supplementary materials


lh5631 scheme

Acta Cryst. (2013). E69, m471    [ doi:10.1107/S1600536813019338 ]

[5,10,15,20-Tetrakis(4-methoxyphenyl)porphyrinato]zinc dichloromethane disolvate

S. McGill, V. N. Nesterov and S. L. Gould

Abstract top

In the title compound, [Zn(C48H36N4O4)]·2CH2Cl2, the ZnII ion lies on an inversion center and is coordinated in an almost ideal square-planar geometry. The asymmetric unit also contains one dichloromethane solvent molecule. The unique methoxy-substituted benzene rings form dihedral angles of 59.38 (6) and 66.77 (6)° with the mean plane (r.m.s. deviation of fitted atoms = 0.0282 Å) of the atoms in the porphyrin core. The packing is characterized by close contacts between the ZnII ion and two symmetry-related molecules through the O atoms of a methoxyphenyl group [Zn...O = 2.694 (2) Å], forming a two-dimensional network parallel to (100).

Comment top

While in pursuit of understanding zinc porphyrin coordination to alkyl alcohol solvents through the central zinc atom, we sought to crystallize zinc 5,10,15,20-tetrakis(p-methoxyphenyl)porphyrin with octanol. The resulting deep red crystals did not contain any octanol coordination, but contained a well ordered porphyrin structure with dichloromethane solvent molecules. The crystal structure of the title compound is presented herein.

The title porphyrin (Fig. 1) has a zinc atom located on a center of inversion and hence the exact center of the mean-plane of the 24 other Non-H atoms with a r.m.s. deviation of the fitted atom = 0.0288Å. The p-methoxy-substituted benzene rings form dihedral angles of 59.38 (6)° (C11-C16) and 66.77 (6)° (C17-C22) with the porphyrin mean plane. The crystal packing (Fig. 2) is characterized by close contacts between the ZnII ion with two symmetry related molecules (-x+1, y-1/2, -z+1/2 and x, -y+3/2, z+1/2) through the oxygen atoms of a methoxy-phenyl group (Zn···O = 2.694 (2) Å) forming a two-dimensional network parallel to (100). This distance is smaller than the sum of corresponding Van der Waals radii of atoms 2.910 Å (Bondi, 1964). There are some reports of Zn···O coordination bonds in porphyrins (Bhuyan & Sarkar, 2011; Adilov & Thalladi, 2007; Teo et al., 2003). These reports indicate a bond distance shorter than what is found in the title compound.

Related literature top

For related structures, see: Adilov & Thalladi (2007); Bhuyan & Sarkar (2011); Teo et al. (2003). For the synthesis, see: Adler et al. (1967). For van der Waals radii, see: Bondi (1964).

Experimental top

The synthesis of the title Zn complex was carried out according literature procedures (Adler et al., 1967). Dark red crystals were grown by liquid diffusion of 1 ml octanol into a 3 ml dichloromethane solution containing 20 mg of zinc 5,10,15,20-tetrakis- (p-methoxyphenyl)porphyrin.

Refinement top

All H atoms attached to C atoms were placed in idealized positions (C—H = 0.95–0.99 Å) and allowed to ride on their parent atoms. All H atoms were constrained so that Uiso(H) were equal to 1.2Ueq or 1.5Ueq of their respective parent atoms.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title complex with 50% probability displacement ellipsoids. The solvent molecules are not shown [symmetry code: (A) -x+1, -y+1, -z+1].
[Figure 2] Fig. 2. Part of the crystal structure of the title compound viewed approximately along the b axis. The short Zn···O contacts are shown as dashed lines.
[5,10,15,20-Tetrakis(4-methoxyphenyl)porphyrinato]zinc dichloromethane disolvate top
Crystal data top
[Zn(C48H36N4O4)]·2CH2Cl2F(000) = 996
Mr = 968.03Dx = 1.491 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 8489 reflections
a = 11.4189 (9) Åθ = 2.2–27.1°
b = 10.6877 (9) ŵ = 0.87 mm1
c = 18.3778 (15) ÅT = 100 K
β = 106.022 (1)°Plate, red
V = 2155.7 (3) Å30.18 × 0.16 × 0.09 mm
Z = 2
Data collection top
Bruker APEXII CCD
diffractometer
4763 independent reflections
Radiation source: fine-focus sealed tube4022 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.036
ω scansθmax = 27.1°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
h = 1414
Tmin = 0.861, Tmax = 0.926k = 1313
25964 measured reflectionsl = 2323
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.121H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.065P)2 + 2.750P]
where P = (Fo2 + 2Fc2)/3
4763 reflections(Δ/σ)max = 0.001
288 parametersΔρmax = 0.52 e Å3
0 restraintsΔρmin = 0.78 e Å3
Crystal data top
[Zn(C48H36N4O4)]·2CH2Cl2V = 2155.7 (3) Å3
Mr = 968.03Z = 2
Monoclinic, P21/cMo Kα radiation
a = 11.4189 (9) ŵ = 0.87 mm1
b = 10.6877 (9) ÅT = 100 K
c = 18.3778 (15) Å0.18 × 0.16 × 0.09 mm
β = 106.022 (1)°
Data collection top
Bruker APEXII CCD
diffractometer
4763 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
4022 reflections with I > 2σ(I)
Tmin = 0.861, Tmax = 0.926Rint = 0.036
25964 measured reflectionsθmax = 27.1°
Refinement top
R[F2 > 2σ(F2)] = 0.039H-atom parameters constrained
wR(F2) = 0.121Δρmax = 0.52 e Å3
S = 1.06Δρmin = 0.78 e Å3
4763 reflectionsAbsolute structure: ?
288 parametersAbsolute structure parameter: ?
0 restraintsRogers parameter: ?
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.

_iucr_refine_instructions_details

TITL 163p21c in P2(1)/c CELL 0.71073 11.4189 10.6877 18.3778 90.000 106.022 90.000 ZERR 2.00 0.0009 0.0009 0.0015 0.000 0.001 0.000 L A T T 1 SYMM –X, 0.5+Y, 0.5-Z SFAC C H N O Cl ZN UNIT 100 80 8 8 8 2 TEMP -173.150 SIZE 0.09 0.157 0.178 acta L.S. 9 BOND $h htab FMAP 2 PLAN 20

WGHT 0.065000 2.750000 FVAR 0.12081 ZN1 6 0.500000 0.500000 0.500000 10.50000 0.01678 0.01721 = 0.01254 0.00333 0.00769 0.00349 O1 4 1.215897 0.070221 0.601887 11.00000 0.01859 0.02001 = 0.02872 0.00177 0.00721 0.00549 O2 4 0.617130 0.788402 0.058282 11.00000 0.02840 0.02118 = 0.01396 0.00475 0.01136 0.00312 N1 3 0.410408 0.615123 0.412964 11.00000 0.01692 0.01511 = 0.01311 0.00039 0.00676 0.00050 N2 3 0.630415 0.466937 0.445394 11.00000 0.01750 0.01366 = 0.01246 0.00085 0.00608 0.00049 C1 1 0.302121 0.675600 0.406600 11.00000 0.01653 0.01391 = 0.01524 0.00044 0.00463 - 0.00014 C2 1 0.266170 0.741753 0.335325 11.00000 0.01740 0.01863 = 0.01566 0.00210 0.00419 0.00153 AFIX 43 H2A 2 0.194325 0.790159 0.316778 11.00000 - 1.20000 AFIX 0 C3 1 0.353693 0.721983 0.299961 11.00000 0.01963 0.01661 = 0.01433 0.00141 0.00568 - 0.00002 AFIX 43 H3A 2 0.355265 0.754260 0.252075 11.00000 - 1.20000 AFIX 0 C4 1 0.444551 0.642392 0.348779 11.00000 0.01762 0.01207 = 0.01339 0.00017 0.00512 - 0.00192 C5 1 0.548850 0.596671 0.331170 11.00000 0.01924 0.01268 = 0.01263 - 0.00106 0.00673 - 0.00246 C6 1 0.633224 0.513271 0.375828 11.00000 0.01723 0.01172 = 0.01311 - 0.00145 0.00686 - 0.00166 C7 1 0.738278 0.463970 0.356292 11.00000 0.01956 0.01661 = 0.01515 - 0.00103 0.00926 - 0.00044 AFIX 43 H7A 2 0.761143 0.480938 0.311343 11.00000 - 1.20000 AFIX 0 C8 1 0.798041 0.389162 0.413882 11.00000 0.01869 0.01599 = 0.01913 - 0.00014 0.01026 0.00066 AFIX 43 H8A 2 0.870486 0.343287 0.416895 11.00000 - 1.20000 AFIX 0 C9 1 0.730571 0.392137 0.470333 11.00000 0.01660 0.01504 = 0.01487 - 0.00104 0.00680 - 0.00111 C10 1 0.764935 0.327078 0.539542 11.00000 0.01688 0.01429 = 0.01636 - 0.00005 0.00623 0.00044 C11 1 0.882439 0.256555 0.556928 11.00000 0.01883 0.01725 = 0.01269 0.00138 0.00620 0.00189 C12 1 0.886843 0.127741 0.569024 11.00000 0.02077 0.01874 = 0.01776 0.00116 0.00814 - 0.00120 AFIX 43 H12A 2 0.813634 0.083729 0.566740 11.00000 - 1.20000 AFIX 0 C13 1 0.996564 0.062037 0.584423 11.00000 0.02345 0.01568 = 0.01776 0.00253 0.00807 0.00209 AFIX 43 H13A 2 0.997909 - 0.025748 0.592730 11.00000 - 1.20000 AFIX 0 C14 1 1.103618 0.125745 0.587519 11.00000 0.01951 0.02112 = 0.01535 - 0.00155 0.00576 0.00383 C15 1 1.100728 0.254478 0.575797 11.00000 0.01912 0.02027 = 0.02373 - 0.00157 0.00886 - 0.00081 AFIX 43 H15A 2 1.174018 0.298301 0.578027 11.00000 - 1.20000 AFIX 0 C16 1 0.991627 0.318901 0.560914 11.00000 0.02134 0.01621 = 0.01980 0.00049 0.00826 0.00002 AFIX 43 H16A 2 0.990892 0.406844 0.553285 11.00000 - 1.20000 AFIX 0 C17 1 0.571704 0.642689 0.259171 11.00000 0.01524 0.01694 = 0.01331 0.00207 0.00612 0.00109 C18 1 0.597241 0.768808 0.251103 11.00000 0.02074 0.01577 = 0.01549 - 0.00087 0.00781 0.00184 AFIX 43 H18A 2 0.603759 0.824277 0.292425 11.00000 - 1.20000 AFIX 0 C19 1 0.613282 0.814710 0.183941 11.00000 0.02334 0.01448 = 0.01985 0.00372 0.00912 0.00164 AFIX 43 H19A 2 0.631183 0.900746 0.179633 11.00000 - 1.20000 AFIX 0 C20 1 0.603100 0.734439 0.122807 11.00000 0.01661 0.02078 = 0.01560 0.00552 0.00780 0.00353 C21 1 0.582218 0.607487 0.130536 11.00000 0.02425 0.02019 = 0.01444 - 0.00264 0.00848 - 0.00086 AFIX 43 H21A 2 0.578898 0.551546 0.089844 11.00000 - 1.20000 AFIX 0 C22 1 0.566208 0.563057 0.198474 11.00000 0.02182 0.01565 = 0.01723 0.00058 0.00701 - 0.00171 AFIX 43 H22A 2 0.551213 0.476471 0.203412 11.00000 - 1.20000 AFIX 0 C23 1 1.224343 - 0.056778 0.626911 11.00000 0.02682 0.02462 = 0.02965 0.00816 0.00768 0.01065 AFIX 137 H23A 2 1.309130 - 0.084899 0.637963 11.00000 - 1.50000 H23B 2 1.172842 - 0.109520 0.587146 11.00000 - 1.50000 H23C 2 1.196853 - 0.063083 0.672799 11.00000 - 1.50000 AFIX 0 C24 1 0.631393 0.705588 0.000316 11.00000 0.03584 0.02625 = 0.01679 0.00430 0.01573 0.00822 AFIX 137 H24A 2 0.649547 0.754219 - 0.040459 11.00000 - 1.50000 H24B 2 0.555899 0.658250 - 0.019910 11.00000 - 1.50000 H24C 2 0.698519 0.647479 0.021551 11.00000 - 1.50000 AFIX 0 C L1 5 1.016160 0.452210 0.737151 11.00000 0.04632 0.03578 = 0.03553 - 0.00369 0.02023 - 0.00035 C L2 5 1.070941 0.244096 0.845764 11.00000 0.05066 0.03732 = 0.04278 0.00165 0.02344 0.00160 C1A 1 1.082372 0.301804 0.757882 11.00000 0.03466 0.04304 = 0.03536 - 0.00169 0.01402 0.00761 AFIX 23 H1AA 2 1.041196 0.242978 0.717252 11.00000 - 1.20000 H1AB 2 1.169354 0.306072 0.758752 11.00000 - 1.20000

HKLF 4

REM 163p21c in P2(1)/c REM R1 = 0.0389 for 4022 Fo > 4sig(Fo) and 0.0479 for all 4763 data REM 288 parameters refined using 0 restraints

END

WGHT 0.0533 3.1302 REM Highest difference peak 0.518, deepest hole -0.783, 1-sigma level 0.081 Q1 1 0.4013 0.6788 0.3211 11.00000 0.05 0.52 Q2 1 0.5621 0.6178 0.2947 11.00000 0.05 0.44 Q3 1 0.7446 0.3627 0.5013 11.00000 0.05 0.39 Q4 1 0.2799 0.7050 0.3700 11.00000 0.05 0.39 Q5 1 1.0627 0.0975 0.6026 11.00000 0.05 0.39 Q6 1 0.8242 0.2821 0.5447 11.00000 0.05 0.38 Q7 1 0.4999 0.5022 0.4666 11.00000 0.05 0.38 Q8 1 0.4430 0.6153 0.4402 11.00000 0.05 0.37 Q9 1 0.6311 0.5006 0.4190 11.00000 0.05 0.37 Q10 1 0.6781 0.4823 0.3609 11.00000 0.05 0.37 Q11 1 0.6142 0.7841 0.2163 11.00000 0.05 0.37 Q12 1 0.4338 0.5471 0.4547 11.00000 0.05 0.37 Q13 1 0.6085 0.7658 0.1538 11.00000 0.05 0.37 Q14 1 0.7640 0.3836 0.4414 11.00000 0.05 0.37 Q15 1 0.7809 0.4420 0.3877 11.00000 0.05 0.36 Q16 1 0.3624 0.6442 0.4135 11.00000 0.05 0.35 Q17 1 0.4265 0.6223 0.3814 11.00000 0.05 0.35 Q18 1 0.2755 0.6830 0.4343 11.00000 0.05 0.34 Q19 1 0.7735 0.4142 0.4510 11.00000 0.05 0.34 Q20 1 0.5817 0.5935 0.1662 11.00000 0.05 0.33

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*/Ueq
Zn10.50000.50000.50000.01479 (12)
O11.21590 (16)0.07022 (16)0.60189 (10)0.0223 (4)
O20.61713 (16)0.78840 (16)0.05828 (9)0.0201 (4)
N10.41041 (17)0.61512 (18)0.41296 (10)0.0145 (4)
N20.63042 (18)0.46694 (18)0.44539 (11)0.0142 (4)
C10.3021 (2)0.6756 (2)0.40660 (13)0.0152 (4)
C20.2662 (2)0.7418 (2)0.33533 (13)0.0173 (5)
H2A0.19430.79020.31680.021*
C30.3537 (2)0.7220 (2)0.29996 (13)0.0167 (5)
H3A0.35530.75430.25210.020*
C40.4446 (2)0.6424 (2)0.34878 (12)0.0142 (4)
C50.5489 (2)0.5967 (2)0.33117 (12)0.0144 (4)
C60.6332 (2)0.5133 (2)0.37583 (13)0.0135 (4)
C70.7383 (2)0.4640 (2)0.35629 (13)0.0162 (4)
H7A0.76110.48090.31130.019*
C80.7980 (2)0.3892 (2)0.41388 (13)0.0169 (5)
H8A0.87050.34330.41690.020*
C90.7306 (2)0.3921 (2)0.47033 (13)0.0150 (4)
C100.7649 (2)0.3271 (2)0.53954 (13)0.0155 (4)
C110.8824 (2)0.2566 (2)0.55693 (13)0.0159 (4)
C120.8868 (2)0.1277 (2)0.56902 (13)0.0185 (5)
H12A0.81360.08370.56670.022*
C130.9966 (2)0.0620 (2)0.58442 (13)0.0185 (5)
H13A0.99790.02570.59270.022*
C141.1036 (2)0.1257 (2)0.58752 (13)0.0185 (5)
C151.1007 (2)0.2545 (2)0.57580 (14)0.0205 (5)
H15A1.17400.29830.57800.025*
C160.9916 (2)0.3189 (2)0.56091 (14)0.0186 (5)
H16A0.99090.40680.55330.022*
C170.5717 (2)0.6427 (2)0.25917 (13)0.0147 (4)
C180.5972 (2)0.7688 (2)0.25110 (13)0.0168 (5)
H18A0.60380.82430.29240.020*
C190.6133 (2)0.8147 (2)0.18394 (14)0.0186 (5)
H19A0.63120.90070.17960.022*
C200.6031 (2)0.7344 (2)0.12281 (13)0.0170 (5)
C210.5822 (2)0.6075 (2)0.13054 (13)0.0190 (5)
H21A0.57890.55150.08980.023*
C220.5662 (2)0.5631 (2)0.19847 (13)0.0179 (5)
H22A0.55120.47650.20340.021*
C231.2243 (3)0.0568 (3)0.62691 (16)0.0270 (6)
H23A1.30910.08490.63800.041*
H23B1.17280.10950.58710.041*
H23C1.19690.06310.67280.041*
C240.6314 (3)0.7056 (3)0.00032 (14)0.0246 (5)
H24A0.64950.75420.04050.037*
H24B0.55590.65820.01990.037*
H24C0.69850.64750.02160.037*
Cl11.01616 (7)0.45221 (7)0.73715 (4)0.03743 (19)
Cl21.07094 (8)0.24410 (8)0.84576 (5)0.0415 (2)
C1A1.0824 (3)0.3018 (3)0.75788 (18)0.0368 (7)
H1AA1.04120.24300.71730.044*
H1AB1.16940.30610.75880.044*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0168 (2)0.0172 (2)0.01254 (19)0.00349 (14)0.00769 (14)0.00333 (14)
O10.0186 (8)0.0200 (9)0.0287 (10)0.0055 (7)0.0072 (7)0.0018 (7)
O20.0284 (9)0.0212 (9)0.0140 (8)0.0031 (7)0.0114 (7)0.0047 (7)
N10.0169 (9)0.0151 (9)0.0131 (9)0.0005 (7)0.0068 (7)0.0004 (7)
N20.0175 (9)0.0137 (9)0.0125 (9)0.0005 (7)0.0061 (7)0.0008 (7)
C10.0165 (11)0.0139 (10)0.0152 (11)0.0001 (8)0.0046 (9)0.0004 (8)
C20.0174 (11)0.0186 (11)0.0157 (11)0.0015 (9)0.0042 (9)0.0021 (9)
C30.0196 (11)0.0166 (11)0.0143 (11)0.0000 (9)0.0057 (9)0.0014 (9)
C40.0176 (11)0.0121 (10)0.0134 (10)0.0019 (8)0.0051 (8)0.0002 (8)
C50.0192 (11)0.0127 (10)0.0126 (10)0.0025 (8)0.0067 (8)0.0011 (8)
C60.0172 (11)0.0117 (10)0.0131 (10)0.0017 (8)0.0069 (8)0.0014 (8)
C70.0196 (11)0.0166 (11)0.0151 (11)0.0004 (9)0.0093 (9)0.0010 (8)
C80.0187 (11)0.0160 (11)0.0191 (11)0.0007 (9)0.0103 (9)0.0001 (9)
C90.0166 (10)0.0150 (10)0.0149 (10)0.0011 (8)0.0068 (8)0.0010 (9)
C100.0169 (11)0.0143 (10)0.0164 (11)0.0004 (8)0.0062 (9)0.0001 (8)
C110.0188 (11)0.0173 (11)0.0127 (10)0.0019 (9)0.0062 (9)0.0014 (8)
C120.0208 (12)0.0187 (12)0.0178 (11)0.0012 (9)0.0081 (9)0.0012 (9)
C130.0234 (12)0.0157 (11)0.0178 (11)0.0021 (9)0.0081 (9)0.0025 (9)
C140.0195 (11)0.0211 (12)0.0153 (11)0.0038 (9)0.0058 (9)0.0016 (9)
C150.0191 (11)0.0203 (12)0.0237 (12)0.0008 (9)0.0089 (10)0.0016 (10)
C160.0213 (12)0.0162 (11)0.0198 (12)0.0000 (9)0.0083 (9)0.0005 (9)
C170.0152 (10)0.0169 (11)0.0133 (10)0.0011 (8)0.0061 (8)0.0021 (8)
C180.0207 (11)0.0158 (11)0.0155 (11)0.0018 (9)0.0078 (9)0.0009 (9)
C190.0233 (12)0.0145 (11)0.0199 (12)0.0016 (9)0.0091 (9)0.0037 (9)
C200.0166 (11)0.0208 (11)0.0156 (11)0.0035 (9)0.0078 (9)0.0055 (9)
C210.0243 (12)0.0202 (12)0.0144 (11)0.0009 (9)0.0085 (9)0.0026 (9)
C220.0218 (12)0.0157 (11)0.0172 (11)0.0017 (9)0.0070 (9)0.0006 (9)
C230.0268 (13)0.0246 (13)0.0296 (14)0.0106 (11)0.0077 (11)0.0082 (11)
C240.0358 (14)0.0263 (13)0.0168 (12)0.0082 (11)0.0157 (11)0.0043 (10)
Cl10.0463 (4)0.0358 (4)0.0355 (4)0.0003 (3)0.0202 (3)0.0037 (3)
Cl20.0507 (5)0.0373 (4)0.0428 (4)0.0016 (3)0.0234 (4)0.0017 (3)
C1A0.0347 (16)0.0430 (18)0.0354 (16)0.0076 (13)0.0140 (13)0.0017 (14)
Geometric parameters (Å, º) top
Zn1—N2i2.0432 (19)C11—C161.398 (3)
Zn1—N22.0432 (19)C12—C131.395 (3)
Zn1—N1i2.0532 (19)C12—H12A0.9500
Zn1—N12.0532 (19)C13—C141.387 (3)
O1—C141.371 (3)C13—H13A0.9500
O1—C231.428 (3)C14—C151.392 (3)
O2—C201.367 (3)C15—C161.383 (3)
O2—C241.428 (3)C15—H15A0.9500
N1—C11.371 (3)C16—H16A0.9500
N1—C41.372 (3)C17—C221.391 (3)
N2—C91.367 (3)C17—C181.396 (3)
N2—C61.380 (3)C18—C191.387 (3)
C1—C10i1.409 (3)C18—H18A0.9500
C1—C21.445 (3)C19—C201.393 (3)
C2—C31.351 (3)C19—H19A0.9500
C2—H2A0.9500C20—C211.392 (3)
C3—C41.446 (3)C21—C221.394 (3)
C3—H3A0.9500C21—H21A0.9500
C4—C51.405 (3)C22—H22A0.9500
C5—C61.400 (3)C23—H23A0.9800
C5—C171.500 (3)C23—H23B0.9800
C6—C71.443 (3)C23—H23C0.9800
C7—C81.351 (3)C24—H24A0.9800
C7—H7A0.9500C24—H24B0.9800
C8—C91.453 (3)C24—H24C0.9800
C8—H8A0.9500Cl1—C1A1.773 (3)
C9—C101.407 (3)Cl2—C1A1.767 (3)
C10—C1i1.409 (3)C1A—H1AA0.9900
C10—C111.495 (3)C1A—H1AB0.9900
C11—C121.393 (3)
N2i—Zn1—N2180.00 (11)C13—C12—H12A119.3
N2i—Zn1—N1i89.71 (8)C14—C13—C12119.6 (2)
N2—Zn1—N1i90.29 (8)C14—C13—H13A120.2
N2i—Zn1—N190.29 (8)C12—C13—H13A120.2
N2—Zn1—N189.71 (8)O1—C14—C13124.2 (2)
N1i—Zn1—N1180.0O1—C14—C15116.0 (2)
C14—O1—C23116.75 (19)C13—C14—C15119.7 (2)
C20—O2—C24116.76 (19)C16—C15—C14120.3 (2)
C1—N1—C4106.86 (18)C16—C15—H15A119.9
C1—N1—Zn1126.34 (15)C14—C15—H15A119.9
C4—N1—Zn1126.75 (15)C15—C16—C11121.0 (2)
C9—N2—C6106.82 (18)C15—C16—H16A119.5
C9—N2—Zn1126.33 (15)C11—C16—H16A119.5
C6—N2—Zn1126.84 (15)C22—C17—C18118.1 (2)
N1—C1—C10i125.6 (2)C22—C17—C5121.8 (2)
N1—C1—C2109.38 (19)C18—C17—C5120.2 (2)
C10i—C1—C2125.0 (2)C19—C18—C17121.3 (2)
C3—C2—C1107.3 (2)C19—C18—H18A119.4
C3—C2—H2A126.4C17—C18—H18A119.4
C1—C2—H2A126.4C18—C19—C20119.9 (2)
C2—C3—C4107.0 (2)C18—C19—H19A120.1
C2—C3—H3A126.5C20—C19—H19A120.1
C4—C3—H3A126.5O2—C20—C21124.3 (2)
N1—C4—C5125.7 (2)O2—C20—C19115.9 (2)
N1—C4—C3109.45 (19)C21—C20—C19119.8 (2)
C5—C4—C3124.8 (2)C20—C21—C22119.5 (2)
C6—C5—C4125.2 (2)C20—C21—H21A120.3
C6—C5—C17117.8 (2)C22—C21—H21A120.3
C4—C5—C17117.0 (2)C17—C22—C21121.5 (2)
N2—C6—C5125.7 (2)C17—C22—H22A119.3
N2—C6—C7109.45 (19)C21—C22—H22A119.3
C5—C6—C7124.8 (2)O1—C23—H23A109.5
C8—C7—C6107.2 (2)O1—C23—H23B109.5
C8—C7—H7A126.4H23A—C23—H23B109.5
C6—C7—H7A126.4O1—C23—H23C109.5
C7—C8—C9107.1 (2)H23A—C23—H23C109.5
C7—C8—H8A126.5H23B—C23—H23C109.5
C9—C8—H8A126.5O2—C24—H24A109.5
N2—C9—C10126.2 (2)O2—C24—H24B109.5
N2—C9—C8109.44 (19)H24A—C24—H24B109.5
C10—C9—C8124.3 (2)O2—C24—H24C109.5
C9—C10—C1i125.1 (2)H24A—C24—H24C109.5
C9—C10—C11116.9 (2)H24B—C24—H24C109.5
C1i—C10—C11118.0 (2)Cl2—C1A—Cl1112.23 (17)
C12—C11—C16118.1 (2)Cl2—C1A—H1AA109.2
C12—C11—C10121.5 (2)Cl1—C1A—H1AA109.2
C16—C11—C10120.4 (2)Cl2—C1A—H1AB109.2
C11—C12—C13121.4 (2)Cl1—C1A—H1AB109.2
C11—C12—H12A119.3H1AA—C1A—H1AB107.9
Symmetry code: (i) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formula[Zn(C48H36N4O4)]·2CH2Cl2
Mr968.03
Crystal system, space groupMonoclinic, P21/c
Temperature (K)100
a, b, c (Å)11.4189 (9), 10.6877 (9), 18.3778 (15)
β (°) 106.022 (1)
V3)2155.7 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.87
Crystal size (mm)0.18 × 0.16 × 0.09
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2007)
Tmin, Tmax0.861, 0.926
No. of measured, independent and
observed [I > 2σ(I)] reflections
25964, 4763, 4022
Rint0.036
(sin θ/λ)max1)0.642
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.121, 1.06
No. of reflections4763
No. of parameters288
No. of restraints0
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.52, 0.78

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements top

This research was funded by in part by the National Science Foundation (CHE-0924153) and a chemistry department grant from the Welch Foundation (AD-0007). X-ray data were collected at the University of North Texas using a Bruker APEXII CCD diffractometer.

references
References top

Adilov, S. & Thalladi, V. R. (2007). Cryst. Growth Des. 7, 481–484.

Adler, A. D., Longo, F. R., Finarelli, J. D., Goldmacher, J., Assour, J. & Korsakoff, L. (1967). J. Org. Chem. 32, 476–477.

Bhuyan, J. & Sarkar, S. (2011). Cryst. Growth Des. 11, 5410–5414.

Bondi, A. (1964). J. Phys. Chem. 68, 441–451.

Bruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Teo, T. L., Vetrichelvan, M. & Lai, Y. H. (2003). Org. Lett. 5, 4207–4210.