Synthesis, growth, structure and characterization of molybdenum zinc thiourea complex crystals

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) ų 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.

Computing details

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

Crystal data

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) Å^3	0.35 × 0.35 × 0.3 mm
Z = 4

Data collection

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

Refinement on F^2	Primary atom site location: iterative
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.032	w = 1/[σ^2(Fo^2) + (0.047P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)