Hydrazinium 2-amino-4-nitro­benzoate dihydrate: crystal structure and Hirshfeld surface analysis

Wardell, J.L.; Jotani, M.M.; Tiekink, E.R.T.

doi:10.1107/S2056989017004352

Hydrazinium 2-amino-4-nitrobenzoate dihydrate: crystal structure and Hirshfeld surface analysis

J. L. Wardell, M. M. Jotani and E. R. T. Tiekink

In the title salt dihydrate, the conrotatory relationship between the carboxylate and nitro groups of the anion leads to a dihedral angle between them of 26.73 (15)°. Substantial charge-assisted water-O—H

O(carboxylate) hydrogen bonding leads to supramolecular zigzag chains. These are connected into a three-dimensional architecture by N—H

O and N—H

N hydrogen bonds.

Keywords: crystal structure; carboxylate; salt; hydrogen bonding; Hirshfeld surface analysis.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989017004352/hb7667sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989017004352/hb7667Isup2.hkl Contains datablock I

CCDC reference: 1538892

checkCIF report

Key indicators

Single-crystal X-ray study
T = 120 K
Mean (C-C) = 0.002 Å
R factor = 0.039
wR factor = 0.110
Data-to-parameter ratio = 13.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          4 Report

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite         16 Note
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT154_ALERT_1_G The s.u.'s on the Cell Angles are Equal ..(Note)      0.002 Degree
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          4 Report
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............         13 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min)           2 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         16 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF ....          1 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          2 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          4 Note

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

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 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

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); data reduction: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Hydrazinium 2-amino-4-nitrobenzoate dihydrate top

Crystal data top

H₅N₂⁺·C₇H₅N₂O₄⁻·2H₂O	Z = 2
M_r = 250.22	F(000) = 264
Triclinic, P1	D_x = 1.533 Mg m⁻³
a = 6.9695 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.0960 (3) Å	Cell parameters from 7476 reflections
c = 10.5316 (3) Å	θ = 2.9–27.5°
α = 76.468 (2)°	µ = 0.13 mm⁻¹
β = 73.251 (2)°	T = 120 K
γ = 75.390 (2)°	Block, red
V = 542.23 (3) Å³	0.41 × 0.22 × 0.13 mm

Data collection top

Bruker–Nonius Roper CCD camera on κ-goniostat diffractometer	2497 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode	2147 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.6°, θ_min = 3.1°
φ & ω scans	h = −9→8
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	k = −10→10
T_min = 0.644, T_max = 0.746	l = −13→13
11539 measured reflections

Refinement top

Refinement on F²	13 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.039	w = 1/[σ²(F_o²) + (0.0646P)² + 0.1366P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.110	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.29 e Å⁻³
2497 reflections	Δρ_min = −0.30 e Å⁻³
187 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.40595 (14)	0.36669 (11)	0.25616 (9)	0.0168 (2)
O2	0.46220 (13)	0.18017 (11)	0.11781 (9)	0.0164 (2)
O3	0.04781 (14)	−0.28112 (12)	0.77375 (9)	0.0224 (2)
O4	0.24000 (15)	−0.47250 (11)	0.65475 (9)	0.0195 (2)
N1	0.15996 (17)	0.28747 (14)	0.50370 (11)	0.0163 (2)
H1N	0.218 (2)	0.3697 (17)	0.4483 (14)	0.020*
H2N	0.107 (2)	0.301 (2)	0.5877 (10)	0.020*
N2	0.17056 (16)	−0.32135 (13)	0.67034 (10)	0.0150 (2)
C1	0.34738 (18)	0.08075 (15)	0.35268 (12)	0.0128 (3)
C2	0.23062 (17)	0.12171 (15)	0.47960 (12)	0.0123 (3)
C3	0.17447 (18)	−0.01538 (16)	0.58371 (12)	0.0133 (3)
H3	0.0949	0.0079	0.6698	0.016*
C4	0.23572 (18)	−0.18300 (15)	0.55975 (12)	0.0132 (3)
C5	0.35262 (19)	−0.22781 (16)	0.43707 (13)	0.0152 (3)
H5	0.3943	−0.3450	0.4241	0.018*
C6	0.40531 (19)	−0.09256 (16)	0.33461 (12)	0.0148 (3)
H6	0.4836	−0.1183	0.2489	0.018*
C7	0.40929 (18)	0.21917 (15)	0.23517 (12)	0.0130 (3)
N3	−0.00982 (17)	0.32666 (14)	0.90634 (11)	0.0161 (2)
H3N	0.045 (2)	0.2268 (14)	0.9450 (14)	0.019*
H4N	0.086 (2)	0.3844 (19)	0.8652 (14)	0.019*
H5N	−0.102 (2)	0.3825 (19)	0.9655 (13)	0.019*
N4	−0.09239 (17)	0.30241 (15)	0.80197 (11)	0.0180 (3)
H6N	−0.179 (2)	0.3973 (15)	0.7857 (16)	0.022*
H7N	−0.159 (2)	0.2192 (17)	0.8375 (15)	0.022*
O1W	0.21973 (14)	0.02486 (12)	0.02803 (10)	0.0184 (2)
H1W	0.279 (3)	0.070 (2)	0.0681 (16)	0.028*
H2W	0.312 (2)	−0.033 (2)	−0.0235 (15)	0.028*
O2W	0.31998 (14)	0.45790 (12)	−0.06089 (9)	0.0170 (2)
H3W	0.381 (2)	0.382 (2)	−0.0080 (15)	0.025*
H4W	0.409 (2)	0.506 (2)	−0.1221 (15)	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0211 (5)	0.0127 (5)	0.0162 (4)	−0.0063 (3)	−0.0025 (3)	−0.0008 (3)
O2	0.0197 (5)	0.0145 (5)	0.0126 (4)	−0.0027 (3)	−0.0020 (3)	−0.0008 (3)
O3	0.0216 (5)	0.0207 (5)	0.0165 (5)	−0.0019 (4)	0.0023 (4)	0.0019 (4)
O4	0.0268 (5)	0.0115 (5)	0.0204 (5)	−0.0057 (4)	−0.0067 (4)	0.0005 (3)
N1	0.0209 (6)	0.0119 (5)	0.0145 (5)	−0.0046 (4)	−0.0005 (4)	−0.0026 (4)
N2	0.0151 (5)	0.0145 (5)	0.0158 (5)	−0.0045 (4)	−0.0059 (4)	0.0009 (4)
C1	0.0127 (6)	0.0121 (6)	0.0139 (6)	−0.0033 (4)	−0.0043 (4)	−0.0004 (4)
C2	0.0113 (6)	0.0120 (6)	0.0147 (6)	−0.0027 (4)	−0.0058 (4)	−0.0009 (4)
C3	0.0122 (6)	0.0148 (6)	0.0126 (6)	−0.0031 (4)	−0.0033 (4)	−0.0012 (4)
C4	0.0129 (6)	0.0127 (6)	0.0140 (6)	−0.0046 (4)	−0.0052 (4)	0.0021 (5)
C5	0.0162 (6)	0.0102 (6)	0.0187 (6)	−0.0014 (4)	−0.0055 (5)	−0.0014 (5)
C6	0.0146 (6)	0.0148 (6)	0.0140 (6)	−0.0025 (4)	−0.0024 (4)	−0.0027 (5)
C7	0.0109 (6)	0.0129 (6)	0.0142 (6)	−0.0016 (4)	−0.0035 (4)	−0.0005 (4)
N3	0.0162 (5)	0.0139 (5)	0.0173 (6)	−0.0033 (4)	−0.0034 (4)	−0.0017 (4)
N4	0.0207 (6)	0.0166 (6)	0.0173 (6)	−0.0050 (4)	−0.0047 (4)	−0.0025 (4)
O1W	0.0177 (5)	0.0171 (5)	0.0203 (5)	−0.0020 (4)	−0.0038 (4)	−0.0056 (4)
O2W	0.0154 (4)	0.0169 (5)	0.0161 (5)	−0.0045 (3)	−0.0037 (3)	0.0029 (4)

Geometric parameters (Å, º) top

O1—C7	1.2579 (15)	C4—C5	1.3886 (18)
O2—C7	1.2746 (15)	C5—C6	1.3855 (18)
O3—N2	1.2299 (14)	C5—H5	0.9500
O4—N2	1.2280 (14)	C6—H6	0.9500
N1—C2	1.3644 (16)	N3—N4	1.4492 (15)
N1—H1N	0.873 (9)	N3—H3N	0.864 (9)
N1—H2N	0.877 (9)	N3—H4N	0.865 (9)
N2—C4	1.4692 (15)	N3—H5N	0.872 (9)
C1—C6	1.4010 (17)	N4—H6N	0.864 (9)
C1—C2	1.4153 (17)	N4—H7N	0.865 (9)
C1—C7	1.5035 (16)	O1W—H1W	0.856 (14)
C2—C3	1.4106 (17)	O1W—H2W	0.834 (13)
C3—C4	1.3760 (18)	O2W—H3W	0.847 (13)
C3—H3	0.9500	O2W—H4W	0.852 (13)

C2—N1—H1N	118.5 (11)	C6—C5—H5	121.8
C2—N1—H2N	117.4 (10)	C4—C5—H5	121.8
H1N—N1—H2N	117.3 (15)	C5—C6—C1	122.44 (12)
O4—N2—O3	122.87 (10)	C5—C6—H6	118.8
O4—N2—C4	118.34 (10)	C1—C6—H6	118.8
O3—N2—C4	118.79 (10)	O1—C7—O2	123.11 (11)
C6—C1—C2	119.62 (11)	O1—C7—C1	119.32 (11)
C6—C1—C7	118.73 (11)	O2—C7—C1	117.57 (11)
C2—C1—C7	121.65 (11)	N4—N3—H3N	109.2 (10)
N1—C2—C3	118.52 (11)	N4—N3—H4N	105.8 (10)
N1—C2—C1	123.24 (11)	H3N—N3—H4N	108.1 (15)
C3—C2—C1	118.13 (11)	N4—N3—H5N	112.3 (10)
C4—C3—C2	119.56 (11)	H3N—N3—H5N	110.6 (15)
C4—C3—H3	120.2	H4N—N3—H5N	110.6 (15)
C2—C3—H3	120.2	N3—N4—H6N	105.4 (11)
C3—C4—C5	123.75 (11)	N3—N4—H7N	106.2 (11)
C3—C4—N2	117.70 (11)	H6N—N4—H7N	108.5 (16)
C5—C4—N2	118.54 (11)	H1W—O1W—H2W	106.4 (15)
C6—C5—C4	116.48 (11)	H3W—O2W—H4W	108.3 (15)

C6—C1—C2—N1	−176.80 (11)	O3—N2—C4—C5	−171.63 (11)
C7—C1—C2—N1	2.39 (18)	C3—C4—C5—C6	−0.98 (18)
C6—C1—C2—C3	−0.76 (17)	N2—C4—C5—C6	178.13 (10)
C7—C1—C2—C3	178.43 (10)	C4—C5—C6—C1	0.86 (18)
N1—C2—C3—C4	176.90 (11)	C2—C1—C6—C5	−0.02 (18)
C1—C2—C3—C4	0.67 (17)	C7—C1—C6—C5	−179.23 (11)
C2—C3—C4—C5	0.22 (18)	C6—C1—C7—O1	−161.98 (11)
C2—C3—C4—N2	−178.90 (10)	C2—C1—C7—O1	18.83 (17)
O4—N2—C4—C3	−173.12 (10)	C6—C1—C7—O2	18.36 (16)
O3—N2—C4—C3	7.53 (16)	C2—C1—C7—O2	−160.84 (11)
O4—N2—C4—C5	7.72 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1	0.88 (1)	2.07 (1)	2.7098 (15)	129 (1)
N1—H2N···N4	0.88 (1)	2.29 (1)	3.1403 (16)	165 (1)
N3—H3N···O1Wⁱ	0.86 (1)	1.97 (1)	2.8136 (15)	167 (1)
N3—H4N···O2Wⁱ	0.87 (2)	2.25 (2)	2.8969 (16)	132 (1)
N3—H4N···O4ⁱⁱ	0.87 (2)	2.34 (1)	3.0739 (15)	143 (1)
N3—H5N···O2Wⁱⁱⁱ	0.87 (1)	1.93 (2)	2.7862 (15)	167 (1)
N4—H6N···O1ⁱⁱⁱ	0.87 (1)	2.20 (1)	3.0623 (15)	178 (1)
N4—H7N···O1W^iv	0.87 (1)	2.20 (1)	3.0106 (15)	155 (1)
O1W—H1W···O2	0.86 (2)	1.97 (2)	2.8071 (14)	166 (2)
O1W—H2W···O2^v	0.83 (2)	1.90 (2)	2.7208 (13)	171 (2)
O2W—H3W···O2	0.85 (2)	1.92 (2)	2.7479 (13)	165 (2)
O2W—H4W···O1^vi	0.85 (2)	1.91 (2)	2.7627 (14)	175 (2)

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

Summary of short interatomic contacts (Å) in (I) top

Contact	Distance	Symmetry operation
H5N···H3W	2.38 (2)	-x, 1 - y, 1 - z
H7N···H2W	2.34 (2)	-x, -y, 1 - z
H4N···O3	2.626 (15)	x, 1 + y, z
H5···O4	2.61	1 - x, -1 - y, 1 - z
H2N···O4	2.652 (15)	x, 1 + y, z
N1···O4	3.0205 (15)	x, 1 + y, z
C7···O3	3.1231 (17)	-x, -y, 1 - z
C2···C4	3.2936 (19)	-x, -y, 1 - z
C3···C3	3.3235 (19)	-x, -y, 1 - z

Percentage contribution to interatomic contacts from the Hirshfeld surface for (I) top

Contact	Percentage contribution
O···H/H···O	46.8
H···H	32.4
C···H/H···C	5.9
C···C	5.7
C···O/O···C	3.3
O···O	1.6
N···O/O···N	1.3
C···N / N···C	1.2
N···N	1.0
N···H/H···N	0.8

Geometric data (°) for ammonium salts of 2-amino-4-nitrobenzoate. Extreme values for each parameter are bolded top

cation	Z'	C₆/CO₂	C₆/NO₂	CO₂/NO₂	Ref.
[NH₄]⁺ ^a	1	26.4 (3)	2.9 (3)	24.1 (4)	Smith (2014b)
[Me₂NH₂]⁺	1	11.45 (13)	3.71 (15)	7.9 (2)	Wardell et al. (2016)
[n-Bu₂NH₂]⁺	2	12.73 (6)	4.30 (10)	17.02 (8)	Wardell et al. (2016)
		8.1 (4)	12.6 (3)	19.0 (5)
[Cy₂NH₂]⁺	2	9.87 (10)	7.58 (15)	3.42 (19)	Smith et al. (2004)
		9.52 (9)	7.86 (11)	3.92 (2)
[O(CH₂CH₂)₂NH₂]⁺	1	17.92 (9)	1.28 (11)	19.19 (13)	Smith & Lynch (2016)
[(H₂N)₂C═NH₂]⁺ ^a	1	5.88 (11)	5.64 (12)		Smith et al. (2007)
[H₃NCH₂CH₂NH₃]²⁺ ^b	1	3.44 (14)	0.69 (11)	3.2 (2)	Smith et al. (2002)
[H₂NNH₃]²⁺ ^b	1	18.80 (10)	8.04 (9)	26.73 (14)	this work

Notes: (a) crystallized as a monohydrate; (b) crystallized as a dihydrate.

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Hydrazinium 2-amino-4-nitro­benzoate dihydrate: crystal structure and Hirshfeld surface analysis

Supporting information

Key indicators

checkCIF/PLATON results

Hydrazinium 2-amino-4-nitrobenzoate dihydrate: crystal structure and Hirshfeld surface analysis