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In the title compound, C22H24N2O4, the mol­ecules are linked into sheets by O—H...O and C—H...π hydrogen bonds, leading to fused R22(10) rings which form sheets parallel to the (001) plane. A crystallographic twofold rotation axis passes through the central benzene ring.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807027742/at2307sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807027742/at2307Isup2.hkl
Contains datablock I

CCDC reference: 649512

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](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

Comment top

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).

Related literature top

For related literature, see: Allen et al. (1987); Bernstein et al. (1995); Xia et al. (2007).

Experimental top

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.

Refinement top

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).

Structure description top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are at the 30% probability level. Unlabelled atoms in the molecular are related to labelled atoms by 1 - x, 1 - y, z.
[Figure 2] Fig. 2. A larger portion of the crystal structure of (I), showing the formation of a hydrogen-bonded sheet built from O—H···O and C—H···π. For clarity, H atoms not involved in the hydrogen bonding have been omitted. Dashed lines indicate hydrogen bonds. [Symmetry codes: (A) x, 1 + y, z; (B) 2 - x, 2 - y, z; (C) 2 - x, 3 - y, z; (D) 1 - x, 2 - y, z; (E) 1 + x, 1 + y, z; (F) 1 + x, 2 + y, z].
6,6'-Dimethoxy-2,2'-[m-phenylenedi(iminomethylene)]diphenol top
Crystal data top
C22H24N2O4F(000) = 404
Mr = 380.43Dx = 1.261 Mg m3
Orthorhombic, Pnc2Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2 -2bcCell parameters from 771 reflections
a = 13.2402 (18) Åθ = 3.1–19.2°
b = 7.7416 (14) ŵ = 0.09 mm1
c = 9.7770 (12) ÅT = 298 K
V = 1002.1 (3) Å3Acerate, red
Z = 20.46 × 0.29 × 0.15 mm
Data collection top
Siemens SMART 1000 CCD area-detector
diffractometer
948 independent reflections
Radiation source: fine-focus sealed tube587 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.064
φ and ω scansθmax = 25.0°, θmin = 1.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1512
Tmin = 0.961, Tmax = 0.987k = 99
4760 measured reflectionsl = 119
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H-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 reflectionsΔρmax = 0.19 e Å3
129 parametersΔρmin = 0.15 e Å3
1 restraintAbsolute structure: Flack (1983), 948 Freidel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 10 (10)
Crystal data top
C22H24N2O4V = 1002.1 (3) Å3
Mr = 380.43Z = 2
Orthorhombic, Pnc2Mo Kα radiation
a = 13.2402 (18) ŵ = 0.09 mm1
b = 7.7416 (14) ÅT = 298 K
c = 9.7770 (12) Å0.46 × 0.29 × 0.15 mm
Data collection top
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 = 0.987Rint = 0.064
4760 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.119Δρmax = 0.19 e Å3
S = 1.05Δρmin = 0.15 e Å3
948 reflectionsAbsolute structure: Flack (1983), 948 Freidel pairs
129 parametersAbsolute structure parameter: 10 (10)
1 restraint
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.

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
N10.6614 (3)0.6391 (5)0.8827 (4)0.0504 (11)
H10.65510.64880.96990.060*
O10.9095 (2)0.8177 (4)0.6588 (4)0.0574 (10)
H1A0.95200.86330.60970.086*
O20.9070 (2)1.1194 (4)0.5231 (4)0.0586 (10)
C10.7547 (3)0.6954 (6)0.8189 (6)0.0511 (13)
H1B0.77470.61040.75130.061*
H1C0.80720.69980.88800.061*
C20.7477 (3)0.8702 (6)0.7503 (5)0.0383 (11)
C30.8274 (3)0.9240 (6)0.6701 (5)0.0385 (11)
C40.8230 (3)1.0816 (6)0.6010 (5)0.0410 (12)
C50.7399 (4)1.1859 (6)0.6149 (5)0.0524 (15)
H50.73701.29180.57010.063*
C60.6608 (4)1.1320 (6)0.6958 (6)0.0578 (15)
H60.60421.20220.70540.069*
C70.6643 (3)0.9769 (6)0.7621 (5)0.0503 (13)
H70.60990.94260.81580.060*
C80.9002 (4)1.2617 (13)0.4308 (8)0.105 (3)
H8A0.89221.36680.48170.157*
H8B0.84311.24600.37160.157*
H8C0.96071.26800.37690.157*
C90.50000.50000.8780 (6)0.0382 (16)
H90.50000.50000.97310.046*
C100.5824 (3)0.5705 (5)0.8084 (5)0.0361 (11)
C110.5805 (3)0.5714 (5)0.6655 (5)0.0437 (12)
H110.63360.62020.61670.052*
C120.50000.50000.5972 (7)0.0446 (17)
H120.50000.50000.50210.054*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.049 (2)0.067 (3)0.035 (2)0.018 (2)0.006 (2)0.009 (2)
O10.0359 (17)0.063 (2)0.074 (2)0.0088 (16)0.0054 (19)0.020 (2)
O20.041 (2)0.072 (2)0.063 (2)0.0089 (18)0.0030 (19)0.026 (2)
C10.039 (3)0.062 (3)0.053 (3)0.009 (2)0.003 (3)0.011 (3)
C20.037 (2)0.043 (3)0.035 (2)0.004 (2)0.004 (2)0.002 (2)
C30.033 (3)0.045 (3)0.037 (3)0.003 (2)0.002 (2)0.002 (3)
C40.037 (3)0.052 (3)0.034 (3)0.008 (2)0.005 (2)0.003 (3)
C50.056 (3)0.042 (3)0.059 (4)0.001 (2)0.007 (3)0.005 (3)
C60.052 (3)0.049 (3)0.072 (4)0.010 (2)0.000 (3)0.006 (3)
C70.040 (3)0.053 (3)0.058 (4)0.003 (2)0.007 (3)0.003 (3)
C80.082 (4)0.138 (6)0.094 (6)0.005 (4)0.006 (4)0.082 (5)
C90.045 (4)0.043 (4)0.026 (4)0.003 (3)0.0000.000
C100.038 (3)0.036 (3)0.035 (3)0.004 (2)0.002 (2)0.003 (2)
C110.054 (3)0.044 (3)0.033 (3)0.004 (2)0.007 (3)0.007 (2)
C120.060 (4)0.050 (4)0.024 (3)0.004 (4)0.0000.000
Geometric parameters (Å, º) top
N1—C101.380 (5)C5—H50.9300
N1—C11.450 (6)C6—C71.365 (7)
N1—H10.8600C6—H60.9300
O1—C31.368 (5)C7—H70.9300
O1—H1A0.8200C8—H8A0.9600
O2—C41.380 (5)C8—H8B0.9600
O2—C81.427 (8)C8—H8C0.9600
C1—C21.513 (6)C9—C10i1.397 (5)
C1—H1B0.9700C9—C101.397 (5)
C1—H1C0.9700C9—H90.9300
C2—C31.380 (6)C10—C111.398 (6)
C2—C71.384 (6)C11—C121.373 (6)
C3—C41.396 (6)C11—H110.9300
C4—C51.371 (6)C12—C11i1.373 (6)
C5—C61.377 (6)C12—H120.9300
C10—N1—C1122.3 (4)C7—C6—H6119.6
C10—N1—H1118.8C5—C6—H6119.6
C1—N1—H1118.8C6—C7—C2120.9 (4)
C3—O1—H1A109.5C6—C7—H7119.6
C4—O2—C8117.5 (4)C2—C7—H7119.6
N1—C1—C2114.0 (4)O2—C8—H8A109.5
N1—C1—H1B108.7O2—C8—H8B109.5
C2—C1—H1B108.7H8A—C8—H8B109.5
N1—C1—H1C108.7O2—C8—H8C109.5
C2—C1—H1C108.7H8A—C8—H8C109.5
H1B—C1—H1C107.6H8B—C8—H8C109.5
C3—C2—C7118.5 (4)C10i—C9—C10121.7 (6)
C3—C2—C1118.4 (4)C10i—C9—H9119.2
C7—C2—C1123.1 (4)C10—C9—H9119.2
O1—C3—C2118.2 (4)N1—C10—C9119.1 (4)
O1—C3—C4121.4 (4)N1—C10—C11122.6 (4)
C2—C3—C4120.4 (4)C9—C10—C11118.4 (4)
C5—C4—O2125.2 (4)C12—C11—C10119.9 (5)
C5—C4—C3120.1 (4)C12—C11—H11120.1
O2—C4—C3114.7 (4)C10—C11—H11120.1
C4—C5—C6119.2 (4)C11—C12—C11i121.9 (6)
C4—C5—H5120.4C11—C12—H12119.1
C6—C5—H5120.4C11i—C12—H12119.1
C7—C6—C5120.9 (4)
C10—N1—C1—C278.5 (5)O2—C4—C5—C6179.8 (4)
N1—C1—C2—C3170.8 (4)C3—C4—C5—C61.0 (7)
N1—C1—C2—C77.9 (7)C4—C5—C6—C70.1 (7)
C7—C2—C3—O1179.9 (4)C5—C6—C7—C20.4 (7)
C1—C2—C3—O11.2 (6)C3—C2—C7—C60.1 (7)
C7—C2—C3—C40.9 (7)C1—C2—C7—C6178.6 (4)
C1—C2—C3—C4177.8 (4)C1—N1—C10—C9172.3 (4)
C8—O2—C4—C511.9 (7)C1—N1—C10—C118.8 (6)
C8—O2—C4—C3168.8 (5)C10i—C9—C10—N1179.7 (4)
O1—C3—C4—C5179.6 (5)C10i—C9—C10—C110.8 (3)
C2—C3—C4—C51.4 (6)N1—C10—C11—C12179.5 (3)
O1—C3—C4—O20.3 (6)C9—C10—C11—C121.6 (6)
C2—C3—C4—O2179.3 (4)C10—C11—C12—C11i0.8 (3)
Symmetry code: (i) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O20.822.242.687 (4)115
O1—H1A···O2ii0.822.052.811 (4)153
Symmetry code: (ii) x+2, y+2, z.

Experimental details

Crystal data
Chemical formulaC22H24N2O4
Mr380.43
Crystal system, space groupOrthorhombic, Pnc2
Temperature (K)298
a, b, c (Å)13.2402 (18), 7.7416 (14), 9.7770 (12)
V3)1002.1 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.46 × 0.29 × 0.15
Data collection
DiffractometerSiemens SMART 1000 CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.961, 0.987
No. of measured, independent and
observed [I > 2σ(I)] reflections
4760, 948, 587
Rint0.064
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.119, 1.05
No. of reflections948
No. of parameters129
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.19, 0.15
Absolute structureFlack (1983), 948 Freidel pairs
Absolute structure parameter10 (10)

Computer programs: SMART (Siemens, 1996), SMART, SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O20.822.242.687 (4)114.9
O1—H1A···O2i0.822.052.811 (4)153.3
Symmetry code: (i) x+2, y+2, z.
 

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