Crystal structure of bis(3,5-dichloro-2-hydroxybenzyl)(2-methoxyethyl)amine

The title compound was prepared via a modified Mannich reaction between 2-meth­oxy­ethyl­amine, 2,4-di­chloro­phenol, and aqueous formaldehyde. The resulting amine bis­(phenol) provides an inter­esting comparison to related species as a result of the electron-withdrawing substituents on the phenol rings, in combination with similar steric parameters.

Key indicators

Structure: global

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.002 Å
• Disorder in main residue
• R factor = 0.035
• wR factor = 0.100
• Data-to-parameter ratio = 20.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT242_ALERT_2_C Low    'MainMol' Ueq as Compared to Neighbors of         C6 Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      2.483 Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600         19 Report

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          7 Note
PLAT003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ...          6 Report
PLAT154_ALERT_1_G The s.u.'s on the Cell Angles are Equal ..(Note)      0.002 Degree
PLAT176_ALERT_4_G The CIF-Embedded .res File Contains SADI Records          5 Report
PLAT178_ALERT_4_G The CIF-Embedded .res File Contains SIMU Records          1 Report
PLAT188_ALERT_3_G A Non-default SIMU Restraint Value has been used     0.0100 Report
PLAT191_ALERT_3_G A Non-default SADI Restraint Value has been used     0.0400 Report
PLAT191_ALERT_3_G A Non-default SADI Restraint Value has been used     0.0400 Report
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT301_ALERT_3_G Main Residue  Disorder ..............(Resd  1  )        16% Note
PLAT802_ALERT_4_G CIF Input Record(s) with more than 80 Characters          1 Info
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............         71 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          1 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        185 Note
PLAT933_ALERT_2_G Number of HKL-OMIT Records in Embedded .res File          1 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         15 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  17 ALERT level G = General information/check it is not something unexpected

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   8 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

---

Computing details

Data collection: CrysAlis PRO 1.171.40.55a (Rigaku OD, 2019); cell refinement: CrysAlis PRO 1.171.40.55a (Rigaku OD, 2019); data reduction: CrysAlis PRO 1.171.40.55a (Rigaku OD, 2019); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2015b); molecular graphics: Olex2 1.3-ac4 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 1.3-ac4 (Dolomanov et al., 2009), PLATON (Spek, 2020).

2,4-Dichloro-6-({[(3,5-dichloro-2-hydroxyphenyl)methyl](2-methoxyethyl)amino}methyl)phenol

Crystal data

C17H17Cl4NO3	Z = 2
Mr = 425.11	F(000) = 436
Triclinic, P1	Dx = 1.501 Mg m^−3
a = 9.4912 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.0464 (2) Å	Cell parameters from 18216 reflections
c = 11.1169 (3) Å	θ = 2.1–29.4°
α = 103.930 (2)°	µ = 0.65 mm^−1
β = 113.048 (2)°	T = 293 K
γ = 90.543 (2)°	Block, light yellow
V = 940.32 (4) Å^3	0.56 × 0.36 × 0.31 mm

Data collection

XtaLAB Mini II diffractometer	4418 reflections with I > 2σ(I)
Detector resolution: 10.0000 pixels mm^-1	Rint = 0.056
ω scans	θmax = 30.9°, θmin = 2.1°
Absorption correction: analytical (CrysAlisPro; Rigaku OD, 2019)	h = −13→13
Tmin = 0.886, Tmax = 0.940	k = −14→14
56643 measured reflections	l = −15→15
5724 independent reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.100	w = 1/[σ^2(Fo^2) + (0.0501P)^2 + 0.1137P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
5724 reflections	Δρmax = 0.34 e Å^−3
274 parameters	Δρmin = −0.25 e Å^−3
71 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl1	1.01005 (4)	1.16885 (4)	0.82889 (4)	0.05322 (11)
Cl3	1.22323 (4)	0.61557 (4)	0.38567 (4)	0.05383 (11)
Cl4	0.84093 (5)	0.14540 (4)	0.20134 (5)	0.06363 (13)
O1	0.82934 (14)	1.03365 (11)	0.52755 (11)	0.0510 (3)
H1	0.900 (2)	1.097 (2)	0.568 (2)	0.069 (6)*
O2	0.96180 (11)	0.74608 (9)	0.42712 (10)	0.0400 (2)
H2	0.872 (2)	0.774 (2)	0.414 (2)	0.074 (6)*
N1	0.66091 (12)	0.74842 (10)	0.34291 (10)	0.0318 (2)
C1	0.57399 (14)	0.84027 (13)	0.40526 (13)	0.0367 (3)
H1A	0.474597	0.791182	0.382398	0.044*
H1B	0.555600	0.919147	0.367423	0.044*
C2	0.65628 (14)	0.89107 (12)	0.55747 (13)	0.0341 (2)
C3	0.78319 (14)	0.99260 (12)	0.61437 (13)	0.0354 (3)
C4	0.85263 (14)	1.04400 (13)	0.75464 (14)	0.0376 (3)
C5	0.80028 (16)	0.99664 (15)	0.83826 (14)	0.0435 (3)
H5	0.848114	1.031911	0.931918	0.052*
C6	0.67633 (16)	0.89655 (16)	0.78049 (15)	0.0466 (3)
C7	0.60415 (15)	0.84369 (14)	0.64163 (14)	0.0418 (3)
H7	0.520189	0.775990	0.604414	0.050*
C8	0.66952 (14)	0.61504 (12)	0.37752 (13)	0.0320 (2)
H8A	0.569909	0.559766	0.327692	0.038*
H8B	0.694307	0.631215	0.473573	0.038*
C9	0.79009 (13)	0.53710 (12)	0.34387 (11)	0.0300 (2)
C10	0.93273 (14)	0.60756 (12)	0.37335 (12)	0.0314 (2)
C11	1.04486 (14)	0.53163 (14)	0.34808 (13)	0.0358 (3)
C12	1.01851 (15)	0.38994 (14)	0.29476 (13)	0.0405 (3)
H12	1.094355	0.340736	0.277973	0.049*
C13	0.87734 (16)	0.32319 (13)	0.26702 (13)	0.0394 (3)
C14	0.76347 (14)	0.39528 (12)	0.29014 (12)	0.0348 (3)
H14	0.668492	0.348467	0.269575	0.042*
C15	0.60508 (17)	0.73494 (15)	0.19605 (13)	0.0430 (3)
H15A	0.659421	0.666455	0.159482	0.052*	0.867 (3)
H15B	0.633807	0.822342	0.184310	0.052*	0.867 (3)
H15C	0.690386	0.713498	0.170147	0.052*	0.133 (3)
H15D	0.579251	0.824618	0.181553	0.052*	0.133 (3)
Cl2A	0.5985 (10)	0.8517 (9)	0.8845 (5)	0.0813 (12)	0.49 (3)
O3	0.38914 (17)	0.56244 (17)	0.11430 (15)	0.0620 (5)	0.867 (3)
C16	0.4335 (2)	0.6951 (2)	0.11144 (19)	0.0510 (5)	0.867 (3)
H16A	0.376368	0.761397	0.146831	0.061*	0.867 (3)
H16B	0.409768	0.696484	0.018604	0.061*	0.867 (3)
C17	0.2289 (4)	0.5234 (5)	0.0411 (4)	0.0727 (10)	0.867 (3)
H17A	0.203010	0.508710	−0.054032	0.109*	0.867 (3)
H17B	0.174109	0.595322	0.070034	0.109*	0.867 (3)
H17C	0.200589	0.439687	0.057594	0.109*	0.867 (3)
Cl2B	0.6178 (8)	0.8240 (12)	0.8838 (5)	0.0852 (13)	0.51 (3)
O3A	0.3455 (10)	0.6544 (11)	0.1361 (8)	0.058 (2)	0.133 (3)
C16A	0.4692 (13)	0.6306 (17)	0.1002 (12)	0.055 (3)	0.133 (3)
H16C	0.441195	0.637306	0.008277	0.066*	0.133 (3)
H16D	0.496146	0.538240	0.103566	0.066*	0.133 (3)
C17A	0.215 (3)	0.552 (3)	0.065 (3)	0.090 (7)	0.133 (3)
H17D	0.159714	0.561535	−0.024522	0.135*	0.133 (3)
H17E	0.148807	0.563079	0.112909	0.135*	0.133 (3)
H17F	0.249224	0.461729	0.060152	0.135*	0.133 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0519 (2)	0.03981 (18)	0.0515 (2)	−0.01450 (15)	0.01056 (17)	0.00156 (15)
Cl3	0.03336 (16)	0.0688 (3)	0.0631 (2)	0.00036 (16)	0.02120 (16)	0.02153 (19)
Cl4	0.0699 (3)	0.03300 (18)	0.0738 (3)	0.00873 (17)	0.0259 (2)	−0.00547 (17)
O1	0.0605 (7)	0.0419 (5)	0.0461 (6)	−0.0170 (5)	0.0224 (5)	0.0031 (5)
O2	0.0371 (5)	0.0301 (4)	0.0494 (5)	−0.0045 (4)	0.0169 (4)	0.0057 (4)
N1	0.0347 (5)	0.0278 (5)	0.0325 (5)	0.0036 (4)	0.0138 (4)	0.0067 (4)
C1	0.0330 (6)	0.0336 (6)	0.0383 (6)	0.0054 (5)	0.0122 (5)	0.0042 (5)
C2	0.0310 (6)	0.0287 (5)	0.0387 (6)	0.0051 (5)	0.0139 (5)	0.0023 (5)
C3	0.0373 (6)	0.0274 (5)	0.0401 (6)	0.0030 (5)	0.0170 (5)	0.0044 (5)
C4	0.0344 (6)	0.0285 (6)	0.0425 (7)	0.0001 (5)	0.0125 (5)	0.0017 (5)
C5	0.0391 (7)	0.0475 (8)	0.0369 (7)	0.0012 (6)	0.0129 (6)	0.0034 (6)
C6	0.0402 (7)	0.0570 (9)	0.0432 (7)	−0.0030 (6)	0.0194 (6)	0.0103 (6)
C7	0.0334 (6)	0.0435 (7)	0.0441 (7)	−0.0033 (5)	0.0156 (6)	0.0044 (6)
C8	0.0326 (5)	0.0292 (5)	0.0344 (6)	0.0015 (4)	0.0145 (5)	0.0071 (5)
C9	0.0309 (5)	0.0290 (5)	0.0282 (5)	0.0015 (4)	0.0110 (4)	0.0060 (4)
C10	0.0314 (5)	0.0315 (6)	0.0280 (5)	−0.0004 (4)	0.0094 (4)	0.0068 (4)
C11	0.0293 (5)	0.0450 (7)	0.0330 (6)	0.0029 (5)	0.0121 (5)	0.0111 (5)
C12	0.0378 (6)	0.0477 (7)	0.0341 (6)	0.0128 (6)	0.0143 (5)	0.0079 (5)
C13	0.0448 (7)	0.0308 (6)	0.0354 (6)	0.0065 (5)	0.0119 (5)	0.0035 (5)
C14	0.0346 (6)	0.0305 (6)	0.0337 (6)	−0.0008 (5)	0.0110 (5)	0.0039 (5)
C15	0.0507 (8)	0.0445 (7)	0.0360 (7)	0.0067 (6)	0.0182 (6)	0.0135 (6)
Cl2A	0.080 (2)	0.106 (2)	0.0540 (16)	−0.0391 (15)	0.0384 (17)	−0.0025 (18)
O3	0.0505 (8)	0.0610 (10)	0.0552 (8)	−0.0033 (7)	0.0030 (6)	0.0130 (7)
C16	0.0561 (12)	0.0518 (11)	0.0344 (8)	0.0134 (9)	0.0077 (8)	0.0103 (8)
C17	0.0510 (13)	0.098 (3)	0.0480 (18)	−0.0115 (16)	0.0108 (11)	−0.0010 (15)
Cl2B	0.0609 (12)	0.139 (3)	0.0544 (16)	−0.0285 (17)	0.0132 (13)	0.042 (2)
O3A	0.053 (4)	0.069 (5)	0.038 (3)	−0.004 (4)	0.014 (3)	−0.001 (3)
C16A	0.054 (5)	0.068 (5)	0.038 (4)	0.010 (5)	0.016 (4)	0.007 (4)
C17A	0.065 (9)	0.102 (10)	0.051 (10)	0.007 (9)	−0.011 (8)	−0.013 (8)

Geometric parameters (Å, º)

Cl1—C4	1.7284 (13)	C9—C14	1.3841 (16)
Cl3—C11	1.7324 (13)	C10—C11	1.3927 (17)
Cl4—C13	1.7337 (13)	C11—C12	1.3825 (19)
O1—H1	0.82 (2)	C12—H12	0.9300
O1—C3	1.3465 (16)	C12—C13	1.378 (2)
O2—H2	0.87 (2)	C13—C14	1.3789 (18)
O2—C10	1.3540 (14)	C14—H14	0.9300
N1—C1	1.4720 (15)	C15—H15A	0.9700
N1—C8	1.4752 (15)	C15—H15B	0.9700
N1—C15	1.4763 (16)	C15—H15C	0.9700
C1—H1A	0.9700	C15—H15D	0.9700
C1—H1B	0.9700	C15—C16	1.518 (2)
C1—C2	1.5085 (17)	C15—C16A	1.502 (12)
C2—C3	1.4002 (17)	O3—C16	1.405 (3)
C2—C7	1.3854 (19)	O3—C17	1.413 (4)
C3—C4	1.3906 (18)	C16—H16A	0.9700
C4—C5	1.381 (2)	C16—H16B	0.9700
C5—H5	0.9300	C17—H17A	0.9600
C5—C6	1.372 (2)	C17—H17B	0.9600
C6—C7	1.380 (2)	C17—H17C	0.9600
C6—Cl2A	1.732 (7)	O3A—C16A	1.386 (13)
C6—Cl2B	1.748 (6)	O3A—C17A	1.427 (16)
C7—H7	0.9300	C16A—H16C	0.9700
C8—H8A	0.9700	C16A—H16D	0.9700
C8—H8B	0.9700	C17A—H17D	0.9600
C8—C9	1.5079 (16)	C17A—H17E	0.9600
C9—C10	1.4015 (16)	C17A—H17F	0.9600
C3—O1—H1	111.2 (14)	C13—C12—C11	118.54 (12)
C10—O2—H2	105.1 (13)	C13—C12—H12	120.7
C1—N1—C8	111.85 (10)	C12—C13—Cl4	119.75 (10)
C1—N1—C15	112.00 (10)	C12—C13—C14	121.22 (12)
C8—N1—C15	113.80 (10)	C14—C13—Cl4	119.03 (11)
N1—C1—H1A	109.0	C9—C14—H14	119.9
N1—C1—H1B	109.0	C13—C14—C9	120.21 (12)
N1—C1—C2	113.07 (10)	C13—C14—H14	119.9
H1A—C1—H1B	107.8	N1—C15—H15A	108.0
C2—C1—H1A	109.0	N1—C15—H15B	108.0
C2—C1—H1B	109.0	N1—C15—H15C	107.6
C3—C2—C1	119.30 (12)	N1—C15—H15D	107.6
C7—C2—C1	121.13 (11)	N1—C15—C16	117.22 (13)
C7—C2—C3	119.50 (12)	N1—C15—C16A	118.7 (6)
O1—C3—C2	116.78 (12)	H15A—C15—H15B	107.2
O1—C3—C4	124.53 (12)	H15C—C15—H15D	107.1
C4—C3—C2	118.69 (12)	C16—C15—H15A	108.0
C3—C4—Cl1	120.12 (10)	C16—C15—H15B	108.0
C5—C4—Cl1	118.21 (10)	C16A—C15—H15C	107.6
C5—C4—C3	121.67 (12)	C16A—C15—H15D	107.6
C4—C5—H5	120.6	C16—O3—C17	112.0 (3)
C6—C5—C4	118.72 (13)	C15—C16—H16A	109.6
C6—C5—H5	120.6	C15—C16—H16B	109.6
C5—C6—C7	121.17 (13)	O3—C16—C15	110.13 (15)
C5—C6—Cl2A	118.2 (2)	O3—C16—H16A	109.6
C5—C6—Cl2B	119.8 (2)	O3—C16—H16B	109.6
C7—C6—Cl2A	120.2 (2)	H16A—C16—H16B	108.1
C7—C6—Cl2B	118.9 (3)	O3—C17—H17A	109.5
C2—C7—H7	119.9	O3—C17—H17B	109.5
C6—C7—C2	120.26 (13)	O3—C17—H17C	109.5
C6—C7—H7	119.9	H17A—C17—H17B	109.5
N1—C8—H8A	109.4	H17A—C17—H17C	109.5
N1—C8—H8B	109.4	H17B—C17—H17C	109.5
N1—C8—C9	111.23 (10)	C16A—O3A—C17A	115.8 (15)
H8A—C8—H8B	108.0	C15—C16A—H16C	109.7
C9—C8—H8A	109.4	C15—C16A—H16D	109.7
C9—C8—H8B	109.4	O3A—C16A—C15	109.7 (10)
C10—C9—C8	119.85 (10)	O3A—C16A—H16C	109.7
C14—C9—C8	120.31 (10)	O3A—C16A—H16D	109.7
C14—C9—C10	119.77 (11)	H16C—C16A—H16D	108.2
O2—C10—C9	120.78 (11)	O3A—C17A—H17D	109.5
O2—C10—C11	120.70 (11)	O3A—C17A—H17E	109.5
C11—C10—C9	118.52 (11)	O3A—C17A—H17F	109.5
C10—C11—Cl3	119.57 (10)	H17D—C17A—H17E	109.5
C12—C11—Cl3	118.68 (10)	H17D—C17A—H17F	109.5
C12—C11—C10	121.74 (11)	H17E—C17A—H17F	109.5
C11—C12—H12	120.7

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Cl1	0.82 (2)	2.58 (2)	3.0455 (12)	117.4 (17)
O2—H2···N1	0.87 (2)	1.83 (2)	2.6365 (16)	153 (2)
O1—H1···O2^i	0.82 (2)	2.01 (2)	2.7709 (14)	152.5 (19)

Symmetry code: (i) −x+2, −y+2, −z+1.