


Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S205698901500050X/cv5479sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S205698901500050X/cv5479Isup2.hkl |
CCDC reference: 1042885
Key indicators
- Single-crystal X-ray study
- T = 180 K
- Mean
(C-C) = 0.003 Å
- R factor = 0.041
- wR factor = 0.107
- Data-to-parameter ratio = 14.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT230_ALERT_2_C Hirshfeld Test Diff for N6 -- C46 .. 5.5 su PLAT230_ALERT_2_C Hirshfeld Test Diff for C30 -- C31 .. 5.5 su PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.3 Note PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 14 Report
Alert level G PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please Do ! PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms .............. 4 Report PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings Differ Please Check PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd. # 2 Note C5 H6 N2 PLAT899_ALERT_4_G SHELXL97 is Deprecated and Succeeded by SHELXL 2014 Note PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ... 1 Report
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 4 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 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 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 2 ALERT type 4 Improvement, methodology, query or suggestion 2 ALERT type 5 Informative message, check
In a continuation of our studies of metalloporphyrins, which are usually used as models of hemoproteins and have various applications in many fields such as catalysis (Amiri et al., 2014), photodynamic therapy (Kolarova et al., 2005), conception of sensors (Garg et al., 2013) or the design of photoluminescent species (Harry et al., 2003), we report herein the synthesis and crystal structure of the title compound, (I).
In (I), the central MnIII atom has a square-pyramidal coordination geometry (Fig. 1). The equatorial plane is formed by four nitrogen atoms of the porphyrin whereas, the apical position is occupied by the chlorido ligand. The asymmetric unit of (I) consists of the [MnIII(TPP)Cl] complex (TPP is the 5,10,15,20-tetraphenylporphyrinato ligand) and two 2-aminopyridine solvent molecules. The average equatorial manganese– N(pyrrole) atom distance (Mn—Np) is 2.0117 (17) Å, while the Mn—Cl bond length is 2.4315 (7) Å. The manganese atom is displaced by 0.1616 (5) Å from the 24-atom porphyrin mean plane. The porphyrin core presents a major ruffling deformation, as seen in the positions of the meso carbons alternatively above and below the mean plane of the 24-atom porphyrin macrocycle, and a saddle distortion involving the displacement of the pyrrole rings alternately above and below the porphyrin macrocycle mean plane (Scheidt & Lee, 1987). This is confirmed by normal structural decomposition (NSD) calculations (Jentzen et al., 1998), with ruffling and saddle percentages of ~40% and ~36%, respectively.
In the crystal structure, two 2-aminopyridine solvent molecules are paired into dimers via the N—H···N hydrogen bonds involving the amino groups of these two molecules (Table 1). In these dimers, one amino atom has a short Mn···N contact of 2.642 (1) Å and another amino atom generates weak N—H···Cl hydrogen bonds, which further link the components into chains along the a-axis direction (Fig. 2).
The majority of the known manganese–porphyrin species with halides are penta-coordinated, e.g. [MnIII(TPP)Cl] (Stute et al., 2013), [MnIII(TPP)Br] and [MnIII(TPP)I] (Turner et al., 1998). Nevertheless, the six-coordinated difluoro-manganese(IV) porphyrin species is also known: [MnIV(TMP)F2] (TMP is the 5,10,15,20-tetramesitylporphyrinato ligand) (Liu et al., 2012). In the Cambridge Structural Database (CSD, Version 5.35; Groom & Allen, 2014), there are fourteen penta-coordinated manganese(III) chlorido porphyrin structures, five of them with the 5,10,15,20-tetraphenylporphyrin (TPP) ligand. For the known [MnIII(Porph)Cl] complexes (Porph = porphyrinato ligand) [CSD refcodes HIFMIS (Cheng & Scheidt, 1996) and SENMUU (Paulat et al., 2006)], the equatorial manganese—N(pyrrole) distances (Mn—Np) are in the range 2.002–2.0185 (1) Å. This is also the case for (I), where the Mn—Np bond length is 2.0117 (17) Å. The manganese–chlorido distance of 2.4315 (7) Å in (I) is in agreement with those reported for related compounds [CSD refcodes HIFMIS (Cheng & Scheidt, 1996) and YEFYAL (Ishikawa et al., 2012)], with Mn—Cl bond lengths covering the range 2.30–2.66 Å.
To a solution of [MnIII(TPP)Cl] (100 mg, 0.142 mmol) (Cheng & Scheidt, 1996) in chlorobenzene (10 ml) was added an excess of 2-aminopyridine (50 mg, 0.531 mmol). The reaction mixture was stirred at room temperature for 12 hours. Crystals of the title complex were obtained by diffusion of hexanes through the chlorobenzene solution.
Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008, 2015); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: WinGX (Farrugia, 2012).
[Mn(C44H28N4)Cl]·2C5H6N2 | Z = 2 |
Mr = 891.33 | F(000) = 924 |
Triclinic, P1 | Dx = 1.372 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.9617 (4) Å | Cell parameters from 8818 reflections |
b = 12.1247 (6) Å | θ = 2.2–27.8° |
c = 18.9100 (9) Å | µ = 0.42 mm−1 |
α = 92.441 (3)° | T = 180 K |
β = 94.699 (2)° | Block, brown |
γ = 108.186 (2)° | 0.48 × 0.38 × 0.16 mm |
V = 2157.01 (17) Å3 |
Bruker APEXII CCD diffractometer | 8499 independent reflections |
Radiation source: fine-focus sealed tube | 6523 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
ϕ and ω scans | θmax = 26.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | h = −12→12 |
Tmin = 0.701, Tmax = 0.746 | k = −14→14 |
35821 measured reflections | l = −20→23 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0438P)2 + 1.0654P] where P = (Fo2 + 2Fc2)/3 |
8487 reflections | (Δ/σ)max = 0.001 |
577 parameters | Δρmax = 0.49 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
[Mn(C44H28N4)Cl]·2C5H6N2 | γ = 108.186 (2)° |
Mr = 891.33 | V = 2157.01 (17) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.9617 (4) Å | Mo Kα radiation |
b = 12.1247 (6) Å | µ = 0.42 mm−1 |
c = 18.9100 (9) Å | T = 180 K |
α = 92.441 (3)° | 0.48 × 0.38 × 0.16 mm |
β = 94.699 (2)° |
Bruker APEXII CCD diffractometer | 8499 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2006) | 6523 reflections with I > 2σ(I) |
Tmin = 0.701, Tmax = 0.746 | Rint = 0.041 |
35821 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.49 e Å−3 |
8487 reflections | Δρmin = −0.37 e Å−3 |
577 parameters |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 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. |
x | y | z | Uiso*/Ueq | ||
Mn | 0.71850 (3) | 0.20739 (3) | 0.748853 (16) | 0.02309 (10) | |
Cl | 0.47678 (6) | 0.07348 (5) | 0.73057 (3) | 0.03758 (15) | |
N1 | 0.77802 (17) | 0.14667 (15) | 0.66018 (9) | 0.0234 (4) | |
N2 | 0.80369 (18) | 0.10608 (15) | 0.80656 (9) | 0.0250 (4) | |
N3 | 0.68922 (18) | 0.28550 (15) | 0.83972 (9) | 0.0244 (4) | |
N4 | 0.66655 (18) | 0.32903 (15) | 0.69325 (9) | 0.0234 (4) | |
N5 | 0.9736 (2) | 0.36456 (17) | 0.76389 (10) | 0.0359 (5) | |
H5A | 0.9784 | 0.3197 | 0.7283 | 0.043* | |
H5B | 0.9219 | 0.4093 | 0.7592 | 0.043* | |
N6 | 1.1266 (2) | 0.29239 (19) | 0.83104 (11) | 0.0427 (5) | |
N7 | 1.2610 (2) | 0.2348 (2) | 0.70136 (14) | 0.0552 (6) | |
H7A | 1.2301 | 0.2540 | 0.7396 | 0.066* | |
H7B | 1.3217 | 0.1975 | 0.7035 | 0.066* | |
N8 | 1.1197 (2) | 0.32107 (18) | 0.63848 (11) | 0.0410 (5) | |
C1 | 0.7439 (2) | 0.17043 (18) | 0.59150 (11) | 0.0233 (4) | |
C2 | 0.7927 (2) | 0.10102 (18) | 0.54253 (11) | 0.0272 (5) | |
H2 | 0.7837 | 0.1013 | 0.4932 | 0.033* | |
C3 | 0.8539 (2) | 0.03566 (19) | 0.58099 (11) | 0.0275 (5) | |
H3 | 0.8953 | −0.0173 | 0.5632 | 0.033* | |
C4 | 0.8439 (2) | 0.06235 (18) | 0.65415 (11) | 0.0239 (4) | |
C5 | 0.8866 (2) | 0.00644 (18) | 0.71051 (11) | 0.0249 (5) | |
C6 | 0.8707 (2) | 0.03070 (18) | 0.78147 (11) | 0.0257 (5) | |
C7 | 0.9224 (2) | −0.0208 (2) | 0.84009 (12) | 0.0322 (5) | |
H7 | 0.9723 | −0.0739 | 0.8374 | 0.039* | |
C8 | 0.8855 (2) | 0.0216 (2) | 0.89976 (12) | 0.0322 (5) | |
H8 | 0.9056 | 0.0035 | 0.9459 | 0.039* | |
C9 | 0.8098 (2) | 0.09952 (19) | 0.87930 (11) | 0.0260 (5) | |
C10 | 0.7539 (2) | 0.16021 (19) | 0.92676 (11) | 0.0270 (5) | |
C11 | 0.6954 (2) | 0.24586 (19) | 0.90708 (11) | 0.0261 (5) | |
C12 | 0.6382 (2) | 0.3106 (2) | 0.95446 (12) | 0.0311 (5) | |
H12 | 0.6278 | 0.2992 | 1.0023 | 0.037* | |
C13 | 0.6022 (2) | 0.39102 (19) | 0.91726 (11) | 0.0301 (5) | |
H13 | 0.5639 | 0.4462 | 0.9348 | 0.036* | |
C14 | 0.6336 (2) | 0.37604 (19) | 0.84551 (11) | 0.0261 (5) | |
C15 | 0.6088 (2) | 0.44238 (18) | 0.79069 (11) | 0.0252 (5) | |
C16 | 0.6228 (2) | 0.41858 (18) | 0.71991 (11) | 0.0245 (5) | |
C17 | 0.5830 (2) | 0.47860 (19) | 0.66212 (11) | 0.0291 (5) | |
H17 | 0.5532 | 0.5439 | 0.6660 | 0.035* | |
C18 | 0.5967 (2) | 0.42307 (19) | 0.60135 (12) | 0.0283 (5) | |
H18 | 0.5755 | 0.4416 | 0.5554 | 0.034* | |
C19 | 0.6499 (2) | 0.33038 (18) | 0.62017 (11) | 0.0241 (4) | |
C20 | 0.6799 (2) | 0.25316 (18) | 0.57174 (11) | 0.0239 (4) | |
C21 | 0.9456 (2) | −0.09079 (19) | 0.69477 (11) | 0.0255 (5) | |
C22 | 1.0792 (2) | −0.0706 (2) | 0.67155 (12) | 0.0310 (5) | |
H22 | 1.1331 | 0.0046 | 0.6632 | 0.037* | |
C23 | 1.1328 (2) | −0.1620 (2) | 0.66072 (12) | 0.0348 (5) | |
H23 | 1.2228 | −0.1477 | 0.6456 | 0.042* | |
C24 | 1.0536 (3) | −0.2736 (2) | 0.67222 (12) | 0.0358 (6) | |
H24 | 1.0902 | −0.3347 | 0.6654 | 0.043* | |
C25 | 0.9196 (3) | −0.2945 (2) | 0.69389 (13) | 0.0364 (6) | |
H25 | 0.8652 | −0.3701 | 0.7010 | 0.044* | |
C26 | 0.8656 (2) | −0.2043 (2) | 0.70511 (12) | 0.0319 (5) | |
H26 | 0.7751 | −0.2195 | 0.7197 | 0.038* | |
C27 | 0.7585 (2) | 0.1328 (2) | 1.00308 (11) | 0.0297 (5) | |
C28 | 0.6758 (3) | 0.0259 (2) | 1.02330 (13) | 0.0359 (6) | |
H28 | 0.6216 | −0.0310 | 0.9888 | 0.043* | |
C29 | 0.6734 (3) | 0.0032 (2) | 1.09463 (14) | 0.0430 (6) | |
H29 | 0.6161 | −0.0679 | 1.1077 | 0.052* | |
C30 | 0.7548 (3) | 0.0850 (3) | 1.14558 (14) | 0.0469 (7) | |
H30 | 0.7520 | 0.0698 | 1.1933 | 0.056* | |
C31 | 0.8410 (3) | 0.1896 (3) | 1.12667 (13) | 0.0432 (7) | |
H31 | 0.8985 | 0.2441 | 1.1616 | 0.052* | |
C32 | 0.8427 (3) | 0.2145 (2) | 1.05562 (12) | 0.0358 (5) | |
H32 | 0.9003 | 0.2860 | 1.0432 | 0.043* | |
C33 | 0.5585 (2) | 0.54284 (19) | 0.81056 (11) | 0.0271 (5) | |
C34 | 0.6532 (3) | 0.6437 (2) | 0.84414 (13) | 0.0379 (6) | |
H34 | 0.7487 | 0.6501 | 0.8526 | 0.045* | |
C35 | 0.6072 (3) | 0.7357 (2) | 0.86545 (14) | 0.0448 (6) | |
H35 | 0.6719 | 0.8033 | 0.8880 | 0.054* | |
C36 | 0.4665 (3) | 0.7271 (2) | 0.85329 (13) | 0.0417 (6) | |
H36 | 0.4357 | 0.7887 | 0.8676 | 0.050* | |
C37 | 0.3715 (3) | 0.6272 (2) | 0.81989 (14) | 0.0418 (6) | |
H37 | 0.2760 | 0.6211 | 0.8118 | 0.050* | |
C38 | 0.4171 (2) | 0.5354 (2) | 0.79812 (13) | 0.0347 (5) | |
H38 | 0.3521 | 0.4684 | 0.7750 | 0.042* | |
C39 | 0.6393 (2) | 0.25768 (18) | 0.49454 (11) | 0.0243 (4) | |
C40 | 0.7006 (2) | 0.35470 (19) | 0.45743 (11) | 0.0289 (5) | |
H40 | 0.7709 | 0.4185 | 0.4807 | 0.035* | |
C41 | 0.6578 (2) | 0.3570 (2) | 0.38642 (12) | 0.0322 (5) | |
H41 | 0.6983 | 0.4227 | 0.3624 | 0.039* | |
C42 | 0.5555 (2) | 0.2625 (2) | 0.35099 (12) | 0.0348 (5) | |
H42 | 0.5275 | 0.2643 | 0.3030 | 0.042* | |
C43 | 0.4945 (2) | 0.1651 (2) | 0.38668 (12) | 0.0343 (5) | |
H43 | 0.4262 | 0.1008 | 0.3627 | 0.041* | |
C44 | 0.5351 (2) | 0.16335 (19) | 0.45802 (11) | 0.0290 (5) | |
H44 | 0.4922 | 0.0982 | 0.4821 | 0.035* | |
C45 | 1.0496 (2) | 0.3647 (2) | 0.82897 (13) | 0.0367 (6) | |
C46 | 1.1971 (3) | 0.2868 (3) | 0.89372 (17) | 0.0570 (8) | |
H46 | 1.2503 | 0.2360 | 0.8960 | 0.068* | |
C47 | 1.1952 (3) | 0.3518 (3) | 0.95452 (16) | 0.0635 (9) | |
H47 | 1.2454 | 0.3454 | 0.9970 | 0.076* | |
C48 | 1.1166 (3) | 0.4267 (3) | 0.95052 (16) | 0.0600 (8) | |
H48 | 1.1145 | 0.4732 | 0.9905 | 0.072* | |
C49 | 1.0412 (3) | 0.4330 (2) | 0.88792 (14) | 0.0474 (7) | |
H49 | 0.9857 | 0.4820 | 0.8850 | 0.057* | |
C50 | 1.0728 (3) | 0.3510 (2) | 0.57616 (15) | 0.0513 (7) | |
H50 | 1.0070 | 0.3910 | 0.5762 | 0.062* | |
C51 | 1.1165 (4) | 0.3258 (3) | 0.51199 (16) | 0.0669 (10) | |
H51 | 1.0816 | 0.3484 | 0.4698 | 0.080* | |
C52 | 1.2135 (4) | 0.2663 (3) | 0.51215 (19) | 0.0770 (12) | |
H52 | 1.2454 | 0.2483 | 0.4696 | 0.092* | |
C53 | 1.2625 (3) | 0.2338 (3) | 0.57395 (19) | 0.0633 (9) | |
H53 | 1.3272 | 0.1927 | 0.5743 | 0.076* | |
C54 | 1.2141 (3) | 0.2631 (2) | 0.63784 (15) | 0.0436 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn | 0.02838 (18) | 0.02739 (19) | 0.01763 (17) | 0.01494 (14) | 0.00212 (13) | 0.00061 (13) |
Cl | 0.0315 (3) | 0.0396 (3) | 0.0404 (4) | 0.0096 (2) | 0.0044 (2) | 0.0016 (3) |
N1 | 0.0267 (9) | 0.0253 (9) | 0.0205 (9) | 0.0118 (7) | 0.0020 (7) | 0.0010 (7) |
N2 | 0.0288 (9) | 0.0303 (10) | 0.0199 (9) | 0.0154 (8) | 0.0026 (7) | 0.0002 (8) |
N3 | 0.0285 (9) | 0.0295 (10) | 0.0189 (9) | 0.0147 (8) | 0.0014 (7) | 0.0009 (7) |
N4 | 0.0273 (9) | 0.0267 (10) | 0.0186 (9) | 0.0124 (7) | 0.0021 (7) | −0.0004 (7) |
N5 | 0.0387 (11) | 0.0423 (12) | 0.0300 (11) | 0.0197 (9) | −0.0001 (9) | −0.0066 (9) |
N6 | 0.0391 (12) | 0.0477 (13) | 0.0399 (13) | 0.0146 (10) | −0.0048 (10) | −0.0007 (10) |
N7 | 0.0464 (13) | 0.0565 (15) | 0.0671 (18) | 0.0259 (12) | 0.0012 (12) | −0.0122 (13) |
N8 | 0.0362 (11) | 0.0405 (12) | 0.0412 (13) | 0.0052 (9) | 0.0054 (10) | −0.0041 (10) |
C1 | 0.0255 (10) | 0.0250 (11) | 0.0191 (11) | 0.0075 (9) | 0.0025 (8) | 0.0010 (9) |
C2 | 0.0345 (12) | 0.0296 (12) | 0.0192 (11) | 0.0128 (10) | 0.0039 (9) | −0.0003 (9) |
C3 | 0.0326 (11) | 0.0284 (12) | 0.0251 (12) | 0.0141 (9) | 0.0072 (9) | −0.0008 (9) |
C4 | 0.0268 (11) | 0.0246 (11) | 0.0219 (11) | 0.0106 (9) | 0.0033 (9) | 0.0001 (9) |
C5 | 0.0242 (10) | 0.0267 (12) | 0.0251 (12) | 0.0103 (9) | 0.0020 (9) | −0.0012 (9) |
C6 | 0.0271 (11) | 0.0291 (12) | 0.0243 (12) | 0.0147 (9) | 0.0004 (9) | 0.0004 (9) |
C7 | 0.0367 (12) | 0.0390 (14) | 0.0286 (13) | 0.0236 (11) | 0.0005 (10) | 0.0031 (10) |
C8 | 0.0391 (13) | 0.0416 (14) | 0.0220 (12) | 0.0223 (11) | −0.0003 (10) | 0.0041 (10) |
C9 | 0.0292 (11) | 0.0319 (12) | 0.0196 (11) | 0.0141 (9) | −0.0002 (9) | 0.0020 (9) |
C10 | 0.0290 (11) | 0.0347 (13) | 0.0196 (11) | 0.0139 (10) | 0.0008 (9) | 0.0016 (9) |
C11 | 0.0290 (11) | 0.0331 (12) | 0.0186 (11) | 0.0138 (9) | 0.0011 (9) | −0.0004 (9) |
C12 | 0.0394 (13) | 0.0406 (14) | 0.0186 (11) | 0.0202 (11) | 0.0042 (9) | 0.0008 (10) |
C13 | 0.0379 (12) | 0.0336 (13) | 0.0237 (12) | 0.0191 (10) | 0.0038 (10) | −0.0026 (10) |
C14 | 0.0284 (11) | 0.0292 (12) | 0.0237 (11) | 0.0140 (9) | 0.0018 (9) | −0.0014 (9) |
C15 | 0.0260 (11) | 0.0263 (11) | 0.0252 (11) | 0.0113 (9) | 0.0027 (9) | −0.0002 (9) |
C16 | 0.0254 (10) | 0.0253 (11) | 0.0247 (12) | 0.0106 (9) | 0.0032 (9) | 0.0024 (9) |
C17 | 0.0366 (12) | 0.0290 (12) | 0.0273 (12) | 0.0183 (10) | 0.0033 (10) | 0.0035 (10) |
C18 | 0.0349 (12) | 0.0323 (12) | 0.0224 (12) | 0.0175 (10) | 0.0006 (9) | 0.0042 (9) |
C19 | 0.0254 (10) | 0.0270 (11) | 0.0212 (11) | 0.0102 (9) | 0.0018 (8) | 0.0018 (9) |
C20 | 0.0253 (10) | 0.0256 (11) | 0.0198 (11) | 0.0070 (9) | 0.0017 (8) | 0.0020 (9) |
C21 | 0.0302 (11) | 0.0321 (12) | 0.0185 (11) | 0.0170 (10) | 0.0003 (9) | −0.0003 (9) |
C22 | 0.0341 (12) | 0.0315 (13) | 0.0307 (13) | 0.0145 (10) | 0.0063 (10) | 0.0020 (10) |
C23 | 0.0337 (12) | 0.0458 (15) | 0.0326 (13) | 0.0224 (11) | 0.0097 (10) | 0.0015 (11) |
C24 | 0.0459 (14) | 0.0394 (14) | 0.0302 (13) | 0.0261 (12) | 0.0021 (11) | −0.0037 (11) |
C25 | 0.0400 (13) | 0.0284 (13) | 0.0417 (15) | 0.0131 (11) | 0.0010 (11) | 0.0008 (11) |
C26 | 0.0287 (11) | 0.0351 (13) | 0.0342 (13) | 0.0133 (10) | 0.0041 (10) | 0.0022 (10) |
C27 | 0.0370 (12) | 0.0413 (14) | 0.0201 (11) | 0.0252 (11) | 0.0042 (9) | 0.0031 (10) |
C28 | 0.0417 (13) | 0.0431 (15) | 0.0294 (13) | 0.0216 (11) | 0.0052 (10) | 0.0065 (11) |
C29 | 0.0489 (15) | 0.0558 (17) | 0.0366 (15) | 0.0303 (13) | 0.0126 (12) | 0.0187 (13) |
C30 | 0.0550 (16) | 0.077 (2) | 0.0263 (14) | 0.0421 (16) | 0.0109 (12) | 0.0179 (14) |
C31 | 0.0506 (15) | 0.0693 (19) | 0.0228 (13) | 0.0410 (15) | −0.0052 (11) | −0.0058 (12) |
C32 | 0.0411 (13) | 0.0448 (15) | 0.0267 (13) | 0.0223 (11) | −0.0002 (10) | 0.0002 (11) |
C33 | 0.0373 (12) | 0.0295 (12) | 0.0202 (11) | 0.0173 (10) | 0.0078 (9) | 0.0036 (9) |
C34 | 0.0382 (13) | 0.0354 (14) | 0.0416 (15) | 0.0149 (11) | 0.0042 (11) | −0.0057 (11) |
C35 | 0.0573 (17) | 0.0303 (14) | 0.0462 (16) | 0.0141 (12) | 0.0080 (13) | −0.0096 (11) |
C36 | 0.0632 (17) | 0.0386 (15) | 0.0366 (15) | 0.0320 (13) | 0.0175 (13) | 0.0041 (12) |
C37 | 0.0437 (14) | 0.0479 (16) | 0.0450 (16) | 0.0278 (13) | 0.0136 (12) | 0.0066 (13) |
C38 | 0.0353 (12) | 0.0339 (13) | 0.0377 (14) | 0.0145 (10) | 0.0059 (10) | 0.0014 (11) |
C39 | 0.0282 (11) | 0.0279 (12) | 0.0206 (11) | 0.0143 (9) | 0.0023 (9) | 0.0009 (9) |
C40 | 0.0327 (12) | 0.0291 (12) | 0.0259 (12) | 0.0113 (10) | 0.0026 (9) | 0.0004 (9) |
C41 | 0.0390 (13) | 0.0362 (13) | 0.0274 (13) | 0.0185 (11) | 0.0083 (10) | 0.0092 (10) |
C42 | 0.0403 (13) | 0.0513 (16) | 0.0199 (12) | 0.0248 (12) | 0.0012 (10) | 0.0044 (11) |
C43 | 0.0339 (12) | 0.0397 (14) | 0.0282 (13) | 0.0132 (11) | −0.0038 (10) | −0.0074 (10) |
C44 | 0.0327 (12) | 0.0296 (12) | 0.0252 (12) | 0.0107 (10) | 0.0028 (9) | 0.0026 (9) |
C45 | 0.0294 (12) | 0.0419 (14) | 0.0351 (14) | 0.0068 (11) | 0.0026 (10) | −0.0006 (11) |
C46 | 0.0472 (16) | 0.062 (2) | 0.060 (2) | 0.0181 (14) | −0.0072 (14) | 0.0082 (16) |
C47 | 0.0538 (18) | 0.088 (2) | 0.0372 (17) | 0.0111 (17) | −0.0118 (14) | 0.0014 (16) |
C48 | 0.0478 (17) | 0.078 (2) | 0.0399 (17) | 0.0036 (16) | 0.0007 (13) | −0.0175 (15) |
C49 | 0.0413 (15) | 0.0527 (17) | 0.0417 (16) | 0.0079 (13) | 0.0027 (12) | −0.0129 (13) |
C50 | 0.0511 (16) | 0.0459 (17) | 0.0456 (17) | −0.0001 (13) | 0.0015 (13) | 0.0027 (13) |
C51 | 0.081 (2) | 0.055 (2) | 0.0391 (18) | −0.0149 (18) | 0.0059 (16) | −0.0031 (14) |
C52 | 0.085 (3) | 0.062 (2) | 0.057 (2) | −0.0197 (19) | 0.037 (2) | −0.0230 (18) |
C53 | 0.0516 (17) | 0.0527 (19) | 0.076 (2) | 0.0002 (14) | 0.0282 (17) | −0.0235 (17) |
C54 | 0.0337 (13) | 0.0394 (15) | 0.0496 (17) | 0.0016 (11) | 0.0061 (12) | −0.0129 (12) |
Mn—N2 | 2.0083 (17) | C22—H22 | 0.9300 |
Mn—N1 | 2.0089 (16) | C23—C24 | 1.374 (3) |
Mn—N3 | 2.0127 (17) | C23—H23 | 0.9300 |
Mn—N4 | 2.0169 (16) | C24—C25 | 1.379 (3) |
Mn—Cl | 2.4351 (7) | C24—H24 | 0.9300 |
N1—C1 | 1.381 (3) | C25—C26 | 1.376 (3) |
N1—C4 | 1.382 (2) | C25—H25 | 0.9300 |
N2—C9 | 1.378 (3) | C26—H26 | 0.9300 |
N2—C6 | 1.379 (3) | C27—C32 | 1.390 (3) |
N3—C14 | 1.380 (3) | C27—C28 | 1.391 (3) |
N3—C11 | 1.384 (3) | C28—C29 | 1.389 (3) |
N4—C19 | 1.380 (3) | C28—H28 | 0.9300 |
N4—C16 | 1.381 (3) | C29—C30 | 1.363 (4) |
N5—C45 | 1.391 (3) | C29—H29 | 0.9300 |
N5—H5A | 0.8600 | C30—C31 | 1.372 (4) |
N5—H5B | 0.8600 | C30—H30 | 0.9300 |
N6—C45 | 1.333 (3) | C31—C32 | 1.390 (3) |
N6—C46 | 1.343 (3) | C31—H31 | 0.9300 |
N7—C54 | 1.350 (3) | C32—H32 | 0.9300 |
N7—H7A | 0.8600 | C33—C34 | 1.380 (3) |
N7—H7B | 0.8600 | C33—C38 | 1.383 (3) |
N8—C54 | 1.338 (3) | C34—C35 | 1.388 (3) |
N8—C50 | 1.338 (3) | C34—H34 | 0.9300 |
C1—C20 | 1.394 (3) | C35—C36 | 1.372 (4) |
C1—C2 | 1.438 (3) | C35—H35 | 0.9300 |
C2—C3 | 1.344 (3) | C36—C37 | 1.372 (4) |
C2—H2 | 0.9300 | C36—H36 | 0.9300 |
C3—C4 | 1.426 (3) | C37—C38 | 1.386 (3) |
C3—H3 | 0.9300 | C37—H37 | 0.9300 |
C4—C5 | 1.394 (3) | C38—H38 | 0.9300 |
C5—C6 | 1.394 (3) | C39—C44 | 1.392 (3) |
C5—C21 | 1.502 (3) | C39—C40 | 1.393 (3) |
C6—C7 | 1.432 (3) | C40—C41 | 1.379 (3) |
C7—C8 | 1.345 (3) | C40—H40 | 0.9300 |
C7—H7 | 0.9300 | C41—C42 | 1.376 (3) |
C8—C9 | 1.428 (3) | C41—H41 | 0.9300 |
C8—H8 | 0.9300 | C42—C43 | 1.381 (3) |
C9—C10 | 1.392 (3) | C42—H42 | 0.9300 |
C10—C11 | 1.390 (3) | C43—C44 | 1.379 (3) |
C10—C27 | 1.495 (3) | C43—H43 | 0.9300 |
C11—C12 | 1.431 (3) | C44—H44 | 0.9300 |
C12—C13 | 1.345 (3) | C45—C49 | 1.384 (3) |
C12—H12 | 0.9300 | C46—C47 | 1.371 (4) |
C13—C14 | 1.434 (3) | C46—H46 | 0.9300 |
C13—H13 | 0.9300 | C47—C48 | 1.372 (4) |
C14—C15 | 1.391 (3) | C47—H47 | 0.9300 |
C15—C16 | 1.385 (3) | C48—C49 | 1.367 (4) |
C15—C33 | 1.500 (3) | C48—H48 | 0.9300 |
C16—C17 | 1.435 (3) | C49—H49 | 0.9300 |
C17—C18 | 1.345 (3) | C50—C51 | 1.376 (4) |
C17—H17 | 0.9300 | C50—H50 | 0.9300 |
C18—C19 | 1.430 (3) | C51—C52 | 1.374 (5) |
C18—H18 | 0.9300 | C51—H51 | 0.9300 |
C19—C20 | 1.397 (3) | C52—C53 | 1.351 (5) |
C20—C39 | 1.490 (3) | C52—H52 | 0.9300 |
C21—C22 | 1.387 (3) | C53—C54 | 1.409 (4) |
C21—C26 | 1.390 (3) | C53—H53 | 0.9300 |
C22—C23 | 1.386 (3) | ||
N2—Mn—N1 | 89.86 (7) | C24—C23—C22 | 120.4 (2) |
N2—Mn—N3 | 89.23 (7) | C24—C23—H23 | 119.8 |
N1—Mn—N3 | 171.24 (7) | C22—C23—H23 | 119.8 |
N2—Mn—N4 | 170.21 (7) | C23—C24—C25 | 119.5 (2) |
N1—Mn—N4 | 89.56 (7) | C23—C24—H24 | 120.2 |
N3—Mn—N4 | 89.85 (7) | C25—C24—H24 | 120.2 |
N2—Mn—Cl | 97.32 (5) | C26—C25—C24 | 120.6 (2) |
N1—Mn—Cl | 94.06 (5) | C26—C25—H25 | 119.7 |
N3—Mn—Cl | 94.70 (5) | C24—C25—H25 | 119.7 |
N4—Mn—Cl | 92.47 (5) | C25—C26—C21 | 120.4 (2) |
C1—N1—C4 | 106.00 (16) | C25—C26—H26 | 119.8 |
C1—N1—Mn | 125.95 (13) | C21—C26—H26 | 119.8 |
C4—N1—Mn | 127.55 (13) | C32—C27—C28 | 118.5 (2) |
C9—N2—C6 | 106.07 (16) | C32—C27—C10 | 120.9 (2) |
C9—N2—Mn | 127.08 (13) | C28—C27—C10 | 120.6 (2) |
C6—N2—Mn | 126.83 (14) | C29—C28—C27 | 120.6 (2) |
C14—N3—C11 | 106.01 (16) | C29—C28—H28 | 119.7 |
C14—N3—Mn | 126.43 (14) | C27—C28—H28 | 119.7 |
C11—N3—Mn | 126.57 (14) | C30—C29—C28 | 120.2 (3) |
C19—N4—C16 | 106.07 (16) | C30—C29—H29 | 119.9 |
C19—N4—Mn | 126.53 (13) | C28—C29—H29 | 119.9 |
C16—N4—Mn | 126.92 (13) | C29—C30—C31 | 120.2 (2) |
C45—N5—H5A | 120.0 | C29—C30—H30 | 119.9 |
C45—N5—H5B | 120.0 | C31—C30—H30 | 119.9 |
H5A—N5—H5B | 120.0 | C30—C31—C32 | 120.3 (3) |
C45—N6—C46 | 117.3 (2) | C30—C31—H31 | 119.8 |
C54—N7—H7A | 120.0 | C32—C31—H31 | 119.8 |
C54—N7—H7B | 120.0 | C31—C32—C27 | 120.2 (2) |
H7A—N7—H7B | 120.0 | C31—C32—H32 | 119.9 |
C54—N8—C50 | 117.7 (2) | C27—C32—H32 | 119.9 |
N1—C1—C20 | 126.20 (18) | C34—C33—C38 | 118.8 (2) |
N1—C1—C2 | 109.18 (17) | C34—C33—C15 | 119.9 (2) |
C20—C1—C2 | 124.51 (19) | C38—C33—C15 | 121.3 (2) |
C3—C2—C1 | 107.55 (19) | C33—C34—C35 | 120.6 (2) |
C3—C2—H2 | 126.2 | C33—C34—H34 | 119.7 |
C1—C2—H2 | 126.2 | C35—C34—H34 | 119.7 |
C2—C3—C4 | 107.50 (18) | C36—C35—C34 | 120.2 (3) |
C2—C3—H3 | 126.3 | C36—C35—H35 | 119.9 |
C4—C3—H3 | 126.3 | C34—C35—H35 | 119.9 |
N1—C4—C5 | 125.35 (18) | C37—C36—C35 | 119.7 (2) |
N1—C4—C3 | 109.74 (17) | C37—C36—H36 | 120.1 |
C5—C4—C3 | 124.80 (19) | C35—C36—H36 | 120.1 |
C6—C5—C4 | 123.90 (19) | C36—C37—C38 | 120.3 (2) |
C6—C5—C21 | 116.96 (18) | C36—C37—H37 | 119.8 |
C4—C5—C21 | 119.04 (18) | C38—C37—H37 | 119.8 |
N2—C6—C5 | 126.34 (19) | C33—C38—C37 | 120.4 (2) |
N2—C6—C7 | 109.38 (18) | C33—C38—H38 | 119.8 |
C5—C6—C7 | 124.28 (19) | C37—C38—H38 | 119.8 |
C8—C7—C6 | 107.47 (19) | C44—C39—C40 | 118.3 (2) |
C8—C7—H7 | 126.3 | C44—C39—C20 | 119.52 (18) |
C6—C7—H7 | 126.3 | C40—C39—C20 | 122.15 (19) |
C7—C8—C9 | 107.47 (19) | C41—C40—C39 | 120.6 (2) |
C7—C8—H8 | 126.3 | C41—C40—H40 | 119.7 |
C9—C8—H8 | 126.3 | C39—C40—H40 | 119.7 |
N2—C9—C10 | 126.17 (19) | C42—C41—C40 | 120.3 (2) |
N2—C9—C8 | 109.58 (18) | C42—C41—H41 | 119.8 |
C10—C9—C8 | 124.24 (19) | C40—C41—H41 | 119.8 |
C11—C10—C9 | 123.46 (19) | C41—C42—C43 | 120.0 (2) |
C11—C10—C27 | 118.20 (18) | C41—C42—H42 | 120.0 |
C9—C10—C27 | 118.34 (18) | C43—C42—H42 | 120.0 |
N3—C11—C10 | 125.52 (19) | C44—C43—C42 | 119.8 (2) |
N3—C11—C12 | 109.44 (18) | C44—C43—H43 | 120.1 |
C10—C11—C12 | 124.97 (19) | C42—C43—H43 | 120.1 |
C13—C12—C11 | 107.56 (19) | C43—C44—C39 | 120.9 (2) |
C13—C12—H12 | 126.2 | C43—C44—H44 | 119.5 |
C11—C12—H12 | 126.2 | C39—C44—H44 | 119.5 |
C12—C13—C14 | 107.46 (19) | N6—C45—C49 | 122.7 (2) |
C12—C13—H13 | 126.3 | N6—C45—N5 | 115.6 (2) |
C14—C13—H13 | 126.3 | C49—C45—N5 | 121.7 (2) |
N3—C14—C15 | 126.07 (18) | N6—C46—C47 | 123.7 (3) |
N3—C14—C13 | 109.49 (18) | N6—C46—H46 | 118.1 |
C15—C14—C13 | 124.43 (19) | C47—C46—H46 | 118.1 |
C16—C15—C14 | 124.14 (19) | C46—C47—C48 | 117.7 (3) |
C16—C15—C33 | 119.05 (18) | C46—C47—H47 | 121.2 |
C14—C15—C33 | 116.77 (18) | C48—C47—H47 | 121.2 |
N4—C16—C15 | 125.90 (18) | C49—C48—C47 | 120.2 (3) |
N4—C16—C17 | 109.38 (18) | C49—C48—H48 | 119.9 |
C15—C16—C17 | 124.55 (19) | C47—C48—H48 | 119.9 |
C18—C17—C16 | 107.37 (19) | C48—C49—C45 | 118.4 (3) |
C18—C17—H17 | 126.3 | C48—C49—H49 | 120.8 |
C16—C17—H17 | 126.3 | C45—C49—H49 | 120.8 |
C17—C18—C19 | 107.57 (19) | N8—C50—C51 | 123.7 (3) |
C17—C18—H18 | 126.2 | N8—C50—H50 | 118.2 |
C19—C18—H18 | 126.2 | C51—C50—H50 | 118.2 |
N4—C19—C20 | 125.45 (18) | C52—C51—C50 | 117.9 (3) |
N4—C19—C18 | 109.55 (18) | C52—C51—H51 | 121.0 |
C20—C19—C18 | 125.00 (19) | C50—C51—H51 | 121.0 |
C1—C20—C19 | 123.73 (19) | C53—C52—C51 | 120.1 (3) |
C1—C20—C39 | 117.83 (18) | C53—C52—H52 | 119.9 |
C19—C20—C39 | 118.43 (18) | C51—C52—H52 | 119.9 |
C22—C21—C26 | 118.8 (2) | C52—C53—C54 | 119.1 (3) |
C22—C21—C5 | 122.0 (2) | C52—C53—H53 | 120.5 |
C26—C21—C5 | 119.19 (18) | C54—C53—H53 | 120.5 |
C23—C22—C21 | 120.3 (2) | N8—C54—N7 | 116.7 (2) |
C23—C22—H22 | 119.8 | N8—C54—C53 | 121.5 (3) |
C21—C22—H22 | 119.8 | N7—C54—C53 | 121.8 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5A···N8 | 0.86 | 2.29 | 2.993 (3) | 139 |
N7—H7A···N6 | 0.86 | 2.19 | 3.045 (3) | 173 |
N7—H7B···Cli | 0.86 | 2.51 | 3.358 (2) | 169 |
Symmetry code: (i) x+1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5A···N8 | 0.86 | 2.29 | 2.993 (3) | 139 |
N7—H7A···N6 | 0.86 | 2.19 | 3.045 (3) | 173 |
N7—H7B···Cli | 0.86 | 2.51 | 3.358 (2) | 169 |
Symmetry code: (i) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Mn(C44H28N4)Cl]·2C5H6N2 |
Mr | 891.33 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 180 |
a, b, c (Å) | 9.9617 (4), 12.1247 (6), 18.9100 (9) |
α, β, γ (°) | 92.441 (3), 94.699 (2), 108.186 (2) |
V (Å3) | 2157.01 (17) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.42 |
Crystal size (mm) | 0.48 × 0.38 × 0.16 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2006) |
Tmin, Tmax | 0.701, 0.746 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 35821, 8499, 6523 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.107, 1.05 |
No. of reflections | 8487 |
No. of parameters | 577 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.49, −0.37 |
Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008, 2015), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008), WinGX (Farrugia, 2012).