Hydro­gen bonding in m-carboxy­phenyl­ammonium bi­sulfate

In the title compound, C₇H₈NO₂⁺·HSO₄⁻, there is an intricate cation–cation, cation–anion and anion–anion three-dimensional hydrogen-bond network. Cations are linked two-dimensionally by C—H...O hydrogen bonds, and anions are linked two-dimensionally by O—H...O hydrogen bonds; however, interactions between cations and anions involve a three-dimensional network of N—H...O and O—H...O hydrogen bonds. The strongest hydrogen bond is observed between anions.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.035
• wR factor = 0.115
• Data-to-parameter ratio = 19.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.99
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

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

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Computing details

Data collection: KappaCCD Reference Manual (Nonius, 1998); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 (Farrugia, 1997) and CAMERON (Watkin et al., 1993); software used to prepare material for publication: WinGX (Farrugia, 1999).

(I)

Crystal data

C7H8NO2^+·HSO4^−	F(000) = 488
Mr = 235.21	Dx = 1.697 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 12041 reflections
a = 11.4160 (3) Å	θ = 1.8–30.0°
b = 10.5090 (3) Å	µ = 0.36 mm^−1
c = 7.6810 (2) Å	T = 293 K
β = 92.562 (2)°	Prism, brown
V = 920.57 (4) Å^3	0.4 × 0.3 × 0.25 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	2331 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.034
Graphite monochromator	θmax = 30.0°, θmin = 1.8°
φ scans	h = 0→16
12041 measured reflections	k = −14→0
2694 independent reflections	l = −10→10

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	w = 1/[σ^2(Fo^2) + (0.0573P)^2 + 0.3395P] where P = (Fo^2 + 2Fc^2)/3
2654 reflections	(Δ/σ)max < 0.001
137 parameters	Δρmax = 0.44 e Å^−3
0 restraints	Δρmin = −0.48 e Å^−3

Special details

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
S	1.08057 (3)	0.41668 (3)	0.81551 (4)	0.02310 (13)
O6	1.03192 (11)	0.54457 (11)	0.79674 (16)	0.0321 (3)
C2	0.55502 (12)	0.37274 (14)	0.65857 (19)	0.0238 (3)
O3	1.18335 (10)	0.41531 (13)	0.93462 (16)	0.0351 (3)
N	0.79902 (11)	0.60929 (12)	0.66838 (17)	0.0251 (3)
H11	0.7559	0.6645	0.7257	0.038*
H12	0.8174	0.6428	0.5667	0.038*
H13	0.8644	0.5920	0.7314	0.038*
C4	0.73202 (12)	0.49166 (14)	0.63767 (18)	0.0221 (3)
O2	0.36894 (10)	0.27236 (12)	0.6651 (2)	0.0408 (3)
O5	0.98590 (11)	0.33295 (12)	0.89992 (16)	0.0340 (3)
H5	0.9711	0.3624	0.9953	0.051*
O4	1.09769 (13)	0.35504 (14)	0.65199 (16)	0.0414 (3)
C5	0.78403 (13)	0.39216 (16)	0.5513 (2)	0.0285 (3)
H51	0.8606	0.3992	0.5157	0.034*
C6	0.71984 (14)	0.28176 (16)	0.5188 (2)	0.0330 (3)
H6	0.7537	0.2139	0.4617	0.040*
O1	0.40013 (10)	0.44931 (13)	0.82109 (19)	0.0395 (3)
H1	0.3322	0.4370	0.8472	0.059*
C7	0.60533 (14)	0.27223 (15)	0.5710 (2)	0.0291 (3)
H7	0.5623	0.1986	0.5475	0.035*
C3	0.61902 (12)	0.48396 (14)	0.69359 (19)	0.0232 (3)
H3	0.5862	0.5512	0.7532	0.028*
C1	0.43239 (13)	0.35927 (14)	0.7140 (2)	0.0266 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S	0.02055 (19)	0.0274 (2)	0.02172 (19)	0.00378 (12)	0.00483 (12)	−0.00036 (12)
O6	0.0343 (6)	0.0289 (6)	0.0335 (6)	0.0066 (5)	0.0055 (5)	0.0050 (5)
C2	0.0179 (6)	0.0261 (7)	0.0275 (7)	−0.0009 (5)	0.0029 (5)	0.0019 (5)
O3	0.0196 (5)	0.0535 (8)	0.0322 (6)	0.0049 (5)	0.0016 (4)	0.0019 (5)
N	0.0199 (5)	0.0275 (6)	0.0281 (6)	−0.0027 (4)	0.0031 (4)	−0.0004 (5)
C4	0.0183 (6)	0.0244 (6)	0.0236 (6)	−0.0009 (5)	0.0010 (5)	0.0016 (5)
O2	0.0274 (6)	0.0327 (6)	0.0635 (9)	−0.0095 (5)	0.0128 (6)	−0.0083 (6)
O5	0.0341 (6)	0.0346 (6)	0.0338 (6)	−0.0090 (5)	0.0064 (5)	−0.0001 (5)
O4	0.0483 (8)	0.0485 (7)	0.0282 (6)	0.0056 (6)	0.0110 (5)	−0.0099 (5)
C5	0.0206 (6)	0.0341 (8)	0.0313 (7)	0.0010 (6)	0.0066 (5)	−0.0032 (6)
C6	0.0278 (7)	0.0315 (8)	0.0402 (8)	0.0026 (6)	0.0072 (6)	−0.0097 (7)
O1	0.0226 (5)	0.0421 (7)	0.0549 (8)	−0.0059 (5)	0.0141 (5)	−0.0155 (6)
C7	0.0267 (7)	0.0259 (7)	0.0349 (8)	−0.0019 (5)	0.0025 (6)	−0.0044 (6)
C3	0.0204 (6)	0.0230 (6)	0.0264 (7)	0.0006 (5)	0.0035 (5)	−0.0006 (5)
C1	0.0209 (6)	0.0251 (7)	0.0340 (7)	−0.0004 (5)	0.0046 (5)	0.0030 (6)

Geometric parameters (Å, º)

S—O4	1.4343 (12)	C4—C5	1.386 (2)
S—O3	1.4554 (12)	O2—C1	1.2149 (19)
S—O6	1.4589 (12)	O5—H5	0.8200
S—O5	1.5574 (12)	C5—C6	1.389 (2)
C2—C7	1.390 (2)	C5—H51	0.9300
C2—C3	1.398 (2)	C6—C7	1.388 (2)
C2—C1	1.4881 (19)	C6—H6	0.9300
N—C4	1.4672 (18)	O1—C1	1.317 (2)
N—H11	0.8900	O1—H1	0.8200
N—H12	0.8900	C7—H7	0.9300
N—H13	0.8900	C3—H3	0.9300
C4—C3	1.3801 (19)
O4—S—O3	114.11 (8)	S—O5—H5	109.5
O4—S—O6	113.31 (8)	C4—C5—C6	118.84 (14)
O3—S—O6	111.34 (8)	C4—C5—H51	120.6
O4—S—O5	103.51 (8)	C6—C5—H51	120.6
O3—S—O5	106.72 (7)	C7—C6—C5	120.29 (14)
O6—S—O5	107.06 (7)	C7—C6—H6	119.9
C7—C2—C3	120.31 (13)	C5—C6—H6	119.9
C7—C2—C1	118.71 (14)	C1—O1—H1	109.5
C3—C2—C1	120.98 (13)	C6—C7—C2	119.99 (14)
C4—N—H11	109.5	C6—C7—H7	120.0
C4—N—H12	109.5	C2—C7—H7	120.0
H11—N—H12	109.5	C4—C3—C2	118.48 (13)
C4—N—H13	109.5	C4—C3—H3	120.8
H11—N—H13	109.5	C2—C3—H3	120.8
H12—N—H13	109.5	O2—C1—O1	123.63 (14)
C3—C4—C5	122.08 (13)	O2—C1—C2	122.59 (14)
C3—C4—N	119.15 (13)	O1—C1—C2	113.78 (13)
C5—C4—N	118.76 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N—H11···O2^i	0.89	2.03	2.9101 (18)	169
N—H12···O4^ii	0.89	1.98	2.8010 (18)	153
N—H13···O6	0.89	2.02	2.8757 (18)	162
O5—H5···O6^iii	0.82	1.87	2.6776 (17)	166
O1—H1···O3^iv	0.82	1.87	2.6843 (16)	173

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