The crystal structure of the hydrated proton-transfer compound hydrate of 3-carboxy-4-hydroxybenzenesulfonic acid (5-sulfosalicylic acid) with guanidine, 2CH6N3+·C7H4O6S2-·H2O, reveals the presence of an extensively hydrogen-bonded three-dimensional network polymer in which all proton donor and acceptor atoms on the two guanidine cations, the dianionic sulfosalicylate anion and the water molecule are utilized. The structure is significantly different chemically and structurally from that of the previously reported anhydrous guanidinium sulfosalicylate compound CH6N3+·C7H5O6S-.
Supporting information
CCDC reference: 238828
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.005 Å
- R factor = 0.046
- wR factor = 0.140
- Data-to-parameter ratio = 8.3
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT242_ALERT_2_C Check Low U(eq) as Compared to Neighbors .... C12
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 5
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 4
H2 O
Alert level G
REFLT03_ALERT_4_G WARNING: Large fraction of Friedel related reflns may
be needed to determine absolute structure
From the CIF: _diffrn_reflns_theta_max 27.49
From the CIF: _reflns_number_total 2173
Count of symmetry unique reflns 2094
Completeness (_total/calc) 103.77%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 79
Fraction of Friedel pairs measured 0.038
Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
4 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
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
1 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1999); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON for Windows (Spek, 1999); software used to prepare material for publication: PLATON for Windows.
Crystal data top
2CH6N3+·C7H4O6S2−·H2O | Dx = 1.490 Mg m−3 |
Mr = 354.35 | Melting point = 478.5–484.1 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 25 reflections |
a = 12.030 (3) Å | θ = 12.5–17.4° |
b = 18.010 (5) Å | µ = 0.25 mm−1 |
c = 7.290 (2) Å | T = 295 K |
V = 1579.5 (7) Å3 | Prism, colourless |
Z = 4 | 0.45 × 0.35 × 0.30 mm |
F(000) = 744 | |
Data collection top
Rigaku AFC-7R diffractometer | 1644 reflections with I > 2σ(I) |
Radiation source: Rigaku rotating anode | Rint = 0.028 |
Graphite monochromator | θmax = 27.5°, θmin = 2.8° |
ω–2θ scans | h = −6→15 |
Absorption correction: ψ scan (TEXSAN for Windows; Molecular Structure Corporation, 1999) | k = 0→23 |
Tmin = 0.895, Tmax = 0.928 | l = −3→9 |
2428 measured reflections | 3 standard reflections every 150 reflections |
2173 independent reflections | intensity decay: 0.3% |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.046 | w = 1/[σ2(Fo2) + (0.1P)2 + 2.556P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.140 | (Δ/σ)max = 0.015 |
S = 0.90 | Δρmax = 0.44 e Å−3 |
2173 reflections | Δρmin = −0.45 e Å−3 |
261 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.059 (4) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 79 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.1 (2) |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded
fractional coordinates. All e.s.d.'s are estimated from the variances of the
(full) variance-covariance matrix. The cell e.s.d.'s are taken into account in
the estimation of distances, angles and torsion angles |
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 (Å2) top | x | y | z | Uiso*/Ueq | |
S5 | 0.31812 (7) | 0.21494 (5) | 0.5031 (2) | 0.0359 (3) | |
O2 | 0.2675 (2) | −0.11002 (13) | 0.5046 (7) | 0.0456 (9) | |
O51 | 0.4352 (2) | 0.23381 (15) | 0.5074 (7) | 0.0484 (9) | |
O52 | 0.2646 (3) | 0.2396 (2) | 0.3331 (5) | 0.0487 (12) | |
O53 | 0.2590 (3) | 0.2426 (2) | 0.6645 (5) | 0.0467 (12) | |
O71 | −0.0090 (2) | 0.02380 (17) | 0.5051 (8) | 0.0641 (12) | |
O72 | 0.0603 (2) | −0.09012 (15) | 0.5092 (8) | 0.0548 (9) | |
C1 | 0.1857 (3) | 0.01113 (18) | 0.5073 (8) | 0.0320 (9) | |
C2 | 0.2797 (3) | −0.03504 (18) | 0.5055 (9) | 0.0343 (9) | |
C3 | 0.3852 (3) | −0.0046 (2) | 0.5030 (11) | 0.0426 (10) | |
C4 | 0.3993 (3) | 0.0716 (2) | 0.5026 (9) | 0.0390 (10) | |
C5 | 0.3066 (3) | 0.11746 (18) | 0.5068 (7) | 0.0326 (9) | |
C6 | 0.2013 (3) | 0.08740 (18) | 0.5108 (8) | 0.0325 (9) | |
C7 | 0.0706 (3) | −0.0196 (2) | 0.5083 (11) | 0.0432 (11) | |
N12 | 0.6373 (4) | 0.1236 (3) | 0.7752 (8) | 0.0573 (19) | |
N22 | 0.8109 (4) | 0.0943 (3) | 0.6753 (8) | 0.0620 (16) | |
N32 | 0.6961 (5) | 0.0027 (3) | 0.7800 (10) | 0.080 (2) | |
C12 | 0.7150 (4) | 0.0736 (3) | 0.7432 (7) | 0.0507 (14) | |
N11 | 0.0412 (5) | 0.2039 (3) | 0.8465 (8) | 0.0513 (17) | |
N21 | 0.0364 (4) | 0.1951 (3) | 1.1595 (8) | 0.0550 (19) | |
N31 | −0.1173 (3) | 0.23667 (19) | 1.0044 (8) | 0.0455 (10) | |
C11 | −0.0130 (3) | 0.21230 (19) | 1.0045 (9) | 0.0378 (10) | |
O1W | 0.8614 (5) | −0.1118 (3) | 0.7534 (9) | 0.0727 (18) | |
H2 | 0.188 (5) | −0.117 (3) | 0.526 (9) | 0.066 (16)* | |
H3 | 0.448400 | −0.036300 | 0.501600 | 0.0510* | |
H4 | 0.471700 | 0.092400 | 0.498000 | 0.0470* | |
H6 | 0.138300 | 0.119300 | 0.519000 | 0.0390* | |
H12A | 0.578 (3) | 0.114 (3) | 0.846 (6) | 0.065 (10)* | |
H12B | 0.655 (4) | 0.169 (3) | 0.739 (7) | 0.061 (14)* | |
H22A | 0.864 (6) | 0.062 (4) | 0.639 (9) | 0.09 (2)* | |
H22B | 0.837 (7) | 0.147 (5) | 0.677 (12) | 0.10 (3)* | |
H32A | 0.750 (7) | −0.035 (5) | 0.771 (11) | 0.11 (3)* | |
H32B | 0.635 (6) | −0.009 (4) | 0.817 (12) | 0.09 (2)* | |
H11A | 0.106 (6) | 0.215 (4) | 0.838 (9) | 0.08 (2)* | |
H11B | 0.010 (4) | 0.222 (3) | 0.744 (7) | 0.061 (15)* | |
H21A | 0.103 (4) | 0.184 (3) | 1.160 (7) | 0.065 (14)* | |
H21B | 0.006 (5) | 0.198 (3) | 1.270 (8) | 0.060 (16)* | |
H1A | 0.921 (9) | −0.105 (6) | 0.681 (10) | 0.10 (3)* | |
H1B | 0.825 (10) | −0.156 (6) | 0.778 (10) | 0.11 (3)* | |
H31A | −0.164 (5) | 0.246 (5) | 1.114 (9) | 0.08 (3)* | |
H31B | −0.157 (5) | 0.245 (5) | 0.892 (9) | 0.09 (3)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S5 | 0.0386 (5) | 0.0307 (4) | 0.0385 (5) | −0.0045 (3) | 0.0000 (8) | −0.0005 (7) |
O2 | 0.0437 (14) | 0.0272 (12) | 0.0660 (18) | 0.0035 (10) | 0.004 (3) | 0.004 (2) |
O51 | 0.0460 (15) | 0.0437 (14) | 0.0554 (17) | −0.0127 (11) | −0.001 (2) | −0.002 (3) |
O52 | 0.061 (2) | 0.037 (2) | 0.048 (2) | 0.0053 (19) | −0.0051 (19) | 0.0085 (16) |
O53 | 0.055 (2) | 0.041 (2) | 0.044 (2) | −0.0067 (19) | 0.0050 (18) | −0.0082 (16) |
O71 | 0.0271 (12) | 0.0512 (16) | 0.114 (3) | 0.0016 (11) | 0.000 (3) | −0.015 (3) |
O72 | 0.0399 (14) | 0.0365 (13) | 0.088 (2) | −0.0082 (11) | 0.001 (3) | −0.002 (3) |
C1 | 0.0302 (15) | 0.0317 (15) | 0.0340 (17) | −0.0007 (12) | 0.000 (3) | −0.004 (2) |
C2 | 0.0369 (16) | 0.0302 (15) | 0.0357 (18) | 0.0018 (13) | 0.006 (3) | 0.003 (3) |
C3 | 0.0307 (15) | 0.0410 (18) | 0.056 (2) | 0.0075 (14) | 0.002 (4) | 0.003 (4) |
C4 | 0.0281 (15) | 0.0410 (18) | 0.048 (2) | −0.0022 (13) | −0.003 (3) | −0.005 (4) |
C5 | 0.0357 (16) | 0.0317 (15) | 0.0303 (16) | −0.0026 (12) | −0.002 (3) | 0.001 (2) |
C6 | 0.0323 (15) | 0.0300 (15) | 0.0352 (18) | 0.0021 (12) | −0.001 (3) | −0.002 (2) |
C7 | 0.0359 (17) | 0.0407 (18) | 0.053 (2) | −0.0032 (14) | 0.002 (3) | −0.002 (4) |
N12 | 0.040 (3) | 0.046 (3) | 0.086 (4) | 0.002 (2) | 0.017 (3) | 0.013 (3) |
N22 | 0.051 (2) | 0.045 (2) | 0.090 (4) | 0.003 (2) | 0.020 (3) | 0.000 (2) |
N32 | 0.059 (3) | 0.047 (2) | 0.134 (5) | 0.007 (2) | 0.021 (4) | 0.027 (3) |
C12 | 0.046 (2) | 0.043 (2) | 0.063 (3) | 0.000 (2) | 0.004 (2) | 0.007 (2) |
N11 | 0.047 (3) | 0.058 (3) | 0.049 (3) | 0.005 (3) | 0.005 (3) | −0.002 (3) |
N21 | 0.046 (3) | 0.073 (4) | 0.046 (3) | 0.017 (3) | −0.004 (3) | −0.009 (3) |
N31 | 0.0389 (16) | 0.0494 (17) | 0.0483 (18) | 0.0098 (14) | −0.003 (3) | 0.002 (3) |
C11 | 0.0374 (17) | 0.0315 (16) | 0.0444 (19) | −0.0001 (13) | −0.001 (3) | −0.006 (3) |
O1W | 0.062 (3) | 0.050 (2) | 0.106 (4) | 0.003 (2) | 0.007 (3) | 0.006 (3) |
Geometric parameters (Å, º) top
S5—O51 | 1.449 (3) | N12—C12 | 1.319 (7) |
S5—O52 | 1.465 (4) | N22—C12 | 1.310 (7) |
S5—O53 | 1.462 (4) | N32—C12 | 1.324 (8) |
S5—C5 | 1.761 (3) | N12—H12B | 0.89 (5) |
O2—C2 | 1.358 (4) | N12—H12A | 0.90 (4) |
O71—C7 | 1.236 (5) | N22—H22A | 0.90 (7) |
O72—C7 | 1.276 (5) | N22—H22B | 1.00 (9) |
O2—H2 | 0.98 (6) | N32—H32B | 0.81 (7) |
O1W—H1B | 0.93 (11) | N32—H32A | 0.94 (9) |
O1W—H1A | 0.90 (10) | C1—C6 | 1.387 (5) |
N11—C11 | 1.332 (8) | C1—C7 | 1.491 (5) |
N21—C11 | 1.314 (8) | C1—C2 | 1.404 (5) |
N31—C11 | 1.329 (5) | C2—C3 | 1.383 (5) |
N11—H11B | 0.90 (5) | C3—C4 | 1.383 (5) |
N11—H11A | 0.81 (7) | C4—C5 | 1.388 (5) |
N21—H21A | 0.83 (5) | C5—C6 | 1.378 (5) |
N21—H21B | 0.89 (6) | C3—H3 | 0.9508 |
N31—H31A | 0.99 (7) | C4—H4 | 0.9487 |
N31—H31B | 0.96 (7) | C6—H6 | 0.9529 |
| | | |
O51—S5—O52 | 112.0 (2) | C2—C1—C6 | 118.6 (3) |
O51—S5—O53 | 112.0 (2) | C2—C1—C7 | 121.9 (3) |
O51—S5—C5 | 108.05 (17) | C1—C2—C3 | 120.3 (3) |
O52—S5—O53 | 111.3 (2) | O2—C2—C3 | 119.6 (3) |
O52—S5—C5 | 106.3 (2) | O2—C2—C1 | 120.1 (3) |
O53—S5—C5 | 106.8 (2) | C2—C3—C4 | 120.4 (3) |
C2—O2—H2 | 103 (3) | C3—C4—C5 | 119.5 (3) |
H1A—O1W—H1B | 127 (9) | S5—C5—C4 | 122.0 (3) |
H11A—N11—H11B | 104 (6) | S5—C5—C6 | 117.7 (3) |
C11—N11—H11A | 121 (5) | C4—C5—C6 | 120.3 (3) |
C11—N11—H11B | 118 (3) | C1—C6—C5 | 120.9 (3) |
H21A—N21—H21B | 114 (5) | O72—C7—C1 | 117.4 (3) |
C11—N21—H21A | 120 (4) | O71—C7—O72 | 123.7 (3) |
C11—N21—H21B | 126 (4) | O71—C7—C1 | 119.0 (3) |
H31A—N31—H31B | 112 (5) | C4—C3—H3 | 119.85 |
C11—N31—H31B | 121 (4) | C2—C3—H3 | 119.74 |
C11—N31—H31A | 126 (4) | C3—C4—H4 | 120.30 |
C12—N12—H12B | 114 (3) | C5—C4—H4 | 120.23 |
H12A—N12—H12B | 123 (5) | C5—C6—H6 | 119.71 |
C12—N12—H12A | 122 (3) | C1—C6—H6 | 119.39 |
C12—N22—H22B | 123 (5) | N11—C11—N21 | 119.7 (4) |
H22A—N22—H22B | 113 (7) | N11—C11—N31 | 119.9 (6) |
C12—N22—H22A | 123 (5) | N21—C11—N31 | 120.4 (6) |
H32A—N32—H32B | 117 (7) | N12—C12—N22 | 119.8 (5) |
C12—N32—H32B | 118 (5) | N12—C12—N32 | 120.1 (5) |
C12—N32—H32A | 124 (5) | N22—C12—N32 | 120.1 (5) |
C6—C1—C7 | 119.6 (3) | | |
| | | |
O51—S5—C5—C4 | −3.6 (6) | C6—C1—C2—C3 | −1.5 (9) |
O51—S5—C5—C6 | 177.5 (4) | C7—C1—C2—O2 | 0.0 (9) |
O52—S5—C5—C4 | 116.7 (5) | C7—C1—C2—C3 | 179.4 (7) |
O52—S5—C5—C6 | −62.1 (5) | C2—C1—C7—O71 | −178.2 (7) |
O53—S5—C5—C4 | −124.3 (5) | O2—C2—C3—C4 | 179.6 (7) |
O53—S5—C5—C6 | 56.8 (5) | C1—C2—C3—C4 | 0.1 (11) |
C6—C1—C7—O72 | −178.4 (6) | C2—C3—C4—C5 | 0.7 (11) |
C6—C1—C7—O71 | 2.8 (10) | C3—C4—C5—S5 | −179.0 (5) |
C2—C1—C6—C5 | 2.0 (9) | C3—C4—C5—C6 | −0.2 (9) |
C7—C1—C6—C5 | −178.9 (6) | C4—C5—C6—C1 | −1.2 (9) |
C2—C1—C7—O72 | 0.6 (10) | S5—C5—C6—C1 | 177.7 (5) |
C6—C1—C2—O2 | 179.1 (6) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O72 | 0.98 (6) | 1.62 (6) | 2.518 (3) | 152 (5) |
O1W—H1A···O72i | 0.90 (10) | 2.11 (10) | 3.008 (7) | 179 (9) |
O1W—H1B···O53ii | 0.93 (11) | 2.13 (11) | 3.055 (7) | 180 (8) |
N11—H11A···O53 | 0.81 (7) | 2.29 (7) | 3.018 (7) | 151 (6) |
N11—H11B···O51iii | 0.90 (5) | 2.19 (5) | 3.089 (7) | 180 (5) |
N12—H12A···O72iv | 0.90 (4) | 2.09 (4) | 2.987 (7) | 179 (5) |
N12—H12B···O52v | 0.89 (5) | 2.17 (5) | 3.006 (6) | 157 (4) |
N21—H21A···O52vi | 0.83 (5) | 2.52 (5) | 3.127 (6) | 131 (5) |
N21—H21A···O2iv | 0.83 (5) | 2.34 (5) | 3.031 (6) | 141 (5) |
N21—H21B···O51vii | 0.89 (6) | 2.21 (6) | 3.003 (7) | 149 (5) |
N22—H22A···O71i | 0.90 (7) | 1.94 (7) | 2.801 (6) | 159 (6) |
N22—H22B···O52v | 1.00 (9) | 2.22 (9) | 3.043 (7) | 139 (7) |
N31—H31A···O53vii | 0.99 (7) | 1.87 (6) | 2.860 (6) | 174 (6) |
N31—H31B···O52iii | 0.96 (7) | 1.91 (7) | 2.873 (7) | 179 (8) |
N32—H32A···O1W | 0.94 (9) | 1.93 (9) | 2.871 (8) | 180 (8) |
N32—H32B···O71iv | 0.81 (7) | 2.06 (8) | 2.826 (8) | 157 (8) |
C4—H4···O51 | 0.95 | 2.59 | 2.953 (5) | 103 |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, y−1/2, −z+3/2; (iii) x−1/2, −y+1/2, −z+1; (iv) −x+1/2, −y, z+1/2; (v) x+1/2, −y+1/2, −z+1; (vi) x, y, z+1; (vii) x−1/2, −y+1/2, −z+2. |