Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680904241X/ci2939sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680904241X/ci2939Isup2.hkl |
CCDC reference: 754137
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.002 Å
- R factor = 0.028
- wR factor = 0.080
- Data-to-parameter ratio = 16.2
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT230_ALERT_2_C Hirshfeld Test Diff for O4 -- C8_b .. 5.14 su PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 7
Alert level G PLAT128_ALERT_4_G Non-standard setting of Space-group P21/c .... P21/n PLAT164_ALERT_4_G Nr. of Refined C-H H-Atoms in Heavy-Atom Struct. 2
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The title compound was prepared by the reaction of ZnSO4.H2O (0.90 g, 5 mmol) in H2O (25 ml) and INA (1.22 g, 10 mmol) in H2O (40 ml) with sodium 4-formylbenzoate (1.72 g, 10 mmol) in H2O (50 ml). The mixture was filtered and set aside to crystallize at ambient temperature for several days, giving colourless single crystals.
Atoms H21 and H22 (for methine) were located in a difference Fourier map and refined isotropically. The remaining H atoms were positioned geometrically with N-H = 0.86 Å (for NH2) and C-H = 0.93 Å for aromatic H atoms and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C,N).
As a part of our ongoing investigation on transition metal complexes of nicotinamide (NA), one form of niacin (Krishnamachari, 1974), and/or the nicotinic acid derivative N,N-diethylnicotinamide (DENA), an important respiratory stimulant (Bigoli et al., 1972), the title compound was synthesized and its crystal structure is reported herein.
In the crystal structure of the title compound, each ZnII ion is coordinated by two formylbenzoate (FB) and one isonicotinamide (INA) ligands (Fig. 1), while symmetry related FB ligands bridge the ZnII ions forming polymeric chains along the b axis (Fig.2). The structures of similar complexes of ZnII ion, [Zn2(C10H14N2O)2(C7H5O3)4].2H2O (Hökelek & Necefouglu, 1996) and [Zn(C9H10NO2)2(C6H6N2O)(H2O)2] (Hökelek et al., 2009) have also been reported.
The average Zn—O bond length (Table 1) is 1.9442 (11) Å and the Zn1 atom is displaced out of the least-squares planes of the carboxylate groups (O1/C1/O2) and (O3/C8/O4*) by 0.687 (5) Å and 0.703 (2) Å, respectively. The O1/C1/O2 and O3/C8/O4* carboxylate planes form dihedral angles of 9.07 (2)° and 26.2 (2)°, respectively, with benzene rings A(C2-C7) and B(C9-C14), while the angles between rings A, B and C (N1/C15-C19) are A/B = 81.30 (5), A/C = 63.17 (5) and B/C = 46.11 (5)°.
In the crystal structure, N—H···O and C—H···O hydrogen bonds (Table 2) link adjacent chains into a three-dimensional network. In addition, π–π contacts between symmetry related A(C2-C7) formylbenzoate rings at (x, y, z) and (5/2-x, -1/2+y, 1/2-z)/(5/2-x, 1/2+y, 1/2-z) with a centroid-to-centroid distance of 3.7736 (8) Å, and weak C—H···π interaction (Table 2) involving the B(C9-C14) ring stabilize the structure.
For general background to niacin, see: Krishnamachari (1974). For the crystal structure of N,N-diethylnicotinamide, see: Bigoli et al. (1972). For related structures, see: Hökelek & Necefouglu (1996); Hökelek et al. (2009). Cg1 is the centroid of the C9–C14 ring.
Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).
[Zn(C8H5O3)2(C6H6N2O)] | F(000) = 992 |
Mr = 485.74 | Dx = 1.670 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 9448 reflections |
a = 13.3143 (2) Å | θ = 3.1–28.4° |
b = 6.7857 (1) Å | µ = 1.32 mm−1 |
c = 21.3927 (3) Å | T = 100 K |
β = 91.458 (1)° | Needle, colourless |
V = 1932.14 (5) Å3 | 0.22 × 0.12 × 0.08 mm |
Z = 4 |
Bruker Kappa APEXII CCD area-detector diffractometer | 4812 independent reflections |
Radiation source: fine-focus sealed tube | 4086 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.072 |
φ and ω scans | θmax = 28.4°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −17→14 |
Tmin = 0.829, Tmax = 0.903 | k = −8→9 |
17841 measured reflections | l = −28→28 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.080 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0394P)2 + 0.0092P] where P = (Fo2 + 2Fc2)/3 |
4812 reflections | (Δ/σ)max = 0.001 |
297 parameters | Δρmax = 0.47 e Å−3 |
0 restraints | Δρmin = −0.39 e Å−3 |
[Zn(C8H5O3)2(C6H6N2O)] | V = 1932.14 (5) Å3 |
Mr = 485.74 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 13.3143 (2) Å | µ = 1.32 mm−1 |
b = 6.7857 (1) Å | T = 100 K |
c = 21.3927 (3) Å | 0.22 × 0.12 × 0.08 mm |
β = 91.458 (1)° |
Bruker Kappa APEXII CCD area-detector diffractometer | 4812 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 4086 reflections with I > 2σ(I) |
Tmin = 0.829, Tmax = 0.903 | Rint = 0.072 |
17841 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.080 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | Δρmax = 0.47 e Å−3 |
4812 reflections | Δρmin = −0.39 e Å−3 |
297 parameters |
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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0.816160 (13) | 0.51300 (2) | 0.187880 (8) | 0.01058 (7) | |
O1 | 0.95052 (8) | 0.60767 (16) | 0.20123 (5) | 0.0149 (2) | |
O2 | 1.00643 (8) | 0.55706 (16) | 0.10502 (5) | 0.0149 (2) | |
O3 | 0.77863 (8) | 0.37932 (15) | 0.26575 (5) | 0.0134 (2) | |
O4 | 0.70741 (8) | 0.67550 (14) | 0.15404 (5) | 0.0137 (2) | |
O5 | 0.83582 (11) | −0.07543 (19) | −0.07713 (6) | 0.0312 (3) | |
O6 | 1.49773 (9) | 0.61367 (17) | 0.23858 (5) | 0.0199 (3) | |
O7 | 1.10801 (11) | 0.97953 (16) | 0.45862 (6) | 0.0236 (3) | |
N1 | 0.81632 (9) | 0.29546 (17) | 0.12295 (6) | 0.0112 (3) | |
N2 | 0.91501 (11) | −0.28715 (18) | −0.01158 (6) | 0.0182 (3) | |
H2A | 0.9269 | −0.3695 | −0.0410 | 0.022* | |
H2B | 0.9348 | −0.3125 | 0.0262 | 0.022* | |
C1 | 1.02044 (11) | 0.5821 (2) | 0.16202 (7) | 0.0110 (3) | |
C2 | 1.12564 (11) | 0.5862 (2) | 0.18971 (7) | 0.0109 (3) | |
C3 | 1.14051 (12) | 0.5879 (2) | 0.25423 (7) | 0.0126 (3) | |
H3 | 1.0857 | 0.5867 | 0.2803 | 0.015* | |
C4 | 1.23802 (12) | 0.5913 (2) | 0.27978 (7) | 0.0131 (3) | |
H4 | 1.2487 | 0.5906 | 0.3229 | 0.016* | |
C5 | 1.31866 (11) | 0.5957 (2) | 0.24033 (7) | 0.0122 (3) | |
C6 | 1.30379 (12) | 0.5942 (2) | 0.17551 (7) | 0.0143 (3) | |
H6 | 1.3585 | 0.5979 | 0.1494 | 0.017* | |
C7 | 1.20746 (12) | 0.5872 (2) | 0.15043 (7) | 0.0134 (3) | |
H7 | 1.1971 | 0.5832 | 0.1073 | 0.016* | |
C8 | 0.81930 (11) | 0.3293 (2) | 0.31722 (7) | 0.0115 (3) | |
C9 | 0.89783 (12) | 0.4527 (2) | 0.34954 (7) | 0.0114 (3) | |
C10 | 0.96360 (12) | 0.3649 (2) | 0.39317 (7) | 0.0149 (3) | |
H10 | 0.9603 | 0.2299 | 0.4004 | 0.018* | |
C11 | 1.03354 (13) | 0.4785 (2) | 0.42548 (8) | 0.0162 (3) | |
H11 | 1.0792 | 0.4188 | 0.4531 | 0.019* | |
C12 | 1.03609 (12) | 0.6823 (2) | 0.41700 (7) | 0.0140 (3) | |
C13 | 0.97104 (12) | 0.7698 (2) | 0.37288 (7) | 0.0138 (3) | |
H13 | 0.9730 | 0.9053 | 0.3666 | 0.017* | |
C14 | 0.90409 (12) | 0.6556 (2) | 0.33872 (7) | 0.0122 (3) | |
H14 | 0.8627 | 0.7138 | 0.3083 | 0.015* | |
C15 | 0.86757 (11) | 0.1289 (2) | 0.13520 (7) | 0.0125 (3) | |
H15 | 0.8924 | 0.1074 | 0.1757 | 0.015* | |
C16 | 0.88489 (13) | −0.0119 (2) | 0.09003 (8) | 0.0139 (3) | |
H16 | 0.9213 | −0.1251 | 0.1000 | 0.017* | |
C17 | 0.84719 (12) | 0.0179 (2) | 0.02948 (8) | 0.0126 (3) | |
C18 | 0.79165 (12) | 0.1872 (2) | 0.01756 (7) | 0.0147 (3) | |
H18 | 0.7639 | 0.2097 | −0.0221 | 0.018* | |
C19 | 0.77770 (12) | 0.3220 (2) | 0.06473 (7) | 0.0136 (3) | |
H19 | 0.7404 | 0.4350 | 0.0561 | 0.016* | |
C20 | 0.86597 (12) | −0.1204 (2) | −0.02441 (7) | 0.0157 (3) | |
C21 | 1.42128 (13) | 0.6036 (2) | 0.26818 (8) | 0.0161 (3) | |
H21 | 1.4266 (13) | 0.600 (3) | 0.3157 (9) | 0.028 (5)* | |
C22 | 1.10601 (13) | 0.8010 (2) | 0.45686 (8) | 0.0188 (4) | |
H22 | 1.1561 (13) | 0.714 (3) | 0.4842 (9) | 0.020 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.01001 (11) | 0.01290 (10) | 0.00882 (11) | 0.00080 (6) | −0.00023 (7) | −0.00111 (6) |
O1 | 0.0092 (6) | 0.0225 (6) | 0.0129 (5) | −0.0007 (4) | 0.0003 (4) | −0.0045 (4) |
O2 | 0.0144 (6) | 0.0195 (5) | 0.0106 (5) | 0.0021 (5) | −0.0019 (5) | −0.0020 (4) |
O3 | 0.0120 (6) | 0.0184 (5) | 0.0098 (5) | −0.0013 (4) | −0.0021 (4) | 0.0016 (4) |
O4 | 0.0134 (6) | 0.0141 (5) | 0.0135 (5) | 0.0030 (4) | −0.0013 (5) | −0.0022 (4) |
O5 | 0.0524 (9) | 0.0310 (7) | 0.0097 (6) | 0.0163 (7) | −0.0092 (6) | −0.0050 (5) |
O6 | 0.0130 (6) | 0.0295 (6) | 0.0172 (6) | −0.0013 (5) | −0.0005 (5) | 0.0005 (5) |
O7 | 0.0279 (8) | 0.0248 (6) | 0.0181 (7) | −0.0107 (5) | 0.0007 (6) | −0.0038 (5) |
N1 | 0.0094 (7) | 0.0145 (6) | 0.0096 (6) | −0.0011 (5) | −0.0002 (5) | 0.0003 (5) |
N2 | 0.0256 (8) | 0.0193 (6) | 0.0094 (6) | 0.0055 (6) | −0.0018 (6) | −0.0037 (5) |
C1 | 0.0111 (8) | 0.0103 (6) | 0.0115 (7) | 0.0008 (6) | −0.0008 (6) | −0.0005 (6) |
C2 | 0.0111 (8) | 0.0102 (6) | 0.0113 (7) | 0.0000 (6) | −0.0016 (6) | 0.0001 (6) |
C3 | 0.0128 (8) | 0.0145 (7) | 0.0106 (7) | 0.0009 (6) | 0.0017 (6) | 0.0001 (6) |
C4 | 0.0164 (8) | 0.0143 (7) | 0.0085 (7) | 0.0000 (6) | −0.0008 (6) | −0.0002 (6) |
C5 | 0.0121 (8) | 0.0110 (7) | 0.0135 (8) | 0.0003 (6) | −0.0016 (6) | 0.0002 (6) |
C6 | 0.0113 (8) | 0.0190 (7) | 0.0127 (7) | −0.0008 (6) | 0.0028 (6) | −0.0003 (6) |
C7 | 0.0143 (8) | 0.0183 (7) | 0.0076 (7) | 0.0006 (6) | −0.0008 (6) | 0.0006 (6) |
C8 | 0.0096 (8) | 0.0138 (7) | 0.0113 (7) | 0.0029 (6) | 0.0015 (6) | −0.0023 (6) |
C9 | 0.0098 (8) | 0.0154 (7) | 0.0091 (7) | −0.0002 (6) | 0.0015 (6) | −0.0020 (6) |
C10 | 0.0173 (9) | 0.0137 (7) | 0.0137 (8) | 0.0002 (6) | −0.0001 (7) | −0.0003 (6) |
C11 | 0.0144 (9) | 0.0206 (8) | 0.0134 (8) | 0.0021 (6) | −0.0043 (7) | −0.0003 (6) |
C12 | 0.0113 (8) | 0.0191 (7) | 0.0117 (7) | −0.0021 (6) | −0.0004 (6) | −0.0029 (6) |
C13 | 0.0149 (8) | 0.0136 (7) | 0.0129 (7) | −0.0015 (6) | 0.0041 (6) | −0.0024 (6) |
C14 | 0.0111 (8) | 0.0164 (7) | 0.0090 (7) | 0.0020 (6) | 0.0012 (6) | 0.0004 (6) |
C15 | 0.0116 (8) | 0.0171 (7) | 0.0087 (7) | 0.0004 (6) | −0.0023 (6) | 0.0008 (6) |
C16 | 0.0157 (9) | 0.0140 (7) | 0.0120 (8) | 0.0026 (6) | −0.0017 (7) | −0.0003 (5) |
C17 | 0.0147 (8) | 0.0143 (7) | 0.0088 (8) | −0.0022 (6) | 0.0006 (6) | −0.0003 (5) |
C18 | 0.0169 (9) | 0.0176 (7) | 0.0094 (7) | −0.0006 (6) | −0.0029 (6) | 0.0014 (6) |
C19 | 0.0130 (8) | 0.0150 (7) | 0.0128 (7) | 0.0019 (6) | −0.0011 (6) | 0.0029 (6) |
C20 | 0.0180 (9) | 0.0185 (7) | 0.0106 (7) | 0.0001 (6) | −0.0013 (7) | −0.0024 (6) |
C21 | 0.0173 (9) | 0.0171 (7) | 0.0139 (8) | 0.0003 (6) | −0.0024 (7) | −0.0003 (6) |
C22 | 0.0174 (9) | 0.0260 (8) | 0.0131 (8) | −0.0046 (7) | 0.0007 (7) | −0.0018 (7) |
Zn1—O1 | 1.9153 (11) | C7—C6 | 1.378 (2) |
Zn1—O3 | 1.9723 (11) | C7—H7 | 0.93 |
Zn1—O4 | 1.9450 (10) | C8—O4ii | 1.2669 (18) |
Zn1—N1 | 2.0270 (12) | C8—C9 | 1.495 (2) |
O1—C1 | 1.2807 (18) | C9—C10 | 1.397 (2) |
O2—C1 | 1.2405 (18) | C9—C14 | 1.3990 (19) |
O3—C8 | 1.2611 (17) | C10—H10 | 0.93 |
O4—C8i | 1.2669 (18) | C11—C10 | 1.381 (2) |
O5—C20 | 1.2261 (18) | C11—H11 | 0.93 |
O6—C21 | 1.214 (2) | C12—C11 | 1.395 (2) |
O7—C22 | 1.2124 (19) | C12—C13 | 1.397 (2) |
N1—C15 | 1.3427 (18) | C12—C22 | 1.484 (2) |
N1—C19 | 1.3474 (18) | C13—C14 | 1.377 (2) |
N2—C20 | 1.332 (2) | C13—H13 | 0.93 |
N2—H2A | 0.86 | C14—H14 | 0.93 |
N2—H2B | 0.86 | C15—H15 | 0.93 |
C2—C1 | 1.507 (2) | C16—C15 | 1.382 (2) |
C2—C3 | 1.390 (2) | C16—C17 | 1.392 (2) |
C2—C7 | 1.393 (2) | C16—H16 | 0.93 |
C3—C4 | 1.396 (2) | C18—C17 | 1.386 (2) |
C3—H3 | 0.93 | C18—H18 | 0.93 |
C4—H4 | 0.93 | C19—C18 | 1.378 (2) |
C5—C4 | 1.383 (2) | C19—H19 | 0.93 |
C5—C6 | 1.396 (2) | C20—C17 | 1.512 (2) |
C5—C21 | 1.478 (2) | C21—H21 | 1.018 (19) |
C6—H6 | 0.93 | C22—H22 | 1.057 (17) |
O1—Zn1—O3 | 106.50 (4) | C14—C9—C8 | 121.23 (13) |
O1—Zn1—O4 | 123.30 (5) | C9—C10—H10 | 120.0 |
O1—Zn1—N1 | 109.22 (5) | C11—C10—C9 | 119.95 (14) |
O3—Zn1—N1 | 104.39 (5) | C11—C10—H10 | 120.0 |
O4—Zn1—O3 | 111.89 (5) | C10—C11—C12 | 120.45 (15) |
O4—Zn1—N1 | 99.88 (5) | C10—C11—H11 | 119.8 |
C1—O1—Zn1 | 123.27 (10) | C12—C11—H11 | 119.8 |
C8—O3—Zn1 | 138.48 (10) | C11—C12—C13 | 119.50 (14) |
C8i—O4—Zn1 | 120.13 (10) | C11—C12—C22 | 118.70 (15) |
C15—N1—Zn1 | 119.26 (10) | C13—C12—C22 | 121.77 (14) |
C15—N1—C19 | 118.22 (13) | C12—C13—H13 | 120.0 |
C19—N1—Zn1 | 121.95 (10) | C14—C13—C12 | 120.09 (14) |
C20—N2—H2A | 120.0 | C14—C13—H13 | 120.0 |
C20—N2—H2B | 120.0 | C9—C14—H14 | 119.8 |
H2A—N2—H2B | 120.0 | C13—C14—C9 | 120.42 (14) |
O1—C1—C2 | 115.07 (13) | C13—C14—H14 | 119.8 |
O2—C1—O1 | 124.67 (14) | N1—C15—C16 | 122.57 (14) |
O2—C1—C2 | 120.25 (14) | N1—C15—H15 | 118.7 |
C3—C2—C1 | 119.87 (14) | C16—C15—H15 | 118.7 |
C3—C2—C7 | 120.36 (14) | C15—C16—C17 | 119.19 (14) |
C7—C2—C1 | 119.76 (13) | C15—C16—H16 | 120.4 |
C2—C3—C4 | 119.77 (14) | C17—C16—H16 | 120.4 |
C2—C3—H3 | 120.1 | C16—C17—C20 | 123.82 (13) |
C4—C3—H3 | 120.1 | C18—C17—C16 | 118.00 (14) |
C3—C4—H4 | 120.3 | C18—C17—C20 | 118.16 (14) |
C5—C4—C3 | 119.36 (14) | C17—C18—H18 | 120.1 |
C5—C4—H4 | 120.3 | C19—C18—C17 | 119.77 (14) |
C4—C5—C6 | 120.90 (14) | C19—C18—H18 | 120.1 |
C4—C5—C21 | 118.62 (14) | N1—C19—C18 | 122.20 (14) |
C6—C5—C21 | 120.48 (14) | N1—C19—H19 | 118.9 |
C5—C6—H6 | 120.2 | C18—C19—H19 | 118.9 |
C7—C6—C5 | 119.60 (14) | O5—C20—N2 | 123.26 (15) |
C7—C6—H6 | 120.2 | O5—C20—C17 | 119.35 (14) |
C2—C7—H7 | 120.0 | N2—C20—C17 | 117.39 (13) |
C6—C7—C2 | 119.98 (14) | O6—C21—C5 | 124.78 (15) |
C6—C7—H7 | 120.0 | O6—C21—H21 | 119.0 (11) |
O3—C8—O4ii | 121.72 (14) | C5—C21—H21 | 116.3 (11) |
O3—C8—C9 | 122.19 (13) | O7—C22—C12 | 124.98 (17) |
O4ii—C8—C9 | 116.01 (13) | O7—C22—H22 | 121.9 (9) |
C10—C9—C8 | 119.27 (13) | C12—C22—H22 | 113.1 (9) |
C10—C9—C14 | 119.45 (14) | ||
O3—Zn1—O1—C1 | 132.27 (11) | C21—C5—C4—C3 | 178.69 (13) |
O4—Zn1—O1—C1 | −96.44 (12) | C4—C5—C6—C7 | −0.3 (2) |
N1—Zn1—O1—C1 | 20.07 (13) | C21—C5—C6—C7 | −179.85 (14) |
O1—Zn1—O3—C8 | −6.56 (15) | C4—C5—C21—O6 | −177.81 (15) |
O4—Zn1—O3—C8 | −143.97 (14) | C6—C5—C21—O6 | 1.7 (2) |
N1—Zn1—O3—C8 | 108.94 (15) | C2—C7—C6—C5 | 1.5 (2) |
O1—Zn1—O4—C8i | −60.90 (13) | O3—C8—C9—C10 | −158.23 (15) |
O3—Zn1—O4—C8i | 68.17 (12) | O3—C8—C9—C14 | 24.3 (2) |
N1—Zn1—O4—C8i | 178.16 (11) | O4ii—C8—C9—C10 | 24.8 (2) |
O1—Zn1—N1—C15 | 62.86 (12) | O4ii—C8—C9—C14 | −152.61 (15) |
O1—Zn1—N1—C19 | −108.32 (12) | C8—C9—C10—C11 | −177.06 (15) |
O3—Zn1—N1—C15 | −50.72 (12) | C14—C9—C10—C11 | 0.4 (2) |
O3—Zn1—N1—C19 | 138.10 (12) | C8—C9—C14—C13 | 174.28 (14) |
O4—Zn1—N1—C15 | −166.53 (11) | C10—C9—C14—C13 | −3.2 (2) |
O4—Zn1—N1—C19 | 22.29 (13) | C12—C11—C10—C9 | 2.9 (3) |
Zn1—O1—C1—O2 | 25.4 (2) | C13—C12—C11—C10 | −3.6 (3) |
Zn1—O1—C1—C2 | −155.21 (9) | C22—C12—C11—C10 | 174.41 (16) |
Zn1—O3—C8—O4ii | −147.48 (12) | C11—C12—C13—C14 | 0.9 (2) |
Zn1—O3—C8—C9 | 35.8 (2) | C22—C12—C13—C14 | −177.08 (15) |
Zn1—N1—C15—C16 | −169.24 (12) | C11—C12—C22—O7 | −171.97 (17) |
C19—N1—C15—C16 | 2.3 (2) | C13—C12—C22—O7 | 6.0 (3) |
Zn1—N1—C19—C18 | 169.38 (12) | C12—C13—C14—C9 | 2.5 (2) |
C15—N1—C19—C18 | −1.9 (2) | C17—C16—C15—N1 | −0.7 (2) |
C3—C2—C1—O1 | 9.2 (2) | C15—C16—C17—C18 | −1.4 (2) |
C3—C2—C1—O2 | −171.42 (14) | C15—C16—C17—C20 | 176.70 (15) |
C7—C2—C1—O1 | −171.18 (13) | C19—C18—C17—C16 | 1.7 (2) |
C7—C2—C1—O2 | 8.2 (2) | C19—C18—C17—C20 | −176.45 (14) |
C1—C2—C3—C4 | 179.87 (13) | N1—C19—C18—C17 | −0.1 (2) |
C7—C2—C3—C4 | 0.2 (2) | N2—C20—C17—C16 | 5.3 (2) |
C1—C2—C7—C6 | 178.94 (14) | N2—C20—C17—C18 | −176.65 (15) |
C3—C2—C7—C6 | −1.4 (2) | O5—C20—C17—C16 | −174.85 (17) |
C2—C3—C4—C5 | 0.9 (2) | O5—C20—C17—C18 | 3.2 (2) |
C6—C5—C4—C3 | −0.8 (2) |
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x+3/2, y−1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O2iii | 0.86 | 2.08 | 2.9242 (17) | 165 |
N2—H2B···O2iv | 0.86 | 2.11 | 2.9439 (17) | 163 |
C4—H4···O5v | 0.93 | 2.41 | 3.298 (2) | 160 |
C6—H6···O7vi | 0.93 | 2.50 | 3.223 (2) | 135 |
C15—H15···O6vi | 0.93 | 2.32 | 3.2049 (19) | 159 |
C16—H16···O2iv | 0.93 | 2.44 | 3.3541 (18) | 169 |
C3—H3···Cg1 | 0.93 | 2.73 | 3.6332 (17) | 163 |
Symmetry codes: (iii) −x+2, −y, −z; (iv) x, y−1, z; (v) x+1/2, −y+1/2, z+1/2; (vi) −x+5/2, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C8H5O3)2(C6H6N2O)] |
Mr | 485.74 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 100 |
a, b, c (Å) | 13.3143 (2), 6.7857 (1), 21.3927 (3) |
β (°) | 91.458 (1) |
V (Å3) | 1932.14 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.32 |
Crystal size (mm) | 0.22 × 0.12 × 0.08 |
Data collection | |
Diffractometer | Bruker Kappa APEXII CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
Tmin, Tmax | 0.829, 0.903 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17841, 4812, 4086 |
Rint | 0.072 |
(sin θ/λ)max (Å−1) | 0.668 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.080, 1.10 |
No. of reflections | 4812 |
No. of parameters | 297 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.47, −0.39 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O2i | 0.86 | 2.08 | 2.9242 (17) | 165 |
N2—H2B···O2ii | 0.86 | 2.11 | 2.9439 (17) | 163 |
C4—H4···O5iii | 0.93 | 2.41 | 3.298 (2) | 160 |
C6—H6···O7iv | 0.93 | 2.50 | 3.223 (2) | 135 |
C15—H15···O6iv | 0.93 | 2.32 | 3.2049 (19) | 159 |
C16—H16···O2ii | 0.93 | 2.44 | 3.3541 (18) | 169 |
C3—H3···Cg1 | 0.93 | 2.73 | 3.6332 (17) | 163 |
Symmetry codes: (i) −x+2, −y, −z; (ii) x, y−1, z; (iii) x+1/2, −y+1/2, z+1/2; (iv) −x+5/2, y−1/2, −z+1/2. |
As a part of our ongoing investigation on transition metal complexes of nicotinamide (NA), one form of niacin (Krishnamachari, 1974), and/or the nicotinic acid derivative N,N-diethylnicotinamide (DENA), an important respiratory stimulant (Bigoli et al., 1972), the title compound was synthesized and its crystal structure is reported herein.
In the crystal structure of the title compound, each ZnII ion is coordinated by two formylbenzoate (FB) and one isonicotinamide (INA) ligands (Fig. 1), while symmetry related FB ligands bridge the ZnII ions forming polymeric chains along the b axis (Fig.2). The structures of similar complexes of ZnII ion, [Zn2(C10H14N2O)2(C7H5O3)4].2H2O (Hökelek & Necefouglu, 1996) and [Zn(C9H10NO2)2(C6H6N2O)(H2O)2] (Hökelek et al., 2009) have also been reported.
The average Zn—O bond length (Table 1) is 1.9442 (11) Å and the Zn1 atom is displaced out of the least-squares planes of the carboxylate groups (O1/C1/O2) and (O3/C8/O4*) by 0.687 (5) Å and 0.703 (2) Å, respectively. The O1/C1/O2 and O3/C8/O4* carboxylate planes form dihedral angles of 9.07 (2)° and 26.2 (2)°, respectively, with benzene rings A(C2-C7) and B(C9-C14), while the angles between rings A, B and C (N1/C15-C19) are A/B = 81.30 (5), A/C = 63.17 (5) and B/C = 46.11 (5)°.
In the crystal structure, N—H···O and C—H···O hydrogen bonds (Table 2) link adjacent chains into a three-dimensional network. In addition, π–π contacts between symmetry related A(C2-C7) formylbenzoate rings at (x, y, z) and (5/2-x, -1/2+y, 1/2-z)/(5/2-x, 1/2+y, 1/2-z) with a centroid-to-centroid distance of 3.7736 (8) Å, and weak C—H···π interaction (Table 2) involving the B(C9-C14) ring stabilize the structure.