A trinuclear Cu₂Mn complex, [Mn(CuL)₂(DMF)₂](SCN)₂, where H₂L is 3,10,18,21-tetra­azatetra­cyclo­[20.4.0.0^4,9.0^12,17]hexa­cosa-2,10,12,14,16,22,24,26-octa­ene-19,20-dionate(2−) and DMF is dimethylformamide

A new trinuclear Cu₂Mn complex, bis­(dimethylformamide)bis­[μ-3,10,18,21-tetra­azatetra­cyclo[20.4.0.0^4,9.0^12,17]hexa­cosa-2,10,12,14,16,22,24,26-octa­ene-19,20-dionato(2−)]bis­(thio­cyanato)dicopper(II)manganese(II),[Cu₂Mn(C₂₂H₂₀N₄O₂)₂(NCS)₂(C₃H₇NO)₂], has been synthesized and structurally characterized. The Cu^II atom is five-coordinated by four N atoms from the tetraza macrocycle and one dimethyl­formamide N atom. The central Mn^II atom is coordinated by four O atoms of the oxamide group and two N atoms. The Mn^II atom lies on a centre of symmetry. The Cu^II atoms reside in the cavities of the macrocyclic ligands.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.045
• wR factor = 0.110
• Data-to-parameter ratio = 13.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT048_ALERT_1_C MoietyFormula Not Given ........................          ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.64 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         N6
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C23
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          7
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C1     -   C2     ...       1.54 Ang.
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          1
            O1  -MN1 -O1  -C1      1.00  0.00   2.686   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          8
            O2  -MN1 -O2  -C2   -108.00 17.00   2.686   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         47
            N6  -MN1 -N6  -C23     5.00  6.00   2.686   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #        121
            MN1 -N6  -C23 -S1     11.00  0.00   1.555   1.555   1.555   1.555
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C52 H54 Cu2 Mn N12 O6 S2

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

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 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
   6 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.

bis(dimethylformamide)bis[µ-3,10,18,21- tetraazatetracyclo[20.4.0.0^4,9.0^12,17]hexacosa-2,10,12,14,16,22,24,26- octaene-19,20-dionato(2-)]bis(thiocyanato)dicopper(II)manganese(II)

Crystal data

[Cu2Mn(C22H20N4O2)2(NCS)2(C3H7NO)2]	Z = 1
Mr = 1189.21	F(000) = 613
Triclinic, P1	Dx = 1.517 Mg m^−3
a = 9.9510 (19) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.188 (2) Å	Cell parameters from 1948 reflections
c = 13.907 (3) Å	θ = 2.7–24.4°
α = 69.960 (3)°	µ = 1.19 mm^−1
β = 83.727 (4)°	T = 293 K
γ = 63.665 (3)°	Block, red
V = 1301.9 (4) Å^3	0.24 × 0.16 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer	4570 independent reflections
Radiation source: fine-focus sealed tube	3128 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
φ and ω scans	θmax = 25.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→8
Tmin = 0.780, Tmax = 0.867	k = −13→11
6623 measured reflections	l = −15→16

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.110	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0548P)^2 + 0.188P] where P = (Fo^2 + 2Fc^2)/3
4570 reflections	(Δ/σ)max = 0.005
342 parameters	Δρmax = 0.44 e Å^−3
0 restraints	Δρmin = −0.33 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
Mn1	0.5000	1.5000	0.5000	0.0406 (3)
Cu1	0.58773 (5)	0.95391 (5)	0.69167 (4)	0.03305 (16)
S1	0.71508 (17)	1.56602 (15)	0.18012 (14)	0.0884 (5)
O1	0.6538 (3)	1.3006 (3)	0.6063 (2)	0.0481 (8)
O2	0.3950 (3)	1.3582 (3)	0.5222 (2)	0.0420 (7)
N1	0.6927 (3)	1.0676 (3)	0.6870 (2)	0.0318 (7)
N2	0.4215 (3)	1.1330 (3)	0.6203 (2)	0.0316 (8)
N3	0.4991 (3)	0.8419 (3)	0.6670 (3)	0.0358 (8)
N4	0.7713 (4)	0.7759 (3)	0.7237 (3)	0.0391 (8)
N5	0.3224 (4)	1.0146 (3)	0.9628 (3)	0.0426 (9)
N6	0.6303 (5)	1.4399 (5)	0.3699 (4)	0.0689 (12)
C1	0.6162 (4)	1.2017 (4)	0.6309 (3)	0.0329 (9)
C2	0.4623 (4)	1.2379 (4)	0.5859 (3)	0.0308 (9)
C3	0.2804 (4)	1.1525 (4)	0.5886 (3)	0.0315 (9)
C4	0.1533 (4)	1.2813 (4)	0.5696 (3)	0.0422 (11)
H4	0.1594	1.3558	0.5812	0.051*
C5	0.0189 (4)	1.3009 (4)	0.5340 (3)	0.0478 (12)
H5	−0.0642	1.3879	0.5225	0.057*
C6	0.0059 (5)	1.1924 (4)	0.5149 (4)	0.0501 (12)
H6	−0.0826	1.2074	0.4862	0.060*
C7	0.1275 (4)	1.0625 (4)	0.5398 (3)	0.0463 (11)
H7	0.1183	0.9884	0.5298	0.056*
C8	0.2650 (4)	1.0366 (4)	0.5795 (3)	0.0341 (9)
C9	0.3758 (4)	0.8887 (4)	0.6167 (3)	0.0399 (10)
H9	0.3548	0.8232	0.6024	0.048*
C10	0.5921 (4)	0.6886 (4)	0.7108 (3)	0.0411 (11)
H10	0.5689	0.6405	0.6724	0.049*
C11	0.5558 (5)	0.6375 (4)	0.8215 (4)	0.0555 (13)
H11A	0.4531	0.6488	0.8246	0.067*
H11B	0.5638	0.6949	0.8574	0.067*
C12	0.6622 (6)	0.4819 (5)	0.8748 (4)	0.0771 (17)
H12A	0.6395	0.4533	0.9464	0.093*
H12B	0.6484	0.4232	0.8429	0.093*
C13	0.8237 (6)	0.4622 (5)	0.8666 (5)	0.0807 (18)
H13A	0.8388	0.5161	0.9026	0.097*
H13B	0.8908	0.3633	0.8989	0.097*
C14	0.8606 (5)	0.5098 (5)	0.7567 (5)	0.0689 (16)
H14A	0.8557	0.4487	0.7232	0.083*
H14B	0.9629	0.4996	0.7542	0.083*
C15	0.7553 (4)	0.6635 (4)	0.6973 (3)	0.0440 (11)
H15	0.7740	0.6786	0.6244	0.053*
C16	0.8991 (4)	0.7624 (4)	0.7474 (3)	0.0420 (11)
H16	0.9799	0.6745	0.7565	0.050*
C17	0.9316 (4)	0.8703 (4)	0.7617 (3)	0.0371 (10)
C18	1.0754 (4)	0.8196 (5)	0.8067 (3)	0.0495 (12)
H18	1.1400	0.7239	0.8240	0.059*
C19	1.1218 (5)	0.9076 (5)	0.8255 (4)	0.0541 (12)
H19	1.2171	0.8721	0.8551	0.065*
C20	1.0264 (5)	1.0498 (5)	0.8004 (3)	0.0512 (12)
H20	1.0569	1.1101	0.8141	0.061*
C21	0.8855 (4)	1.1031 (4)	0.7550 (3)	0.0406 (10)
H21	0.8225	1.1992	0.7383	0.049*
C22	0.8361 (4)	1.0157 (4)	0.7339 (3)	0.0330 (9)
C23	0.6668 (5)	1.4930 (5)	0.2908 (5)	0.0553 (13)
O3	0.5002 (3)	0.9352 (3)	0.8545 (2)	0.0507 (8)
C24	0.3948 (5)	1.0314 (4)	0.8777 (3)	0.0414 (10)
H24	0.3642	1.1226	0.8315	0.050*
C25	0.2042 (5)	1.1331 (5)	0.9874 (4)	0.0643 (14)
H25A	0.2370	1.1434	1.0452	0.097*
H25B	0.1163	1.1166	1.0037	0.097*
H25C	0.1809	1.2178	0.9296	0.097*
C26	0.3634 (5)	0.8749 (5)	1.0386 (3)	0.0578 (13)
H26A	0.4465	0.8062	1.0159	0.087*
H26B	0.2793	0.8525	1.0472	0.087*
H26C	0.3914	0.8741	1.1029	0.087*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0380 (5)	0.0242 (5)	0.0558 (6)	−0.0184 (4)	−0.0095 (4)	0.0013 (4)
Cu1	0.0286 (3)	0.0217 (3)	0.0432 (3)	−0.0109 (2)	−0.0040 (2)	−0.0026 (2)
S1	0.0658 (9)	0.0495 (8)	0.1064 (13)	−0.0139 (7)	0.0121 (9)	0.0073 (8)
O1	0.0371 (16)	0.0291 (15)	0.071 (2)	−0.0194 (13)	−0.0179 (15)	0.0044 (14)
O2	0.0370 (15)	0.0261 (15)	0.0541 (19)	−0.0167 (12)	−0.0153 (14)	0.0063 (13)
N1	0.0273 (17)	0.0248 (17)	0.037 (2)	−0.0109 (14)	−0.0039 (14)	−0.0020 (14)
N2	0.0268 (17)	0.0213 (16)	0.044 (2)	−0.0129 (14)	−0.0020 (14)	−0.0031 (14)
N3	0.0344 (18)	0.0222 (17)	0.047 (2)	−0.0107 (14)	−0.0041 (16)	−0.0081 (15)
N4	0.0337 (19)	0.0292 (18)	0.047 (2)	−0.0117 (15)	0.0016 (16)	−0.0068 (16)
N5	0.040 (2)	0.042 (2)	0.039 (2)	−0.0144 (17)	−0.0001 (17)	−0.0092 (17)
N6	0.067 (3)	0.064 (3)	0.089 (4)	−0.037 (2)	0.010 (3)	−0.032 (3)
C1	0.033 (2)	0.030 (2)	0.034 (2)	−0.0177 (18)	−0.0013 (18)	−0.0026 (18)
C2	0.029 (2)	0.022 (2)	0.038 (2)	−0.0117 (16)	−0.0024 (17)	−0.0043 (18)
C3	0.027 (2)	0.027 (2)	0.037 (2)	−0.0143 (17)	−0.0015 (17)	−0.0011 (17)
C4	0.035 (2)	0.027 (2)	0.060 (3)	−0.0161 (18)	−0.001 (2)	−0.004 (2)
C5	0.030 (2)	0.033 (2)	0.069 (3)	−0.0124 (19)	−0.003 (2)	−0.005 (2)
C6	0.031 (2)	0.048 (3)	0.063 (3)	−0.016 (2)	−0.011 (2)	−0.007 (2)
C7	0.042 (3)	0.044 (3)	0.061 (3)	−0.026 (2)	−0.005 (2)	−0.014 (2)
C8	0.033 (2)	0.029 (2)	0.039 (2)	−0.0149 (18)	−0.0025 (18)	−0.0060 (18)
C9	0.040 (2)	0.033 (2)	0.051 (3)	−0.0197 (19)	0.000 (2)	−0.014 (2)
C10	0.041 (2)	0.025 (2)	0.057 (3)	−0.0132 (18)	−0.004 (2)	−0.012 (2)
C11	0.047 (3)	0.032 (2)	0.075 (4)	−0.014 (2)	0.004 (2)	−0.008 (2)
C12	0.065 (3)	0.038 (3)	0.098 (5)	−0.018 (3)	−0.006 (3)	0.009 (3)
C13	0.059 (3)	0.042 (3)	0.099 (5)	−0.005 (3)	−0.020 (3)	0.011 (3)
C14	0.040 (3)	0.033 (3)	0.125 (5)	−0.006 (2)	0.000 (3)	−0.028 (3)
C15	0.043 (2)	0.035 (2)	0.054 (3)	−0.014 (2)	0.008 (2)	−0.020 (2)
C16	0.029 (2)	0.029 (2)	0.053 (3)	−0.0039 (18)	−0.001 (2)	−0.006 (2)
C17	0.030 (2)	0.036 (2)	0.038 (3)	−0.0112 (18)	−0.0030 (18)	−0.0064 (19)
C18	0.032 (2)	0.046 (3)	0.059 (3)	−0.008 (2)	−0.006 (2)	−0.014 (2)
C19	0.034 (2)	0.065 (3)	0.060 (3)	−0.016 (2)	−0.012 (2)	−0.020 (3)
C20	0.049 (3)	0.054 (3)	0.055 (3)	−0.026 (2)	−0.011 (2)	−0.014 (2)
C21	0.040 (2)	0.039 (2)	0.040 (3)	−0.017 (2)	−0.003 (2)	−0.008 (2)
C22	0.031 (2)	0.036 (2)	0.028 (2)	−0.0157 (18)	0.0011 (17)	−0.0045 (18)
C23	0.036 (3)	0.041 (3)	0.086 (4)	−0.014 (2)	0.001 (3)	−0.021 (3)
O3	0.0589 (19)	0.0404 (18)	0.047 (2)	−0.0181 (16)	0.0105 (15)	−0.0147 (15)
C24	0.045 (3)	0.036 (2)	0.041 (3)	−0.019 (2)	0.000 (2)	−0.007 (2)
C25	0.048 (3)	0.059 (3)	0.068 (4)	−0.010 (2)	0.010 (3)	−0.020 (3)
C26	0.067 (3)	0.050 (3)	0.042 (3)	−0.024 (3)	0.003 (2)	−0.001 (2)

Geometric parameters (Å, º)

Mn1—O1	2.170 (3)	C9—H9	0.9300
Mn1—O1^i	2.170 (3)	C10—C11	1.512 (6)
Mn1—O2	2.184 (2)	C10—C15	1.522 (5)
Mn1—O2^i	2.184 (2)	C10—H10	0.9800
Mn1—N6^i	2.226 (5)	C11—C12	1.534 (6)
Mn1—N6	2.226 (5)	C11—H11A	0.9700
Cu1—N2	1.947 (3)	C11—H11B	0.9700
Cu1—N3	1.951 (3)	C12—C13	1.519 (7)
Cu1—N1	1.954 (3)	C12—H12A	0.9700
Cu1—N4	1.961 (3)	C12—H12B	0.9700
Cu1—O3	2.310 (3)	C13—C14	1.499 (7)
S1—C23	1.610 (6)	C13—H13A	0.9700
O1—C1	1.250 (4)	C13—H13B	0.9700
O2—C2	1.248 (4)	C14—C15	1.534 (6)
N1—C1	1.324 (4)	C14—H14A	0.9700
N1—C22	1.417 (4)	C14—H14B	0.9700
N2—C2	1.329 (4)	C15—H15	0.9800
N2—C3	1.418 (4)	C16—C17	1.458 (5)
N3—C9	1.279 (5)	C16—H16	0.9300
N3—C10	1.473 (4)	C17—C22	1.406 (5)
N4—C16	1.279 (5)	C17—C18	1.412 (5)
N4—C15	1.499 (5)	C18—C19	1.363 (6)
N5—C24	1.319 (5)	C18—H18	0.9300
N5—C25	1.448 (5)	C19—C20	1.381 (6)
N5—C26	1.456 (5)	C19—H19	0.9300
N6—C23	1.162 (6)	C20—C21	1.383 (5)
C1—C2	1.544 (5)	C20—H20	0.9300
C3—C4	1.393 (5)	C21—C22	1.393 (5)
C3—C8	1.419 (5)	C21—H21	0.9300
C4—C5	1.375 (5)	O3—C24	1.234 (5)
C4—H4	0.9300	C24—H24	0.9300
C5—C6	1.388 (6)	C25—H25A	0.9600
C5—H5	0.9300	C25—H25B	0.9600
C6—C7	1.372 (5)	C25—H25C	0.9600
C6—H6	0.9300	C26—H26A	0.9600
C7—C8	1.402 (5)	C26—H26B	0.9600
C7—H7	0.9300	C26—H26C	0.9600
C8—C9	1.463 (5)
O1—Mn1—O1^i	179.999 (1)	C11—C10—C15	113.4 (4)
O1—Mn1—O2	75.39 (9)	N3—C10—H10	109.0
O1^i—Mn1—O2	104.61 (9)	C11—C10—H10	109.0
O1—Mn1—O2^i	104.61 (9)	C15—C10—H10	109.0
O1^i—Mn1—O2^i	75.39 (9)	C10—C11—C12	111.5 (4)
O2—Mn1—O2^i	179.999 (1)	C10—C11—H11A	109.3
O1—Mn1—N6^i	90.22 (15)	C12—C11—H11A	109.3
O1^i—Mn1—N6^i	89.78 (15)	C10—C11—H11B	109.3
O2—Mn1—N6^i	86.65 (13)	C12—C11—H11B	109.3
O2^i—Mn1—N6^i	93.35 (13)	H11A—C11—H11B	108.0
O1—Mn1—N6	89.78 (15)	C13—C12—C11	109.7 (4)
O1^i—Mn1—N6	90.22 (15)	C13—C12—H12A	109.7
O2—Mn1—N6	93.36 (13)	C11—C12—H12A	109.7
O2^i—Mn1—N6	86.65 (13)	C13—C12—H12B	109.7
N6^i—Mn1—N6	180.00 (14)	C11—C12—H12B	109.7
N2—Cu1—N3	93.43 (12)	H12A—C12—H12B	108.2
N2—Cu1—N1	85.44 (12)	C14—C13—C12	110.9 (5)
N3—Cu1—N1	167.64 (14)	C14—C13—H13A	109.5
N2—Cu1—N4	163.73 (14)	C12—C13—H13A	109.5
N3—Cu1—N4	83.60 (13)	C14—C13—H13B	109.5
N1—Cu1—N4	94.04 (13)	C12—C13—H13B	109.5
N2—Cu1—O3	96.82 (12)	H13A—C13—H13B	108.0
N3—Cu1—O3	93.99 (12)	C13—C14—C15	113.5 (4)
N1—Cu1—O3	98.36 (12)	C13—C14—H14A	108.9
N4—Cu1—O3	99.34 (12)	C15—C14—H14A	108.9
C1—O1—Mn1	116.1 (2)	C13—C14—H14B	108.9
C2—O2—Mn1	115.1 (2)	C15—C14—H14B	108.9
C1—N1—C22	122.4 (3)	H14A—C14—H14B	107.7
C1—N1—Cu1	112.1 (2)	N4—C15—C10	107.1 (3)
C22—N1—Cu1	125.4 (2)	N4—C15—C14	116.7 (4)
C2—N2—C3	120.4 (3)	C10—C15—C14	110.5 (3)
C2—N2—Cu1	112.0 (2)	N4—C15—H15	107.4
C3—N2—Cu1	126.6 (2)	C10—C15—H15	107.4
C9—N3—C10	120.1 (3)	C14—C15—H15	107.4
C9—N3—Cu1	126.8 (3)	N4—C16—C17	126.9 (4)
C10—N3—Cu1	113.1 (2)	N4—C16—H16	116.6
C16—N4—C15	121.9 (3)	C17—C16—H16	116.6
C16—N4—Cu1	124.1 (3)	C22—C17—C18	118.7 (4)
C15—N4—Cu1	113.0 (2)	C22—C17—C16	126.6 (3)
C24—N5—C25	122.1 (4)	C18—C17—C16	114.7 (4)
C24—N5—C26	120.7 (4)	C19—C18—C17	121.6 (4)
C25—N5—C26	117.1 (4)	C19—C18—H18	119.2
C23—N6—Mn1	139.0 (4)	C17—C18—H18	119.2
O1—C1—N1	129.0 (3)	C18—C19—C20	119.5 (4)
O1—C1—C2	116.1 (3)	C18—C19—H19	120.2
N1—C1—C2	114.8 (3)	C20—C19—H19	120.2
O2—C2—N2	129.0 (3)	C19—C20—C21	120.3 (4)
O2—C2—C1	116.9 (3)	C19—C20—H20	119.9
N2—C2—C1	114.1 (3)	C21—C20—H20	119.9
C4—C3—N2	122.2 (3)	C20—C21—C22	121.3 (4)
C4—C3—C8	118.2 (3)	C20—C21—H21	119.4
N2—C3—C8	119.6 (3)	C22—C21—H21	119.4
C5—C4—C3	121.6 (4)	C21—C22—C17	118.5 (3)
C5—C4—H4	119.2	C21—C22—N1	122.4 (3)
C3—C4—H4	119.2	C17—C22—N1	119.0 (3)
C4—C5—C6	120.8 (4)	N6—C23—S1	178.9 (5)
C4—C5—H5	119.6	C24—O3—Cu1	124.6 (3)
C6—C5—H5	119.6	O3—C24—N5	125.0 (4)
C7—C6—C5	118.1 (4)	O3—C24—H24	117.5
C7—C6—H6	121.0	N5—C24—H24	117.5
C5—C6—H6	121.0	N5—C25—H25A	109.5
C6—C7—C8	122.9 (4)	N5—C25—H25B	109.5
C6—C7—H7	118.6	H25A—C25—H25B	109.5
C8—C7—H7	118.6	N5—C25—H25C	109.5
C7—C8—C3	117.9 (3)	H25A—C25—H25C	109.5
C7—C8—C9	116.2 (3)	H25B—C25—H25C	109.5
C3—C8—C9	125.6 (3)	N5—C26—H26A	109.5
N3—C9—C8	125.6 (4)	N5—C26—H26B	109.5
N3—C9—H9	117.2	H26A—C26—H26B	109.5
C8—C9—H9	117.2	N5—C26—H26C	109.5
N3—C10—C11	109.1 (3)	H26A—C26—H26C	109.5
N3—C10—C15	107.1 (3)	H26B—C26—H26C	109.5
O1^i—Mn1—O1—C1	8 (23)	Cu1—N2—C3—C4	158.3 (3)
O2—Mn1—O1—C1	−0.1 (3)	C2—N2—C3—C8	148.1 (4)
O2^i—Mn1—O1—C1	179.9 (3)	Cu1—N2—C3—C8	−19.1 (5)
N6^i—Mn1—O1—C1	86.4 (3)	N2—C3—C4—C5	176.7 (4)
N6—Mn1—O1—C1	−93.6 (3)	C8—C3—C4—C5	−5.8 (6)
O1—Mn1—O2—C2	3.6 (3)	C3—C4—C5—C6	−0.5 (7)
O1^i—Mn1—O2—C2	−176.4 (3)	C4—C5—C6—C7	4.7 (7)
O2^i—Mn1—O2—C2	−108 (17)	C5—C6—C7—C8	−2.5 (7)
N6^i—Mn1—O2—C2	−87.5 (3)	C6—C7—C8—C3	−3.7 (6)
N6—Mn1—O2—C2	92.5 (3)	C6—C7—C8—C9	171.0 (4)
N2—Cu1—N1—C1	−7.2 (3)	C4—C3—C8—C7	7.7 (6)
N3—Cu1—N1—C1	78.0 (6)	N2—C3—C8—C7	−174.7 (4)
N4—Cu1—N1—C1	156.5 (3)	C4—C3—C8—C9	−166.4 (4)
O3—Cu1—N1—C1	−103.5 (3)	N2—C3—C8—C9	11.1 (6)
N2—Cu1—N1—C22	174.9 (3)	C10—N3—C9—C8	172.5 (4)
N3—Cu1—N1—C22	−99.9 (6)	Cu1—N3—C9—C8	−9.3 (6)
N4—Cu1—N1—C22	−21.4 (3)	C7—C8—C9—N3	−170.6 (4)
O3—Cu1—N1—C22	78.7 (3)	C3—C8—C9—N3	3.6 (7)
N3—Cu1—N2—C2	−156.0 (3)	C9—N3—C10—C11	−95.6 (5)
N1—Cu1—N2—C2	11.7 (3)	Cu1—N3—C10—C11	86.0 (3)
N4—Cu1—N2—C2	−77.1 (5)	C9—N3—C10—C15	141.3 (4)
O3—Cu1—N2—C2	109.6 (3)	Cu1—N3—C10—C15	−37.1 (4)
N3—Cu1—N2—C3	12.2 (3)	N3—C10—C11—C12	−173.3 (4)
N1—Cu1—N2—C3	179.8 (3)	C15—C10—C11—C12	−54.0 (5)
N4—Cu1—N2—C3	91.0 (5)	C10—C11—C12—C13	56.7 (6)
O3—Cu1—N2—C3	−82.3 (3)	C11—C12—C13—C14	−57.7 (6)
N2—Cu1—N3—C9	2.0 (4)	C12—C13—C14—C15	56.2 (6)
N1—Cu1—N3—C9	−82.4 (7)	C16—N4—C15—C10	160.2 (4)
N4—Cu1—N3—C9	−162.0 (4)	Cu1—N4—C15—C10	−31.1 (4)
O3—Cu1—N3—C9	99.1 (4)	C16—N4—C15—C14	35.9 (6)
N2—Cu1—N3—C10	−179.8 (3)	Cu1—N4—C15—C14	−155.4 (3)
N1—Cu1—N3—C10	95.9 (6)	N3—C10—C15—N4	42.5 (4)
N4—Cu1—N3—C10	16.3 (3)	C11—C10—C15—N4	−78.0 (4)
O3—Cu1—N3—C10	−82.7 (3)	N3—C10—C15—C14	170.5 (4)
N2—Cu1—N4—C16	97.3 (5)	C11—C10—C15—C14	50.0 (5)
N3—Cu1—N4—C16	177.5 (4)	C13—C14—C15—N4	71.2 (5)
N1—Cu1—N4—C16	9.7 (4)	C13—C14—C15—C10	−51.4 (6)
O3—Cu1—N4—C16	−89.5 (3)	C15—N4—C16—C17	171.7 (4)
N2—Cu1—N4—C15	−71.1 (5)	Cu1—N4—C16—C17	4.2 (6)
N3—Cu1—N4—C15	9.1 (3)	N4—C16—C17—C22	−12.8 (7)
N1—Cu1—N4—C15	−158.7 (3)	N4—C16—C17—C18	168.3 (4)
O3—Cu1—N4—C15	102.1 (3)	C22—C17—C18—C19	1.4 (6)
O1—Mn1—N6—C23	−144.3 (6)	C16—C17—C18—C19	−179.6 (4)
O1^i—Mn1—N6—C23	35.7 (6)	C17—C18—C19—C20	0.2 (7)
O2—Mn1—N6—C23	140.4 (6)	C18—C19—C20—C21	−1.0 (7)
O2^i—Mn1—N6—C23	−39.6 (6)	C19—C20—C21—C22	0.2 (7)
N6^i—Mn1—N6—C23	5 (6)	C20—C21—C22—C17	1.3 (6)
Mn1—O1—C1—N1	174.1 (3)	C20—C21—C22—N1	−179.6 (4)
Mn1—O1—C1—C2	−2.8 (4)	C18—C17—C22—C21	−2.1 (6)
C22—N1—C1—O1	2.9 (7)	C16—C17—C22—C21	179.0 (4)
Cu1—N1—C1—O1	−175.0 (4)	C18—C17—C22—N1	178.8 (4)
C22—N1—C1—C2	179.9 (3)	C16—C17—C22—N1	0.0 (6)
Cu1—N1—C1—C2	1.9 (4)	C1—N1—C22—C21	22.4 (6)
Mn1—O2—C2—N2	175.2 (3)	Cu1—N1—C22—C21	−160.0 (3)
Mn1—O2—C2—C1	−6.1 (4)	C1—N1—C22—C17	−158.6 (4)
C3—N2—C2—O2	−3.5 (6)	Cu1—N1—C22—C17	19.1 (5)
Cu1—N2—C2—O2	165.4 (4)	Mn1—N6—C23—S1	−110 (27)
C3—N2—C2—C1	177.7 (3)	N2—Cu1—O3—C24	−11.7 (3)
Cu1—N2—C2—C1	−13.3 (4)	N3—Cu1—O3—C24	−105.7 (3)
O1—C1—C2—O2	6.2 (5)	N1—Cu1—O3—C24	74.6 (3)
N1—C1—C2—O2	−171.1 (4)	N4—Cu1—O3—C24	170.2 (3)
O1—C1—C2—N2	−174.9 (3)	Cu1—O3—C24—N5	164.0 (3)
N1—C1—C2—N2	7.8 (5)	C25—N5—C24—O3	177.1 (4)
C2—N2—C3—C4	−34.5 (6)	C26—N5—C24—O3	−0.2 (6)

Symmetry code: (i) −x+1, −y+3, −z+1.