Crystal structure studies and Hirshfeld surface analysis of 4-(di­methyl­aza­nium­yl)-2-hy­droxy­anilinium dichloride monohydrate at 90 K

The low-temperature (90 K) crystal structure of 4-(di­methyl­aza­nium­yl)-2-hy­droxy­anilinium dichloride monohydrate is presented along with a Hirshfeld surface analysis of the organic cation.

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 90 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.021
• wR factor = 0.063
• Data-to-parameter ratio = 17.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600         13 Report
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          5 Note

Alert level G
PLAT480_ALERT_4_G Long H...A H-Bond Reported H5       ..CL1      .       2.98 Ang.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H8B      ..O1       .       2.64 Ang.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H8C      ..CL1      .       2.87 Ang.
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          5 Note
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          4 Note
              H2 O
PLAT802_ALERT_4_G CIF Input Record(s) with more than 80 Characters          1 Info
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          1 Note
PLAT954_ALERT_1_G Reported (CIF) and Actual (FCF) Kmax Differ by .          1 Units
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          6 Info

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

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

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Computing details

Data collection: APEX3 (Bruker, 2016); cell refinement: APEX3 (Bruker, 2016); data reduction: APEX3 (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2019/2 (Sheldrick, 2015b); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELX (Sheldrick, 2008) and publCIF (Westrip, 2010).

4-(Dimethylazaniumyl)-2-hydroxyanilinium dichloride monohydrate

Crystal data

C8H14N2O^2+·2Cl^−·H2O	F(000) = 512
Mr = 243.13	Dx = 1.374 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.6493 (7) Å	Cell parameters from 9459 reflections
b = 13.0873 (8) Å	θ = 2.4–27.5°
c = 10.4634 (7) Å	µ = 0.53 mm^−1
β = 117.188 (2)°	T = 90 K
V = 1175.36 (14) Å^3	Irregular block, colourless
Z = 4	0.32 × 0.30 × 0.22 mm

Data collection

Bruker D8 Venture dual source diffractometer	2693 independent reflections
Radiation source: microsource	2505 reflections with I > 2σ(I)
Detector resolution: 7.41 pixels mm^-1	Rint = 0.032
φ and ω scans	θmax = 27.5°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −12→12
Tmin = 0.888, Tmax = 0.971	k = −16→17
36719 measured reflections	l = −13→13

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.021	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.063	w = 1/[σ^2(Fo^2) + (0.034P)^2 + 0.2669P] where P = (Fo^2 + 2Fc^2)/3
S = 1.13	(Δ/σ)max = 0.001
2693 reflections	Δρmax = 0.34 e Å^−3
158 parameters	Δρmin = −0.22 e Å^−3
0 restraints	Extinction correction: SHELXL-2019/2 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.008 (2)

Special details

Experimental. The crystal was mounted using polyisobutene oil on the tip of a fine glass fibre, which was fastened in a copper mounting pin with electrical solder. It was placed directly into the cold gas stream of a liquid-nitrogen based cryostat (Hope, 1994; Parkin & Hope, 1998).

Diffraction data were collected with the crystal at 90K, which is standard practice in this laboratory for the majority of flash-cooled crystals.

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. Refinement progress was checked using Platon (Spek, 2020) and by an R-tensor (Parkin, 2000). The final model was further checked with the IUCr utility checkCIF.

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

	x	y	z	Uiso*/Ueq
N1	0.75930 (11)	0.61398 (6)	0.87704 (9)	0.01338 (18)
H1N1	0.7194 (15)	0.6712 (11)	0.8938 (14)	0.022 (3)*
H2N1	0.7151 (15)	0.5598 (11)	0.8907 (13)	0.023 (3)*
H3N1	0.858 (2)	0.6134 (10)	0.9459 (17)	0.028 (4)*
C1	0.74643 (11)	0.61590 (6)	0.73284 (10)	0.01215 (19)
O1	0.47817 (9)	0.62201 (5)	0.65346 (8)	0.01714 (17)
H1O	0.392 (2)	0.6321 (11)	0.5805 (18)	0.037 (4)*
Cl1	0.15713 (2)	0.66738 (2)	0.42367 (2)	0.01449 (9)
C2	0.59693 (11)	0.62072 (7)	0.61890 (11)	0.0128 (2)
N2	0.68764 (10)	0.62236 (6)	0.30958 (9)	0.01355 (18)
H2N	0.5849 (17)	0.6154 (9)	0.2501 (15)	0.021 (3)*
Cl2	0.35654 (3)	0.59763 (2)	0.06980 (2)	0.01665 (9)
C3	0.57844 (11)	0.62244 (7)	0.47882 (11)	0.0132 (2)
H3	0.477593	0.625003	0.399057	0.016*
C4	0.71073 (12)	0.62031 (7)	0.45870 (11)	0.0123 (2)
C5	0.85995 (11)	0.61711 (7)	0.57131 (11)	0.0137 (2)
H5	0.948406	0.616984	0.554007	0.016*
C6	0.87688 (11)	0.61406 (7)	0.71058 (11)	0.0136 (2)
H6	0.977827	0.610731	0.790114	0.016*
C7	0.73470 (12)	0.72278 (8)	0.27212 (11)	0.0172 (2)
H7A	0.699595	0.725867	0.168286	0.026*
H7B	0.848358	0.729470	0.323059	0.026*
H7C	0.686888	0.778611	0.300525	0.026*
C8	0.76558 (12)	0.53561 (8)	0.27443 (11)	0.0184 (2)
H8A	0.725765	0.531196	0.170044	0.028*
H8B	0.743641	0.471597	0.310319	0.028*
H8C	0.878337	0.547275	0.319913	0.028*
O1W	1.05118 (10)	0.61432 (6)	1.09862 (9)	0.0249 (2)
H1W1	1.075 (2)	0.6295 (12)	1.180 (2)	0.041 (5)*
H2W1	1.137 (2)	0.6187 (10)	1.0942 (18)	0.035 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0133 (4)	0.0154 (4)	0.0105 (4)	0.0000 (3)	0.0046 (4)	0.0005 (3)
C1	0.0142 (5)	0.0115 (4)	0.0107 (4)	−0.0004 (3)	0.0056 (4)	0.0000 (3)
O1	0.0104 (4)	0.0288 (4)	0.0127 (4)	0.0019 (3)	0.0057 (3)	0.0013 (3)
Cl1	0.01198 (13)	0.01708 (14)	0.01299 (13)	−0.00068 (8)	0.00449 (10)	0.00011 (8)
C2	0.0121 (5)	0.0132 (4)	0.0136 (5)	0.0002 (3)	0.0063 (4)	0.0000 (3)
N2	0.0119 (4)	0.0173 (4)	0.0112 (4)	−0.0011 (3)	0.0050 (3)	−0.0009 (3)
Cl2	0.01496 (14)	0.01780 (14)	0.01421 (14)	−0.00158 (8)	0.00409 (10)	0.00050 (8)
C3	0.0113 (4)	0.0146 (5)	0.0121 (5)	0.0002 (3)	0.0038 (4)	−0.0006 (3)
C4	0.0149 (5)	0.0116 (4)	0.0108 (4)	−0.0004 (3)	0.0061 (4)	−0.0003 (3)
C5	0.0113 (5)	0.0157 (5)	0.0145 (5)	−0.0002 (3)	0.0062 (4)	0.0003 (3)
C6	0.0108 (5)	0.0147 (5)	0.0128 (5)	−0.0002 (3)	0.0031 (4)	0.0002 (3)
C7	0.0190 (5)	0.0174 (5)	0.0157 (5)	0.0015 (4)	0.0084 (4)	0.0044 (4)
C8	0.0227 (5)	0.0180 (5)	0.0192 (5)	−0.0004 (4)	0.0135 (4)	−0.0039 (4)
O1W	0.0160 (4)	0.0415 (5)	0.0139 (4)	−0.0006 (3)	0.0039 (3)	−0.0056 (3)

Geometric parameters (Å, º)

N1—C1	1.4565 (12)	C3—H3	0.9500
N1—H1N1	0.895 (14)	C4—C5	1.3831 (14)
N1—H2N1	0.873 (14)	C5—C6	1.3908 (14)
N1—H3N1	0.893 (17)	C5—H5	0.9500
C1—C6	1.3810 (14)	C6—H6	0.9500
C1—C2	1.3909 (14)	C7—H7A	0.9800
O1—C2	1.3502 (12)	C7—H7B	0.9800
O1—H1O	0.843 (18)	C7—H7C	0.9800
C2—C3	1.3934 (14)	C8—H8A	0.9800
N2—C4	1.4721 (12)	C8—H8B	0.9800
N2—C8	1.4976 (12)	C8—H8C	0.9800
N2—C7	1.4998 (12)	O1W—H1W1	0.802 (19)
N2—H2N	0.903 (15)	O1W—H2W1	0.857 (18)
C3—C4	1.3857 (14)
C1—N1—H1N1	110.3 (8)	C5—C4—C3	122.95 (9)
C1—N1—H2N1	111.5 (8)	C5—C4—N2	119.86 (9)
H1N1—N1—H2N1	111.2 (13)	C3—C4—N2	117.19 (9)
C1—N1—H3N1	113 (1)	C4—C5—C6	118.14 (9)
H1N1—N1—H3N1	104.1 (12)	C4—C5—H5	120.9
H2N1—N1—H3N1	106.3 (12)	C6—C5—H5	120.9
C6—C1—C2	121.64 (9)	C1—C6—C5	119.76 (9)
C6—C1—N1	121.44 (9)	C1—C6—H6	120.1
C2—C1—N1	116.93 (9)	C5—C6—H6	120.1
C2—O1—H1O	111.4 (11)	N2—C7—H7A	109.5
O1—C2—C1	116.47 (9)	N2—C7—H7B	109.5
O1—C2—C3	124.41 (9)	H7A—C7—H7B	109.5
C1—C2—C3	119.11 (9)	N2—C7—H7C	109.5
C4—N2—C8	113.37 (8)	H7A—C7—H7C	109.5
C4—N2—C7	112.07 (7)	H7B—C7—H7C	109.5
C8—N2—C7	110.74 (8)	N2—C8—H8A	109.5
C4—N2—H2N	108.4 (9)	N2—C8—H8B	109.5
C8—N2—H2N	105.7 (8)	H8A—C8—H8B	109.5
C7—N2—H2N	106.1 (8)	N2—C8—H8C	109.5
C4—C3—C2	118.39 (9)	H8A—C8—H8C	109.5
C4—C3—H3	120.8	H8B—C8—H8C	109.5
C2—C3—H3	120.8	H1W1—O1W—H2W1	103.4 (16)
C6—C1—C2—O1	179.93 (8)	C7—N2—C4—C5	−71.16 (11)
N1—C1—C2—O1	−0.70 (12)	C8—N2—C4—C3	−125.32 (9)
C6—C1—C2—C3	0.81 (13)	C7—N2—C4—C3	108.41 (9)
N1—C1—C2—C3	−179.82 (8)	C3—C4—C5—C6	1.17 (13)
O1—C2—C3—C4	−179.70 (8)	N2—C4—C5—C6	−179.27 (8)
C1—C2—C3—C4	−0.65 (13)	C2—C1—C6—C5	0.03 (13)
C2—C3—C4—C5	−0.34 (13)	N1—C1—C6—C5	−179.31 (8)
C2—C3—C4—N2	−179.91 (8)	C4—C5—C6—C1	−0.99 (13)
C8—N2—C4—C5	55.10 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H2N1···Cl2^i	0.873 (14)	2.270 (14)	3.1299 (9)	168.5 (12)
N1—H1N1···Cl1^ii	0.895 (14)	2.257 (14)	3.1364 (9)	167.4 (12)
N1—H3N1···O1W	0.893 (17)	1.819 (17)	2.7093 (12)	174.4 (14)
O1—H1O···Cl1	0.843 (18)	2.156 (18)	2.9873 (8)	168.9 (15)
N2—H2N···Cl2	0.903 (15)	2.161 (15)	3.0467 (9)	166.7 (12)
C5—H5···Cl1^iii	0.95	2.98	3.8846 (10)	160
C7—H7A···Cl1^iv	0.98	2.78	3.6641 (10)	151
C7—H7B···Cl1^iii	0.98	2.79	3.7079 (11)	156
C8—H8A···Cl2^v	0.98	2.82	3.6774 (10)	147
C8—H8B···O1^i	0.98	2.64	3.4610 (13)	142
C8—H8C···Cl1^iii	0.98	2.87	3.7809 (11)	156
O1W—H2W1···Cl2^vi	0.857 (18)	2.259 (18)	3.1036 (9)	168.7 (13)
O1W—H1W1···Cl1^vi	0.802 (19)	2.348 (19)	3.1493 (9)	176.4 (16)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1/2, −y+3/2, z+1/2; (iii) x+1, y, z; (iv) x+1/2, −y+3/2, z−1/2; (v) −x+1, −y+1, −z; (vi) x+1, y, z+1.