A new monoclinic (P21/c) polymorph of the title compound has the same overall conformation as a previously reported (Cc) form with the exception of the conformation of the outer hydroxy H atom. This difference results in very different crystal packing based on hydrogen bonding, i.e. supramolecular tubes in the new form as opposed to a three-dimensional architecture in the Cc form.
Supporting information
CCDC reference: 960620
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean
(C-C) = 0.002 Å
- R factor = 0.035
- wR factor = 0.086
- Data-to-parameter ratio = 15.0
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 2 Report
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
0 ALERT level G = General information/check it is not something unexpected
0 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
0 ALERT type 5 Informative message, check
Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), QMol (Gans & Shalloway,
2001)
and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2008), PLATON (Spek, 2009 and publCIF
(Westrip, 2010).
2,4-Dihydroxybenzaldehyde 4-methylthiosemicarbazone
top
Crystal data top
C9H11N3O2S | F(000) = 472 |
Mr = 225.27 | Dx = 1.496 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.3058 (2) Å | Cell parameters from 3917 reflections |
b = 6.0582 (1) Å | θ = 3.3–29.8° |
c = 22.6041 (6) Å | µ = 0.31 mm−1 |
β = 91.100 (2)° | T = 100 K |
V = 1000.27 (4) Å3 | Block, colourless |
Z = 4 | 0.48 × 0.19 × 0.14 mm |
Data collection top
Bruker APEXII CCD diffractometer | 2302 independent reflections |
Radiation source: sealed tube | 1950 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
φ and ω scans | θmax = 27.5°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→9 |
Tmin = 0.866, Tmax = 0.957 | k = −7→7 |
9696 measured reflections | l = −29→24 |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.035 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.086 | w = 1/[σ2(Fo2) + (0.0336P)2 + 0.7405P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
2302 reflections | Δρmax = 0.30 e Å−3 |
153 parameters | Δρmin = −0.31 e Å−3 |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.15271 (5) | 1.11056 (7) | 1.14702 (2) | 0.01707 (12) | |
O1 | 0.33247 (16) | 0.2527 (2) | 1.00557 (5) | 0.0174 (3) | |
H1o | 0.301 (3) | 0.362 (4) | 1.0247 (11) | 0.044 (7)* | |
O2 | 0.45517 (16) | 0.0527 (2) | 0.80619 (5) | 0.0204 (3) | |
H2o | 0.541 (3) | −0.033 (4) | 0.8232 (11) | 0.051 (7)* | |
N1 | 0.15573 (18) | 0.6695 (2) | 1.14178 (6) | 0.0148 (3) | |
H1n | 0.153 (3) | 0.557 (3) | 1.1220 (9) | 0.019 (5)* | |
N2 | 0.15295 (18) | 0.8552 (2) | 1.05291 (6) | 0.0152 (3) | |
H2n | 0.183 (3) | 0.984 (4) | 1.0359 (9) | 0.029 (5)* | |
N3 | 0.19726 (17) | 0.6617 (2) | 1.02301 (6) | 0.0139 (3) | |
C1 | 0.1544 (2) | 0.8599 (3) | 1.11312 (7) | 0.0135 (3) | |
C2 | 0.1526 (2) | 0.6471 (3) | 1.20604 (7) | 0.0197 (4) | |
H2A | 0.2699 | 0.6968 | 1.2231 | 0.030* | |
H2B | 0.1326 | 0.4920 | 1.2164 | 0.030* | |
H2C | 0.0534 | 0.7374 | 1.2217 | 0.030* | |
C3 | 0.1997 (2) | 0.6841 (3) | 0.96619 (7) | 0.0141 (3) | |
H3 | 0.1592 | 0.8197 | 0.9494 | 0.017* | |
C4 | 0.2616 (2) | 0.5119 (3) | 0.92679 (7) | 0.0137 (3) | |
C5 | 0.3302 (2) | 0.3078 (3) | 0.94674 (7) | 0.0135 (3) | |
C6 | 0.3978 (2) | 0.1534 (3) | 0.90734 (7) | 0.0154 (3) | |
H6 | 0.4461 | 0.0173 | 0.9214 | 0.019* | |
C7 | 0.3941 (2) | 0.1999 (3) | 0.84699 (7) | 0.0157 (3) | |
C8 | 0.3264 (2) | 0.4006 (3) | 0.82584 (7) | 0.0177 (3) | |
H8 | 0.3239 | 0.4312 | 0.7846 | 0.021* | |
C9 | 0.2630 (2) | 0.5540 (3) | 0.86554 (7) | 0.0168 (3) | |
H9 | 0.2192 | 0.6920 | 0.8512 | 0.020* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0239 (2) | 0.0115 (2) | 0.0158 (2) | 0.00296 (15) | 0.00059 (15) | −0.00209 (15) |
O1 | 0.0274 (6) | 0.0135 (6) | 0.0114 (6) | 0.0017 (5) | 0.0029 (5) | 0.0007 (5) |
O2 | 0.0214 (6) | 0.0243 (7) | 0.0154 (6) | 0.0041 (5) | 0.0010 (5) | −0.0062 (5) |
N1 | 0.0223 (7) | 0.0099 (7) | 0.0120 (7) | −0.0017 (5) | 0.0015 (5) | −0.0019 (6) |
N2 | 0.0215 (7) | 0.0103 (7) | 0.0137 (7) | 0.0012 (5) | 0.0019 (5) | −0.0007 (5) |
N3 | 0.0163 (6) | 0.0116 (6) | 0.0139 (7) | −0.0005 (5) | 0.0011 (5) | −0.0023 (5) |
C1 | 0.0119 (7) | 0.0145 (8) | 0.0141 (8) | 0.0005 (6) | 0.0004 (6) | −0.0009 (6) |
C2 | 0.0279 (9) | 0.0177 (8) | 0.0137 (8) | −0.0017 (7) | 0.0020 (6) | 0.0019 (7) |
C3 | 0.0144 (7) | 0.0125 (7) | 0.0153 (8) | −0.0008 (6) | 0.0001 (6) | 0.0006 (6) |
C4 | 0.0140 (7) | 0.0143 (8) | 0.0129 (7) | −0.0016 (6) | 0.0011 (6) | 0.0002 (6) |
C5 | 0.0145 (7) | 0.0150 (8) | 0.0110 (7) | −0.0036 (6) | 0.0004 (5) | 0.0005 (6) |
C6 | 0.0150 (7) | 0.0136 (8) | 0.0177 (8) | −0.0006 (6) | 0.0018 (6) | 0.0009 (6) |
C7 | 0.0139 (7) | 0.0180 (8) | 0.0152 (8) | −0.0016 (6) | 0.0025 (6) | −0.0043 (6) |
C8 | 0.0184 (7) | 0.0240 (9) | 0.0106 (7) | 0.0022 (6) | 0.0006 (6) | 0.0008 (7) |
C9 | 0.0163 (7) | 0.0187 (8) | 0.0153 (8) | 0.0008 (6) | 0.0005 (6) | 0.0027 (7) |
Geometric parameters (Å, º) top
S1—C1 | 1.7011 (16) | C2—H2B | 0.9800 |
O1—C5 | 1.3707 (19) | C2—H2C | 0.9800 |
O1—H1o | 0.83 (3) | C3—C4 | 1.449 (2) |
O2—C7 | 1.3640 (19) | C3—H3 | 0.9500 |
O2—H2o | 0.90 (3) | C4—C5 | 1.405 (2) |
N1—C1 | 1.323 (2) | C4—C9 | 1.408 (2) |
N1—C2 | 1.459 (2) | C5—C6 | 1.389 (2) |
N1—H1n | 0.81 (2) | C6—C7 | 1.393 (2) |
N2—C1 | 1.361 (2) | C6—H6 | 0.9500 |
N2—N3 | 1.3945 (18) | C7—C8 | 1.394 (2) |
N2—H2n | 0.90 (2) | C8—C9 | 1.378 (2) |
N3—C3 | 1.292 (2) | C8—H8 | 0.9500 |
C2—H2A | 0.9800 | C9—H9 | 0.9500 |
| | | |
C5—O1—H1o | 108.3 (17) | C4—C3—H3 | 118.5 |
C7—O2—H2o | 108.9 (16) | C5—C4—C9 | 117.76 (14) |
C1—N1—C2 | 124.63 (14) | C5—C4—C3 | 123.32 (14) |
C1—N1—H1n | 117.4 (14) | C9—C4—C3 | 118.82 (14) |
C2—N1—H1n | 117.9 (14) | O1—C5—C6 | 117.41 (14) |
C1—N2—N3 | 120.33 (13) | O1—C5—C4 | 121.55 (14) |
C1—N2—H2n | 114.2 (13) | C6—C5—C4 | 121.04 (14) |
N3—N2—H2n | 117.6 (13) | C5—C6—C7 | 119.46 (15) |
C3—N3—N2 | 113.67 (13) | C5—C6—H6 | 120.3 |
N1—C1—N2 | 118.11 (14) | C7—C6—H6 | 120.3 |
N1—C1—S1 | 123.91 (12) | O2—C7—C6 | 122.00 (15) |
N2—C1—S1 | 117.98 (12) | O2—C7—C8 | 117.19 (14) |
N1—C2—H2A | 109.5 | C6—C7—C8 | 120.81 (14) |
N1—C2—H2B | 109.5 | C9—C8—C7 | 119.10 (15) |
H2A—C2—H2B | 109.5 | C9—C8—H8 | 120.4 |
N1—C2—H2C | 109.5 | C7—C8—H8 | 120.4 |
H2A—C2—H2C | 109.5 | C8—C9—C4 | 121.80 (15) |
H2B—C2—H2C | 109.5 | C8—C9—H9 | 119.1 |
N3—C3—C4 | 123.08 (15) | C4—C9—H9 | 119.1 |
N3—C3—H3 | 118.5 | | |
| | | |
C1—N2—N3—C3 | −176.54 (14) | C3—C4—C5—C6 | −176.13 (14) |
C2—N1—C1—N2 | −178.35 (14) | O1—C5—C6—C7 | 178.45 (13) |
C2—N1—C1—S1 | 1.2 (2) | C4—C5—C6—C7 | −1.3 (2) |
N3—N2—C1—N1 | −15.6 (2) | C5—C6—C7—O2 | −178.64 (14) |
N3—N2—C1—S1 | 164.83 (11) | C5—C6—C7—C8 | 1.1 (2) |
N2—N3—C3—C4 | 173.05 (13) | O2—C7—C8—C9 | 179.92 (14) |
N3—C3—C4—C5 | −2.2 (2) | C6—C7—C8—C9 | 0.2 (2) |
N3—C3—C4—C9 | −178.56 (14) | C7—C8—C9—C4 | −1.3 (2) |
C9—C4—C5—O1 | −179.49 (14) | C5—C4—C9—C8 | 1.0 (2) |
C3—C4—C5—O1 | 4.1 (2) | C3—C4—C9—C8 | 177.60 (14) |
C9—C4—C5—C6 | 0.3 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1o···N3 | 0.83 (2) | 1.97 (2) | 2.6992 (17) | 147 (2) |
N1—H1n···N3 | 0.815 (19) | 2.35 (2) | 2.7080 (19) | 107.1 (16) |
O2—H2o···S1i | 0.90 (2) | 2.37 (2) | 3.1918 (12) | 152 (2) |
N1—H1n···S1ii | 0.815 (19) | 2.763 (18) | 3.3883 (13) | 134.9 (17) |
N2—H2n···O1iii | 0.90 (2) | 2.08 (2) | 2.9527 (17) | 162 (2) |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x, y−1, z; (iii) x, y+1, z. |