2-[(4-Chloro­phen­yl)amino­meth­yl]-6-methoxy­phenol

In the title compound, C₁₄H₁₄ClNO₂, mol­ecules are linked by a pair of O—H...O hydrogen bonds, generating dimers involving R₂²(10) rings. Neighbouring dimers are linked by C—H...π hydrogen bonds into sheets parallel to the (010) plane, and neighbouring sheets are linked into a three-dimensional network structure through N—H...π hydrogen bonds between the dimers.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.053
• wR factor = 0.158
• Data-to-parameter ratio = 13.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C12
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          5
PLAT420_ALERT_2_C D-H Without Acceptor       N1     -   H1     ...          ?

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

We have recently reported the crystal structure of o-vanillin diamine derivatives (Xia et al., 2006, 2007a, b, c). We report here the crystal structure of o-vanillin 4-chlorobenzen amine derivative(I).

The molecular structure of (I) is illustrated in Fig. 1. In (I), the dihedral angle between the two benzene rings is 88.47 (10)°, the bond lengths and angles are normal (Allen et al., 1987). The molecules are linked into the dimer by a pair of O—H···O hydrogen bonds, atom O1 in the molecule (x, y, z) and O2 in the molecule (1 - x, y, 1/2 - z) act as hydrogen-bond donor to atom O2 in the molecule (1 - x, y, 1/2 - z) and O1 in the molecule (x, y, z), respectively, generating a dimer involving R₂²(10) rings (Bernstein et al., 1995) (Fig. 2 and Table 1). A neighboring dimers are linked by C—H···π hydrogen bonds into sheets parallel to the [010] plane (Fig. 3), and neighboring sheets are linked into three-dimensional network structure through N—H···π hydrogen bonds between the dimers (Fig. 4).

Related literature

For related literature, see: Allen et al. (1987); Bernstein et al. (1995); Xia et al. (2006, 2007a,b,c).

S2. Experimental

A solution of 2-[(4-chlorophenylimino)methyl]-6-methoxy phenol (10 mmol) in methanol–chloroform (v/v = 1/1) (20 ml) and NaBH₄ (20 mmol) were mixed, the mixture solution was stirred under room temperature for 48 h and then mixtures was filtered, and then solution was left to produce crystals of (I) slowly.

S3. Refinement

All H atoms were located in difference Fourier maps. H atoms were treated as riding atoms, with C—H distances of 0.93 Å (aryl), 0.96 Å (methyl), 0.97 Å (methylene), N—H distances of 0.86 Å (amino) and O—H distances of 0.82 Å and with U_iso(H) = 1.2 (C_{aryl, methylene} or N_amino) or 1.5 U_eq(C_methyl or O_hydroxy).

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; 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

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are at the 30% probability level.
	Fig. 2. A larger portion of the crystal structure of (I), showing the formation of a hydrogen-bonded sheet built from O—H···O. For clarity, H atoms not involved in the hydrogen bonding have been omitted. Dashed lines indicate hydrogen bonds. [Symmetry code: (A) 1 - x, y, 1/2 - z].
	Fig. 3. A larger portion of the crystal structure of (I), showing the formation of a hydrogen-bonded sheet built from C—H···π. For clarity, H atoms not involved in the hydrogen bonding have been omitted. Dashed lines indicate hydrogen bonds. [Symmetry code: (A) 1 - x, y, 1/2 - z; (F) 1/2 + x, 1/2 + y, z; (I) 1 - x, 1 - y, 1 - z; (J) 1/2 + x, 1/2 - y, 1/2 + z].
	Fig. 4. A different view of the crystal struture of (I), showing the formation of a three-dimensional network struture built from N—H···π hydrogen-bonded. For clarity, H atoms not involved in the hydrogen bonding have been omitted. Dashed lines indicate hydrogen bonds. [Symmetry code: (A) 1 - x, y, 1/2 - z; (B) 1 - x, -1 + y, 1/2 - z; (C) x, -1 + y, z; (D) x, 1 + y, z; (E) 1 - x, 1 + y, 1/2 - z].

2-[(4-Chlorophenyl)aminomethyl]-6-methoxyphenol

Crystal data

C14H14ClNO2	F(000) = 1104
Mr = 263.71	Dx = 1.369 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1485 reflections
a = 24.346 (2) Å	θ = 3.2–22.5°
b = 5.4437 (12) Å	µ = 0.29 mm^−1
c = 20.478 (2) Å	T = 298 K
β = 109.496 (2)°	Block, colourless
V = 2558.5 (7) Å^3	0.59 × 0.42 × 0.30 mm
Z = 8

Data collection

Siemens SMART 1000 CCD area-detector diffractometer	2264 independent reflections
Radiation source: fine-focus sealed tube	1305 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.068
φ and ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −28→20
Tmin = 0.847, Tmax = 0.918	k = −6→6
6143 measured reflections	l = −24→24

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.158	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.058P)^2 + 2.5185P] where P = (Fo^2 + 2Fc^2)/3
2264 reflections	(Δ/σ)max < 0.001
164 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.36 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.04664 (4)	0.6829 (2)	0.07190 (5)	0.0730 (4)
N1	0.30405 (13)	0.7025 (6)	0.17647 (17)	0.0618 (9)
H1	0.3194	0.8409	0.1719	0.074*
O1	0.43176 (9)	0.1644 (5)	0.25625 (10)	0.0528 (7)
H1A	0.4576	0.0604	0.2658	0.079*
O2	0.46516 (10)	−0.1488 (4)	0.17665 (11)	0.0522 (7)
C1	0.34326 (15)	0.5057 (7)	0.20886 (18)	0.0559 (10)
H1B	0.3266	0.4155	0.2386	0.067*
H1C	0.3796	0.5772	0.2382	0.067*
C2	0.35693 (13)	0.3247 (6)	0.15996 (16)	0.0410 (8)
C3	0.40223 (13)	0.1606 (6)	0.18656 (15)	0.0371 (8)
C4	0.41828 (13)	−0.0012 (6)	0.14358 (16)	0.0401 (8)
C5	0.38754 (15)	−0.0042 (7)	0.07349 (16)	0.0492 (9)
H5	0.3976	−0.1139	0.0445	0.059*
C6	0.34193 (15)	0.1566 (7)	0.04686 (17)	0.0530 (10)
H6	0.3210	0.1543	−0.0003	0.064*
C7	0.32685 (15)	0.3204 (7)	0.08898 (17)	0.0492 (9)
H7	0.2963	0.4294	0.0699	0.059*
C8	0.48033 (15)	−0.3420 (7)	0.13784 (19)	0.0556 (10)
H8A	0.4469	−0.4441	0.1170	0.083*
H8B	0.5112	−0.4393	0.1683	0.083*
H8C	0.4930	−0.2716	0.1023	0.083*
C9	0.24382 (14)	0.6881 (7)	0.15203 (18)	0.0457 (9)
C10	0.21322 (16)	0.5003 (7)	0.17032 (18)	0.0528 (9)
H10	0.2333	0.3736	0.1989	0.063*
C11	0.15244 (16)	0.5013 (7)	0.14589 (19)	0.0538 (10)
H11	0.1322	0.3748	0.1582	0.065*
C12	0.12270 (14)	0.6849 (7)	0.10439 (16)	0.0457 (9)
C13	0.15200 (16)	0.8713 (7)	0.08636 (19)	0.0572 (10)
H13	0.1316	0.9980	0.0582	0.069*
C14	0.21174 (17)	0.8717 (7)	0.1099 (2)	0.0567 (10)
H14	0.2313	0.9998	0.0970	0.068*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0505 (6)	0.1044 (9)	0.0590 (6)	−0.0045 (6)	0.0117 (5)	−0.0064 (6)
N1	0.0519 (19)	0.0502 (19)	0.083 (2)	−0.0038 (17)	0.0220 (17)	−0.0036 (18)
O1	0.0489 (13)	0.0746 (17)	0.0284 (12)	0.0063 (14)	0.0040 (10)	−0.0055 (13)
O2	0.0528 (14)	0.0581 (16)	0.0402 (13)	0.0090 (13)	0.0081 (11)	−0.0035 (13)
C1	0.045 (2)	0.067 (3)	0.050 (2)	0.005 (2)	0.0076 (17)	−0.009 (2)
C2	0.0374 (17)	0.046 (2)	0.0382 (18)	−0.0056 (17)	0.0108 (15)	−0.0015 (17)
C3	0.0385 (17)	0.0428 (19)	0.0282 (16)	−0.0087 (16)	0.0087 (14)	−0.0015 (16)
C4	0.0407 (18)	0.044 (2)	0.0340 (18)	−0.0035 (17)	0.0110 (15)	0.0001 (17)
C5	0.058 (2)	0.055 (2)	0.0333 (18)	0.000 (2)	0.0135 (17)	−0.0085 (18)
C6	0.058 (2)	0.065 (3)	0.0287 (17)	−0.002 (2)	0.0048 (16)	0.0006 (19)
C7	0.0440 (19)	0.055 (2)	0.044 (2)	−0.0001 (19)	0.0085 (16)	0.0052 (19)
C8	0.060 (2)	0.046 (2)	0.062 (2)	0.002 (2)	0.0216 (19)	−0.004 (2)
C9	0.046 (2)	0.046 (2)	0.047 (2)	−0.0067 (19)	0.0193 (16)	−0.0142 (19)
C10	0.061 (2)	0.046 (2)	0.050 (2)	0.005 (2)	0.0163 (18)	0.0047 (19)
C11	0.060 (2)	0.054 (2)	0.055 (2)	−0.013 (2)	0.0289 (19)	0.000 (2)
C12	0.048 (2)	0.053 (2)	0.0360 (18)	−0.0043 (19)	0.0146 (16)	−0.0067 (18)
C13	0.060 (2)	0.051 (2)	0.054 (2)	0.000 (2)	0.0097 (19)	0.003 (2)
C14	0.061 (2)	0.040 (2)	0.071 (3)	−0.011 (2)	0.025 (2)	0.003 (2)

Geometric parameters (Å, º)

Cl1—C12	1.746 (3)	C6—C7	1.373 (5)
N1—C9	1.384 (4)	C6—H6	0.9300
N1—C1	1.441 (4)	C7—H7	0.9300
N1—H1	0.8600	C8—H8A	0.9600
O1—C3	1.367 (3)	C8—H8B	0.9600
O1—H1A	0.8200	C8—H8C	0.9600
O2—C4	1.375 (4)	C9—C14	1.380 (5)
O2—C8	1.439 (4)	C9—C10	1.388 (5)
C1—C2	1.519 (5)	C10—C11	1.395 (5)
C1—H1B	0.9700	C10—H10	0.9300
C1—H1C	0.9700	C11—C12	1.355 (5)
C2—C3	1.382 (4)	C11—H11	0.9300
C2—C7	1.393 (4)	C12—C13	1.360 (5)
C3—C4	1.390 (4)	C13—C14	1.371 (5)
C4—C5	1.380 (4)	C13—H13	0.9300
C5—C6	1.376 (5)	C14—H14	0.9300
C5—H5	0.9300
C9—N1—C1	125.7 (3)	C6—C7—H7	119.7
C9—N1—H1	117.1	C2—C7—H7	119.7
C1—N1—H1	117.1	O2—C8—H8A	109.5
C3—O1—H1A	109.5	O2—C8—H8B	109.5
C4—O2—C8	118.6 (3)	H8A—C8—H8B	109.5
N1—C1—C2	115.9 (3)	O2—C8—H8C	109.5
N1—C1—H1B	108.3	H8A—C8—H8C	109.5
C2—C1—H1B	108.3	H8B—C8—H8C	109.5
N1—C1—H1C	108.3	C14—C9—N1	119.7 (3)
C2—C1—H1C	108.3	C14—C9—C10	117.4 (3)
H1B—C1—H1C	107.4	N1—C9—C10	122.9 (3)
C3—C2—C7	118.3 (3)	C9—C10—C11	120.1 (3)
C3—C2—C1	118.8 (3)	C9—C10—H10	120.0
C7—C2—C1	123.0 (3)	C11—C10—H10	120.0
O1—C3—C2	118.3 (3)	C12—C11—C10	120.6 (3)
O1—C3—C4	120.6 (3)	C12—C11—H11	119.7
C2—C3—C4	121.1 (3)	C10—C11—H11	119.7
O2—C4—C5	125.3 (3)	C11—C12—C13	120.1 (3)
O2—C4—C3	114.9 (3)	C11—C12—Cl1	120.7 (3)
C5—C4—C3	119.8 (3)	C13—C12—Cl1	119.1 (3)
C6—C5—C4	119.4 (3)	C12—C13—C14	119.8 (4)
C6—C5—H5	120.3	C12—C13—H13	120.1
C4—C5—H5	120.3	C14—C13—H13	120.1
C7—C6—C5	120.9 (3)	C13—C14—C9	122.1 (3)
C7—C6—H6	119.5	C13—C14—H14	119.0
C5—C6—H6	119.5	C9—C14—H14	119.0
C6—C7—C2	120.6 (3)
C9—N1—C1—C2	82.9 (4)	C5—C6—C7—C2	−1.0 (5)
N1—C1—C2—C3	167.8 (3)	C3—C2—C7—C6	0.2 (5)
N1—C1—C2—C7	−10.4 (5)	C1—C2—C7—C6	178.4 (3)
C7—C2—C3—O1	−179.9 (3)	C1—N1—C9—C14	−166.9 (3)
C1—C2—C3—O1	1.8 (4)	C1—N1—C9—C10	15.9 (5)
C7—C2—C3—C4	1.3 (5)	C14—C9—C10—C11	0.4 (5)
C1—C2—C3—C4	−177.0 (3)	N1—C9—C10—C11	177.7 (3)
C8—O2—C4—C5	−7.4 (5)	C9—C10—C11—C12	−0.2 (5)
C8—O2—C4—C3	172.5 (3)	C10—C11—C12—C13	−0.3 (5)
O1—C3—C4—O2	−0.6 (4)	C10—C11—C12—Cl1	178.4 (3)
C2—C3—C4—O2	178.1 (3)	C11—C12—C13—C14	0.5 (5)
O1—C3—C4—C5	179.3 (3)	Cl1—C12—C13—C14	−178.1 (3)
C2—C3—C4—C5	−2.0 (5)	C12—C13—C14—C9	−0.3 (6)
O2—C4—C5—C6	−179.0 (3)	N1—C9—C14—C13	−177.5 (3)
C3—C4—C5—C6	1.1 (5)	C10—C9—C14—C13	−0.1 (5)
C4—C5—C6—C7	0.3 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2	0.82	2.21	2.667 (3)	115
O1—H1A···O2^i	0.82	2.18	2.965 (3)	161
C7—H7···N1	0.93	2.59	2.917 (5)	101

Symmetry code: (i) −x+1, y, −z+1/2.