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Acta Cryst. (2007). E63, m2393-m2394    [ doi:10.1107/S1600536807040391 ]

Bis[4'-(4-methylphenyl)-2,2':6',2''-terpyridine-[kappa]3N,N',N'']manganese(II) bis(perchlorate)

H.-G. Liu, Y.-C. Qiu and J.-Z. Wu

Abstract top

In the title complex, [Mn(C22H17N3)2](ClO4)2, the MnN6 coordination geometry is distorted octahedral, involving the six N atoms of two 4'-(4-methylphenyl)-2,2':6',2''-terpyridine (ttp) ligands. The two chelated ttp planes are almost perpendicular, with a dihedral angle of 89.1 (5)°. The packing involves intermolecular C-H...O hydrogen bonds between the ttp ligands and perchlorate anions. The latter are disordered over two positions, one with almost equal occupancy and the other in a ratio of ca 0.7:0.3.

Comment top

Terpyridines are a family of widely used ligands (Schubert et al. 2006). Whereas a large number of metal derivatives of terpyridine and its substituted derivatives have been reported, there are few examples of metal derivatives of 4'-(4-methylphenyl)-2,2':6',2"-terpyridine ligand (denoted as ttp), and examples of crystal structure reports are limited to those of ruthenium (Chamchoumis & Potvin, 1999; Barigelletti et al., 2000; Al-Noaimi et al., 2004), copper (Uma et al., 2005; Yucesan et al., 2005), iridium (Yutaka et al., 2005; Wilkinson et al., 2004) and manganese (Duboc et al., 2006). The complex of Duboc et al. is [Mn(ttp)Cl2], in which Mn(II) is penta-coordinated. Here we report the title structure (I) from a hydrothermal reaction of manganese perchlorate and ttp.

As illustrated in Fig. 1, the Mn(II) centre is coordinated by six N atoms from two ttp ligands, and displays a distorted octahedral geometry. The tri-coordinating mode of the ttp ligands restricts the three pyridyl rings of each ttp and the central Mn(II) ion are very close to be coplanar. Such two planes are almost perpendicular with a dihedral angle of 89.1 (5)°. The two tolyl groups are twisted out of their connected terpyridyl moieties by 35.62 (4)° and 20.23 (6)°, respectively. Both perchlorate anions are disordered and were refined with two sets of disordered O atom positions for each. There are several C—H···O hydrogen bonds (Steiner, 1997) between the ttp ligand and the neighbouring perchloartes which involve the cations and counter-anions (Table 1).

Related literature top

For related literature, see: Al-Noaimi, Yap & Crutchley (2004); Barigelletti et al. (2000); Chamchoumis & Potvin (1999); Collin et al. (1991); Duboc et al. (2006); Schubert et al. (2006); Steiner (1997); Uma et al. (2005); Wang et al. (2007); Wilkinson et al. (2004); Yucesan et al. (2005); Yutaka et al. (2005).

Experimental top

4'-(4-Methylphenyl)-2,2':6',2"-terpyridine (ttp) was prepared by an improved Kröhnke condensation method (Wang et al., 2007; Collin et al., 1991). A mixture of Mn(ClO4)2·6H2O (1 mmol), ttp (2 mmol) and H2O/MeOH (10 ml; 1:1) was placed in a 25 ml of Teflon-lined stainless steel vessel and heated under autogenous pressure at 432 K for 4 days, followed by cooling to room temperature at a rate of 5 K/h. Yellow block crystals of the title complex (I) were obtained in a yield of 38% based on Mn.

Refinement top

Each of the two [ClO4]− moieties was disordered and they were split into two sets of positions, with occupancy ratios of 0.505:0.495 and 0.738:0.262. The intra Cl—O and O—O distances were restrained to be 1.44 (1) and 2.35 (2) Å, respectively. Carbon-bound H atoms were placed at calculated positions and were treated as riding on the parent C atoms with C—H = 0.93 to 0.97 Å, with Uiso(H) = 1.2 or 1.5 Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2004); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The structure of (I), showing the numbering scheme and displacement ellipsoids drawn at the 20% probability level. Only one set of disordered positions for each perchlorate is displayed for clarity.
Bis[4'-(4-methylphenyl)-2,2':6',2''-terpyridine-κ3N,N', N'']manganese(II) bis(perchlorate) top
Crystal data top
[Mn(C22H17N3)2](ClO4)2F000 = 1852
Mr = 900.61Dx = 1.417 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 8356 reflections
a = 18.2372 (4) Åθ = 1.4–28.0º
b = 15.4778 (4) ŵ = 0.50 mm−1
c = 15.9465 (4) ÅT = 293 (2) K
β = 110.339 (2)ºBlock, yellow
V = 4220.60 (18) Å30.25 × 0.19 × 0.16 mm
Z = 4
Data collection top
Bruker APEXII area-detector
diffractometer		8296 independent reflections
Radiation source: fine-focus sealed tube4836 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.090
T = 293(2) Kθmax = 26.0º
φ and ω scansθmin = 1.2º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −22→22
Tmin = 0.885, Tmax = 0.924k = −17→19
45630 measured reflectionsl = −19→19
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.060H-atom parameters constrained
wR(F2) = 0.204  w = 1/[σ2(Fo2) + (0.1047P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.98(Δ/σ)max = 0.002
8296 reflectionsΔρmax = 0.44 e Å−3
644 parametersΔρmin = −0.45 e Å−3
176 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Mn(C22H17N3)2](ClO4)2V = 4220.60 (18) Å3
Mr = 900.61Z = 4
Monoclinic, P21/cMo Kα
a = 18.2372 (4) ŵ = 0.50 mm−1
b = 15.4778 (4) ÅT = 293 (2) K
c = 15.9465 (4) Å0.25 × 0.19 × 0.16 mm
β = 110.339 (2)º
Data collection top
Bruker APEXII area-detector
diffractometer		8296 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		4836 reflections with I > 2σ(I)
Tmin = 0.885, Tmax = 0.924Rint = 0.090
45630 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.060176 restraints
wR(F2) = 0.204H-atom parameters constrained
S = 0.98Δρmax = 0.44 e Å−3
8296 reflectionsΔρmin = −0.45 e Å−3
644 parameters
Special details top

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 (Å2) top
xyzUiso*/UeqOcc. (<1)
C10.7202 (3)0.6693 (3)0.4596 (3)0.0771 (15)
H10.77420.67470.47590.092*
C20.6874 (4)0.6750 (4)0.5240 (4)0.0880 (17)
H20.71850.68370.58350.106*
C30.6072 (4)0.6677 (4)0.4998 (4)0.0935 (18)
H30.58350.67070.54280.112*
C40.5628 (3)0.6559 (4)0.4110 (4)0.0846 (17)
H40.50870.65170.39350.102*
C50.5989 (3)0.6504 (3)0.3479 (3)0.0557 (12)
C60.5569 (3)0.6388 (3)0.2515 (3)0.0545 (11)
C70.4766 (3)0.6394 (3)0.2116 (3)0.0626 (13)
H70.44560.64810.24650.075*
C80.4413 (3)0.6272 (3)0.1198 (3)0.0644 (13)
C90.4919 (3)0.6151 (3)0.0721 (3)0.0632 (13)
H90.47120.60550.01080.076*
C100.5717 (3)0.6171 (3)0.1141 (3)0.0550 (12)
C110.6290 (3)0.6082 (3)0.0682 (3)0.0583 (12)
C120.6073 (3)0.5995 (3)−0.0238 (3)0.0698 (14)
H120.55480.5968−0.05960.084*
C130.6650 (4)0.5951 (4)−0.0612 (3)0.0809 (16)
H130.65160.5887−0.12270.097*
C140.7417 (3)0.6002 (4)−0.0077 (4)0.0814 (16)
H140.78120.5977−0.03190.098*
C150.7593 (3)0.6092 (3)0.0832 (3)0.0757 (15)
H150.81160.61330.11950.091*
C160.3552 (3)0.6262 (3)0.0749 (4)0.0742 (15)
C170.3057 (3)0.6089 (3)0.1227 (4)0.0838 (17)
H170.32660.60050.18420.101*
C180.2248 (3)0.6042 (4)0.0786 (5)0.096 (2)
H180.19240.59400.11150.115*
C190.1920 (4)0.6145 (4)−0.0137 (6)0.105 (2)
C200.2407 (4)0.6317 (5)−0.0603 (5)0.125 (3)
H200.21960.6388−0.12200.150*
C210.3212 (4)0.6388 (4)−0.0173 (5)0.112 (2)
H210.35280.6522−0.05040.134*
C220.1048 (4)0.6031 (6)−0.0606 (6)0.164 (4)
H22A0.09070.5443−0.05450.247*
H22B0.09130.6168−0.12290.247*
H22C0.07720.6410−0.03420.247*
C230.7323 (3)0.8362 (4)0.2579 (3)0.0607 (12)
H230.67900.83010.24660.073*
C240.7615 (3)0.9169 (4)0.2579 (3)0.0695 (14)
H240.72870.96470.24730.083*
C250.8405 (3)0.9271 (4)0.2737 (4)0.0836 (16)
H250.86180.98150.27300.100*
C260.8870 (3)0.8537 (4)0.2909 (4)0.0765 (15)
H260.94050.85850.30240.092*
C270.8542 (3)0.7738 (3)0.2908 (3)0.0526 (11)
C280.8998 (3)0.6925 (3)0.3100 (3)0.0511 (11)
C290.9783 (3)0.6870 (3)0.3250 (3)0.0569 (12)
H291.00570.73680.32140.068*
C301.0176 (3)0.6093 (3)0.3452 (3)0.0576 (12)
C310.9733 (3)0.5368 (3)0.3503 (3)0.0643 (13)
H310.99700.48290.36460.077*
C320.8946 (3)0.5458 (3)0.3341 (3)0.0582 (12)
C330.8412 (3)0.4725 (3)0.3363 (3)0.0661 (13)
C340.8671 (4)0.3912 (4)0.3655 (5)0.097 (2)
H340.92020.37840.38470.117*
C350.8139 (4)0.3288 (4)0.3663 (5)0.113 (2)
H350.83070.27310.38530.135*
C360.7364 (4)0.3486 (4)0.3390 (5)0.105 (2)
H360.69970.30720.33970.126*
C370.7140 (3)0.4313 (4)0.3104 (4)0.0926 (18)
H370.66110.44490.29110.111*
C381.1023 (3)0.6038 (3)0.3604 (3)0.0613 (13)
C391.1345 (3)0.6565 (3)0.3126 (3)0.0739 (15)
H391.10230.69300.26890.089*
C401.2146 (3)0.6558 (4)0.3292 (4)0.0788 (15)
H401.23480.69170.29590.095*
C411.2643 (3)0.6038 (4)0.3929 (4)0.0776 (15)
C421.2313 (3)0.5503 (4)0.4403 (4)0.0874 (18)
H421.26360.51440.48460.105*
C431.1523 (3)0.5490 (4)0.4233 (3)0.0802 (16)
H431.13180.51070.45440.096*
C441.3513 (3)0.6065 (4)0.4123 (4)0.108 (2)
H44A1.36190.63880.36640.162*
H44B1.37080.54860.41370.162*
H44C1.37670.63360.46920.162*
Mn10.73059 (4)0.63041 (5)0.26895 (4)0.0557 (3)
N10.6769 (2)0.6561 (2)0.3723 (2)0.0605 (10)
N20.6036 (2)0.6273 (2)0.2033 (2)0.0541 (9)
N30.7050 (2)0.6124 (2)0.1215 (2)0.0605 (10)
N40.7769 (2)0.7645 (2)0.2734 (2)0.0548 (9)
N50.8585 (2)0.6222 (2)0.3133 (2)0.0542 (9)
N60.7649 (2)0.4934 (3)0.3088 (3)0.0692 (11)
Cl1A0.9435 (4)0.7412 (4)0.5646 (5)0.103 (2)0.505 (7)
Cl2A0.50345 (19)0.9028 (2)0.1940 (2)0.0725 (12)0.739 (9)
O1A0.8876 (6)0.7478 (8)0.6104 (6)0.155 (4)0.505 (7)
O2A1.0179 (6)0.7748 (10)0.6119 (10)0.200 (7)0.505 (7)
O3A0.9374 (5)0.6574 (5)0.5272 (6)0.119 (4)0.505 (7)
O4A0.9015 (7)0.8002 (7)0.4925 (7)0.164 (5)0.505 (7)
O5A0.5726 (3)0.9584 (4)0.2206 (5)0.106 (2)0.739 (9)
O6A0.5221 (5)0.8284 (4)0.1549 (6)0.131 (3)0.739 (9)
O7A0.4830 (5)0.8790 (7)0.2698 (5)0.134 (3)0.739 (9)
O8A0.4411 (3)0.9499 (5)0.1343 (4)0.121 (3)0.739 (9)
Cl1B0.9560 (5)0.7580 (7)0.5794 (7)0.164 (4)0.495 (7)
Cl2B0.5018 (10)0.8960 (11)0.2035 (11)0.167 (7)0.261 (9)
O1B0.9831 (7)0.7036 (7)0.6559 (6)0.146 (4)0.495 (7)
O2B1.0134 (6)0.7686 (8)0.5385 (8)0.151 (5)0.495 (7)
O3B0.8915 (9)0.7227 (15)0.5115 (11)0.291 (9)0.495 (7)
O4B0.9392 (9)0.8412 (9)0.6074 (10)0.228 (6)0.495 (7)
O5B0.5485 (16)0.9575 (18)0.1749 (18)0.197 (10)0.261 (9)
O6B0.5510 (11)0.8237 (12)0.2409 (19)0.168 (9)0.261 (9)
O7B0.4791 (13)0.9387 (15)0.2706 (14)0.139 (8)0.261 (9)
O8B0.4373 (11)0.867 (2)0.1298 (13)0.176 (9)0.261 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.087 (4)0.077 (4)0.063 (3)0.000 (3)0.021 (3)0.004 (3)
C20.120 (5)0.088 (4)0.061 (3)−0.009 (4)0.037 (4)0.001 (3)
C30.129 (6)0.091 (5)0.085 (4)−0.001 (4)0.069 (4)0.002 (3)
C40.088 (4)0.099 (5)0.077 (4)−0.006 (3)0.041 (3)−0.010 (3)
C50.062 (3)0.053 (3)0.060 (3)−0.006 (2)0.031 (2)−0.001 (2)
C60.056 (3)0.049 (3)0.062 (3)−0.001 (2)0.026 (2)0.000 (2)
C70.056 (3)0.059 (3)0.082 (3)−0.005 (2)0.036 (3)0.003 (3)
C80.065 (3)0.045 (3)0.082 (3)−0.004 (2)0.023 (3)0.004 (2)
C90.066 (3)0.058 (3)0.062 (3)−0.009 (2)0.019 (2)−0.005 (2)
C100.060 (3)0.050 (3)0.056 (3)−0.012 (2)0.021 (2)−0.006 (2)
C110.070 (3)0.055 (3)0.057 (3)−0.014 (2)0.031 (2)−0.005 (2)
C120.076 (3)0.071 (4)0.068 (3)−0.021 (3)0.032 (3)−0.013 (3)
C130.108 (5)0.082 (4)0.066 (3)−0.021 (3)0.046 (3)−0.017 (3)
C140.095 (4)0.083 (4)0.085 (4)−0.019 (3)0.056 (3)−0.022 (3)
C150.073 (3)0.092 (4)0.073 (3)−0.010 (3)0.039 (3)−0.015 (3)
C160.059 (3)0.057 (3)0.096 (4)−0.004 (3)0.014 (3)0.011 (3)
C170.059 (3)0.080 (4)0.115 (4)−0.001 (3)0.034 (3)−0.006 (3)
C180.059 (4)0.074 (4)0.155 (6)0.002 (3)0.038 (4)−0.012 (4)
C190.061 (4)0.084 (5)0.147 (6)0.005 (3)0.009 (4)0.013 (4)
C200.076 (5)0.131 (7)0.136 (6)−0.001 (4)−0.004 (4)0.050 (5)
C210.073 (4)0.121 (6)0.126 (5)−0.006 (4)0.015 (4)0.047 (4)
C220.065 (4)0.175 (9)0.206 (9)0.011 (5)−0.014 (5)0.010 (7)
C230.066 (3)0.062 (4)0.063 (3)0.010 (3)0.034 (2)0.003 (2)
C240.074 (4)0.061 (4)0.082 (3)0.019 (3)0.038 (3)0.011 (3)
C250.089 (4)0.049 (4)0.126 (5)0.004 (3)0.054 (4)0.007 (3)
C260.055 (3)0.062 (4)0.116 (4)0.002 (3)0.034 (3)0.007 (3)
C270.053 (3)0.053 (3)0.056 (3)−0.001 (2)0.025 (2)−0.001 (2)
C280.054 (3)0.050 (3)0.051 (2)0.001 (2)0.021 (2)−0.001 (2)
C290.054 (3)0.053 (3)0.066 (3)−0.002 (2)0.024 (2)0.003 (2)
C300.059 (3)0.057 (3)0.059 (3)0.003 (2)0.022 (2)−0.001 (2)
C310.060 (3)0.055 (3)0.080 (3)0.011 (3)0.026 (2)0.003 (3)
C320.060 (3)0.053 (3)0.065 (3)0.002 (2)0.025 (2)0.000 (2)
C330.059 (3)0.058 (4)0.084 (3)0.000 (3)0.030 (3)0.001 (3)
C340.083 (4)0.054 (4)0.160 (6)0.010 (3)0.050 (4)0.015 (4)
C350.111 (6)0.059 (4)0.175 (7)−0.007 (4)0.059 (5)0.019 (4)
C360.088 (5)0.069 (5)0.167 (6)−0.015 (4)0.058 (4)0.009 (4)
C370.072 (4)0.067 (4)0.147 (5)−0.011 (3)0.049 (4)0.010 (4)
C380.054 (3)0.064 (3)0.069 (3)0.003 (2)0.025 (2)−0.003 (3)
C390.057 (3)0.079 (4)0.089 (4)0.007 (3)0.029 (3)0.014 (3)
C400.062 (3)0.087 (4)0.089 (4)0.000 (3)0.029 (3)0.007 (3)
C410.054 (3)0.090 (4)0.089 (4)0.000 (3)0.026 (3)−0.010 (3)
C420.065 (4)0.107 (5)0.082 (4)0.026 (3)0.015 (3)0.012 (3)
C430.068 (4)0.092 (4)0.081 (3)0.016 (3)0.028 (3)0.016 (3)
C440.057 (4)0.144 (6)0.125 (5)0.005 (4)0.033 (3)−0.009 (4)
Mn10.0487 (4)0.0608 (5)0.0601 (4)−0.0020 (3)0.0222 (3)−0.0027 (3)
N10.067 (3)0.061 (3)0.057 (2)−0.003 (2)0.025 (2)0.0038 (19)
N20.059 (2)0.054 (2)0.054 (2)−0.0068 (18)0.0249 (18)−0.0054 (17)
N30.059 (2)0.067 (3)0.060 (2)−0.010 (2)0.027 (2)−0.0097 (19)
N40.053 (2)0.059 (3)0.058 (2)0.0064 (19)0.0251 (17)−0.0008 (18)
N50.059 (2)0.046 (3)0.061 (2)−0.001 (2)0.0239 (18)−0.0036 (18)
N60.063 (3)0.056 (3)0.095 (3)−0.007 (2)0.037 (2)0.003 (2)
Cl1A0.064 (3)0.143 (4)0.086 (3)0.013 (3)0.006 (2)−0.028 (3)
Cl2A0.065 (2)0.077 (2)0.0813 (19)0.0177 (15)0.0326 (15)0.0062 (14)
O1A0.154 (8)0.206 (11)0.118 (7)0.024 (8)0.065 (6)−0.052 (7)
O2A0.100 (7)0.234 (13)0.211 (13)−0.002 (8)−0.017 (7)−0.091 (11)
O3A0.098 (6)0.144 (7)0.096 (6)0.034 (5)0.008 (5)−0.042 (5)
O4A0.158 (9)0.174 (9)0.138 (8)0.041 (8)0.025 (6)0.035 (7)
O5A0.082 (4)0.100 (5)0.127 (5)−0.011 (3)0.024 (3)−0.002 (4)
O6A0.168 (7)0.068 (4)0.194 (7)0.002 (4)0.111 (6)−0.016 (4)
O7A0.110 (5)0.213 (10)0.094 (4)0.014 (6)0.056 (4)0.030 (5)
O8A0.094 (4)0.132 (6)0.115 (4)0.031 (4)0.010 (3)0.026 (4)
Cl1B0.086 (5)0.301 (10)0.098 (4)0.035 (5)0.024 (4)−0.063 (5)
Cl2B0.116 (12)0.184 (15)0.182 (14)0.005 (9)0.029 (9)−0.003 (11)
O1B0.160 (9)0.198 (10)0.123 (7)−0.022 (7)0.104 (6)−0.049 (6)
O2B0.128 (8)0.193 (11)0.157 (9)0.048 (7)0.079 (7)0.047 (8)
O3B0.176 (11)0.421 (19)0.226 (13)−0.096 (14)0.006 (10)−0.041 (13)
O4B0.201 (12)0.299 (13)0.179 (11)0.104 (11)0.060 (9)−0.021 (9)
O5B0.177 (19)0.208 (19)0.20 (2)−0.025 (15)0.061 (14)0.009 (16)
O6B0.111 (13)0.149 (15)0.215 (19)0.007 (10)0.020 (12)−0.020 (13)
O7B0.105 (13)0.121 (16)0.167 (15)−0.005 (11)0.018 (10)−0.009 (12)
O8B0.126 (14)0.22 (2)0.152 (15)0.008 (13)0.017 (11)−0.020 (14)
Geometric parameters (Å, °) top
C1—N11.357 (6)C28—N51.334 (5)
C1—C21.359 (7)C28—C291.370 (6)
C1—H10.9300C29—C301.380 (6)
C2—C31.382 (7)C29—H290.9300
C2—H20.9300C30—C311.403 (6)
C3—C41.377 (7)C30—C381.480 (6)
C3—H30.9300C31—C321.373 (6)
C4—C51.383 (7)C31—H310.9300
C4—H40.9300C32—N51.339 (5)
C5—N11.341 (5)C32—C331.503 (6)
C5—C61.472 (6)C33—N61.346 (6)
C6—N21.343 (5)C33—C341.368 (7)
C6—C71.379 (6)C34—C351.373 (8)
C7—C81.392 (7)C34—H340.9300
C7—H70.9300C35—C361.360 (8)
C8—C91.398 (7)C35—H350.9300
C8—C161.481 (7)C36—C371.372 (8)
C9—C101.374 (6)C36—H360.9300
C9—H90.9300C37—N61.342 (6)
C10—N21.346 (5)C37—H370.9300
C10—C111.476 (6)C38—C391.379 (7)
C11—N31.352 (6)C38—C431.386 (6)
C11—C121.386 (6)C39—C401.391 (6)
C12—C131.380 (7)C39—H390.9300
C12—H120.9300C40—C411.364 (7)
C13—C141.365 (7)C40—H400.9300
C13—H130.9300C41—C421.391 (8)
C14—C151.377 (7)C41—C441.508 (7)
C14—H140.9300C42—C431.371 (7)
C15—N31.333 (6)C42—H420.9300
C15—H150.9300C43—H430.9300
C16—C171.395 (7)C44—H44A0.9600
C16—C211.397 (8)C44—H44B0.9600
C17—C181.397 (7)C44—H44C0.9600
C17—H170.9300Mn1—N22.185 (4)
C18—C191.392 (9)Mn1—N52.193 (4)
C18—H180.9300Mn1—N12.225 (4)
C19—C201.368 (10)Mn1—N42.233 (4)
C19—C221.514 (8)Mn1—N62.240 (4)
C20—C211.392 (8)Mn1—N32.250 (4)
C20—H200.9300Cl1A—O2A1.404 (8)
C21—H210.9300Cl1A—O3A1.416 (8)
C22—H22A0.9600Cl1A—O1A1.448 (8)
C22—H22B0.9600Cl1A—O4A1.459 (8)
C22—H22C0.9600Cl2A—O6A1.406 (6)
C23—N41.347 (6)Cl2A—O8A1.407 (5)
C23—C241.358 (7)Cl2A—O7A1.431 (6)
C23—H230.9300Cl2A—O5A1.462 (5)
C24—C251.382 (7)Cl1B—O3B1.403 (9)
C24—H240.9300Cl1B—O1B1.422 (9)
C25—C261.388 (7)Cl1B—O2B1.423 (9)
C25—H250.9300Cl1B—O4B1.430 (9)
C26—C271.373 (6)Cl2B—O8B1.416 (10)
C26—H260.9300Cl2B—O6B1.430 (10)
C27—N41.347 (5)Cl2B—O7B1.435 (10)
C27—C281.481 (6)Cl2B—O5B1.452 (10)
N1—C1—C2122.2 (5)C31—C32—C33124.2 (4)
N1—C1—H1118.9N6—C33—C34121.8 (5)
C2—C1—H1118.9N6—C33—C32114.7 (4)
C1—C2—C3119.0 (5)C34—C33—C32123.5 (5)
C1—C2—H2120.5C33—C34—C35119.3 (6)
C3—C2—H2120.5C33—C34—H34120.3
C4—C3—C2119.0 (5)C35—C34—H34120.3
C4—C3—H3120.5C36—C35—C34119.8 (6)
C2—C3—H3120.5C36—C35—H35120.1
C3—C4—C5119.9 (5)C34—C35—H35120.1
C3—C4—H4120.1C35—C36—C37118.2 (6)
C5—C4—H4120.1C35—C36—H36120.9
N1—C5—C4120.7 (4)C37—C36—H36120.9
N1—C5—C6115.2 (4)N6—C37—C36123.1 (5)
C4—C5—C6124.1 (5)N6—C37—H37118.4
N2—C6—C7121.3 (4)C36—C37—H37118.4
N2—C6—C5114.2 (4)C39—C38—C43117.6 (5)
C7—C6—C5124.4 (4)C39—C38—C30119.7 (4)
C6—C7—C8120.9 (5)C43—C38—C30122.7 (5)
C6—C7—H7119.5C38—C39—C40120.7 (5)
C8—C7—H7119.5C38—C39—H39119.6
C7—C8—C9116.0 (4)C40—C39—H39119.6
C7—C8—C16122.3 (5)C41—C40—C39121.9 (5)
C9—C8—C16121.7 (5)C41—C40—H40119.0
C10—C9—C8121.3 (4)C39—C40—H40119.0
C10—C9—H9119.3C40—C41—C42117.0 (5)
C8—C9—H9119.3C40—C41—C44121.1 (6)
N2—C10—C9120.8 (4)C42—C41—C44121.9 (5)
N2—C10—C11114.5 (4)C43—C42—C41121.6 (5)
C9—C10—C11124.7 (4)C43—C42—H42119.2
N3—C11—C12121.6 (4)C41—C42—H42119.2
N3—C11—C10115.6 (4)C42—C43—C38121.1 (5)
C12—C11—C10122.8 (4)C42—C43—H43119.5
C13—C12—C11118.8 (5)C38—C43—H43119.5
C13—C12—H12120.6N2—Mn1—N5169.82 (13)
C11—C12—H12120.6N2—Mn1—N172.13 (13)
C14—C13—C12119.7 (5)N5—Mn1—N1117.65 (13)
C14—C13—H13120.1N2—Mn1—N4111.21 (13)
C12—C13—H13120.1N5—Mn1—N472.26 (14)
C13—C14—C15118.5 (5)N1—Mn1—N494.00 (13)
C13—C14—H14120.7N2—Mn1—N6105.07 (14)
C15—C14—H14120.7N5—Mn1—N672.12 (14)
N3—C15—C14123.2 (5)N1—Mn1—N696.33 (14)
N3—C15—H15118.4N4—Mn1—N6143.71 (14)
C14—C15—H15118.4N2—Mn1—N372.32 (14)
C17—C16—C21117.8 (5)N5—Mn1—N398.07 (14)
C17—C16—C8121.1 (5)N1—Mn1—N3144.22 (14)
C21—C16—C8121.0 (6)N4—Mn1—N394.98 (13)
C16—C17—C18120.4 (6)N6—Mn1—N396.61 (14)
C16—C17—H17119.8C5—N1—C1119.2 (4)
C18—C17—H17119.8C5—N1—Mn1118.0 (3)
C19—C18—C17121.1 (6)C1—N1—Mn1122.5 (3)
C19—C18—H18119.5C6—N2—C10119.5 (4)
C17—C18—H18119.5C6—N2—Mn1120.0 (3)
C20—C19—C18118.4 (6)C10—N2—Mn1120.4 (3)
C20—C19—C22121.5 (7)C15—N3—C11118.1 (4)
C18—C19—C22120.1 (7)C15—N3—Mn1124.6 (3)
C19—C20—C21121.3 (7)C11—N3—Mn1117.3 (3)
C19—C20—H20119.3C27—N4—C23118.2 (4)
C21—C20—H20119.3C27—N4—Mn1117.6 (3)
C20—C21—C16120.9 (7)C23—N4—Mn1124.2 (3)
C20—C21—H21119.5C28—N5—C32119.6 (4)
C16—C21—H21119.5C28—N5—Mn1119.5 (3)
N4—C23—C24123.1 (5)C32—N5—Mn1120.5 (3)
N4—C23—H23118.5C37—N6—C33117.7 (5)
C24—C23—H23118.5C37—N6—Mn1123.9 (4)
C23—C24—C25119.3 (5)C33—N6—Mn1118.3 (3)
C23—C24—H24120.4O2A—Cl1A—O3A119.0 (8)
C25—C24—H24120.4O2A—Cl1A—O1A114.9 (9)
C24—C25—C26118.0 (5)O3A—Cl1A—O1A108.1 (7)
C24—C25—H25121.0O2A—Cl1A—O4A109.7 (9)
C26—C25—H25121.0O3A—Cl1A—O4A107.5 (8)
C27—C26—C25120.0 (5)O1A—Cl1A—O4A94.8 (7)
C27—C26—H26120.0O6A—Cl2A—O8A112.8 (5)
C25—C26—H26120.0O6A—Cl2A—O7A109.8 (5)
N4—C27—C26121.4 (4)O8A—Cl2A—O7A108.6 (5)
N4—C27—C28115.0 (4)O6A—Cl2A—O5A107.1 (4)
C26—C27—C28123.5 (4)O8A—Cl2A—O5A107.7 (4)
N5—C28—C29120.9 (4)O7A—Cl2A—O5A111.0 (5)
N5—C28—C27114.7 (4)O3B—Cl1B—O1B112.3 (12)
C29—C28—C27124.4 (4)O3B—Cl1B—O2B104.1 (10)
C28—C29—C30121.4 (4)O1B—Cl1B—O2B111.7 (8)
C28—C29—H29119.3O3B—Cl1B—O4B112.2 (11)
C30—C29—H29119.3O1B—Cl1B—O4B108.3 (9)
C29—C30—C31116.6 (4)O2B—Cl1B—O4B108.1 (10)
C29—C30—C38121.1 (4)O8B—Cl2B—O6B108.5 (13)
C31—C30—C38122.3 (4)O8B—Cl2B—O7B113.2 (13)
C32—C31—C30119.6 (4)O6B—Cl2B—O7B110.5 (13)
C32—C31—H31120.2O8B—Cl2B—O5B110.9 (14)
C30—C31—H31120.2O6B—Cl2B—O5B106.9 (13)
N5—C32—C31121.9 (4)O7B—Cl2B—O5B106.6 (13)
N5—C32—C33113.9 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C1—H1···O3B0.932.153.055 (15)165
C3—H3···O6Ai0.932.423.347 (9)176
C13—H13···O5Aii0.932.523.400 (9)158
C15—H15···O4Bii0.932.503.260 (16)139
C22—H22C···O2Biii0.962.373.324 (14)177
C23—H23···O6B0.932.313.23 (2)171
C34—H34···O3Aiv0.932.553.458 (11)167
C34—H34···O1Biv0.932.443.223 (12)142
C37—H37···O8Av0.932.543.255 (9)134
C37—H37···O7Bv0.932.403.31 (2)164
C39—H39···O2Aii0.932.493.341 (12)152
C44—H44C···O8Bvi0.962.413.30 (2)153
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x, −y+3/2, z−1/2; (iii) x−1, −y+3/2, z−1/2; (iv) −x+2, −y+1, −z+1; (v) −x+1, y−1/2, −z+1/2; (vi) x+1, −y+3/2, z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C1—H1···O3B0.932.153.055 (15)165
C3—H3···O6Ai0.932.423.347 (9)176
C13—H13···O5Aii0.932.523.400 (9)158
C15—H15···O4Bii0.932.503.260 (16)139
C22—H22C···O2Biii0.962.373.324 (14)177
C23—H23···O6B0.932.313.23 (2)171
C34—H34···O3Aiv0.932.553.458 (11)167
C34—H34···O1Biv0.932.443.223 (12)142
C37—H37···O8Av0.932.543.255 (9)134
C37—H37···O7Bv0.932.403.31 (2)164
C39—H39···O2Aii0.932.493.341 (12)152
C44—H44C···O8Bvi0.962.413.30 (2)153
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x, −y+3/2, z−1/2; (iii) x−1, −y+3/2, z−1/2; (iv) −x+2, −y+1, −z+1; (v) −x+1, y−1/2, −z+1/2; (vi) x+1, −y+3/2, z+1/2.
Acknowledgements top

The authors acknowledge the Guangdong Natural Science Foundation (grant No. 5005935) and the SRFROCS, State Education Ministry of China, for financial support.

references
References top

Al-Noaimi, M., Yap, G. P. A. & Crutchley, R. J. (2004). Inorg. Chem. 43, 1770–1778.

Barigelletti, F., Ventura, B., Collin, J. P., Kayhanian, P., Gavina, R. & Sauvage, J.-P. (2000). Eur. J. Inorg. Chem. pp. 113–119.

Bruker (2004). APEX2 (Version 6.12), SMART (Version 6.12) [Should this be SAINT?] and SHELXTL (Version?). Bruker AXS Inc, Madison, Wisconsin, USA.

Chamchoumis, C. M. & Potvin, P. G. (1999). J. Chem. Soc. Dalton Trans. pp. 1373–1374.

Collin, J. P., Guillerez, S., Sauvage, J. P., Barigelletti, F., De Cola, L., Flamigni, L. & Balzani, V. (1991). Inorg. Chem. 30, 4230—4238.

Duboc, C., Astier-Perret, U., Chen, H.-Y., Pecaut, J., Crabtree, R. H., Brudvig, G. W. & Collomb, M.-N. (2006). Inorg. Chim. Acta, 359, 1541–1548.

Schubert, U. S., Hofmeier, H. & Newkome, G. R. (2006). Modern Terpyridine Chemistry. Weinheim: Wiley–VCH.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.

Steiner, T. (1997). J. Chem. Soc. Chem. Commun. pp. 727–734.

Uma, U., Vaidyanathan, U. G. & Nair, B. U. (2005). Bull. Chem. Soc. Jpn, 78, 845–850.

Wang, X.-X., Liu, H.-G., Wan, X., Yin, X., Zhou, F.-S. & Wu, J.-Z. (2007). Chem. Reagnts (Huaxue Shiji), 29, 247–248.

Wilkinson, A. J., Goeta, A. E., Foster, C. E. & Williams, J. A. G. (2004). Inorg. Chem. 43, 6513–6515.

Yucesan, G., Yu, M. H., O'Connor, C. J. & Zubieta, J. (2005). CrystEngComm, 7, 711–721.

Yutaka, T., Obara, S., Haga, M., Yokoyama, Y. & Sakai, K. (2005). Acta Cryst. E61, m1357–m1359.