3686	0.0239	0.3975	0.281*
H3w1	0.1271	−0.1747	0.2136	0.383*
H3w2	0.1685	−0.2483	0.2417	0.383*
H4w1	0.5343	0.8442	0.4098	0.499*
H4w2	0.3753	0.8281	0.4397	0.499*
H5w1	0.9031	0.8533	0.4004	0.332*
H5w2	0.8912	0.9198	0.4886	0.332*
H2	0.3548	0.2481	0.4473	0.082*
H3	0.4192	0.3420	0.6019	0.092*
H4	0.3788	0.5067	0.6615	0.095*
H6	0.2872	0.6546	0.6322	0.101*
H7	0.1739	0.7128	0.5351	0.106*
H9	0.0554	0.6804	0.3724	0.105*
H10	−0.0159	0.5689	0.2213	0.104*
H11	0.0276	0.4041	0.1779	0.088*
H14	0.2064	0.2721	0.0499	0.078*
H15	0.0510	0.1847	−0.0942	0.093*
H16	−0.1857	0.0444	−0.1142	0.093*
H18	−0.3870	−0.0705	−0.0458	0.094*
H19	−0.4682	−0.1051	0.0800	0.098*
H21	−0.4161	−0.0644	0.2497	0.101*
H22	−0.2438	0.0290	0.3863	0.102*
H23	0.0015	0.1605	0.3928	0.084*
H27	0.5521	0.5046	0.1704	0.075*
H29	0.8273	0.5174	−0.0360	0.115*
H30	0.8545	0.3528	−0.0600	0.116*
H31	0.7338	0.2628	0.0302	0.085*
H32c	0.5257	0.6392	0.1752	0.090*	0.44 (1)
H32d	0.5720	0.7380	0.1453	0.090*	0.44 (1)
H32a	0.4820	0.6309	0.1387	0.158*	0.56 (1)
H32b	0.5722	0.7358	0.1278	0.158*	0.56 (1)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0600 (4)	0.0459 (3)	0.0471 (4)	0.0116 (3)	−0.0045 (3)	0.0095 (3)
O1	0.066 (2)	0.052 (2)	0.070 (2)	0.019 (1)	0.0134 (16)	0.016 (1)
O2	0.086 (2)	0.067 (2)	0.099 (3)	0.034 (2)	0.017 (2)	0.033 (2)
O3	0.101 (3)	0.084 (3)	0.120 (4)	0.010 (2)	−0.007 (3)	0.057 (3)
O1w	0.091 (2)	0.072 (2)	0.086 (2)	0.034 (2)	0.007 (2)	0.032 (2)
O2w	0.221 (7)	0.195 (6)	0.40 (1)	0.116 (6)	0.100 (8)	0.202 (8)
O3w	0.54 (2)	0.209 (8)	0.28 (1)	0.13 (1)	0.11 (1)	0.144 (8)
O4w	0.47 (2)	0.39 (2)	0.57 (2)	0.17 (2)	0.16 (2)	0.35 (2)
O5w	0.44 (1)	0.169 (6)	0.157 (6)	−0.015 (7)	−0.149 (7)	0.059 (5)
N1	0.056 (2)	0.046 (2)	0.053 (2)	0.002 (2)	−0.006 (2)	0.015 (2)
N2	0.055 (2)	0.056 (2)	0.053 (2)	0.013 (2)	−0.003 (2)	0.016 (2)
N3	0.063 (2)	0.055 (2)	0.052 (2)	0.019 (2)	0.001 (2)	0.014 (2)
N4	0.064 (2)	0.047 (2)	0.054 (2)	0.014 (2)	−0.001 (2)	0.013 (2)
C1	0.047 (2)	0.048 (2)	0.051 (2)	0.001 (2)	0.006 (2)	0.011 (2)
C2	0.075 (3)	0.062 (3)	0.060 (3)	0.001 (2)	−0.007 (2)	0.026 (2)
C3	0.083 (4)	0.081 (3)	0.060 (3)	−0.002 (3)	−0.009 (3)	0.037 (3)
C4	0.075 (3)	0.089 (4)	0.048 (3)	−0.004 (3)	−0.002 (2)	0.014 (3)
C5	0.059 (3)	0.061 (3)	0.051 (3)	0.001 (2)	0.005 (2)	0.006 (2)
C6	0.081 (4)	0.071 (3)	0.064 (3)	0.008 (3)	0.006 (3)	−0.010 (3)
C7	0.081 (4)	0.055 (3)	0.098 (4)	0.020 (3)	0.007 (3)	−0.010 (3)
C8	0.051 (3)	0.052 (2)	0.085 (3)	0.014 (2)	0.006 (2)	0.014 (2)
C9	0.069 (3)	0.060 (3)	0.126 (5)	0.024 (3)	0.001 (3)	0.021 (3)
C10	0.078 (4)	0.077 (3)	0.118 (5)	0.030 (3)	−0.007 (3)	0.046 (3)
C11	0.074 (3)	0.076 (3)	0.071 (3)	0.025 (2)	−0.006 (3)	0.027 (3)
C12	0.045 (2)	0.047 (2)	0.061 (3)	0.009 (2)	0.006 (2)	0.014 (2)
C13	0.061 (3)	0.047 (2)	0.055 (3)	0.028 (2)	−0.001 (2)	0.007 (2)
C14	0.069 (3)	0.071 (3)	0.056 (3)	0.025 (2)	0.004 (2)	0.020 (2)
C15	0.096 (4)	0.092 (4)	0.051 (3)	0.045 (3)	0.003 (3)	0.020 (3)
C16	0.089 (4)	0.082 (3)	0.053 (3)	0.047 (3)	−0.015 (3)	0.002 (3)
C17	0.069 (3)	0.053 (2)	0.065 (3)	0.033 (2)	−0.014 (2)	0.000 (2)
C18	0.079 (4)	0.055 (3)	0.084 (4)	0.026 (3)	−0.027 (3)	0.002 (3)
C19	0.064 (3)	0.046 (2)	0.115 (5)	0.011 (2)	−0.025 (3)	0.010 (3)
C20	0.059 (3)	0.044 (2)	0.088 (4)	0.017 (2)	−0.001 (3)	0.020 (2)
C21	0.074 (3)	0.056 (3)	0.119 (5)	0.010 (2)	0.004 (3)	0.032 (3)
C22	0.097 (4)	0.073 (3)	0.095 (4)	0.017 (3)	0.021 (3)	0.046 (3)
C23	0.083 (3)	0.061 (3)	0.067 (3)	0.018 (2)	0.007 (3)	0.024 (2)
C24	0.055 (2)	0.040 (2)	0.067 (3)	0.020 (2)	−0.001 (2)	0.011 (2)
C25	0.056 (3)	0.047 (2)	0.055 (3)	0.009 (2)	−0.008 (2)	0.006 (2)
C26	0.044 (2)	0.057 (2)	0.063 (3)	0.011 (2)	−0.008 (2)	0.010 (2)
C27	0.055 (3)	0.062 (2)	0.063 (3)	0.013 (2)	−0.005 (2)	0.020 (2)
C28	0.059 (3)	0.078 (3)	0.087 (4)	0.006 (2)	−0.007 (3)	0.041 (3)
C29	0.072 (4)	0.128 (5)	0.102 (5)	0.020 (3)	0.019 (3)	0.064 (4)
C30	0.080 (4)	0.120 (5)	0.096 (4)	0.038 (4)	0.030 (3)	0.037 (4)
C31	0.059 (3)	0.076 (3)	0.075 (3)	0.021 (2)	0.007 (3)	0.021 (3)
O4'	0.067 (6)	0.099 (6)	0.101 (8)	0.023 (5)	−0.007 (5)	0.042 (5)
O5'	0.12 (1)	0.079 (8)	0.09 (1)	0.002 (7)	−0.017 (8)	0.043 (7)
C32'	0.09 (1)	0.05 (1)	0.09 (2)	0.025 (9)	0.01 (1)	0.03 (1)
C33'	0.09 (1)	0.051 (7)	0.09 (1)	0.006 (7)	−0.016 (10)	0.043 (9)
O4	0.25 (2)	0.098 (6)	0.095 (7)	0.021 (7)	−0.012 (8)	0.050 (5)
O5	0.20 (2)	0.080 (7)	0.13 (1)	0.017 (8)	−0.07 (1)	0.033 (8)
C32	0.20 (2)	0.09 (2)	0.11 (2)	0.048 (15)	−0.05 (1)	0.03 (1)
C33	0.16 (2)	0.072 (8)	0.11 (1)	0.01 (1)	−0.01 (1)	0.060 (9)

Geometric parameters (Å, º)

Mn1—O1	2.099 (3)	C26—C27	1.393 (6)
Mn1—O1w	2.177 (3)	C27—C28	1.363 (7)
Mn1—N1	2.268 (3)	C28—C29	1.391 (8)
Mn1—N2	2.269 (3)	C29—C30	1.368 (8)
Mn1—N3	2.284 (4)	C30—C31	1.364 (8)
Mn1—N4	2.267 (4)	O4'—C33'	1.273 (11)
O1—C25	1.276 (5)	O5'—C33'	1.273 (10)
O2—C25	1.239 (5)	C32'—C33'	1.565 (15)
O3—C32'	1.387 (10)	O4—C33	1.283 (10)
O3—C28	1.391 (6)	O5—C33	1.277 (10)
O3—C32	1.391 (10)	C32—C33	1.570 (14)
N1—C2	1.322 (5)	O1w—H1w1	0.85
N1—C1	1.360 (5)	O1w—H1w2	0.85
N2—C11	1.320 (5)	O2w—H2w1	0.88
N2—C12	1.362 (5)	O2w—H2w2	0.86
N3—C14	1.311 (6)	O3w—H3w1	0.90
N3—C13	1.364 (5)	O3w—H3w2	0.88
N4—C23	1.326 (6)	O4w—H4w1	0.87
N4—C24	1.367 (5)	O4w—H4w2	0.89
C1—C5	1.410 (6)	O5w—H5w1	0.86
C1—C12	1.434 (6)	O5w—H5w2	0.90
C2—C3	1.381 (7)	C2—H2	0.93
C3—C4	1.358 (7)	C3—H3	0.93
C4—C5	1.406 (7)	C4—H4	0.93
C5—C6	1.433 (7)	C6—H6	0.93
C6—C7	1.338 (8)	C7—H7	0.93
C7—C8	1.439 (7)	C9—H9	0.93
C8—C12	1.400 (6)	C10—H10	0.93
C8—C9	1.402 (7)	C11—H11	0.93
C9—C10	1.359 (8)	C14—H14	0.93
C10—C11	1.396 (7)	C15—H15	0.93
C13—C17	1.414 (6)	C16—H16	0.93
C13—C24	1.428 (6)	C18—H18	0.93
C14—C15	1.401 (6)	C19—H19	0.93
C15—C16	1.368 (7)	C21—H21	0.93
C16—C17	1.391 (7)	C22—H22	0.93
C17—C18	1.427 (7)	C23—H23	0.93
C18—C19	1.346 (8)	C27—H27	0.93
C19—C20	1.417 (7)	C29—H29	0.93
C20—C21	1.389 (7)	C30—H30	0.93
C20—C24	1.411 (6)	C31—H31	0.93
C21—C22	1.363 (8)	C32'—H32c	0.97
C22—C23	1.406 (7)	C32'—H32d	0.97
C25—C26	1.507 (6)	C32—H32a	0.97
C26—C31	1.382 (6)	C32—H32b	0.97
O1—Mn1—O1w	86.5 (1)	O1—C25—C26	115.5 (4)
O1—Mn1—N1	104.3 (1)	C31—C26—C27	119.5 (5)
O1—Mn1—N2	87.4 (1)	C31—C26—C25	119.6 (4)
O1—Mn1—N3	90.4 (1)	C27—C26—C25	120.9 (4)
O1—Mn1—N4	161.3 (1)	C28—C27—C26	120.5 (5)
O1w—Mn1—N1	93.9 (1)	C27—C28—O3	125.4 (5)
O1w—Mn1—N2	164.1 (1)	C27—C28—C29	119.2 (5)
O1w—Mn1—N3	101.1 (1)	O3—C28—C29	115.3 (5)
O1w—Mn1—N4	87.5 (1)	C30—C29—C28	120.2 (6)
N1—Mn1—N2	73.4 (1)	C31—C30—C29	120.9 (5)
N1—Mn1—N3	159.7 (1)	C30—C31—C26	119.7 (5)
N1—Mn1—N4	93.8 (1)	O3—C32'—C33'	101.5 (9)
N2—Mn1—N3	93.7 (1)	O4'—C33'—O5'	126.2 (15)
N2—Mn1—N4	102.6 (1)	O4'—C33'—C32'	124.3 (10)
N3—Mn1—N4	73.5 (1)	O5'—C33'—C32'	109.5 (12)
C25—O1—Mn1	132.5 (3)	O3—C32—C33	129.3 (15)
C32'—O3—C28	118.0 (13)	O5—C33—O4	131.3 (19)
C28—O3—C32	119.7 (16)	O5—C33—C32	110.1 (17)
C2—N1—C1	117.8 (4)	O4—C33—C32	118.5 (11)
C2—N1—Mn1	127.2 (3)	Mn1—O1w—H1w1	109.5
C1—N1—Mn1	114.8 (3)	Mn1—O1w—H1w2	109.4
C11—N2—C12	117.7 (4)	H1w1—O1w—H1w2	109.8
C11—N2—Mn1	126.8 (3)	H2w1—O2w—H2w2	107.4
C12—N2—Mn1	115.0 (3)	H3w1—O3w—H3w2	101.4
C14—N3—C13	118.2 (4)	H4w1—O4w—H4w2	102.3
C14—N3—Mn1	127.1 (3)	H5w1—O5w—H5w2	105.0
C13—N3—Mn1	114.6 (3)	N1—C2—H2	117.9
C23—N4—C24	118.5 (4)	C3—C2—H2	117.9
C23—N4—Mn1	126.2 (3)	C4—C3—H3	120.7
C24—N4—Mn1	115.2 (3)	C2—C3—H3	120.7
N1—C1—C5	122.0 (4)	C3—C4—H4	119.9
N1—C1—C12	118.3 (3)	C5—C4—H4	119.9
C5—C1—C12	119.7 (4)	C7—C6—H6	118.9
N1—C2—C3	124.2 (5)	C5—C6—H6	118.9
C4—C3—C2	118.6 (5)	C6—C7—H7	119.6
C3—C4—C5	120.1 (4)	C8—C7—H7	119.6
C4—C5—C1	117.2 (4)	C10—C9—H9	120.0
C4—C5—C6	124.4 (5)	C8—C9—H9	120.0
C1—C5—C6	118.3 (5)	N2—C11—H11	118.0
C7—C6—C5	122.1 (5)	C10—C11—H11	118.0
C6—C7—C8	120.8 (5)	N3—C14—H14	117.9
C12—C8—C9	117.8 (4)	C15—C14—H14	117.9
C12—C8—C7	118.8 (5)	C16—C15—H15	121.1
C9—C8—C7	123.4 (5)	C14—C15—H15	121.1
C10—C9—C8	120.0 (5)	C15—C16—H16	119.7
C9—C10—C11	118.2 (5)	C17—C16—H16	119.7
C9—C10—H10	120.9	C19—C18—H18	119.6
C11—C10—H10	120.9	C17—C18—H18	119.6
N2—C11—C10	124.1 (5)	C18—C19—H19	119.1
N2—C12—C8	122.2 (4)	C20—C19—H19	119.1
N2—C12—C1	117.6 (3)	C22—C21—H21	119.5
C8—C12—C1	120.2 (4)	C20—C21—H21	119.5
N3—C13—C17	121.9 (4)	C21—C22—H22	120.6
N3—C13—C24	118.3 (4)	C23—C22—H22	120.6
C17—C13—C24	119.8 (4)	N4—C23—H23	118.8
N3—C14—C15	124.1 (5)	C22—C23—H23	118.8
C16—C15—C14	117.7 (5)	C28—C27—H27	119.7
C15—C16—C17	120.7 (4)	C26—C27—H27	119.7
C16—C17—C13	117.4 (5)	C30—C29—H29	119.9
C16—C17—C18	123.5 (5)	C28—C29—H29	119.9
C13—C17—C18	119.1 (5)	C31—C30—H30	119.6
C19—C18—C17	120.7 (5)	C29—C30—H30	119.6
C18—C19—C20	121.8 (5)	C30—C31—H31	120.2
C21—C20—C24	116.8 (4)	C26—C31—H31	120.2
C21—C20—C19	123.9 (5)	O3—C32'—H32c	111.5
C24—C20—C19	119.3 (5)	C33'—C32'—H32c	111.5
C22—C21—C20	121.1 (5)	O3—C32'—H32d	111.5
C21—C22—C23	118.8 (5)	C33'—C32'—H32d	111.5
N4—C23—C22	122.3 (5)	H32c—C32'—H32d	109.3
N4—C24—C20	122.5 (4)	O3—C32—H32a	105.0
N4—C24—C13	118.2 (4)	C33—C32—H32a	105.0
C20—C24—C13	119.3 (4)	O3—C32—H32b	105.0
O2—C25—O1	124.9 (4)	C33—C32—H32b	105.0
O2—C25—C26	119.5 (4)	H32a—C32—H32b	105.8
O1w—Mn1—O1—C25	19.5 (4)	C9—C8—C12—N2	−0.1 (7)
N4—Mn1—O1—C25	−52.0 (6)	C7—C8—C12—N2	178.2 (4)
N1—Mn1—O1—C25	112.6 (4)	C9—C8—C12—C1	−179.3 (4)
N2—Mn1—O1—C25	−175.3 (4)	C7—C8—C12—C1	−1.0 (6)
N3—Mn1—O1—C25	−81.6 (4)	N1—C1—C12—N2	2.8 (6)
O1—Mn1—N1—C2	−99.0 (4)	C5—C1—C12—N2	−177.6 (4)
O1w—Mn1—N1—C2	−11.6 (4)	N1—C1—C12—C8	−178.1 (4)
N4—Mn1—N1—C2	76.1 (4)	C5—C1—C12—C8	1.6 (6)
N2—Mn1—N1—C2	178.2 (4)	C14—N3—C13—C17	1.5 (5)
N3—Mn1—N1—C2	126.1 (4)	Mn1—N3—C13—C17	−174.7 (3)
O1—Mn1—N1—C1	76.1 (3)	C14—N3—C13—C24	−179.2 (3)
O1w—Mn1—N1—C1	163.5 (3)	Mn1—N3—C13—C24	4.6 (4)
N4—Mn1—N1—C1	−108.8 (3)	C13—N3—C14—C15	−0.1 (6)
N2—Mn1—N1—C1	−6.7 (3)	Mn1—N3—C14—C15	175.6 (3)
N3—Mn1—N1—C1	−58.9 (5)	N3—C14—C15—C16	−1.6 (7)
O1—Mn1—N2—C11	73.9 (4)	C14—C15—C16—C17	1.9 (7)
O1w—Mn1—N2—C11	141.5 (5)	C15—C16—C17—C13	−0.6 (6)
N4—Mn1—N2—C11	−90.2 (4)	C15—C16—C17—C18	179.6 (4)
N1—Mn1—N2—C11	179.6 (4)	N3—C13—C17—C16	−1.2 (6)
N3—Mn1—N2—C11	−16.3 (4)	C24—C13—C17—C16	179.5 (3)
O1—Mn1—N2—C12	−97.5 (3)	N3—C13—C17—C18	178.7 (3)
O1w—Mn1—N2—C12	−29.9 (6)	C24—C13—C17—C18	−0.6 (5)
N4—Mn1—N2—C12	98.4 (3)	C16—C17—C18—C19	−178.2 (4)
N1—Mn1—N2—C12	8.2 (3)	C13—C17—C18—C19	1.9 (6)
N3—Mn1—N2—C12	172.3 (3)	C17—C18—C19—C20	−1.7 (7)
O1—Mn1—N3—C14	−9.7 (3)	C18—C19—C20—C21	−179.2 (4)
O1w—Mn1—N3—C14	−96.2 (3)	C18—C19—C20—C24	0.1 (6)
N4—Mn1—N3—C14	179.8 (4)	C24—C20—C21—C22	−2.2 (7)
N1—Mn1—N3—C14	127.0 (4)	C19—C20—C21—C22	177.1 (4)
N2—Mn1—N3—C14	77.7 (3)	C20—C21—C22—C23	1.1 (8)
O1—Mn1—N3—C13	166.1 (3)	C24—N4—C23—C22	−1.3 (6)
O1w—Mn1—N3—C13	79.6 (3)	Mn1—N4—C23—C22	−176.9 (3)
N4—Mn1—N3—C13	−4.4 (2)	C21—C22—C23—N4	0.7 (7)
N1—Mn1—N3—C13	−57.2 (5)	C23—N4—C24—C20	0.1 (5)
N2—Mn1—N3—C13	−106.4 (3)	Mn1—N4—C24—C20	176.2 (3)
O1—Mn1—N4—C23	148.4 (4)	C23—N4—C24—C13	−178.8 (3)
O1w—Mn1—N4—C23	77.1 (3)	Mn1—N4—C24—C13	−2.7 (4)
N1—Mn1—N4—C23	−16.6 (3)	C21—C20—C24—N4	1.6 (6)
N2—Mn1—N4—C23	−90.5 (3)	C19—C20—C24—N4	−177.7 (4)
N3—Mn1—N4—C23	179.4 (4)	C21—C20—C24—C13	−179.5 (4)
O1—Mn1—N4—C24	−27.4 (5)	C19—C20—C24—C13	1.2 (5)
O1w—Mn1—N4—C24	−98.7 (3)	N3—C13—C24—N4	−1.3 (5)
N1—Mn1—N4—C24	167.6 (3)	C17—C13—C24—N4	178.0 (3)
N2—Mn1—N4—C24	93.8 (3)	N3—C13—C24—C20	179.7 (3)
N3—Mn1—N4—C24	3.7 (2)	C17—C13—C24—C20	−0.9 (5)
C2—N1—C1—C5	0.6 (6)	Mn1—O1—C25—O2	−22.8 (6)
Mn1—N1—C1—C5	−174.9 (3)	Mn1—O1—C25—C26	156.2 (3)
C2—N1—C1—C12	−179.7 (4)	O2—C25—C26—C31	19.3 (6)
Mn1—N1—C1—C12	4.7 (4)	O1—C25—C26—C31	−159.6 (4)
C1—N1—C2—C3	0.8 (7)	O2—C25—C26—C27	−161.5 (4)
Mn1—N1—C2—C3	175.8 (4)	O1—C25—C26—C27	19.6 (5)
N1—C2—C3—C4	−1.4 (8)	C31—C26—C27—C28	−0.8 (6)
C2—C3—C4—C5	0.6 (7)	C25—C26—C27—C28	180.0 (4)
C3—C4—C5—C1	0.7 (7)	C26—C27—C28—O3	−179.7 (4)
C3—C4—C5—C6	−178.3 (5)	C26—C27—C28—C29	2.6 (7)
N1—C1—C5—C4	−1.3 (6)	C32'—O3—C28—C27	9.2 (10)
C12—C1—C5—C4	179.0 (4)	C32—O3—C28—C27	−1.1 (12)
N1—C1—C5—C6	177.7 (4)	C32'—O3—C28—C29	−173.1 (9)
C12—C1—C5—C6	−2.0 (6)	C32—O3—C28—C29	176.6 (11)
C4—C5—C6—C7	−179.2 (5)	C27—C28—C29—C30	−2.8 (8)
C1—C5—C6—C7	1.8 (8)	O3—C28—C29—C30	179.4 (5)
C5—C6—C7—C8	−1.2 (9)	C28—C29—C30—C31	1.1 (9)
C6—C7—C8—C12	0.8 (8)	C29—C30—C31—C26	0.7 (8)
C6—C7—C8—C9	179.0 (5)	C27—C26—C31—C30	−0.9 (7)
C12—C8—C9—C10	−0.2 (8)	C25—C26—C31—C30	178.3 (5)
C7—C8—C9—C10	−178.4 (5)	C28—O3—C32'—C33'	86.1 (16)
C8—C9—C10—C11	0.7 (8)	C32—O3—C32'—C33'	−171 (18)
C12—N2—C11—C10	0.8 (7)	O3—C32'—C33'—O4'	5 (3)
Mn1—N2—C11—C10	−170.4 (4)	O3—C32'—C33'—O5'	−172.4 (15)
C9—C10—C11—N2	−1.1 (8)	C32'—O3—C32—C33	−6 (14)
C11—N2—C12—C8	−0.2 (6)	C28—O3—C32—C33	75 (3)
Mn1—N2—C12—C8	172.1 (3)	O3—C32—C33—O5	10 (4)
C11—N2—C12—C1	179.0 (4)	O3—C32—C33—O4	−169 (2)
Mn1—N2—C12—C1	−8.8 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H1w1···O2w	0.85	1.96	2.712 (7)	147
O1w—H1w2···O2	0.85	1.91	2.638 (5)	143
O2w—H2w1···O3w	0.88	2.19	2.83 (1)	129
O3w—H3w1···O4′^i	0.90	1.82	2.23 (2)	105
O4w—H4w1···O4	0.87	1.64	2.39 (2)	144
O5w—H5w1···O5′	0.86	1.80	2.62 (2)	159

Symmetry code: (i) x−1, y−1, z.