Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807027742/at2307sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807027742/at2307Isup2.hkl |
CCDC reference: 649512
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.006 Å
- R factor = 0.042
- wR factor = 0.119
- Data-to-parameter ratio = 7.3
checkCIF/PLATON results
No syntax errors found
Alert level C STRVA01_ALERT_2_C Chirality of atom sites is inverted? From the CIF: _refine_ls_abs_structure_Flack 10.000 From the CIF: _refine_ls_abs_structure_Flack_su 10.000 PLAT032_ALERT_4_C Std. Uncertainty in Flack Parameter too High ... 10.00 PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) ..... 7.35 PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.89 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.41 Ratio PLAT318_ALERT_2_C Check Hybridisation of N1 in Main Residue . ? PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 6 PLAT420_ALERT_2_C D-H Without Acceptor N1 - H1 ... ?
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 25.02 From the CIF: _reflns_number_total 948 Count of symmetry unique reflns 948 Completeness (_total/calc) 100.00% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 9 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Solutions of N,N'-bis(2-hydroxy-3-methoxy benzylene)benzene-1,4-diamine (10 mmol) in methanol-chloroform (v/v = 1/1) (20 ml) and NaBH4 (40 mmol) were mixed, the mixture solution was stirred under room temperature for 30 h and then mixtures was filtered, and then solution was left to produce crystals of (I) slowly.
All H atoms were located in difference Fourier maps. H atoms bonded to C, O and N atoms were treated as riding atoms, with C—H distances of 0.93 Å (aryl), 0.96 Å (methyl), 0.97 Å (methylene), O—H distances of 0.82 Å (hydroxy) and N—H distances of 0.86 Å (amino), Uiso(H) = 1.2 (aryl, methylene, amino) or 1.5 Ueq(C) (methyl or hydroxy).
As part of our investigation of crystal structure of o-vanillin diamine derivatives, we report here the crystal structure of a diamine derivative, N,N'-(2-hydroxy-3-methoxy benzyl) benzene-1,3-diamine, (I).
The asymmetric unit consists of one half-molecule and the molecule has a twofold axis on the atoms C9—C12 line, Fig. (1). The dihedral angle between the neighbouring benzen rings in the molecule is 77.95(0.11) °. Its bond lengths and angles are in agreement with that of similar compounds (Xia et al., 2007; 2007a, b, c).) and are normal (Allen et al., 1987). The most closely related compound is N,N'-(2-hydroxy-3-methoxy benzyl) benzene-1,4-diamine, (II) (Xia et al., 2007). The principal difference between (I) and (II) concerns the intermoleculae aggregation. In (I), The molecules are linked into sheets involving a R22(10) rings (Bernstein et al., 1995) through O—H···O and C—H···π hydrogen bonds (Fig. 2). Atoms O1 in the molecule (x, y, z) and O2 in the molecule (2 - x, 2 - y, z) act as hydrogen-bond donors to atoms O2 in the molecule (2 - x, 2 - y, z) and O1 in the molecule (x, y, z), respectively, in addition, atom C6 in the molecule (x, y, z) act as hydrogen-bond donor to central aryl ring of the molecule at (x, 1 + y, z), forming a sheet parallel to the [001] plane and there are no direction-specific interactions between adjacent sheets. By contrast, in (II), the molecule are linked into sheets by means of N—H···O and O—H···N hydrogen-bonds; the latter are absent from the structure of (I).
For related literature, see: Allen et al. (1987); Bernstein et al. (1995); Xia et al. (2007).
Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
C22H24N2O4 | F(000) = 404 |
Mr = 380.43 | Dx = 1.261 Mg m−3 |
Orthorhombic, Pnc2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2 -2bc | Cell parameters from 771 reflections |
a = 13.2402 (18) Å | θ = 3.1–19.2° |
b = 7.7416 (14) Å | µ = 0.09 mm−1 |
c = 9.7770 (12) Å | T = 298 K |
V = 1002.1 (3) Å3 | Acerate, red |
Z = 2 | 0.46 × 0.29 × 0.15 mm |
Siemens SMART 1000 CCD area-detector diffractometer | 948 independent reflections |
Radiation source: fine-focus sealed tube | 587 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.064 |
φ and ω scans | θmax = 25.0°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −15→12 |
Tmin = 0.961, Tmax = 0.987 | k = −9→9 |
4760 measured reflections | l = −11→9 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.119 | w = 1/[σ2(Fo2) + (0.0579P)2 + 0.0331P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
948 reflections | Δρmax = 0.19 e Å−3 |
129 parameters | Δρmin = −0.15 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 948 Freidel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 10 (10) |
C22H24N2O4 | V = 1002.1 (3) Å3 |
Mr = 380.43 | Z = 2 |
Orthorhombic, Pnc2 | Mo Kα radiation |
a = 13.2402 (18) Å | µ = 0.09 mm−1 |
b = 7.7416 (14) Å | T = 298 K |
c = 9.7770 (12) Å | 0.46 × 0.29 × 0.15 mm |
Siemens SMART 1000 CCD area-detector diffractometer | 948 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 587 reflections with I > 2σ(I) |
Tmin = 0.961, Tmax = 0.987 | Rint = 0.064 |
4760 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.119 | Δρmax = 0.19 e Å−3 |
S = 1.05 | Δρmin = −0.15 e Å−3 |
948 reflections | Absolute structure: Flack (1983), 948 Freidel pairs |
129 parameters | Absolute structure parameter: 10 (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 | ||
N1 | 0.6614 (3) | 0.6391 (5) | 0.8827 (4) | 0.0504 (11) | |
H1 | 0.6551 | 0.6488 | 0.9699 | 0.060* | |
O1 | 0.9095 (2) | 0.8177 (4) | 0.6588 (4) | 0.0574 (10) | |
H1A | 0.9520 | 0.8633 | 0.6097 | 0.086* | |
O2 | 0.9070 (2) | 1.1194 (4) | 0.5231 (4) | 0.0586 (10) | |
C1 | 0.7547 (3) | 0.6954 (6) | 0.8189 (6) | 0.0511 (13) | |
H1B | 0.7747 | 0.6104 | 0.7513 | 0.061* | |
H1C | 0.8072 | 0.6998 | 0.8880 | 0.061* | |
C2 | 0.7477 (3) | 0.8702 (6) | 0.7503 (5) | 0.0383 (11) | |
C3 | 0.8274 (3) | 0.9240 (6) | 0.6701 (5) | 0.0385 (11) | |
C4 | 0.8230 (3) | 1.0816 (6) | 0.6010 (5) | 0.0410 (12) | |
C5 | 0.7399 (4) | 1.1859 (6) | 0.6149 (5) | 0.0524 (15) | |
H5 | 0.7370 | 1.2918 | 0.5701 | 0.063* | |
C6 | 0.6608 (4) | 1.1320 (6) | 0.6958 (6) | 0.0578 (15) | |
H6 | 0.6042 | 1.2022 | 0.7054 | 0.069* | |
C7 | 0.6643 (3) | 0.9769 (6) | 0.7621 (5) | 0.0503 (13) | |
H7 | 0.6099 | 0.9426 | 0.8158 | 0.060* | |
C8 | 0.9002 (4) | 1.2617 (13) | 0.4308 (8) | 0.105 (3) | |
H8A | 0.8922 | 1.3668 | 0.4817 | 0.157* | |
H8B | 0.8431 | 1.2460 | 0.3716 | 0.157* | |
H8C | 0.9607 | 1.2680 | 0.3769 | 0.157* | |
C9 | 0.5000 | 0.5000 | 0.8780 (6) | 0.0382 (16) | |
H9 | 0.5000 | 0.5000 | 0.9731 | 0.046* | |
C10 | 0.5824 (3) | 0.5705 (5) | 0.8084 (5) | 0.0361 (11) | |
C11 | 0.5805 (3) | 0.5714 (5) | 0.6655 (5) | 0.0437 (12) | |
H11 | 0.6336 | 0.6202 | 0.6167 | 0.052* | |
C12 | 0.5000 | 0.5000 | 0.5972 (7) | 0.0446 (17) | |
H12 | 0.5000 | 0.5000 | 0.5021 | 0.054* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.049 (2) | 0.067 (3) | 0.035 (2) | −0.018 (2) | −0.006 (2) | 0.009 (2) |
O1 | 0.0359 (17) | 0.063 (2) | 0.074 (2) | 0.0088 (16) | 0.0054 (19) | 0.020 (2) |
O2 | 0.041 (2) | 0.072 (2) | 0.063 (2) | −0.0089 (18) | 0.0030 (19) | 0.026 (2) |
C1 | 0.039 (3) | 0.062 (3) | 0.053 (3) | −0.009 (2) | −0.003 (3) | 0.011 (3) |
C2 | 0.037 (2) | 0.043 (3) | 0.035 (2) | −0.004 (2) | −0.004 (2) | 0.002 (2) |
C3 | 0.033 (3) | 0.045 (3) | 0.037 (3) | −0.003 (2) | −0.002 (2) | 0.002 (3) |
C4 | 0.037 (3) | 0.052 (3) | 0.034 (3) | −0.008 (2) | −0.005 (2) | 0.003 (3) |
C5 | 0.056 (3) | 0.042 (3) | 0.059 (4) | −0.001 (2) | −0.007 (3) | 0.005 (3) |
C6 | 0.052 (3) | 0.049 (3) | 0.072 (4) | 0.010 (2) | 0.000 (3) | −0.006 (3) |
C7 | 0.040 (3) | 0.053 (3) | 0.058 (4) | −0.003 (2) | 0.007 (3) | −0.003 (3) |
C8 | 0.082 (4) | 0.138 (6) | 0.094 (6) | −0.005 (4) | 0.006 (4) | 0.082 (5) |
C9 | 0.045 (4) | 0.043 (4) | 0.026 (4) | −0.003 (3) | 0.000 | 0.000 |
C10 | 0.038 (3) | 0.036 (3) | 0.035 (3) | −0.004 (2) | −0.002 (2) | 0.003 (2) |
C11 | 0.054 (3) | 0.044 (3) | 0.033 (3) | −0.004 (2) | 0.007 (3) | 0.007 (2) |
C12 | 0.060 (4) | 0.050 (4) | 0.024 (3) | −0.004 (4) | 0.000 | 0.000 |
N1—C10 | 1.380 (5) | C5—H5 | 0.9300 |
N1—C1 | 1.450 (6) | C6—C7 | 1.365 (7) |
N1—H1 | 0.8600 | C6—H6 | 0.9300 |
O1—C3 | 1.368 (5) | C7—H7 | 0.9300 |
O1—H1A | 0.8200 | C8—H8A | 0.9600 |
O2—C4 | 1.380 (5) | C8—H8B | 0.9600 |
O2—C8 | 1.427 (8) | C8—H8C | 0.9600 |
C1—C2 | 1.513 (6) | C9—C10i | 1.397 (5) |
C1—H1B | 0.9700 | C9—C10 | 1.397 (5) |
C1—H1C | 0.9700 | C9—H9 | 0.9300 |
C2—C3 | 1.380 (6) | C10—C11 | 1.398 (6) |
C2—C7 | 1.384 (6) | C11—C12 | 1.373 (6) |
C3—C4 | 1.396 (6) | C11—H11 | 0.9300 |
C4—C5 | 1.371 (6) | C12—C11i | 1.373 (6) |
C5—C6 | 1.377 (6) | C12—H12 | 0.9300 |
C10—N1—C1 | 122.3 (4) | C7—C6—H6 | 119.6 |
C10—N1—H1 | 118.8 | C5—C6—H6 | 119.6 |
C1—N1—H1 | 118.8 | C6—C7—C2 | 120.9 (4) |
C3—O1—H1A | 109.5 | C6—C7—H7 | 119.6 |
C4—O2—C8 | 117.5 (4) | C2—C7—H7 | 119.6 |
N1—C1—C2 | 114.0 (4) | O2—C8—H8A | 109.5 |
N1—C1—H1B | 108.7 | O2—C8—H8B | 109.5 |
C2—C1—H1B | 108.7 | H8A—C8—H8B | 109.5 |
N1—C1—H1C | 108.7 | O2—C8—H8C | 109.5 |
C2—C1—H1C | 108.7 | H8A—C8—H8C | 109.5 |
H1B—C1—H1C | 107.6 | H8B—C8—H8C | 109.5 |
C3—C2—C7 | 118.5 (4) | C10i—C9—C10 | 121.7 (6) |
C3—C2—C1 | 118.4 (4) | C10i—C9—H9 | 119.2 |
C7—C2—C1 | 123.1 (4) | C10—C9—H9 | 119.2 |
O1—C3—C2 | 118.2 (4) | N1—C10—C9 | 119.1 (4) |
O1—C3—C4 | 121.4 (4) | N1—C10—C11 | 122.6 (4) |
C2—C3—C4 | 120.4 (4) | C9—C10—C11 | 118.4 (4) |
C5—C4—O2 | 125.2 (4) | C12—C11—C10 | 119.9 (5) |
C5—C4—C3 | 120.1 (4) | C12—C11—H11 | 120.1 |
O2—C4—C3 | 114.7 (4) | C10—C11—H11 | 120.1 |
C4—C5—C6 | 119.2 (4) | C11—C12—C11i | 121.9 (6) |
C4—C5—H5 | 120.4 | C11—C12—H12 | 119.1 |
C6—C5—H5 | 120.4 | C11i—C12—H12 | 119.1 |
C7—C6—C5 | 120.9 (4) | ||
C10—N1—C1—C2 | 78.5 (5) | O2—C4—C5—C6 | 179.8 (4) |
N1—C1—C2—C3 | −170.8 (4) | C3—C4—C5—C6 | −1.0 (7) |
N1—C1—C2—C7 | 7.9 (7) | C4—C5—C6—C7 | 0.1 (7) |
C7—C2—C3—O1 | −179.9 (4) | C5—C6—C7—C2 | 0.4 (7) |
C1—C2—C3—O1 | −1.2 (6) | C3—C2—C7—C6 | 0.1 (7) |
C7—C2—C3—C4 | −0.9 (7) | C1—C2—C7—C6 | −178.6 (4) |
C1—C2—C3—C4 | 177.8 (4) | C1—N1—C10—C9 | 172.3 (4) |
C8—O2—C4—C5 | −11.9 (7) | C1—N1—C10—C11 | −8.8 (6) |
C8—O2—C4—C3 | 168.8 (5) | C10i—C9—C10—N1 | 179.7 (4) |
O1—C3—C4—C5 | −179.6 (5) | C10i—C9—C10—C11 | 0.8 (3) |
C2—C3—C4—C5 | 1.4 (6) | N1—C10—C11—C12 | 179.5 (3) |
O1—C3—C4—O2 | −0.3 (6) | C9—C10—C11—C12 | −1.6 (6) |
C2—C3—C4—O2 | −179.3 (4) | C10—C11—C12—C11i | 0.8 (3) |
Symmetry code: (i) −x+1, −y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O2 | 0.82 | 2.24 | 2.687 (4) | 115 |
O1—H1A···O2ii | 0.82 | 2.05 | 2.811 (4) | 153 |
Symmetry code: (ii) −x+2, −y+2, z. |
Experimental details
Crystal data | |
Chemical formula | C22H24N2O4 |
Mr | 380.43 |
Crystal system, space group | Orthorhombic, Pnc2 |
Temperature (K) | 298 |
a, b, c (Å) | 13.2402 (18), 7.7416 (14), 9.7770 (12) |
V (Å3) | 1002.1 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.46 × 0.29 × 0.15 |
Data collection | |
Diffractometer | Siemens SMART 1000 CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.961, 0.987 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4760, 948, 587 |
Rint | 0.064 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.119, 1.05 |
No. of reflections | 948 |
No. of parameters | 129 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.15 |
Absolute structure | Flack (1983), 948 Freidel pairs |
Absolute structure parameter | 10 (10) |
Computer programs: SMART (Siemens, 1996), SMART, SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O2 | 0.82 | 2.24 | 2.687 (4) | 114.9 |
O1—H1A···O2i | 0.82 | 2.05 | 2.811 (4) | 153.3 |
Symmetry code: (i) −x+2, −y+2, z. |
As part of our investigation of crystal structure of o-vanillin diamine derivatives, we report here the crystal structure of a diamine derivative, N,N'-(2-hydroxy-3-methoxy benzyl) benzene-1,3-diamine, (I).
The asymmetric unit consists of one half-molecule and the molecule has a twofold axis on the atoms C9—C12 line, Fig. (1). The dihedral angle between the neighbouring benzen rings in the molecule is 77.95(0.11) °. Its bond lengths and angles are in agreement with that of similar compounds (Xia et al., 2007; 2007a, b, c).) and are normal (Allen et al., 1987). The most closely related compound is N,N'-(2-hydroxy-3-methoxy benzyl) benzene-1,4-diamine, (II) (Xia et al., 2007). The principal difference between (I) and (II) concerns the intermoleculae aggregation. In (I), The molecules are linked into sheets involving a R22(10) rings (Bernstein et al., 1995) through O—H···O and C—H···π hydrogen bonds (Fig. 2). Atoms O1 in the molecule (x, y, z) and O2 in the molecule (2 - x, 2 - y, z) act as hydrogen-bond donors to atoms O2 in the molecule (2 - x, 2 - y, z) and O1 in the molecule (x, y, z), respectively, in addition, atom C6 in the molecule (x, y, z) act as hydrogen-bond donor to central aryl ring of the molecule at (x, 1 + y, z), forming a sheet parallel to the [001] plane and there are no direction-specific interactions between adjacent sheets. By contrast, in (II), the molecule are linked into sheets by means of N—H···O and O—H···N hydrogen-bonds; the latter are absent from the structure of (I).