Synthesis and structures of photoactive manganese–carbonyl complexes derived from 2-(pyridin-2-yl)-1,3-benzo­thia­zole and 2-(quinolin-2-yl)-1,3-benzo­thia­zole

PhotoCORMs (photo-active CO-releasing mol­ecules) have emerged as a class of CO donors where the CO release process can be triggered upon illumination with light of appropriate wavelength. We have recently reported an Mn-based photoCORM, namely [MnBr(pbt)(CO)₃] [pbt is 2-(pyridin-2-yl)-1,3-benzo­thia­zole], where the CO release event can be tracked within cellular milieu by virtue of the emergence of strong blue fluorescence. In pursuit of developing more such trackable photoCORMs, we report herein the syntheses and structural characterization of two Mn^I–carbonyl complexes, namely fac-tri­carbonyl­chlor­ido­[2-(pyridin-2-yl)-1,3-benzo­thia­zole-κ²N,N′]manganese(I), [MnCl(C₁₂H₈N₂S)(CO)₃], (1), and fac-tri­car­bonyl­chlorido­[2-(quinolin-2-yl)-1,3-benzo­thia­zole-κ²N,N′]manganese(I), [MnCl(C₁₆H₁₀N₂S)(CO)₃], (2). In both complexes, the Mn^I center resides in a distorted octa­hedral coordination environment. Weak inter­molecular C—H...Cl contacts in complex (1) and Cl...S contacts in complex (2) consolidate their extended structures. These complexes also exhibit CO release upon exposure to low-power broadband visible light. The apparent CO release rates for the two complexes have been measured to compare their CO donating capacity. The fluoro­genic 2-(pyridin-2-yl)-1,3-benzo­thia­zole and 2-(quinolin-2-yl)-1,3-benzo­thia­zole ligands provide a convenient way to track the CO release event through the `turn-ON' fluorescence which results upon de-ligation of the ligands from their respective metal centers following CO photorelease.

Computing details

For both compounds, data collection: APEX2 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

(1) Tricarbonylchlorido[2-(pyridin-2-yl)-1,3-benzothiazole-κ²N,N']manganese(I)

Crystal data

[MnCl(C12H8N2S)(CO)3]	F(000) = 776
Mr = 386.68	Dx = 1.676 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.008 (3) Å	Cell parameters from 2080 reflections
b = 11.798 (3) Å	θ = 2.8–23.3°
c = 9.0384 (19) Å	µ = 1.19 mm^−1
β = 106.756 (2)°	T = 296 K
V = 1532.4 (6) Å^3	Block, orange
Z = 4	0.20 × 0.18 × 0.15 mm

Data collection

Bruker APEX-II CCD diffractometer	2011 reflections with I > 2σ(I)
ω scans	Rint = 0.063
Absorption correction: multi-scan (SADABS; Bruker, 2015)	θmax = 28.4°, θmin = 2.2°
Tmin = 0.637, Tmax = 0.746	h = −15→19
12045 measured reflections	k = −15→14
3769 independent reflections	l = −12→11

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.196	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0911P)^2 + 0.5032P] where P = (Fo^2 + 2Fc^2)/3
3769 reflections	(Δ/σ)max < 0.001
208 parameters	Δρmax = 1.42 e Å^−3
0 restraints	Δρmin = −0.73 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq
Mn1	0.21696 (5)	0.58024 (6)	0.54247 (8)	0.0446 (3)
Cl1	0.33441 (10)	0.54251 (11)	0.77959 (15)	0.0539 (4)
S1	0.32007 (10)	0.25126 (12)	0.40244 (17)	0.0562 (4)
N2	0.2301 (3)	0.4123 (3)	0.4925 (5)	0.0438 (10)
N1	0.3228 (3)	0.5858 (3)	0.4367 (5)	0.0470 (10)
O1	0.0652 (3)	0.6233 (4)	0.2622 (5)	0.0739 (12)
O3	0.2145 (3)	0.8264 (3)	0.5838 (5)	0.0738 (12)
O2	0.0768 (3)	0.5793 (3)	0.7135 (5)	0.0762 (13)
C9	0.2976 (4)	0.3910 (4)	0.4308 (5)	0.0426 (11)
C8	0.3485 (4)	0.4873 (5)	0.3921 (6)	0.0486 (13)
C10	0.2299 (3)	0.2129 (4)	0.4774 (5)	0.0436 (11)
C15	0.1901 (4)	0.3112 (4)	0.5174 (5)	0.0467 (12)
C14	0.1145 (4)	0.2997 (4)	0.5814 (6)	0.0502 (13)
H14	0.0866	0.3628	0.6108	0.060*
C4	0.3669 (4)	0.6794 (5)	0.4075 (7)	0.0555 (14)
H4	0.3509	0.7493	0.4401	0.067*
C1	0.1272 (4)	0.6041 (4)	0.3686 (6)	0.0518 (13)
C3	0.2186 (3)	0.7305 (5)	0.5728 (6)	0.0489 (13)
C13	0.0845 (4)	0.1936 (5)	0.5981 (6)	0.0568 (14)
H13	0.0348	0.1844	0.6392	0.068*
C2	0.1313 (4)	0.5749 (4)	0.6474 (6)	0.0516 (13)
C11	0.1987 (4)	0.1060 (5)	0.4960 (6)	0.0600 (15)
H11	0.2265	0.0419	0.4688	0.072*
C7	0.4159 (4)	0.4759 (5)	0.3145 (7)	0.0622 (16)
H7	0.4314	0.4049	0.2845	0.075*
C12	0.1253 (5)	0.0978 (5)	0.5559 (7)	0.0637 (16)
H12	0.1021	0.0266	0.5688	0.076*
C5	0.4343 (4)	0.6760 (5)	0.3322 (7)	0.0641 (16)
H5	0.4626	0.7427	0.3146	0.077*
C6	0.4599 (4)	0.5741 (6)	0.2827 (8)	0.0739 (18)
H6	0.5047	0.5704	0.2301	0.089*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0526 (5)	0.0372 (4)	0.0472 (5)	0.0091 (3)	0.0196 (4)	−0.0022 (3)
Cl1	0.0635 (9)	0.0466 (8)	0.0506 (7)	0.0070 (6)	0.0146 (6)	−0.0024 (6)
S1	0.0699 (10)	0.0419 (8)	0.0618 (9)	0.0092 (6)	0.0269 (7)	−0.0058 (6)
N2	0.052 (3)	0.035 (2)	0.045 (2)	0.0037 (18)	0.0160 (19)	−0.0028 (18)
N1	0.051 (3)	0.039 (2)	0.053 (2)	0.0034 (19)	0.018 (2)	0.0075 (19)
O1	0.068 (3)	0.086 (3)	0.063 (3)	0.014 (2)	0.011 (2)	0.002 (2)
O3	0.095 (3)	0.046 (3)	0.086 (3)	0.009 (2)	0.034 (3)	−0.001 (2)
O2	0.087 (3)	0.066 (3)	0.096 (3)	0.013 (2)	0.058 (3)	0.010 (2)
C9	0.050 (3)	0.038 (3)	0.042 (3)	0.004 (2)	0.017 (2)	−0.002 (2)
C8	0.051 (3)	0.050 (3)	0.048 (3)	0.008 (2)	0.018 (2)	0.000 (2)
C10	0.054 (3)	0.038 (3)	0.040 (3)	0.002 (2)	0.015 (2)	−0.001 (2)
C15	0.060 (3)	0.037 (3)	0.039 (3)	−0.005 (2)	0.007 (2)	0.001 (2)
C14	0.052 (3)	0.045 (3)	0.059 (3)	−0.002 (2)	0.024 (3)	0.000 (2)
C4	0.057 (4)	0.044 (3)	0.070 (4)	0.001 (2)	0.026 (3)	0.012 (3)
C1	0.056 (3)	0.049 (3)	0.056 (3)	0.012 (2)	0.025 (3)	−0.002 (2)
C3	0.052 (3)	0.047 (3)	0.050 (3)	0.007 (2)	0.017 (3)	0.000 (2)
C13	0.067 (4)	0.050 (3)	0.059 (3)	−0.006 (3)	0.026 (3)	0.003 (3)
C2	0.066 (4)	0.034 (3)	0.058 (3)	0.008 (2)	0.023 (3)	0.000 (2)
C11	0.083 (4)	0.039 (3)	0.057 (3)	0.002 (3)	0.018 (3)	−0.002 (2)
C7	0.063 (4)	0.069 (4)	0.064 (4)	0.020 (3)	0.033 (3)	0.003 (3)
C12	0.075 (4)	0.054 (4)	0.060 (3)	−0.011 (3)	0.015 (3)	0.004 (3)
C5	0.053 (4)	0.060 (4)	0.083 (4)	−0.001 (3)	0.026 (3)	0.014 (3)
C6	0.063 (4)	0.083 (5)	0.085 (5)	0.011 (4)	0.035 (4)	0.020 (4)

Geometric parameters (Å, º)

Mn1—Cl1	2.3916 (15)	C10—C15	1.399 (7)
Mn1—N2	2.054 (4)	C10—C11	1.371 (7)
Mn1—N1	2.078 (4)	C15—C14	1.422 (7)
Mn1—C1	1.773 (6)	C14—H14	0.9300
Mn1—C3	1.793 (6)	C14—C13	1.353 (7)
Mn1—C2	1.805 (6)	C4—H4	0.9300
S1—C9	1.717 (5)	C4—C5	1.372 (7)
S1—C10	1.740 (5)	C13—H13	0.9300
N2—C9	1.314 (6)	C13—C12	1.390 (8)
N2—C15	1.383 (6)	C11—H11	0.9300
N1—C8	1.324 (6)	C11—C12	1.364 (8)
N1—C4	1.352 (6)	C7—H7	0.9300
O1—C1	1.150 (6)	C7—C6	1.403 (8)
O3—C3	1.140 (6)	C12—H12	0.9300
O2—C2	1.145 (6)	C5—H5	0.9300
C9—C8	1.466 (7)	C5—C6	1.376 (8)
C8—C7	1.394 (7)	C6—H6	0.9300
N2—Mn1—Cl1	85.68 (12)	N2—C15—C10	115.8 (5)
N2—Mn1—N1	78.15 (16)	N2—C15—C14	125.7 (5)
N1—Mn1—Cl1	87.39 (12)	C10—C15—C14	118.5 (5)
C1—Mn1—Cl1	177.79 (19)	C15—C14—H14	121.2
C1—Mn1—N2	93.2 (2)	C13—C14—C15	117.6 (5)
C1—Mn1—N1	94.2 (2)	C13—C14—H14	121.2
C1—Mn1—C3	87.2 (2)	N1—C4—H4	118.5
C1—Mn1—C2	89.8 (2)	N1—C4—C5	123.0 (5)
C3—Mn1—Cl1	94.19 (16)	C5—C4—H4	118.5
C3—Mn1—N2	171.6 (2)	O1—C1—Mn1	175.0 (5)
C3—Mn1—N1	93.5 (2)	O3—C3—Mn1	175.5 (5)
C3—Mn1—C2	86.2 (2)	C14—C13—H13	118.8
C2—Mn1—Cl1	88.60 (18)	C14—C13—C12	122.3 (6)
C2—Mn1—N2	102.1 (2)	C12—C13—H13	118.8
C2—Mn1—N1	175.9 (2)	O2—C2—Mn1	175.4 (5)
C9—S1—C10	89.1 (2)	C10—C11—H11	121.4
C9—N2—Mn1	114.4 (3)	C12—C11—C10	117.2 (5)
C9—N2—C15	109.2 (4)	C12—C11—H11	121.4
C15—N2—Mn1	136.2 (3)	C8—C7—H7	120.8
C8—N1—Mn1	116.1 (3)	C8—C7—C6	118.4 (6)
C8—N1—C4	117.1 (5)	C6—C7—H7	120.8
C4—N1—Mn1	126.7 (4)	C13—C12—H12	119.3
N2—C9—S1	117.1 (4)	C11—C12—C13	121.4 (5)
N2—C9—C8	118.1 (4)	C11—C12—H12	119.3
C8—C9—S1	124.8 (4)	C4—C5—H5	119.9
N1—C8—C9	113.0 (4)	C4—C5—C6	120.1 (6)
N1—C8—C7	123.7 (5)	C6—C5—H5	119.9
C7—C8—C9	123.3 (5)	C7—C6—H6	121.2
C15—C10—S1	108.8 (4)	C5—C6—C7	117.6 (6)
C11—C10—S1	128.2 (4)	C5—C6—H6	121.2
C11—C10—C15	123.0 (5)
Mn1—N2—C9—S1	174.1 (2)	C9—N2—C15—C10	1.6 (6)
Mn1—N2—C9—C8	−5.5 (6)	C9—N2—C15—C14	−179.5 (5)
Mn1—N2—C15—C10	−172.6 (3)	C9—C8—C7—C6	179.6 (5)
Mn1—N2—C15—C14	6.4 (8)	C8—N1—C4—C5	1.5 (8)
Mn1—N1—C8—C9	−1.5 (5)	C8—C7—C6—C5	0.7 (9)
Mn1—N1—C8—C7	177.6 (4)	C10—S1—C9—N2	0.8 (4)
Mn1—N1—C4—C5	−177.7 (4)	C10—S1—C9—C8	−179.6 (4)
S1—C9—C8—N1	−174.9 (4)	C10—C15—C14—C13	−0.8 (7)
S1—C9—C8—C7	6.0 (7)	C10—C11—C12—C13	−0.7 (9)
S1—C10—C15—N2	−1.0 (5)	C15—N2—C9—S1	−1.5 (5)
S1—C10—C15—C14	179.9 (4)	C15—N2—C9—C8	178.9 (4)
S1—C10—C11—C12	−179.1 (4)	C15—C10—C11—C12	0.2 (8)
N2—C9—C8—N1	4.7 (7)	C15—C14—C13—C12	0.4 (8)
N2—C9—C8—C7	−174.4 (5)	C14—C13—C12—C11	0.4 (9)
N2—C15—C14—C13	−179.7 (5)	C4—N1—C8—C9	179.2 (4)
N1—C8—C7—C6	0.6 (8)	C4—N1—C8—C7	−1.7 (8)
N1—C4—C5—C6	−0.1 (9)	C4—C5—C6—C7	−1.0 (9)
C9—S1—C10—C15	0.1 (4)	C11—C10—C15—N2	179.5 (5)
C9—S1—C10—C11	179.5 (5)	C11—C10—C15—C14	0.5 (7)

(2) fac-Tricarbonylchlorido[2-(quinolin-2-yl)-1,3-benzothiazole-κ²N,N']manganese(I)

Crystal data

[MnCl(C16H10N2S)(CO)3]	F(000) = 880
Mr = 436.74	Dx = 1.596 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.1239 (5) Å	Cell parameters from 4307 reflections
b = 16.4292 (9) Å	θ = 2.5–25.0°
c = 12.2101 (6) Å	µ = 1.01 mm^−1
β = 96.737 (1)°	T = 296 K
V = 1817.64 (17) Å^3	Block, orange
Z = 4	0.15 × 0.12 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer	3291 reflections with I > 2σ(I)
ω scans	Rint = 0.046
Absorption correction: multi-scan (SADABS; Bruker, 2015)	θmax = 28.3°, θmin = 2.1°
Tmin = 0.648, Tmax = 0.746	h = −12→11
20380 measured reflections	k = −21→21
4479 independent reflections	l = −16→16

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.093	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0349P)^2 + 0.6251P] where P = (Fo^2 + 2Fc^2)/3
4479 reflections	(Δ/σ)max < 0.001
266 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mn1	0.32118 (4)	0.41174 (2)	0.30429 (3)	0.03446 (11)
Cl1	0.22439 (7)	0.29074 (4)	0.37609 (5)	0.04868 (17)
S1	0.04380 (14)	0.30201 (6)	0.01570 (7)	0.0414 (4)	0.843 (6)
C10	0.4982 (5)	0.1876 (3)	0.0980 (3)	0.0475 (9)	0.843 (6)
H10	0.5203	0.1381	0.0668	0.057*	0.843 (6)
C11	0.3590 (5)	0.2199 (2)	0.0787 (3)	0.0436 (8)	0.843 (6)
H11	0.2853	0.1945	0.0317	0.052*	0.843 (6)
S1B	0.4515 (9)	0.2244 (5)	0.0774 (5)	0.061 (3)	0.157 (6)
C10B	0.128 (4)	0.2962 (13)	0.0209 (18)	0.060 (5)	0.157 (6)
H10B	0.1716	0.2580	−0.0211	0.071*	0.157 (6)
C11B	−0.006 (3)	0.3249 (18)	0.001 (2)	0.060 (5)	0.157 (6)
H11B	−0.0683	0.2999	−0.0546	0.071*	0.157 (6)
N2	0.1630 (2)	0.39650 (11)	0.17022 (15)	0.0367 (4)
O3	0.5311 (2)	0.40577 (11)	0.50662 (15)	0.0579 (5)
N1	0.4285 (2)	0.33246 (11)	0.20534 (15)	0.0379 (4)
O2	0.1494 (2)	0.50450 (14)	0.45115 (18)	0.0747 (6)
O1	0.4538 (2)	0.55991 (12)	0.22406 (18)	0.0729 (6)
C4	0.5717 (3)	0.30312 (14)	0.21962 (19)	0.0383 (5)
C19	0.0240 (2)	0.42886 (13)	0.13645 (19)	0.0373 (5)
C9	0.6078 (3)	0.23103 (15)	0.1661 (2)	0.0427 (6)
C14	−0.0588 (3)	0.38520 (15)	0.05218 (19)	0.0399 (5)
C13	0.1891 (3)	0.33182 (14)	0.11286 (19)	0.0396 (5)
C12	0.3322 (3)	0.29314 (14)	0.13328 (19)	0.0417 (5)
C3	0.4542 (3)	0.40787 (13)	0.4251 (2)	0.0405 (5)
C18	−0.0349 (3)	0.49920 (15)	0.1778 (2)	0.0493 (6)
H18	0.0191	0.5298	0.2326	0.059*
C5	0.6844 (3)	0.34619 (15)	0.2833 (2)	0.0452 (6)
H5	0.6636	0.3954	0.3159	0.054*
C1	0.4006 (3)	0.50218 (15)	0.2534 (2)	0.0446 (6)
C8	0.7539 (3)	0.20115 (16)	0.1834 (2)	0.0511 (6)
H8	0.7779	0.1531	0.1494	0.061*
C2	0.2118 (3)	0.46925 (16)	0.3897 (2)	0.0476 (6)
C6	0.8247 (3)	0.31557 (18)	0.2971 (2)	0.0506 (6)
H6	0.8987	0.3444	0.3395	0.061*
C15	−0.2010 (3)	0.40884 (17)	0.0108 (2)	0.0529 (7)
H15	−0.2557	0.3789	−0.0443	0.064*
C7	0.8594 (3)	0.24198 (17)	0.2491 (2)	0.0521 (7)
H7	0.9546	0.2210	0.2620	0.063*
C17	−0.1764 (3)	0.52230 (17)	0.1349 (2)	0.0574 (7)
H17	−0.2178	0.5691	0.1614	0.069*
C16	−0.2575 (3)	0.47657 (18)	0.0530 (2)	0.0587 (7)
H16	−0.3527	0.4930	0.0266	0.070*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0300 (2)	0.03499 (19)	0.0372 (2)	−0.00116 (14)	−0.00114 (14)	−0.00364 (14)
Cl1	0.0435 (4)	0.0507 (4)	0.0510 (4)	−0.0101 (3)	0.0015 (3)	0.0064 (3)
S1	0.0328 (8)	0.0449 (6)	0.0436 (5)	0.0015 (4)	−0.0082 (5)	−0.0081 (4)
C10	0.040 (2)	0.044 (2)	0.058 (2)	0.0059 (16)	0.0058 (16)	−0.0102 (18)
C11	0.030 (2)	0.0492 (18)	0.0493 (19)	0.0020 (16)	−0.0038 (16)	−0.0169 (14)
S1B	0.063 (6)	0.060 (4)	0.054 (3)	0.016 (4)	−0.009 (3)	−0.026 (3)
C10B	0.040 (12)	0.068 (11)	0.066 (10)	−0.014 (9)	−0.010 (9)	0.001 (8)
C11B	0.040 (12)	0.068 (11)	0.066 (10)	−0.014 (9)	−0.010 (9)	0.001 (8)
N2	0.0335 (11)	0.0362 (10)	0.0387 (10)	−0.0010 (8)	−0.0024 (8)	−0.0010 (8)
O3	0.0583 (12)	0.0606 (12)	0.0489 (10)	0.0039 (9)	−0.0184 (9)	−0.0058 (9)
N1	0.0335 (10)	0.0411 (11)	0.0391 (10)	0.0047 (8)	0.0047 (8)	0.0013 (8)
O2	0.0644 (14)	0.0898 (16)	0.0731 (14)	0.0183 (12)	0.0207 (11)	−0.0207 (12)
O1	0.0806 (15)	0.0553 (12)	0.0800 (15)	−0.0236 (11)	−0.0014 (12)	0.0140 (11)
C4	0.0342 (13)	0.0429 (13)	0.0384 (12)	0.0025 (10)	0.0066 (10)	0.0064 (10)
C19	0.0332 (12)	0.0372 (12)	0.0398 (12)	0.0012 (9)	−0.0025 (10)	0.0045 (10)
C9	0.0335 (13)	0.0527 (14)	0.0422 (13)	0.0016 (11)	0.0060 (10)	0.0004 (11)
C14	0.0329 (13)	0.0446 (13)	0.0410 (13)	0.0003 (10)	−0.0009 (10)	0.0038 (11)
C13	0.0399 (13)	0.0391 (12)	0.0374 (12)	−0.0006 (10)	−0.0051 (10)	−0.0010 (10)
C12	0.0422 (14)	0.0427 (13)	0.0393 (13)	0.0070 (10)	0.0009 (10)	−0.0016 (10)
C3	0.0387 (13)	0.0363 (12)	0.0463 (14)	0.0003 (10)	0.0038 (11)	−0.0059 (10)
C18	0.0542 (17)	0.0425 (14)	0.0497 (15)	0.0052 (12)	0.0002 (12)	−0.0009 (11)
C5	0.0415 (14)	0.0497 (14)	0.0458 (14)	−0.0058 (11)	0.0110 (11)	−0.0005 (11)
C1	0.0421 (14)	0.0450 (14)	0.0441 (14)	−0.0009 (11)	−0.0059 (11)	−0.0037 (11)
C8	0.0407 (15)	0.0522 (15)	0.0617 (17)	0.0109 (12)	0.0119 (12)	0.0023 (13)
C2	0.0388 (14)	0.0512 (15)	0.0512 (15)	0.0002 (11)	−0.0008 (12)	−0.0032 (12)
C6	0.0350 (14)	0.0699 (18)	0.0459 (14)	−0.0110 (12)	0.0003 (11)	0.0068 (13)
C15	0.0337 (14)	0.0684 (18)	0.0538 (15)	0.0014 (12)	−0.0073 (11)	0.0037 (14)
C7	0.0302 (14)	0.0646 (17)	0.0612 (17)	0.0048 (12)	0.0037 (12)	0.0124 (14)
C17	0.0558 (18)	0.0493 (15)	0.0686 (19)	0.0174 (13)	0.0132 (15)	0.0069 (14)
C16	0.0395 (16)	0.0694 (19)	0.0652 (18)	0.0150 (13)	−0.0018 (13)	0.0118 (15)

Geometric parameters (Å, º)

Mn1—Cl1	2.3837 (7)	N1—C12	1.335 (3)
Mn1—N2	2.0668 (18)	O2—C2	1.150 (3)
Mn1—N1	2.0962 (18)	O1—C1	1.142 (3)
Mn1—C3	1.798 (2)	C4—C9	1.410 (3)
Mn1—C1	1.796 (3)	C4—C5	1.405 (3)
Mn1—C2	1.795 (3)	C19—C14	1.401 (3)
S1—C14	1.744 (3)	C19—C18	1.394 (3)
S1—C13	1.742 (2)	C9—C8	1.413 (3)
C10—H10	0.9300	C14—C15	1.391 (3)
C10—C11	1.372 (7)	C13—C12	1.447 (3)
C10—C9	1.417 (4)	C18—H18	0.9300
C11—H11	0.9300	C18—C17	1.388 (4)
C11—C12	1.411 (4)	C5—H5	0.9300
S1B—C9	1.690 (7)	C5—C6	1.368 (3)
S1B—C12	1.761 (7)	C8—H8	0.9300
C10B—H10B	0.9300	C8—C7	1.356 (4)
C10B—C11B	1.30 (5)	C6—H6	0.9300
C10B—C13	1.33 (2)	C6—C7	1.396 (4)
C11B—H11B	0.9300	C15—H15	0.9300
C11B—C14	1.30 (3)	C15—C16	1.353 (4)
N2—C19	1.392 (3)	C7—H7	0.9300
N2—C13	1.310 (3)	C17—H17	0.9300
O3—C3	1.149 (3)	C17—C16	1.392 (4)
N1—C4	1.384 (3)	C16—H16	0.9300
N2—Mn1—Cl1	86.32 (5)	C8—C9—C10	120.1 (3)
N2—Mn1—N1	78.36 (7)	C8—C9—S1B	141.6 (3)
N1—Mn1—Cl1	84.96 (5)	C11B—C14—C19	123.1 (13)
C3—Mn1—Cl1	84.97 (8)	C11B—C14—C15	115.1 (13)
C3—Mn1—N2	170.75 (9)	C19—C14—S1	109.24 (17)
C3—Mn1—N1	97.75 (9)	C15—C14—S1	129.2 (2)
C1—Mn1—Cl1	177.82 (8)	C15—C14—C19	121.6 (2)
C1—Mn1—N2	95.68 (9)	C10B—C13—C12	103.6 (14)
C1—Mn1—N1	94.57 (10)	N2—C13—S1	114.85 (17)
C1—Mn1—C3	92.99 (10)	N2—C13—C10B	136.3 (14)
C2—Mn1—Cl1	88.28 (9)	N2—C13—C12	118.8 (2)
C2—Mn1—N2	98.04 (10)	C12—C13—S1	126.36 (18)
C2—Mn1—N1	172.52 (10)	C11—C12—C13	119.8 (3)
C2—Mn1—C3	84.82 (11)	N1—C12—C11	125.9 (3)
C2—Mn1—C1	92.31 (11)	N1—C12—S1B	100.2 (3)
C13—S1—C14	89.66 (12)	N1—C12—C13	114.3 (2)
C11—C10—H10	120.6	C13—C12—S1B	143.2 (3)
C11—C10—C9	118.8 (4)	O3—C3—Mn1	175.2 (2)
C9—C10—H10	120.6	C19—C18—H18	120.9
C10—C11—H11	121.4	C17—C18—C19	118.1 (2)
C10—C11—C12	117.2 (3)	C17—C18—H18	120.9
C12—C11—H11	121.4	C4—C5—H5	120.1
C9—S1B—C12	102.9 (3)	C6—C5—C4	119.8 (2)
C11B—C10B—H10B	126.6	C6—C5—H5	120.1
C11B—C10B—C13	107 (3)	O1—C1—Mn1	177.9 (2)
C13—C10B—H10B	126.6	C9—C8—H8	119.7
C10B—C11B—H11B	117.2	C7—C8—C9	120.5 (2)
C14—C11B—C10B	126 (3)	C7—C8—H8	119.7
C14—C11B—H11B	117.2	O2—C2—Mn1	174.8 (2)
C19—N2—Mn1	135.69 (15)	C5—C6—H6	119.3
C13—N2—Mn1	111.58 (14)	C5—C6—C7	121.4 (2)
C13—N2—C19	111.60 (18)	C7—C6—H6	119.3
C4—N1—Mn1	129.92 (16)	C14—C15—H15	120.9
C12—N1—Mn1	111.36 (15)	C16—C15—C14	118.2 (3)
C12—N1—C4	116.96 (19)	C16—C15—H15	120.9
N1—C4—C9	120.1 (2)	C8—C7—C6	119.8 (2)
N1—C4—C5	120.9 (2)	C8—C7—H7	120.1
C5—C4—C9	119.0 (2)	C6—C7—H7	120.1
N2—C19—C14	114.6 (2)	C18—C17—H17	119.5
N2—C19—C18	125.9 (2)	C18—C17—C16	121.0 (3)
C18—C19—C14	119.5 (2)	C16—C17—H17	119.5
C4—C9—C10	120.6 (3)	C15—C16—C17	121.5 (3)
C4—C9—S1B	97.3 (3)	C15—C16—H16	119.2
C4—C9—C8	119.3 (2)	C17—C16—H16	119.2
Mn1—N2—C19—C14	−164.67 (17)	C4—N1—C12—C11	6.8 (4)
Mn1—N2—C19—C18	16.2 (4)	C4—N1—C12—S1B	−6.5 (4)
Mn1—N2—C13—S1	167.46 (12)	C4—N1—C12—C13	−173.5 (2)
Mn1—N2—C13—C10B	−177.8 (15)	C4—C9—C8—C7	−1.2 (4)
Mn1—N2—C13—C12	−13.6 (3)	C4—C5—C6—C7	0.1 (4)
Mn1—N1—C4—C9	158.47 (17)	C19—N2—C13—S1	−2.3 (3)
Mn1—N1—C4—C5	−24.4 (3)	C19—N2—C13—C10B	12.5 (15)
Mn1—N1—C12—C11	−159.7 (3)	C19—N2—C13—C12	176.6 (2)
Mn1—N1—C12—S1B	−172.9 (3)	C19—C14—C15—C16	1.1 (4)
Mn1—N1—C12—C13	20.1 (2)	C19—C18—C17—C16	0.1 (4)
S1—C14—C15—C16	179.9 (2)	C9—C10—C11—C12	−3.1 (5)
S1—C13—C12—C11	−6.1 (4)	C9—S1B—C12—N1	13.3 (5)
S1—C13—C12—N1	174.15 (18)	C9—S1B—C12—C13	173.2 (3)
C10—C11—C12—N1	−2.7 (5)	C9—C4—C5—C6	−3.5 (3)
C10—C11—C12—C13	177.5 (3)	C9—C8—C7—C6	−2.1 (4)
C10—C9—C8—C7	−179.6 (3)	C14—S1—C13—N2	1.9 (2)
C11—C10—C9—C4	4.5 (5)	C14—S1—C13—C12	−177.0 (2)
C11—C10—C9—C8	−177.1 (3)	C14—C19—C18—C17	1.5 (4)
S1B—C9—C8—C7	159.1 (6)	C14—C15—C16—C17	0.5 (4)
C10B—C11B—C14—C19	1 (4)	C13—S1—C14—C19	−0.80 (19)
C10B—C11B—C14—C15	175 (2)	C13—S1—C14—C15	−179.8 (3)
C10B—C13—C12—S1B	5.9 (11)	C13—C10B—C11B—C14	9 (4)
C10B—C13—C12—N1	164.1 (10)	C13—N2—C19—C14	1.7 (3)
C11B—C10B—C13—N2	−18 (3)	C13—N2—C19—C18	−177.4 (2)
C11B—C10B—C13—C12	176.3 (17)	C12—S1B—C9—C4	−14.8 (5)
C11B—C14—C15—C16	−173.4 (14)	C12—S1B—C9—C8	−177.5 (3)
N2—C19—C14—S1	−0.3 (3)	C12—N1—C4—C9	−5.0 (3)
N2—C19—C14—C11B	−7.2 (15)	C12—N1—C4—C5	172.2 (2)
N2—C19—C14—C15	178.8 (2)	C18—C19—C14—S1	178.85 (19)
N2—C19—C18—C17	−179.5 (2)	C18—C19—C14—C11B	172.0 (15)
N2—C13—C12—C11	175.1 (3)	C18—C19—C14—C15	−2.1 (4)
N2—C13—C12—S1B	−163.0 (6)	C18—C17—C16—C15	−1.1 (4)
N2—C13—C12—N1	−4.7 (3)	C5—C4—C9—C10	−177.6 (3)
N1—C4—C9—C10	−0.4 (4)	C5—C4—C9—S1B	−163.8 (4)
N1—C4—C9—S1B	13.4 (4)	C5—C4—C9—C8	4.0 (3)
N1—C4—C9—C8	−178.8 (2)	C5—C6—C7—C8	2.7 (4)
N1—C4—C5—C6	179.3 (2)