Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807040688/cs2044sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807040688/cs2044Isup2.hkl |
CCDC reference: 660156
A methanol solution of PAN (0.3 mmol, 3 ml) was mixed with a methanol solution of chromium(III) nitrate (0.3 mmol, 3 ml). The resulting solution was kept under stirring for about 30 min, and then an aqueous solution of KSCN (0.6 mmol, 6 ml) was added to the mixture. Dark green single crystals were obtained after three weeks (yield 32%).
The hydrogen atoms were assigned with isotropic displacement factors and included in the final refinement cycles by use of geometrical restraints (Car–H = 0.93 Å; CMe–H = 0.96 Å; N–H = 0.86 Å; O–H = 0.82 Å).
The color reactions of metal ions and PAN (1-(pyridin-2-yldiazenyl)naphthalen-2-ol) were a useful method in spectrophotometric determination. We report herein the crystal structure of a chromium(III) complex where the CrIII ion is coordinated by a PAN- and three thiocyanate ions.
The crystal structure of (I) consists of a [Cr(PAN)(NCS)3]- anion, an uncoordinated protonated PAN cation and a methanol molecule (Fig. 1). The chromium ion has a slightly distorted octahedral coordination geometry, its symmetry being close to C2V. The Cr—N(PAN) bond distances are 2.006 (4) and 2.058 (5) Å, the Cr—O bond distance is 1.970 (4) Å. The ligand is planar, the dihedral angle between two aromatic rings is 6.5 (3)°. The Cr—N(NCS) bond distances vary in the range 1.981 (6)–2.001 (6) Å, and the thiocyanate ligands are almost linear with N–C–S angles 178.6 (6)–179.4 (7)°.
The uncoordinated PAN is protonated at (N9), the dihedral angle between two aromatic rings is 15.4 (2)°. Related aromatic rings A and Bi [ring A: C5, C6, C7, C8, C9 and C10; ring B: N9, C29, C30, C31, C32 and C33; symmetry code: (i) 1 - x, y, 1 - z) show π-π stacking with a ring-ring separation of 3.594 (4) Å. A C—S···Cg (π-ring centre) interaction from the C17—S2 bond to ring Rii [ring R: C19, C20, C21, C22, C23 and C28; symmetry code: (ii) -x, 1 - y, 1 - z) is also obsered [C17···Cg = 3.684 (7), S···Cg = 3.483 (5) Å and C17—S···Cg = 84.1 (2)°] (Fig. 2). The crystal packing is characterized by three conventional hydrogen bonds, c.f. Table (Spek, 2003).
For related literature, see: Spek (2003).
Data collection: APEX2 (Bruker, DATE?); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997a).
(C15H12N3O)[Cr(C15H10N3O)(NCS)3]·CH4O | Z = 2 |
Mr = 756.82 | F(000) = 778 |
Triclinic, P1 | Dx = 1.435 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 11.5045 (11) Å | Cell parameters from 943 reflections |
b = 12.3189 (11) Å | θ = 2.4–18.5° |
c = 12.5197 (12) Å | µ = 0.56 mm−1 |
α = 95.568 (2)° | T = 273 K |
β = 91.851 (2)° | Block, dark green |
γ = 96.973 (2)° | 0.25 × 0.22 × 0.17 mm |
V = 1751.1 (3) Å3 |
Bruker SMART APEX II CCD diffractometer | 7770 independent reflections |
Radiation source: fine-focus sealed tube | 2997 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
φ and ω scans | θmax = 27.5°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −15→10 |
Tmin = 0.874, Tmax = 0.912 | k = −16→16 |
11793 measured reflections | l = −16→16 |
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)] = 0.067 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.209 | H-atom parameters constrained |
S = 0.96 | w = 1/[σ2(Fo2) + (0.0826P)2] where P = (Fo2 + 2Fc2)/3 |
7770 reflections | (Δ/σ)max < 0.001 |
454 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.40 e Å−3 |
(C15H12N3O)[Cr(C15H10N3O)(NCS)3]·CH4O | γ = 96.973 (2)° |
Mr = 756.82 | V = 1751.1 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.5045 (11) Å | Mo Kα radiation |
b = 12.3189 (11) Å | µ = 0.56 mm−1 |
c = 12.5197 (12) Å | T = 273 K |
α = 95.568 (2)° | 0.25 × 0.22 × 0.17 mm |
β = 91.851 (2)° |
Bruker SMART APEX II CCD diffractometer | 7770 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2997 reflections with I > 2σ(I) |
Tmin = 0.874, Tmax = 0.912 | Rint = 0.039 |
11793 measured reflections |
R[F2 > 2σ(F2)] = 0.067 | 0 restraints |
wR(F2) = 0.209 | H-atom parameters constrained |
S = 0.96 | Δρmax = 0.30 e Å−3 |
7770 reflections | Δρmin = −0.40 e Å−3 |
454 parameters |
x | y | z | Uiso*/Ueq | ||
Cr1 | 0.67707 (7) | 0.78088 (6) | 0.54026 (6) | 0.0578 (3) | |
C1 | 0.4376 (4) | 0.7422 (4) | 0.4627 (4) | 0.0548 (12) | |
C2 | 0.4604 (4) | 0.6584 (4) | 0.5301 (4) | 0.0559 (13) | |
C3 | 0.3659 (5) | 0.5775 (4) | 0.5483 (4) | 0.0677 (15) | |
H3 | 0.3784 | 0.5222 | 0.5913 | 0.081* | |
C4 | 0.2590 (5) | 0.5803 (4) | 0.5038 (5) | 0.0727 (16) | |
H4 | 0.1985 | 0.5276 | 0.5190 | 0.087* | |
C5 | 0.2331 (4) | 0.6610 (4) | 0.4336 (5) | 0.0665 (15) | |
C6 | 0.1223 (5) | 0.6589 (5) | 0.3868 (6) | 0.0886 (19) | |
H6 | 0.0619 | 0.6078 | 0.4051 | 0.106* | |
C7 | 0.0996 (5) | 0.7317 (5) | 0.3128 (6) | 0.102 (2) | |
H7 | 0.0250 | 0.7287 | 0.2807 | 0.122* | |
C8 | 0.1902 (5) | 0.8092 (5) | 0.2875 (6) | 0.100 (2) | |
H8 | 0.1760 | 0.8576 | 0.2374 | 0.120* | |
C9 | 0.2999 (4) | 0.8154 (4) | 0.3350 (5) | 0.0741 (16) | |
H9A | 0.3587 | 0.8689 | 0.3180 | 0.089* | |
C10 | 0.3250 (4) | 0.7413 (4) | 0.4100 (4) | 0.0620 (14) | |
C11 | 0.6506 (4) | 0.9631 (4) | 0.4199 (4) | 0.0536 (12) | |
C12 | 0.6706 (5) | 1.0577 (4) | 0.3700 (4) | 0.0674 (15) | |
H12 | 0.6115 | 1.0803 | 0.3281 | 0.081* | |
C13 | 0.7799 (5) | 1.1187 (4) | 0.3829 (5) | 0.0785 (17) | |
H13 | 0.7958 | 1.1828 | 0.3495 | 0.094* | |
C14 | 0.8649 (5) | 1.0833 (5) | 0.4458 (5) | 0.0891 (19) | |
H14 | 0.9392 | 1.1229 | 0.4549 | 0.107* | |
C15 | 0.8397 (4) | 0.9896 (5) | 0.4951 (5) | 0.0799 (17) | |
H15 | 0.8968 | 0.9684 | 0.5402 | 0.096* | |
C16 | 0.7459 (4) | 0.6619 (4) | 0.3243 (5) | 0.0631 (14) | |
C17 | 0.8993 (4) | 0.7003 (4) | 0.6412 (4) | 0.0530 (12) | |
C18 | 0.6145 (4) | 0.9187 (5) | 0.7523 (5) | 0.0639 (14) | |
C19 | 0.9169 (7) | 0.2356 (8) | 1.0362 (5) | 0.106 (3) | |
C20 | 1.0369 (13) | 0.2950 (12) | 1.0400 (8) | 0.156 (6) | |
C21 | 1.1309 (12) | 0.2374 (15) | 1.0798 (11) | 0.221 (10) | |
H21 | 1.2080 | 0.2703 | 1.0786 | 0.265* | |
C22 | 1.1116 (19) | 0.1451 (17) | 1.1155 (14) | 0.244 (14) | |
H22 | 1.1756 | 0.1118 | 1.1369 | 0.293* | |
C23 | 0.9927 (12) | 0.0864 (11) | 1.1256 (7) | 0.171 (5) | |
C24 | 0.9728 (15) | −0.0160 (12) | 1.1704 (12) | 0.214 (10) | |
H24 | 1.0357 | −0.0445 | 1.2011 | 0.256* | |
C25 | 0.8660 (16) | −0.0715 (12) | 1.1694 (12) | 0.223 (10) | |
H25 | 0.8551 | −0.1393 | 1.1969 | 0.268* | |
C26 | 0.7713 (10) | −0.0280 (7) | 1.1273 (6) | 0.157 (4) | |
H26 | 0.6962 | −0.0657 | 1.1276 | 0.188* | |
C27 | 0.7892 (10) | 0.0735 (7) | 1.0842 (6) | 0.130 (4) | |
H27 | 0.7253 | 0.1026 | 1.0561 | 0.156* | |
C28 | 0.8979 (9) | 0.1299 (9) | 1.0829 (6) | 0.120 (4) | |
C29 | 0.7445 (5) | 0.3957 (6) | 0.8938 (4) | 0.0848 (18) | |
C30 | 0.7542 (5) | 0.4775 (6) | 0.8238 (4) | 0.097 (2) | |
H30 | 0.8272 | 0.5149 | 0.8122 | 0.116* | |
C31 | 0.6560 (7) | 0.5021 (6) | 0.7725 (5) | 0.105 (2) | |
H31 | 0.6620 | 0.5569 | 0.7261 | 0.126* | |
C32 | 0.5476 (6) | 0.4462 (6) | 0.7889 (6) | 0.102 (2) | |
H32 | 0.4804 | 0.4622 | 0.7534 | 0.123* | |
C33 | 0.5414 (6) | 0.3685 (6) | 0.8571 (5) | 0.103 (2) | |
H33 | 0.4689 | 0.3305 | 0.8695 | 0.124* | |
C34 | 0.4037 (9) | 0.7067 (6) | 0.8293 (7) | 0.171 (4) | |
H34A | 0.3448 | 0.7471 | 0.8023 | 0.256* | |
H34B | 0.3691 | 0.6336 | 0.8392 | 0.256* | |
H34C | 0.4647 | 0.7031 | 0.7790 | 0.256* | |
N1 | 0.5352 (3) | 0.8163 (3) | 0.4601 (3) | 0.0515 (10) | |
N2 | 0.5393 (3) | 0.9016 (3) | 0.4073 (3) | 0.0543 (10) | |
N3 | 0.7350 (3) | 0.9268 (3) | 0.4807 (3) | 0.0617 (11) | |
N4 | 0.7172 (4) | 0.7007 (4) | 0.4042 (4) | 0.0668 (12) | |
N5 | 0.8219 (4) | 0.7427 (4) | 0.6115 (3) | 0.0690 (12) | |
N6 | 0.6368 (4) | 0.8688 (4) | 0.6740 (4) | 0.0663 (12) | |
N7 | 0.8267 (4) | 0.2708 (5) | 0.9922 (4) | 0.0939 (17) | |
N8 | 0.8414 (4) | 0.3668 (6) | 0.9466 (4) | 0.0974 (18) | |
N9 | 0.6382 (4) | 0.3447 (4) | 0.9076 (4) | 0.0877 (15) | |
H9 | 0.6312 | 0.2944 | 0.9509 | 0.105* | |
O1 | 0.5634 (3) | 0.6576 (3) | 0.5728 (3) | 0.0601 (9) | |
O2 | 1.0568 (5) | 0.3861 (8) | 1.0048 (5) | 0.158 (4) | |
H2 | 0.9979 | 0.3994 | 0.9724 | 0.236* | |
O3 | 0.4523 (5) | 0.7608 (5) | 0.9300 (4) | 0.1310 (18) | |
H3A | 0.5003 | 0.8131 | 0.9193 | 0.196* | |
S1 | 0.78500 (16) | 0.60433 (18) | 0.21174 (16) | 0.1208 (7) | |
S2 | 1.00656 (11) | 0.64120 (11) | 0.68460 (12) | 0.0674 (4) | |
S3 | 0.58372 (16) | 0.98911 (14) | 0.86114 (13) | 0.0944 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cr1 | 0.0502 (5) | 0.0543 (5) | 0.0720 (6) | 0.0090 (4) | −0.0011 (4) | 0.0206 (4) |
C1 | 0.047 (3) | 0.048 (3) | 0.071 (3) | 0.000 (2) | 0.001 (3) | 0.021 (3) |
C2 | 0.053 (3) | 0.048 (3) | 0.068 (3) | 0.006 (2) | 0.001 (3) | 0.013 (3) |
C3 | 0.072 (4) | 0.049 (3) | 0.085 (4) | 0.002 (3) | 0.018 (3) | 0.025 (3) |
C4 | 0.068 (4) | 0.047 (3) | 0.102 (4) | −0.008 (3) | 0.016 (3) | 0.014 (3) |
C5 | 0.049 (3) | 0.046 (3) | 0.101 (4) | −0.006 (2) | −0.002 (3) | 0.007 (3) |
C6 | 0.055 (4) | 0.064 (4) | 0.141 (6) | −0.010 (3) | −0.013 (4) | 0.008 (4) |
C7 | 0.057 (4) | 0.084 (5) | 0.160 (7) | −0.001 (4) | −0.028 (4) | 0.014 (5) |
C8 | 0.059 (4) | 0.086 (4) | 0.151 (6) | −0.011 (3) | −0.043 (4) | 0.032 (4) |
C9 | 0.054 (3) | 0.058 (3) | 0.109 (4) | −0.005 (3) | −0.022 (3) | 0.025 (3) |
C10 | 0.051 (3) | 0.044 (3) | 0.090 (4) | −0.001 (2) | −0.001 (3) | 0.012 (3) |
C11 | 0.044 (3) | 0.044 (3) | 0.073 (3) | 0.000 (2) | −0.002 (3) | 0.017 (3) |
C12 | 0.059 (3) | 0.054 (3) | 0.090 (4) | −0.002 (3) | −0.007 (3) | 0.024 (3) |
C13 | 0.065 (4) | 0.056 (3) | 0.115 (5) | −0.003 (3) | 0.008 (4) | 0.022 (3) |
C14 | 0.047 (3) | 0.070 (4) | 0.149 (6) | −0.014 (3) | 0.001 (4) | 0.034 (4) |
C15 | 0.040 (3) | 0.078 (4) | 0.124 (5) | 0.002 (3) | −0.008 (3) | 0.031 (4) |
C16 | 0.049 (3) | 0.064 (4) | 0.077 (4) | −0.002 (3) | 0.001 (3) | 0.021 (3) |
C17 | 0.051 (3) | 0.052 (3) | 0.058 (3) | 0.003 (2) | 0.005 (3) | 0.018 (2) |
C18 | 0.052 (3) | 0.064 (4) | 0.077 (4) | 0.005 (3) | −0.012 (3) | 0.021 (3) |
C19 | 0.092 (5) | 0.167 (8) | 0.062 (4) | 0.069 (6) | −0.024 (4) | −0.034 (5) |
C20 | 0.132 (10) | 0.257 (16) | 0.081 (7) | 0.087 (12) | −0.018 (7) | −0.046 (8) |
C21 | 0.125 (9) | 0.38 (2) | 0.150 (11) | 0.169 (15) | −0.083 (8) | −0.158 (14) |
C22 | 0.234 (16) | 0.34 (3) | 0.167 (13) | 0.24 (2) | −0.118 (12) | −0.149 (16) |
C23 | 0.204 (11) | 0.199 (12) | 0.117 (7) | 0.153 (10) | −0.081 (8) | −0.079 (7) |
C24 | 0.34 (2) | 0.171 (15) | 0.145 (9) | 0.201 (17) | −0.130 (14) | −0.068 (10) |
C25 | 0.41 (3) | 0.142 (12) | 0.126 (8) | 0.147 (16) | −0.101 (16) | −0.042 (8) |
C26 | 0.263 (12) | 0.109 (7) | 0.111 (6) | 0.100 (8) | −0.041 (7) | −0.006 (5) |
C27 | 0.209 (10) | 0.114 (7) | 0.078 (5) | 0.100 (7) | −0.050 (6) | −0.018 (5) |
C28 | 0.134 (7) | 0.156 (9) | 0.079 (5) | 0.108 (7) | −0.045 (5) | −0.036 (5) |
C29 | 0.067 (4) | 0.127 (5) | 0.059 (4) | −0.009 (4) | −0.006 (3) | 0.033 (4) |
C30 | 0.071 (4) | 0.150 (6) | 0.064 (4) | −0.029 (4) | −0.012 (3) | 0.042 (4) |
C31 | 0.116 (6) | 0.119 (6) | 0.077 (4) | −0.017 (5) | −0.032 (4) | 0.050 (4) |
C32 | 0.076 (5) | 0.121 (6) | 0.115 (5) | 0.003 (4) | −0.021 (4) | 0.058 (5) |
C33 | 0.074 (4) | 0.118 (6) | 0.121 (5) | 0.005 (4) | −0.019 (4) | 0.054 (5) |
C34 | 0.278 (13) | 0.092 (6) | 0.141 (8) | 0.003 (7) | 0.079 (9) | 0.009 (6) |
N1 | 0.048 (2) | 0.046 (2) | 0.064 (2) | 0.0084 (19) | 0.002 (2) | 0.016 (2) |
N2 | 0.048 (2) | 0.043 (2) | 0.072 (3) | −0.0033 (18) | −0.009 (2) | 0.023 (2) |
N3 | 0.043 (2) | 0.059 (3) | 0.084 (3) | 0.002 (2) | −0.005 (2) | 0.021 (2) |
N4 | 0.064 (3) | 0.063 (3) | 0.076 (3) | 0.010 (2) | 0.013 (3) | 0.018 (3) |
N5 | 0.057 (3) | 0.073 (3) | 0.082 (3) | 0.019 (2) | −0.003 (2) | 0.025 (2) |
N6 | 0.062 (3) | 0.064 (3) | 0.075 (3) | 0.013 (2) | −0.004 (3) | 0.013 (3) |
N7 | 0.082 (4) | 0.149 (5) | 0.058 (3) | 0.045 (4) | −0.012 (3) | 0.011 (3) |
N8 | 0.065 (3) | 0.169 (6) | 0.062 (3) | 0.021 (4) | −0.012 (3) | 0.032 (4) |
N9 | 0.072 (3) | 0.113 (4) | 0.083 (3) | 0.001 (3) | −0.006 (3) | 0.053 (3) |
O1 | 0.057 (2) | 0.052 (2) | 0.075 (2) | 0.0083 (17) | 0.0027 (18) | 0.0236 (17) |
O2 | 0.050 (3) | 0.331 (12) | 0.083 (4) | 0.039 (6) | −0.017 (3) | −0.034 (5) |
O3 | 0.162 (5) | 0.117 (4) | 0.122 (4) | 0.006 (4) | 0.041 (4) | 0.059 (4) |
S1 | 0.0898 (13) | 0.1460 (18) | 0.1114 (14) | −0.0141 (12) | 0.0249 (12) | −0.0339 (13) |
S2 | 0.0527 (8) | 0.0620 (9) | 0.0906 (10) | 0.0118 (7) | −0.0018 (7) | 0.0200 (8) |
S3 | 0.1116 (14) | 0.0906 (12) | 0.0783 (11) | 0.0090 (10) | 0.0017 (10) | 0.0002 (9) |
Cr1—O1 | 1.964 (3) | C18—S3 | 1.616 (6) |
Cr1—N4 | 1.981 (5) | C19—N7 | 1.299 (7) |
Cr1—N5 | 1.992 (4) | C19—C28 | 1.473 (12) |
Cr1—N1 | 2.003 (4) | C19—C20 | 1.479 (15) |
Cr1—N6 | 2.003 (5) | C20—O2 | 1.244 (13) |
Cr1—N3 | 2.058 (4) | C20—C21 | 1.463 (15) |
C1—N1 | 1.362 (5) | C21—C22 | 1.26 (3) |
C1—C10 | 1.433 (6) | C21—H21 | 0.9300 |
C1—C2 | 1.438 (6) | C22—C23 | 1.48 (2) |
C2—O1 | 1.286 (5) | C22—H22 | 0.9300 |
C2—C3 | 1.422 (6) | C23—C28 | 1.387 (10) |
C3—C4 | 1.339 (7) | C23—C24 | 1.43 (2) |
C3—H3 | 0.9300 | C24—C25 | 1.33 (2) |
C4—C5 | 1.440 (7) | C24—H24 | 0.9300 |
C4—H4 | 0.9300 | C25—C26 | 1.382 (14) |
C5—C6 | 1.381 (7) | C25—H25 | 0.9300 |
C5—C10 | 1.416 (6) | C26—C27 | 1.404 (11) |
C6—C7 | 1.391 (8) | C26—H26 | 0.9300 |
C6—H6 | 0.9300 | C27—C28 | 1.356 (12) |
C7—C8 | 1.392 (8) | C27—H27 | 0.9300 |
C7—H7 | 0.9300 | C29—N9 | 1.330 (7) |
C8—C9 | 1.368 (7) | C29—N8 | 1.379 (7) |
C8—H8 | 0.9300 | C29—C30 | 1.395 (8) |
C9—C10 | 1.419 (7) | C30—C31 | 1.362 (8) |
C9—H9A | 0.9300 | C30—H30 | 0.9300 |
C11—N3 | 1.358 (5) | C31—C32 | 1.381 (8) |
C11—C12 | 1.374 (6) | C31—H31 | 0.9300 |
C11—N2 | 1.403 (5) | C32—C33 | 1.341 (8) |
C12—C13 | 1.380 (7) | C32—H32 | 0.9300 |
C12—H12 | 0.9300 | C33—N9 | 1.340 (7) |
C13—C14 | 1.374 (7) | C33—H33 | 0.9300 |
C13—H13 | 0.9300 | C34—O3 | 1.430 (9) |
C14—C15 | 1.366 (7) | C34—H34A | 0.9600 |
C14—H14 | 0.9300 | C34—H34B | 0.9600 |
C15—N3 | 1.346 (6) | C34—H34C | 0.9600 |
C15—H15 | 0.9300 | N1—N2 | 1.292 (4) |
C16—N4 | 1.143 (6) | N7—N8 | 1.356 (7) |
C16—S1 | 1.617 (6) | N9—H9 | 0.8600 |
C17—N5 | 1.155 (5) | O2—H2 | 0.8200 |
C17—S2 | 1.612 (5) | O3—H3A | 0.8200 |
C18—N6 | 1.159 (6) | ||
O1—Cr1—N4 | 92.38 (16) | O2—C20—C21 | 122.2 (16) |
O1—Cr1—N5 | 100.34 (15) | O2—C20—C19 | 121.2 (12) |
N4—Cr1—N5 | 89.61 (17) | C21—C20—C19 | 116.5 (13) |
O1—Cr1—N1 | 80.57 (14) | C22—C21—C20 | 123 (2) |
N4—Cr1—N1 | 87.03 (16) | C22—C21—H21 | 118.7 |
N5—Cr1—N1 | 176.56 (16) | C20—C21—H21 | 118.7 |
O1—Cr1—N6 | 89.83 (16) | C21—C22—C23 | 123.9 (15) |
N4—Cr1—N6 | 177.12 (17) | C21—C22—H22 | 118.0 |
N5—Cr1—N6 | 91.81 (17) | C23—C22—H22 | 118.0 |
N1—Cr1—N6 | 91.51 (16) | C28—C23—C24 | 118.9 (15) |
O1—Cr1—N3 | 157.01 (15) | C28—C23—C22 | 118.1 (14) |
N4—Cr1—N3 | 89.21 (17) | C24—C23—C22 | 122.9 (12) |
N5—Cr1—N3 | 102.61 (16) | C25—C24—C23 | 121.4 (15) |
N1—Cr1—N3 | 76.61 (15) | C25—C24—H24 | 119.3 |
N6—Cr1—N3 | 88.04 (17) | C23—C24—H24 | 119.3 |
N1—C1—C10 | 128.6 (4) | C24—C25—C26 | 119.7 (17) |
N1—C1—C2 | 110.1 (4) | C24—C25—H25 | 120.1 |
C10—C1—C2 | 121.3 (4) | C26—C25—H25 | 120.1 |
O1—C2—C3 | 121.4 (4) | C25—C26—C27 | 119.6 (13) |
O1—C2—C1 | 120.5 (4) | C25—C26—H26 | 120.2 |
C3—C2—C1 | 118.1 (5) | C27—C26—H26 | 120.2 |
C4—C3—C2 | 120.5 (5) | C28—C27—C26 | 121.3 (10) |
C4—C3—H3 | 119.8 | C28—C27—H27 | 119.4 |
C2—C3—H3 | 119.8 | C26—C27—H27 | 119.4 |
C3—C4—C5 | 123.2 (5) | C27—C28—C23 | 119.1 (12) |
C3—C4—H4 | 118.4 | C27—C28—C19 | 121.3 (7) |
C5—C4—H4 | 118.4 | C23—C28—C19 | 119.6 (11) |
C6—C5—C10 | 120.1 (5) | N9—C29—N8 | 120.4 (5) |
C6—C5—C4 | 121.3 (5) | N9—C29—C30 | 117.9 (6) |
C10—C5—C4 | 118.6 (5) | N8—C29—C30 | 121.7 (6) |
C5—C6—C7 | 121.3 (6) | C31—C30—C29 | 119.5 (6) |
C5—C6—H6 | 119.4 | C31—C30—H30 | 120.2 |
C7—C6—H6 | 119.4 | C29—C30—H30 | 120.2 |
C6—C7—C8 | 118.9 (6) | C30—C31—C32 | 120.4 (6) |
C6—C7—H7 | 120.6 | C30—C31—H31 | 119.8 |
C8—C7—H7 | 120.6 | C32—C31—H31 | 119.8 |
C9—C8—C7 | 121.1 (6) | C33—C32—C31 | 118.5 (6) |
C9—C8—H8 | 119.4 | C33—C32—H32 | 120.8 |
C7—C8—H8 | 119.4 | C31—C32—H32 | 120.8 |
C8—C9—C10 | 120.8 (5) | N9—C33—C32 | 120.9 (6) |
C8—C9—H9A | 119.6 | N9—C33—H33 | 119.6 |
C10—C9—H9A | 119.6 | C32—C33—H33 | 119.6 |
C5—C10—C9 | 117.8 (5) | O3—C34—H34A | 109.5 |
C5—C10—C1 | 118.1 (4) | O3—C34—H34B | 109.5 |
C9—C10—C1 | 124.0 (4) | H34A—C34—H34B | 109.5 |
N3—C11—C12 | 122.3 (4) | O3—C34—H34C | 109.5 |
N3—C11—N2 | 118.9 (4) | H34A—C34—H34C | 109.5 |
C12—C11—N2 | 118.8 (4) | H34B—C34—H34C | 109.5 |
C11—C12—C13 | 118.8 (5) | N2—N1—C1 | 123.5 (4) |
C11—C12—H12 | 120.6 | N2—N1—Cr1 | 121.4 (3) |
C13—C12—H12 | 120.6 | C1—N1—Cr1 | 115.1 (3) |
C14—C13—C12 | 119.0 (5) | N1—N2—C11 | 110.8 (4) |
C14—C13—H13 | 120.5 | C15—N3—C11 | 117.7 (4) |
C12—C13—H13 | 120.5 | C15—N3—Cr1 | 130.0 (4) |
C15—C14—C13 | 119.7 (5) | C11—N3—Cr1 | 112.2 (3) |
C15—C14—H14 | 120.1 | C16—N4—Cr1 | 174.6 (5) |
C13—C14—H14 | 120.1 | C17—N5—Cr1 | 166.2 (4) |
N3—C15—C14 | 122.3 (5) | C18—N6—Cr1 | 179.0 (4) |
N3—C15—H15 | 118.9 | C19—N7—N8 | 119.3 (7) |
C14—C15—H15 | 118.9 | N7—N8—C29 | 116.7 (5) |
N4—C16—S1 | 178.7 (5) | C29—N9—C33 | 122.8 (5) |
N5—C17—S2 | 179.1 (5) | C29—N9—H9 | 118.6 |
N6—C18—S3 | 179.6 (6) | C33—N9—H9 | 118.6 |
N7—C19—C28 | 117.8 (8) | C2—O1—Cr1 | 113.7 (3) |
N7—C19—C20 | 123.4 (10) | C20—O2—H2 | 109.5 |
C28—C19—C20 | 118.8 (8) | C34—O3—H3A | 109.5 |
N1—C1—C2—O1 | −3.8 (6) | C29—C30—C31—C32 | −0.4 (11) |
C10—C1—C2—O1 | 176.8 (4) | C30—C31—C32—C33 | 0.7 (11) |
N1—C1—C2—C3 | 175.9 (4) | C31—C32—C33—N9 | −0.5 (11) |
C10—C1—C2—C3 | −3.4 (7) | C10—C1—N1—N2 | 0.6 (8) |
O1—C2—C3—C4 | 179.4 (5) | C2—C1—N1—N2 | −178.7 (4) |
C1—C2—C3—C4 | −0.3 (8) | C10—C1—N1—Cr1 | −177.0 (4) |
C2—C3—C4—C5 | 2.0 (8) | C2—C1—N1—Cr1 | 3.7 (5) |
C3—C4—C5—C6 | 178.0 (5) | O1—Cr1—N1—N2 | −180.0 (4) |
C3—C4—C5—C10 | 0.1 (8) | N4—Cr1—N1—N2 | −87.1 (3) |
C10—C5—C6—C7 | 2.7 (9) | N6—Cr1—N1—N2 | 90.4 (4) |
C4—C5—C6—C7 | −175.1 (6) | N3—Cr1—N1—N2 | 2.8 (3) |
C5—C6—C7—C8 | −1.2 (10) | O1—Cr1—N1—C1 | −2.3 (3) |
C6—C7—C8—C9 | −0.8 (10) | N4—Cr1—N1—C1 | 90.6 (3) |
C7—C8—C9—C10 | 1.3 (10) | N6—Cr1—N1—C1 | −91.9 (3) |
C6—C5—C10—C9 | −2.1 (8) | N3—Cr1—N1—C1 | −179.5 (4) |
C4—C5—C10—C9 | 175.8 (5) | C1—N1—N2—C11 | 179.7 (4) |
C6—C5—C10—C1 | 178.4 (5) | Cr1—N1—N2—C11 | −2.9 (5) |
C4—C5—C10—C1 | −3.8 (7) | N3—C11—N2—N1 | 0.9 (6) |
C8—C9—C10—C5 | 0.1 (8) | C12—C11—N2—N1 | −179.4 (4) |
C8—C9—C10—C1 | 179.6 (5) | C14—C15—N3—C11 | −4.1 (8) |
N1—C1—C10—C5 | −173.8 (5) | C14—C15—N3—Cr1 | 177.6 (4) |
C2—C1—C10—C5 | 5.4 (7) | C12—C11—N3—C15 | 2.9 (7) |
N1—C1—C10—C9 | 6.7 (9) | N2—C11—N3—C15 | −177.4 (5) |
C2—C1—C10—C9 | −174.1 (5) | C12—C11—N3—Cr1 | −178.5 (4) |
N3—C11—C12—C13 | −0.7 (8) | N2—C11—N3—Cr1 | 1.2 (5) |
N2—C11—C12—C13 | 179.6 (5) | O1—Cr1—N3—C15 | 169.4 (4) |
C11—C12—C13—C14 | −0.4 (9) | N4—Cr1—N3—C15 | −96.4 (5) |
C12—C13—C14—C15 | −0.6 (9) | N5—Cr1—N3—C15 | −7.0 (5) |
C13—C14—C15—N3 | 3.0 (10) | N1—Cr1—N3—C15 | 176.4 (5) |
N7—C19—C20—O2 | 3.4 (16) | N6—Cr1—N3—C15 | 84.4 (5) |
C28—C19—C20—O2 | −177.7 (10) | O1—Cr1—N3—C11 | −9.0 (6) |
N7—C19—C20—C21 | −172.2 (8) | N4—Cr1—N3—C11 | 85.2 (3) |
C28—C19—C20—C21 | 6.6 (12) | N5—Cr1—N3—C11 | 174.6 (3) |
O2—C20—C21—C22 | −180.0 (17) | N1—Cr1—N3—C11 | −1.9 (3) |
C19—C20—C21—C22 | −4 (2) | N6—Cr1—N3—C11 | −94.0 (3) |
C20—C21—C22—C23 | −2 (3) | O1—Cr1—N5—C17 | 50.8 (17) |
C21—C22—C23—C28 | 7 (2) | N4—Cr1—N5—C17 | −41.6 (16) |
C21—C22—C23—C24 | −177.3 (15) | N6—Cr1—N5—C17 | 140.9 (16) |
C28—C23—C24—C25 | 2 (2) | N3—Cr1—N5—C17 | −130.7 (16) |
C22—C23—C24—C25 | −173.8 (16) | C28—C19—N7—N8 | −178.7 (5) |
C23—C24—C25—C26 | −2 (3) | C20—C19—N7—N8 | 0.2 (10) |
C24—C25—C26—C27 | 1 (2) | C19—N7—N8—C29 | 175.0 (5) |
C25—C26—C27—C28 | 0.1 (13) | N9—C29—N8—N7 | 14.2 (9) |
C26—C27—C28—C23 | −0.4 (12) | C30—C29—N8—N7 | −165.0 (6) |
C26—C27—C28—C19 | 179.1 (6) | N8—C29—N9—C33 | −179.0 (6) |
C24—C23—C28—C27 | −0.5 (13) | C30—C29—N9—C33 | 0.3 (10) |
C22—C23—C28—C27 | 175.3 (10) | C32—C33—N9—C29 | 0.0 (11) |
C24—C23—C28—C19 | 180.0 (9) | C3—C2—O1—Cr1 | −177.8 (4) |
C22—C23—C28—C19 | −4.2 (13) | C1—C2—O1—Cr1 | 2.0 (6) |
N7—C19—C28—C27 | −2.9 (11) | N4—Cr1—O1—C2 | −86.4 (3) |
C20—C19—C28—C27 | 178.1 (8) | N5—Cr1—O1—C2 | −176.4 (3) |
N7—C19—C28—C23 | 176.6 (6) | N1—Cr1—O1—C2 | 0.2 (3) |
C20—C19—C28—C23 | −2.3 (11) | N6—Cr1—O1—C2 | 91.7 (3) |
N9—C29—C30—C31 | −0.1 (10) | N3—Cr1—O1—C2 | 7.2 (6) |
N8—C29—C30—C31 | 179.2 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···S3 | 0.82 | 2.45 | 3.234 (5) | 161 |
O2—H2···N7 | 0.82 | 2.41 | 2.840 (9) | 114 |
O2—H2···N8 | 0.82 | 1.81 | 2.536 (8) | 147 |
Experimental details
Crystal data | |
Chemical formula | (C15H12N3O)[Cr(C15H10N3O)(NCS)3]·CH4O |
Mr | 756.82 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 273 |
a, b, c (Å) | 11.5045 (11), 12.3189 (11), 12.5197 (12) |
α, β, γ (°) | 95.568 (2), 91.851 (2), 96.973 (2) |
V (Å3) | 1751.1 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.56 |
Crystal size (mm) | 0.25 × 0.22 × 0.17 |
Data collection | |
Diffractometer | Bruker SMART APEX II CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.874, 0.912 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11793, 7770, 2997 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.067, 0.209, 0.96 |
No. of reflections | 7770 |
No. of parameters | 454 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.40 |
Computer programs: APEX2 (Bruker, DATE?), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b) and PLATON (Spek, 2003).
Cr1—O1 | 1.964 (3) | Cr1—N1 | 2.003 (4) |
Cr1—N4 | 1.981 (5) | Cr1—N6 | 2.003 (5) |
Cr1—N5 | 1.992 (4) | Cr1—N3 | 2.058 (4) |
O1—Cr1—N4 | 92.38 (16) | N5—Cr1—N6 | 91.81 (17) |
O1—Cr1—N5 | 100.34 (15) | N1—Cr1—N6 | 91.51 (16) |
N4—Cr1—N5 | 89.61 (17) | O1—Cr1—N3 | 157.01 (15) |
O1—Cr1—N1 | 80.57 (14) | N4—Cr1—N3 | 89.21 (17) |
N4—Cr1—N1 | 87.03 (16) | N5—Cr1—N3 | 102.61 (16) |
N5—Cr1—N1 | 176.56 (16) | N1—Cr1—N3 | 76.61 (15) |
O1—Cr1—N6 | 89.83 (16) | N6—Cr1—N3 | 88.04 (17) |
N4—Cr1—N6 | 177.12 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···S3 | 0.82 | 2.45 | 3.234 (5) | 161 |
O2—H2···N7 | 0.82 | 2.41 | 2.840 (9) | 114 |
O2—H2···N8 | 0.82 | 1.81 | 2.536 (8) | 147 |
The color reactions of metal ions and PAN (1-(pyridin-2-yldiazenyl)naphthalen-2-ol) were a useful method in spectrophotometric determination. We report herein the crystal structure of a chromium(III) complex where the CrIII ion is coordinated by a PAN- and three thiocyanate ions.
The crystal structure of (I) consists of a [Cr(PAN)(NCS)3]- anion, an uncoordinated protonated PAN cation and a methanol molecule (Fig. 1). The chromium ion has a slightly distorted octahedral coordination geometry, its symmetry being close to C2V. The Cr—N(PAN) bond distances are 2.006 (4) and 2.058 (5) Å, the Cr—O bond distance is 1.970 (4) Å. The ligand is planar, the dihedral angle between two aromatic rings is 6.5 (3)°. The Cr—N(NCS) bond distances vary in the range 1.981 (6)–2.001 (6) Å, and the thiocyanate ligands are almost linear with N–C–S angles 178.6 (6)–179.4 (7)°.
The uncoordinated PAN is protonated at (N9), the dihedral angle between two aromatic rings is 15.4 (2)°. Related aromatic rings A and Bi [ring A: C5, C6, C7, C8, C9 and C10; ring B: N9, C29, C30, C31, C32 and C33; symmetry code: (i) 1 - x, y, 1 - z) show π-π stacking with a ring-ring separation of 3.594 (4) Å. A C—S···Cg (π-ring centre) interaction from the C17—S2 bond to ring Rii [ring R: C19, C20, C21, C22, C23 and C28; symmetry code: (ii) -x, 1 - y, 1 - z) is also obsered [C17···Cg = 3.684 (7), S···Cg = 3.483 (5) Å and C17—S···Cg = 84.1 (2)°] (Fig. 2). The crystal packing is characterized by three conventional hydrogen bonds, c.f. Table (Spek, 2003).