Structure and third-order nonlinear optical properties of the two-dimensional Co^II coordination polymer [Co(1,2-BIB)(PA)]_n {1,2-BIB is 1,2-bis­[(1H-imidazol-1-yl)meth­yl]benzene and H₂PA is phthalic acid}

The design of nonlinear optical (NLO) materials with large NLO responses has been a challenge for materials scientists and chemists. Recently, organic polymers have received attention regarding their NLO properties and fast nonlinear response, and clusters involving delocalized d[pi]-p[pi] systems and conjugated d[pi]-p[pi] systems are expected to be a new class of NLO materials. Metal-organic coordination polymers combine the advantages of the organic and inorganic species. Thus far, tuning the third-order NLO properties of these materials has been a significant challenge. A two-dimensional coordination polymer, namely poly[([mu]-benzene-1,2-di­carboxyl­ato-[kappa]³O¹,O^1':O³){[mu]-1,2-bis­[(1H-imidazol-1-yl)meth­yl]benzene-[kappa]²N³:N^3'}cobalt(II)], [Co(C₈H₄O₄)(C₁₄H₁₄N₄)]_n, was synthesized by hydro­thermal methods. In the structure, the Co^II ion is penta­coordinated by two N atoms from two different 1,2-bis­[(1H-imidazol-1-yl)meth­yl]benzene (1,2-BIB) ligands and three O atoms from two symmetry-related benzene-1,2-di­carboxyl­ate (isophthalate, PA) anions. The penta­coordinated Co^II ions are linked by PA ligands to form a chain structure parallel to the c axis. Adjacent chains are further connected by 1,2-BIB ligands to produce a two-dimensional layered structure. The compound exhibits strong third-order nonlinear absorption and nonlinear refraction effects as a thin film. The third-order susceptibility [chi]⁽³⁾ is calculated to be 1.07 × 10^-8 esu, which is much larger than the values found for pure inorganic semi­con­ductors and some polymers.

Computing details

Data collection: SAINT (Bruker, 2009); cell refinement: SMART (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Poly[(µ-benzene-1,2-dicarboxylato-κ³O¹,O^1':O³){µ-1,2-bis[(1H-imidazol-1-yl)methyl]benzene-κ²N³:N^3'}cobalt(II)]

Crystal data

[Co(C8H4O4)(C14H14N4)]	F(000) = 948
Mr = 461.33	Dx = 1.591 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.4659 (15) Å	Cell parameters from 4171 reflections
b = 14.4336 (17) Å	θ = 2.4–27.3°
c = 11.8490 (15) Å	µ = 0.93 mm^−1
β = 115.366 (2)°	T = 293 K
V = 1926.4 (4) Å^3	Block, red
Z = 4	0.32 × 0.29 × 0.27 mm

Data collection

CCD area detector diffractometer	4414 independent reflections
Radiation source: sealed X-ray tube	3513 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
Detector resolution: 5.6 pixels mm^-1	θmax = 27.6°, θmin = 2.4°
phi and ω scans	h = −13→16
Absorption correction: multi-scan (SADABS; Bruker, 2008)	k = −18→16
Tmin = 0.684, Tmax = 0.746	l = −15→15
14006 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.033	H-atom parameters constrained
wR(F^2) = 0.087	w = 1/[σ^2(Fo^2) + (0.0404P)^2 + 0.5389P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
4414 reflections	Δρmax = 0.28 e Å^−3
280 parameters	Δρmin = −0.29 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Co1	0.72228 (2)	0.19811 (2)	0.45467 (2)	0.02947 (9)
O1	0.80007 (13)	0.27038 (9)	0.62246 (13)	0.0330 (3)
O2	0.79146 (14)	0.34428 (10)	0.45722 (13)	0.0400 (3)
O3	0.68729 (14)	0.38448 (12)	0.76591 (14)	0.0473 (4)
O4	0.85778 (15)	0.34697 (11)	0.91744 (14)	0.0444 (4)
N1	0.55897 (15)	0.26417 (12)	0.39860 (16)	0.0336 (4)
N2	0.43664 (15)	0.35864 (11)	0.42996 (16)	0.0334 (4)
N3	0.34036 (17)	0.49839 (12)	0.82524 (17)	0.0379 (4)
N4	0.30870 (16)	0.58099 (11)	0.96384 (16)	0.0345 (4)
C1	0.87249 (16)	0.42592 (12)	0.64999 (17)	0.0260 (4)
C2	0.86557 (16)	0.44461 (12)	0.76226 (17)	0.0264 (4)
C3	0.92445 (19)	0.52201 (14)	0.83084 (19)	0.0350 (4)
H3	0.9198	0.5355	0.9054	0.042*
C4	0.98980 (19)	0.57937 (14)	0.7902 (2)	0.0390 (5)
H4	1.0293	0.6304	0.8378	0.047*
C5	0.99635 (19)	0.56078 (15)	0.6793 (2)	0.0392 (5)
H5	1.0404	0.5989	0.6517	0.047*
C6	0.93696 (18)	0.48509 (14)	0.60969 (19)	0.0334 (4)
H6	0.9401	0.4733	0.5340	0.040*
C7	0.81757 (17)	0.34272 (13)	0.57175 (18)	0.0282 (4)
C8	0.79806 (19)	0.38665 (13)	0.81601 (19)	0.0327 (4)
C9	0.30031 (17)	0.36528 (14)	0.53465 (19)	0.0326 (4)
C10	0.28054 (18)	0.39818 (13)	0.63509 (19)	0.0325 (4)
C11	0.1908 (2)	0.35766 (15)	0.6592 (2)	0.0419 (5)
H11	0.1752	0.3801	0.7242	0.050*
C12	0.1249 (2)	0.28466 (17)	0.5877 (3)	0.0500 (6)
H12	0.0652	0.2585	0.6046	0.060*
C13	0.1472 (2)	0.25037 (17)	0.4916 (3)	0.0525 (6)
H13	0.1039	0.2003	0.4446	0.063*
C14	0.2342 (2)	0.29070 (15)	0.4653 (2)	0.0436 (5)
H14	0.2490	0.2676	0.4000	0.052*
C15	0.3880 (2)	0.41562 (14)	0.4993 (2)	0.0395 (5)
H15A	0.3490	0.4692	0.4490	0.047*
H15B	0.4530	0.4380	0.5749	0.047*
C16	0.3933 (2)	0.34558 (17)	0.3043 (2)	0.0446 (5)
H16	0.3248	0.3715	0.2430	0.054*
C17	0.4693 (2)	0.28775 (15)	0.2863 (2)	0.0405 (5)
H17	0.4617	0.2670	0.2089	0.049*
C18	0.53597 (18)	0.30876 (14)	0.48373 (19)	0.0337 (4)
H18	0.5828	0.3057	0.5694	0.040*
C19	0.3566 (2)	0.47670 (15)	0.7130 (2)	0.0400 (5)
H19A	0.4393	0.4611	0.7378	0.048*
H19B	0.3393	0.5318	0.6614	0.048*
C20	0.30622 (19)	0.58052 (13)	0.8515 (2)	0.0339 (4)
H20	0.2836	0.6308	0.7973	0.041*
C21	0.3669 (2)	0.44267 (15)	0.9278 (2)	0.0460 (6)
H21	0.3937	0.3817	0.9372	0.055*
C22	0.3467 (2)	0.49350 (15)	1.0117 (2)	0.0407 (5)
H22	0.3567	0.4730	1.0900	0.049*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.03473 (15)	0.02651 (15)	0.03405 (16)	0.00092 (11)	0.02130 (12)	−0.00147 (11)
O1	0.0465 (8)	0.0260 (7)	0.0319 (8)	−0.0019 (6)	0.0220 (7)	0.0006 (6)
O2	0.0547 (9)	0.0433 (8)	0.0277 (8)	−0.0074 (7)	0.0231 (7)	−0.0022 (6)
O3	0.0425 (9)	0.0666 (10)	0.0419 (9)	−0.0171 (8)	0.0269 (8)	−0.0130 (8)
O4	0.0601 (10)	0.0462 (9)	0.0408 (9)	0.0041 (8)	0.0349 (8)	0.0135 (7)
N1	0.0380 (9)	0.0332 (9)	0.0350 (10)	0.0015 (7)	0.0208 (8)	−0.0042 (7)
N2	0.0331 (9)	0.0362 (9)	0.0345 (9)	0.0048 (7)	0.0181 (8)	−0.0014 (7)
N3	0.0520 (11)	0.0287 (9)	0.0399 (10)	0.0048 (8)	0.0264 (9)	−0.0002 (7)
N4	0.0427 (10)	0.0290 (9)	0.0368 (10)	0.0010 (7)	0.0218 (8)	0.0011 (7)
C1	0.0284 (9)	0.0262 (9)	0.0279 (10)	0.0024 (7)	0.0163 (8)	0.0039 (7)
C2	0.0296 (9)	0.0263 (9)	0.0259 (10)	0.0012 (7)	0.0143 (8)	0.0036 (7)
C3	0.0417 (11)	0.0366 (11)	0.0278 (10)	−0.0024 (9)	0.0160 (9)	−0.0039 (8)
C4	0.0380 (11)	0.0312 (11)	0.0422 (13)	−0.0078 (9)	0.0117 (10)	−0.0036 (9)
C5	0.0373 (11)	0.0377 (11)	0.0457 (13)	−0.0063 (9)	0.0206 (10)	0.0073 (10)
C6	0.0351 (10)	0.0392 (11)	0.0338 (11)	−0.0012 (9)	0.0222 (9)	0.0043 (8)
C7	0.0302 (9)	0.0310 (10)	0.0303 (10)	0.0023 (8)	0.0194 (8)	−0.0007 (8)
C8	0.0474 (12)	0.0296 (10)	0.0332 (11)	−0.0052 (9)	0.0287 (10)	−0.0076 (8)
C9	0.0296 (10)	0.0303 (10)	0.0391 (11)	0.0063 (8)	0.0158 (9)	−0.0014 (8)
C10	0.0331 (10)	0.0287 (10)	0.0367 (11)	0.0082 (8)	0.0158 (9)	0.0027 (8)
C11	0.0419 (12)	0.0422 (12)	0.0497 (14)	0.0069 (10)	0.0272 (11)	0.0051 (10)
C12	0.0429 (13)	0.0486 (14)	0.0621 (17)	−0.0046 (10)	0.0258 (13)	0.0090 (12)
C13	0.0476 (14)	0.0419 (13)	0.0637 (17)	−0.0106 (11)	0.0197 (13)	−0.0087 (12)
C14	0.0428 (12)	0.0417 (12)	0.0463 (14)	0.0017 (10)	0.0191 (11)	−0.0075 (10)
C15	0.0414 (12)	0.0357 (11)	0.0506 (14)	0.0036 (9)	0.0286 (11)	−0.0055 (9)
C16	0.0373 (11)	0.0608 (15)	0.0313 (12)	0.0085 (11)	0.0104 (9)	0.0045 (10)
C17	0.0436 (12)	0.0511 (13)	0.0285 (11)	−0.0035 (10)	0.0171 (10)	−0.0089 (9)
C18	0.0308 (10)	0.0416 (11)	0.0287 (10)	0.0034 (8)	0.0128 (8)	−0.0020 (9)
C19	0.0514 (13)	0.0371 (12)	0.0410 (12)	−0.0009 (10)	0.0289 (11)	−0.0059 (9)
C20	0.0412 (11)	0.0263 (10)	0.0384 (12)	0.0021 (8)	0.0211 (10)	0.0005 (8)
C21	0.0651 (15)	0.0297 (11)	0.0457 (14)	0.0121 (11)	0.0261 (12)	0.0065 (9)
C22	0.0545 (13)	0.0348 (11)	0.0358 (12)	0.0046 (10)	0.0221 (11)	0.0079 (9)

Geometric parameters (Å, º)

Co1—O1	2.0807 (14)	C3—C4	1.384 (3)
Co1—O2	2.2746 (15)	C4—H4	0.9300
Co1—O3^i	2.4037 (16)	C4—C5	1.377 (3)
Co1—O4^i	2.0272 (14)	C5—H5	0.9300
Co1—N1	2.0824 (17)	C5—C6	1.378 (3)
Co1—N4^ii	2.0636 (16)	C6—H6	0.9300
Co1—C7	2.506 (2)	C9—C10	1.398 (3)
O1—C7	1.269 (2)	C9—C14	1.390 (3)
O2—C7	1.253 (2)	C9—C15	1.513 (3)
O3—Co1^iii	2.4036 (16)	C10—C11	1.396 (3)
O3—C8	1.248 (3)	C10—C19	1.512 (3)
O4—Co1^iii	2.0271 (14)	C11—H11	0.9300
O4—C8	1.249 (3)	C11—C12	1.381 (3)
N1—C17	1.365 (3)	C12—H12	0.9300
N1—C18	1.327 (2)	C12—C13	1.375 (3)
N2—C15	1.466 (2)	C13—H13	0.9300
N2—C16	1.363 (3)	C13—C14	1.379 (3)
N2—C18	1.335 (3)	C14—H14	0.9300
N3—C19	1.462 (2)	C15—H15A	0.9700
N3—C20	1.340 (2)	C15—H15B	0.9700
N3—C21	1.374 (3)	C16—H16	0.9300
N4—Co1^iv	2.0637 (16)	C16—C17	1.346 (3)
N4—C20	1.318 (3)	C17—H17	0.9300
N4—C22	1.382 (3)	C18—H18	0.9300
C1—C2	1.396 (2)	C19—H19A	0.9700
C1—C6	1.390 (2)	C19—H19B	0.9700
C1—C7	1.492 (3)	C20—H20	0.9300
C2—C3	1.391 (3)	C21—H21	0.9300
C2—C8	1.508 (2)	C21—C22	1.344 (3)
C3—H3	0.9300	C22—H22	0.9300
O1—Co1—O2	60.23 (5)	O1—C7—C1	119.61 (16)
O1—Co1—O3^i	164.20 (5)	O2—C7—Co1	64.77 (11)
O1—Co1—N1	93.85 (6)	O2—C7—O1	120.66 (18)
O1—Co1—C7	30.36 (5)	O2—C7—C1	119.71 (17)
O2—Co1—O3^i	112.89 (5)	C1—C7—Co1	175.38 (12)
O2—Co1—C7	29.89 (5)	O3—C8—O4	121.87 (18)
O3^i—Co1—C7	141.46 (6)	O3—C8—C2	121.14 (19)
O4^i—Co1—O1	106.15 (6)	O4—C8—C2	116.77 (19)
O4^i—Co1—O2	87.36 (6)	C10—C9—C15	118.94 (18)
O4^i—Co1—O3^i	58.29 (6)	C14—C9—C10	119.36 (19)
O4^i—Co1—N1	150.39 (7)	C14—C9—C15	121.58 (18)
O4^i—Co1—N4^ii	100.34 (6)	C9—C10—C19	118.81 (17)
O4^i—Co1—C7	98.41 (6)	C11—C10—C9	118.7 (2)
N1—Co1—O2	83.85 (6)	C11—C10—C19	122.46 (18)
N1—Co1—O3^i	99.63 (6)	C10—C11—H11	119.6
N1—Co1—C7	87.82 (6)	C12—C11—C10	120.8 (2)
N4^ii—Co1—O1	93.87 (6)	C12—C11—H11	119.6
N4^ii—Co1—O2	154.09 (6)	C11—C12—H12	119.8
N4^ii—Co1—O3^i	91.92 (6)	C13—C12—C11	120.3 (2)
N4^ii—Co1—N1	99.84 (7)	C13—C12—H12	119.8
N4^ii—Co1—C7	124.23 (7)	C12—C13—H13	120.2
C7—O1—Co1	93.69 (11)	C12—C13—C14	119.5 (2)
C7—O2—Co1	85.34 (11)	C14—C13—H13	120.2
C8—O3—Co1^iii	81.21 (12)	C9—C14—H14	119.4
C8—O4—Co1^iii	98.50 (13)	C13—C14—C9	121.2 (2)
C17—N1—Co1	134.90 (13)	C13—C14—H14	119.4
C18—N1—Co1	118.65 (14)	N2—C15—C9	114.04 (17)
C18—N1—C17	105.47 (17)	N2—C15—H15A	108.7
C16—N2—C15	128.70 (18)	N2—C15—H15B	108.7
C18—N2—C15	123.87 (18)	C9—C15—H15A	108.7
C18—N2—C16	107.43 (17)	C9—C15—H15B	108.7
C20—N3—C19	125.60 (18)	H15A—C15—H15B	107.6
C20—N3—C21	107.01 (17)	N2—C16—H16	126.8
C21—N3—C19	127.15 (18)	C17—C16—N2	106.41 (19)
C20—N4—Co1^iv	123.28 (13)	C17—C16—H16	126.8
C20—N4—C22	105.39 (16)	N1—C17—H17	125.1
C22—N4—Co1^iv	131.01 (14)	C16—C17—N1	109.77 (18)
C2—C1—C7	123.26 (16)	C16—C17—H17	125.1
C6—C1—C2	119.31 (17)	N1—C18—N2	110.92 (18)
C6—C1—C7	117.38 (16)	N1—C18—H18	124.5
C1—C2—C8	124.68 (17)	N2—C18—H18	124.5
C3—C2—C1	118.64 (16)	N3—C19—C10	114.94 (17)
C3—C2—C8	116.69 (16)	N3—C19—H19A	108.5
C2—C3—H3	119.4	N3—C19—H19B	108.5
C4—C3—C2	121.26 (18)	C10—C19—H19A	108.5
C4—C3—H3	119.4	C10—C19—H19B	108.5
C3—C4—H4	120.0	H19A—C19—H19B	107.5
C5—C4—C3	119.95 (19)	N3—C20—H20	124.2
C5—C4—H4	120.0	N4—C20—N3	111.52 (18)
C4—C5—H5	120.3	N4—C20—H20	124.2
C4—C5—C6	119.30 (18)	N3—C21—H21	126.7
C6—C5—H5	120.3	C22—C21—N3	106.51 (18)
C1—C6—H6	119.2	C22—C21—H21	126.7
C5—C6—C1	121.52 (18)	N4—C22—H22	125.2
C5—C6—H6	119.2	C21—C22—N4	109.57 (19)
O1—C7—Co1	55.95 (9)	C21—C22—H22	125.2
Co1—O1—C7—O2	−2.96 (19)	C8—C2—C3—C4	179.46 (19)
Co1—O1—C7—C1	178.51 (14)	C9—C10—C11—C12	1.9 (3)
Co1—O2—C7—O1	2.71 (17)	C9—C10—C19—N3	−172.36 (18)
Co1—O2—C7—C1	−178.76 (15)	C10—C9—C14—C13	1.9 (3)
Co1^iii—O3—C8—O4	3.38 (18)	C10—C9—C15—N2	157.33 (18)
Co1^iii—O3—C8—C2	−171.09 (16)	C10—C11—C12—C13	0.3 (4)
Co1^iii—O4—C8—O3	−4.0 (2)	C11—C10—C19—N3	8.1 (3)
Co1^iii—O4—C8—C2	170.70 (13)	C11—C12—C13—C14	−1.4 (4)
Co1—N1—C17—C16	−168.26 (16)	C12—C13—C14—C9	0.3 (4)
Co1—N1—C18—N2	170.44 (13)	C14—C9—C10—C11	−2.9 (3)
Co1^iv—N4—C20—N3	174.02 (14)	C14—C9—C10—C19	177.46 (19)
Co1^iv—N4—C22—C21	−173.06 (16)	C14—C9—C15—N2	−26.5 (3)
N2—C16—C17—N1	0.3 (3)	C15—N2—C16—C17	179.81 (19)
N3—C21—C22—N4	−0.6 (3)	C15—N2—C18—N1	−179.94 (17)
C1—C2—C3—C4	−0.6 (3)	C15—C9—C10—C11	173.36 (19)
C1—C2—C8—O3	−69.6 (3)	C15—C9—C10—C19	−6.2 (3)
C1—C2—C8—O4	115.6 (2)	C15—C9—C14—C13	−174.3 (2)
C2—C1—C6—C5	1.4 (3)	C16—N2—C15—C9	88.9 (3)
C2—C1—C7—O1	−25.4 (3)	C16—N2—C18—N1	0.1 (2)
C2—C1—C7—O2	156.02 (18)	C17—N1—C18—N2	0.1 (2)
C2—C3—C4—C5	0.7 (3)	C18—N1—C17—C16	−0.2 (2)
C3—C2—C8—O3	110.3 (2)	C18—N2—C15—C9	−91.1 (2)
C3—C2—C8—O4	−64.5 (2)	C18—N2—C16—C17	−0.2 (2)
C3—C4—C5—C6	0.3 (3)	C19—N3—C20—N4	−174.9 (2)
C4—C5—C6—C1	−1.3 (3)	C19—N3—C21—C22	175.1 (2)
C6—C1—C2—C3	−0.4 (3)	C19—C10—C11—C12	−178.5 (2)
C6—C1—C2—C8	179.52 (19)	C20—N3—C19—C10	−121.1 (2)
C6—C1—C7—O1	152.17 (18)	C20—N3—C21—C22	0.5 (3)
C6—C1—C7—O2	−26.4 (3)	C20—N4—C22—C21	0.4 (3)
C7—C1—C2—C3	177.16 (18)	C21—N3—C19—C10	65.2 (3)
C7—C1—C2—C8	−2.9 (3)	C21—N3—C20—N4	−0.3 (3)
C7—C1—C6—C5	−176.33 (19)	C22—N4—C20—N3	−0.1 (2)

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, y−1/2, −z+3/2; (iii) x, −y+1/2, z+1/2; (iv) −x+1, y+1/2, −z+3/2.