Crystal structure of bis­(2,2′-bi­pyridine-κ²N,N′)bis­(thio­cyanato-κN)mang­anese(II) 2,2′-bi­pyridine monosolvate

In the crystal structure of the mononuclear title compound, [Mn(NCS)₂(C₁₀H₈N₂)₂]·C₁₀H₈N₂, the Mn^II cation is coordin­ated in an all-cis configuration by two N-bound thio­cyanate anions and two 2,2′-bi­pyridine ligands within a slightly distorted octa­hedral environment. The asymmetric unit consists of one Mn^II cation, two thio­cyanate anions and two 2,2′-bi­pyridine ligands, as well as two non-coordinating 2,2′-bi­pyridine ligands that are each located on centres of inversion. In the crystal structure, the discrete [Mn(NCS)₂(C₁₀H₈N₂)₂] complex mol­ecules are arranged in such a way that cavities are formed, in which the solvent 2,2′-bi­pyridine mol­ecules are located. Apart from van der Waals forces, there are no remarkable inter­molecular inter­actions present in the crystal structure.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.041
• wR factor = 0.094
• Data-to-parameter ratio = 17.0

checkCIF/PLATON results

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Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    C16    --  C17     ..        7.5 su

Alert level C
PLAT031_ALERT_4_C Refined Extinction Parameter within Range ......      2.778 Sigma
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C11    --  C12     ..        5.5 su
PLAT241_ALERT_2_C High      Ueq as Compared to Neighbors for .....         N1 Check
PLAT242_ALERT_2_C Low       Ueq as Compared to Neighbors for .....         C1 Check
PLAT242_ALERT_2_C Low       Ueq as Compared to Neighbors for .....         C2 Check
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      6.619 Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         32 Report
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....         25 Note

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT230_ALERT_2_G Hirshfeld Test Diff for    S1     --  C1      ..        6.7 su
PLAT230_ALERT_2_G Hirshfeld Test Diff for    S2     --  C2      ..        6.6 su
PLAT899_ALERT_4_G SHELXL97   is Deprecated and Succeeded by SHELXL       2014 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
   8 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   6 ALERT level G = General information/check it is not something unexpected

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

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S1. Synthesis and crystallization

MnSO₄·H₂O was purchased from Merck and 2,2'-bi­pyridine and Ba(NCS)₂·3H₂O were purchased from Alfa Aesar. Mn(NCS)₂ was synthesized by stirring 17.97 g (58.44 mmol) Ba(NCS)₂·3H₂O and 9.88 g (58.44 mmol) MnSO₄·H₂O in 300 ml water at room temperature for three hours. The white residue of BaSO₄ was filtered off and the solvent removed with a rotary evaporator. The homogeneity of the product was investigated by X-ray powder diffraction and elemental analysis. The title compound was prepared by the reaction of 25.7 mg (0.15 mmol) Mn(NCS)₂ and 93.7 mg (0.60 mmol) 2,2'-bi­pyridine in 1.0 ml water at room temperature. After few days, yellow plates of the title compound were obtained.

S2. Refinement

The hydrogen atoms were positioned with idealized geometry and were refined with C—H = 0.93 Å and U_eq(H) = 1.2 U_eq(C) using a riding model approximation.

Related literature

For similar crystal structures with thiocyanate anions in cis-coordination to a manganese(II) cation, see: Ma\/ecki et al. (2011).

Structure description

For similar crystal structures with thiocyanate anions in cis-coordination to a manganese(II) cation, see: Ma\/ecki et al. (2011).

Synthesis and crystallization

MnSO₄·H₂O was purchased from Merck and 2,2'-bi­pyridine and Ba(NCS)₂·3H₂O were purchased from Alfa Aesar. Mn(NCS)₂ was synthesized by stirring 17.97 g (58.44 mmol) Ba(NCS)₂·3H₂O and 9.88 g (58.44 mmol) MnSO₄·H₂O in 300 ml water at room temperature for three hours. The white residue of BaSO₄ was filtered off and the solvent removed with a rotary evaporator. The homogeneity of the product was investigated by X-ray powder diffraction and elemental analysis. The title compound was prepared by the reaction of 25.7 mg (0.15 mmol) Mn(NCS)₂ and 93.7 mg (0.60 mmol) 2,2'-bi­pyridine in 1.0 ml water at room temperature. After few days, yellow plates of the title compound were obtained.

Refinement details

The hydrogen atoms were positioned with idealized geometry and were refined with C—H = 0.93 Å and U_eq(H) = 1.2 U_eq(C) using a riding model approximation.

Computing details

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA (Stoe & Cie, 2008); data reduction: X-AREA (Stoe & Cie, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. The molecular components of the title compound with labelling and displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: (i) -x+1,-y+1,-z+1; (ii) -x+2,-y+1,-z+1.]
	Fig. 2. The packing of the molecules in the crystal structure of the title compound in a view along [010].

Bis(2,2'-bipyridine-κ²N,N')bis(thiocyanato-κN)manganese(II) 2,2'-bipyridine monosolvate

Crystal data

[Mn(NCS)2(C10H8N2)2]·C10H8N2	Z = 4
Mr = 639.65	F(000) = 1316
Monoclinic, P21/c	Dx = 1.395 Mg m^−3
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 14.5263 (6) Å	θ = 1.5–27.0°
b = 13.5383 (4) Å	µ = 0.61 mm^−1
c = 16.0726 (7) Å	T = 293 K
β = 105.535 (3)°	Plate, yellow
V = 3045.4 (2) Å^3	0.32 × 0.19 × 0.07 mm

Data collection

Stoe IPDS-2 diffractometer	6630 independent reflections
Radiation source: fine-focus sealed tube	5766 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
ω scans	θmax = 27.0°, θmin = 1.5°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	h = −18→18
Tmin = 0.820, Tmax = 0.919	k = −17→17
41565 measured reflections	l = −20→20

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.094	w = 1/[σ^2(Fo^2) + (0.0384P)^2 + 0.9654P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
6630 reflections	Δρmax = 0.27 e Å^−3
389 parameters	Δρmin = −0.35 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0025 (9)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Mn1	0.734793 (17)	0.128336 (19)	0.478914 (17)	0.04106 (9)
N1	0.70830 (14)	0.02009 (14)	0.37737 (12)	0.0665 (5)
C1	0.71894 (13)	−0.04547 (14)	0.33491 (12)	0.0502 (4)
S1	0.73507 (5)	−0.13676 (5)	0.27623 (4)	0.0792 (2)
N2	0.75999 (12)	0.02533 (13)	0.58481 (11)	0.0583 (4)
C2	0.77308 (12)	−0.03438 (13)	0.63794 (12)	0.0453 (4)
S2	0.79008 (5)	−0.11880 (5)	0.71196 (4)	0.07089 (17)
N10	0.88949 (10)	0.14680 (12)	0.47586 (10)	0.0513 (4)
C10	0.92943 (15)	0.09366 (18)	0.42424 (15)	0.0652 (6)
H10	0.8898	0.0546	0.3818	0.078*
C11	1.02539 (17)	0.0938 (2)	0.43073 (19)	0.0824 (8)
H11	1.0502	0.0572	0.3928	0.099*
C12	1.08341 (17)	0.1492 (2)	0.4943 (2)	0.0908 (9)
H12	1.1490	0.1497	0.5010	0.109*
C13	1.04482 (15)	0.2043 (2)	0.54863 (18)	0.0792 (7)
H13	1.0840	0.2420	0.5924	0.095*
C14	0.94611 (13)	0.20298 (15)	0.53718 (13)	0.0541 (5)
C15	0.89768 (13)	0.26359 (14)	0.58963 (12)	0.0517 (4)
C16	0.94487 (18)	0.33141 (19)	0.65064 (15)	0.0728 (6)
H16	1.0108	0.3385	0.6629	0.087*
C17	0.8933 (2)	0.3882 (2)	0.69288 (16)	0.0852 (8)
H17	0.9244	0.4343	0.7337	0.102*
C18	0.7964 (2)	0.37728 (17)	0.67522 (16)	0.0771 (7)
H18	0.7605	0.4157	0.7030	0.092*
C19	0.75380 (16)	0.30723 (16)	0.61475 (13)	0.0607 (5)
H19	0.6880	0.2987	0.6025	0.073*
N11	0.80238 (10)	0.25125 (11)	0.57302 (10)	0.0488 (3)
N20	0.67171 (10)	0.24892 (11)	0.38090 (9)	0.0470 (3)
C20	0.72036 (15)	0.29317 (17)	0.33176 (14)	0.0624 (5)
H20	0.7831	0.2736	0.3374	0.075*
C21	0.68249 (19)	0.36615 (18)	0.27327 (15)	0.0726 (6)
H21	0.7188	0.3955	0.2404	0.087*
C22	0.59047 (19)	0.39454 (17)	0.26467 (14)	0.0713 (6)
H22	0.5632	0.4443	0.2260	0.086*
C24	0.58074 (12)	0.27636 (13)	0.37188 (11)	0.0446 (4)
C25	0.53069 (12)	0.22504 (13)	0.42834 (11)	0.0438 (4)
C26	0.43568 (13)	0.24294 (17)	0.42531 (14)	0.0613 (5)
H26	0.4000	0.2878	0.3858	0.074*
C27	0.39498 (14)	0.19383 (19)	0.48122 (15)	0.0689 (6)
H27	0.3314	0.2050	0.4797	0.083*
C28	0.44834 (15)	0.12849 (17)	0.53914 (15)	0.0652 (6)
H28	0.4223	0.0955	0.5782	0.078*
C29	0.54214 (14)	0.11259 (15)	0.53824 (13)	0.0538 (4)
H29	0.5782	0.0671	0.5768	0.065*
N21	0.58328 (10)	0.15956 (11)	0.48459 (9)	0.0427 (3)
N30	0.45727 (13)	0.57292 (15)	0.40356 (13)	0.0690 (5)
C30	0.52000 (14)	0.52678 (15)	0.46832 (13)	0.0557 (5)
C31	0.61789 (15)	0.52953 (17)	0.47611 (15)	0.0654 (5)
H31	0.6605	0.4974	0.5216	0.078*
C23	0.53780 (16)	0.34899 (15)	0.31364 (13)	0.0597 (5)
H23	0.4745	0.3668	0.3076	0.072*
C32	0.65066 (18)	0.5801 (2)	0.41603 (18)	0.0766 (6)
H32	0.7158	0.5826	0.4203	0.092*
C33	0.5866 (2)	0.6271 (2)	0.34934 (19)	0.0813 (7)
H33	0.6069	0.6617	0.3075	0.098*
C34	0.4917 (2)	0.6212 (2)	0.34664 (18)	0.0822 (7)
H34	0.4483	0.6533	0.3017	0.099*
N40	0.89931 (14)	0.56056 (16)	0.52370 (14)	0.0753 (5)
C40	0.99023 (15)	0.53074 (16)	0.53470 (14)	0.0617 (5)
C41	1.06105 (17)	0.55483 (19)	0.60838 (17)	0.0756 (6)
H41	1.1234	0.5332	0.6150	0.091*
C42	1.0391 (2)	0.6106 (2)	0.67145 (19)	0.0877 (8)
H42	1.0863	0.6269	0.7212	0.105*
C43	0.9471 (2)	0.6423 (2)	0.6607 (2)	0.0887 (8)
H43	0.9301	0.6808	0.7022	0.106*
C44	0.8805 (2)	0.6148 (2)	0.5856 (2)	0.0891 (8)
H44	0.8179	0.6360	0.5779	0.107*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.03601 (14)	0.04340 (15)	0.04746 (15)	0.00108 (10)	0.01753 (10)	0.00063 (11)
N1	0.0761 (12)	0.0621 (10)	0.0701 (11)	−0.0069 (9)	0.0350 (9)	−0.0150 (9)
C1	0.0426 (9)	0.0562 (11)	0.0537 (10)	−0.0084 (8)	0.0160 (8)	−0.0048 (9)
S1	0.0676 (4)	0.0790 (4)	0.0828 (4)	0.0061 (3)	0.0057 (3)	−0.0377 (3)
N2	0.0596 (10)	0.0556 (9)	0.0651 (10)	0.0078 (8)	0.0263 (8)	0.0123 (8)
C2	0.0384 (9)	0.0475 (9)	0.0520 (10)	0.0034 (7)	0.0156 (7)	−0.0024 (8)
S2	0.0751 (4)	0.0693 (4)	0.0641 (3)	0.0054 (3)	0.0114 (3)	0.0214 (3)
N10	0.0365 (7)	0.0616 (9)	0.0595 (9)	0.0044 (7)	0.0193 (7)	0.0112 (7)
C10	0.0494 (11)	0.0803 (14)	0.0749 (14)	0.0122 (10)	0.0322 (10)	0.0105 (11)
C11	0.0504 (13)	0.110 (2)	0.0989 (19)	0.0219 (13)	0.0401 (13)	0.0237 (16)
C12	0.0393 (12)	0.122 (2)	0.118 (2)	0.0176 (13)	0.0336 (14)	0.0357 (19)
C13	0.0369 (10)	0.1010 (19)	0.0934 (17)	−0.0024 (11)	0.0064 (11)	0.0213 (15)
C14	0.0358 (9)	0.0635 (11)	0.0622 (11)	0.0022 (8)	0.0118 (8)	0.0231 (9)
C15	0.0438 (10)	0.0546 (10)	0.0511 (10)	−0.0077 (8)	0.0028 (8)	0.0144 (8)
C16	0.0667 (14)	0.0834 (16)	0.0601 (13)	−0.0265 (12)	0.0026 (11)	0.0038 (12)
C17	0.107 (2)	0.0806 (17)	0.0594 (13)	−0.0404 (15)	0.0067 (13)	−0.0107 (12)
C18	0.105 (2)	0.0623 (13)	0.0658 (14)	−0.0101 (13)	0.0267 (13)	−0.0163 (11)
C19	0.0612 (12)	0.0589 (12)	0.0613 (12)	0.0014 (9)	0.0152 (10)	−0.0102 (9)
N11	0.0435 (8)	0.0482 (8)	0.0525 (8)	−0.0004 (6)	0.0092 (6)	−0.0006 (7)
N20	0.0417 (8)	0.0520 (8)	0.0484 (8)	−0.0029 (6)	0.0138 (6)	0.0047 (6)
C20	0.0565 (12)	0.0711 (13)	0.0632 (12)	−0.0047 (10)	0.0224 (10)	0.0149 (10)
C21	0.0851 (17)	0.0725 (14)	0.0640 (13)	−0.0082 (12)	0.0263 (12)	0.0184 (11)
C22	0.0941 (18)	0.0619 (13)	0.0537 (12)	0.0076 (12)	0.0124 (11)	0.0127 (10)
C24	0.0443 (9)	0.0451 (9)	0.0416 (8)	−0.0004 (7)	0.0067 (7)	−0.0065 (7)
C25	0.0356 (8)	0.0490 (9)	0.0449 (9)	−0.0015 (7)	0.0074 (7)	−0.0106 (7)
C26	0.0382 (10)	0.0787 (14)	0.0643 (12)	0.0056 (9)	0.0092 (9)	−0.0058 (10)
C27	0.0356 (10)	0.0932 (17)	0.0808 (15)	−0.0046 (10)	0.0204 (10)	−0.0164 (13)
C28	0.0515 (11)	0.0793 (14)	0.0750 (14)	−0.0152 (11)	0.0347 (10)	−0.0095 (11)
C29	0.0471 (10)	0.0600 (11)	0.0604 (11)	−0.0049 (8)	0.0252 (9)	0.0006 (9)
N21	0.0356 (7)	0.0481 (8)	0.0470 (7)	−0.0026 (6)	0.0156 (6)	−0.0036 (6)
N30	0.0588 (11)	0.0760 (12)	0.0703 (11)	0.0131 (9)	0.0142 (9)	0.0083 (10)
C30	0.0503 (10)	0.0544 (11)	0.0604 (11)	0.0062 (8)	0.0114 (9)	−0.0080 (9)
C31	0.0506 (11)	0.0706 (13)	0.0729 (13)	0.0050 (10)	0.0130 (10)	−0.0043 (11)
C23	0.0614 (12)	0.0612 (12)	0.0510 (10)	0.0114 (9)	0.0057 (9)	0.0024 (9)
C32	0.0615 (14)	0.0809 (16)	0.0920 (17)	−0.0015 (12)	0.0284 (13)	−0.0054 (14)
C33	0.0883 (18)	0.0790 (16)	0.0859 (17)	0.0012 (14)	0.0393 (15)	0.0057 (13)
C34	0.0789 (17)	0.0874 (18)	0.0802 (16)	0.0168 (14)	0.0213 (13)	0.0194 (14)
N40	0.0546 (11)	0.0821 (13)	0.0871 (14)	0.0114 (9)	0.0154 (10)	0.0058 (11)
C40	0.0504 (11)	0.0597 (12)	0.0739 (13)	−0.0028 (9)	0.0149 (10)	0.0118 (10)
C41	0.0511 (12)	0.0830 (16)	0.0892 (17)	−0.0076 (11)	0.0129 (11)	−0.0039 (13)
C42	0.0705 (16)	0.101 (2)	0.0909 (19)	−0.0179 (14)	0.0202 (14)	−0.0150 (16)
C43	0.0837 (18)	0.0873 (18)	0.102 (2)	−0.0051 (14)	0.0361 (16)	−0.0132 (15)
C44	0.0668 (16)	0.095 (2)	0.106 (2)	0.0150 (14)	0.0247 (15)	−0.0003 (17)

Geometric parameters (Å, º)

Mn1—N1	2.1501 (18)	C22—C23	1.381 (3)
Mn1—N2	2.1546 (17)	C22—H22	0.9300
Mn1—N21	2.2669 (13)	C24—C23	1.386 (3)
Mn1—N10	2.2746 (14)	C24—C25	1.479 (2)
Mn1—N20	2.2833 (15)	C25—N21	1.348 (2)
Mn1—N11	2.2859 (15)	C25—C26	1.389 (2)
N1—C1	1.155 (2)	C26—C27	1.372 (3)
C1—S1	1.609 (2)	C26—H26	0.9300
N2—C2	1.154 (2)	C27—C28	1.365 (3)
C2—S2	1.6203 (19)	C27—H27	0.9300
N10—C14	1.339 (3)	C28—C29	1.383 (3)
N10—C10	1.342 (3)	C28—H28	0.9300
C10—C11	1.370 (3)	C29—N21	1.335 (2)
C10—H10	0.9300	C29—H29	0.9300
C11—C12	1.362 (4)	N30—C34	1.326 (3)
C11—H11	0.9300	N30—C30	1.340 (3)
C12—C13	1.377 (4)	C30—C31	1.394 (3)
C12—H12	0.9300	C30—C30^i	1.489 (4)
C13—C14	1.396 (3)	C31—C32	1.369 (3)
C13—H13	0.9300	C31—H31	0.9300
C14—C15	1.482 (3)	C23—H23	0.9300
C15—N11	1.348 (2)	C32—C33	1.373 (4)
C15—C16	1.384 (3)	C32—H32	0.9300
C16—C17	1.373 (4)	C33—C34	1.370 (4)
C16—H16	0.9300	C33—H33	0.9300
C17—C18	1.367 (4)	C34—H34	0.9300
C17—H17	0.9300	N40—C44	1.322 (3)
C18—C19	1.380 (3)	N40—C40	1.347 (3)
C18—H18	0.9300	C40—C41	1.384 (3)
C19—N11	1.333 (2)	C40—C40^ii	1.479 (5)
C19—H19	0.9300	C41—C42	1.368 (4)
N20—C20	1.335 (2)	C41—H41	0.9300
N20—C24	1.343 (2)	C42—C43	1.371 (4)
C20—C21	1.373 (3)	C42—H42	0.9300
C20—H20	0.9300	C43—C44	1.380 (4)
C21—C22	1.362 (4)	C43—H43	0.9300
C21—H21	0.9300	C44—H44	0.9300
N1—Mn1—N2	96.69 (7)	C22—C21—H21	120.8
N1—Mn1—N21	100.33 (6)	C20—C21—H21	120.8
N2—Mn1—N21	92.88 (6)	C21—C22—C23	119.6 (2)
N1—Mn1—N10	92.04 (7)	C21—C22—H22	120.2
N2—Mn1—N10	97.38 (6)	C23—C22—H22	120.2
N21—Mn1—N10	162.91 (6)	N20—C24—C23	121.42 (18)
N1—Mn1—N20	90.37 (7)	N20—C24—C25	115.79 (15)
N2—Mn1—N20	163.68 (6)	C23—C24—C25	122.79 (17)
N21—Mn1—N20	71.33 (5)	N21—C25—C26	121.16 (18)
N10—Mn1—N20	97.05 (5)	N21—C25—C24	115.91 (14)
N1—Mn1—N11	163.00 (6)	C26—C25—C24	122.92 (17)
N2—Mn1—N11	89.80 (6)	C27—C26—C25	119.4 (2)
N21—Mn1—N11	95.00 (5)	C27—C26—H26	120.3
N10—Mn1—N11	71.49 (6)	C25—C26—H26	120.3
N20—Mn1—N11	87.59 (5)	C28—C27—C26	119.67 (19)
C1—N1—Mn1	161.31 (18)	C28—C27—H27	120.2
N1—C1—S1	179.3 (2)	C26—C27—H27	120.2
C2—N2—Mn1	175.86 (16)	C27—C28—C29	118.3 (2)
N2—C2—S2	179.25 (19)	C27—C28—H28	120.8
C14—N10—C10	118.54 (17)	C29—C28—H28	120.8
C14—N10—Mn1	117.53 (12)	N21—C29—C28	123.0 (2)
C10—N10—Mn1	123.21 (14)	N21—C29—H29	118.5
N10—C10—C11	123.5 (2)	C28—C29—H29	118.5
N10—C10—H10	118.3	C29—N21—C25	118.38 (15)
C11—C10—H10	118.3	C29—N21—Mn1	123.00 (12)
C12—C11—C10	118.1 (3)	C25—N21—Mn1	118.53 (11)
C12—C11—H11	121.0	C34—N30—C30	117.5 (2)
C10—C11—H11	121.0	N30—C30—C31	121.5 (2)
C11—C12—C13	119.9 (2)	N30—C30—C30^i	116.7 (2)
C11—C12—H12	120.0	C31—C30—C30^i	121.8 (2)
C13—C12—H12	120.0	C32—C31—C30	119.3 (2)
C12—C13—C14	119.2 (3)	C32—C31—H31	120.4
C12—C13—H13	120.4	C30—C31—H31	120.4
C14—C13—H13	120.4	C22—C23—C24	119.0 (2)
N10—C14—C13	120.7 (2)	C22—C23—H23	120.5
N10—C14—C15	116.21 (15)	C24—C23—H23	120.5
C13—C14—C15	123.0 (2)	C31—C32—C33	119.4 (2)
N11—C15—C16	120.7 (2)	C31—C32—H32	120.3
N11—C15—C14	115.93 (16)	C33—C32—H32	120.3
C16—C15—C14	123.36 (19)	C34—C33—C32	117.6 (2)
C17—C16—C15	119.3 (2)	C34—C33—H33	121.2
C17—C16—H16	120.3	C32—C33—H33	121.2
C15—C16—H16	120.3	N30—C34—C33	124.7 (2)
C18—C17—C16	120.3 (2)	N30—C34—H34	117.7
C18—C17—H17	119.9	C33—C34—H34	117.7
C16—C17—H17	119.9	C44—N40—C40	117.4 (2)
C17—C18—C19	117.6 (2)	N40—C40—C41	121.3 (2)
C17—C18—H18	121.2	N40—C40—C40^ii	116.7 (2)
C19—C18—H18	121.2	C41—C40—C40^ii	122.0 (3)
N11—C19—C18	123.2 (2)	C42—C41—C40	119.8 (2)
N11—C19—H19	118.4	C42—C41—H41	120.1
C18—C19—H19	118.4	C40—C41—H41	120.1
C19—N11—C15	118.94 (17)	C41—C42—C43	119.5 (3)
C19—N11—Mn1	123.75 (13)	C41—C42—H42	120.3
C15—N11—Mn1	117.23 (13)	C43—C42—H42	120.3
C20—N20—C24	118.28 (17)	C42—C43—C44	117.2 (3)
C20—N20—Mn1	123.43 (13)	C42—C43—H43	121.4
C24—N20—Mn1	118.28 (11)	C44—C43—H43	121.4
N20—C20—C21	123.3 (2)	N40—C44—C43	124.8 (3)
N20—C20—H20	118.3	N40—C44—H44	117.6
C21—C20—H20	118.3	C43—C44—H44	117.6
C22—C21—C20	118.4 (2)

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