Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807037944/hb2489sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807037944/hb2489Isup2.hkl |
CCDC reference: 660225
4-Chloro-3-nitrobenzoic acid (1 mmol, 0.201 g) was added to an aqueous solution (10 ml) of guanidinium carbonate (1 mmol, 0.180 g) with stirring. This solution yielded single crystals of (I) after 2 days.
The H atoms from the water molecule as well as from the guanidinium cation were found in a difference map, then relocated in idealized positions (O—H = 0.82 Å, N—H = 0.86 Å) and refined as riding with Ueq(H) = 1.5Ueq(carrier). The C-bound H atoms were geometrically placed (C—H = 0.98 Å) and refined as riding with Ueq(H) = 1.2Ueq(C). The highest peak in the final difference map is situated on the C1—C2 bond.
The crystal engineering of guanidinium salts has been widely explored and numerous supramolecular synthons have been found (Abrahams et al., 2004). These structural units include, e.g. two-dimensional hydrogen-bonded networks in guanidinium hydrogen carboxylates (Videnova-Adrabińska et al., 2007). The attempts to manipulate the hydrogen bonds formation include e.g. cation substitution in guanidinium sulfonates (Burke et al., 2006). Thus gained knowledge is of help e.g. in the modelling of Arg–Glu or Arg–Asp side-chain interactions in proteins (Melo et al., 1999; Fülscher & Mehler, 1988; Singh et al., 1987).
In this paper we report on the synthesis and roentgenographic studies of the title compound, (I), containing 4-chloro-3-nitrobenzoate anions, guanidinium cations and water molecules in the molar ratio of 1:1:1 (Fig. 1). In the anion the carboxylate group lies approximately in the plane of the phenyl ring, whereas the nitro group plane is twisted with respect to the phenyl group plane (the twist angle with respect to the phenyl ring plane is 41.7 (1)°). The nitro group twist angle with respect to the phenyl ring plane is comparable to the analogous parameter reported for 4-chloro-3-nitrobenzoic acid (Ishida & Fukunaga, 2003). The guanidinium cation geometrical parameters are typical (Cygler et al., 1976).
The crystal structure is stabilized mainly by a network of O—H···O, N—H···O and N—H···Cl hydrogen bonds (Table 1). In this network the carboxylate O atoms act as hydrogen bond acceptors, water O atoms act as donors as well as acceptors and guanidinium N atoms provide the most extensive part as donors. Each of the guanidinium H atoms is involved in hydrogen bonds as a donor. The well known synthon in which guanidinium amine group and carboxylate group are involved in hydrogen bonds to form a R22(6) ring (Videnova-Adrabińska et al., 2007; McKee & Najafpour, 2007; Etter et al., 1990) is not present in (I). Instead, a water molecule donates one of its H atoms (H2W) to form a bifurcated hydrogen bond. In this hydrogen bond the two carboxyl O atoms (O1 and O2) act as acceptors. The second water H1W atom is involved in the O1W—H1W···O1v (see Table 1 for symmetry code) hydrogen bond which seems to be the strongest of all hydrogen bonds present (Table 1). The water O1W atom accepts two hydrogen bonds, N10—H101···O1Wi and N30—H302···O1Wi to form a R21(6) motif (Etter et al., 1990). Furthermore, the carboxyl O1 atom is involved in one hydrogen bond as acceptor with H102 atom from the guanidinium cation amine group. The nitro O3iii atom is bonded to the H262 atom via N—H···O hydrogen bond. The remaining nitro O4 atom participates in no other hydrogen bonds. The H201 and H301 atoms from two guanidinium amino groups participate in hydrogen bonds to the carboxyl O2ii atom. The H301 atom is further bonded to the Cliv atom.
The phenyl rings form chains extending along [010] (the neighbouring phenyl rings constituting each chain are generated with the following symmetry operations: [vi] 1 - x, 2 - y, 1 - z; [vii] x, 1 + y, z etc.; Fig. 2). A weak stacking interaction stabilizes this pattern (3.69 Å distance between the neighbouring rings centroids). The phenyl ring chains are parallel to guanidinium cations and water molecules layers perpendicular to [100] which via hydrogen bonds create a three-dimensional crystal structure (Fig. 3).
For related literature, see: Abrahams et al. (2004); Burke et al. (2006); Cygler et al. (1976); Etter et al. (1990); Fülscher & Mehler (1988); Ishida & Fukunaga (2003); McKee & Najafpour (2007); Melo et al. (1999); Singh et al. (1987); Videnova-Adrabińska, Obara & Lis (2007).
Data collection: CrysAlis CCD (Oxford Diffraction, 2000); cell refinement: CrysAlis RED (Oxford Diffraction, 2000); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97.
CH6N3+·C7H3ClNO4−·H2O | F(000) = 576 |
Mr = 278.66 | Dx = 1.584 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 11041 reflections |
a = 10.814 (4) Å | θ = 3.0–35.0° |
b = 7.040 (3) Å | µ = 0.35 mm−1 |
c = 15.487 (6) Å | T = 100 K |
β = 97.68 (3)° | Block, colourless |
V = 1168.5 (8) Å3 | 0.60 × 0.18 × 0.09 mm |
Z = 4 |
Oxford Diffraction KM-4 CCD diffractometer | 3766 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.039 |
Graphite monochromator | θmax = 36.6°, θmin = 3.2° |
ω scans | h = −17→15 |
17154 measured reflections | k = −11→9 |
5166 independent reflections | l = −25→25 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.047P)2] where P = (Fo2 + 2Fc2)/3 |
5166 reflections | (Δ/σ)max = 0.001 |
187 parameters | Δρmax = 0.54 e Å−3 |
8 restraints | Δρmin = −0.26 e Å−3 |
CH6N3+·C7H3ClNO4−·H2O | V = 1168.5 (8) Å3 |
Mr = 278.66 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.814 (4) Å | µ = 0.35 mm−1 |
b = 7.040 (3) Å | T = 100 K |
c = 15.487 (6) Å | 0.60 × 0.18 × 0.09 mm |
β = 97.68 (3)° |
Oxford Diffraction KM-4 CCD diffractometer | 3766 reflections with I > 2σ(I) |
17154 measured reflections | Rint = 0.039 |
5166 independent reflections |
R[F2 > 2σ(F2)] = 0.041 | 8 restraints |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.54 e Å−3 |
5166 reflections | Δρmin = −0.26 e Å−3 |
187 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cl | 0.79594 (2) | 0.61834 (4) | 0.582414 (16) | 0.01727 (7) | |
O1 | 0.19850 (8) | 0.90314 (12) | 0.54668 (5) | 0.01884 (16) | |
O2 | 0.22004 (8) | 0.89017 (12) | 0.40527 (5) | 0.01845 (17) | |
C7 | 0.26099 (10) | 0.87298 (14) | 0.48485 (7) | 0.01390 (19) | |
C2 | 0.44468 (10) | 0.79857 (15) | 0.59641 (6) | 0.01337 (19) | |
H1 | 0.3957 | 0.8347 | 0.6403 | 0.016* | |
C5 | 0.59217 (10) | 0.69974 (15) | 0.46892 (6) | 0.01446 (19) | |
H2 | 0.6424 | 0.6689 | 0.4250 | 0.017* | |
C4 | 0.64170 (10) | 0.68633 (15) | 0.55647 (6) | 0.01310 (18) | |
C3 | 0.56635 (10) | 0.73678 (15) | 0.61942 (6) | 0.01326 (19) | |
C1 | 0.39437 (10) | 0.80762 (14) | 0.50887 (6) | 0.01273 (19) | |
O3 | 0.67402 (8) | 0.59089 (13) | 0.74134 (5) | 0.02499 (19) | |
C6 | 0.46960 (10) | 0.75806 (15) | 0.44558 (6) | 0.01430 (19) | |
H3 | 0.4363 | 0.7644 | 0.3857 | 0.017* | |
O4 | 0.58141 (9) | 0.85905 (14) | 0.75857 (5) | 0.0289 (2) | |
N | 0.61144 (9) | 0.72820 (15) | 0.71326 (6) | 0.01803 (19) | |
N10 | 0.10087 (10) | 0.55842 (15) | 0.60786 (6) | 0.0205 (2) | |
H101 | 0.0796 | 0.4460 | 0.5899 | 0.031* | |
H102 | 0.1187 | 0.6532 | 0.5767 | 0.031* | |
N20 | 0.17533 (10) | 0.73976 (14) | 0.72783 (6) | 0.0198 (2) | |
H201 | 0.1983 | 0.748 | 0.7831 | 0.030* | |
H202 | 0.1871 | 0.8291 | 0.6920 | 0.030* | |
N30 | 0.11900 (10) | 0.42771 (14) | 0.74506 (6) | 0.01893 (19) | |
H301 | 0.1390 | 0.443 | 0.8003 | 0.028* | |
H302 | 0.0987 | 0.3184 | 0.7228 | 0.028* | |
C10 | 0.13265 (10) | 0.57518 (16) | 0.69380 (7) | 0.0150 (2) | |
O1W | −0.04003 (9) | 0.83150 (13) | 0.39911 (6) | 0.02309 (19) | |
H1W | −0.0839 | 0.9069 | 0.4216 | 0.035* | |
H2W | 0.0334 | 0.864 | 0.4075 | 0.035* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl | 0.01357 (13) | 0.02021 (13) | 0.01785 (12) | 0.00384 (10) | 0.00142 (8) | −0.00186 (9) |
O1 | 0.0158 (4) | 0.0226 (4) | 0.0184 (4) | 0.0039 (3) | 0.0034 (3) | 0.0021 (3) |
O2 | 0.0186 (4) | 0.0200 (4) | 0.0151 (3) | 0.0020 (3) | −0.0036 (3) | 0.0012 (3) |
C7 | 0.0141 (5) | 0.0117 (4) | 0.0152 (4) | −0.0010 (4) | −0.0006 (3) | 0.0016 (3) |
C2 | 0.0136 (5) | 0.0149 (5) | 0.0116 (4) | 0.0007 (4) | 0.0019 (3) | 0.0009 (3) |
C5 | 0.0161 (5) | 0.0152 (5) | 0.0124 (4) | 0.0001 (4) | 0.0029 (3) | −0.0015 (3) |
C4 | 0.0121 (5) | 0.0120 (4) | 0.0150 (4) | 0.0013 (4) | 0.0010 (3) | −0.0004 (3) |
C3 | 0.0145 (5) | 0.0156 (5) | 0.0094 (4) | 0.0002 (4) | 0.0006 (3) | 0.0007 (3) |
C1 | 0.0138 (5) | 0.0120 (4) | 0.0121 (4) | −0.0004 (4) | 0.0005 (3) | 0.0012 (3) |
O3 | 0.0205 (5) | 0.0324 (5) | 0.0212 (4) | 0.0048 (4) | −0.0005 (3) | 0.0122 (3) |
C6 | 0.0166 (5) | 0.0143 (5) | 0.0116 (4) | −0.0012 (4) | 0.0005 (3) | −0.0001 (3) |
O4 | 0.0261 (5) | 0.0467 (6) | 0.0133 (4) | 0.0117 (4) | 0.0004 (3) | −0.0082 (4) |
N | 0.0139 (5) | 0.0281 (5) | 0.0120 (4) | 0.0016 (4) | 0.0011 (3) | 0.0028 (3) |
N10 | 0.0260 (6) | 0.0214 (5) | 0.0136 (4) | −0.0046 (4) | 0.0010 (3) | −0.0004 (3) |
N20 | 0.0249 (5) | 0.0180 (5) | 0.0159 (4) | −0.0023 (4) | 0.0011 (4) | −0.0011 (3) |
N30 | 0.0236 (5) | 0.0182 (4) | 0.0146 (4) | −0.0033 (4) | 0.0014 (3) | −0.0014 (3) |
C10 | 0.0114 (5) | 0.0187 (5) | 0.0153 (4) | 0.0006 (4) | 0.0024 (3) | −0.0012 (4) |
O1W | 0.0169 (4) | 0.0242 (4) | 0.0282 (4) | −0.0020 (4) | 0.0033 (3) | −0.0101 (3) |
Cl—C4 | 1.7302 (12) | C4—C3 | 1.3974 (16) |
O1—C7 | 1.2616 (14) | C3—N | 1.4711 (14) |
O2—C7 | 1.2585 (13) | C1—C6 | 1.3990 (16) |
C7—C1 | 1.5123 (16) | O3—N | 1.2259 (13) |
C2—C3 | 1.3863 (15) | C6—H3 | 0.95 |
C2—C1 | 1.3932 (14) | O4—N | 1.2277 (14) |
C2—H1 | 0.95 | N10—C10 | 1.3346 (15) |
C5—C6 | 1.3886 (16) | N20—C10 | 1.3298 (15) |
C5—C4 | 1.3929 (15) | N30—C10 | 1.3271 (15) |
C5—H2 | 0.95 | ||
O2—C7—O1 | 124.96 (10) | C5—C6—H3 | 119.5 |
O2—C7—C1 | 117.99 (10) | C1—C6—H3 | 119.5 |
O1—C7—C1 | 117.04 (9) | O3—N—O4 | 124.37 (9) |
C3—C2—C1 | 119.89 (10) | O3—N—C3 | 118.50 (9) |
C3—C2—H1 | 120.1 | O4—N—C3 | 117.12 (9) |
C1—C2—H1 | 120.1 | C10—N10—H101 | 115 |
C6—C5—C4 | 120.20 (10) | C10—N10—H102 | 116 |
C6—C5—H2 | 119.9 | H101—N10—H102 | 127 |
C4—C5—H2 | 119.9 | C10—N20—H201 | 120 |
C5—C4—C3 | 118.53 (10) | C10—N20—H202 | 117 |
C5—C4—Cl | 118.56 (9) | H201—N20—H202 | 122 |
C3—C4—Cl | 122.84 (8) | C10—N30—H301 | 117 |
C2—C3—C4 | 121.49 (9) | C10—N30—H302 | 120 |
C2—C3—N | 116.40 (9) | H301—N30—H302 | 121 |
C4—C3—N | 122.11 (9) | N30—C10—N20 | 120.33 (10) |
C2—C1—C6 | 118.84 (10) | N30—C10—N10 | 119.54 (10) |
C2—C1—C7 | 119.26 (10) | N20—C10—N10 | 120.11 (10) |
C6—C1—C7 | 121.89 (9) | H1W—O1W—H2W | 111 |
C5—C6—C1 | 121.03 (9) | ||
C6—C5—C4—C3 | −1.42 (16) | O1—C7—C1—C2 | −5.10 (15) |
C6—C5—C4—Cl | −178.53 (8) | O2—C7—C1—C6 | −3.11 (15) |
C1—C2—C3—C4 | 1.32 (16) | O1—C7—C1—C6 | 175.73 (10) |
C1—C2—C3—N | −178.93 (9) | C4—C5—C6—C1 | 1.18 (16) |
C5—C4—C3—C2 | 0.19 (16) | C2—C1—C6—C5 | 0.33 (16) |
Cl—C4—C3—C2 | 177.16 (8) | C7—C1—C6—C5 | 179.50 (10) |
C5—C4—C3—N | −179.55 (10) | C2—C3—N—O3 | 138.15 (11) |
Cl—C4—C3—N | −2.58 (15) | C4—C3—N—O3 | −42.10 (15) |
C3—C2—C1—C6 | −1.56 (15) | C2—C3—N—O4 | −40.57 (14) |
C3—C2—C1—C7 | 179.25 (10) | C4—C3—N—O4 | 139.18 (11) |
O2—C7—C1—C2 | 176.06 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
N10—H101···O1Wi | 0.86 | 2.01 | 2.822 (2) | 156 |
N10—H102···O1 | 0.86 | 2.04 | 2.858 (2) | 158 |
N20—H201···O2ii | 0.86 | 2.11 | 2.875 (2) | 147 |
N20—H202···O3iii | 0.86 | 2.51 | 2.964 (2) | 114 |
N30—H301···O2ii | 0.86 | 2.10 | 2.876 (2) | 150 |
N30—H301···Cliv | 0.86 | 2.94 | 3.474 (2) | 122 |
N30—H302···O1Wi | 0.86 | 2.18 | 2.921 (2) | 144 |
O1W—H1W···O1v | 0.82 | 1.93 | 2.742 (2) | 170 |
O1W—H2W···O2 | 0.82 | 2.03 | 2.832 (2) | 165 |
O1W—H2W···O1 | 0.82 | 2.62 | 3.249 (2) | 134 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, −y+3/2, z+1/2; (iii) −x+1, y+1/2, −z+3/2; (iv) −x+1, y−1/2, −z+3/2; (v) −x, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | CH6N3+·C7H3ClNO4−·H2O |
Mr | 278.66 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 10.814 (4), 7.040 (3), 15.487 (6) |
β (°) | 97.68 (3) |
V (Å3) | 1168.5 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.35 |
Crystal size (mm) | 0.60 × 0.18 × 0.09 |
Data collection | |
Diffractometer | Oxford Diffraction KM-4 CCD |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17154, 5166, 3766 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.838 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.094, 1.01 |
No. of reflections | 5166 |
No. of parameters | 187 |
No. of restraints | 8 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.54, −0.26 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2000), CrysAlis RED (Oxford Diffraction, 2000), CrysAlis RED, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg & Putz, 2005), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N10—H101···O1Wi | 0.86 | 2.01 | 2.822 (2) | 156 |
N10—H102···O1 | 0.86 | 2.04 | 2.858 (2) | 158 |
N20—H201···O2ii | 0.86 | 2.11 | 2.875 (2) | 147 |
N20—H202···O3iii | 0.86 | 2.51 | 2.964 (2) | 114 |
N30—H301···O2ii | 0.86 | 2.10 | 2.876 (2) | 150 |
N30—H301···Cliv | 0.86 | 2.94 | 3.474 (2) | 122 |
N30—H302···O1Wi | 0.86 | 2.18 | 2.921 (2) | 144 |
O1W—H1W···O1v | 0.82 | 1.93 | 2.742 (2) | 170 |
O1W—H2W···O2 | 0.82 | 2.03 | 2.832 (2) | 165 |
O1W—H2W···O1 | 0.82 | 2.62 | 3.249 (2) | 134 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, −y+3/2, z+1/2; (iii) −x+1, y+1/2, −z+3/2; (iv) −x+1, y−1/2, −z+3/2; (v) −x, −y+2, −z+1. |
The crystal engineering of guanidinium salts has been widely explored and numerous supramolecular synthons have been found (Abrahams et al., 2004). These structural units include, e.g. two-dimensional hydrogen-bonded networks in guanidinium hydrogen carboxylates (Videnova-Adrabińska et al., 2007). The attempts to manipulate the hydrogen bonds formation include e.g. cation substitution in guanidinium sulfonates (Burke et al., 2006). Thus gained knowledge is of help e.g. in the modelling of Arg–Glu or Arg–Asp side-chain interactions in proteins (Melo et al., 1999; Fülscher & Mehler, 1988; Singh et al., 1987).
In this paper we report on the synthesis and roentgenographic studies of the title compound, (I), containing 4-chloro-3-nitrobenzoate anions, guanidinium cations and water molecules in the molar ratio of 1:1:1 (Fig. 1). In the anion the carboxylate group lies approximately in the plane of the phenyl ring, whereas the nitro group plane is twisted with respect to the phenyl group plane (the twist angle with respect to the phenyl ring plane is 41.7 (1)°). The nitro group twist angle with respect to the phenyl ring plane is comparable to the analogous parameter reported for 4-chloro-3-nitrobenzoic acid (Ishida & Fukunaga, 2003). The guanidinium cation geometrical parameters are typical (Cygler et al., 1976).
The crystal structure is stabilized mainly by a network of O—H···O, N—H···O and N—H···Cl hydrogen bonds (Table 1). In this network the carboxylate O atoms act as hydrogen bond acceptors, water O atoms act as donors as well as acceptors and guanidinium N atoms provide the most extensive part as donors. Each of the guanidinium H atoms is involved in hydrogen bonds as a donor. The well known synthon in which guanidinium amine group and carboxylate group are involved in hydrogen bonds to form a R22(6) ring (Videnova-Adrabińska et al., 2007; McKee & Najafpour, 2007; Etter et al., 1990) is not present in (I). Instead, a water molecule donates one of its H atoms (H2W) to form a bifurcated hydrogen bond. In this hydrogen bond the two carboxyl O atoms (O1 and O2) act as acceptors. The second water H1W atom is involved in the O1W—H1W···O1v (see Table 1 for symmetry code) hydrogen bond which seems to be the strongest of all hydrogen bonds present (Table 1). The water O1W atom accepts two hydrogen bonds, N10—H101···O1Wi and N30—H302···O1Wi to form a R21(6) motif (Etter et al., 1990). Furthermore, the carboxyl O1 atom is involved in one hydrogen bond as acceptor with H102 atom from the guanidinium cation amine group. The nitro O3iii atom is bonded to the H262 atom via N—H···O hydrogen bond. The remaining nitro O4 atom participates in no other hydrogen bonds. The H201 and H301 atoms from two guanidinium amino groups participate in hydrogen bonds to the carboxyl O2ii atom. The H301 atom is further bonded to the Cliv atom.
The phenyl rings form chains extending along [010] (the neighbouring phenyl rings constituting each chain are generated with the following symmetry operations: [vi] 1 - x, 2 - y, 1 - z; [vii] x, 1 + y, z etc.; Fig. 2). A weak stacking interaction stabilizes this pattern (3.69 Å distance between the neighbouring rings centroids). The phenyl ring chains are parallel to guanidinium cations and water molecules layers perpendicular to [100] which via hydrogen bonds create a three-dimensional crystal structure (Fig. 3).