Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107030089/gg3098sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107030089/gg3098Isup2.hkl |
CCDC reference: 659110
Violet crystals of (I) were obtained by recrystallization of MgPc crystals obtained as described elsewhere (Janczak & Kubiak, 2001) in 3-chloropyridine. MgPc (about 1 g) was added to 20 ml of 3-Clpyr. The suspension was degassed and sealed into a glass ampoule. The ampoule was heated at 433 K over a period of 15 h. Crystals of (I) were formed during the cooling process (at about 363–368 K). The presence of water in these crystals results from the high affinity of water to MgPc (Janczak & Idemori, 2003).
H atoms bonded to C atoms were positioned geometrically and treated as riding, with Uiso(H) values of 1.2Ueq(C). H atoms of the coordinated water molecules were located in difference Fourier syntheses and in the final refinement cycles were constrained to O—H distances of 0.82 Å, with Uiso(H) equal to 1.5Ueq(O).
Data collection: CrysAlis CCD (Oxford Diffraction, 2005); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELTXL (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.
[Mg(C32H16N8)(H2O)]·2C5H4ClN | F(000) = 1608 |
Mr = 781.94 | Dx = 1.410 Mg m−3 Dm = 1.41 Mg m−3 Dm measured by floatation |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 1452 reflections |
a = 14.981 (3) Å | θ = 3.1–28.0° |
b = 13.956 (2) Å | µ = 0.24 mm−1 |
c = 18.309 (3) Å | T = 295 K |
β = 105.80 (1)° | Paralellepiped, violet |
V = 3683.3 (11) Å3 | 0.38 × 0.27 × 0.24 mm |
Z = 4 |
Kuma KM-4 CCD area-detector diffractometer | 8890 independent reflections |
Radiation source: fine-focus sealed tube | 5340 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
Detector resolution: 1024x1024 with blocks 2x2 pixels mm-1 | θmax = 28.0°, θmin = 3.1° |
ω scans | h = −19→19 |
Absorption correction: analytical [face-indexed (SHELXTL; Sheldrick, 1990)] | k = −18→18 |
Tmin = 0.929, Tmax = 0.947 | l = −24→22 |
39524 measured reflections |
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)] = 0.063 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0319P)2] where P = (Fo2 + 2Fc2)/3 |
8890 reflections | (Δ/σ)max = 0.002 |
511 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
[Mg(C32H16N8)(H2O)]·2C5H4ClN | V = 3683.3 (11) Å3 |
Mr = 781.94 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 14.981 (3) Å | µ = 0.24 mm−1 |
b = 13.956 (2) Å | T = 295 K |
c = 18.309 (3) Å | 0.38 × 0.27 × 0.24 mm |
β = 105.80 (1)° |
Kuma KM-4 CCD area-detector diffractometer | 8890 independent reflections |
Absorption correction: analytical [face-indexed (SHELXTL; Sheldrick, 1990)] | 5340 reflections with I > 2σ(I) |
Tmin = 0.929, Tmax = 0.947 | Rint = 0.045 |
39524 measured reflections |
R[F2 > 2σ(F2)] = 0.063 | 0 restraints |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.17 e Å−3 |
8890 reflections | Δρmin = −0.16 e Å−3 |
511 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Mg1 | 0.62169 (6) | 0.03543 (5) | 0.18097 (4) | 0.0547 (2) | |
O1 | 0.72046 (13) | 0.12833 (10) | 0.23786 (9) | 0.0654 (5) | |
H1O | 0.734 | 0.1076 | 0.2814 | 0.098* | |
H2O | 0.7234 | 0.1864 | 0.2322 | 0.098* | |
N1 | 0.49933 (14) | 0.08370 (12) | 0.19572 (12) | 0.0619 (6) | |
N2 | 0.44368 (14) | 0.18068 (13) | 0.08241 (12) | 0.0564 (6) | |
N3 | 0.57503 (14) | 0.08185 (13) | 0.07250 (12) | 0.0551 (6) | |
N4 | 0.68184 (15) | 0.00287 (13) | 0.01283 (11) | 0.0579 (6) | |
N5 | 0.69979 (13) | −0.06165 (12) | 0.14174 (11) | 0.0517 (5) | |
N6 | 0.74722 (13) | −0.16814 (11) | 0.24922 (11) | 0.0484 (5) | |
N7 | 0.62365 (14) | −0.06268 (12) | 0.26326 (11) | 0.0535 (5) | |
N8 | 0.49858 (16) | 0.00134 (12) | 0.31276 (11) | 0.0634 (6) | |
C1 | 0.46631 (19) | 0.06281 (17) | 0.25586 (15) | 0.0614 (7) | |
C2 | 0.38220 (19) | 0.11853 (17) | 0.24924 (16) | 0.0669 (7) | |
C3 | 0.3188 (2) | 0.1181 (2) | 0.29476 (16) | 0.0752 (9) | |
H3 | 0.3258 | 0.0781 | 0.3366 | 0.102* | |
C4 | 0.2452 (2) | 0.1827 (3) | 0.2714 (2) | 0.1126 (12) | |
H4 | 0.2061 | 0.1912 | 0.3027 | 0.135* | |
C5 | 0.2275 (2) | 0.2331 (2) | 0.2069 (2) | 0.1094 (13) | |
H5 | 0.1733 | 0.2690 | 0.1916 | 0.143* | |
C6 | 0.2920 (2) | 0.2318 (2) | 0.16113 (18) | 0.0851 (10) | |
H6 | 0.2842 | 0.2710 | 0.1188 | 0.101* | |
C7 | 0.36432 (18) | 0.17098 (18) | 0.18290 (15) | 0.0629 (7) | |
C8 | 0.43741 (18) | 0.14804 (17) | 0.14921 (15) | 0.0600 (7) | |
C9 | 0.5040 (2) | 0.14912 (16) | 0.04720 (15) | 0.0608 (7) | |
C10 | 0.50284 (18) | 0.17982 (16) | −0.03049 (15) | 0.0650 (7) | |
C11 | 0.4497 (2) | 0.24579 (17) | −0.08059 (18) | 0.0691 (8) | |
H11 | 0.4035 | 0.2798 | −0.0667 | 0.081* | |
C12 | 0.4639 (2) | 0.26106 (19) | −0.14831 (18) | 0.0796 (9) | |
H12 | 0.4291 | 0.3057 | −0.1819 | 0.095* | |
C13 | 0.5349 (3) | 0.2061 (2) | −0.16743 (15) | 0.0675 (11) | |
H13 | 0.5445 | 0.2166 | −0.2149 | 0.081* | |
C14 | 0.59074 (19) | 0.13823 (17) | −0.12091 (17) | 0.0606 (8) | |
H14 | 0.6367 | 0.1043 | −0.1352 | 0.073* | |
C15 | 0.57188 (19) | 0.12536 (16) | −0.05090 (15) | 0.0584 (7) | |
C16 | 0.61587 (18) | 0.06479 (16) | 0.01351 (14) | 0.0560 (7) | |
C17 | 0.71758 (17) | −0.05499 (15) | 0.07196 (15) | 0.0533 (6) | |
C18 | 0.78908 (18) | −0.12552 (16) | 0.06830 (14) | 0.0607 (7) | |
C19 | 0.8345 (2) | −0.14733 (19) | 0.01586 (16) | 0.0682 (9) | |
H19 | 0.8202 | −0.1140 | −0.0298 | 0.082* | |
C20 | 0.8990 (2) | −0.2152 (2) | 0.02813 (17) | 0.0890 (10) | |
H20 | 0.9283 | −0.2304 | −0.0091 | 0.107* | |
C21 | 0.9224 (2) | −0.2636 (2) | 0.09782 (18) | 0.0801 (11) | |
H21 | 0.9696 | −0.3091 | 0.1070 | 0.091* | |
C22 | 0.87883 (18) | −0.24658 (17) | 0.15230 (15) | 0.0696 (8) | |
H22 | 0.8921 | −0.2820 | 0.1970 | 0.084* | |
C23 | 0.81326 (17) | −0.17367 (15) | 0.13814 (13) | 0.0578 (7) | |
C24 | 0.75169 (16) | −0.13523 (15) | 0.18163 (14) | 0.0526 (6) | |
C25 | 0.68733 (17) | −0.13498 (16) | 0.28590 (13) | 0.0528 (6) | |
C26 | 0.68006 (17) | −0.17477 (15) | 0.35770 (13) | 0.0509 (6) | |
C27 | 0.72911 (18) | −0.24348 (16) | 0.40789 (13) | 0.0629 (7) | |
H27 | 0.7772 | −0.2776 | 0.3969 | 0.075* | |
C28 | 0.70477 (19) | −0.26005 (19) | 0.47490 (15) | 0.0650 (8) | |
H28 | 0.7383 | −0.3046 | 0.5093 | 0.078* | |
C29 | 0.6331 (2) | −0.2128 (2) | 0.49156 (15) | 0.0704 (9) | |
H29 | 0.6158 | −0.2299 | 0.5349 | 0.085* | |
C30 | 0.58555 (18) | −0.1402 (2) | 0.44588 (15) | 0.0624 (8) | |
H30 | 0.5403 | −0.1044 | 0.4595 | 0.072* | |
C31 | 0.60948 (19) | −0.12291 (16) | 0.37647 (15) | 0.0627 (7) | |
C32 | 0.57514 (19) | −0.05527 (16) | 0.31673 (15) | 0.0616 (7) | |
Cl1 | 0.76872 (10) | 0.02373 (8) | 0.57342 (7) | 0.0907 (5) | |
N41 | 0.8139 (2) | 0.0462 (2) | 0.37421 (16) | 0.0986 (9) | |
C42 | 0.7800 (3) | 0.0583 (2) | 0.4303 (2) | 0.0873 (12) | |
H42 | 0.7328 | 0.1027 | 0.4273 | 0.129* | |
C43 | 0.8160 (3) | 0.0017 (3) | 0.49960 (17) | 0.0945 (12) | |
C44 | 0.8833 (3) | −0.0613 (3) | 0.5016 (2) | 0.1132 (13) | |
H44 | 0.9101 | −0.0962 | 0.5454 | 0.136* | |
C45 | 0.9118 (3) | −0.0732 (3) | 0.4371 (3) | 0.1110 (16) | |
H45 | 0.9532 | −0.1220 | 0.4347 | 0.135* | |
C46 | 0.8822 (3) | −0.0180 (3) | 0.3809 (2) | 0.1078 (12) | |
H46 | 0.9099 | −0.0223 | 0.3413 | 0.129* | |
Cl2 | 1.17661 (11) | −0.07811 (11) | 0.13922 (9) | 0.1194 (7) | |
N51 | 0.9870 (5) | 0.0064 (6) | 0.2424 (4) | 0.124 (3) | |
C52 | 1.0608 (4) | −0.0476 (4) | 0.2258 (4) | 0.1172 (19) | |
H52 | 1.0918 | −0.0955 | 0.2582 | 0.141* | |
C53 | 1.0833 (3) | −0.0257 (3) | 0.1611 (3) | 0.1147 (13) | |
C54 | 1.0233 (5) | 0.0240 (5) | 0.1054 (3) | 0.130 (2) | |
H54 | 1.0287 | 0.0270 | 0.0560 | 0.166* | |
C55 | 0.9557 (6) | 0.0684 (5) | 0.1269 (7) | 0.111 (5) | |
H55 | 0.9164 | 0.1092 | 0.0926 | 0.133* | |
C56 | 0.9425 (5) | 0.0578 (5) | 0.1911 (5) | 0.116 (3) | |
H56 | 0.8940 | 0.0925 | 0.2008 | 0.139* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mg1 | 0.0646 (6) | 0.0359 (4) | 0.0656 (5) | 0.0027 (4) | 0.0213 (4) | 0.0048 (4) |
O1 | 0.0717 (13) | 0.0436 (9) | 0.0854 (13) | 0.0022 (10) | 0.0195 (12) | 0.0040 (9) |
N1 | 0.0607 (16) | 0.0457 (11) | 0.0758 (15) | 0.0067 (11) | 0.0141 (13) | 0.0107 (11) |
N2 | 0.0609 (15) | 0.0409 (12) | 0.0724 (15) | 0.0102 (10) | 0.0065 (13) | 0.0054 (11) |
N3 | 0.0637 (15) | 0.0406 (12) | 0.0688 (16) | 0.0126 (11) | 0.0119 (13) | 0.0007 (11) |
N4 | 0.0711 (16) | 0.0396 (11) | 0.0617 (14) | 0.0069 (11) | 0.0161 (12) | 0.0113 (10) |
N5 | 0.0531 (13) | 0.0434 (12) | 0.0599 (13) | 0.0055 (10) | 0.0177 (11) | 0.0088 (10) |
N6 | 0.0609 (14) | 0.0293 (10) | 0.0607 (13) | 0.0055 (10) | 0.0261 (11) | 0.0003 (9) |
N7 | 0.0516 (13) | 0.0427 (11) | 0.0717 (14) | 0.0032 (10) | 0.0262 (12) | 0.0028 (10) |
N8 | 0.0919 (18) | 0.0343 (11) | 0.0766 (15) | 0.0043 (12) | 0.0441 (13) | 0.0022 (10) |
C1 | 0.073 (2) | 0.0472 (15) | 0.0580 (17) | 0.0006 (14) | 0.0085 (16) | 0.0015 (13) |
C2 | 0.062 (2) | 0.0528 (16) | 0.087 (2) | 0.0011 (15) | 0.0101 (17) | 0.0011 (15) |
C3 | 0.079 (2) | 0.081 (2) | 0.083 (2) | 0.0022 (19) | 0.011 (2) | 0.0106 (17) |
C4 | 0.096 (3) | 0.133 (3) | 0.121 (3) | 0.038 (2) | 0.049 (2) | 0.009 (3) |
C5 | 0.092 (3) | 0.115 (3) | 0.138 (4) | 0.049 (2) | 0.043 (3) | 0.010 (3) |
C6 | 0.073 (2) | 0.082 (2) | 0.087 (2) | 0.0352 (19) | 0.002 (2) | 0.0089 (18) |
C7 | 0.0563 (18) | 0.0637 (17) | 0.0703 (19) | 0.0093 (15) | 0.0020 (16) | 0.0024 (15) |
C8 | 0.0637 (19) | 0.0484 (15) | 0.0669 (19) | 0.0108 (14) | 0.0103 (16) | 0.0051 (14) |
C9 | 0.0646 (19) | 0.0324 (14) | 0.0717 (19) | 0.0154 (14) | 0.0049 (16) | 0.0039 (13) |
C10 | 0.067 (2) | 0.0539 (13) | 0.063 (2) | 0.0061 (14) | 0.0015 (17) | 0.0090 (14) |
C11 | 0.065 (2) | 0.0575 (16) | 0.076 (2) | 0.0075 (16) | 0.0101 (19) | 0.0088 (16) |
C12 | 0.078 (3) | 0.0707 (17) | 0.085 (2) | −0.0097 (17) | 0.014 (2) | 0.0102 (16) |
C13 | 0.066 (3) | 0.059 (2) | 0.0706 (19) | −0.011 (2) | 0.013 (2) | 0.0101 (19) |
C14 | 0.061 (2) | 0.0539 (15) | 0.065 (2) | −0.0011 (15) | 0.0111 (18) | 0.0097 (15) |
C15 | 0.060 (2) | 0.0528 (13) | 0.0607 (17) | 0.0016 (14) | 0.0100 (15) | 0.0075 (13) |
C16 | 0.0697 (19) | 0.0403 (14) | 0.0581 (17) | 0.0129 (14) | 0.0113 (16) | 0.0010 (13) |
C17 | 0.0616 (17) | 0.0417 (13) | 0.0611 (18) | 0.0070 (12) | 0.0158 (15) | 0.0013 (13) |
C18 | 0.063 (2) | 0.0599 (14) | 0.0603 (17) | 0.0081 (14) | 0.0182 (16) | 0.0061 (13) |
C19 | 0.082 (2) | 0.0682 (19) | 0.071 (2) | 0.0114 (18) | 0.0233 (19) | 0.0096 (16) |
C20 | 0.099 (3) | 0.083 (2) | 0.084 (2) | 0.031 (2) | 0.0235 (19) | 0.0032 (18) |
C21 | 0.091 (3) | 0.073 (2) | 0.082 (2) | 0.027 (2) | 0.022 (2) | 0.0031 (18) |
C22 | 0.082 (2) | 0.0585 (16) | 0.0845 (19) | 0.0247 (15) | 0.0225 (17) | 0.0030 (14) |
C23 | 0.0606 (19) | 0.0474 (13) | 0.0652 (17) | 0.0086 (13) | 0.0180 (15) | 0.0009 (12) |
C24 | 0.0589 (17) | 0.0378 (12) | 0.0625 (18) | 0.0072 (12) | 0.0205 (15) | 0.0018 (12) |
C25 | 0.0559 (17) | 0.0425 (13) | 0.0541 (17) | 0.0103 (13) | 0.0117 (14) | 0.0011 (12) |
C26 | 0.0535 (17) | 0.0438 (13) | 0.0547 (16) | 0.0064 (13) | 0.0140 (13) | 0.0057 (12) |
C27 | 0.081 (2) | 0.0455 (14) | 0.0585 (16) | 0.0001 (14) | 0.0131 (15) | 0.0108 (13) |
C28 | 0.075 (2) | 0.063 (2) | 0.0639 (19) | 0.0104 (17) | 0.0236 (17) | 0.0148 (16) |
C29 | 0.078 (3) | 0.066 (2) | 0.069 (2) | 0.0080 (19) | 0.0258 (18) | 0.0181 (17) |
C30 | 0.0653 (19) | 0.068 (2) | 0.0645 (19) | 0.0058 (17) | 0.0367 (17) | 0.0093 (16) |
C31 | 0.065 (2) | 0.0631 (13) | 0.0651 (19) | 0.0063 (14) | 0.0290 (17) | 0.0080 (13) |
C32 | 0.0635 (19) | 0.0535 (14) | 0.063 (2) | 0.0018 (13) | 0.0183 (16) | 0.0018 (13) |
Cl1 | 0.1053 (14) | 0.0834 (10) | 0.0888 (10) | −0.0118 (9) | 0.0101 (9) | 0.0086 (8) |
N41 | 0.102 (3) | 0.099 (2) | 0.085 (2) | −0.0089 (19) | 0.0079 (19) | 0.0048 (17) |
C42 | 0.104 (3) | 0.060 (2) | 0.086 (3) | −0.016 (2) | 0.014 (3) | −0.003 (2) |
C43 | 0.105 (4) | 0.083 (2) | 0.085 (2) | −0.011 (2) | 0.011 (2) | 0.010 (2) |
C44 | 0.117 (3) | 0.088 (3) | 0.120 (3) | 0.003 (2) | 0.008 (3) | 0.031 (2) |
C45 | 0.113 (4) | 0.092 (3) | 0.113 (4) | −0.002 (3) | 0.015 (4) | 0.016 (3) |
C46 | 0.098 (3) | 0.080 (3) | 0.132 (4) | −0.004 (2) | 0.009 (3) | 0.013 (2) |
Cl2 | 0.1022 (15) | 0.1222 (15) | 0.1432 (15) | 0.0098 (12) | 0.0114 (12) | 0.0119 (12) |
N51 | 0.123 (7) | 0.117 (8) | 0.126 (6) | 0.004 (5) | 0.044 (5) | 0.010 (5) |
C52 | 0.103 (5) | 0.115 (5) | 0.118 (6) | 0.001 (4) | 0.016 (4) | 0.017 (4) |
C53 | 0.113 (4) | 0.115 (3) | 0.118 (3) | 0.001 (3) | 0.019 (3) | 0.011 (3) |
C54 | 0.143 (5) | 0.113 (6) | 0.121 (5) | 0.018 (4) | 0.019 (5) | 0.049 (5) |
C55 | 0.124 (8) | 0.135 (6) | 0.115 (16) | 0.016 (5) | 0.028 (10) | 0.040 (8) |
C56 | 0.113 (6) | 0.128 (7) | 0.123 (7) | 0.011 (5) | 0.024 (5) | 0.035 (6) |
Mg1—O1 | 2.029 (2) | C17—C18 | 1.470 (3) |
Mg1—N1 | 2.039 (2) | C18—C19 | 1.354 (3) |
Mg1—N3 | 2.024 (2) | C18—C23 | 1.402 (3) |
Mg1—N5 | 2.044 (2) | C19—C20 | 1.328 (3) |
Mg1—N7 | 2.030 (2) | C19—H19 | 0.9300 |
O1—H1O | 0.8200 | C20—C21 | 1.401 (3) |
O1—H2O | 0.8200 | C20—H20 | 0.9300 |
N1—C1 | 1.356 (3) | C21—C22 | 1.354 (3) |
N1—C8 | 1.401 (3) | C21—H21 | 0.9300 |
N2—C9 | 1.320 (3) | C22—C23 | 1.389 (3) |
N2—C8 | 1.332 (3) | C22—H22 | 0.9300 |
N3—C16 | 1.399 (3) | C23—C24 | 1.474 (3) |
N3—C9 | 1.400 (3) | C25—C26 | 1.458 (3) |
N4—C16 | 1.315 (3) | C26—C27 | 1.391 (3) |
N4—C17 | 1.340 (3) | C26—C31 | 1.399 (3) |
N5—C24 | 1.372 (3) | C27—C28 | 1.391 (3) |
N5—C17 | 1.377 (3) | C27—H27 | 0.9300 |
N6—C24 | 1.339 (3) | C28—C29 | 1.363 (3) |
N6—C25 | 1.341 (3) | C28—H28 | 0.9300 |
N7—C32 | 1.373 (3) | C29—C30 | 1.381 (3) |
N7—C25 | 1.373 (3) | C29—H29 | 0.9300 |
N8—C1 | 1.334 (3) | C30—C31 | 1.432 (3) |
N8—C32 | 1.378 (3) | C30—H30 | 0.9300 |
C1—C2 | 1.457 (3) | C31—C32 | 1.430 (3) |
C2—C7 | 1.380 (3) | Cl1—C43 | 1.716 (3) |
C2—C3 | 1.424 (3) | N41—C42 | 1.276 (4) |
C3—C4 | 1.399 (3) | N41—C46 | 1.339 (4) |
C3—H3 | 0.9300 | C42—C43 | 1.467 (4) |
C4—C5 | 1.337 (3) | C42—H42 | 0.9300 |
C4—H4 | 0.9300 | C43—C44 | 1.330 (4) |
C5—C6 | 1.442 (3) | C44—C45 | 1.371 (5) |
C5—H5 | 0.9300 | C44—H44 | 0.9300 |
C6—C7 | 1.348 (3) | C45—C46 | 1.266 (4) |
C6—H6 | 0.9300 | C45—H45 | 0.9300 |
C7—C8 | 1.432 (3) | C46—H46 | 0.9300 |
C9—C10 | 1.481 (3) | Cl2—C53 | 1.719 (3) |
C10—C11 | 1.388 (3) | N51—C56 | 1.225 (7) |
C10—C15 | 1.413 (3) | N51—C52 | 1.438 (6) |
C11—C12 | 1.331 (3) | C52—C53 | 1.351 (5) |
C11—H11 | 0.9300 | C52—H52 | 0.9300 |
C12—C13 | 1.430 (3) | C53—C54 | 1.354 (5) |
C12—H12 | 0.9300 | C54—C55 | 1.335 (6) |
C13—C14 | 1.391 (3) | C54—H54 | 0.9300 |
C13—H13 | 0.9300 | C55—C56 | 1.252 (8) |
C14—C15 | 1.397 (3) | C55—H55 | 0.9300 |
C14—H14 | 0.9300 | C56—H56 | 0.9300 |
C15—C16 | 1.455 (3) | ||
O1—Mg1—N1 | 106.09 (8) | N5—C17—C18 | 108.9 (2) |
O1—Mg1—N3 | 107.94 (7) | C19—C18—C23 | 118.9 (2) |
O1—Mg1—N5 | 101.35 (8) | C19—C18—C17 | 134.1 (2) |
O1—Mg1—N7 | 100.88 (8) | C23—C18—C17 | 106.9 (2) |
N1—Mg1—N3 | 86.64 (9) | C20—C19—C18 | 121.6 (3) |
N1—Mg1—N5 | 152.49 (8) | C20—C19—H19 | 119.2 |
N1—Mg1—N7 | 87.50 (9) | C18—C19—H19 | 119.2 |
N3—Mg1—N5 | 86.86 (8) | C19—C20—C21 | 119.2 (3) |
N3—Mg1—N7 | 151.10 (8) | C19—C20—H20 | 120.4 |
N5—Mg1—N7 | 85.40 (8) | C21—C20—H20 | 120.4 |
Mg1—O1—H1O | 103 | C22—C21—C20 | 122.3 (3) |
Mg1—O1—H2O | 129 | C22—C21—H21 | 118.8 |
H1O—O1—H2O | 118 | C20—C21—H21 | 118.8 |
C1—N1—C8 | 107.7 (2) | C21—C22—C23 | 116.7 (3) |
C1—N1—Mg1 | 125.20 (17) | C21—C22—H22 | 121.6 |
C8—N1—Mg1 | 127.00 (18) | C23—C22—H22 | 121.6 |
C9—N2—C8 | 124.3 (2) | C22—C23—C18 | 121.0 (2) |
C16—N3—C9 | 108.1 (2) | C22—C23—C24 | 132.9 (2) |
C16—N3—Mg1 | 126.60 (17) | C18—C23—C24 | 105.9 (2) |
C9—N3—Mg1 | 124.59 (18) | N6—C24—N5 | 125.8 (2) |
C16—N4—C17 | 121.6 (2) | N6—C24—C23 | 124.8 (2) |
C24—N5—C17 | 108.63 (19) | N5—C24—C23 | 109.4 (2) |
C24—N5—Mg1 | 127.20 (16) | N6—C25—N7 | 127.4 (2) |
C17—N5—Mg1 | 123.71 (15) | N6—C25—C26 | 123.0 (2) |
C24—N6—C25 | 123.59 (19) | N7—C25—C26 | 109.6 (2) |
C32—N7—C25 | 107.4 (2) | C27—C26—C31 | 119.5 (2) |
C32—N7—Mg1 | 125.09 (16) | C27—C26—C25 | 134.6 (2) |
C25—N7—Mg1 | 126.03 (16) | C31—C26—C25 | 105.7 (2) |
C1—N8—C32 | 121.9 (2) | C28—C27—C26 | 118.6 (2) |
N8—C1—N1 | 129.6 (2) | C28—C27—H27 | 120.7 |
N8—C1—C2 | 122.0 (3) | C26—C27—H27 | 120.7 |
N1—C1—C2 | 108.4 (2) | C29—C28—C27 | 121.9 (2) |
C7—C2—C3 | 121.1 (3) | C29—C28—H28 | 119.1 |
C7—C2—C1 | 108.2 (3) | C27—C28—H28 | 119.1 |
C3—C2—C1 | 130.4 (3) | C28—C29—C30 | 121.8 (3) |
C4—C3—C2 | 114.5 (3) | C28—C29—H29 | 119.1 |
C4—C3—H3 | 122.7 | C30—C29—H29 | 119.1 |
C2—C3—H3 | 122.7 | C29—C30—C31 | 116.7 (3) |
C5—C4—C3 | 123.9 (3) | C29—C30—H30 | 121.7 |
C5—C4—H4 | 118.0 | C31—C30—H30 | 121.7 |
C3—C4—H4 | 118.0 | C26—C31—C32 | 107.0 (2) |
C4—C5—C6 | 120.3 (3) | C26—C31—C30 | 121.3 (2) |
C4—C5—H5 | 119.9 | C32—C31—C30 | 131.7 (3) |
C6—C5—H5 | 119.9 | N7—C32—N8 | 126.9 (2) |
C7—C6—C5 | 116.6 (3) | N7—C32—C31 | 110.2 (2) |
C7—C6—H6 | 121.7 | N8—C32—C31 | 122.7 (3) |
C5—C6—H6 | 121.7 | C42—N41—C46 | 118.5 (3) |
C6—C7—C2 | 122.8 (3) | N41—C42—C43 | 119.4 (4) |
C6—C7—C8 | 131.3 (3) | N41—C42—H42 | 120.3 |
C2—C7—C8 | 105.8 (2) | C43—C42—H42 | 120.3 |
N2—C8—N1 | 125.2 (2) | C44—C43—C42 | 118.5 (3) |
N2—C8—C7 | 124.9 (2) | C44—C43—Cl1 | 124.7 (4) |
N1—C8—C7 | 109.8 (2) | C42—C43—Cl1 | 116.8 (4) |
N2—C9—N3 | 128.4 (2) | C43—C44—C45 | 117.9 (4) |
N2—C9—C10 | 122.8 (2) | C43—C44—H44 | 121.1 |
N3—C9—C10 | 108.7 (3) | C45—C44—H44 | 121.1 |
C11—C10—C15 | 120.8 (3) | C46—C45—C44 | 120.3 (5) |
C11—C10—C9 | 133.0 (3) | C46—C45—H45 | 119.9 |
C15—C10—C9 | 106.3 (2) | C44—C45—H45 | 119.9 |
C12—C11—C10 | 120.9 (3) | C45—C46—N41 | 124.9 (5) |
C12—C11—H11 | 119.6 | C45—C46—H46 | 117.6 |
C10—C11—H11 | 119.6 | N41—C46—H46 | 117.6 |
C11—C12—C13 | 117.4 (3) | C56—N51—C52 | 115.7 (8) |
C11—C12—H12 | 121.3 | C53—C52—N51 | 117.2 (5) |
C13—C12—H12 | 121.3 | C53—C52—H52 | 121.4 |
C14—C13—C12 | 125.4 (3) | N51—C52—H52 | 121.4 |
C14—C13—H13 | 117.3 | C52—C53—C54 | 120.3 (4) |
C12—C13—H13 | 117.3 | C52—C53—Cl2 | 121.4 (5) |
C13—C14—C15 | 114.3 (3) | C54—C53—Cl2 | 117.2 (6) |
C13—C14—H14 | 122.9 | C55—C54—C53 | 114.6 (7) |
C15—C14—H14 | 122.9 | C55—C54—H54 | 122.7 |
C14—C15—C10 | 121.2 (2) | C53—C54—H54 | 122.7 |
C14—C15—C16 | 131.2 (3) | C56—C55—C54 | 123.3 (10) |
C10—C15—C16 | 107.5 (2) | C56—C55—H55 | 118.3 |
N4—C16—N3 | 127.3 (2) | C54—C55—H55 | 118.3 |
N4—C16—C15 | 123.4 (2) | N51—C56—C55 | 126.6 (10) |
N3—C16—C15 | 109.3 (2) | N51—C56—H56 | 116.7 |
N4—C17—N5 | 130.9 (2) | C55—C56—H56 | 116.7 |
N4—C17—C18 | 120.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···N41 | 0.82 | 1.99 | 2.758 (3) | 156 |
O1—H2O···N6i | 0.82 | 2.09 | 2.880 (2) | 163 |
C46—H46···N51 | 0.93 | 2.43 | 3.344 (8) | 167 |
Symmetry code: (i) −x+3/2, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Mg(C32H16N8)(H2O)]·2C5H4ClN |
Mr | 781.94 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 295 |
a, b, c (Å) | 14.981 (3), 13.956 (2), 18.309 (3) |
β (°) | 105.80 (1) |
V (Å3) | 3683.3 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.24 |
Crystal size (mm) | 0.38 × 0.27 × 0.24 |
Data collection | |
Diffractometer | Kuma KM-4 CCD area-detector diffractometer |
Absorption correction | Analytical [face-indexed (SHELXTL; Sheldrick, 1990)] |
Tmin, Tmax | 0.929, 0.947 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 39524, 8890, 5340 |
Rint | 0.045 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.063, 0.111, 1.01 |
No. of reflections | 8890 |
No. of parameters | 511 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.16 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2005), CrysAlis CCD, CrysAlis RED (Oxford Diffraction, 2005), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELTXL (Sheldrick, 1990), SHELXL97.
Mg1—O1 | 2.029 (2) | Mg1—N5 | 2.044 (2) |
Mg1—N1 | 2.039 (2) | Mg1—N7 | 2.030 (2) |
Mg1—N3 | 2.024 (2) | ||
O1—Mg1—N1 | 106.09 (8) | N1—Mg1—N5 | 152.49 (8) |
O1—Mg1—N3 | 107.94 (7) | N1—Mg1—N7 | 87.50 (9) |
O1—Mg1—N5 | 101.35 (8) | N3—Mg1—N5 | 86.86 (8) |
O1—Mg1—N7 | 100.88 (8) | N3—Mg1—N7 | 151.10 (8) |
N1—Mg1—N3 | 86.64 (9) | N5—Mg1—N7 | 85.40 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···N41 | 0.82 | 1.99 | 2.758 (3) | 156 |
O1—H2O···N6i | 0.82 | 2.09 | 2.880 (2) | 163 |
C46—H46···N51 | 0.93 | 2.43 | 3.344 (8) | 167 |
Symmetry code: (i) −x+3/2, y+1/2, −z+1/2. |
Our interest in magnesium phthalocyanine (Pc) and its complexes exhibiting (4 + 1)-coordination of the central Mg atom (Kubiak et al., 1995; Janczak & Kubiak, 2001; Janczak & Idemori, 2002) arises from their similarities to chlorophyll (Clayton, 1966; Sauer et al., 1968; Balischmiter & Katz, 1969; Larkum & Kühl, 2005), as they possess a similar coordination environment of the central Mg atom, as well as from their solid-state optical properties (especially the `X-phase'). However, the origin and the nature of the near-IR broad absorption are not completely understood, though a few possible explanations are found in the literature. Endo et al. (1999) assigned the MgPc(H2O)2 composition to the `X-phase' and suggested that the near-IR broad absorption band arises from exciton coupling effects. Janczak & Idemori (2003) studied the solid-state near-IR absorption spectra of MgPc and the triclinic modification of MgPc(H2O), suggesting that the origin of this near-IR absorption arises from the specific molecular arrangement in the crystal structures. In both structures, a similar arrangement of the structural motif is present, i.e. face-to-face dimers of π–π stacked molecules (Janczak & Kubiak, 2001; Janczak & Idemori, 2003). Furthermore, the monoclinic modification of MgPc(H2O) does not exhibit near-IR absorption, since the molecular arrangement is different from that in the active triclinic form (Mizuguchi, 2002). This hypothesis is supported by work reporting the solid-state spectra of titanyl phthalocyanine (TiOPc) and vanadyl phthalocyanine (VOPc), which analogously to MgPc(H2O) appear in two crystallographic modifications, i.e. in monoclinic and triclinic forms (Ziolo et al., 1980; Yamada et al., 1996; Hiller et al., 1982; Oka et al., 1992). However, only the triclinic form is near-IR active (Saito et al., 1993, 1994; Naleva et al., 1993; Mizuguchi et al., 1995). Thus, the electronic spectra vary significantly as a result of molecular interactions and, especially, of the molecular arrangement in the crystals. The present structure analysis has been carried out in order to study the correlation between the crystal and electronic structures in the title compound, (I).
The asymmetric unit in (I) consists of an aqua(phthalocyaninato)magnesium(II) and two 3-chloropyridine (A and B) molecules (Fig. 1). The geometry of the MgPcH2O unit is not planar and the central Mg atom exhibits (4 + 1) geometry, coordinated equatorially by four N-isoindole atoms of the Pc macrocycle and by the O atom of an axial water molecule (Table 1). This coordination environment of the central Mg atom is similar to that found in several chlorophyll derivatives (Kratky & Dunitz, 1975; Chow et al., 1975; Serlin et al., 1975). Owing to the interaction with the axially coordinated water O atom, the central Mg atom is significantly displaced [0.496 (2) Å] from the weighted least-squares plane defined by the four isoindole N atoms. The displacement of the Mg atom from the N4 plane is comparable to that observed in other aqua–magnesium–phthalocyanine complexes solvated by pyridine (Fischer et al., 1971; Mizuguchi & Mochizuki, 2002), diethylamine (Kinzhybalo & Janczak, 2007a), n-propylamine (Kinzhybalo & Janczak, 2007b) or 2-methoxyethylamine (Kinzhybalo & Janczak, 2007c), as well as in the triclinic and monoclinic modifications of MgPcH2O (Janczak & Idemori, 2003; Mizuguchi, 2002). In all cases, the Mg atom displacement from the N4 plane lies between 0.442 (2) and 0.502 (2) Å.
The displacement of Mg from the N4 plane in magnesium–phthalocyaninate complexes is significantly greater (by about 0.15 Å) than that in aqua–magnesium–porphyrinate complexes (Choon et al., 1986; McKee & Rodley, 1988; Yang & Jacobson, 1991; Timkovich or??? Timkovitch & Tulinsky, 1969; Velazquez et al., 1992; Barkigia et al. 1983) and in chlorophyll derivatives (Kratky & Dunitz, 1975; Chow et al., 1975; Serlin et al., 1975) owing to the greater flexibilty of the porphyrinate ring, as well as to the larger central hole in comparison with the Pc macroring. The saucer-shape geometry of MgPcH2O in (I) results from the interaction of the positively charged central Mg atom of about +0.5 (Zerner et al. 1966) with the negatively charged O atom of the water molecule and is comparable to that in the gas phase obtained by molecular orbital calculations (Janczak & Idemori, 2003). However, the ab-initio calculated axial Mg—O bond (2.142 Å) is significantly longer than that in (I) [2.029 (2) Å].
The electron-rich N atom of one 3-chloropyridine (3-Clpyr) molecule (A) accepts the O donor atom of the water molecule and forms an O—H···N hydrogen bond (Fig. 1 and Table 2). Molecule A is almost parallel to the mean Pc plane [~6.1 (2)°]. The second 3-Clpyr molecule (B) is also almost parallel to the Pc plane, although it is not hydrogen bonded with the MgPcH2O molecule; rign atom N51 is oriented towards H46/C46 of the 3-Clpyr molecule (A). The C···N distance between these halopyridines [the ring plane dihedral angle is 7.7 (2)°] is long [C46···N51 = 3.343 (3) Å] but important, as shown by the molecular orbital calculations (Frisch et al., 1998) on 3-Clpyr dimers with geometry similar to that of A and B in (I). The electrostatic potential calculated for the 3-Clpyr molecules has an opposite sign around the interacting N51···H46 atoms. The lone electron pair on atom N51 is oriented towards H46/C46 of the other 3-Clpyr molecule (A), and between the N51 and H46 atoms the (3,-1) critical point characterizing the interaction between N51 and H46 can be localized (Bader, 1990). Molecules A and B are essentially parallel to the Pc macroring, at 1.1 (2) and 3.8 (2)° to their closest Pc C6 rings; however, owing to the saucer shape of the ring, the distances are slightly longer (by about 0.1 Å) but indicate significant π–π overlaps between the aromatic ring π clouds (the ring centroid distances are 3.4–3.6 Å). As a result of the π–π interactions, the C18–C23 and C26–C31 phenyl rings are less distorted from the Pc N4 plane than the other half of the Pc macrocycle. The average deviations of the C atoms of these two C6 aromatic rings are 0.269 and 0.143 Å, while the average deviations of the C atoms of the C2–C7 and C10–C15 rings are 0.569 and 0.324 Å, respectively.
MgPcH2O–3-chloropyridine systems related by a twofold screw axes interact via O—H···Nazamethine hydrogen bonds, forming pseudo-one-dimensional chains along the b axis (Fig. 2). MgPcH2O molecules related by an inversion interact via π–π interactions in a back-to-back fashion [the interplanar N4 distance is 3.392 (3) Å]. The overlap of the Pc ligands in this manner in (I) is characteristic of five-coordinate (4 + 1) Mg–phthalocyaninate(2-) complexes (Fig. 3). Scheidt & Lee (1987) examined the overlap in neutral, structurally characterized, sterically unhindered metal–porphyrinate complexes and discovered that the distribution of the lateral shift of the ligands is trimodal rather than continuous. The values appear to cluster at ~1.5 Å for dimers with strong π–π overlap, at ~3.5 Å with intermediate π–π overlap and at ~6.5 Å with weak overlap. The Pc ligands in the dimers of (I) [with an N4 interplanar distance of 3.392 (3) Å] represent an intermediate overlap between the ligand π-systems. However, owing to the saucer shape of the Pc ligands, the mean interplanar separation between the dimer 40-atom rings (~3.22 Å) is nearly midway between the sum of the C atom van der Waals radii of the π-ring system (~3.4 Å) and the distance at which the steric interactions between the π-aromatic ring system becomes predominantly repulsive (~3.08 Å; Pauling, 1960). Thus, a degree of π–π stabilization in (I) is evident, and the O—H···N hydrogen bonds play an important role in the molecular packing pattern. Besides these dimers, π–π interactions between the 3-chloropyridine molecules and half of the Pc macroring add to the energetically favourable molecular arrangement, and yield to greater planarity in half of the Pc ligand (as noted above).
In (I), chains of MgPcH2O and 3-chloropyridine molecules related by inversion centres interact via the π–π clouds, forming a hole at the (1/2, 1/2, 1/2) site and symmetrically equivalent positions in which the 3-chloropyridine molecules are located (Fig. 3). Since the molecular arrangement of the MgPcH2O and 3-Clpyr molecules is different from that of the triclinic modification of MgPcH2O (Janczak & Idemori, 2003) and MgPcH2O·MPA (MPA is 2-methoxyethylamine; Kinzhybalo & Janczak, 2007b), both being near-IR active, the present crystal does not show near-IR broad absorption bands. Instead, it exhibits characteristic absorption bands caused by the molecular distortion. In 3-chloropyridine solution, this compound has a UV–vis spectrum that is quite similiar to that of MgPcH2O in pyridine solution (Janczak & Idemori, 2003). In the solid state, a slight broadening of the bands was observed, since upon crystallization the double degeneracy of the excited state is lifted because of the molecular distortion (approximately C4v in solution and C1 in the solid state).
Thermogravimetric analysis shows three characteristic steps, the first at ca 400 K, the second at ca 440 K and the third at ca 478 K, and these correspond exactly to the successive weight loss of one 3-Clpyr molecule (14.51%), the second 3-Clpyr molecule and the water molecule (3.25%). The third step, at 478 K, correlates well with the loss of water in the MgPcH2O complex (Janczak & Idemori, 2003). Finally, above 478 K, the sample transforms into the β-modification of MgPc (Kubiak et al., 1995).