The crystal structure of the zwitterionic co-crystal of 2,4-di­chloro-6-{[(3-hy­droxy­prop­yl)azaniumyl]­meth­yl}phenolate and 2,4-di­chloro­phenol

The title compound was isolated serendipitously as the co-crystal of 2,4-di­chloro­phenol and 2,4-di­chloro-6-{[(3-hy­droxy­prop­yl)azaniumyl]­meth­yl}phenolate in its zwitterionic form, from an incomplete Mannich condensation. The co-crystal is held together by extensive intra- and inter­molecular hydrogen bonds as well as π–π inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.037
• wR factor = 0.092
• Data-to-parameter ratio = 19.2

checkCIF/PLATON results

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Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.04 Report
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....        2.3 Note
PLAT309_ALERT_2_C Single Bonded Oxygen (C-O > 1.3 Ang) ...........         O1 Check
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............    0.00427 Ang.
PLAT915_ALERT_3_C No Flack x Check Done: Low Friedel Pair Coverage         89 %

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          4 Note
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          4 Report
PLAT128_ALERT_4_G Alternate Setting for Input Space Group  Cc              Ia Note
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          1 Report
PLAT176_ALERT_4_G The CIF-Embedded .res File Contains SADI Records          1 Report
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          1 Note
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          4 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         12 Info

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

   0 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
   3 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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Computing details

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015b); program(s) used to refine structure: SHELXL (Sheldrick, 2015a); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

2,4-Dichlorophenol– 2,4-dichloro-6-{[(3-hydroxypropyl)azaniumyl]methyl}phenolate (1/1)

Crystal data

C10H13Cl2NO2·C6H4Cl2O	F(000) = 848
Mr = 413.10	Dx = 1.560 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 26.406 (2) Å	Cell parameters from 6679 reflections
b = 9.5558 (9) Å	θ = 2.3–28.6°
c = 7.1019 (6) Å	µ = 0.69 mm^−1
β = 101.076 (2)°	T = 100 K
V = 1758.6 (3) Å^3	Plank, colourless
Z = 4	0.39 × 0.20 × 0.17 mm

Data collection

Bruker APEXII CCD diffractometer	3842 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.053
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θmax = 28.6°, θmin = 1.6°
Tmin = 0.688, Tmax = 0.746	h = −34→35
15694 measured reflections	k = −12→12
4227 independent reflections	l = −9→9

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.037	w = 1/[σ^2(Fo^2) + (0.051P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.092	(Δ/σ)max = 0.001
S = 1.03	Δρmax = 0.52 e Å^−3
4227 reflections	Δρmin = −0.25 e Å^−3
220 parameters	Absolute structure: Refined as an inversion twin
4 restraints	Absolute structure parameter: 0.03 (8)
Primary atom site location: dual

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.

Refinement. Refined as a 2-component inversion twin.

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

	x	y	z	Uiso*/Ueq
C1	0.60636 (12)	0.3974 (3)	0.4792 (4)	0.0142 (6)
C2	0.63604 (11)	0.2750 (3)	0.5205 (4)	0.0157 (6)
C3	0.68630 (12)	0.2726 (3)	0.6225 (4)	0.0165 (6)
H3	0.704950	0.187257	0.645494	0.020*
C4	0.70848 (12)	0.3991 (3)	0.6902 (5)	0.0168 (6)
C5	0.68172 (11)	0.5238 (3)	0.6521 (4)	0.0165 (6)
H5	0.697687	0.609545	0.698121	0.020*
C6	0.63169 (11)	0.5240 (3)	0.5469 (4)	0.0147 (6)
O1	0.55807 (8)	0.3971 (2)	0.3846 (3)	0.0155 (5)
C7	0.60594 (11)	0.6628 (3)	0.4870 (4)	0.0158 (5)
H7A	0.625976	0.738673	0.561830	0.019*
H7B	0.606421	0.679235	0.349730	0.019*
N1	0.55136 (9)	0.6690 (2)	0.5164 (3)	0.0147 (4)
H1A	0.550581	0.642000	0.638674	0.018*
H1B	0.532185	0.606588	0.435781	0.018*
C8	0.52697 (11)	0.8107 (3)	0.4826 (4)	0.0175 (5)
H8A	0.550100	0.879869	0.559396	0.021*
H8B	0.494264	0.809926	0.531229	0.021*
C9	0.51540 (11)	0.8601 (3)	0.2744 (4)	0.0175 (6)
H9A	0.503078	0.958053	0.271129	0.021*
H9B	0.547924	0.859396	0.224456	0.021*
C10	0.47556 (12)	0.7729 (3)	0.1416 (4)	0.0202 (6)
H10A	0.443328	0.769495	0.193267	0.024*
H10B	0.467599	0.817985	0.013813	0.024*
O2	0.49333 (8)	0.6335 (2)	0.1213 (3)	0.0184 (4)
H2	0.513930	0.633301	0.044658	0.028*
Cl1	0.60850 (3)	0.11500 (7)	0.43483 (9)	0.01842 (17)
Cl2	0.77111 (3)	0.39949 (8)	0.82500 (10)	0.0250 (2)
O1B	0.44186 (9)	0.3939 (2)	0.1038 (4)	0.0241 (6)
H1BA	0.455585	0.473101	0.102256	0.036*
C1B	0.39283 (14)	0.3987 (3)	0.0027 (5)	0.0199 (7)
C2B	0.36413 (13)	0.2748 (4)	−0.0255 (5)	0.0222 (7)
C3B	0.31382 (13)	0.2721 (4)	−0.1258 (5)	0.0248 (7)
H3B	0.295037	0.186795	−0.143940	0.030*
C4B	0.29142 (13)	0.3965 (3)	−0.1992 (5)	0.0218 (7)
C5B	0.31829 (12)	0.5215 (4)	−0.1709 (4)	0.0216 (7)
H5B	0.302285	0.606604	−0.219504	0.026*
C6B	0.36880 (12)	0.5211 (3)	−0.0710 (4)	0.0205 (6)
H6B	0.387375	0.606724	−0.052605	0.025*
Cl2B	0.22825 (3)	0.39666 (9)	−0.32799 (12)	0.0308 (2)
Cl1B	0.39215 (3)	0.11872 (9)	0.07078 (15)	0.0370 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0169 (16)	0.0145 (16)	0.0124 (14)	−0.0011 (11)	0.0055 (11)	−0.0008 (9)
C2	0.0192 (15)	0.0122 (15)	0.0165 (13)	−0.0052 (12)	0.0057 (11)	−0.0028 (10)
C3	0.0178 (15)	0.0129 (16)	0.0189 (13)	0.0016 (12)	0.0036 (11)	−0.0006 (10)
C4	0.0110 (15)	0.0175 (17)	0.0210 (15)	−0.0005 (11)	0.0011 (12)	−0.0027 (11)
C5	0.0172 (15)	0.0150 (16)	0.0177 (14)	−0.0015 (12)	0.0048 (11)	−0.0019 (10)
C6	0.0178 (14)	0.0128 (15)	0.0151 (13)	0.0005 (12)	0.0069 (10)	−0.0004 (10)
O1	0.0145 (12)	0.0156 (12)	0.0163 (10)	−0.0013 (8)	0.0029 (8)	−0.0017 (7)
C7	0.0168 (13)	0.0120 (14)	0.0193 (13)	0.0005 (10)	0.0049 (10)	0.0008 (9)
N1	0.0168 (11)	0.0144 (11)	0.0130 (11)	−0.0011 (9)	0.0033 (8)	0.0003 (8)
C8	0.0223 (14)	0.0120 (13)	0.0182 (13)	0.0004 (10)	0.0038 (10)	0.0005 (10)
C9	0.0199 (14)	0.0154 (14)	0.0174 (14)	0.0010 (10)	0.0037 (11)	0.0026 (10)
C10	0.0212 (14)	0.0191 (15)	0.0197 (14)	0.0031 (11)	0.0026 (10)	−0.0015 (11)
O2	0.0193 (10)	0.0168 (10)	0.0201 (10)	−0.0005 (8)	0.0060 (8)	−0.0012 (7)
Cl1	0.0201 (4)	0.0128 (4)	0.0216 (3)	−0.0027 (3)	0.0023 (3)	−0.0022 (3)
Cl2	0.0169 (4)	0.0194 (4)	0.0353 (5)	0.0010 (3)	−0.0038 (3)	−0.0041 (3)
O1B	0.0159 (13)	0.0151 (13)	0.0403 (15)	−0.0022 (8)	0.0027 (10)	−0.0003 (9)
C1B	0.0152 (16)	0.0220 (19)	0.0235 (17)	−0.0002 (12)	0.0062 (12)	−0.0015 (11)
C2B	0.0199 (16)	0.0120 (17)	0.0352 (17)	0.0023 (13)	0.0068 (13)	0.0024 (12)
C3B	0.0211 (18)	0.0162 (19)	0.0373 (18)	−0.0030 (13)	0.0059 (14)	−0.0017 (13)
C4B	0.0184 (18)	0.0197 (18)	0.0274 (17)	−0.0020 (12)	0.0046 (14)	−0.0020 (12)
C5B	0.0234 (17)	0.0164 (17)	0.0251 (16)	−0.0007 (13)	0.0045 (12)	0.0015 (12)
C6B	0.0243 (17)	0.0142 (16)	0.0242 (16)	−0.0043 (13)	0.0076 (12)	−0.0022 (11)
Cl2B	0.0200 (5)	0.0207 (5)	0.0474 (6)	−0.0024 (3)	−0.0038 (4)	0.0031 (4)
Cl1B	0.0209 (5)	0.0167 (5)	0.0705 (7)	0.0004 (3)	0.0018 (5)	0.0095 (4)

Geometric parameters (Å, º)

C1—C2	1.407 (4)	C9—H9A	0.9900
C1—C6	1.421 (4)	C9—H9B	0.9900
C1—O1	1.322 (4)	C9—C10	1.520 (4)
C2—C3	1.385 (4)	C10—H10A	0.9900
C2—Cl1	1.751 (3)	C10—H10B	0.9900
C3—H3	0.9500	C10—O2	1.429 (3)
C3—C4	1.388 (4)	O2—H2	0.8400
C4—C5	1.386 (4)	O1B—H1BA	0.8400
C4—Cl2	1.744 (3)	O1B—C1B	1.355 (4)
C5—H5	0.9500	C1B—C2B	1.400 (5)
C5—C6	1.387 (4)	C1B—C6B	1.384 (5)
C6—C7	1.514 (4)	C2B—C3B	1.382 (5)
C7—H7A	0.9900	C2B—Cl1B	1.745 (3)
C7—H7B	0.9900	C3B—H3B	0.9500
C7—N1	1.496 (3)	C3B—C4B	1.384 (5)
N1—H1A	0.9100	C4B—C5B	1.385 (4)
N1—H1B	0.9100	C4B—Cl2B	1.742 (4)
N1—C8	1.499 (3)	C5B—H5B	0.9500
C8—H8A	0.9900	C5B—C6B	1.385 (4)
C8—H8B	0.9900	C6B—H6B	0.9500
C8—C9	1.526 (4)
C2—C1—C6	115.5 (3)	C9—C8—H8A	108.3
O1—C1—C2	123.3 (3)	C9—C8—H8B	108.3
O1—C1—C6	121.3 (3)	C8—C9—H9A	108.6
C1—C2—Cl1	118.4 (2)	C8—C9—H9B	108.6
C3—C2—C1	124.2 (3)	H9A—C9—H9B	107.6
C3—C2—Cl1	117.3 (2)	C10—C9—C8	114.7 (2)
C2—C3—H3	121.2	C10—C9—H9A	108.6
C2—C3—C4	117.7 (3)	C10—C9—H9B	108.6
C4—C3—H3	121.2	C9—C10—H10A	109.2
C3—C4—Cl2	119.0 (2)	C9—C10—H10B	109.2
C5—C4—C3	121.1 (3)	H10A—C10—H10B	107.9
C5—C4—Cl2	120.0 (2)	O2—C10—C9	111.8 (2)
C4—C5—H5	119.9	O2—C10—H10A	109.2
C4—C5—C6	120.2 (3)	O2—C10—H10B	109.2
C6—C5—H5	119.9	C10—O2—H2	109.5
C1—C6—C7	119.6 (3)	C1B—O1B—H1BA	109.5
C5—C6—C1	121.3 (3)	O1B—C1B—C2B	118.9 (3)
C5—C6—C7	118.8 (3)	O1B—C1B—C6B	123.4 (3)
C6—C7—H7A	109.0	C6B—C1B—C2B	117.7 (3)
C6—C7—H7B	109.0	C1B—C2B—Cl1B	119.3 (3)
H7A—C7—H7B	107.8	C3B—C2B—C1B	122.0 (3)
N1—C7—C6	112.8 (2)	C3B—C2B—Cl1B	118.6 (3)
N1—C7—H7A	109.0	C2B—C3B—H3B	120.8
N1—C7—H7B	109.0	C2B—C3B—C4B	118.5 (3)
C7—N1—H1A	108.7	C4B—C3B—H3B	120.8
C7—N1—H1B	108.7	C3B—C4B—C5B	121.1 (3)
C7—N1—C8	114.1 (2)	C3B—C4B—Cl2B	119.7 (3)
H1A—N1—H1B	107.6	C5B—C4B—Cl2B	119.2 (3)
C8—N1—H1A	108.7	C4B—C5B—H5B	120.4
C8—N1—H1B	108.7	C4B—C5B—C6B	119.2 (3)
N1—C8—H8A	108.3	C6B—C5B—H5B	120.4
N1—C8—H8B	108.3	C1B—C6B—C5B	121.5 (3)
N1—C8—C9	115.8 (2)	C1B—C6B—H6B	119.3
H8A—C8—H8B	107.4	C5B—C6B—H6B	119.3
C1—C2—C3—C4	0.8 (4)	N1—C8—C9—C10	64.5 (3)
C1—C6—C7—N1	50.1 (3)	C8—C9—C10—O2	−65.1 (3)
C2—C1—C6—C5	−2.1 (4)	Cl1—C2—C3—C4	179.7 (2)
C2—C1—C6—C7	171.6 (2)	Cl2—C4—C5—C6	−179.2 (2)
C2—C3—C4—C5	−1.8 (5)	O1B—C1B—C2B—C3B	179.5 (3)
C2—C3—C4—Cl2	178.3 (2)	O1B—C1B—C2B—Cl1B	0.3 (4)
C3—C4—C5—C6	0.8 (5)	O1B—C1B—C6B—C5B	−179.0 (3)
C4—C5—C6—C1	1.2 (4)	C1B—C2B—C3B—C4B	−0.3 (5)
C4—C5—C6—C7	−172.6 (3)	C2B—C1B—C6B—C5B	−0.6 (5)
C5—C6—C7—N1	−136.0 (3)	C2B—C3B—C4B—C5B	−0.9 (5)
C6—C1—C2—C3	1.2 (4)	C2B—C3B—C4B—Cl2B	179.5 (2)
C6—C1—C2—Cl1	−177.8 (2)	C3B—C4B—C5B—C6B	1.4 (5)
C6—C7—N1—C8	172.5 (2)	C4B—C5B—C6B—C1B	−0.6 (5)
O1—C1—C2—C3	−178.7 (3)	C6B—C1B—C2B—C3B	1.1 (5)
O1—C1—C2—Cl1	2.4 (4)	C6B—C1B—C2B—Cl1B	−178.2 (2)
O1—C1—C6—C5	177.7 (3)	Cl2B—C4B—C5B—C6B	−179.0 (2)
O1—C1—C6—C7	−8.6 (4)	Cl1B—C2B—C3B—C4B	178.9 (3)
C7—N1—C8—C9	69.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1^i	0.91	1.76	2.663 (3)	171
N1—H1B···O1	0.91	2.17	2.779 (3)	124
N1—H1B···O2	0.91	2.29	2.947 (3)	129
O2—H2···O1^ii	0.84	1.80	2.634 (3)	171
O1B—H1BA···O2	0.84	1.82	2.653 (3)	172

Symmetry codes: (i) x, −y+1, z+1/2; (ii) x, −y+1, z−1/2.