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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520615005922/ao5002sup1.cif
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520615005922/ao5002Isup2.hkl
Contains datablock I

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2052520615005922/ao5002sup3.pdf
Supporting figures and tables

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
C3H12Mo0.2N6O4S4Zn0.75F(000) = 797.3593
Mr = 397.44Dx = 1.953 Mg m3
Orthorhombic, Pca21Mo Kα radiation, λ = 0.71073 Å
a = 11.153 (2) ŵ = 2.27 mm1
b = 7.7691 (14) ÅT = 273 K
c = 15.408 (3) ÅIrregular, metallic orangish yellow
V = 1335.1 (4) Å30.35 × 0.35 × 0.3 mm
Z = 4
Data collection top
Bruker SMART CCD 1K area detector
diffractometer
2028 independent reflections
Graphite monochromator1894 reflections with I 2u(I)
Detector resolution: 7.9 pixels mm-1Rint = 0.032
ω scansθmax = 29.1°, θmin = 3.2°
Absorption correction: analyticalh = 1314
Tmin = 0.469, Tmax = 0.514k = 610
3997 measured reflectionsl = 2113
Refinement top
Refinement on F2Primary atom site location: iterative
Least-squares matrix: fullH-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 = 1.04Δρmax = 0.28 e Å3
2028 reflectionsΔρmin = 0.50 e Å3
173 parametersAbsolute structure: Flack, H. D. (1983). Acta Cryst. A39, 876-881.
0 restraintsAbsolute structure parameter: 0.071 (15)
18 constraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Zn10.5633 (4)0.6587 (8)0.45483 (6)0.0197 (7)0.750000
S10.62684 (9)0.84503 (13)0.28297 (7)0.0208 (2)
S20.47872 (11)0.83180 (15)0.55875 (8)0.0297 (3)
S40.70392 (9)0.49846 (15)0.52949 (8)0.0279 (3)
S30.41938 (10)0.49755 (14)0.38265 (8)0.0275 (3)
O30.6953 (3)0.9969 (4)0.2573 (2)0.0293 (7)
O40.4979 (3)0.8763 (4)0.2748 (2)0.0325 (7)
O10.6537 (3)0.8149 (4)0.3771 (2)0.0316 (8)
N40.4315 (4)0.2546 (5)0.2684 (3)0.0358 (10)
C10.4924 (4)0.3376 (5)0.3273 (3)0.0253 (10)
O20.6637 (3)0.6956 (4)0.2338 (2)0.0330 (7)
N10.6634 (4)0.3573 (6)0.6797 (3)0.0480 (12)
N30.6043 (4)0.2925 (5)0.3425 (3)0.0413 (11)
C20.6147 (4)0.3997 (6)0.6064 (3)0.0271 (9)
N50.2801 (4)1.0060 (5)0.5647 (3)0.0448 (11)
C50.3618 (4)0.9429 (6)0.5123 (3)0.0298 (10)
N70.3498 (4)0.9613 (6)0.4289 (2)0.0412 (11)
N60.5008 (4)0.3651 (6)0.5932 (3)0.0451 (12)
Mo10.5649 (14)0.660 (2)0.44495 (4)0.029 (2)0.200000
H4a0.3579 (4)0.2810 (5)0.2587 (3)0.0429 (11)*
H4b0.4651 (4)0.1734 (5)0.2392 (3)0.0429 (11)*
H1a0.7380 (4)0.3786 (6)0.6889 (3)0.0576 (14)*
H1b0.6212 (4)0.3080 (6)0.7192 (3)0.0576 (14)*
H3a0.6449 (4)0.3443 (5)0.3821 (3)0.0495 (13)*
H3b0.6368 (4)0.2111 (5)0.3128 (3)0.0495 (13)*
H5a0.2864 (4)0.9910 (5)0.6199 (3)0.0538 (14)*
H5b0.2202 (4)1.0624 (5)0.5440 (3)0.0538 (14)*
H7a0.4017 (4)0.9169 (6)0.3943 (2)0.0494 (13)*
H7b0.2899 (4)1.0180 (6)0.4084 (2)0.0494 (13)*
H6a0.4677 (4)0.3918 (6)0.5447 (3)0.0542 (14)*
H6b0.4594 (4)0.3157 (6)0.6332 (3)0.0542 (14)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0194 (11)0.0249 (15)0.0149 (6)0.0016 (8)0.0010 (6)0.0011 (7)
S10.0200 (5)0.0266 (5)0.0158 (5)0.0005 (4)0.0017 (4)0.0013 (4)
S20.0288 (6)0.0401 (6)0.0203 (5)0.0115 (5)0.0056 (5)0.0043 (5)
S40.0176 (5)0.0412 (6)0.0250 (5)0.0012 (4)0.0025 (4)0.0115 (5)
S30.0200 (5)0.0339 (5)0.0285 (6)0.0002 (4)0.0002 (4)0.0104 (5)
O30.0323 (16)0.0304 (16)0.0250 (16)0.0016 (14)0.0017 (14)0.0061 (13)
O40.0186 (15)0.0437 (18)0.0353 (18)0.0041 (14)0.0062 (14)0.0040 (17)
O10.0357 (18)0.0406 (17)0.0185 (15)0.0154 (14)0.0066 (14)0.0078 (14)
N40.039 (2)0.035 (2)0.033 (2)0.0011 (18)0.0025 (18)0.013 (2)
C10.022 (2)0.029 (2)0.024 (2)0.0054 (17)0.0035 (19)0.0019 (19)
O20.0302 (17)0.0346 (15)0.0342 (18)0.0030 (14)0.0031 (16)0.0117 (15)
N10.034 (2)0.082 (3)0.028 (2)0.002 (2)0.002 (2)0.027 (2)
N30.032 (2)0.039 (2)0.052 (3)0.006 (2)0.006 (2)0.020 (2)
C20.028 (2)0.029 (2)0.024 (2)0.0034 (18)0.0056 (19)0.004 (2)
N50.038 (2)0.068 (3)0.028 (2)0.030 (2)0.000 (2)0.003 (2)
C50.030 (2)0.035 (2)0.025 (2)0.0051 (18)0.003 (2)0.003 (2)
N70.039 (2)0.059 (3)0.025 (2)0.026 (2)0.0025 (19)0.0045 (19)
N60.032 (2)0.066 (3)0.038 (3)0.011 (2)0.000 (2)0.027 (2)
Mo10.036 (4)0.031 (5)0.021 (2)0.007 (3)0.002 (2)0.000 (2)
Geometric parameters (Å, º) top
Zn1—S22.294 (4)S4—C21.727 (4)
Zn1—S42.309 (4)S4—Mo12.381 (13)
Zn1—S32.320 (5)S3—C11.713 (5)
Zn1—O11.981 (6)S3—Mo12.267 (17)
Zn1—Mo10.153 (3)O1—Mo11.879 (16)
S1—O31.460 (3)N4—C11.305 (6)
S1—O41.464 (3)C1—N31.318 (7)
S1—O11.499 (3)N1—C21.296 (6)
S1—O21.446 (3)C2—N61.315 (7)
S1—Mo12.964 (11)N5—C51.314 (6)
S2—C51.720 (4)C5—N71.299 (5)
S2—Mo12.406 (11)
S4—Zn1—S2104.34 (7)Mo1—S3—C1105.9 (4)
S3—Zn1—S2111.50 (19)S1—O1—Zn1125.4 (2)
S3—Zn1—S4114.7 (2)Mo1—O1—Zn13.4 (4)
O1—Zn1—S2105.8 (3)Mo1—O1—S1122.2 (4)
O1—Zn1—S4106.6 (2)N4—C1—S3117.2 (4)
O1—Zn1—S3113.14 (11)N3—C1—S3123.7 (4)
Mo1—Zn1—S2136 (8)N3—C1—N4119.0 (4)
Mo1—Zn1—S4116 (7)N1—C2—S4118.0 (4)
Mo1—Zn1—S368 (9)N6—C2—S4122.8 (4)
Mo1—Zn1—O147 (9)N6—C2—N1119.2 (4)
O4—S1—O3110.89 (18)N5—C5—S2117.2 (4)
O1—S1—O3106.49 (18)N7—C5—S2123.1 (4)
O1—S1—O4107.79 (19)N7—C5—N5119.7 (4)
O2—S1—O3111.0 (2)S1—Mo1—Zn1152 (10)
O2—S1—O4111.5 (2)S2—Mo1—Zn142 (8)
O2—S1—O1108.97 (19)S2—Mo1—S1115.9 (7)
Mo1—S1—O3138.0 (3)S4—Mo1—Zn161 (7)
Mo1—S1—O485.7 (3)S4—Mo1—S1124.4 (6)
Mo1—S1—O132.4 (3)S4—Mo1—S298.85 (13)
Mo1—S1—O296.7 (3)S3—Mo1—Zn1108 (9)
C5—S2—Zn1108.38 (18)S3—Mo1—S194.60 (15)
Mo1—S2—Zn12.6 (4)S3—Mo1—S2109.4 (6)
Mo1—S2—C5106.2 (3)S3—Mo1—S4114.0 (8)
C2—S4—Zn1100.96 (19)O1—Mo1—Zn1130 (10)
Mo1—S4—Zn13.3 (3)O1—Mo1—S125.34 (11)
Mo1—S4—C2103.5 (4)O1—Mo1—S2105.0 (8)
C1—S3—Zn1107.53 (19)O1—Mo1—S4107.4 (7)
Mo1—S3—Zn13.6 (3)O1—Mo1—S3119.9 (2)
 

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