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Single crystals of molybdenum-incorporated tris(thiourea)zinc(II) sulfate (MoZTS) are grown by the slow evaporation solution growth technique. Crystal composition as determined by single-crystal X-ray diffraction analysis reveals that it belongs to the orthorhombic system with space group Pca21 and cell parameters a = 11.153 (2), b = 7.7691 (14), c = 15.408 (3) Å, V = 1335.14 (4) Å3 and Z = 4. The surface morphological changes are studied by scanning electron microscopy. The vibrational patterns in FT-IR are used to identify the functional group and TGA/DTA (thermogravimetric analysis/differential thermal analysis) indicates the stability of the material. The structure and the crystallinity of the material were confirmed by powder X-ray diffraction analysis and the simulated X-ray diffraction (XRD) closely matches the experimental one with varied intensity patterns. The band gap energy is estimated using diffuse reflectance data by the application of the Kubelka-Munk algorithm. The relative second harmonic generation (SHG) efficiency measurements reveal that MoZTS has an efficiency comparable to that of tris(thiourea)zinc(II) sulfate (ZTS). Hirshfeld surfaces were derived using single-crystal X-ray diffraction data. Investigation of the intermolecular interactions and crystal packing via Hirshfeld surface analysis reveal that the close contacts are associated with strong interactions. Intermolecular interactions as revealed by the fingerprint plot and close packing could be the possible reasons for facile charge transfer leading to SHG activity.
Keywords: crystal growth; nonlinear optics; scanning electron microscopy; energy dispersive spectroscopy.
Supporting information
 | Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520615005922/ao5002sup1.cif |
 | Structure factor file (CIF format) https://doi.org/10.1107/S2052520615005922/ao5002Isup2.hkl |
 | Portable Document Format (PDF) file https://doi.org/10.1107/S2052520615005922/ao5002sup3.pdf |
CCDC reference: 1055810
Computing details top
Program(s) used to solve structure: olex2.solve (Bourhis et al., 2015); program(s) used to refine structure: olex2.refine (Bourhis et al., 2015); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).
MoZTS top
Crystal data top
| C3H12Mo0.2N6O4S4Zn0.75 | F(000) = 797.3593 |
| Mr = 397.44 | Dx = 1.953 Mg m−3 |
| Orthorhombic, Pca21 | Mo Kα radiation, λ = 0.71073 Å |
| a = 11.153 (2) Å | µ = 2.27 mm−1 |
| b = 7.7691 (14) Å | T = 273 K |
| c = 15.408 (3) Å | Irregular, metallic orangish yellow |
| V = 1335.1 (4) Å3 | 0.35 × 0.35 × 0.3 mm |
| Z = 4 |
Data collection top
| Bruker SMART CCD 1K area detector diffractometer | 2028 independent reflections |
| Graphite monochromator | 1894 reflections with I ≥ 2u(I) |
| Detector resolution: 7.9 pixels mm-1 | Rint = 0.032 |
| ω scans | θmax = 29.1°, θmin = 3.2° |
| Absorption correction: analytical | h = −13→14 |
| Tmin = 0.469, Tmax = 0.514 | k = −6→10 |
| 3997 measured reflections | l = −21→13 |
Refinement top
| Refinement on F2 | Primary atom site location: iterative |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.032 | w = 1/[σ2(Fo2) + (0.047P)2] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.080 | (Δ/σ)max = 0.116 |
| S = 1.04 | Δρmax = 0.28 e Å−3 |
| 2028 reflections | Δρmin = −0.50 e Å−3 |
| 173 parameters | Absolute structure: Flack, H. D. (1983). Acta Cryst. A39, 876-881. |
| 0 restraints | Absolute structure parameter: −0.071 (15) |
| 18 constraints |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Zn1 | 0.5633 (4) | 0.6587 (8) | 0.45483 (6) | 0.0197 (7) | 0.750000 |
| S1 | 0.62684 (9) | 0.84503 (13) | 0.28297 (7) | 0.0208 (2) | |
| S2 | 0.47872 (11) | 0.83180 (15) | 0.55875 (8) | 0.0297 (3) | |
| S4 | 0.70392 (9) | 0.49846 (15) | 0.52949 (8) | 0.0279 (3) | |
| S3 | 0.41938 (10) | 0.49755 (14) | 0.38265 (8) | 0.0275 (3) | |
| O3 | 0.6953 (3) | 0.9969 (4) | 0.2573 (2) | 0.0293 (7) | |
| O4 | 0.4979 (3) | 0.8763 (4) | 0.2748 (2) | 0.0325 (7) | |
| O1 | 0.6537 (3) | 0.8149 (4) | 0.3771 (2) | 0.0316 (8) | |
| N4 | 0.4315 (4) | 0.2546 (5) | 0.2684 (3) | 0.0358 (10) | |
| C1 | 0.4924 (4) | 0.3376 (5) | 0.3273 (3) | 0.0253 (10) | |
| O2 | 0.6637 (3) | 0.6956 (4) | 0.2338 (2) | 0.0330 (7) | |
| N1 | 0.6634 (4) | 0.3573 (6) | 0.6797 (3) | 0.0480 (12) | |
| N3 | 0.6043 (4) | 0.2925 (5) | 0.3425 (3) | 0.0413 (11) | |
| C2 | 0.6147 (4) | 0.3997 (6) | 0.6064 (3) | 0.0271 (9) | |
| N5 | 0.2801 (4) | 1.0060 (5) | 0.5647 (3) | 0.0448 (11) | |
| C5 | 0.3618 (4) | 0.9429 (6) | 0.5123 (3) | 0.0298 (10) | |
| N7 | 0.3498 (4) | 0.9613 (6) | 0.4289 (2) | 0.0412 (11) | |
| N6 | 0.5008 (4) | 0.3651 (6) | 0.5932 (3) | 0.0451 (12) | |
| Mo1 | 0.5649 (14) | 0.660 (2) | 0.44495 (4) | 0.029 (2) | 0.200000 |
| H4a | 0.3579 (4) | 0.2810 (5) | 0.2587 (3) | 0.0429 (11)* | |
| H4b | 0.4651 (4) | 0.1734 (5) | 0.2392 (3) | 0.0429 (11)* | |
| H1a | 0.7380 (4) | 0.3786 (6) | 0.6889 (3) | 0.0576 (14)* | |
| H1b | 0.6212 (4) | 0.3080 (6) | 0.7192 (3) | 0.0576 (14)* | |
| H3a | 0.6449 (4) | 0.3443 (5) | 0.3821 (3) | 0.0495 (13)* | |
| H3b | 0.6368 (4) | 0.2111 (5) | 0.3128 (3) | 0.0495 (13)* | |
| H5a | 0.2864 (4) | 0.9910 (5) | 0.6199 (3) | 0.0538 (14)* | |
| H5b | 0.2202 (4) | 1.0624 (5) | 0.5440 (3) | 0.0538 (14)* | |
| H7a | 0.4017 (4) | 0.9169 (6) | 0.3943 (2) | 0.0494 (13)* | |
| H7b | 0.2899 (4) | 1.0180 (6) | 0.4084 (2) | 0.0494 (13)* | |
| H6a | 0.4677 (4) | 0.3918 (6) | 0.5447 (3) | 0.0542 (14)* | |
| H6b | 0.4594 (4) | 0.3157 (6) | 0.6332 (3) | 0.0542 (14)* |
Atomic displacement parameters (Å2) top
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Zn1 | 0.0194 (11) | 0.0249 (15) | 0.0149 (6) | 0.0016 (8) | −0.0010 (6) | 0.0011 (7) |
| S1 | 0.0200 (5) | 0.0266 (5) | 0.0158 (5) | 0.0005 (4) | −0.0017 (4) | −0.0013 (4) |
| S2 | 0.0288 (6) | 0.0401 (6) | 0.0203 (5) | 0.0115 (5) | −0.0056 (5) | −0.0043 (5) |
| S4 | 0.0176 (5) | 0.0412 (6) | 0.0250 (5) | 0.0012 (4) | 0.0025 (4) | 0.0115 (5) |
| S3 | 0.0200 (5) | 0.0339 (5) | 0.0285 (6) | 0.0002 (4) | 0.0002 (4) | −0.0104 (5) |
| O3 | 0.0323 (16) | 0.0304 (16) | 0.0250 (16) | −0.0016 (14) | 0.0017 (14) | 0.0061 (13) |
| O4 | 0.0186 (15) | 0.0437 (18) | 0.0353 (18) | 0.0041 (14) | −0.0062 (14) | −0.0040 (17) |
| O1 | 0.0357 (18) | 0.0406 (17) | 0.0185 (15) | −0.0154 (14) | −0.0066 (14) | 0.0078 (14) |
| N4 | 0.039 (2) | 0.035 (2) | 0.033 (2) | −0.0011 (18) | −0.0025 (18) | −0.013 (2) |
| C1 | 0.022 (2) | 0.029 (2) | 0.024 (2) | −0.0054 (17) | 0.0035 (19) | 0.0019 (19) |
| O2 | 0.0302 (17) | 0.0346 (15) | 0.0342 (18) | 0.0030 (14) | −0.0031 (16) | −0.0117 (15) |
| N1 | 0.034 (2) | 0.082 (3) | 0.028 (2) | 0.002 (2) | 0.002 (2) | 0.027 (2) |
| N3 | 0.032 (2) | 0.039 (2) | 0.052 (3) | 0.006 (2) | −0.006 (2) | −0.020 (2) |
| C2 | 0.028 (2) | 0.029 (2) | 0.024 (2) | 0.0034 (18) | 0.0056 (19) | 0.004 (2) |
| N5 | 0.038 (2) | 0.068 (3) | 0.028 (2) | 0.030 (2) | 0.000 (2) | −0.003 (2) |
| C5 | 0.030 (2) | 0.035 (2) | 0.025 (2) | 0.0051 (18) | −0.003 (2) | −0.003 (2) |
| N7 | 0.039 (2) | 0.059 (3) | 0.025 (2) | 0.026 (2) | −0.0025 (19) | 0.0045 (19) |
| N6 | 0.032 (2) | 0.066 (3) | 0.038 (3) | −0.011 (2) | 0.000 (2) | 0.027 (2) |
| Mo1 | 0.036 (4) | 0.031 (5) | 0.021 (2) | −0.007 (3) | −0.002 (2) | 0.000 (2) |
Geometric parameters (Å, º) top
| Zn1—S2 | 2.294 (4) | S4—C2 | 1.727 (4) |
| Zn1—S4 | 2.309 (4) | S4—Mo1 | 2.381 (13) |
| Zn1—S3 | 2.320 (5) | S3—C1 | 1.713 (5) |
| Zn1—O1 | 1.981 (6) | S3—Mo1 | 2.267 (17) |
| Zn1—Mo1 | 0.153 (3) | O1—Mo1 | 1.879 (16) |
| S1—O3 | 1.460 (3) | N4—C1 | 1.305 (6) |
| S1—O4 | 1.464 (3) | C1—N3 | 1.318 (7) |
| S1—O1 | 1.499 (3) | N1—C2 | 1.296 (6) |
| S1—O2 | 1.446 (3) | C2—N6 | 1.315 (7) |
| S1—Mo1 | 2.964 (11) | N5—C5 | 1.314 (6) |
| S2—C5 | 1.720 (4) | C5—N7 | 1.299 (5) |
| S2—Mo1 | 2.406 (11) | ||
| S4—Zn1—S2 | 104.34 (7) | Mo1—S3—C1 | 105.9 (4) |
| S3—Zn1—S2 | 111.50 (19) | S1—O1—Zn1 | 125.4 (2) |
| S3—Zn1—S4 | 114.7 (2) | Mo1—O1—Zn1 | 3.4 (4) |
| O1—Zn1—S2 | 105.8 (3) | Mo1—O1—S1 | 122.2 (4) |
| O1—Zn1—S4 | 106.6 (2) | N4—C1—S3 | 117.2 (4) |
| O1—Zn1—S3 | 113.14 (11) | N3—C1—S3 | 123.7 (4) |
| Mo1—Zn1—S2 | 136 (8) | N3—C1—N4 | 119.0 (4) |
| Mo1—Zn1—S4 | 116 (7) | N1—C2—S4 | 118.0 (4) |
| Mo1—Zn1—S3 | 68 (9) | N6—C2—S4 | 122.8 (4) |
| Mo1—Zn1—O1 | 47 (9) | N6—C2—N1 | 119.2 (4) |
| O4—S1—O3 | 110.89 (18) | N5—C5—S2 | 117.2 (4) |
| O1—S1—O3 | 106.49 (18) | N7—C5—S2 | 123.1 (4) |
| O1—S1—O4 | 107.79 (19) | N7—C5—N5 | 119.7 (4) |
| O2—S1—O3 | 111.0 (2) | S1—Mo1—Zn1 | 152 (10) |
| O2—S1—O4 | 111.5 (2) | S2—Mo1—Zn1 | 42 (8) |
| O2—S1—O1 | 108.97 (19) | S2—Mo1—S1 | 115.9 (7) |
| Mo1—S1—O3 | 138.0 (3) | S4—Mo1—Zn1 | 61 (7) |
| Mo1—S1—O4 | 85.7 (3) | S4—Mo1—S1 | 124.4 (6) |
| Mo1—S1—O1 | 32.4 (3) | S4—Mo1—S2 | 98.85 (13) |
| Mo1—S1—O2 | 96.7 (3) | S3—Mo1—Zn1 | 108 (9) |
| C5—S2—Zn1 | 108.38 (18) | S3—Mo1—S1 | 94.60 (15) |
| Mo1—S2—Zn1 | 2.6 (4) | S3—Mo1—S2 | 109.4 (6) |
| Mo1—S2—C5 | 106.2 (3) | S3—Mo1—S4 | 114.0 (8) |
| C2—S4—Zn1 | 100.96 (19) | O1—Mo1—Zn1 | 130 (10) |
| Mo1—S4—Zn1 | 3.3 (3) | O1—Mo1—S1 | 25.34 (11) |
| Mo1—S4—C2 | 103.5 (4) | O1—Mo1—S2 | 105.0 (8) |
| C1—S3—Zn1 | 107.53 (19) | O1—Mo1—S4 | 107.4 (7) |
| Mo1—S3—Zn1 | 3.6 (3) | O1—Mo1—S3 | 119.9 (2) |
