Synthesis and crystal structures of two related Co and Mn complexes: a celebration of collaboration between the universities of Dakar and Southampton

The synthesis and structures are reported of two transition-metal complexes involving 2-(2-hy­droxy­phen­yl)benzimidazole with cobalt and manganese, arising from a UK–Africa collaboration.

Key indicators

Structure: Struct-1

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.029
• wR factor = 0.079
• Data-to-parameter ratio = 15.1

Structure: Struct-2

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.039
• wR factor = 0.107
• Data-to-parameter ratio = 13.8

checkCIF/PLATON results

No syntax errors found



Datablock: Struct-1



Alert level C
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          2 Report

Alert level G
PLAT230_ALERT_2_G Hirshfeld Test Diff for    S1       --C14      .        5.6 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Co1      --N3       .        5.9 s.u.
PLAT432_ALERT_2_G Short Inter X...Y Contact  S1       ..C8       .       3.25 Ang.
                                                    1+x,y,z  =      1_655 Check
PLAT794_ALERT_5_G Tentative Bond Valency for Co1       (II)      .       2.05 Info
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          6 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         11 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 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

   0 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
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check




Datablock: Struct-2



Alert level B
PLAT420_ALERT_2_B D-H Bond Without Acceptor  O3       --H3B      .     Please Check

Author Response: The water molecule (including atom O3) is involved in two other hydrogen bonds, orentating the O3-H3b bond into a cavity.

Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.59 Report
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          5 Report

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          4 Note
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          1 Report
PLAT230_ALERT_2_G Hirshfeld Test Diff for    S1       --C27      .        5.2 s.u.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H3B      ..S1       .       2.94 Ang.
PLAT794_ALERT_5_G Tentative Bond Valency for Mn1       (III)     .       3.16 Info
PLAT802_ALERT_4_G CIF Input Record(s) with more than 80 Characters          1 Info
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          2 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         90 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         11 Info

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

   0 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
   2 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

Computing details

Bis[µ-2-(1H-1,3-benzodiazol-2-yl)phenolato]bis[ethanol(thiocyanato)cobalt(II)] (Struct-1)

Crystal data

[Co2(C13H9N2O)2(NCS)2(C2H6O)2]	F(000) = 764
Mr = 744.60	Dx = 1.549 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
a = 7.74843 (10) Å	Cell parameters from 12655 reflections
b = 19.2895 (3) Å	θ = 4.6–74.2°
c = 10.69753 (11) Å	µ = 9.76 mm^−1
β = 93.3777 (10)°	T = 100 K
V = 1596.11 (4) Å^3	(cut) block, dark_red
Z = 2	0.12 × 0.1 × 0.1 mm

Data collection

Rigaku 007HF diffractometer with HF Varimax confocal mirrors, an UG2 goniometer and HyPix Arc-100 detector	3248 independent reflections
Radiation source: Rotating anode, Rigaku 007 HF	3113 reflections with I > 2σ(I)
HF Varimax focusing mirrors monochromator	Rint = 0.037
Detector resolution: 10 pixels mm^-1	θmax = 74.5°, θmin = 4.6°
profile data from ω–scans	h = −9→9
Absorption correction: analytical (CrysAlisPro; Rigaku OD, 2023)	k = −24→24
Tmin = 0.785, Tmax = 0.826	l = −13→9
46610 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.079	w = 1/[σ^2(Fo^2) + (0.0428P)^2 + 1.1982P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
3248 reflections	Δρmax = 0.32 e Å^−3
215 parameters	Δρmin = −0.47 e Å^−3
0 restraints

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
C1	0.3063 (2)	0.52949 (10)	0.66344 (16)	0.0155 (3)
C2	0.2850 (2)	0.59244 (9)	0.73665 (16)	0.0162 (3)
C3	0.3522 (2)	0.59966 (9)	0.86219 (16)	0.0160 (3)
C4	0.3285 (2)	0.66357 (10)	0.92215 (17)	0.0191 (4)
H4	0.374718	0.669594	1.005696	0.023*
C5	0.2404 (3)	0.71778 (10)	0.86349 (18)	0.0214 (4)
H5	0.225874	0.760134	0.906971	0.026*
C6	0.1726 (3)	0.71056 (10)	0.74058 (19)	0.0243 (4)
H6	0.111657	0.747697	0.699798	0.029*
C7	0.1954 (3)	0.64873 (10)	0.67909 (17)	0.0205 (4)
H7	0.149354	0.643886	0.595268	0.025*
C8	0.3772 (2)	0.42614 (10)	0.60066 (16)	0.0160 (3)
C9	0.2867 (2)	0.45834 (9)	0.49991 (17)	0.0171 (4)
C10	0.2497 (3)	0.42482 (10)	0.38593 (17)	0.0221 (4)
H10	0.187768	0.447169	0.318040	0.027*
C11	0.3079 (3)	0.35727 (11)	0.37699 (18)	0.0240 (4)
H11	0.284963	0.332479	0.301094	0.029*
C12	0.4001 (3)	0.32444 (10)	0.47743 (18)	0.0218 (4)
H12	0.439085	0.278180	0.467481	0.026*
C13	0.4355 (2)	0.35798 (10)	0.59071 (17)	0.0198 (4)
H13	0.496974	0.335530	0.658703	0.024*
C14	0.8273 (2)	0.40481 (9)	0.76185 (17)	0.0172 (4)
C15	0.2158 (3)	0.35669 (11)	1.00665 (18)	0.0237 (4)
H15A	0.304462	0.344454	1.073436	0.028*
H15B	0.145670	0.314781	0.986900	0.028*
C16	0.1014 (3)	0.41258 (12)	1.05322 (19)	0.0273 (4)
H16A	0.011958	0.424087	0.987951	0.041*
H16B	0.170835	0.453916	1.074040	0.041*
H16C	0.046744	0.396271	1.128112	0.041*
Co1	0.48673 (4)	0.45310 (2)	0.88029 (3)	0.01554 (10)
N1	0.38704 (19)	0.47189 (8)	0.70165 (14)	0.0156 (3)
N2	0.2446 (2)	0.52316 (8)	0.54190 (14)	0.0172 (3)
H2	0.191 (3)	0.5513 (13)	0.504 (2)	0.021*
N3	0.7117 (2)	0.41951 (9)	0.82031 (15)	0.0208 (3)
O1	0.43735 (17)	0.54921 (6)	0.92620 (12)	0.0176 (3)
O2	0.30061 (18)	0.37837 (7)	0.89578 (13)	0.0216 (3)
H2A	0.226 (4)	0.3794 (14)	0.836 (3)	0.032*
S1	0.99084 (6)	0.38539 (2)	0.67772 (4)	0.01919 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0154 (8)	0.0185 (8)	0.0126 (8)	−0.0021 (7)	0.0002 (6)	0.0019 (7)
C2	0.0166 (8)	0.0154 (8)	0.0164 (8)	−0.0003 (7)	0.0000 (7)	0.0007 (7)
C3	0.0166 (8)	0.0152 (8)	0.0162 (8)	−0.0002 (6)	0.0000 (7)	0.0018 (6)
C4	0.0212 (9)	0.0185 (9)	0.0172 (9)	−0.0007 (7)	−0.0031 (7)	−0.0008 (7)
C5	0.0256 (10)	0.0163 (9)	0.0219 (9)	0.0016 (7)	−0.0017 (7)	−0.0016 (7)
C6	0.0303 (10)	0.0183 (9)	0.0234 (10)	0.0054 (8)	−0.0046 (8)	0.0026 (7)
C7	0.0240 (9)	0.0204 (9)	0.0165 (9)	0.0033 (7)	−0.0042 (7)	0.0019 (7)
C8	0.0156 (8)	0.0187 (9)	0.0136 (8)	−0.0021 (7)	0.0016 (6)	−0.0006 (7)
C9	0.0190 (9)	0.0174 (9)	0.0151 (9)	−0.0020 (7)	0.0010 (7)	0.0006 (7)
C10	0.0294 (10)	0.0232 (10)	0.0133 (8)	−0.0015 (8)	−0.0019 (7)	0.0004 (7)
C11	0.0325 (11)	0.0232 (10)	0.0163 (9)	−0.0036 (8)	0.0006 (8)	−0.0044 (7)
C12	0.0258 (10)	0.0179 (9)	0.0217 (9)	0.0007 (7)	0.0024 (7)	−0.0030 (7)
C13	0.0206 (9)	0.0197 (9)	0.0189 (9)	0.0003 (7)	0.0001 (7)	0.0011 (7)
C14	0.0187 (9)	0.0169 (8)	0.0154 (8)	−0.0011 (7)	−0.0042 (7)	0.0021 (7)
C15	0.0244 (10)	0.0276 (10)	0.0192 (9)	−0.0038 (8)	0.0018 (7)	0.0051 (8)
C16	0.0238 (10)	0.0365 (12)	0.0213 (9)	−0.0016 (9)	−0.0011 (8)	−0.0031 (8)
Co1	0.01633 (16)	0.01559 (16)	0.01441 (16)	0.00107 (11)	−0.00140 (11)	−0.00038 (10)
N1	0.0162 (7)	0.0163 (7)	0.0141 (7)	0.0007 (6)	−0.0006 (6)	−0.0006 (6)
N2	0.0224 (8)	0.0152 (7)	0.0137 (7)	0.0009 (6)	−0.0029 (6)	0.0022 (6)
N3	0.0196 (8)	0.0241 (8)	0.0184 (8)	0.0017 (6)	−0.0019 (6)	0.0021 (6)
O1	0.0216 (7)	0.0160 (6)	0.0147 (6)	0.0018 (5)	−0.0031 (5)	0.0002 (5)
O2	0.0202 (7)	0.0285 (7)	0.0157 (6)	−0.0041 (6)	−0.0018 (5)	0.0016 (5)
S1	0.0169 (2)	0.0248 (2)	0.0158 (2)	−0.00064 (16)	−0.00012 (16)	0.00111 (16)

Geometric parameters (Å, º)

C1—C2	1.460 (2)	C11—H11	0.9500
C1—N1	1.328 (2)	C11—C12	1.405 (3)
C1—N2	1.364 (2)	C12—H12	0.9500
C2—C3	1.418 (2)	C12—C13	1.387 (3)
C2—C7	1.410 (3)	C13—H13	0.9500
C3—C4	1.407 (3)	C14—N3	1.158 (3)
C3—O1	1.341 (2)	C14—S1	1.6402 (19)
C4—H4	0.9500	C15—H15A	0.9900
C4—C5	1.380 (3)	C15—H15B	0.9900
C5—H5	0.9500	C15—C16	1.499 (3)
C5—C6	1.394 (3)	C15—O2	1.451 (2)
C6—H6	0.9500	C16—H16A	0.9800
C6—C7	1.378 (3)	C16—H16B	0.9800
C7—H7	0.9500	C16—H16C	0.9800
C8—C9	1.396 (3)	Co1—N1	2.0509 (15)
C8—C13	1.396 (3)	Co1—N3	2.0002 (17)
C8—N1	1.393 (2)	Co1—O1^i	2.1189 (13)
C9—C10	1.395 (3)	Co1—O1	1.9612 (13)
C9—N2	1.374 (2)	Co1—O2	2.0527 (14)
C10—H10	0.9500	N2—H2	0.78 (3)
C10—C11	1.384 (3)	O2—H2A	0.84 (3)
N1—C1—C2	126.68 (16)	C12—C13—H13	121.4
N1—C1—N2	110.54 (16)	N3—C14—S1	178.93 (18)
N2—C1—C2	122.77 (16)	H15A—C15—H15B	107.9
C3—C2—C1	122.87 (16)	C16—C15—H15A	109.3
C7—C2—C1	118.34 (16)	C16—C15—H15B	109.3
C7—C2—C3	118.79 (17)	O2—C15—H15A	109.3
C4—C3—C2	117.86 (16)	O2—C15—H15B	109.3
O1—C3—C2	123.68 (16)	O2—C15—C16	111.68 (17)
O1—C3—C4	118.47 (16)	C15—C16—H16A	109.5
C3—C4—H4	119.0	C15—C16—H16B	109.5
C5—C4—C3	122.09 (17)	C15—C16—H16C	109.5
C5—C4—H4	119.0	H16A—C16—H16B	109.5
C4—C5—H5	119.9	H16A—C16—H16C	109.5
C4—C5—C6	120.15 (18)	H16B—C16—H16C	109.5
C6—C5—H5	119.9	N1—Co1—O1^i	169.03 (6)
C5—C6—H6	120.5	N1—Co1—O2	88.36 (6)
C7—C6—C5	119.01 (18)	N3—Co1—N1	92.62 (6)
C7—C6—H6	120.5	N3—Co1—O1^i	96.29 (6)
C2—C7—H7	119.0	N3—Co1—O2	115.34 (6)
C6—C7—C2	122.09 (17)	O1—Co1—N1	89.89 (6)
C6—C7—H7	119.0	O1—Co1—N3	124.97 (6)
C9—C8—C13	120.67 (17)	O1—Co1—O1^i	79.76 (5)
N1—C8—C9	108.59 (16)	O1—Co1—O2	119.68 (6)
N1—C8—C13	130.70 (17)	O2—Co1—O1^i	93.57 (5)
C10—C9—C8	122.45 (17)	C1—N1—C8	106.74 (15)
N2—C9—C8	105.70 (16)	C1—N1—Co1	125.41 (12)
N2—C9—C10	131.81 (18)	C8—N1—Co1	127.66 (12)
C9—C10—H10	121.8	C1—N2—C9	108.43 (16)
C11—C10—C9	116.47 (18)	C1—N2—H2	125.3 (18)
C11—C10—H10	121.8	C9—N2—H2	126.2 (18)
C10—C11—H11	119.2	C14—N3—Co1	165.77 (15)
C10—C11—C12	121.63 (18)	C3—O1—Co1	130.96 (11)
C12—C11—H11	119.2	C3—O1—Co1^i	127.89 (11)
C11—C12—H12	119.2	Co1—O1—Co1^i	100.24 (5)
C13—C12—C11	121.55 (18)	C15—O2—Co1	128.51 (12)
C13—C12—H12	119.2	C15—O2—H2A	108.1 (19)
C8—C13—H13	121.4	Co1—O2—H2A	112.0 (19)
C12—C13—C8	117.23 (17)
C1—C2—C3—C4	177.94 (17)	C9—C10—C11—C12	−0.3 (3)
C1—C2—C3—O1	−1.7 (3)	C10—C9—N2—C1	177.3 (2)
C1—C2—C7—C6	−178.60 (18)	C10—C11—C12—C13	0.7 (3)
C2—C1—N1—C8	−179.32 (17)	C11—C12—C13—C8	−0.6 (3)
C2—C1—N1—Co1	5.4 (3)	C13—C8—C9—C10	0.3 (3)
C2—C1—N2—C9	179.57 (16)	C13—C8—C9—N2	178.22 (16)
C2—C3—C4—C5	1.2 (3)	C13—C8—N1—C1	−177.78 (19)
C2—C3—O1—Co1	−3.7 (3)	C13—C8—N1—Co1	−2.6 (3)
C2—C3—O1—Co1^i	−170.47 (13)	C16—C15—O2—Co1	67.7 (2)
C3—C2—C7—C6	0.6 (3)	N1—C1—C2—C3	0.5 (3)
C3—C4—C5—C6	−0.6 (3)	N1—C1—C2—C7	179.66 (18)
C4—C3—O1—Co1	176.65 (13)	N1—C1—N2—C9	0.3 (2)
C4—C3—O1—Co1^i	9.8 (2)	N1—C8—C9—C10	−177.63 (18)
C4—C5—C6—C7	−0.1 (3)	N1—C8—C9—N2	0.3 (2)
C5—C6—C7—C2	0.1 (3)	N1—C8—C13—C12	177.49 (18)
C7—C2—C3—C4	−1.2 (3)	N2—C1—C2—C3	−178.64 (17)
C7—C2—C3—O1	179.14 (17)	N2—C1—C2—C7	0.5 (3)
C8—C9—C10—C11	−0.2 (3)	N2—C1—N1—C8	−0.1 (2)
C8—C9—N2—C1	−0.4 (2)	N2—C1—N1—Co1	−175.33 (12)
C9—C8—C13—C12	0.1 (3)	N2—C9—C10—C11	−177.55 (19)
C9—C8—N1—C1	−0.2 (2)	O1—C3—C4—C5	−179.09 (17)
C9—C8—N1—Co1	174.96 (12)

Symmetry code: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1^ii	0.78 (3)	2.63 (3)	3.3843 (17)	162 (2)
O2—H2A···S1^iii	0.84 (3)	2.42 (3)	3.2498 (15)	174 (2)

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

Bis[µ-2-(1H-1,3-benzodiazol-2-yl)phenolato]bis{[2-(1H-1,3-benzodiazol-2-yl)phenolato](thiocyanato)manganese(III)} dihydrate (Struct-2)

Crystal data

[Mn2(C13H9N2O)4(NCS)2]·2H2O	F(000) = 2256
Mr = 1098.96	Dx = 1.535 Mg m^−3
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
a = 21.8914 (6) Å	Cell parameters from 8754 reflections
b = 16.3110 (4) Å	θ = 3.4–74.0°
c = 13.5260 (4) Å	µ = 5.69 mm^−1
β = 100.163 (2)°	T = 100 K
V = 4754.0 (2) Å^3	(cut) plate, pale-brown
Z = 4	0.07 × 0.05 × 0.02 mm

Data collection

Rigaku 007HF diffractometer with HF Varimax confocal mirrors, an UG2 goniometer and HyPix Arc-100 detector	4776 independent reflections
Radiation source: Rotating anode, Rigaku 007 HF	3991 reflections with I > 2σ(I)
HF Varimax focusing mirrors monochromator	Rint = 0.043
Detector resolution: 10 pixels mm^-1	θmax = 74.5°, θmin = 3.4°
profile data from ω–scans	h = −26→27
Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2023)	k = −20→16
Tmin = 0.940, Tmax = 1.000	l = −16→16
34537 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.107	w = 1/[σ^2(Fo^2) + (0.0594P)^2 + 4.7168P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
4776 reflections	Δρmax = 1.24 e Å^−3
346 parameters	Δρmin = −0.48 e Å^−3
2 restraints

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. The N-H bond lengths (N2-H2 and N4-H4a) have been restrained, otherwise they refined to unrealistic values. A peak of residual electron density (c.a. 1.2e-) at position (0.5, 0.264, 0.5 - close to atoms S1 and O3) remains unmodelled in the final refinement. During Structure development, a low occupancy water was modelled at this site (which also necessitated some disorder of the adjacent SCN ion). This arrangement gave rise to a chemically sensible hydrogen bond network and improved the refinement statistics; however, this arrangement freely refined to <8% occupancy and it has been omitted as this was deemed too low for reasonable certainty of the modelled disorder.

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

	x	y	z	Uiso*/Ueq
C1	0.45395 (11)	0.41180 (13)	0.62465 (15)	0.0255 (4)
C2	0.39349 (11)	0.37490 (13)	0.62530 (16)	0.0262 (5)
C3	0.38936 (10)	0.29465 (13)	0.66257 (16)	0.0254 (4)
C4	0.33086 (11)	0.26158 (14)	0.66495 (17)	0.0289 (5)
H4	0.327511	0.207719	0.690175	0.035*
C5	0.27751 (11)	0.30661 (15)	0.63085 (18)	0.0340 (5)
H5	0.237927	0.283114	0.631971	0.041*
C6	0.28171 (12)	0.38602 (16)	0.59500 (19)	0.0361 (5)
H6	0.245109	0.416890	0.572369	0.043*
C7	0.33893 (11)	0.41961 (14)	0.59247 (17)	0.0318 (5)
H7	0.341616	0.473887	0.568136	0.038*
C8	0.55415 (11)	0.43002 (13)	0.63085 (16)	0.0269 (5)
C9	0.52603 (12)	0.50736 (14)	0.62745 (16)	0.0283 (5)
C10	0.56009 (12)	0.58000 (14)	0.63208 (17)	0.0335 (5)
H10	0.540499	0.632110	0.629760	0.040*
C11	0.62322 (13)	0.57260 (14)	0.64016 (18)	0.0363 (6)
H11	0.647992	0.620678	0.643493	0.044*
C12	0.65211 (12)	0.49509 (14)	0.64362 (17)	0.0330 (5)
H12	0.695897	0.492175	0.648797	0.040*
C13	0.61812 (11)	0.42302 (14)	0.63965 (17)	0.0298 (5)
H13	0.637816	0.370946	0.642823	0.036*
C14	0.56524 (10)	0.08065 (13)	0.63916 (15)	0.0231 (4)
C15	0.62696 (10)	0.11510 (13)	0.64054 (16)	0.0254 (4)
C16	0.63244 (10)	0.19544 (13)	0.60372 (16)	0.0266 (5)
C17	0.69149 (11)	0.22342 (15)	0.59277 (17)	0.0312 (5)
H17	0.695807	0.276429	0.565713	0.037*
C18	0.74332 (11)	0.17511 (16)	0.62069 (17)	0.0334 (5)
H18	0.782969	0.195372	0.613417	0.040*
C19	0.73803 (11)	0.09661 (16)	0.65960 (18)	0.0336 (5)
H19	0.773913	0.063791	0.679809	0.040*
C20	0.68016 (11)	0.06732 (14)	0.66835 (17)	0.0301 (5)
H20	0.676390	0.013613	0.693782	0.036*
C21	0.46421 (10)	0.06703 (13)	0.61863 (15)	0.0238 (4)
C22	0.48984 (10)	−0.01194 (13)	0.62563 (15)	0.0247 (4)
C23	0.45339 (11)	−0.08204 (13)	0.61694 (16)	0.0271 (5)
H23	0.471226	−0.135302	0.622449	0.032*
C24	0.38993 (11)	−0.07056 (14)	0.59990 (16)	0.0288 (5)
H24	0.363415	−0.117075	0.593848	0.035*
C25	0.36361 (11)	0.00813 (14)	0.59129 (16)	0.0281 (5)
H25	0.319720	0.013620	0.579369	0.034*
C26	0.40020 (10)	0.07811 (13)	0.59978 (16)	0.0268 (5)
H26	0.382304	0.131321	0.593015	0.032*
C27	0.41872 (11)	0.21771 (13)	0.40867 (17)	0.0280 (5)
Mn1	0.50948 (2)	0.24690 (2)	0.62879 (2)	0.02207 (11)
N1	0.50728 (8)	0.37102 (11)	0.62871 (13)	0.0253 (4)
N2	0.46335 (10)	0.49371 (11)	0.62275 (14)	0.0282 (4)
H2	0.4364 (10)	0.5316 (14)	0.623 (2)	0.034*
N3	0.51284 (8)	0.12376 (10)	0.62987 (12)	0.0231 (4)
N4	0.55341 (9)	−0.00065 (11)	0.63934 (13)	0.0250 (4)
H4A	0.5802 (10)	−0.0389 (13)	0.6434 (19)	0.030*
N5	0.44756 (10)	0.23983 (11)	0.48419 (15)	0.0309 (4)
O1	0.44065 (7)	0.25005 (8)	0.69943 (11)	0.0240 (3)
O2	0.58367 (8)	0.24520 (8)	0.57549 (12)	0.0275 (3)
O3	0.59279 (9)	0.34515 (12)	0.39364 (16)	0.0419 (4)
H3A	0.5869 (17)	0.319 (2)	0.444 (3)	0.063*
H3B	0.5904 (16)	0.310 (2)	0.343 (3)	0.063*
S1	0.37974 (3)	0.18737 (4)	0.30045 (5)	0.03899 (17)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0363 (12)	0.0218 (10)	0.0181 (10)	0.0027 (9)	0.0041 (8)	0.0014 (8)
C2	0.0338 (12)	0.0237 (11)	0.0215 (10)	0.0026 (9)	0.0060 (9)	−0.0008 (8)
C3	0.0311 (11)	0.0234 (10)	0.0220 (10)	0.0047 (9)	0.0054 (8)	−0.0011 (8)
C4	0.0328 (12)	0.0275 (11)	0.0264 (11)	0.0011 (9)	0.0058 (9)	0.0000 (9)
C5	0.0300 (12)	0.0369 (13)	0.0350 (13)	0.0032 (10)	0.0052 (10)	−0.0008 (10)
C6	0.0345 (13)	0.0376 (13)	0.0349 (13)	0.0110 (11)	0.0027 (10)	0.0016 (10)
C7	0.0414 (13)	0.0273 (11)	0.0265 (11)	0.0088 (10)	0.0058 (10)	0.0033 (9)
C8	0.0400 (13)	0.0207 (10)	0.0207 (10)	−0.0045 (9)	0.0069 (9)	0.0018 (8)
C9	0.0429 (13)	0.0233 (11)	0.0187 (10)	−0.0010 (10)	0.0051 (9)	0.0017 (8)
C10	0.0488 (15)	0.0201 (11)	0.0318 (12)	−0.0028 (10)	0.0073 (11)	0.0038 (9)
C11	0.0505 (15)	0.0259 (11)	0.0323 (12)	−0.0111 (11)	0.0072 (11)	0.0016 (10)
C12	0.0400 (13)	0.0300 (12)	0.0294 (12)	−0.0075 (10)	0.0074 (10)	0.0005 (9)
C13	0.0383 (13)	0.0257 (11)	0.0260 (11)	−0.0028 (10)	0.0078 (9)	0.0004 (9)
C14	0.0306 (11)	0.0216 (10)	0.0172 (9)	0.0018 (9)	0.0048 (8)	0.0007 (8)
C15	0.0313 (11)	0.0252 (10)	0.0205 (10)	0.0005 (9)	0.0064 (8)	−0.0028 (8)
C16	0.0319 (12)	0.0256 (11)	0.0235 (10)	−0.0010 (9)	0.0078 (9)	−0.0024 (8)
C17	0.0361 (13)	0.0292 (11)	0.0295 (12)	−0.0025 (10)	0.0089 (10)	−0.0011 (9)
C18	0.0311 (12)	0.0381 (13)	0.0326 (12)	−0.0046 (10)	0.0101 (10)	−0.0028 (10)
C19	0.0313 (12)	0.0379 (13)	0.0313 (12)	0.0047 (10)	0.0050 (9)	−0.0010 (10)
C20	0.0350 (12)	0.0271 (11)	0.0284 (11)	0.0018 (10)	0.0058 (9)	0.0000 (9)
C21	0.0333 (12)	0.0197 (10)	0.0193 (10)	−0.0023 (9)	0.0073 (8)	−0.0001 (8)
C22	0.0323 (12)	0.0235 (10)	0.0186 (10)	0.0013 (9)	0.0053 (8)	0.0008 (8)
C23	0.0372 (12)	0.0199 (10)	0.0248 (11)	−0.0014 (9)	0.0074 (9)	−0.0004 (8)
C24	0.0388 (13)	0.0266 (11)	0.0220 (11)	−0.0076 (10)	0.0080 (9)	−0.0027 (8)
C25	0.0300 (12)	0.0299 (11)	0.0246 (11)	−0.0022 (9)	0.0055 (9)	−0.0021 (9)
C26	0.0323 (12)	0.0233 (11)	0.0251 (11)	0.0007 (9)	0.0056 (9)	−0.0007 (8)
C27	0.0311 (12)	0.0204 (10)	0.0333 (13)	0.0039 (9)	0.0082 (10)	−0.0012 (9)
Mn1	0.02793 (19)	0.01535 (18)	0.02377 (19)	0.00071 (13)	0.00685 (14)	0.00080 (12)
N1	0.0340 (10)	0.0187 (9)	0.0239 (9)	0.0003 (7)	0.0067 (8)	0.0021 (7)
N2	0.0403 (11)	0.0185 (9)	0.0264 (9)	0.0031 (8)	0.0072 (8)	0.0025 (7)
N3	0.0298 (10)	0.0181 (8)	0.0217 (9)	−0.0011 (7)	0.0054 (7)	−0.0004 (6)
N4	0.0315 (10)	0.0192 (9)	0.0248 (9)	0.0021 (7)	0.0065 (8)	−0.0001 (7)
N5	0.0400 (11)	0.0235 (9)	0.0283 (10)	0.0036 (8)	0.0037 (9)	0.0030 (8)
O1	0.0281 (8)	0.0200 (7)	0.0238 (8)	0.0007 (6)	0.0038 (6)	0.0022 (5)
O2	0.0325 (9)	0.0217 (8)	0.0295 (8)	0.0009 (6)	0.0085 (7)	0.0035 (6)
O3	0.0521 (11)	0.0348 (10)	0.0406 (11)	0.0063 (8)	0.0130 (9)	0.0089 (8)
S1	0.0398 (3)	0.0360 (3)	0.0373 (3)	0.0049 (3)	−0.0040 (2)	−0.0100 (3)

Geometric parameters (Å, º)

C1—C2	1.455 (3)	C16—O2	1.342 (3)
C1—N1	1.336 (3)	C17—H17	0.9500
C1—N2	1.353 (3)	C17—C18	1.378 (4)
C2—C3	1.411 (3)	C18—H18	0.9500
C2—C7	1.403 (3)	C18—C19	1.397 (4)
C3—C4	1.395 (3)	C19—H19	0.9500
C3—O1	1.357 (3)	C19—C20	1.379 (3)
C4—H4	0.9500	C20—H20	0.9500
C4—C5	1.388 (3)	C21—C22	1.402 (3)
C5—H5	0.9500	C21—C26	1.391 (3)
C5—C6	1.392 (4)	C21—N3	1.398 (3)
C6—H6	0.9500	C22—C23	1.387 (3)
C6—C7	1.373 (4)	C22—N4	1.383 (3)
C7—H7	0.9500	C23—H23	0.9500
C8—C9	1.401 (3)	C23—C24	1.380 (3)
C8—C13	1.389 (3)	C24—H24	0.9500
C8—N1	1.403 (3)	C24—C25	1.403 (3)
C9—C10	1.395 (3)	C25—H25	0.9500
C9—N2	1.380 (3)	C25—C26	1.388 (3)
C10—H10	0.9500	C26—H26	0.9500
C10—C11	1.372 (4)	C27—N5	1.160 (3)
C11—H11	0.9500	C27—S1	1.636 (2)
C11—C12	1.411 (4)	Mn1—N1	2.0251 (18)
C12—H12	0.9500	Mn1—N3	2.0099 (17)
C12—C13	1.387 (3)	Mn1—N5	2.177 (2)
C13—H13	0.9500	Mn1—O1^i	2.3869 (16)
C14—C15	1.460 (3)	Mn1—O1	1.9219 (16)
C14—N3	1.332 (3)	Mn1—O2	1.8898 (17)
C14—N4	1.351 (3)	N2—H2	0.854 (17)
C15—C16	1.415 (3)	N4—H4A	0.851 (17)
C15—C20	1.397 (3)	O3—H3A	0.83 (4)
C16—C17	1.403 (3)	O3—H3B	0.89 (4)
N1—C1—C2	125.64 (19)	C20—C19—H19	120.4
N1—C1—N2	111.0 (2)	C15—C20—H20	119.4
N2—C1—C2	123.4 (2)	C19—C20—C15	121.2 (2)
C3—C2—C1	120.1 (2)	C19—C20—H20	119.4
C7—C2—C1	120.5 (2)	C26—C21—C22	120.7 (2)
C7—C2—C3	119.4 (2)	C26—C21—N3	131.1 (2)
C4—C3—C2	118.9 (2)	N3—C21—C22	108.22 (19)
O1—C3—C2	121.8 (2)	C23—C22—C21	122.3 (2)
O1—C3—C4	119.20 (19)	N4—C22—C21	105.55 (18)
C3—C4—H4	119.7	N4—C22—C23	132.1 (2)
C5—C4—C3	120.7 (2)	C22—C23—H23	121.7
C5—C4—H4	119.7	C24—C23—C22	116.7 (2)
C4—C5—H5	119.8	C24—C23—H23	121.7
C4—C5—C6	120.3 (2)	C23—C24—H24	119.2
C6—C5—H5	119.8	C23—C24—C25	121.6 (2)
C5—C6—H6	120.1	C25—C24—H24	119.2
C7—C6—C5	119.8 (2)	C24—C25—H25	119.2
C7—C6—H6	120.1	C26—C25—C24	121.5 (2)
C2—C7—H7	119.5	C26—C25—H25	119.2
C6—C7—C2	120.9 (2)	C21—C26—H26	121.4
C6—C7—H7	119.5	C25—C26—C21	117.2 (2)
C9—C8—N1	107.5 (2)	C25—C26—H26	121.4
C13—C8—C9	120.5 (2)	N5—C27—S1	178.3 (2)
C13—C8—N1	131.9 (2)	N1—Mn1—N5	92.38 (7)
C10—C9—C8	122.3 (2)	N1—Mn1—O1^i	89.18 (6)
N2—C9—C8	106.49 (19)	N3—Mn1—N1	179.23 (8)
N2—C9—C10	131.1 (2)	N3—Mn1—N5	88.27 (7)
C9—C10—H10	121.6	N3—Mn1—O1^i	90.26 (6)
C11—C10—C9	116.8 (2)	N5—Mn1—O1^i	168.77 (7)
C11—C10—H10	121.6	O1—Mn1—N1	87.30 (7)
C10—C11—H11	119.3	O1—Mn1—N3	93.10 (6)
C10—C11—C12	121.4 (2)	O1—Mn1—N5	91.70 (7)
C12—C11—H11	119.3	O1—Mn1—O1^i	77.26 (7)
C11—C12—H12	119.2	O2—Mn1—N1	92.09 (7)
C13—C12—C11	121.6 (2)	O2—Mn1—N3	87.43 (7)
C13—C12—H12	119.2	O2—Mn1—N5	95.58 (8)
C8—C13—H13	121.3	O2—Mn1—O1	172.72 (7)
C12—C13—C8	117.3 (2)	O2—Mn1—O1^i	95.48 (6)
C12—C13—H13	121.3	C1—N1—C8	106.84 (18)
N3—C14—C15	125.27 (19)	C1—N1—Mn1	121.21 (15)
N3—C14—N4	110.85 (19)	C8—N1—Mn1	131.94 (15)
N4—C14—C15	123.69 (19)	C1—N2—C9	108.16 (19)
C16—C15—C14	119.19 (19)	C1—N2—H2	127.4 (19)
C20—C15—C14	120.96 (19)	C9—N2—H2	124.4 (19)
C20—C15—C16	119.6 (2)	C14—N3—C21	106.70 (17)
C17—C16—C15	118.4 (2)	C14—N3—Mn1	123.91 (14)
O2—C16—C15	123.2 (2)	C21—N3—Mn1	129.36 (14)
O2—C16—C17	118.3 (2)	C14—N4—C22	108.60 (18)
C16—C17—H17	119.5	C14—N4—H4A	126.1 (18)
C18—C17—C16	120.9 (2)	C22—N4—H4A	125.2 (18)
C18—C17—H17	119.5	C27—N5—Mn1	164.52 (17)
C17—C18—H18	119.7	C3—O1—Mn1	120.15 (13)
C17—C18—C19	120.6 (2)	C3—O1—Mn1^i	125.16 (12)
C19—C18—H18	119.7	Mn1—O1—Mn1^i	102.67 (7)
C18—C19—H19	120.4	C16—O2—Mn1	126.48 (13)
C20—C19—C18	119.2 (2)	H3A—O3—H3B	108 (3)
C1—C2—C3—C4	178.2 (2)	C20—C15—C16—C17	2.4 (3)
C1—C2—C3—O1	0.7 (3)	C20—C15—C16—O2	−180.0 (2)
C1—C2—C7—C6	−178.5 (2)	C21—C22—C23—C24	0.6 (3)
C2—C1—N1—C8	−177.4 (2)	C21—C22—N4—C14	−0.8 (2)
C2—C1—N1—Mn1	3.5 (3)	C22—C21—C26—C25	1.8 (3)
C2—C1—N2—C9	177.21 (19)	C22—C21—N3—C14	2.3 (2)
C2—C3—C4—C5	0.3 (3)	C22—C21—N3—Mn1	−179.52 (14)
C2—C3—O1—Mn1^i	91.4 (2)	C22—C23—C24—C25	0.3 (3)
C2—C3—O1—Mn1	−44.6 (2)	C23—C22—N4—C14	177.7 (2)
C3—C2—C7—C6	−0.8 (3)	C23—C24—C25—C26	−0.2 (3)
C3—C4—C5—C6	−0.9 (4)	C24—C25—C26—C21	−0.9 (3)
C4—C3—O1—Mn1	137.83 (17)	C26—C21—C22—C23	−1.7 (3)
C4—C3—O1—Mn1^i	−86.2 (2)	C26—C21—C22—N4	177.00 (18)
C4—C5—C6—C7	0.7 (4)	C26—C21—N3—C14	−175.3 (2)
C5—C6—C7—C2	0.2 (4)	C26—C21—N3—Mn1	2.8 (3)
C7—C2—C3—C4	0.5 (3)	N1—C1—C2—C3	20.7 (3)
C7—C2—C3—O1	−177.02 (19)	N1—C1—C2—C7	−161.7 (2)
C8—C9—C10—C11	0.0 (3)	N1—C1—N2—C9	−1.0 (2)
C8—C9—N2—C1	0.8 (2)	N1—C8—C9—C10	177.6 (2)
C9—C8—C13—C12	−0.7 (3)	N1—C8—C9—N2	−0.4 (2)
C9—C8—N1—C1	−0.2 (2)	N1—C8—C13—C12	−177.3 (2)
C9—C8—N1—Mn1	178.78 (15)	N1—Mn1—O2—C16	138.39 (17)
C9—C10—C11—C12	0.0 (4)	N2—C1—C2—C3	−157.3 (2)
C10—C9—N2—C1	−176.9 (2)	N2—C1—C2—C7	20.4 (3)
C10—C11—C12—C13	−0.4 (4)	N2—C1—N1—C8	0.8 (2)
C11—C12—C13—C8	0.8 (3)	N2—C1—N1—Mn1	−178.37 (13)
C13—C8—C9—C10	0.3 (3)	N2—C9—C10—C11	177.5 (2)
C13—C8—C9—N2	−177.64 (19)	N3—C14—C15—C16	−17.8 (3)
C13—C8—N1—C1	176.6 (2)	N3—C14—C15—C20	168.5 (2)
C13—C8—N1—Mn1	−4.4 (4)	N3—C14—N4—C22	2.4 (2)
C14—C15—C16—C17	−171.4 (2)	N3—C21—C22—C23	−179.65 (19)
C14—C15—C16—O2	6.2 (3)	N3—C21—C22—N4	−0.9 (2)
C14—C15—C20—C19	173.0 (2)	N3—C21—C26—C25	179.2 (2)
C15—C14—N3—C21	172.27 (19)	N3—Mn1—O2—C16	−41.01 (17)
C15—C14—N3—Mn1	−6.0 (3)	N4—C14—C15—C16	156.8 (2)
C15—C14—N4—C22	−172.89 (19)	N4—C14—C15—C20	−17.0 (3)
C15—C16—C17—C18	−2.4 (3)	N4—C14—N3—C21	−2.9 (2)
C15—C16—O2—Mn1	30.7 (3)	N4—C14—N3—Mn1	178.83 (13)
C16—C15—C20—C19	−0.7 (3)	N4—C22—C23—C24	−177.7 (2)
C16—C17—C18—C19	0.7 (4)	N5—Mn1—O2—C16	−129.02 (17)
C17—C16—O2—Mn1	−151.68 (16)	O1—C3—C4—C5	177.9 (2)
C17—C18—C19—C20	1.0 (4)	O1^i—Mn1—O2—C16	49.01 (17)
C18—C19—C20—C15	−1.0 (4)	O2—C16—C17—C18	179.8 (2)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O3^ii	0.85 (2)	2.11 (2)	2.893 (3)	152 (2)
N4—H4A···S1^iii	0.85 (2)	2.64 (2)	3.4147 (19)	152 (2)
O3—H3A···O2	0.83 (4)	2.17 (4)	2.987 (2)	173 (3)
O3—H3B···S1^iv	0.89 (4)	2.94 (4)	3.799 (2)	163 (3)

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