Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536809013531/xu2504sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536809013531/xu2504Isup2.hkl |
CCDC reference: 731290
Key indicators
- Single-crystal X-ray study
- T = 273 K
- Mean (C-C) = 0.003 Å
- R factor = 0.033
- wR factor = 0.102
- Data-to-parameter ratio = 11.7
checkCIF/PLATON results
No syntax errors found
Alert level C Value of measurement temperature given = 273.000 Value of melting point given = 0.000 PLAT158_ALERT_4_C The Input Unitcell is NOT Standard/Reduced ..... ? PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for Cl1
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 25.48 From the CIF: _reflns_number_total 1204 Count of symmetry unique reflns 747 Completeness (_total/calc) 161.18% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 457 Fraction of Friedel pairs measured 0.612 Are heavy atom types Z>Si present yes PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 273 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 273 K PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) . 1.13 Ratio
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 4 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
NITpPy was synthesized according to a literature procedure (Ullman et al., 1970; Ullman et al., 1972). The title compound was obtained serendipitously from the reaction of copper perchlorate hydrate (1 mmol) and NITpPy (2 mmol) in methanol (10 ml). The mixture was stirred for 4 h at room temperature and then filtered. Subsequently, the filtrate was diffused with diethyl ether vapor and dark-purple block crystals were obtained one week later.
The H atoms were positioned geometrically and refined using the riding-model approximation, with C—H = 0.93 (aromatic), 0.96 Å (methyl) and N—H = 0.86 Å, and Uiso(H) = 1.5Ueq(C) for methyl groups and 1.2Ueq(C,N) for others.
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
C12H17N3O2+·ClO4− | F(000) = 1400 |
Mr = 334.74 | Dx = 1.438 Mg m−3 |
Orthorhombic, Fdd2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: F 2 -2d | Cell parameters from 2949 reflections |
a = 17.485 (4) Å | θ = 2.3–29.0° |
b = 11.854 (2) Å | µ = 0.28 mm−1 |
c = 14.921 (2) Å | T = 273 K |
V = 3092.6 (10) Å3 | Block, dark-purple |
Z = 8 | 0.33 × 0.26 × 0.23 mm |
Bruker SMART CCD area-detector diffractometer | 1204 independent reflections |
Radiation source: fine-focus sealed tube | 1169 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
ϕ and ω scans | θmax = 25.5°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −21→20 |
Tmin = 0.915, Tmax = 0.930 | k = −11→14 |
3994 measured reflections | l = −15→18 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.033 | w = 1/[σ2(Fo2) + (0.0762P)2 + 1.0334P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.102 | (Δ/σ)max < 0.001 |
S = 1.06 | Δρmax = 0.27 e Å−3 |
1204 reflections | Δρmin = −0.15 e Å−3 |
103 parameters | Extinction correction: SHELXTL (Bruker, 2000), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.0026 (5) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 457 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.12 (10) |
C12H17N3O2+·ClO4− | V = 3092.6 (10) Å3 |
Mr = 334.74 | Z = 8 |
Orthorhombic, Fdd2 | Mo Kα radiation |
a = 17.485 (4) Å | µ = 0.28 mm−1 |
b = 11.854 (2) Å | T = 273 K |
c = 14.921 (2) Å | 0.33 × 0.26 × 0.23 mm |
Bruker SMART CCD area-detector diffractometer | 1204 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1169 reflections with I > 2σ(I) |
Tmin = 0.915, Tmax = 0.930 | Rint = 0.016 |
3994 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.102 | Δρmax = 0.27 e Å−3 |
S = 1.06 | Δρmin = −0.15 e Å−3 |
1204 reflections | Absolute structure: Flack (1983), 457 Friedel pairs |
103 parameters | Absolute structure parameter: 0.12 (10) |
1 restraint |
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 | ||
Cl1 | 0.0000 | 0.5000 | 0.05797 (7) | 0.0787 (4) | |
O2 | 0.0203 (2) | 0.4065 (5) | 0.0039 (3) | 0.1497 (15) | |
O3 | 0.06280 (15) | 0.5281 (3) | 0.1140 (2) | 0.1055 (9) | |
N1 | 0.0000 | 0.5000 | 0.2971 (2) | 0.0684 (10) | |
H1B | 0.0000 | 0.5000 | 0.2395 | 0.082* | |
N2 | 0.05399 (9) | 0.54721 (12) | 0.62987 (12) | 0.0399 (4) | |
C1 | 0.04640 (17) | 0.5698 (2) | 0.33929 (18) | 0.0626 (6) | |
H1A | 0.0785 | 0.6169 | 0.3067 | 0.075* | |
C2 | 0.04743 (13) | 0.57302 (19) | 0.43134 (16) | 0.0520 (5) | |
H2A | 0.0793 | 0.6232 | 0.4614 | 0.062* | |
C3 | 0.0000 | 0.5000 | 0.4789 (2) | 0.0417 (6) | |
C4 | 0.0000 | 0.5000 | 0.5764 (2) | 0.0379 (6) | |
C5 | 0.02991 (11) | 0.54883 (16) | 0.72622 (14) | 0.0425 (5) | |
C6 | 0.09853 (14) | 0.5301 (2) | 0.78664 (19) | 0.0630 (6) | |
H6A | 0.1322 | 0.5939 | 0.7827 | 0.095* | |
H6B | 0.1253 | 0.4634 | 0.7680 | 0.095* | |
H6C | 0.0816 | 0.5213 | 0.8474 | 0.095* | |
C7 | −0.00457 (14) | 0.66478 (19) | 0.74312 (19) | 0.0616 (7) | |
H7A | 0.0352 | 0.7206 | 0.7422 | 0.092* | |
H7B | −0.0293 | 0.6654 | 0.8006 | 0.092* | |
H7C | −0.0414 | 0.6815 | 0.6972 | 0.092* | |
O1 | 0.11652 (8) | 0.59302 (15) | 0.60418 (12) | 0.0599 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0631 (5) | 0.1338 (9) | 0.0392 (5) | −0.0116 (5) | 0.000 | 0.000 |
O2 | 0.154 (3) | 0.199 (4) | 0.096 (3) | 0.023 (3) | 0.013 (2) | −0.053 (3) |
O3 | 0.0789 (14) | 0.167 (2) | 0.0707 (17) | −0.0372 (15) | −0.0088 (13) | 0.0105 (16) |
N1 | 0.092 (2) | 0.0776 (18) | 0.0360 (17) | 0.0404 (17) | 0.000 | 0.000 |
N2 | 0.0356 (7) | 0.0440 (7) | 0.0400 (10) | −0.0075 (6) | −0.0005 (7) | −0.0002 (6) |
C1 | 0.0729 (15) | 0.0692 (14) | 0.0457 (14) | 0.0203 (11) | 0.0104 (11) | 0.0154 (11) |
C2 | 0.0547 (12) | 0.0570 (10) | 0.0443 (13) | 0.0068 (9) | 0.0035 (9) | 0.0088 (9) |
C3 | 0.0394 (13) | 0.0430 (12) | 0.0425 (18) | 0.0116 (10) | 0.000 | 0.000 |
C4 | 0.0367 (12) | 0.0376 (12) | 0.0394 (18) | −0.0002 (9) | 0.000 | 0.000 |
C5 | 0.0409 (10) | 0.0499 (10) | 0.0368 (11) | −0.0056 (9) | −0.0015 (9) | −0.0025 (8) |
C6 | 0.0548 (12) | 0.0865 (15) | 0.0478 (15) | −0.0160 (12) | −0.0141 (11) | 0.0046 (11) |
C7 | 0.0683 (14) | 0.0550 (11) | 0.0614 (17) | −0.0014 (10) | 0.0048 (12) | −0.0153 (10) |
O1 | 0.0461 (7) | 0.0784 (10) | 0.0553 (11) | −0.0250 (7) | 0.0047 (7) | 0.0008 (8) |
Cl1—O2i | 1.416 (4) | C2—H2A | 0.9300 |
Cl1—O2 | 1.416 (4) | C3—C2i | 1.393 (3) |
Cl1—O3 | 1.420 (3) | C3—C4 | 1.455 (4) |
Cl1—O3i | 1.420 (3) | C4—N2i | 1.357 (2) |
N1—C1 | 1.318 (4) | C5—C6 | 1.517 (3) |
N1—C1i | 1.318 (4) | C5—C7 | 1.522 (3) |
N1—H1B | 0.8600 | C5—C5i | 1.560 (4) |
N2—O1 | 1.280 (2) | C6—H6A | 0.9600 |
N2—C4 | 1.357 (2) | C6—H6B | 0.9600 |
N2—C5 | 1.498 (3) | C6—H6C | 0.9600 |
C1—C2 | 1.374 (4) | C7—H7A | 0.9600 |
C1—H1A | 0.9300 | C7—H7B | 0.9600 |
C2—C3 | 1.393 (3) | C7—H7C | 0.9600 |
O2i—Cl1—O2 | 110.5 (5) | N2—C4—N2i | 108.0 (3) |
O2i—Cl1—O3 | 110.2 (3) | N2—C4—C3 | 126.01 (13) |
O2—Cl1—O3 | 109.0 (2) | N2i—C4—C3 | 126.01 (13) |
O2i—Cl1—O3i | 109.0 (2) | N2—C5—C6 | 110.26 (18) |
O2—Cl1—O3i | 110.2 (3) | N2—C5—C7 | 106.37 (18) |
O3—Cl1—O3i | 107.9 (2) | C6—C5—C7 | 110.28 (19) |
C1—N1—C1i | 123.0 (3) | N2—C5—C5i | 100.31 (10) |
C1—N1—H1B | 118.5 | C6—C5—C5i | 114.96 (17) |
C1i—N1—H1B | 118.5 | C7—C5—C5i | 113.9 (2) |
O1—N2—C4 | 126.40 (18) | C5—C6—H6A | 109.5 |
O1—N2—C5 | 121.47 (16) | C5—C6—H6B | 109.5 |
C4—N2—C5 | 111.96 (16) | H6A—C6—H6B | 109.5 |
N1—C1—C2 | 120.2 (3) | C5—C6—H6C | 109.5 |
N1—C1—H1A | 119.9 | H6A—C6—H6C | 109.5 |
C2—C1—H1A | 119.9 | H6B—C6—H6C | 109.5 |
C1—C2—C3 | 118.9 (2) | C5—C7—H7A | 109.5 |
C1—C2—H2A | 120.5 | C5—C7—H7B | 109.5 |
C3—C2—H2A | 120.5 | H7A—C7—H7B | 109.5 |
C2i—C3—C2 | 118.8 (3) | C5—C7—H7C | 109.5 |
C2i—C3—C4 | 120.61 (16) | H7A—C7—H7C | 109.5 |
C2—C3—C4 | 120.61 (16) | H7B—C7—H7C | 109.5 |
C1i—N1—C1—C2 | −0.68 (16) | C2—C3—C4—N2 | −15.56 (13) |
N1—C1—C2—C3 | 1.3 (3) | C2i—C3—C4—N2i | −15.56 (13) |
C1—C2—C3—C2i | −0.65 (15) | C2—C3—C4—N2i | 164.44 (13) |
C1—C2—C3—C4 | 179.35 (15) | O1—N2—C5—C6 | −39.6 (2) |
O1—N2—C4—N2i | 175.0 (2) | C4—N2—C5—C6 | 144.69 (16) |
C5—N2—C4—N2i | −9.58 (9) | O1—N2—C5—C7 | 80.0 (2) |
O1—N2—C4—C3 | −5.0 (2) | C4—N2—C5—C7 | −95.74 (16) |
C5—N2—C4—C3 | 170.42 (9) | O1—N2—C5—C5i | −161.21 (18) |
C2i—C3—C4—N2 | 164.44 (13) | C4—N2—C5—C5i | 23.1 (2) |
Symmetry code: (i) −x, −y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C12H17N3O2+·ClO4− |
Mr | 334.74 |
Crystal system, space group | Orthorhombic, Fdd2 |
Temperature (K) | 273 |
a, b, c (Å) | 17.485 (4), 11.854 (2), 14.921 (2) |
V (Å3) | 3092.6 (10) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.28 |
Crystal size (mm) | 0.33 × 0.26 × 0.23 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.915, 0.930 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3994, 1204, 1169 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.605 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.102, 1.06 |
No. of reflections | 1204 |
No. of parameters | 103 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.15 |
Absolute structure | Flack (1983), 457 Friedel pairs |
Absolute structure parameter | 0.12 (10) |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXTL (Sheldrick, 2008).
The major research aims in the field of molecular magnetism are on one hand the chemical design of molecular assemblies that exhibit a spontaneous magnetization and on the other hand the rationalization of magneto-structural correlation (Wang et al., 2004; Li et al., 2003; Kahn et al., 2000; Tsukahara et al., 2003). Nitronyl nitroxide radicals (NITR), stable organic radicals, have played an important role in the design and synthesis of molecular magnetic materials (Fettouhi et al., 2003; Zhang et al., 2004; Fokin et al., 2004). Many structures have been investigated on the coordination of nitronyl nitroxide radicals to metals, but less on the non-covalent weak interactions of nitronyl nitroxide radicals with other molecules (Chang et al., 2009). Taking account of these, we report on the molecular assemblies of NITpPy and perchlorate anion in order to further understand the coordination chemistry of nitronyl nitroxide radicals.
The structure of the title compound is shown in Fig. 1. The compound consists of a discrete [NITpPyH] cation and a perchlorate anion. NITpPy acts as a proton sponge by accepting a proton. The transfer of protons results in symmetric intermolecular hydrogen bonds: the double hydrogen bonds occur between two oxygen atoms from perchlorate anion and one nitrogen atom from the pyridyl ring (Table 1). The nitronyl nitroxide fragment O—N—C—N—O is almost coplanar, but make a dihedral angle of 17.0° with the pyridyl ring. In the unit cell cations and anions are alternatively arranged.