cis-Diaqua­bis(1,10-phenanthroline)manganese(II) 4-sulfonatobenzoate 6.5-hydrate

In the title complex salt, [Mn(C₁₂H₈N₂)₂(H₂O)₂](C₇H₄O₅S)·6.5H₂O, the coordination geometry about the Mn^II atom is distorted octahedral, defined by four N atoms from two 1,10-phenanthroline ligands and two O atoms from two water mol­ecules. O—H...O hydrogen-bonding inter­actions among cations, anions, and solvent water mol­ecules generate a three-dimensional network and enhance the stability of the crystal structure.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.005 Å
• H-atom completeness 88%
• Disorder in main residue
• R factor = 0.050
• wR factor = 0.145
• Data-to-parameter ratio = 11.2

checkCIF/PLATON results

No syntax errors found



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         S1
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.21
PLAT301_ALERT_3_C Main Residue  Disorder .........................       6.00 Perc.
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      32.00 Perc.
PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) .....       >O14
PLAT417_ALERT_2_C Short Inter D-H..H-D       H1B    ..  H8A     ..       2.13 Ang.

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C31 H37 Mn1 N4 O13.5 S1
            Atom count from the _atom_site data:  C31 H32.5 Mn1 N4 O13.5 S1
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
           From the CIF: _cell_formula_units_Z    2
           From the CIF: _chemical_formula_sum  C31 H37 Mn1 N4 O13.5 S1
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C         62.00     62.00    0.00
           H         74.00     65.00    9.00
           Mn         2.00      2.00    0.00
           N          8.00      8.00    0.00
           O         27.00     27.00    0.00
           S          2.00      2.00    0.00

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

   5 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
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

cis-Diaquabis(1,10-phenanthroline)manganese(II) 4-sulfonatobenzoate 6.5-hydrate

Crystal data

[Mn(C12H8N2)2(H2O)2](C7H4O5S)·6.5H2O	Z = 2
Mr = 769.15	F(000) = 791
Triclinic, P1	Dx = 1.46 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 12.4689 (10) Å	Cell parameters from 4511 reflections
b = 13.0731 (11) Å	θ = 2.5–28.2°
c = 13.3104 (11) Å	µ = 0.51 mm^−1
α = 106.408 (2)°	T = 295 K
β = 101.908 (1)°	Brick, pale yellow
γ = 114.895 (1)°	0.51 × 0.50 × 0.49 mm
V = 1751.1 (3) Å^3

Data collection

Bruker APEX area-detector diffractometer	6101 independent reflections
Radiation source: fine-focus sealed tube	5105 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.059
φ and ω scans	θmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −14→14
Tmin = 0.782, Tmax = 0.789	k = −15→13
8888 measured reflections	l = −15→13

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.145	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0852P)^2 + 0.1951P] where P = (Fo^2 + 2Fc^2)/3
6101 reflections	(Δ/σ)max = 0.001
544 parameters	Δρmax = 0.65 e Å^−3
102 restraints	Δρmin = −0.48 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)
Mn1	0.92760 (4)	0.79498 (4)	0.66465 (3)	0.03468 (16)
S1	0.28760 (10)	0.71297 (9)	0.89214 (8)	0.0643 (3)
O1	1.11239 (19)	0.8205 (2)	0.7200 (2)	0.0537 (5)
O2	0.99551 (19)	0.88508 (19)	0.55933 (17)	0.0452 (5)
O3	0.1597 (2)	0.12924 (18)	0.62656 (17)	0.0484 (5)
O4	0.3371 (2)	0.2024 (2)	0.76996 (19)	0.0586 (6)
O5	0.3731 (8)	0.7918 (5)	0.8501 (8)	0.094 (3)	0.610 (13)
O6	0.3342 (9)	0.7653 (6)	1.0119 (3)	0.078 (2)	0.610 (13)
O7	0.1618 (5)	0.6901 (8)	0.8420 (7)	0.071 (2)	0.610 (13)
O5'	0.4152 (7)	0.8041 (7)	0.9255 (15)	0.116 (5)	0.390 (13)
O6'	0.2559 (15)	0.7043 (14)	0.9898 (9)	0.110 (4)	0.390 (13)
O7'	0.1867 (13)	0.7063 (17)	0.8128 (13)	0.106 (6)	0.390 (13)
O8	0.3034 (2)	0.9719 (2)	0.6770 (2)	0.0663 (7)
O9	0.5152 (3)	0.9921 (3)	0.8241 (3)	0.1056 (11)
O10	0.6032 (3)	0.3058 (4)	0.8187 (3)	0.1160 (13)
O11	0.7925 (6)	0.3388 (5)	0.7320 (4)	0.166 (2)
O12	0.7904 (8)	0.1390 (8)	0.5744 (7)	0.126 (3)	0.587 (12)
O12'	0.6544 (17)	0.0848 (17)	0.5319 (16)	0.186 (8)	0.413 (12)
O13	0.5731 (10)	−0.0053 (10)	0.6195 (9)	0.149 (3)	0.50
O14'	1.029 (3)	0.534 (3)	0.997 (3)	0.219 (15)	0.337 (18)
O14	0.9894 (10)	0.4788 (11)	0.8916 (11)	0.193 (6)	0.663 (18)
N1	0.9227 (2)	0.9590 (2)	0.77597 (18)	0.0402 (5)
N2	0.8792 (2)	0.7528 (2)	0.81144 (18)	0.0408 (5)
N3	0.7281 (2)	0.7226 (2)	0.54206 (19)	0.0410 (5)
N4	0.8424 (2)	0.5887 (2)	0.56089 (19)	0.0430 (6)
C1	0.9448 (3)	1.0604 (3)	0.7593 (3)	0.0504 (7)
H1	0.9799	1.0740	0.7058	0.060*
C2	0.9178 (3)	1.1476 (3)	0.8185 (3)	0.0625 (9)
H2	0.9356	1.2179	0.8048	0.075*
C3	0.8656 (3)	1.1286 (3)	0.8957 (3)	0.0625 (9)
H3	0.8464	1.1855	0.9350	0.075*
C4	0.8405 (3)	1.0238 (3)	0.9162 (2)	0.0503 (8)
C5	0.7850 (3)	0.9966 (4)	0.9955 (3)	0.0669 (10)
H5	0.7623	1.0501	1.0350	0.080*
C6	0.7646 (3)	0.8959 (4)	1.0148 (3)	0.0663 (10)
H6	0.7289	0.8814	1.0678	0.080*
C7	0.7968 (3)	0.8098 (3)	0.9549 (2)	0.0525 (8)
C8	0.7786 (3)	0.7047 (4)	0.9722 (3)	0.0650 (10)
H8	0.7439	0.6870	1.0249	0.078*
C9	0.8118 (4)	0.6271 (3)	0.9118 (3)	0.0649 (10)
H9	0.8017	0.5575	0.9239	0.078*
C10	0.8609 (3)	0.6549 (3)	0.8319 (3)	0.0538 (8)
H10	0.8821	0.6012	0.7904	0.065*
C11	0.8486 (2)	0.8313 (3)	0.8738 (2)	0.0410 (6)
C12	0.8716 (2)	0.9401 (3)	0.8541 (2)	0.0398 (6)
C13	0.6739 (3)	0.7889 (3)	0.5297 (3)	0.0516 (8)
H13	0.7191	0.8734	0.5760	0.062*
C14	0.5523 (3)	0.7377 (4)	0.4507 (3)	0.0623 (9)
H14	0.5179	0.7873	0.4441	0.075*
C15	0.4850 (3)	0.6145 (4)	0.3836 (3)	0.0611 (9)
H15	0.4031	0.5789	0.3314	0.073*
C16	0.5378 (3)	0.5411 (3)	0.3926 (2)	0.0508 (8)
C17	0.4738 (3)	0.4119 (4)	0.3240 (3)	0.0634 (10)
H17	0.3919	0.3731	0.2707	0.076*
C18	0.5290 (3)	0.3438 (3)	0.3344 (3)	0.0650 (10)
H18	0.4843	0.2592	0.2889	0.078*
C19	0.6548 (3)	0.4004 (3)	0.4140 (3)	0.0531 (8)
C20	0.7164 (4)	0.3349 (3)	0.4275 (3)	0.0675 (10)
H20	0.6751	0.2501	0.3836	0.081*
C21	0.8378 (4)	0.3955 (3)	0.5056 (3)	0.0669 (10)
H21	0.8797	0.3525	0.5151	0.080*
C22	0.8977 (3)	0.5227 (3)	0.5709 (3)	0.0532 (8)
H22	0.9801	0.5631	0.6238	0.064*
C23	0.7216 (3)	0.5282 (3)	0.4838 (2)	0.0417 (6)
C24	0.6615 (3)	0.5997 (3)	0.4734 (2)	0.0405 (6)
C25	0.2626 (3)	0.3392 (2)	0.7581 (2)	0.0365 (6)
C26	0.3728 (3)	0.4426 (3)	0.8427 (2)	0.0446 (7)
H26	0.4424	0.4356	0.8726	0.053*
C27	0.3803 (3)	0.5558 (3)	0.8830 (3)	0.0502 (7)
H27	0.4550	0.6247	0.9393	0.060*
C28	0.2776 (3)	0.5669 (3)	0.8401 (2)	0.0468 (7)
C29	0.1675 (3)	0.4645 (3)	0.7560 (3)	0.0602 (9)
H29	0.0980	0.4719	0.7266	0.072*
C30	0.1599 (3)	0.3516 (3)	0.7154 (3)	0.0532 (8)
H30	0.0851	0.2830	0.6588	0.064*
C31	0.2533 (3)	0.2150 (3)	0.7143 (2)	0.0388 (6)
H1A	1.132 (3)	0.784 (3)	0.757 (3)	0.080*
H1B	1.175 (2)	0.866 (3)	0.707 (3)	0.080*
H2A	1.060 (2)	0.9574 (18)	0.584 (3)	0.080*
H2B	0.937 (2)	0.872 (3)	0.504 (2)	0.080*
H8B	0.307 (3)	1.0411 (19)	0.694 (3)	0.080*
H8A	0.366 (3)	0.980 (3)	0.725 (3)	0.080*
H9A	0.474 (3)	0.9398 (18)	0.850 (2)	0.080*
H9B	0.571 (2)	1.0594 (11)	0.8805 (18)	0.080*
H10A	0.5228 (10)	0.273 (3)	0.803 (3)	0.080*
H10B	0.633 (3)	0.278 (3)	0.861 (3)	0.080*
H11A	0.8257	0.3719	0.6891	0.080*
H12A	0.7109 (18)	0.092 (4)	0.555 (4)	0.080*
H13A	0.573 (8)	−0.047 (6)	0.658 (6)	0.080*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0371 (2)	0.0356 (3)	0.0327 (2)	0.02055 (19)	0.01268 (18)	0.01309 (18)
S1	0.0887 (7)	0.0546 (5)	0.0501 (5)	0.0496 (5)	0.0107 (5)	0.0126 (4)
O1	0.0452 (12)	0.0688 (15)	0.0619 (14)	0.0356 (12)	0.0179 (11)	0.0374 (12)
O2	0.0458 (11)	0.0450 (11)	0.0390 (11)	0.0182 (9)	0.0109 (9)	0.0213 (9)
O3	0.0536 (12)	0.0393 (11)	0.0440 (11)	0.0219 (10)	0.0091 (10)	0.0161 (9)
O4	0.0618 (14)	0.0521 (13)	0.0601 (14)	0.0366 (12)	0.0076 (11)	0.0200 (11)
O5	0.128 (5)	0.045 (3)	0.117 (5)	0.033 (3)	0.072 (4)	0.042 (3)
O6	0.124 (5)	0.058 (3)	0.038 (2)	0.061 (4)	−0.002 (2)	0.004 (2)
O7	0.077 (3)	0.052 (3)	0.084 (4)	0.045 (2)	0.007 (3)	0.027 (3)
O5'	0.104 (6)	0.059 (5)	0.135 (9)	0.043 (5)	−0.002 (5)	0.004 (5)
O6'	0.134 (8)	0.104 (8)	0.100 (6)	0.098 (7)	0.014 (5)	0.016 (5)
O7'	0.153 (9)	0.086 (7)	0.087 (7)	0.075 (7)	0.006 (5)	0.051 (5)
O8	0.0568 (14)	0.0501 (14)	0.0912 (19)	0.0306 (12)	0.0229 (13)	0.0265 (13)
O9	0.091 (2)	0.077 (2)	0.107 (3)	0.0340 (18)	−0.002 (2)	0.0256 (18)
O10	0.0681 (19)	0.174 (4)	0.121 (3)	0.050 (2)	0.024 (2)	0.107 (3)
O11	0.248 (6)	0.187 (5)	0.180 (4)	0.149 (5)	0.149 (5)	0.118 (4)
O12	0.130 (4)	0.124 (4)	0.121 (4)	0.061 (3)	0.047 (3)	0.053 (3)
O12'	0.189 (8)	0.186 (8)	0.184 (8)	0.096 (5)	0.071 (4)	0.075 (4)
O13	0.147 (3)	0.149 (3)	0.148 (3)	0.0759 (19)	0.0578 (16)	0.0591 (16)
O14'	0.218 (15)	0.220 (15)	0.221 (15)	0.114 (8)	0.079 (6)	0.093 (7)
O14	0.188 (6)	0.195 (6)	0.197 (7)	0.099 (4)	0.079 (3)	0.075 (4)
N1	0.0414 (13)	0.0412 (13)	0.0359 (12)	0.0224 (11)	0.0143 (10)	0.0114 (10)
N2	0.0411 (12)	0.0433 (13)	0.0340 (12)	0.0205 (11)	0.0107 (10)	0.0150 (10)
N3	0.0388 (12)	0.0448 (14)	0.0384 (13)	0.0191 (11)	0.0136 (10)	0.0203 (11)
N4	0.0472 (14)	0.0407 (13)	0.0389 (13)	0.0218 (11)	0.0174 (11)	0.0138 (11)
C1	0.0579 (19)	0.0442 (17)	0.0523 (18)	0.0295 (15)	0.0220 (15)	0.0180 (14)
C2	0.069 (2)	0.0461 (19)	0.070 (2)	0.0350 (18)	0.0205 (19)	0.0154 (17)
C3	0.066 (2)	0.059 (2)	0.059 (2)	0.0423 (19)	0.0196 (18)	0.0075 (17)
C4	0.0445 (16)	0.059 (2)	0.0370 (15)	0.0306 (15)	0.0100 (13)	0.0036 (14)
C5	0.067 (2)	0.087 (3)	0.0445 (19)	0.046 (2)	0.0241 (17)	0.0099 (18)
C6	0.062 (2)	0.099 (3)	0.0354 (17)	0.041 (2)	0.0270 (16)	0.0206 (18)
C7	0.0430 (17)	0.068 (2)	0.0313 (15)	0.0206 (16)	0.0097 (13)	0.0164 (15)
C8	0.063 (2)	0.081 (3)	0.0422 (18)	0.025 (2)	0.0207 (16)	0.0312 (18)
C9	0.072 (2)	0.062 (2)	0.054 (2)	0.0245 (19)	0.0171 (18)	0.0351 (18)
C10	0.0611 (19)	0.0521 (19)	0.0465 (18)	0.0289 (16)	0.0160 (15)	0.0214 (15)
C11	0.0325 (14)	0.0488 (17)	0.0286 (13)	0.0164 (13)	0.0058 (11)	0.0102 (12)
C12	0.0322 (14)	0.0447 (16)	0.0295 (13)	0.0180 (12)	0.0055 (11)	0.0053 (12)
C13	0.0457 (17)	0.060 (2)	0.0512 (18)	0.0280 (16)	0.0154 (14)	0.0268 (16)
C14	0.0516 (19)	0.086 (3)	0.063 (2)	0.040 (2)	0.0192 (17)	0.043 (2)
C15	0.0397 (17)	0.085 (3)	0.0520 (19)	0.0235 (18)	0.0108 (15)	0.0368 (19)
C16	0.0405 (16)	0.065 (2)	0.0340 (15)	0.0150 (15)	0.0134 (13)	0.0227 (15)
C17	0.0441 (18)	0.070 (2)	0.0394 (17)	0.0067 (17)	0.0077 (14)	0.0163 (17)
C18	0.059 (2)	0.050 (2)	0.0435 (18)	0.0047 (17)	0.0155 (16)	0.0045 (15)
C19	0.0582 (19)	0.0425 (17)	0.0455 (17)	0.0156 (15)	0.0269 (15)	0.0116 (14)
C20	0.081 (3)	0.0410 (18)	0.064 (2)	0.0223 (18)	0.033 (2)	0.0088 (16)
C21	0.084 (3)	0.051 (2)	0.076 (2)	0.041 (2)	0.039 (2)	0.0233 (19)
C22	0.0569 (19)	0.0496 (18)	0.0550 (19)	0.0314 (16)	0.0217 (15)	0.0168 (15)
C23	0.0440 (15)	0.0446 (16)	0.0314 (14)	0.0167 (13)	0.0194 (12)	0.0148 (12)
C24	0.0372 (14)	0.0489 (17)	0.0301 (13)	0.0143 (13)	0.0159 (12)	0.0192 (13)
C25	0.0421 (15)	0.0398 (15)	0.0327 (14)	0.0218 (13)	0.0158 (12)	0.0190 (12)
C26	0.0434 (16)	0.0456 (17)	0.0464 (16)	0.0260 (14)	0.0133 (13)	0.0188 (14)
C27	0.0463 (17)	0.0416 (17)	0.0506 (18)	0.0199 (14)	0.0099 (14)	0.0135 (14)
C28	0.0618 (19)	0.0461 (17)	0.0393 (15)	0.0336 (16)	0.0157 (14)	0.0193 (13)
C29	0.063 (2)	0.058 (2)	0.0538 (19)	0.0414 (18)	0.0014 (16)	0.0132 (16)
C30	0.0494 (17)	0.0448 (17)	0.0491 (18)	0.0244 (15)	0.0008 (14)	0.0105 (14)
C31	0.0428 (15)	0.0424 (16)	0.0371 (15)	0.0226 (13)	0.0164 (13)	0.0218 (13)

Geometric parameters (Å, º)

Mn1—O1	2.116 (2)	C4—C5	1.424 (5)
Mn1—O2	2.1570 (19)	C5—C6	1.342 (6)
Mn1—N1	2.269 (2)	C5—H5	0.9300
Mn1—N2	2.303 (2)	C6—C7	1.438 (5)
Mn1—N3	2.284 (2)	C6—H6	0.9300
Mn1—N4	2.278 (2)	C7—C8	1.390 (5)
S1—O5'	1.401 (7)	C7—C11	1.403 (4)
S1—O7'	1.418 (7)	C8—C9	1.369 (5)
S1—O6	1.419 (4)	C8—H8	0.9300
S1—O7	1.434 (5)	C9—C10	1.392 (5)
S1—O6'	1.455 (7)	C9—H9	0.9300
S1—O5	1.469 (4)	C10—H10	0.9300
S1—C28	1.778 (3)	C11—C12	1.439 (4)
O1—H1A	0.84 (4)	C13—C14	1.394 (4)
O1—H1B	0.85 (4)	C13—H13	0.9300
O2—H2A	0.85 (3)	C14—C15	1.355 (5)
O2—H2B	0.84 (3)	C14—H14	0.9300
O3—C31	1.257 (3)	C15—C16	1.389 (5)
O4—C31	1.250 (3)	C15—H15	0.9300
O8—H8B	0.85 (3)	C16—C24	1.406 (4)
O8—H8A	0.85 (4)	C16—C17	1.420 (5)
O9—H9A	0.87 (3)	C17—C18	1.353 (5)
O9—H9B	0.85 (2)	C17—H17	0.9300
O10—H10A	0.86 (3)	C18—C19	1.423 (5)
O10—H10B	0.85 (4)	C18—H18	0.9300
O11—H11A	0.8800	C19—C20	1.392 (5)
O12—H12A	0.848 (11)	C19—C23	1.408 (4)
O12'—H12A	0.66 (4)	C20—C21	1.370 (5)
O13—H13A	0.846 (11)	C20—H20	0.9300
O14'—O14'^i	0.92 (5)	C21—C22	1.396 (5)
N1—C1	1.329 (4)	C21—H21	0.9300
N1—C12	1.355 (4)	C22—H22	0.9300
N2—C10	1.319 (4)	C23—C24	1.441 (4)
N2—C11	1.368 (4)	C25—C30	1.384 (4)
N3—C13	1.327 (4)	C25—C26	1.386 (4)
N3—C24	1.357 (4)	C25—C31	1.506 (4)
N4—C22	1.329 (4)	C26—C27	1.378 (4)
N4—C23	1.360 (4)	C26—H26	0.9300
C1—C2	1.400 (4)	C27—C28	1.374 (4)
C1—H1	0.9300	C27—H27	0.9300
C2—C3	1.351 (5)	C28—C29	1.379 (5)
C2—H2	0.9300	C29—C30	1.375 (4)
C3—C4	1.392 (5)	C29—H29	0.9300
C3—H3	0.9300	C30—H30	0.9300
C4—C12	1.417 (4)
O1—Mn1—O2	84.02 (8)	C11—C7—C6	119.0 (3)
O1—Mn1—N1	110.56 (9)	C9—C8—C7	120.1 (3)
O2—Mn1—N1	93.02 (9)	C9—C8—H8	120.0
O1—Mn1—N4	91.09 (9)	C7—C8—H8	120.0
O2—Mn1—N4	105.67 (8)	C8—C9—C10	118.5 (3)
N1—Mn1—N4	152.91 (9)	C8—C9—H9	120.8
O1—Mn1—N3	157.91 (9)	C10—C9—H9	120.8
O2—Mn1—N3	85.67 (8)	N2—C10—C9	124.0 (3)
N1—Mn1—N3	89.43 (8)	N2—C10—H10	118.0
N4—Mn1—N3	72.99 (9)	C9—C10—H10	118.0
O1—Mn1—N2	94.97 (9)	N2—C11—C7	122.7 (3)
O2—Mn1—N2	164.63 (8)	N2—C11—C12	117.6 (2)
N1—Mn1—N2	72.91 (8)	C7—C11—C12	119.7 (3)
N4—Mn1—N2	89.67 (8)	N1—C12—C4	121.9 (3)
N3—Mn1—N2	100.04 (8)	N1—C12—C11	118.4 (2)
O5'—S1—O7'	122.1 (8)	C4—C12—C11	119.6 (3)
O5'—S1—O6	75.5 (6)	N3—C13—C14	123.0 (3)
O7'—S1—O6	130.5 (8)	N3—C13—H13	118.5
O5'—S1—O7	139.9 (6)	C14—C13—H13	118.5
O6—S1—O7	113.0 (4)	C15—C14—C13	119.0 (3)
O5'—S1—O6'	110.9 (7)	C15—C14—H14	120.5
O7'—S1—O6'	109.5 (8)	C13—C14—H14	120.5
O7—S1—O6'	86.8 (5)	C14—C15—C16	120.2 (3)
O7'—S1—O5	86.6 (7)	C14—C15—H15	119.9
O6—S1—O5	111.6 (4)	C16—C15—H15	119.9
O7—S1—O5	108.8 (4)	C15—C16—C24	117.5 (3)
O6'—S1—O5	146.0 (6)	C15—C16—C17	123.4 (3)
O5'—S1—C28	107.0 (4)	C24—C16—C17	119.2 (3)
O7'—S1—C28	107.4 (8)	C18—C17—C16	121.6 (3)
O6—S1—C28	110.0 (2)	C18—C17—H17	119.2
O7—S1—C28	106.1 (4)	C16—C17—H17	119.2
O6'—S1—C28	96.7 (5)	C17—C18—C19	120.7 (3)
O5—S1—C28	107.0 (3)	C17—C18—H18	119.6
Mn1—O1—H1A	123 (2)	C19—C18—H18	119.6
Mn1—O1—H1B	126 (2)	C20—C19—C23	117.5 (3)
H1A—O1—H1B	111 (4)	C20—C19—C18	123.1 (3)
Mn1—O2—H2A	125 (2)	C23—C19—C18	119.5 (3)
Mn1—O2—H2B	114 (2)	C21—C20—C19	119.9 (3)
H2A—O2—H2B	110.9 (17)	C21—C20—H20	120.0
H8B—O8—H8A	109 (4)	C19—C20—H20	120.0
H9A—O9—H9B	107.2 (17)	C20—C21—C22	119.0 (3)
H10A—O10—H10B	109 (4)	C20—C21—H21	120.5
C1—N1—C12	117.9 (2)	C22—C21—H21	120.5
C1—N1—Mn1	126.0 (2)	N4—C22—C21	123.0 (3)
C12—N1—Mn1	115.02 (18)	N4—C22—H22	118.5
C10—N2—C11	117.3 (3)	C21—C22—H22	118.5
C10—N2—Mn1	128.1 (2)	N4—C23—C19	122.7 (3)
C11—N2—Mn1	113.93 (18)	N4—C23—C24	117.8 (3)
C13—N3—C24	117.8 (3)	C19—C23—C24	119.5 (3)
C13—N3—Mn1	126.7 (2)	N3—C24—C16	122.5 (3)
C24—N3—Mn1	115.45 (18)	N3—C24—C23	118.1 (2)
C22—N4—C23	117.9 (3)	C16—C24—C23	119.5 (3)
C22—N4—Mn1	126.4 (2)	C30—C25—C26	118.7 (3)
C23—N4—Mn1	115.66 (19)	C30—C25—C31	120.3 (3)
N1—C1—C2	123.1 (3)	C26—C25—C31	121.0 (2)
N1—C1—H1	118.4	C27—C26—C25	120.7 (3)
C2—C1—H1	118.4	C27—C26—H26	119.6
C3—C2—C1	119.3 (3)	C25—C26—H26	119.6
C3—C2—H2	120.4	C28—C27—C26	120.1 (3)
C1—C2—H2	120.4	C28—C27—H27	120.0
C2—C3—C4	119.8 (3)	C26—C27—H27	120.0
C2—C3—H3	120.1	C27—C28—C29	119.7 (3)
C4—C3—H3	120.1	C27—C28—S1	120.0 (2)
C3—C4—C12	117.9 (3)	C29—C28—S1	120.3 (2)
C3—C4—C5	123.3 (3)	C30—C29—C28	120.4 (3)
C12—C4—C5	118.8 (3)	C30—C29—H29	119.8
C6—C5—C4	121.7 (3)	C28—C29—H29	119.8
C6—C5—H5	119.2	C29—C30—C25	120.5 (3)
C4—C5—H5	119.2	C29—C30—H30	119.8
C5—C6—C7	121.2 (3)	C25—C30—H30	119.8
C5—C6—H6	119.4	O4—C31—O3	123.9 (3)
C7—C6—H6	119.4	O4—C31—C25	117.8 (2)
C8—C7—C11	117.5 (3)	O3—C31—C25	118.3 (2)
C8—C7—C6	123.5 (3)
O1—Mn1—N1—C1	90.5 (2)	C5—C4—C12—N1	178.9 (3)
O2—Mn1—N1—C1	5.8 (2)	C3—C4—C12—C11	179.3 (3)
N4—Mn1—N1—C1	−128.4 (3)	C5—C4—C12—C11	−1.0 (4)
N3—Mn1—N1—C1	−79.8 (2)	N2—C11—C12—N1	−0.4 (4)
N2—Mn1—N1—C1	179.5 (3)	C7—C11—C12—N1	179.4 (2)
O1—Mn1—N1—C12	−101.24 (19)	N2—C11—C12—C4	179.6 (2)
O2—Mn1—N1—C12	174.02 (18)	C7—C11—C12—C4	−0.6 (4)
N4—Mn1—N1—C12	39.8 (3)	C24—N3—C13—C14	0.5 (4)
N3—Mn1—N1—C12	88.38 (18)	Mn1—N3—C13—C14	178.4 (2)
N2—Mn1—N1—C12	−12.30 (17)	N3—C13—C14—C15	0.7 (5)
O1—Mn1—N2—C10	−68.1 (3)	C13—C14—C15—C16	−1.1 (5)
O2—Mn1—N2—C10	−153.6 (3)	C14—C15—C16—C24	0.4 (5)
N1—Mn1—N2—C10	−178.1 (3)	C14—C15—C16—C17	−179.0 (3)
N4—Mn1—N2—C10	22.9 (3)	C15—C16—C17—C18	179.2 (3)
N3—Mn1—N2—C10	95.6 (3)	C24—C16—C17—C18	−0.1 (5)
O1—Mn1—N2—C11	121.98 (19)	C16—C17—C18—C19	−0.8 (5)
O2—Mn1—N2—C11	36.5 (4)	C17—C18—C19—C20	−179.5 (3)
N1—Mn1—N2—C11	11.98 (17)	C17—C18—C19—C23	0.9 (5)
N4—Mn1—N2—C11	−146.95 (19)	C23—C19—C20—C21	−0.7 (5)
N3—Mn1—N2—C11	−74.29 (19)	C18—C19—C20—C21	179.8 (3)
O1—Mn1—N3—C13	−131.7 (3)	C19—C20—C21—C22	0.2 (5)
O2—Mn1—N3—C13	−69.4 (2)	C23—N4—C22—C21	0.4 (5)
N1—Mn1—N3—C13	23.7 (2)	Mn1—N4—C22—C21	178.5 (2)
N4—Mn1—N3—C13	−177.3 (3)	C20—C21—C22—N4	−0.1 (5)
N2—Mn1—N3—C13	96.2 (2)	C22—N4—C23—C19	−0.9 (4)
O1—Mn1—N3—C24	46.2 (3)	Mn1—N4—C23—C19	−179.2 (2)
O2—Mn1—N3—C24	108.54 (18)	C22—N4—C23—C24	179.7 (3)
N1—Mn1—N3—C24	−158.38 (18)	Mn1—N4—C23—C24	1.4 (3)
N4—Mn1—N3—C24	0.70 (17)	C20—C19—C23—N4	1.1 (4)
N2—Mn1—N3—C24	−85.85 (18)	C18—C19—C23—N4	−179.3 (3)
O1—Mn1—N4—C22	16.4 (3)	C20—C19—C23—C24	−179.6 (3)
O2—Mn1—N4—C22	100.4 (3)	C18—C19—C23—C24	0.0 (4)
N1—Mn1—N4—C22	−127.6 (3)	C13—N3—C24—C16	−1.3 (4)
N3—Mn1—N4—C22	−179.2 (3)	Mn1—N3—C24—C16	−179.5 (2)
N2—Mn1—N4—C22	−78.6 (3)	C13—N3—C24—C23	177.9 (2)
O1—Mn1—N4—C23	−165.56 (19)	Mn1—N3—C24—C23	−0.2 (3)
O2—Mn1—N4—C23	−81.47 (19)	C15—C16—C24—N3	0.9 (4)
N1—Mn1—N4—C23	50.5 (3)	C17—C16—C24—N3	−179.8 (3)
N3—Mn1—N4—C23	−1.13 (18)	C15—C16—C24—C23	−178.3 (3)
N2—Mn1—N4—C23	99.47 (19)	C17—C16—C24—C23	1.0 (4)
C12—N1—C1—C2	0.0 (4)	N4—C23—C24—N3	−0.8 (4)
Mn1—N1—C1—C2	167.9 (2)	C19—C23—C24—N3	179.8 (2)
N1—C1—C2—C3	−0.7 (5)	N4—C23—C24—C16	178.4 (2)
C1—C2—C3—C4	0.6 (5)	C19—C23—C24—C16	−0.9 (4)
C2—C3—C4—C12	0.1 (5)	C30—C25—C26—C27	−0.4 (4)
C2—C3—C4—C5	−179.6 (3)	C31—C25—C26—C27	−179.5 (3)
C3—C4—C5—C6	−178.6 (3)	C25—C26—C27—C28	0.6 (5)
C12—C4—C5—C6	1.7 (5)	C26—C27—C28—C29	−0.5 (5)
C4—C5—C6—C7	−0.7 (5)	C26—C27—C28—S1	−180.0 (2)
C5—C6—C7—C8	179.5 (3)	O5'—S1—C28—C27	30.4 (8)
C5—C6—C7—C11	−1.0 (5)	O7'—S1—C28—C27	163.1 (8)
C11—C7—C8—C9	0.5 (5)	O6—S1—C28—C27	−50.0 (5)
C6—C7—C8—C9	180.0 (3)	O7—S1—C28—C27	−172.6 (5)
C7—C8—C9—C10	−1.4 (5)	O6'—S1—C28—C27	−83.9 (7)
C11—N2—C10—C9	0.6 (5)	O5—S1—C28—C27	71.4 (5)
Mn1—N2—C10—C9	−169.0 (2)	O5'—S1—C28—C29	−149.1 (8)
C8—C9—C10—N2	0.9 (5)	O7'—S1—C28—C29	−16.4 (8)
C10—N2—C11—C7	−1.5 (4)	O6—S1—C28—C29	130.6 (5)
Mn1—N2—C11—C7	169.6 (2)	O7—S1—C28—C29	8.0 (5)
C10—N2—C11—C12	178.3 (2)	O6'—S1—C28—C29	96.6 (7)
Mn1—N2—C11—C12	−10.6 (3)	O5—S1—C28—C29	−108.1 (5)
C8—C7—C11—N2	1.0 (4)	C27—C28—C29—C30	0.3 (5)
C6—C7—C11—N2	−178.5 (3)	S1—C28—C29—C30	179.8 (3)
C8—C7—C11—C12	−178.8 (3)	C28—C29—C30—C25	−0.2 (5)
C6—C7—C11—C12	1.6 (4)	C26—C25—C30—C29	0.2 (5)
C1—N1—C12—C4	0.7 (4)	C31—C25—C30—C29	179.3 (3)
Mn1—N1—C12—C4	−168.5 (2)	C30—C25—C31—O4	−165.8 (3)
C1—N1—C12—C11	−179.3 (2)	C26—C25—C31—O4	13.2 (4)
Mn1—N1—C12—C11	11.5 (3)	C30—C25—C31—O3	11.7 (4)
C3—C4—C12—N1	−0.8 (4)	C26—C25—C31—O3	−169.3 (3)

Symmetry code: (i) −x+2, −y+1, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O7′^ii	0.84 (4)	1.69 (2)	2.521 (11)	168 (4)
O1—H1A···O7^ii	0.84 (4)	1.98 (1)	2.821 (8)	175 (3)
O1—H1B···O8^ii	0.85 (4)	1.83 (4)	2.674 (3)	175 (3)
O2—H2A···O3^iii	0.85 (3)	1.89 (2)	2.704 (3)	162 (3)
O2—H2B···O3^iv	0.84 (3)	1.89 (3)	2.713 (3)	166 (3)
O8—H8B···O4^v	0.85 (3)	1.89 (2)	2.721 (3)	165 (3)
O8—H8A···O9	0.85 (4)	1.96 (4)	2.804 (4)	174 (4)
O9—H9A···O5	0.87 (3)	1.81 (1)	2.641 (5)	158 (3)
O9—H9A···O5′	0.87 (3)	2.21 (2)	3.066 (16)	165 (4)
O9—H9B···O6^vi	0.85 (2)	1.97 (1)	2.781 (7)	161 (3)
O10—H10A···O4	0.86 (3)	1.99 (3)	2.846 (4)	178 (4)
O10—H10B···O6^vii	0.85 (4)	1.95 (2)	2.762 (5)	158 (4)
O10—H10B···O6′^vii	0.85 (4)	2.07 (2)	2.853 (10)	154 (4)
O13—H13A···O9^viii	0.85 (1)	2.45 (7)	2.964 (12)	120 (7)

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